Manual 746 VA Trace Analyzer en

Section 1
Introduction
CH-9101 Herisau/Switzerland
Phone ++41 71 353 85 85
Fax ++41 71 353 89 01
Internet www.metrohm.ch
E-Mail info@metrohm.ch Section 2
Parts and Controls
746 VA Trace Analyzer Section 3

5.746.0101 program Installation
Section 4
Introduction to the Operation
Section 5
747 VA Stand Operation
Section 6
Data Processing and
Evaluation
Section 7
Safety, Errors, Trouble-
Mains connection
Mains voltage: 100 120 V 10 %
shooting, Diagnosis, GLP
220 240 V 10 %
Mains frequency: 50 60 Hz
Power consumption: 160 VA Section 8
Technical Data
Section 9
8.746.1053 Scope of delivery, Options,
Instructions for Use Warranty
21.11.2000 / d
Section 10
Index
Table of contents
Table of contents
1 Introduction ...................................................................................... 1-1

1.1 Instrument description................................................................ 1-1
1.2 Information about the Instructions for Use ...................... 1-2

1.2.1 Organization.................................................................................1-2
1.2.2 Notation and pictograms .............................................................1-3
1.3 Support documentation.............................................................. 1-4
2 Parts and controls .................................................................... 2-1

2.1 746.0010 VA Trace Analyzer .................................................... 2-2
2.3 747.0010 VA Stand ........................................................................ 2-6
3 Installation ........................................................................................ 3-1

3.1 Setting up the instruments ....................................................... 3-1
3.1.1 Packaging ....................................................................................3-1
3.1.2 Check ...........................................................................................3-1
3.1.3 Location........................................................................................3-1
3.1.4 Arrangement of the instruments ..................................................3-1
3.2 Installation of 746 VA Trace Analyzer ................................. 3-2

3.2.1 Setting the instrument supply voltage .........................................3-2
3.2.2 Fuses............................................................................................3-2
3.2.3 Mains cable and mains connection.............................................3-3
3.2.4 Switching the instrument on/off ...................................................3-3
3.2.5 Installing paper (only for internal printer) .....................................3-3
3.2.6 Handling of data cards ................................................................3-4
3.3 Installation of 747 VA Stand ..................................................... 3-6

3.3.1 Electrical connection at 746 VA Trace Analyzer ..........................3-6
3.3.2 Equipping the measuring head ...................................................3-7
3.3.3 Inert gas connection ..................................................................3-12
746 VA Trace Analyzer / 747 VA Stand I

Table of contents
3.4 Multi-mode electrode (MME) .................................................. 3-14

3.4.1 Construction and operating characteristics of the MME........... 3-14
3.4.2 Filling the MME with mercury..................................................... 3-16
3.4.3 Mounting the capillary ............................................................... 3-17
3.4.4 Filling the capillary without vacuum........................................... 3-18
3.4.5 Filling the capillary using vacuum ............................................. 3-19
3.4.6 Storing the MME ........................................................................ 3-22
3.4.7 Replenishing the mercury (without changing capillary) ............ 3-23
3.4.8 Changing the capillary............................................................... 3-24
3.4.9 Cleaning the MME ..................................................................... 3-25
3.5 Rotating disk electrode (RDE) .............................................. 3-27

3.5.1 Construction and startup of the RDE......................................... 3-27
3.5.2 Regenerating the RDE ............................................................... 3-27
3.6 Reference electrode ................................................................... 3-29

3.6.1 Construction .............................................................................. 3-29
3.6.2 Startup procedure...................................................................... 3-30
3.7 Auxiliary electrode ...................................................................... 3-31

3.7.1 Construction .............................................................................. 3-31
3.7.2 Startup procedure...................................................................... 3-31
3.8 Stirrer ................................................................................................. 3-32
3.9 Connection of 685 Dosimats ................................................. 3-33

3.9.1 Electrical connection.................................................................. 3-33
3.9.2 Tubing connection for addition of standard solutions............... 3-34
3.9.3 Tubing connection for addition of auxiliary solutions ................ 3-35
3.9.4 Changing the Exchange unit ..................................................... 3-37
3.9.5 Installation and use of the pipetting equipment ........................ 3-38
3.10 Connection of 700 Dosinos .................................................... 3-41

3.10.1 Electrical connection.................................................................. 3-41
3.10.2 Tubing connection for addition of standard solutions............... 3-42
3.10.3 Tubing connection for addition of auxiliary solutions ................ 3-43
3.10.4 Changing the Dosing unit.......................................................... 3-45
3.10.5 Installation of Dosinos for rinsing the measuring vessel ........... 3-46
3.10.6 Installation and use of the pipetting equipment ........................ 3-48
3.11 Connection of printers via parallel interface................. 3-51
3.12 Connection of devices via RS232 interfaces ................ 3-52

3.12.1 Connection of a PC ................................................................... 3-53
3.12.2 Connection of a printer .............................................................. 3-54
3.12.3 Connection of a balance ........................................................... 3-55
3.13 Connection of devices via remote interface.................. 3-56
II 746 VA Trace Analyzer / 747 VA Stand

Table of contents
4 Introduction to the operation ..................................... 4-1

4.1 Preparations ..................................................................................... 4-2
4.1.1 Installation of the 746 VA Trace Analyzer.....................................4-2
4.1.2 Installation of the 747 VA Stand ...................................................4-2
4.1.3 Settings on the "VA TRACE ANALYZER" page ............................4-3
4.1.4 Tests to check the 747 VA Stand.................................................4-6
4.2 Lead determination with standard addition ..................... 4-9

4.2.1 Reagents ......................................................................................4-9
4.2.2 Loading the method TESTPb.mth .............................................4-9
4.2.3 Method specifications of the method TESTPb.mth ................4-10
4.2.4 Preparing the sample solution ...................................................4-16
4.2.5 Settings on the "MONITORING" page........................................4-16
4.2.6 Performing the determination ....................................................4-17
4.2.7 Storing the determination...........................................................4-23
4.2.8 Display of the results..................................................................4-25
4.2.9 Display of the curves..................................................................4-27
4.3 Lead determination with calibration curve ..................... 4-29

4.3.1 Reagents and accessories ........................................................4-29
4.3.2 Loading the method CALCRV.mth ...........................................4-30
4.3.3 Method specifications of the method CALCRV.mth ................4-31
4.3.4 Recording the calibration curve .................................................4-34
4.4 Lead determination with internal standard .................... 4-42

4.4.1 Reagents and accessories ........................................................4-42
4.4.2 Loading the method INTSTD.mth ...........................................4-43
4.4.3 Method specifications of the method INTSTD.mth ................4-43
4.4.4 Recording the calibration curve .................................................4-47
4.5 Basic method for DP polarography .................................... 4-56

4.5.1 Reagents ....................................................................................4-56
4.5.2 Loading the method POL.mth..................................................4-56
4.5.3 Method specifications of the method POL.mth .......................4-57
4.6 Basic method for DPASV ......................................................... 4-61

4.6.1 Reagents ....................................................................................4-61
4.6.2 Loading the method ASV.mth..................................................4-61
4.6.3 Method specifications of the method ASV.mth .......................4-62
746 VA Trace Analyzer / 747 VA Stand III

Table of contents
5 Operation ............................................................................................ 5-1

5.1 The keys and their functions .................................................... 5-2
5.1.1 Key categories ............................................................................. 5-2
5.1.2 Alphanumeric keys ...................................................................... 5-3
5.1.3 Dialog keys .................................................................................. 5-4
5.1.4 Main function keys....................................................................... 5-7
5.1.5 Auxiliary function keys and softkeys............................................ 5-9
5.2 Screen dialog ................................................................................. 5-11

5.2.1 Layout of the dialog pages ........................................................ 5-11
5.2.2 Navigation mode........................................................................ 5-12
5.2.3 Edit mode................................................................................... 5-12
5.3 Set Up ................................................................................................ 5-15

5.3.1 VA TRACE ANALYZER............................................................... 5-16
5.3.2 STAND ....................................................................................... 5-21
5.3.3 DOSIMATS................................................................................. 5-37
5.3.4 SOLUTIONS............................................................................... 5-43
5.4 Storages ........................................................................................... 5-46

5.4.1 METHODS ................................................................................. 5-47
5.4.2 DETERMINATIONS.................................................................... 5-51
5.4.3 DATA CARD............................................................................... 5-55
5.4.4 SAMPLES................................................................................... 5-59
5.4.5 COMMON VARIABLES .............................................................. 5-66
5.5 Operation ......................................................................................... 5-68

5.5.1 MONITORING ............................................................................ 5-69
5.5.2 RESULTS ................................................................................... 5-82
5.5.3 CURVES..................................................................................... 5-93
5.6 Method Specifications ............................................................5-121

5.6.1 OPERATION SEQUENCE........................................................ 5-122
5.6.2 SEGMENTS.............................................................................. 5-124
5.6.3 SUBSTANCES ......................................................................... 5-129
5.6.4 CALCULATION ........................................................................ 5-160
5.6.5 DOCUMENTATION.................................................................. 5-166
5.7 Program instructions...............................................................5-175

5.7.1 General guidelines................................................................... 5-175
5.7.2 Overview of the program instructions...................................... 5-177
5.7.3 Alphabetical instruction list ...................................................... 5-183
IV 746 VA Trace Analyzer / 747 VA Stand

Table of contents
6 Data processing and evaluation ............................. 6-1

6.1 Operational chart for determinations .................................. 6-1
6.2 Preparations before start of a determination .................. 6-2

6.2.1 Method definition .........................................................................6-2
6.2.2 Definition of the sample size........................................................6-4
6.2.3 Method-independent settings......................................................6-5
6.3 Data acquisition .............................................................................. 6-6
6.4 Spike elimination and background compensation....... 6-7
6.5 Smoothing and differentiation ................................................ 6-8
6.6 Recognition of peaks and waves .......................................... 6-9
6.7 Baseline calculation ................................................................... 6-11

6.7.1 General.......................................................................................6-11
6.7.2 Baselines for waves ...................................................................6-13
6.7.3 Baselines for peaks....................................................................6-14
6.7.4 Baselines for AC2 curves...........................................................6-17
6.7.5 Baselines for PSA curves...........................................................6-18
6.8 Height/area calculation ............................................................. 6-19
6.9 Content calculation..................................................................... 6-20

6.9.1 General.......................................................................................6-20
6.9.2 Dilution calculation .....................................................................6-21
6.9.3 Result calculation from calibration curves
and error calculation ..................................................................6-22
6.9.4 Standard addition.......................................................................6-24
6.9.5 Calibration curve ........................................................................6-27
6.9.6 Internal standard ........................................................................6-31
6.10 Formula calculation .................................................................... 6-36
746 VA Trace Analyzer / 747 VA Stand V

Table of contents
7 Safety, Errors, Troubleshooting,

Diagnosis, GLP ............................................................................. 7-1
7.1 Electrical safety ............................................................................... 7-1
7.2 Safety considerations concerning mercury ..................... 7-2

7.2.1 Properties of mercury .................................................................. 7-2
7.2.2 Toxicity of mercury and its compounds ...................................... 7-3
7.2.3 Handling of mercury .................................................................... 7-3
7.2.4 References dealing with mercury ................................................ 7-5
7.3 Error messages ............................................................................... 7-6

7.3.1 General information on error messages...................................... 7-6
7.3.2 List of error messages ................................................................. 7-7
7.3.3 Instrument initialization .............................................................. 7-29
7.4 Troubleshooting ........................................................................... 7-33

7.4.1 General rules for VA trace analysis............................................ 7-33
7.4.2 Problems with DME/SMDE ........................................................ 7-35
7.4.3 Problems with HMDE................................................................. 7-37
7.4.4 Problems with RDE .................................................................... 7-40
7.5 Hardware/software faults in the instruments

or simply the vagaries of the chemistry .......................... 7-42
7.5.1 General ...................................................................................... 7-42
7.5.2 Oxygen in the analysis solution ................................................. 7-42
7.5.3 Unsuitable bridging electrolyte solution
in the reference electrode.......................................................... 7-43
7.5.4 Overcharging of the working electrode ..................................... 7-43
7.5.5 Disturbances at the HMDE through gas formation ................... 7-45
7.5.6 Complex formation .................................................................... 7-46
7.5.7 Peak on highly curved baseline................................................. 7-47
7.5.8 Peak overlapping ....................................................................... 7-47
7.5.9 Calibration with chemically non-isoformal standards................ 7-48
7.6 Diagnosis ......................................................................................... 7-49

7.6.1 General ...................................................................................... 7-49
7.6.2 Prepare instrument for diagnostic test ...................................... 7-50
7.6.3 Checking thermal printer ........................................................... 7-50
7.6.4 Checking RS232 interfaces ....................................................... 7-52
7.6.5 Checking control lines ............................................................... 7-52
7.6.6 Checking the keypad................................................................. 7-53
7.6.7 Checking the VA Stand.............................................................. 7-54
7.7 Standard operating procedure in the context of

GLP/ISO 9001 guidelines ......................................................... 7-58
7.7.1 Checking 747 VA Stand with polarogram simulator.................. 7-58
7.7.2 Loading the TESTPb.mth method........................................... 7-60
7.7.3 Preparing the sample solution................................................... 7-60
7.7.4 Performing the determination .................................................... 7-61
7.7.5 Assessment of the determination .............................................. 7-62
VI 746 VA Trace Analyzer / 747 VA Stand

Table of contents
8 Technical data .............................................................................. 8-1

8.1 746 VA Trace Analyzer ................................................................ 8-1
8.2 747 VA Stand .................................................................................... 8-6
8.3 RS232 interfaces .......................................................................... 8-10

8.3.1 Features of the RS232 interfaces...............................................8-10
8.3.2 Data transmission protocols ......................................................8-11
8.3.3 Settings and modes...................................................................8-11
8.3.4 Key remote control mode ..........................................................8-12
8.3.5 Handshake.................................................................................8-14
8.3.6 Pin assignment ..........................................................................8-17
9 Scope of delivery, Options, Warranty ................ 9-1

9.3 747.0010 VA Stand ........................................................................ 9-3
9.4 Options for 747 VA Stand .......................................................... 9-8
9.5 Optional peripherals, cables and software .................... 9-11
9.6 Warranty ........................................................................................... 9-14
9.7 EU Declaration of conformity ................................................ 9-15
9.8 Certificate of conformity and system validation ......... 9-17
10 Index.......................................................................................................10-1
746 VA Trace Analyzer / 747 VA Stand VII

Table of contents
List of figures
Fig. 1: Front of the 746.0010 VA Trace Analyzer ................................ 2-2
Fig. 2: Rear of the 746.0010 VA Trace Analyzer ................................. 2-3
Fig. 3: Front of the 746.0020 VA Trace Analyzer ................................ 2-4
Fig. 4: Rear of the 746.0020 VA Trace Analyzer ................................. 2-5
Fig. 5: Front of the 747.0010 VA Stand .................................................... 2-6
Fig. 6: Rear of the 747.0010 VA Stand ..................................................... 2-6
Fig. 7: Right side view of the 747.0010 VA Stand .............................. 2-8
Fig. 8: Left side view of the 747.0010 VA Stand.................................. 2-8
Fig. 9: Measuring head arm........................................................................... 3-8
Fig. 10: Install accessories for rinsing and siphoning off ............ 3-11
Fig. 11: Scheme showing the inert gas connections
at the 747 VA Stand ......................................................................... 3-13
Fig. 12: Multi-Mode electrode ...................................................................... 3-15
Fig. 13: Adding the mercury ......................................................................... 3-16
Fig. 14: Setting up the filling station ........................................................ 3-20
Fig. 15: Filling the capillary........................................................................... 3-20
Fig. 16: Measuring head arm with rotating disk electrode ........... 3-28
Fig. 17: Construction of the reference electrode ............................... 3-29
Fig. 18: Construction of the auxiliary electrode ................................. 3-32
Fig. 19: Connection of 685 Dosimats to
746 VA Trace Analyzer ................................................................... 3-33
Fig. 20: Pipetting handle................................................................................. 3-38
Fig. 21: Connection of 700 Dosinos to
746 VA Trace Analyzer ................................................................... 3-41
Fig. 22: Scheme of the tubing connections for
Rinsing and Siphoning Dosino .................................................. 3-47
Fig. 23: Connection of a printer to 746 VA Trace Analyzer .......... 3-52
Fig. 24: Connection possibilities for the RS232 interfaces .......... 3-53
Fig. 25: Connection of external devices devices
to remote interface ........................................................................... 3-57
VIII 746 VA Trace Analyzer / 747 VA Stand

1.1 Instrument description
1 Introduction
1.1 Instrument description
The 746 VA Trace Analyzer is a microprocessor-controlled measuring instrument for
universal use in polarographic and voltam(pero)metric analyses. The two concepts
polarography and voltammetry are defined as follows:
Polarography
Polarography is the measurement of current/voltage curves recorded at
electrodes whose material is liquid and whose surface is renewed periodi-
cally or continuously.
Example of such an electrode: DME
Voltammetry (actually voltamperometry, abbreviated to VA)
Voltammetry is the measurement of current/voltage curves recorded at
electrodes whose material is solid and/or whose surface is stationary.
Example of such electrodes: HMDE, RDE
The 746 VA Trace Analyzer is used as a master control unit for the devices at-
tached to it. Up to three 747 VA Stands can be connected as measuring stations
and up to four 685 Dosimats or 700 Dosinos used for dispensing operations. For
automatic determinations of relatively large sample series, the 695 Autosampler is
available as an option.
Operation of the 746 VA Trace Analyzer is based on the principle of interactive dia-
log via screen pages which can be called up directly by pressing the appropriate
yellow dialog keys. The instrument can be given instructions on the total of 17 dif-
ferent screen pages via the keyboard regarding the functions and their associated
parameters which should apply for a determination. A special position here is oc-
cupied by the two pages OP.SEQUENCE and SEGMENTS on which program
instructions can be used freely to define the course of a sample determination and
the recording of measured values. The current signals recorded at the measuring
stands are conditioned by the 746 VA Trace Analyzer and automatically evaluated.
Finally, the results are recorded in suitable form on the built-in or external printer.
The 746 VA Trace Analyzer contains a large, non-volatile data memory with space
for up to 256 fully developed, user-specific methods and up to 256 determinations.
In addition, both methods and determinations can be stored on and reloaded from
data cards. For the storage of data on a PC attached to the RS interface, a PC pro-
gram VA Back Up is supplied.
The 747 VA Stand is the measuring stand accompanying the 746 VA Trace Ana-
lyzer. Its central element is the multi-mode electrode (MME), which combines the
dropping mercury electrode (DME/SMDE) and the stationary hanging mercury drop
electrode (HMDE) in a single construction. The rotating disk electrode (RDE) can
also be used in the stand.
Operation of the 747 VA Stand follows the potentiostatic 3-electrode principle in
which the voltage of the working electrode is controlled by means of a virtually cur-
rentless reference electrode to the preset desired value and the current flows
across a separate auxiliary electrode. The in part extremely small electrode signals
are recorded in the 747 VA Stand in analog form, amplified and digitized. In the
connecting cable to the 746 VA Trace Analyzer only the non-critical, digital signals
are interchanged.
746 VA Trace Analyzer / 747 VA Stand 1-1

1 Introduction
1.2 Information about the Instructions for Use
Please read through these Instructions for Use carefully before you put
the 746 VA Trace Analyzer and 747 VA Stand into operation. The
Instructions for Use contain information and warnings to which the
user must pay attention in order to assure safe operation of the instru-
ments.
1.2.1 Organization
These 8.746.1033 Instructions for Use for the 746 VA Trace Analyzer and the 747
VA Stand provide a comprehensive overview of the installation, operation, fault rec-
tification and technical specifications of these instruments. The Instructions for Use
are divided into the following 10 sections:
Section 1 Introduction
Section 2 Parts and controls
Numbers and designations of the parts and controls
Section 3 Installation
Installation of 746 VA Trace Analyzer and 747 VA Stand
Installation of working, reference and auxiliary electrodes
Attachment of 685 Dosimats and 700 Dosinos
Attachment of devices via RS232 and remote interface
Section 4 Introduction to operation
Introduction to the operation using simple examples
Section 5 Operation
Detailed description of the operation
Explanation of all key functions
Explanation of all dialog pages with parameters and softkeys
Explanation of all program instructions
Section 6 Data processing and evaluation
Description of all steps in data acquisition, data processing
and evaluation
Section 7 Safety, errors, troubleshooting, diagnosis, GLP
Electrical safety, safety considerations in the handling of
mercury, detailed list of the error messages, troubleshooting,
instrument diagnosis and GLP method
Section 8 Technical data
Section 9 Scope of delivery, options, warranty
Section 10 Index
To find the required information on the instruments please use either the Table of
contents or the Index at the back.
1-2 746 VA Trace Analyzer / 747 VA Stand

1.2 Information about the Instructions for Use
1.2.2 Notation and pictograms
The following notations and pictograms (symbols) are used in these Instructions for
Use:
"SAMPLES" Dialog page
<ENTER> Key
<Copy to> Softkey
Mode Parameter or entry value
........ Modifiable parameter
XXXXXXXX Displayed parameter

(not modifiable)
15 Part or control of 746/747
Hazard
This symbol draws attention to a
possible danger to life or of injury if
the associated directions are not
followed correctly.
Warning
This symbol draws attention to
possible damage to instruments or
instrument parts if the associated
directions are not followed cor-
rectly.
Caution
This symbol marks important infor-
mation. First read the associated
directions before you continue.
Comment
This symbol marks additional in-
formation and tips.

1 Introduction
1.3 Support documentation
Application Bulletins
The Application Bulletin is a collection of analytical methods, application exam-
ples and literature references. Of Metrohm's approximately 200 Application Bulle-
tins, ca. 60 refer to Polarography and Voltammetry. All these Application Bulletins
are available on request free of charge from your Metrohm supplier.
The examples listed here substantiate the versatility of the polarographic and volt-
ammetric methods for a range of applications including both inorganic and organic
substances. At any time you will find an updated list of the Application Bulletins in
the Internet under http://www.metrohm.ch.
No. Title
7 Literature dealing with the application of polarography for the analysis of petro-
leum and its derivates
21 Bibliography of polarographic determinations of lead in different materials
23 Some literature indications for the polarographic determination of organic nitro
compounds
36 Polarographic analysis Half-wave potentials of inorganic substances
37 Determination of chromium in iron and steel
50 Polarographic determination of lead in petrochemical products
57 Polarographic determination of nicotine
60 Polarographic determination of fructose
70 Polarographic nitrate determination in water samples, soil and plant extracts,
vegetable juices, meat and sausage products, fertilisers, liquid manure etc.
73 Polarographic analysis Half-wave potentials of organic substances
74 Polarographic and stripping voltammetric analysis methods for thallium, anti-
mony, bismuth and iron (copper, vanadium)
76 Polarographic determination of nitrilotriacetic acid (NTA) and ethylenediamine-
tetraacetic acid (EDTA) according to DIN 38'413 part 5
96 Stripping voltammetric analysis of mercury
97 Voltammetric determination of tocopherols (vitamin E) in edible oils and fats
99 Polarographic determination of sulphide, sulphite and thiosulphate in mixtures
104 Polarographic analysis Half-wave potentials of inorganic substances with
complexing agents in the background electrolytes
105 Determination of permissible lead and cadmium levels in crockery and glassware
108 Polarography Conditions, limits of determination and half-wave potentials of 50
elements not yet listed in Application Bulletins Nos. 36, 73 and 104
110 Polarographic determination of free cyanide
113 Determination of lead, cadmium and copper in foodstuffs, waste water and
sewage sludge by anodic stripping voltammetry after digestion
114 Polarographic determination of five metal ions (copper, cobalt, nickel, zinc and
iron) in a single operation
115 Bibliography concerning inverse voltammetry
116 Polarographic determination of chromium in small quantities
117 Determination of selenium by inverse voltammetry
120 Determination of small quantities of molybdenum in water, effluent, plants, salts
and other samples

No. Title
123 Voltammetric determination of iron and manganese in water samples
124 Polarographic analysis of metals Half-wave potentials in an oxalate-buffer
background electrolyte
126 Polarographic determination of quinine
127 Polarographic determination of ammonium and nitrite
131 Voltammetric determination of aluminium
132 Polarographic determination of molybdenum in strongly ferruginous substances
and ferrous metals
136 Polarographic determination of styrene in polysytrenes and copolymers
146 Direct polarographic determination of trace amounts of molybdenum in water
147 Simultaneous trace determination of seven metal ions in electronic grade
materials with the aid of stripping voltammetry
176 Simultaneous determination of lead and tin by anodic stripping voltammetry
179 Polarographic determination of maleic and fumaric acid alone or in mixtures
186 Adsorptive voltammetric determination of aluminium in water samples
190 Polarographic determination of 4-carboxybenzaldehyde in terephthalic acid
191 Polarographic determination of cystine and cysteine simultaneously
192 Polarographic and stripping voltammetric determination of thiourea in the lower
ppm and ppb range
196 Polarographic determination of formaldehyde
199 Polarographic determination of sulphide and sulphite
207 Stripping voltammetric analysis of silver
213 Polarographic determination of nicotinamide
215 Polarographic determination of folic acid (vitamin B9, vitamin BC)
218 Polarographic determination of thiamine (vitamin B1)
219 Polarographic determination of riboflavin (vitamin B2)
220 Determination of ultratrace levels of platinum by stripping voltammetry
224 Polarographic determination of pyridoxine (vitamin B6)
226 Determination of the total arsenic content by stripping voltammetry at the rotating
gold electrode
231 Voltammetric determination of zinc, cadmium, lead, copper, thallium, nickel and
cobalt in water samples according to DIN 38406 E 16
241 Determination of cadmium and lead at the Ultra Trace graphite electrode by
anodic stripping voltammetry
242 Determination of tungsten at the Ultra Trace graphite electrode by anodic
stripping voltammetry
243 Determination of chromium at the Ultra Trace graphite electrode by cathodic
stripping voltammetry
254 Determination of zinc, cadmium, lead and copper by anodic stripping voltam-
metry using carbon electrodes
256 Voltammetric determination of cadmium and lead in water samples and digestion
solutions using the EFTA flow-through cell (HMDE)
276 Validation of Metrohm VA instruments using Standard Operating Procedures

1 Introduction
Application Notes
The Application Notes present application information in concentrated form, i.e.
on maximum 2 pages. In the field of voltammetry, there are at present approxi-
mately 60 Application Notes (in English). You can order these free of charge from
your Metrohm supplier or view them in the Internet under http://www.metrohm.ch
and copy them from there.
No. Title
V-1 Iron, cadmium, lead and copper in cobalt acetate solution
V-2 Chromium, manganese and titanium in polyterephthalic acid solution
V-3 Nickel, cobalt and iron in polyterephthalic acid solution
V-4 Zinc, cadmium, lead, copper and chromium in triglyceride
V-5 Selenium in standard
V-6 Cadmium, lead and antimony in acetic acid
V-7 Total arsenic in brine
V-8 Mercury in brine
V-9 Cadmium, lead and copper in brine and NaOH
V-10 Zinc, cadmium, lead, copper, iron, nickel and cobalt in NaOH in one run
V-11 Chromium in brine with the Multi-Mode Electrode (MME) and the Ultra Trace
Graphite Electrode (UTGE)
V-12 Zinc, cadmium, lead, copper, iron, nickel and cobalt in elementary sulphur
V-13 Cadmium, lead and mercury in dissolved recycled glass
V-14 Iron and manganese in MgCl2 brine
V-15 Nickel, antimony, cadmium, thallium and copper in a neutral, highly concentrated
zinc solution
V-16 Nickel, iron and copper in silver plating bath
V-17 Chromium and selenium in silver plating bath
V-18 Tin and lead in organo plating bath
V-19 Lead in nickel plating bath
V-20 Zinc, lead and iron in NH4Cl and CuSO4
V-21 Chromium and nickel in NH4Cl and CuSO4
V-22 Antimony and bismuth in alkaline ZnO solution in one run
V-23 Aluminium in alkaline ZnO solution
V-24 Copper and chromium in etching bath
V-25 Iron in a nickel sulphamate bath containing surfactants
V-26 Iron and zinc in a nickel sulphate bath containing surfactants
V-27 Copper in nickel sulphate bath containing surfactants
V-28 Zinc, cadmium, lead, nickel and cobalt in hydrochloric acid
V-29 Zinc, cadmium, lead, nickel and cobalt in Javelle water
V-30 Zinc, cadmium, lead, nickel and cobalt in FeCl3 solution 40%
V-31 Coumarin and Tartrazine in vodka
V-32 Zinc, cadmium, lead, copper, iron, nickel and cobalt in freeze-dried hop
V-33 Zinc, lead, copper and iron in sugar
V-35 Zinc, cadmium, lead and copper in chili sauce after digestion
V-36 Mercury in chili sauce after digestion
V-37 Arsenic in chili sauce after digestion
V-38 Aluminium in albumin lyophilisate after digestion
V-39 Zinc, cadmium, lead and copper in whiskey after digestion

No. Title
V-40 Aluminium and chromium in whiskey after digestion
V-41 Cadmium, lead, copper, nickel and cobalt in soybean oil after digestion
V-42 Mercury in soybean oil after digestion
V-43 Zinc in herbal pharmaceutical drug against cancer of the prostate
V-44 Boron in human plasma using Beryllon(III) as a ligand
V-45 Uranium in water as an uranium(VI) chloranilic acid complex
V-46 Zinc, cadmium, lead, copper, nickel and cobalt in vitamin tablets
V-47 Manganese, iron and molybdenum in vitamin tablets
V-48 Clothiapine in standard
V-49 Standard buffers and reagents in voltammetry
V-50 Concentrations and standards in voltammetry
V-51 Cadmium and lead in herbicide
V-52 Vanadium, nickel, cobalt and chromium in solvent
V-53 Artemisin and Artesunate in standard
V-54 Palladium in pharmaceutical products
V-55 $-Propiolactone in vaccine
V-56 Ascorbic acid in vitamin capsules
V-57 Thiomersal in eye drops
V-58 Cysteine and cystine in infusion solution
V-59 1-Methyl-nicotinamide hydrochloride in standard
V-60 Cysteine and cystine in caseinate
V-61 Speciation of Fe(II) and Fe(III) in standard
V-62 4-Carboxybenzaldehyde in polyterephthalic acid
V-63 Cyanide in gases resulting from the incineration of plastic insulating materials
V-64 Free styrene in polystyrene and mixed polymers
V-65 Tungsten in organic phase
V-67 Formaldehyde, acetaldehyde and acetone in methanol
V-68 Cadmium and lead in sea water
V-69 Nickel and Cobalt in sea water
V-70 Iodide in glacial acetic acid
V-71 Platinum and Rhodium in drinking water
V-72 NTA and EDTA in waste water
V-73 Vitamin C in orange juice
V-74 Riboflavin (vitamin B2) in vitamin tablets
V-75 Nicotinamide (vitamin B3, vitamin PP) in vitamin tablets
V-76 Cobalt in electrolytic gold baths
V-77 Nickel and Cobalt in concentrated Zinc solutions
V-78 Antimony in zinc solutions
V-79 Germanium in electroplating baths
V-80 Germanium in lead
V-81 Copper, iron and vanadium in salt (NaCl)
V-82 Different species of chromium in sea water
V-83 Zincn, cadmium, lead, copper in waste water after UV digestion
V-84 Total chromium in waste water after UV digestion
V-85 Sulphur in gasoline

1 Introduction
Monographs
The Metrohm Monographs listed below impart theoretical fundamentals and
general information on measurement techniques and sample preparation of pola-
rography and voltammetry. All these monographs are available on request free of
charge from your Metrohm supplier.
Title
First aid for polarography and voltammetry (8.693.1073)
Sample preparation techniques in voltammetric trace analysis
Inorganic Adsorptive Stripping Analysis
Organic Stripping Analysis
Stripping Voltammetry
Electrode Reaction Kinetics determined by Cyclic Voltammetry
The Application of VA Techniques to the Galvanic/Plating Industry
Reprints
The following reprints reporting on practical applications are available on request
free of charge from your Metrohm supplier.
Title
Voltammetrie ein Schlssel zur automatisierten Spurenanalytik (in German)
Investigations of oxidative UV photolysis:
I. Sample preparation for the voltammetric determination of Zn, Cd, Pb, Cu, Ni and Co in
waters
Investigations of oxidative UV photolysis:
II. Sample preparation for the voltammetric determination of mercury in water samples
Determination of Zn, Cd, Pb, and Cu in soils and sewage sludges by microprocessor-
controlled voltammetry in comparison with AAS
Polarographie/Voltammetrie.
Grundlagen, Methodik und Anwendungen in der Galvanotechnik (in German)

2.1 746.0010 VA Trace Analyzer
2 Parts and controls

In this section you will find the numbers and designations of the parts
and controls of the 746 VA Trace Analyzer and the 747 VA Stand. The
numbering applies throughout the instructions for use, i.e. bold num-
bers in the text (e.g. 15)
15 refer to the parts and controls illustrated here.

2
3
Fig. 1: Front of the 746.0010 VA Trace Analyzer
1 Screen (LCD) 4 Mains pilot lamp

setting the contrast, lit up when instrument switched
see section 5.3.1 on
2 Eject button for data card 5 Keypad (piezoelectric keypad)

pressing this button ejects the key designations and explana-
inserted data card tions, see section 5.1
3 Slot for data card

(standard JEIDA 4.0)
press data card firmly into slot to
insert

8
Printer Type 1.746.0010
115V: 100V...120V10%
230V: 220V...240V10% 9
230V
Control Lines
10
For continued protection replace only

2A(TH)
with the same type and rating of fuse

Dos. 1 Dos. 3 RS 232 Interface 1
115V
230V
0
I
WARNING - Fire Hazard -

11
External Bus Dos. 2 Dos. 4 RS 232 Interface 2
12
Reset
Made by Metrohm Herisau Switzerland S 50-60Hz 160VA
23 22 21 20 19 18 17 16 15 14 13
Fig. 2: Rear of the 746.0010 VA Trace Analyzer
7 Serial number 16 RS 232 Interface 2

type number below
8 Earth socket 17 RS 232 Interface 1

earthing, see section 3.2.1
9 Mains voltage selector 18 Dos. 4

115: 100...120 V 10% connection for 685 Dosimat /
230: 220...240 V 10% 700 Dosino
10 Mains fuse 19 Dos. 3

(neutral, 2 ATH, slow-blow) connection for 685 Dosimat /
changing the fuse, see section 3.2.1 700 Dosino
11 Mains switch (on/off) 20 Dos. 2

on/off switching of instrument (the pilot connection for 685 Dosimat /
lamp 4 is lit up when the instr. is on) 700 Dosino

(phase, 2 ATH, slow-blow) connection for 685 Dosimat /
13 Mains connection plug 22 External Bus (EBUS)

mains connection, see section 3.2.1 connection for 747 VA Stand, 695
Autosampler and other peripherals with
EBUS connection
14 Printer connection 23 Control Lines

parallel interface for external printer connection for peripherals via control
lines 1...8
15 Reset button
for resetting the program

2
3
Fig. 3: Front of the 746.0020 VA Trace Analyzer
1 Screen (LCD) 4 Mains pilot lamp

setting the contrast, lit up when instrument switched
see section 5.3.1 on
2 Eject button for data card 5 Keypad (piezoelectric keypad)

pressing this button ejects the key designations and explana-
inserted data card tions, see section 5.1
3 Slot for data card 6 Printer

(standard JEIDA 4.0) (built-in thermal printer)
press data card firmly into slot to changing the paper, see
insert section 3.2.5

8
Type 1.746.0010
115V: 100V...120V10%
230V: 220V...240V10% 9
230V
Control Lines
10
For continued protection replace only

2A(TH)
with the same type and rating of fuse

115V
230V
0
I
WARNING - Fire Hazard -

11
12
Reset
Made by Metrohm Herisau Switzerland S 50-60Hz 160VA
23 22 21 20 19 18 17 16 15 13
Fig. 4: Rear of the 746.0020 VA Trace Analyzer
7 Serial number 16 RS 232 Interface 2

type number below
8 Earth socket 17 RS 232 Interface 1

earthing, see section 3.2.1
9 Mains voltage selector 18 Dos. 4

115: 100...120 V 10% connection for 685 Dosimat /
230: 220...240 V 10% 700 Dosino

(neutral, 2 ATH, slow-blow) connection for 685 Dosimat /
11 Mains switch (on/off) 20 Dos. 2

on/off switching of instrument connection for 685 Dosimat /
(the pilot lamp 4 is lit up when the 700 Dosino
instrument is on)

(phase, 2 ATH, slow-blow) connection for 685 Dosimat /
13 Mains connection plug 22 External Bus (EBUS)

mains connection, see section 3.2.1 connection for 747 VA Stand, 695
Autosampler and other peripherals
with EBUS connection
15 Reset button 23 Control Lines

for resetting the program connection for peripherals via control
lines 1...8

2.3 747.0010 VA Stand
24
25
26
27
28
29
Fig. 5: Front of the 747.0010 VA Stand
24 Cover of measuring head arm 27 Gas wash bottle (6.2405.030)

hinged for inert gas supply (filling with
dist. water, see section 3.3.1)
25 Stopper (6.2709.080) 28 Measuring vessel

to close the pipetting opening when measuring head arm is
fully raised, the measuring ves-
sel can be pulled forward out of
the holder 26
26 Holder for measuring vessel 29 Drip pan (6.2711.050)

2.3 747.0010 VA Stand
30
31
32
33
Made by Metrohm Herisau Switzerland
Type 1.747
34
External Bus Address
35
36
Fig. 6: Rear of the 747.0010 VA Stand
30 Connection for inert 34 External Bus (EBUS)

gas lead-off connection socket for
6.2135.000 EBUS Connecting
cable (connection to 746 VA
Trace Analyzer)
31 Connection for waste 35 Stand address

solution lead-off First stand: 1
(see section 3.10.5) Second stand: 2
Third stand: 3
(setting stand address
see section 3.3.1)
32 Connection for inert gas 36 Earth socket

supply earthing, see section 3.2.1
required pressure:
p = 1 0.2 bar
33 Serial number

37
38
25
39
40
41
42
43
44
45 46 43 47 48 49 27 50 51 47 52 53 54
Fig. 7: Right side view of the 747.0010 VA Stand (fully equipped)
55 56 57 58 37 59
38
25
60
40
41
71 70 69 68 67 52 66 65 64 49 63 60 46 62 61
Fig. 8: Left side view of the 747.0010 VA Stand (fully equipped)

2.3 747.0010 VA Stand
25 Stopper (6.2709.080) 48 Electrode cable RE

to close the pipetting opening connection for reference electrode 43
27 Gas wash bottle (6.2405.030) 49 Drive belt (6.1244.020)

for inert gas supply connection between drive wheel 52 and
(must be filled halfway with dist. H2O, drive shaft 45
see section 3.3.3)
50 PTFE tube (4.647.1350)
37 Electrode cable WE for inert gas delivery to gas wash bottle
connection for working electrode 27 (attached)
(MME or RDE)
51 FEP tubing (6.1805.180)
38 Multi-Mode Electrode (MME) for inert gas supply to MME 38
(6.1246.020)
details, see section 3.4 52 Drive wheel of drive motor
39 FEP tubing (6.1805.180) 53 FEP tubing (6.1805.040)

for inert gas supply to measuring vessel for inert gas delivery to gas wash bottle
(attached) 27 (attached)
40 Measuring head arm 54 Slotted screw for controlling the

carrier plate with permanently attached inert gas flow
measuring head, raisable Note: The factory setting of ca. 20 L/h
should not be changed without good
41 Measuring head reason!
measuring vessel upper half made of
PTFE; with openings for electrodes, 55 FEP tubing (6.1805.100)
stirrer, gas and liquid supply lines for waste solution lead-off (attached)
42 Dummy stopper (6.1446.040) 56 FEP tubing (6.1805.090)

for inert gas lead-off (attached)
43 Reference electrode
comprising 6.0728.020 Ag/AgCl Refer- 57 FEP tubing (6.1805.180)
ence system and 6.1245.010 Electrolyte for inert gas supply to tapping mecha-
vessel (details, see section 3.6) nism (attached)
44 Nipple (6.2730.030) 58 Electrode cable AE

for mounting the 4-way microtip 47 or a connection for auxiliary electrode 60
dummy stopper
59 FEP tubing (6.1805.180)
45 Drive shaft (6.1246.010) for inert gas supply to MME 38
holder for stirrer tip 62
60 Auxiliary electrode
46 PTFE tube (6.1819.000) details, see section 3.7
(attached)
61 Dummy stopper (6.1446.040)
47 4-way microtip (6.1824.000)
for delivery of solutions; with 4 lengths 62 Dummy stopper (6.1446.040)
of PTFE tubing with connecting nipples
for 685 Dosimat/700 Dosino
63 Stirrer tip (6.1204.090)

64 PTFE tube (6.1819.010) 68 Dummy cell connection WE-L

for supply of the waste solution to gas linear mode simulation (RC element)
wash bottle 65 (attached); see section
3.3 69 Dummy cell connection RE
65 Gas wash bottle (6.2405.030) 70 Dummy cell connection AE

for separating mercury from the waste
solution (attached) 71 Slotted screw for controlling the
tapping power in the DME case
66 PTFE tube (6.1819.010) Note: The factory setting should not be
for siphoning off the waste solution from changed without good reason!
gas wash bottle 65 (attached)
67 Dummy cell connection WE-D

differential mode simulation
(peak/wave)

3.1 Setting up the instruments
3 Installation
This section offers a full description of the 746 VA Trace Analyzer and
the 747 VA Stand and provides detailed information on the various
electrodes and the stirrer. Reliable operation of the these instruments
is assured only if you follow the instructions in this section exactly.
3.1 Setting up the instruments
3.1.1 Packaging
The 746 VA Trace Analyzer and the 747 VA Stand are supplied together with the
separately packed accessories in special packages designed to ensure excellent
protection. These contain shock-absorbing foam linings foamed to the individual
shape and embedded in blue plastic film. The instruments themselves are packed
in an evacuated polyethylene bag. As only these special packagings guarantee
indemnified transport of the instruments, it is essential you store them in a safe
place.
3.1.2 Check
After receipt, immediately check whether the shipment is complete and has arrived
without damage (compare with delivery note and list of accessories in sections
9.19.3). In the case of transport damage, see instructions in section 9.6
"Warranty".
3.1.3 Location
Place the 746 VA Trace Analyzer and the 747 VA Stand on a laboratory bench in a
position suitable for operation and which is free from vibrations, protected against
corrosive atmospheres and contamination by chemicals.
As the 746 VA Trace Analyzer has an LCD screen, attention should also be paid to
the room lighting: no direct sunlight, as few reflections as possible.
3.1.4 Arrangement of the instruments
The 747 VA Stand can be set up on the right or left of the 746 VA Trace Analyzer.
The drip pan 29 (6.2711.050) is placed in front of the 747 VA Stand beneath the
measuring station to catch drops (see Fig. 5).

3 Installation
3.2 Installation of 746 VA Trace Analyzer
Follow the instructions below for connecting to the power supply. If

the instrument is operated with the mains voltage set wrongly and/or
wrong mains fuse there is a danger of fire!
3.2.1 Setting the instrument supply voltage
Before switching on the 746 VA Trace Analyzer for the first time, check that the
mains voltage set on the instrument (visible in mains voltage selector 9) matches
the local power supply voltage. If this is not the case, you must change the voltage
set on the instrument by moving the mains voltage selector 9 with a screwdriver:
Positions of mains voltage

230V 230: 220 ... 240 V 10%
selector 9:
115V 115: 100 ... 120 V 10%
3.2.2 Fuses
The 746 VA Trace Analyzer contains 2 fuses 10 and 12 built in as standard, both of
type 2 ATH (2 A, slow-blow, high breaking capacity, Metrohm ordering No.
U.600.0107).
Ensure that the instrument is never put into operation with fuses of
another type, otherwise there is danger of fire!
To change blown fuses, proceed as follows
1 Change Fuse 10 (neutral, 2 ATH, slow-blow)

Disconnect mains cable from mains connection plug 13. 13
Using a screwdriver, turn the fuse holder 10 to the left until it can be
pulled out.
Take out fuse holder, remove blown fuse and insert replacement fuse
(2 ATH, slow-blow) in the holder.
Reinsert fuse holder in instrument, push in with a screwdriver and fix by
turning to the right.
2 Change Fuse 12 (phase, 2 ATH, slow-blow)

Disconnect mains cable from mains connection plug 13. 13
Using a screwdriver, push the fuse holder 12 upwards until it can be
pulled out.
Take out fuse holder, remove blown fuse and insert replacement fuse
(2 ATH, slow-blow) in the holder.
Push fuse holder back into instrument until it clicks into place.

3.2.3 Mains cable and mains connection
The instrument is supplied with one of three mains cables:

6.2122.020 with plug SEV 12 (Switzerland, )
6.2122.040 with plug CEE(7), VII (Germany, )
6.2133.070 with plug NEMA 5-15 (USA, )
which are three-cored and fitted with a plug with an earthing pin. If a different plug
has to be fitted, the yellow/green lead (IEC standard) must be connected to protec-
tive earth (protection class I). If there is no socket with earthing available, you must
connect the earth socket 8 of the instrument to a perfect earthing conductor.
Any break in the earthing inside or outside the instrument can make it
a hazard!
Plug the mains cable into mains connection plug 13 of the 746 VA Trace Analyzer
(see Fig. 2 and 4).
3.2.4 Switching the instrument on/off

The 746 VA Trace Analyzer is switched on and off using mains switch 11.
11 When the
instrument is switched on, the pilot lamp 4 on the keypad lights up, at the same
time the LCD screen 1 is switched on and the instrument initialized.
3.2.5 Installing paper (only for internal printer)
The thermal printer 6 of the 746.0020 VA Trace Analyzer is supplied without paper
inserted. The 6.2237.040 Thermal paper in the accessories (roll of length ca. 40 m
130 A4 pages) is inserted in the printer as follows:
1 Preparations
Switch on 746 VA Trace Analyzer.
Tilt cover of the printer 6 backward.
Ensure that the edge of the roll of
6.2237.040 Thermal paper is straight; if
necessary, carefully tear off paper at
first perforation.
2 Insertion
Insert 6.2241.020 Paper spindle in roll of 6.2237.040 Thermal paper.
Insert paper roll with paper spindle in the two side slots of the printer so
that the paper unwinds from the roll from the back and the perforations
are on the left when viewed from the front.
Push paper with straight edge carefully into the paper guide slot by hand
as far as it will go and hold in this position.
3 Transport
Press the two keys <SHIFT> and <FORM FEED>. The paper will be
drawn in automatically and transported to the correct position.
Close cover of paper compartment.

3 Installation
3.2.6 Handling of data cards
The 746 VA Trace Analyzer offers the possibility of writing data to SRAM memory
cards and reading data from such cards. The following data cards or memory cards
can be used:
6.2245.010 Metrohm Data Card (capacity 128 kB)
Commercial SRAM cards of any capacity with the JEIDA 4.0 hard-
ware format (68 pins) as well as PCMCIA cards based on these
Owing to differing file systems, PCMCIA cards can not be used si-
multaneously for the 746 VA Trace Analyzer and PCs.
The following points are important in the handling of data cards for the 746 VA
Trace Analyzer:
Preparing data card

Before data cards are used in the 746 VA Trace Analyzer for the first time, the fol-
lowing preparations are necessary:
New data cards are supplied with a separately enclosed battery. Insert this
in the data card in accordance with the enclosed description.
Data cards can be inserted in the instrument only in the position shown.
You must therefore affix the enclosed label to the top of the data card.
Label
The battery of the data card has a limited lifetime specified in the enclosed
description. To avoid inadvertent data losses, we advise you to write the
date of the next battery change on the data card.
If desired, the date of the battery change can also be stored on the data
card. To do this, proceed as follows:
Insert data card in the 746 VA Trace Analyzer
(see point Inserting data card).
Select dialog page VA TRACE ANALYZER.
Press softkey <Diagn.>.
Press key <1> (memory and data card tests).
Press softkey <F8> (data card, boot block information).
Press softkey <Update bat.date>. The date in the Battery
date field is updated.
Press the <ESC> key three times.

The data card must be formatted before it can be used to store data. Pro-
ceed as follows:
Insert data card in the 746 VA Trace Analyzer (see
point Inserting data card).
Select dialog page DATA CARD. The message
WARNING: Data card not formatted or battery
down appears followed by the inquiry do you want to
[f]ormat, [c]ontinue, [q]uit ?
Enter f for format. With the inquiry Label of the

Data card ?, you are then prompted to enter a title
for the card. This title can contain max. 20 characters
and will henceforth be displayed under the parameter
Label. On completion of the entry with <ENTER>,
the data card is formatted.
Inserting and removing the data card

The data card can be inserted in the 746 VA Trace Analyzer only in a particular po-
sition (see illustration above). It must be pressed firmly into slot 3 of the 746 VA
Trace Analyzer until the eject button 2 has been pushed out to its full extent.
The data card inserted in slot 3 of the VA Processor is ejected by pressing eject
button 2 and can be removed by hand.
As data cards are sensitive to electrostatic charges, before every

insertion or removal of the data card ensure that you are earthed (first
touch, e.g. the earthed, green metal housing of the 746 VA Trace
Analyzer).
Changing the battery

The battery of the data card has a limited lifetime specified in the enclosed descrip-
tion. Note here that the lifetime of batteries depends on the storage temperature.
The storage temperature of data cards and also spare batteries should thus be as
low as possible (but always less than 25C).
The date of the next battery change should be written on the label of the data card
(see above). To avoid inadvertent data losses, this should be regarded as the very
latest date for battery change. When convenient, insert the data card in the 746 VA
Trace Analyzer. The data stored on the data card need then only be copied to the
method and/or determination memory of the 746 VA Trace Analyzer if the data card
does not allow a battery change when inserted. Then proceed as follows:
Change battery as described in the enclosed description.
Enter new date for the next battery change on the data card (see
point Preparing data card).
Store date of the battery change on the data card (see point
Preparing data card).

3 Installation
3.3 Installation of 747 VA Stand
If the 746 VA Trace Analyzer is connected to the power supply, neither

the 746 VA Trace Analyzer nor the 747 VA Stand may be opened or
parts removed as there is a danger of contact with live components.
Before the 746 VA Trace Analyzer or 747 VA Stand is opened to
change components or for maintenance or repair work, the mains
cable must thus always be disconnected from the mains connection
plug 13 of the 746 VA Trace Analyzer!
3.3.1 Electrical connection at 746 VA Trace Analyzer
The 747 VA Stand may be connected to the 746 VA Trace Analyzer

only when the latter is switched off, otherwise both instruments could
suffer electrical damage!
Maximum three 747 VA Stands can be connected to the 746 VA Trace Analyzer.
Each 747 VA Stand is connected to the 746 VA Trace Analyzer with a 6.2135.000
EBUS cable, one end of which offers the possibility to attach further EBUS cables.
The two connectors of the EBUS cable are identical, it is thus immaterial which end
is plugged into which instrument.
1 Attachment of the first 747 VA Stand

Switch off 746 VA Trace Analyzer using the mains switch 11.
11
Plug one end of the 6.2135.000 EBUS cable into connection 22 of the
746 VA Trace Analyzer and fasten to the instrument by tightening the
screws in the cable connector.
Plug the other end of the EBUS cable into connection 34 of the 747 VA
Stand and fasten to the instrument by tightening the screws in the cable
connector.
Using a screwdriver, set stand address 35 of the 747 VA Stand to "1"
(arrow must point to the number "1").
2 Attachment of the second 747 VA Stand

11
Plug one end of the second 6.2135.000 EBUS cable into connector of the
first EBUS cable and fasten together by tightening the screws in the cable
connector.
Plug the other end of the second EBUS cable into connection 34 of the
second 747 VA Stand and fasten to the instrument by tightening the
screws in the cable connector.
Using a screwdriver, set stand address 35 of the second 747 VA Stand to
"2" (arrow must point to the number "2").

3 Attachment of a 747 VA Stand for the 695 Autosampler

11
Plug one end of the third 6.2135.000 EBUS cable into connector of the
second EBUS cable and fasten together by tightening the screws in the
cable connector.
Plug the other end of the third EBUS cable into connection 34 of the third
747 VA Stand and fasten to the instrument by tightening the screws in the
cable connector.
Using a screwdriver, set stand address 35 of the 747 VA Stand to "3"
(arrow must point to the number "3").
3.3.2 Equipping the measuring head
The fixtures inserted in the openings and connections of the measuring head 41 in
the 747 VA Stand depend on the working electrode selected (MME or DME) (see
Fig. 9). The fully equipped measuring head for operation with a multi-mode elec-
trode is illustrated in section 2 (Figs 7 and 8), that for operation with a rotating disk
electrode in section 3.5 (Fig. 16).
When equipping the measuring head for the first time, the best procedure is as fol-
lows:
1 Preparations
Prepare multi-mode electrode MME 38 (details, see section 3.4) or rotat-
ing disk electrode RDE (details, see section 3.5) for operation.
Prepare reference electrode 43 (details, see section 3.6) for operation.
Tilt back cover 24 of measuring head arm.
2 Insert dummy stoppers

without automatic rinsing:
Screw dummy stopper 62 (6.1446.040) into opening 73.73
with and without automatic rinsing:
Insert 6.2730.030 Stopper into enclosed nipple 44 and push enclosed
O-ring over the stopper.
Screw nipple 44 with stopper into opening 80 by hand.
3 Insert 4-way microtip

Remove stopper from nipple 44 and insert 4-way microtip 47 into nipple
44 as far as it will go.
Tighten nipple 44 using a 6.2739.010 Wrench until the 4-way microtip 47
can no longer move.
Pull the 4 lengths of PTFE tubing of the 4-way microtip 47 in succession
from above through the opening 86 (connection of 685 Dosimat, see
section 3.9; connection of 700 Dosino, see section 3.10).

3 Installation
4 Install stirrer or RDE

in operation with MME:
Screw stirrer tip 63 to drive shaft 45 (see also section 3.8).
Insert stirrer in opening 81 as far as it will go.
Stretch drive belt 49 (6.1244.020) between drive wheel 52 and drive shaft
45 of the stirrer.
in operation with RDE (option):
Screw electrode tip 120 (6.1204.XXX) to drive shaft 121 (6.1246.000)
(see also section 3.5).
Insert RDE in opening 81 as far as it will go.
Stretch drive belt 49 (6.1244.020) between drive wheel 52 and drive shaft
121 of the RDE.
Attach electrode cable 37 (WE) to the RDE: push cable lug under the
screw and then tighten screw firmly.
5 Install reference electrode

Insert reference electrode 43 in opening 79.79
Attach electrode cable 48 (RE) to reference electrode 43: 43 push cable lug
under the screw and then tighten screw firmly.
Turn reference electrode 43 so that the electrode cable 48 points to the
rear and not to the side (in the latter position it may become kinked and
damaged when cover 24 is closed).
6 Install auxiliary electrode

Insert auxiliary electrode 60 (6.0343.000 Pt auxiliary electrode or GC
auxiliary electrode, see section 3.7) in opening 72.72
Attach electrode cable 58 (AE) to auxiliary electrode 60:60 push cable lug
under the screw and then tighten screw firmly.
Turn auxiliary electrode 60 so that the electrode cable 58 points to the
72
73
74
41
75
76
40
77 78 79 80 81 82 83 84 85 86 87 88
Fig. 9: Measuring head arm

40 Measuring head arm 81 Opening

41 Measuring head for stirrer, comprising drive shaft 45
(6.1246.010) and stirrer tip 63
72 Opening (6.1204.090)
for auxiliary electrode 60 (6.0343.000 Pt in operation with RDE:
auxiliary electr. or optional GC electr. for rotating disk electrode (option),
comprising 6.1241.020 Electrode holder comprising drive shaft 121 (6.1246.000)
and 6.1247.000 GC tip) and electrode tip 120 (6.1204.XXX)
73 Threaded opening 82 Threaded opening

without automatic rinsing: for FEP tubing 57 (6.1805.180, already
for dummy stopper 62 (6.1446.040) permanently attached); inert gas supply
with automatic rinsing: for tapping mechanism
for FEP tubing 89 (6.1805.180)
83 Threaded opening
74 Threaded opening for FEP tubing 56 (6.1805.090, already
without automatic rinsing: perm. attached); inert gas lead-off
for dummy stopper 61 (6.1446.040)
with automatic rinsing: 84 Threaded opening
for FEP tubing 90 (6.1805.100) for FEP tubing 39 (6.1805.180, already
permanently attached); inert gas supply
75 Pipetting opening from gas wash bottle to measuring
for the manual addition of solutions, vessel 28
closed with stopper 25 (6.2709.080)
85 Threaded opening
76 Opening for FEP tubing 53 (6.1805.040, already
in operation with MME: permanently attached); inert gas supply
for multi-mode electrode 38 to gas wash bottle 27
(6.1246.020)
in operation with RDE: 86 Opening
for 6.2709.040 Stopper (option) for feedthrough of tubing connections of
4-way microtip 47 (6.1824.000)
77 Threaded opening
for FEP tubing 39 (6.1805.180, already 87 Threaded opening
permanently attached); inert gas supply for FEP tubing 89 (6.1805.180); waste
to meas. vessel 28 solution lead-off
78 Threaded opening 88 Threaded opening

for dummy stopper 42 (6.1446.040) for FEP tubing 55 (6.1805.090, already
permanently attached); waste solution
79 Opening supply from gas wash bottle to waste
for reference electrode 43 (6.0728.020
Ag/AgCl reference system and
6.1245.010 Electrolyte vessel)
80 Threaded opening
for nipple 44 (6.2730.030) with dummy
stopper or 4-way microtip 47
(6.1824.000)

3 Installation
7 Install MME or dummy stopper

Carefully insert multi-mode electrode 38 (6.1246.020) in opening 76 (the
underside of the capillary must not touch the measuring head during in-
sertion) and push in as far as it will go.
Screw FEP tubing 51 (6.1805.180) for inert gas supply into connection 93
of the MME 38.
38
Screw FEP tubing 59 (6.1805.180) for inert gas supply into connection 94
of the MME 38.
38
Attach electrode cable 37 (WE) to screw connection 110 of the MME 38: 38
push cable lug under the screw and then tighten screw firmly.
in operation with RDE (option):
Insert stopper 119 (6.2709.040, option) into opening 76 as far as it will go
so that the two blind holes point to the rear of the stand.
Screw FEP tubing 51 (6.1805.180) into upper hole of stopper 119.119
Screw FEP tubing 59 (6.1805.180) into lower hole of stopper 119.
119
8 Install accessories for rinsing and siphoning off (option)
For rinsing the measuring vessel at the 747 VA Stand manually (dialog
page "STAND") or with the RINSE command, two 700 Dosinos with
50 mL Dosing units must be connected to the 746 VA Trace Analyzer
and initialized acc. to section 3.10.5 and the 6.1456.210 measuring
vessel (option) must be used instead of the 6.1415.210 measuring
vessel.
Cut PTFE tube 91 (6.1819.010) to a length of ca. 30 mm and insert from

above in opening 74 of measuring head 41 (see Fig. 10).
Cut the bottom end of PTFE tube 92 (6.1819.010) diagonally and insert
from above in opening 73 of measuring head 41. 41 To ensure that the solu-
tion is siphoned off as completely as possible, the end of the tube must
be located in the deepest part of the 6.1456.210 measuring vessel (left
rear when viewed from front).
Screw FEP tubing 89 (6.1805.180) into the threaded openings 73 and 87. 87
Screw FEP tubing 90 (6.1805.100) into threaded opening 74 of measur-
ing head 41.
41 Screw a 6.1808.000 tubing coupling to the other end of FEP
tubing 90 and insert the coupling in a slot of the tubing holder at the rear
of the VA Stand.
9 Install measuring vessel

Tilt back measuring head arm 40.40
Slide measuring vessel 28 into holder 26 from the front and fill with
analyte solution or dist. H2O (storage solution) until the tips of the MME
and the reference electrode are immersed in the liquid.
Lower measuring head arm 40 and cover 24. 24

55
89
90
40
41
91
92
66 65 64
Fig. 10: Install accessories for rinsing and siphoning off
40 Measuring head arm 89 FEP tubing (6.1805.180)

for transferring the waste solution to gas
41 Measuring head wash bottle 65
55 FEP tubing (6.1805.100) 90 FEP tubing (6.1805.100)
for waste solution lead-off (attached) for supply of the rinsing solution
64 PTFE tube (6.1819.010) 91 PTFE tube (6.1819.010)

for supply of the waste solution to gas for introduction of the rinsing solution to
wash bottle 65 measuring vessel
92 PTFE tube (6.1819.010)

65 Gas wash bottle (6.2405.030) for siphoning off the waste solution
for separating mercury from the waste
solution (attached)
66 PTFE tube (6.1819.010)

for siphoning off the waste solution from
gas wash bottle 65 (attached)

3 Installation
3.3.3 Inert gas connection
Nitrogen (N2) is generally used as the inert gas to deaerate the analyte solution and
for operation of the MME. The nitrogen must be of sufficient purity.
w(N2) 0.99996 (= 99.996%)
for general polarography/voltammetry
w(N2) 0.99999 (= 99.999% = "5 9")
for analyses in organic solvents; for determinations
involving very high current amplification (e.g. in the
determination of very low concentrations without
preceding enrichment)
The scheme for deaeration of the analyte solution and the inert gas connections at
the 747 VA Stand needed for operation of the MME is shown in Fig. 11. The inert
gas connections are established as follows:
1 Fill gas wash bottle

Unscrew gas wash bottle 27 from measuring head arm 40. 40
Fill gas wash bottle 27 half full with dist. H2O (for long-term measure-
ments with supporting electrolytes such as HAc buffer or NH3 buffer, fill
with supporting electrolyte; for measurements in organic solvents fill with
the used solvent).
Screw gas wash bottle 27 back on measuring head arm 40. 40
2 Connect inert gas supply

Attach one end of 6.1801.080 PVC tubing to connection 32 of the 747 VA
Stand.
Attach the other end of the 6.1801.080 PVC tubing to connection of the
inert gas bottle.
Set inert gas pressure at gas bottle using the reducing valve to
p = 1 0.2 bar.
Open gas supply line at gas bottle.
3 Connect inert gas lead-off (option)

Attach a length of suitable tubing (e.g. Metrohm 6.1805.030, length
150 cm) to connection 30 for inert gas lead-off.
Route the other end of the lead-off tubing to a fume cupboard.
Additional VA Stands are attached in exactly the same manner. If only one inert gas
bottle for all stands is desired, the 6.1807.000 Y-Connections available as an option
can be used for the connection of PVC tubings.

Fig. 11: Scheme showing the inert gas connections at the 747 VA Stand
27 Gas wash bottle (6.2405.030)

for inert gas supply (must be filled only halfway with
dist. H2O or supporting electrolyte, see also Fig. 7)
54 Slotted screw for controlling the inert gas flow

for deaeration (see also Fig. 7)
Note: The factory setting of ca. 20 L/h should not
be changed without good reason!
71 Slotted screw for controlling the tapping power in

the DME case (see also Fig. 8)
Note: The factory setting should not be changed
without good reason!
93 Connection for inert gas supply of the MME

for raising and lowering the sealing needle in the MME
(see also section 3.4.1 and Fig. 12)
94 Connection for inert gas supply of the MME

for pressurizing the mercury (see also section 3.4.1
and Fig. 12)
V1 V4 Valves

3 Installation
3.4 Multi-mode electrode (MME)
The multi-mode electrode combines the most important polarographic and volt-
ammetric mercury electrodes in a single construction:
HMDE Hanging mercury drop electrode

Mercury is forced through a glass capillary until a drop
forms at the capillary tip and the entire voltage sweep
performed on this single stationary drop; in general
with preceding enrichment (stripping voltammetry).
DME Dropping mercury electrode

The classical electrode, the mercury drops fall from the
glass capillary at a controlled rate.
SMDE Static mercury drop electrode

The latest electrode, it combines the features of the
DME and the HMDE: during the measurement, the
drop surface is constant and stationary (as with the
HMDE); however, for the complete voltage sweep sev-
eral drops are needed (renewal as with the DME).
3.4.1 Construction and operating characteristics of the MME
The construction of the 6.1246.020 Multi-mode electrode is shown in Fig. 12. The
mercury in the reservoir 103 flows through the glass capillary 109 forming a drop at
its end. The mercury flow is controlled by the sealing needle 97, 97 which can be
raised or lowered pneumatically. The different types of electrodes (HMDE, DME,
SMDE) are implemented by timed opening or closing of the mercury flow using this
sealing needle.
The operating characteristics of the MME are illustrated by Figs. 11 and 12. After
valve V1 (inert gas supply) is opened, the mercury in the reservoir 103 is pressur-
ized. In the standby mode, a back pressure is built up in the interior of the slotted
screw 96 which causes the built-in spring to press the sealing needle 97 onto the
capillary opening of the glass capillary 109 thus preventing the outflow of mercury.
Switching the valve V3 allows the inert gas to escape thus releasing the back pres-
sure. The inert gas pressure in the mercury reservoir 103 presses the sealing nee-
dle 97 fixed to the PTFE membrane of the slotted screw 96 upwards and the mer-
cury can now flow out. The tapping mechanism of the DME and SMDE is triggered
by brief opening and closing of valve V4.
The mercury drops formed at the end of the capillary are very small and stable and
thus afford a very good signal/noise ratio. The mercury hermetically sealed in the
reservoir comes into contact only with inert gas and other inert materials and suf-
fices for around 200'000 drops.

95
96
97
98
94
99
100 93 110
93 Connection for inert gas supply
94 Connection for inert gas supply

(for all MME operating modes)
95 Locking ring (4.420.2920)

for slotted screw 96
101
96 Slotted screw (3.420.3920)
102 with PTFE membrane and built-in spring
97 Sealing needle (6.1247.020)

103
98 Screw thread for slotted screw 96
104
99 Unused connection
105
100 Screw thread for slotted screw 101
106 101 Slotted screw (4.420.2960)
for replenishing the mercury with capil-
107 lary fitted
102 Electrical contact pin for mercury

108
103 Mercury reservoir
104 Screw thread for retaining nut 108
105 Insert ring (4.420.3011)
106 Sealing ring (4.420.2800)

made of silicone rubber
109
107 Locking ring (4.420.2870)
108 Retaining nut (4.420.2850)
109 Glass capillary (6.1226.030)
110 Screw connection

Fig. 12: Multi-mode electrode electrical contact for "WE" electrode
cable

3 Installation
3.4.2 Filling the MME with mercury
When handling mercury, it is necessary to take special precautionary

measures. These are described in detail in section 7.2.
All actions involving the electrode and mercury vessels must be

performed in or over the drip pan 113 supplied (see Fig. 14).
The Hg reservoir 103 of the multi-mode electrode 38 is filled with mercury of the
highest degree of purity (mass fraction w 0.99999) as follows:
1 Prepare multi-mode electrode

Unscrew locking ring 95 from slotted screw 96 (this gray PVC ring is
needed only to remove the slotted screws 96 or 101,101 see section 3.4.7
and section 3.4.9).
Turn slotted screw 96 in or out of the screw thread 98 using a suitable
coin until the contact surface of the black O-ring at the Plexiglas wall (thin,
black stripe) is just visible below the metal thread 98.
98
Remove the plastic cap used as a transport safeguard from the retaining
nut 108.
108
Undo retaining nut 108 fully and remove from screw thread 104. 104
Place multi-mode electrode 38 with the capillary opening facing upwards
in the electrode holder 114 (see Fig. 13).
114
38
111
113
112
Mercury
Fig. 13: Adding the mercury
38 Multi-mode electrode 113 Drip pan (6.2711.030)

(6.1246.0020)
111 Syringe (6.2816.020) 114 Electrode holder

(6.2615.030)
112 Needle (6.2816.030)

2 Draw up mercury
Attach needle 112 to syringe 111.
111
Draw up 6 mL ultrapure mercury slowly and carefully using syringe 111.
111
3 Add mercury to MME

Lower syringe needle 112 into the top opening of the MME 38 between
sealing ring 106 and sealing needle 97.
97
Expel mercury slowly and carefully from the syringe to allow it to flow into
the Hg reservoir 103.
103
3.4.3 Mounting the capillary
The glass capillaries 109 for the multi-mode electrode 38 are supplied separately in
a protective plastic package. After they have been unpacked, avoid any contact
whatsoever with the sensitive capillary tip. The capillary 109 is mounted in the MME
filled with mercury as described in section 3.4.2 as follows:
1 Insert retaining nut

Screw retaining nut 108 into screw thread 104 until a slight resistance is
noticeable (on no account screw in retaining nut fully!).
2 Insert capillary
Cut open plastic package containing the glass capillary 109 on the side
of the large capillary opening using scissors (do not tear open), leave
capillary in the package.
Insert glass capillary 109 directly from its protective plastic package
through the retaining nut 108 into the sealing ring 106 and push in as far
as it will go.
3 Tighten retaining nut

Firmly tighten retaining nut 108 by hand (do not use a tool). The glass
capillary 109 should then be centered in the opening of the retaining nut
108.
108
If this is not the case, undo retaining nut 108 by one full turn and then
retighten by hand. When tightening, move glass capillary 109 in a circle
so that it is centered in the feedthrough of the retaining nut 108.
108

3 Installation
3.4.4 Filling the capillary without vacuum
The glass capillary 109 can normally be filled with mercury by the method de-
scribed here without vacuum. However, if difficulties regarding stability or repro-
ducibility arise with a capillary filled in this manner, try to fill the capillaries by the al-
ternative method with vacuum (section 3.4.5).
To fill the mounted glass capillary 109 (section 3.4.3) with Hg without vacuum, pro-
ceed as follows:
1 Install multi-mode electrode in 747 VA Stand

With the measuring head arm 40 tilted back, slide the empty measuring
vessel 28 into the holder 26 of the 747 VA Stand and then lower the
measuring head arm 40. 40
Carefully insert multi-mode electrode 38 in opening 76 of the measuring
head 41 (during insertion, the tip of the capillary 109 must not touch the
measuring head) and push in carefully as far as it will go. Avoid water
drops touch the tip of the capillary.
2 Connect multi-mode electrode

Screw FEP tubing 51 for the inert gas supply into connection 93 of the
multi-mode electrode 38.
38
38
Attach electrode cable 37 (WE) to screw connection 110 of the multi-
mode electrode 38:
38 push cable lug under the screw and then tighten
screw firmly.
3 Fill capillary with mercury

Switch on 746 VA Trace Analyzer with mains switch 11 (746 VA Trace
Analyzer and 747 VA Stand must first be installed properly as described
in section 3.2 and section 3.3).
Select dialog page "STAND" and then switch on the inert gas supply to
the 747 VA Stand by pressing the softkey <Pressure>. This pressurizes
the multi-mode electrode 38 and the mercury begins to flow slowly out of
the capillary.
Gently tap the MME with your finger (to remove any air bubbles) and
allow the mercury to flow out of the capillary into the empty measuring
vessel for approx. 2 min.
Fill measuring vessel 28 with 10 mL ultrapure water and add 1 drop KCl
solution (in pure water, mercury drops from the capillary only with diffi-
culty).
Allow mercury to flow out of the capillary for ca. 2 min while checking the
drop formation: The drop time should be ca. 3 s.
4 Adjusting the sealing needle 97

Turn slotted screw 96 using a suitable coin slowly in a clockwise direction
until the mercury flow stops.
Open slotted screw 96 slightly in an anticlockwise direction until the
mercury flow restarts.

Gently tap the MME with your finger and turn the slotted screw 96 very
slowly clockwise until the mercury flow just stops. (The tapping action is
used to knock off the mercury drops so that it is easier to see whether
mercury continues to flow.)
Finally, turn slotted screw 96 a quarter of a turn clockwise.
5 Checking the MME for leaks

Select dialog page "STAND" then switch on the dropping mercury elec-
trode by pressing the softkey <DME>. The mercury drops freely out of the
capillary for ca. 1 min.
Press softkey <HMDE>. A single mercury drop is formed. Knock this off by
gently tapping the MME 38 with your finger and check that the mercury
flow has really stopped. Repeat this operation several times.
If mercury continues to flow, turn slotted screw 96 still further in a clock-
wise direction and repeat check.
3.4.5 Filling the capillary using vacuum
Filling of the glass capillary 109 with vacuum is advisable in all cases where diffi-
culties have been found with the method without vacuum described in section
3.4.4. Filling with vacuum is especially recommended when no ultrapure Hg is
available.
To fill the mounted glass capillary 109 (section 3.4.3) with Hg with vacuum, pro-
ceed as follows:
1 Set up filling station

All actions involving the electrode and the mercury vessels must be
performed in or over the drip pan 113 supplied (see Fig. 14).
The MME 38 is placed in the electrode holder 114 for filling.
2 Connection for vacuum pump

For filling the capillary 109,
109 the filling tubing 115 is required. At one end it
is fitted with a filling cone 116 for mounting on the capillary 109,
109 and at
the other end with the tubing coupling 118 for attachment to the line for
the vacuum pump.
To avoid possible mercury losses, two gas wash bottles 117 are attached
to the filling tubing 115.
115
3 Vacuum pump
To draw up mercury a suitable vacuum pump is required (e.g. water jet
pump). The partial vacuum p should be around 25 mbar.
A vacuum release tap must be installed at the vacuum pump or in the line
between the gas wash bottle and the pump for slowly releasing the vac-
uum.
4 Mount filling tubing

Mount filling tubing 115 with filling cone 116 on glass capillary 109.
109
Connect filling tubing 115 with tubing coupling 118 to the two gas wash
bottles 117 and the vacuum pump (see Fig. 14).

3 Installation
118
115
Pump
116
109 Vacuum
release tap
38
113 117
114
117
Fig. 14: Setting up the filling station
Vacuum
115
Vacuum
116
1 2
109
3
113 114 38
Fig. 15: Filling the capillary
38 Multi-mode electrode 115 Filling tubing (6.1817.000)

(6.1246.0020)
109 Glass capillary (6.1226.030) 116 Filling cone (4.420.2860)

(part of the filling tubing 115)
115
113 Drip pan (6.2711.030) 117 Gas wash bottle
114 Electrode holder (6.2615.030) 118 Tubing coupling (6.1809.000)

(part of the filling tubing 115)
115

5 Evacuating in vertical position

Place multi-mode electrode 38 vertically in the electrode holder 114 (see
Fig. 15-1).
Evacuate for ca. 2 min in this position.
6 Evacuating in inclined position

Carefully tilt multi-mode electrode 38 in the electrode holder 114 to an
inclined position and continue evacuating (see Fig. 15-2).
7 Release vacuum
As soon as mercury issues from the tip of the glass capillary 109 into the
filling tubing 115,
115 carefully release the vacuum by opening the vacuum
release tap.
The filling tubing 115 must not be disconnected from the glass capil-
lary 109 when under vacuum, otherwise the mercury which has
issued from the capillary would be sprayed onto the tubing wall and
can no longer be disposed of in drop form!
Tap the glass capillary 109 gently by hand so that any mercury drops at
its tip are knocked into the filling tubing 115.
115
Disconnect filling tubing 115 with filling cone 116 from glass capillary
109.
109
Place multi-mode electrode 38 in a horizontal position in the electrode
holder 114 (see Fig. 15-3).
From now on, the MME must be left in this position until it is installed in
the stand!
8 Install multi-mode electrode in 747 VA Stand

With measuring head arm 40 tilted back, push empty measuring vessel
28 into the holder 26 of the 747 VA Stand and then lower measuring head
arm 40.
40
Carefully insert multi-mode electrode 38 in opening 76 of the measuring
head 41 (during insertion, the tip of the capillary must not touch the
measuring head) and push in as far as it will go.
9 Connect multi-mode electrode

38
38
Attach electrode cable 37 (WE) to screw connection 110 of the multi-
mode electrode 38:
38 push cable lug under the screw and then tighten
screw firmly.

3 Installation
10 Pressurize the MME

Switch on 746 VA Trace Analyzer with mains switch 11 (746 VA Trace
Analyzer and 747 VA Stand must first be installed properly as described
in section 3.2 and section 3.3).
Select dialog page "STAND" and then switch on the inert gas supply to
the 747 VA Stand by pressing the softkey <Pressure>. This pressurizes
the multi-mode electrode 38 and the mercury begins to flow slowly out of
the capillary.
Gently tap the MME with your finger (to remove any air bubbles) and
allow mercury to flow out of the capillary into the empty measuring vessel
for approx. 2 min.
Fill measuring vessel 28 with 10 mL ultrapure water and add 1 drop KCl
solution (in pure water, mercury drops from the capillary only with diffi-
culty).
Allow mercury to flow out of the capillary for ca. 2 min while checking the
drop formation: The drop time should be ca. 3 s.
11 Adjusting the sealing needle 97

Turn slotted screw 96 using a suitable coin slowly in a clockwise direction
until the mercury flow stops.
Open slotted screw 96 slightly in an anticlockwise direction until the
mercury flow restarts.
Gently tap the MME with your finger and turn the slotted screw 96 very
slowly clockwise until the mercury flow just stops. (The tapping action is
used to knock off the mercury drop so that it is easier to see whether
mercury continues to flow.)
Finally, turn slotted screw 96 a quarter of a turn clockwise.
12 Checking the MME for leaks

Select dialog page "STAND" and then switch on the dropping mercury
electrode by pressing the softkey <DME>. The mercury drops freely out of
the capillary for ca. 1 min.
Press softkey <HMDE>. A single mercury drop is formed. Knock this off by
gently tapping the MME 38 with your finger and check that the mercury
flow has really stopped. Repeat this operation several times.
If mercury continues to flow, turn slotted screw 96 still further in a clock-
wise direction and repeat check.
3.4.6 Storing the MME
On completion of the measurements, the MME is stored in the 747 VA Stand so

that the tip of the glass capillary 109 is immersed in pure water (or in the solvent
used). This prevents blockage of the capillary by crystallized salts.
An electrode treated in this manner can be taken out of the 747 VA Stand after a
few hours and stored in air for a lengthy period without suffering any damage. Al-
ways store the MME so that the glass capillary 109 is horizontal.

3.4.7 Replenishing the mercury (without changing capillary)
The multi-mode electrode 38 can also be refilled with mercury without having to
remove the glass capillary 109.
109
1 Dismantle multi-mode electrode

Unscrew FEP tubing 51 and 59 from the MME. Disconnect electrode
cable 37 from the MME.
Take multi-mode electrode 38 out of the measuring head 41 and tap the
MME gently to knock off any mercury drops on the glass capillary into the
measuring vessel.
Place multi-mode electrode 38 horizontally in the electrode holder 114
(see Fig. 15-3). The slotted screw 101 is now at the top.
2 Replenish mercury
Unscrew slotted screw 101 using a suitable coin. If the slotted screw 101
can not be loosened by hand, screw on locking ring 95 and pull out of the
MME.
Draw up mercury using the syringe 111 with attached needle 112 and
expel into the Hg reservoir 103.
103
The Hg reservoir 103 must never be filled more than 2/3 full with
mercury.
Reinsert slotted screw 101 into screw thread 100 and screw flush to
surface using a suitable coin (this action may expel a few drops of mer-
cury from glass capillary 109).
109
Do not turn so tightly that the cemented-in steel threaded ring 100
becomes loose and hence jeopardizes the tightness and safety of the
MME!

3 Installation
3.4.8 Changing the capillary
Contamination of the glass capillary can necessitate its replacement (see also sec-
tions 7.4.2 and 7.4.3). In such a case, proceed as follows:
1 Remove multi-mode electrode from 747 VA Stand

Unscrew FEP tubing 51 and 59 from the MME, disconnect electrode
cable 37 from MME.
Take multi-mode electrode 38 out of measuring head 41 while gently
tapping the MME to knock off any mercury drops on the glass capillary
into the measuring vessel.
holder 114 (see Fig. 15-3).
2 Unscrew slotted screw 96

Using a suitable coin, unscrew slotted screw 96 out of screw thread 98
until the contact surface of the black O-ring at the Plexiglas wall (thin,
98
3 Dismantle old capillary

Position multi-mode electrode 38 vertically in the electrode holder 114
(see Fig. 15-1).
Undo retaining nut 108 completely by turning anticlockwise and lift up
until the lower part of the glass capillary 109 with the wide opening is
visible.
Gently tap the glass capillary 109 to knock off any residual mercury in the
wide opening into the MME.
Press the retaining nut 108 downward with one hand and with your other
hand take glass capillary 109 completely out of the mount.
4 Dispose of old capillary

Connect filling tubing 115 with the tubing coupling 118 to the two gas
wash bottles 117 and the vacuum pump (see Fig. 14).
Insert glass capillary 109 (capillary end) in the filling cone 116 of the filling
tubing 115.
115
Remove mercury from capillary with the vacuum pump.
5 Replenish mercury if necessary

Proceed as described in section 3.4.2.
6 Mount new capillary

7 Fill capillary
Proceed as described in section 3.4.4 or section 3.4.5.

3.4.9 Cleaning the MME
If the mercury in the multi-mode electrode is contaminated and this leads to distur-
bances (see sections 7.4.2 and 7.4.3), the MME must be cleaned and refilled with
ultrapure mercury. Proceed as follows:
1 Remove multi-mode electrode from 747 VA Stand

Unscrew FEP tubing 51 and 59 from the MME, disconnect electrode
cable 37 from MME.
Take multi-mode electrode 38 out of measuring head 41 while gently
tapping the MME to knock off any mercury drops on the glass capillary
2 Remove old mercury

holder 114 (see Fig. 15-3). The slotted screw 101 is now at the top.
Unscrew slotted screw 101 using a suitable coin.
Carefully turn MME and empty mercury through the threaded opening
100 into a waste container placed in the drip pan 113.
113 While doing so,
gently tap the glass capillary 109 and the MME to ensure that all mercury
flows out of the MME.
3 Dismantle MME
Unscrew retaining nut 108.
108
Take glass capillary 109 out of opening 104,
104 the sealing ring 106 and the
locking ring 107 are removed at the same time. Remove these two parts
from the glass capillary 109.
109
Remove insert ring 105 from the MME.
Unscrew slotted screw 96 with a suitable coin in an anticlockwise direc-
tion from screw thread 98.
98
Screw locking ring 95 onto slotted screw 96 and pull out of the MME.
4 Dispose of old capillary

Connect filling tubing 115 with the tubing coupling 118 to the two gas
wash bottles 117 and the vacuum pump (see Fig. 14).
Insert glass capillary 109 (capillary end) in the filling cone 116 of the filling
tubing 115.
115
Remove mercury from the capillary with the vacuum pump.
5 Clean MME
Clean inner compartments of the MME, contact pin 102 and the screw
threads 98,
98 100 and 104 with a lint-free cloth.
Thoroughly rinse all inner compartments of the MME and the unscrewed
individual parts with dist. water and then dry with N2.
Do not use any organic solvents.

3 Installation
6 Replace sealing needle 97 if need be

If problems with leaks arise owing to a worn, deformed or damaged sealing
needle 97 (see sections 7.4.2 and 7.4.3), this must be replaced. Three spare
needles are supplied separately in a protective plastic package. After un-
packing a needle, please avoid any contact whatsoever with the needle tip.
The spare needle 97 is installed as follows:
Carefully pull old sealing needle 97 out of PTFE membrane of the slotted
screw 96.
96
Carefully insert new sealing needle 97 without tilting into the hole in the
PTFE membrane of the slotted screw 96.96
When the sealing needle 97 is changed, it is always necessary to

change the glass capillary 109 !
7 Replace sealing ring 106 if need be

If the sealing ring 106 is contaminated or damaged in any way (see
sections 7.4.2 and 7.4.3), it must be replaced for the subsequent assem-
bly of the MME. Two new sealing rings 106 are enclosed in the package
with the 6.1226.030 glass capillaries.
8 Reassemble MME
Screw slotted screw 101 using a suitable coin flush into screw thread
100.
100
Do not turn so tightly that the cemented-in steel threaded ring 100
becomes loose and hence jeopardizes the tightness and safety of the
MME!
Using a suitable coin, screw slotted screw 96 into the screw thread 98
until the contact surface of the black O-ring at the Plexiglas wall (thin,
98
Place multi-mode electrode 38 with the opening 104 facing upwards in
the electrode holder 114 (see Fig. 15-1).
Insert insert ring 105 in opening 104.
104
Push sealing ring 106 onto locking ring 107 and insert both in the open-
ing 104.
104
Screw retaining nut 108 by hand into screw thread 104 until a slight
resistance is felt.
9 Add mercury
10 Mount new capillary

11 Fill capillary
Proceed as described in section 3.4.4 or section 3.4.5.

3.5 Rotating disk electrode (RDE)
3.5 Rotating disk electrode (RDE)
The rotating disk electrode (RDE) is available as an option and can be used in
place of the MME in the 747 VA Stand with different electrode tips as a working
electrode. The following accessories have to be ordered (see also section 9.4):
6.1246.000 Drive shaft for rotating electrode
6.1204.XXX Electrode tip for rotating electrode
6.1204.100 Ultra Trace Graphite
6.1204.110 GC (Glassy Carbon)
6.1204.120 Pt
6.1204.130 Ag
6.1204.140 Au
6.2709.040 Stopper for closing the MME opening
6.2802.000 Polishing kit for 6.1204.XXX Electrode tips
(Pt, Ag, Au, GC)
6.2827.000 Trimming tool for 6.1204.100 Electrode tip
(Graphite)
3.5.1 Construction and startup of the RDE
The rotating disk electrode RDE comprises the two parts drive shaft 121
(6.1246.000) and electrode tip 120 (6.1204.XXX), which must be screwed together.
The procedure for installing the RDE in the measuring head arm of the 747 VA
Stand is described in detail in section 3.3.2. The fully equipped measuring head
arm with the RDE is illustrated in Fig. 16.
3.5.2 Regenerating the RDE
The RDE is a solid electrode with a stationary surface. This becomes contaminated
with the products of the electrode redox processes with increasing use. The surface
of the 6.1204.XXX electrode tips (Pt, Ag, Au, GC) must therefore be regenerated
from time to time by mechanical cleaning with extremely fine aluminium oxide pow-
der. Proceed as follows:
Affix polishing cloth (part of 6.2802.000 Polishing kit) to a flat surface (e.g. to
the bottom of a Petri dish) then add a little Al2O3 powder (part of 6.2802.000
Polishing kit) and dist. H2O to form a thick paste.
Polish electrode tip by hand in the paste for ca. 10 s with small, circular
movements.
Rinse electrode tip with dist. H2O, immerse in diluted HCl for ca. 10 s, rinse
again with dist. H2O and then dry with a cloth or filter paper. A correctly regen-
erated RDE shows a distinctive and uniformly bright disk surface.
Regeneration of the 6.1204.100 Ultra Trace Graphite Electrode Tip depends on its
use (mercury film or adsorptive stripping voltammetry). The procedure is described
in detail in the Application Bulletins available for the determinations with this elec-
trode.

3 Installation
55 56 57 58 37 51 119
25
60
40
41
52 49 59 121 120 60
Fig. 16: Measuring head arm with rotating disk electrode (RDE)
25 Stopper (6.2709.080) 57 FEP tubing (6.1805.180)

to close the pipetting opening for inert gas supply to tapping mecha-
nism (attached)
37 Electrode cable WE
connection for working electr. (RDE) 58 Electrode cable AE
connection for auxiliary electrode 60
40 Measuring head arm
carrier plate with permanently attached 59 FEP tubing (6.1805.180)
measuring head, raisable
41 Measuring head details, see section 3.7
measuring vessel upper half made of
PTFE; with openings for electrodes, 119 Stopper (6.2709.040)
stirrer, gas and liquid supply lines for closing the MME opening and to
accommodate the two lengths of FEP
49 Drive belt (6.1244.020) tubing 51 and 59
connection between drive wheel 52
and drive shaft 121 120 Electrode tip (6.1204.XXX)
together with drive shaft 121 forms the
51 FEP tubing (6.1805.180) RDE
52 Drive wheel of drive motor 121 Drive shaft (6.1246.000)
together with electrode tip 120 forms
56 FEP tubing (6.1805.090) the RDE
for inert gas lead-off (attached)

3.6 Reference electrode
3.6 Reference electrode
3.6.1 Construction
The complete reference electrode (RE) 43 comprises two parts:
6.0728.0X0 Ag/AgCl reference system (122 122)

with ceramic diaphragm type D, diameter = 1 mm
6.0728.020 Reference system: Ag/AgCl/c(KCl) = 3 mol/L;
supplied in a holder filled with c(KCl) = 3 mol/L
as standard
6.0728.010 Reference system: Ag/AgCl
supplied dry (option)
6.1245.010 123)
Electrolyte vessel (123
with ceramic diaphragm type D, diameter=3 mm;
holds a second electrolyte solution (bridge
electrolyte) and thus forms with the 6.0728.020
Reference system a complete reference electrode
in the so-called double junction construction.
The construction of the reference electrode and the designations of the individual
parts are shown in Fig. 17.
43 Reference electrode
43 122 124
122 Reference system (6.0728.0X0)
123 Electrolyte vessel (6.1245.010)

125
124 Electrical connection for cable
126 "AE"
127 125 Vent opening
128 126 Ag/AgCl reference system
129 127 Electrolyte compartment with

internal electrolyte
128 Diaphragm support made of

PCTFE
129 Diaphragm
130
130 Vent opening
131 131 Electrolyte compartment with
123 bridge electrolyte
132
132 Diaphragm
Fig. 17: Construction of the reference electrode

3 Installation
3.6.2 Startup procedure
The reference electrode 43 is supplied in modular form as the reference system

122 and the electrolyte vessel 123 and has first to be filled and assembled as fol-
lows:
1 Add internal electrolyte

Filling of the reference system is necessary only when the optional
6.0728.010 Reference system supplied dry is used, if the internal electrolyte
solution has to be renewed or if the electrical connection is interrupted by
gas bubbles.
Hold reference system 122 so that diaphragm 129 faces upwards.
Unscrew diaphragm support 128. 128
Fill electrolyte compartment 127 completely with the desired internal
electrolyte. Expel any air bubbles by tapping shaft gently.
Screw diaphragm support 128 back on, the electrolyte solution thus
displaced is expelled through the vent opening 125.
125
2 Add bridge electrolyte

Fill internal compartment 131 of the electrolyte vessel 123 with a suitable
bridge electrolyte whose composition depends on the analyses to be
performed (aqueous or non-aqueous solution, composition of the sup-
porting electrolyte, etc.).
If you use the same solution for the bridge electrolyte and the internal
electrolyte (single-junction operation), the inner diaphragm 129 can
be omitted to reduce the electrical resistance: Unscrew diaphragm
support 128 with diaphragm 129 from the reference system 122. 122
3 Screw reference electrode together

Insert the filled reference system 122 in the vessel 123 filled with bridge
electrolyte and screw tight. The electrolyte solution thus displaced is ex-
pelled through the vent opening 130.
130
4 Install reference electrode in 747 VA Stand and connect

Insert reference electrode 43 in opening 79 of the measuring head 41
(see Fig. 9).
Attach electrode cable 48 (RE) to reference electrode 43: 43
push cable lug under the screw and then tighten screw firmly.
Turn reference electrode 43 so that the electrode cable 48 points to the
Wait approx. 20 min before first measurement (it takes some time for a
new reference electrode to become wet).

3.7 Auxiliary electrode
3.7 Auxiliary electrode
3.7.1 Construction
The following electrodes can be used as the auxiliary electrode 60 (AE):
6.0343.000 Pt auxiliary electrode

supplied as standard
6.1241.020 Electrode holder and
6.1247.000 Glassy carbon tip
together form the glassy carbon auxiliary electrode
available as an option
The construction of the two auxiliary electrodes and the designations of the individ-
ual parts are shown in Fig. 18.
3.7.2 Startup procedure
The 6.0343.000 Pt auxiliary electrode supplied as standard can be inserted directly

in the 747 VA Stand ( 2), whereas the GC auxiliary electrode available as an op-
tion must first be assembled ( 1):
1 Assembly of the GC auxiliary electrode

Insert glassy carbon tip 138 through the locking ring 137 into the elec-
trode holder 136 as far as it will go.
Glassy carbon is a brittle, easily breakable material and must therefore

be inserted carefully into the electrode holder and handled gently.
If the GC tip breaks, the part remaining in the holder can be removed
by pulling out the locking ring 137.
137
2 Install auxiliary electrode in 747 VA Stand and connect

Insert auxiliary electrode 60 in opening 72 of the measuring head 41
(see Fig. 9).
Attach electrode cable 58 (AE) to auxiliary electrode 60:60
Push cable lug under the screw and tighten screw firmly.
Turn auxiliary electrode 60 so that the electrode cable 58 points to the

3 Installation
60
133 Electrical connection for

133 133 cable "AE"
134 Pt Auxiliary electrode

(6.0343.000)
136
134 135 Pt tip
(permanently attached)
137 136 Electrode holder

(6.1241.020)
137 Locking ring

138
135 138 Glassy carbon tip
(6.1247.000)
Fig. 18: Construction of the auxiliary electrode
3.8 Stirrer
The complete stirrer comprises two parts (see also Fig. 8):
6.1246.010 45)
Drive shaft (45
6.1204.090 63)
Stirrer tip (63
The startup procedure for the stirrer is as follows:
1 Assemble stirrer
Screw stirrer tip 63 firmly to drive shaft 45.
45
2 Insert stirrer in 747 VA Stand and connect

Insert complete stirrer in opening 81 of the measuring head 41 as far as it
will go (see Fig. 9).
Stretch drive belt 49 between drive wheel 52 and drive shaft 45 of the
stirrer (see Fig. 9).

3.9 Connection of 685 Dosimats
Up to four 685 Dosimats can be attached to the 746 VA Trace Analyzer for the
automatic addition of standard and auxiliary solutions. The 685 Dosimat and the
accessories needed have the following ordering designations (see also section
9.5):
2.685.0010 Dosimat
6.2134.000 Cable 685 746
6.3014.XXX Exchange unit, with PCTFE/PTFE flat stopcock
6.3014.153 burette volume V = 5 mL
The choice of Exchange unit depends on the volume of liquid the Dosimat should
dispense. A burette volume of 5 mL is recommended for additions in the L range
(standard additions solutions), a burette volume of 10 mL or higher is recom-
mended for additions in the mL range (auxiliary solutions).
This section describes the connection procedure; further details on the 685 Dosi-
mat and the various Exchange units can be found in the 685 Instructions for Use of
the 685 Dosimat.
3.9.1 Electrical connection
Before a Dosimat is attached to the 746 VA Trace Analyzer, the 746 VA

Trace Analyzer must be switched off using the mains switch 11. 11
Connecting a 685 Dosimat to the 746 VA Trace Analyzer when the
latter is switched on can lead to destruction of the Dosimat!
The 685 Dosimat is connected to the 746 VA Trace Analyzer with the optionally
available 6.2134.000 Cable. The "remote control" sockets of the 685 Dosimat are
18 ... 21)
connected to the appropriate socket "Dos 1...4" (18 21 of the 746 VA Trace
Analyzer (see Fig. 19). Maximum 4 Dosimats can be attached in this manner.
For settings (dosing rate, filling rate, etc.) and manual operation (manual filling or
dispensing) of the 685 Dosimat, dialog page "DOSIMATS" must be selected (see
section 5.3.3).
746
Printer
230V
remote
control
685 Control Lines
2A(TH)

115V
230V
0
I
Reset
6.2134.000 cable
Fig. 19: Connection of 685 Dosimats to 746 VA Trace Analyzer

3 Installation
3.9.2 Tubing connection for addition of standard solutions
For the addition of standard solutions in the L-range into the measuring vessel of
the 747 VA Stand the 4-way microtip 47 (6.1824.000) should be used. It is fitted
with 4 lengths of PTFE tubing with connection nipples for direct attachment to the
Exchange unit of the 685 Dosimat. To ready the 685 Dosimat for automatic dis-
pensing, proceed as follows:
1 Mount Exchange unit on 685 Dosimat

Procedure, see section 2 of 685 Instructions for Use.
2 Insert 4-way microtip in 747 VA Stand (see section 3.3.2)

44 as far as it will go (see Figs 7 and 9).
Tighten nipple 44 using a 6.2739.000 Wrench (accessory of 6.3014.XXX
Exchange unit) so that the 4-way microtip 47 can no longer move.
from above through the opening 86. 86
3 Connect PTFE tubing to Exchange unit

Unscrew the attached 6.1805.100 FEP Tubing 2
(L = 40 cm) from connection 2 (connection for burette
tip) of the flat stopcock on the Exchange unit mounted
on the Dosimat.
Screw connection nipple of the PTFE tubing of the
4-way microtip 47 onto connection 2 of the flat stop-
cock on the Exchange unit mounted on the Dosimat.
4 Close unused PTFE tubings

Screw a 6.1808.000 Coupling (accessory of 747 VA Stand) on each
unused PTFE tubing of the 4-way microtip 47.
47
Screw a 6.1446.040 Dummy stopper (accessory of 747 VA Stand) on
each 6.1808.000 Coupling.
5 Initialize Dosimat(s)
Switch on 746 VA Trace Analyzer using the mains switch 11. 11
Select dialog page "DOSIMATS".
If volumes 50 L should be dispensed, set parameter V.init to
0.05 mL.
Set parameter V.tube in to 1.7 mL.
Set parameter V.tube out to 0.2 mL.
Press <Prime all> for initializing all attached Dosimats or select desired
Dosimat with the cursor keys <> or <> and press <Prime Dosi-
mat>: The burette cylinder is filled and excess solution is expelled to the
measuring vessel. With standard accessories, all tubings to the measur-
ing vessel will have been filled at the end of the initializing procedure.
Start the initializing procedure a second time by pressing the softkey
<Prime all> or <Prime Dosimat> again.
Start the initializing procedure a third time by pressing the softkey <Prime
all> or <Prime Dosimat> again.

3.9.3 Tubing connection for addition of auxiliary solutions
The 4-way microtip 47 is not suited for the addition of auxiliary solutions in the mL-
range into the measuring vessel of the 747 VA Stand. For the addition of a first aux-
iliary solution we recommend the use of the following accessories:
1 6.1819.000 PTFE tube, length L = 77 mm, i.d. = 0.8 mm
2 6.1805.100 FEP tubing, length L = 40 cm, i.d. = 2 mm
1 6.1808.000 Coupling
To install these accessories and ready the 685 Dosimat for automatic dispensing,
proceed as follows:

2 Insert PTFE tube in 747 VA Stand

Cut 6.1819.000 PTFE tube (optionally available) to a length of ca. 30 mm
(the tip of the tube should never be immersed into the solution).
Remove dummy stopper 42 and insert PTFE tube from above in the
opening 78 of the measuring head 41 (see Fig. 9).
3 Connect FEP tubing to Exchange unit

Screw 6.1805.100 FEP tubing (optionally available) into opening 78.78
Screw a 1808.000 Coupling (accessory of 747 VA Stand) to the other end
of the 6.1805.100 FEP tubing and insert this in a slot of the tubing holder
at the rear of the 747 VA Stand.
Unscrew the 6.1543.050 Burette tip from the 6.1805.100 FEP tubing
attached to the connection 2 of the Exchange unit (see section 3.9.2).
Screw the other end of the 6.1805.100 FEP tubing attached to the Ex-
change unit to the 6.1808.000 Coupling just inserted in the tubing holder
of the 747 VA Stand.
Set parameter V.init to 0.00 mL.
Press softkey <Prime all> for initializing all attached Dosimats or select
desired Dosimat with the cursor keys and press softkey <Prime Dosimat>:
The burette cylinder is filled and excess solution is expelled to the meas-
uring vessel. With standard accessories, all tubings to the measuring
vessel will have been filled at the end of the initializing procedure.

3 Installation
For the addition of a second auxiliary solution we recommend the use of the fol-
lowing accessories:
1 6.1446.070 Stopper, with M6 thread
1 6.1808.000 Coupling
To install these accessories and ready the 685 Dosimat for automatic dispensing,
proceed as follows:


Remove stopper 25 from pipetting opening 75 and insert 6.1446.070
stopper (optionally available) into this opening (see Fig. 9).
Insert PTFE tube from above into the 6.1446.070 stopper.
3 Change Exchange unit

Screw 6.1805.100 FEP tubing (optionally available) into the threaded
opening of the 6.1446.070 stopper.
Unscrew the 6.1543.050 Burette tip from the 6.1805.100 FEP tubing
attached to the connection 2 of the Exchange unit (see section 3.9.2).
Screw the other end of the 6.1805.100 FEP tubing attached to the Ex-
change unit to the 6.1808.000 Coupling just inserted in the tubing holder
of the 747 VA Stand.
Press softkey <Prime all> for initializing all attached Dosimats or select
desired Dosimat with the cursor keys and press softkey <Prime Dosimat>:
The burette cylinder is filled and excess solution is expelled to the meas-
uring vessel. With standard accessories, all tubings to the measuring
vessel will have been filled at the end of the initializing procedure.

3.9.4 Changing the Exchange unit
The Exchange unit mounted on the 685 Dosimat can be changed only in the
exchange position. Please proceed as follows:
1 Switch to exchange position

Select desired Dosimat with the cursor keys and press softkey <Exchange
position>: The Dosimat is switched to the exchange position and the
parameter Position is set to exchange.
2 Change Exchange unit

Unscrew connection nipple of the PTFE tubing of the 4-way microtip 47
from connection 2 and take off old Exchange unit.
Mount new Exchange unit on Dosimat and screw connection nipple of the
PTFE tubing of the 4-way microtip 47 onto connection 2 of the flat stop-
cock on the Exchange unit.
Select desired Dosimat with the cursor keys and press softkey <Prime
Dosimat> for initializing the Dosimat. The burette cylinder is filled and ex-
cess solution is expelled to the measuring vessel. With standard acces-
sories, all tubings to the measuring vessel will be filled at the end of the
initializing procedure.
<Prime Dosimat> again.
Start the initializing procedure a third time by pressing the softkey or

3 Installation
3.9.5 Installation and use of the pipetting equipment
The optional available Pipetting equipment is suited for pipetting and automatic di-
lution functions with 685 Dosimats. The following accessories have to be ordered in
addition to the standard equipment of the 747 VA Stand (see section 9.4 and 9.5):
1 2.685.0010 Dosimat
1 6.2134.000 Cable 685 746
1 6.3014.213 Exchange unit (10 mL)
1 6.5611.010 Pipetting equipment
To install these accessories and ready a 685 Dosimat for pipetting and automatic
dilution functions, proceed as follows (see Fig. 20):
1 Connect 685 Dosimat to 746 VA Trace Analyzer

Connect 685 Dosimat to the "Dos 14" socket of the 746 VA Trace
Analyzer by means of a 6.2134.000 cable (see Fig. 19). If the pipetting
equipment should be used for dispensing instructions in an operation se-
quence, the 685 Dosimat must be connected to "Dos.1".

Mount the Exchange unit on the 685 Dosimat (procedure, see section 2 of
685 Instructions for Use).
Fill reagent bottle with ultrapure water which has been acidified (100 L
conc. HNO3 per 1 L) and degassed (5 min vacuum with stirring).
3 Connect pipetting handle to 746 VA Trace Analyzer

Connect pipetting handle to the "Control lines" socket of the 746 VA Trace
Analyzer by means of the attached cable. The second plug of this cable
can be used to connect other equipment to the "Control Lines" socket. As
soon as the pipetting handle is connected, the green pilot lamp on the
handle lights up indicating that it is ready for use.
4 Connect pipetting tubing to Exchange unit

Unscrew the attached 6.1805.100 FEP Tubing 2
(L = 40 cm) from connection 2 (connection for burette
tip) of the flat stopcock on the Exchange unit mounted
on the Dosimat.
Screw connection nipple of the pipetting tubing onto
connection 2 of the flat stopcock on the Exchange unit
mounted on the Dosimat.
Connection 685 Connecting cable to 746 VA Trace

Dosimat/700 Dosino Analyzer ("Control Lines")
Black start
6.1562.050 6.1562.040 button Green pilot
Pipetting tubing Pipetting handle lamp
Pipetting
tip
Fig. 20: Pipetting handle

5 Prepare waste beaker

Put 6.2754.000 Rinsing quiver onto the lip of an empty waste beaker.
Before starting any initialization, dilution or pipetting functions with the

pipetting handle, hold the pipetting handle so that any solution leaving
the pipetting tip is expelled into the waste beaker.
6 Initialize Dosimat
Set parameter V.tube in for the desired Dosimat to 1.7 mL.
Set parameter V.tube out for the desired Dosimat to 4.8 mL.
Take pipetting handle by hand and put it into the waste beaker with the
pipetting tip down.
Select desired Dosimat with the cursor keys <> or <> and press
<Prime Dosimat>: The burette cylinder is filled and excess solution is ex-
pelled to the waste beaker.
Dosimat> again. All tubings up to the pipetting tip will have been filled at
the end of the initializing procedure.
7 Use pipetting handle for preparation of diluted solutions

Select desired Dosimat and set parameters C.init std, C.end dilution
and V.end dilution for preparing a diluted solution (details see section
5.3.3).
Put the pipetting handle into the waste beaker so that the pipetting tip is
at about the same level as the container with the concentrated solution
(e.g. standard) and press the softkey <Start dilution>.
If the dilution is carried out for the first time or if the previous dilution has
been terminated by <ESC> (see below), the message Preparing
Dosimat #X appears. Press the black button on the handle.
After automatic aspiration of the dilution solution from the reagent bottle
the message Aspirating standard appears. Put the pipetting handle
into the concentrated solution with the pipetting tip immersed ca.
15 mm and press the black button on the handle.
After aspiration of the concentrated solution the message Dispensing
solution appears. Put the pipetting handle into the desired void con-
tainer with the pipetting tip touching the wall and press the black button
on the handle.
Concentrated and dilution solution are dispensed into the void container.
Afterwards the message Next operation / press <ESC> to break ap-
pears. If you press the black button on the handle or <ENTER>, the Do-
simat will be ready for another dilution, if you press <ESC>, the Dosimat
is switched to the exchange position.

3 Installation
8 Use pipetting handle in an operation sequence

Make sure that the 685 Dosimat with the connected pipetting handle is
connected to the "Dos.1" socket of the 746 VA Trace Analyzer.
Enter the desired dispensing instructions for which the pipetting handle
should be used on the "OP. SEQUENCE" and/or "SEGMENTS" page. If
you enter a solution name Soln.name for this solution, make sure that no
Dosimat is assigned for this solution on the "SOLUTIONS" page
(parameter Pos. must be empty). The following dispensing instructions
are allowed: SMPL>M, CSOLN>M, ADD>M, RADD>M, DOS>M, PDOS>M, SDOS>M.
Start program by pressing the <START> key.
If the desired dispensing instruction is executed, the message for manual
dispensing appears (e.g. DOS "SOLN.name" V.add" > M ).
at about the same level as the container with the solution that should be
pipetted and press the black button on the handle (if you press
<ENTER> at this time, you would have to add the solution manually).
If the pipetting instruction is carried out for the first time or if the previous
pipetting instruction has been terminated by <ESC> (see below), the
message Preparing Dosimat #X appears. Press the black button on the
handle.
After rinsing of the pipetting tubing and formation of an air bubble, the
message Aspirating standard appears. Put the pipetting handle into
the desired solution with the pipetting tip immersed ca. 15 mm and
press the black button on the pipetting handle.
After aspiration of the solution the message Dispensing solution
appears. Put the pipetting handle into the measuring vessel with the pi-
petting tip touching the wall and press the black button on the handle.
The desired solution is dispensed into the measuring vessel. Afterwards
the message Rinsing tube appears. Put the pipetting tip into the rinsing
quiver installed to the waste beaker and press the black button on the pi-
petting handle.
The pipetting tip is rinsed with dilution solution. Afterwards the message
Next operation / press <ESC> to break appears. If you press the black
button on the handle or <ENTER>, the Dosimat will be ready for the next
dispensing instruction, if you press <ESC>, the Dosimat is switched to
the exchange position.

3.10 Connection of 700 Dosinos

Up to four 700 Dosinos can be attached to the 746 VA Trace Analyzer for the auto-
matic addition of standard and auxiliary solutions. The 700 Dosino and the Dosing
Units needed for the addition have the following ordering designations (see also
section 9.5):
2.700.0010 Dosino
6.3030.XXX Dosing unit, with ETFE burette cylinder
6.3030.120 cylinder volume V = 2 mL
The choice of Dosing unit depends on the volume of liquid the Dosino should dis-
pense. A burette volume of 2 or 5 mL is recommended for additions in the L range
(standard additions solutions), a burette volume of 10 mL or higher is recom-
mended for additions in the mL range (auxiliary solutions).
This section describes the connection procedure; further details can be found in the
700 Instructions for Use of the 700 Dosino.
3.10.1 Electrical connection
Before a Dosino is attached to the 746 VA Trace Analyzer, the 746 VA

Trace Analyzer must be switched off using the mains switch 11. 11
Connecting a 700 Dosino to the 746 VA Trace Analyzer when the latter
is switched on can lead to destruction of the Dosino!
18
The 700 Dosino is connected with its cable to the appropriate socket "Dos 1...4" (18
... 21)
21 of the 746 VA Trace Analyzer (see Fig. 21). Maximum 4 Dosinos can be at-
tached in this manner.
For settings (dosing rate, filling rate, etc.) and manual operation (manual filling or
dispensing) of the 700 Dosino, dialog page "DOSIMATS" must be selected (see
section 5.3.3).
700
746
Printer
230V
Control Lines
2A(TH)

115V
230V
0
I
Reset
Cable of 700 Dosino
Fig. 21: Connection of 700 Dosinos to 746 VA Trace Analyzer

3 Installation
3.10.2 Tubing connection for addition of standard solutions
For the addition of standard solutions in the L-range into the measuring vessel of
the 747 VA Stand the 4-way microtip 47 (6.1824.000) should be used. It is fitted
with 4 lengths of PTFE tubing with connection nipples for direct attachment to the
Dosing unit of the 700 Dosino. To ready the 700 Dosino for automatic dispensing,
proceed as follows:
1 Mount Dosing unit on 700 Dosino

Procedure, see section 2.2 of 700 Instructions for Use.
2 Insert 4-way microtip in 747 VA Stand (see section 3.3.2)

44 as far as it will go (see Figs 7 and 9).
Tighten nipple 44 using a 6.2739.000 Wrench (accessory of 6.3030.XXX
Dosing unit) so that the 4-way microtip 47 can no longer move.
from above through the opening 86. 86
3 Connect PTFE tubing to Dosing unit

Screw connection nipple of the PTFE tubing of the 4-way microtip 47 onto
connection 1 of the Dosing Unit mounted on the Dosino.
To lengthen the tubing connection the 6.1805.100 FEP tubing (L = 40
cm, accessory of Dosing Unit) can be inserted between PTFE tubing and
connection 1 of the Dosing Unit using the 1808.000 coupling.
4 Close unused PTFE tubings

Screw a 6.1808.000 Coupling (accessory of 747 VA Stand) on each
unused PTFE tubing of the 4-way microtip 47.
47
Screw a 6.1446.040 Dummy stopper (accessory of 747 VA Stand) on
each 6.1808.000 Coupling.
5 Initialize Dosino(s)
If volumes 50 L should be dispensed, set parameter V.init to
0.05 mL.
Press softkey <Prime all> for initializing all attached Dosinos or select
desired Dosino with the cursor keys and press softkey <Prime Dosimat>:
The cylinder is filled and excess solution is expelled to the measuring
vessel. With standard accessories, all tubings to the measuring vessel will
have been filled at the end of the initializing procedure.

3.10.3 Tubing connection for addition of auxiliary solutions
The 4-way microtip 47 is not suited for the addition of auxiliary solutions in the mL-
range into the measuring vessel of the 747 VA Stand. For the addition of a first aux-
iliary solution we recommend the use of the following accessories:
1 6.1808.000 Coupling
To install these accessories and ready the 700 Dosino for automatic dispensing,
proceed as follows:


Remove dummy stopper 42 and insert PTFE tube from above in the
opening 78 of the measuring head 41 (see Fig. 9).
3 Connect FEP tubing to Dosing unit

Screw 6.1805.100 FEP tubing (optionally available) into opening 78.78
Screw the 6.1805.100 FEP tubing (accessory of Dosing unit) onto con-
nection 1 of the Dosing unit.
Screw the other end of the 6.1805.100 FEP tubing attached to the Dosing
unit to the 6.1808.000 Coupling just inserted in the tubing holder of the
747 VA Stand.

3 Installation
For the addition of a second auxiliary solution we recommend the use of the fol-
lowing accessories:
1 6.1446.070 Stopper, with M6 thread
1 6.1808.000 Coupling
To install these accessories and ready the 700 Dosino for automatic dispensing,
proceed as follows:


Remove stopper 25 from pipetting opening 75 and insert 6.1446.070
stopper (optionally available) into this opening (see Fig. 9).
Insert PTFE tube from above into the 6.1446.070 stopper.
3 Connect FEP tubing to Dosing unit

Screw 6.1805.100 FEP tubing (optionally available) into the threaded
opening of the 6.1446.070 stopper.
Screw the 6.1805.100 FEP tubing (accessory of Dosing unit) onto con-
nection 1 of the Dosing unit.
Screw the other end of the 6.1805.100 FEP tubing attached to the Dosing
unit to the 6.1808.000 Coupling just inserted in the tubing holder of the
747 VA Stand.

3.10.4 Changing the Dosing unit
If the Dosing unit is changed when the Dosino is in the dosing posi-
tion, the Dosino can get destroyed! Therefore always make sure that
the Dosino is in the exchange position (see parameter Position on
dialog page "DOSIMATS") before changing the Dosing unit.
The Dosing unit mounted on the 700 Dosino can be changed only in the exchange
position. Please proceed as follows:
1 Switch to exchange position

Select desired Dosino with the cursor keys and press softkey <Exchange
position>: The Dosino is switched to the exchange position and the pa-
rameter Position is set to exchange.
2 Change Dosing unit

Unscrew connection nipple of the PTFE tubing of the 4-way microtip 47
from connection 1 and change Dosing unit (procedure see 700 Instruc-
tions for use, section 2.3 and 2.4).
Screw connection nipple of the PTFE tubing of the 4-way microtip 47 onto
connection 1 of the new Dosing Unit mounted on the Dosino.
3 Initialize Dosino
Select desired Dosino with the cursor keys and press softkey <Prime
Dosino> for initializing the Dosino. The cylinder is filled and excess solu-
tion is expelled to the measuring vessel. With standard accessories, all
tubings to the measuring vessel will have been filled at the end of the ini-
tializing procedure.

3 Installation
3.10.5 Installation of Dosinos for rinsing the measuring vessel
It is possible to rinse the measuring vessel at the 747 VA Stand manually via dialog
page "STAND" or with the RINSE command by means of two 700 Dosinos with
50 mL Dosing units. To do this, the following accessories have to be ordered in ad-
dition to the standard equipment of the 747 VA Stand (see also section 9.4):
2 2.700.0010 Dosino
1 6.5323.000 Rinsing equipment
The two Dosinos and the accessories have to be installed as follows (see Fig. 22):
1 Install accessories at 747 VA Stand

Install accessories for rinsing and siphoning off at the 747 VA Stand acc.
to section 3.3.2 point 8 (see Fig. 10).
Install 6.1456.210 measuring vessel at the 747 VA Stand.
2 Prepare containers
Unscrew red filling connections from 6.1621.000 Containers.
Using a funnel, add max. 10 L of rinsing solution (normally acidified
ultrapure water with 100 L conc. HCl/L) to the storage container through
its small vent opening.
3 Install Dosinos on containers

Screw a 6.1618.050 Threaded adapter to each container.
Screw a 6.1829.020 Suction tubing (L = 50 cm) to the bottom of the two
6.1567.250 Dosing units (see section 2.1 of the 700 Instructions for use).
Screw the 6.1567.250 Dosing units to the 6.1618.050 Threaded adapters
screwed to the containers.
Mount a 700 Dosino on each 6.1567.250 Dosing unit (procedure, see
section 2.3 of the 700 Instructions for use).
4 Setting up the containers

Set up the waste and storage containers at the desired location next to
the 747 VA Stand (the max. possible distance is limited by the length
1.5 m of the connecting cables of the Dosinos).
5 Define rinsing Dosinos on 746 VA Trace Analyzer

Switch on 746 VA Trace Analyzer using the mains switch 11.
11
Select dialog page "SOLUTIONS".
Add a new solution with Soln.name = RINSE and Pos. = Do.3.
Switch off 746 VA Trace Analyzer.
6 Connect rinsing Dosino to 747 VA Stand

Using either a 6.1805.120 FEP Tubing (L = 1 m) or two 6.1805.120 FEP
Tubings and a 6.1808.000 Connecting sleeve, connect connection 1 of
the 6.1567.250 Dosing unit of the rinsing Dosino with the 6.1808.000
Coupling connected to the FEP tubing 90 and mounted on the 747 VA
Stand (see Fig. 10).
Attach rinsing Dosino using the cable connected to the instrument to
socket 19 (Dos. 3) of the 746 VA Trace Analyzer (see Fig. 2 or Fig. 4).

7 Connect siphoning Dosino to 747 VA Stand

Using either a 6.1805.120 FEP Tubing (L = 1 m) or two 6.1805.120 FEP
Tubings and a 6.1808.000 Connecting sleeve, connect connection 1 of
the 6.1567.250 Dosing unit of the siphoning Dosino with coupling 31
mounted on the 747 VA Stand (see Fig. 6).
Attach siphoning Dosino using the cable connected to the instrument to
socket 18 (Dos. 4) of the 746 VA Trace Analyzer (see Fig. 2 or Fig. 4).
8 Initialize Dosinos
Switch on 746 VA Trace Analyzer using the mains switch 11. 11 The two
Dosing units of the rinsing and siphoning Dosino and the tubing connec-
tions are filled automatically at system start (the initialization procedure
can take several minutes!).
700 Rinsing
Dosino (Dos.3)
6.1618.050 6.1805.120
6.1808.000
Rinsing 6.1829.020
solution
6.1805.120
6.1621.000 6.1808.000 6.1805.100 6.1805.090
6.1805.180
6.1805.120
700 Siphoning
Dosino (Dos.4)
6.1808.000 6.1819.010
6.1618.050 6.1819.010
6.1456.210
1
747 6.1819.010
Waste 6.1805.120 6.1819.010
6.1829.020
6.1621.000
Fig. 22: Scheme of the tubing connections for Rinsing and Siphoning Dosino

3 Installation
3.10.6 Installation and use of the pipetting equipment
The optional available Pipetting equipment is suited for pipetting and automatic di-
lution functions with 700 Dosinos. The following accessories have to be ordered in
addition to the standard equipment of the 747 VA Stand (see section 9.4 and 9.5):
1 2.700.0010 Dosino
1 6.1567.210 Dosing unit (10 mL), without accessories
1 6.5611.010 Pipetting equipment
To install these accessories and ready a 700 Dosino for pipetting and automatic
dilution functions, proceed as follows (see Fig. 20 in section 3.9.5):
1 Connect 700 Dosino to 746 VA Trace Analyzer

Connect 700 Dosino to the "Dos.14" socket of the 746 VA Trace Ana-
lyzer (see Fig. 21). If the pipetting equipment should be used for dis-
pensing instructions in an operation sequence, the 700 Dosino must be
connected to "Dos.1".
2 Mount Dosing unit and 700 Dosino

Fill reagent bottle (bottle with GL 45 thread) with ultrapure water which
has been acidified (100 L conc. HNO3 per 1 L) and degassed (5 min
vacuum with stirring).
Screw 6.1829.020 Aspiration tube (accessory of 6.5611.010 Pipetting
equipment) to bottom of the 6.1657.210 Dosing unit (procedure, see sec-
tion 2.1 of the 700 Instructions for Use).
Screw 6.1567.210 Dosing unit onto the reagent bottle.
Clip 6.2052.010 Pipetting handle holder (accessory of 6.5611.010 Pipet-
ting equipment) to the white flange of the Dosing unit. The 6.1562.040
Pipetting handle can be stored in this holder with the pipetting tip pointing
upwards.
Mount 700 Dosino on 6.1657.210 Dosing unit (procedure, see section 2.3
of the 700 Instructions for Use).
3 Connect pipetting handle to 746 VA Trace Analyzer

Connect pipetting handle to the "Control lines" socket of the 746 VA Trace
Analyzer by means of the attached cable. The second plug of this cable
can be used to connect other equipment to the "Control Lines" socket. As
soon as the pipetting handle is connected, the green pilot lamp on the
handle lights up indicating that it is ready for use.
4 Connect pipetting tubing to Dosing unit

Screw connection nipple of the pipetting tubing onto connection 1 of the
Dosing unit mounted on the Dosino.
5 Prepare waste beaker

Put 6.2754.000 Rinsing quiver onto the lip of an empty waste beaker.
Before starting any initialization, dilution or pipetting functions with the

pipetting handle, hold the pipetting handle so that any solution leaving
the pipetting tip is expelled into the waste beaker.

6 Initialize Dosino
Set parameter V.tube in of the desired Dosino to 0.7 mL.
Set parameter V.tube out of the desired Dosino to 4.8 mL.
Take pipetting handle by hand and put it into the waste beaker with the
pipetting tip down.
Select desired Dosino with the cursor keys <> or <> and press
<Prime Dosimat>: The cylinder is filled and excess solution is expelled to
the waste beaker. All tubings up to the pipetting tip will have been filled at
the end of the initializing procedure.
7 Use pipetting handle for preparation of diluted solutions

Select desired Dosino and set parameters C.init std, C.end dilution
and V.end dilution for preparing a diluted solution (details see section
5.3.3).
at about the same level as the container with the concentrated solution
(e.g. standard) and press the softkey <Start dilution>.
If the dilution is carried out for the first time or if the previous dilution has
been terminated by <ESC> (see below), the message Preparing
Dosimat #X appears. Press the black button on the handle.
After automatic aspiration of the dilution solution from the reagent bottle
the message Aspirating standard appears. Put the pipetting handle
into the concentrated solution with the pipetting tip immersed ca.
15 mm and press the black button on the handle.
After aspiration of the concentrated solution the message Dispensing
solution appears. Put the pipetting handle into the desired void con-
tainer with the pipetting tip touching the wall and press the black button
on the handle.
Concentrated and dilution solution are dispensed into the void container.
Afterwards the message Next operation / press <ESC> to break ap-
pears. If you press the black button on the handle or <ENTER>, the
Dosino will be ready for another dilution, if you press <ESC>, the Dosino
is switched to the exchange position.
8 Use pipetting handle in an operation sequence

Make sure that the 700 Dosino with the connected pipetting handle is
connected to the "Dos.1" socket of the 746 VA Trace Analyzer.
Enter the desired dispensing instructions for which the pipetting handle
should be used on the "OP. SEQUENCE" and/or "SEGMENTS" page. If
you enter a solution name Soln.name for this solution, make sure that no
Dosimat or Dosino is assigned for this solution on the "SOLUTIONS" page
(parameter Pos. must be empty). The following dispensing instructions
are allowed: SMPL>M, CSOLN>M, ADD>M, RADD>M, DOS>M, PDOS>M, SDOS>M.
Start program by pressing the <START> key.
If the desired dispensing instruction is executed, the message for manual
dispensing appears (e.g. DOS "SOLN.name" V.add" > M ).

3 Installation
at about the same level as the container with the solution that should be
pipetted and press the black button on the handle (if you press
<ENTER> at this time, you would have to add the solution manually).
If the pipetting instruction is carried out for the first time or if the previous
pipetting instruction has been terminated by <ESC> (see below), the
message Preparing Dosimat #X appears. Press the black button on the
handle.
After rinsing of the pipetting tubing and formation of an air bubble, the
message Aspirating standard appears. Put the pipetting handle into
the desired solution with the pipetting tip immersed ca. 15 mm and
press the black button on the pipetting handle.
After aspiration of the solution the message Dispensing solution
appears. Put the pipetting handle into the measuring vessel with the pi-
petting tip touching the wall and press the black button on the handle.
The desired solution is dispensed into the measuring vessel. Afterwards
the message Rinsing tube appears. Put the pipetting tip into the rinsing
quiver installed to the waste beaker and press the black button on the pi-
petting handle.
The pipetting tip is rinsed with dilution solution. Afterwards the message
Next operation / press <ESC> to break appears. If you press the black
button on the handle or <ENTER>, the Dosino will be ready for the next
dispensing instruction, if you press <ESC>, the Dosino is switched to the
exchange position.

3.11 Connection of printers via parallel interface
3.11 Connection of printers via parallel interface
The 746.0010 VA Trace Analyzer has a parallel interface dedicated to connect ex-
ternal printers with parallel interfaces. The external printers are connected to the
printer connection 14 of the 746 VA Trace Analyzer by means of the cable delivered
with the printer (see Fig. 23).
Before connecting a printer to the printer connection 14,

14 the 746 VA
Trace Analyzer must be switched off by means of mains switch 11.
11
With the 2.746.0010 VA Trace Analyzer the internal battery of the

instrument can be discharged after comparatively short time if certain
external printers are connected to the parallel printer interface 14.
14 This
malfunction arises when the 746 VA Trace Analyzer is switched
off and the external printer remains switched on. Please mind
that certain printers are still in a stand-by mode when switched off and
thus show the faulty behavior also in the off-state. It is therefore
necessary in any case to separate the external printer from the mains.
To avoid battery discharge we recommend to do the following:
Interconnect the mains cables of the instruments concerned (incl.
external printer) to an ordinary socket board with a common mains
switch. A 615 Mains distributor with RFI filter available from Metrohm
as an option can be used also (this enables additional noise suppres-
sion).
The type of the printer is selected on dialog page "VA TRACE ANALYZER". The fol-
lowing printer drivers are available (see also section 5.3.1):
IBM Propr. IBM Proprinter and printers with IBM emulation

Epson 80*60 EPSON printers and printers with EPSON emulation
with 80 60 dpi graphics resolution (24-pin dot matrix,
ink jet and laser printers)
HP Deskjet HP printers (HP DeskJet, HP LaserJet) and printers
with HP PCL3 emulation
HP Thinkjet HP ThinkJet, HP QuietJet and compatibles
HP Thinkj.E HP ThinkJet in EPSON mode and compatibles
If you connect other printers, ensure that these emulate a printer mode supported
by the 746 VA Trace Analyzer. In some cases, a reset on the printer may be neces-
sary before the printer works properly (see printer manual).
With single sheet printers, graphical printouts (curves, screen) are cut
if they exceed the page. Therefore we recommend to use a printer
with endless paper and the operation with Auto form feed = no (see
section 5.6.5)

3 Installation
746
Printer
230V
Control Lines
2A(TH)
0
115V
230V
I
Reset
Printer cable
Fig. 23: Connection of a printer to 746.0010 VA Trace Analyzer
3.12 Connection of devices via RS232 interfaces

The 746 VA Trace Analyzer has two interfaces 16 and 17 of type RS232C, which
are identical in hardware terms but differ with regard to software (in the functioning
of the 746 VA Trace Analyzer) (see Fig. 24):
RS232 interface 1 Attachment of a PC

(remote keyboard function possible) or
Attachment of a printer
RS232 interface 2 Attachment of a PC
(remote keyboard function not possible) or
Attachment of a printer and/or
Attachment of a balance (balance and printer
can both be attached at the same time)
The technical data of the RS232 interfaces can be found in section 8.3. The present
section describes the procedure for the attachment of devices to the RS232 inter-
faces. To configure these interfaces, dialog page VA TRACE ANALYZER must be
selected (see section 5.3.1).
Before connecting a device to the RS interfaces, the 746 VA Trace

Analyzer must be switched off by means of mains switch 11. 11 The
attachment of devices to the 746 VA Trace Analyzer when it is
switched on can necessitate initialization of the RS232 interfaces (see
section 5.3.1)!

RS232 interface 1
PC
746
Printer
230V
Control Lines
2A(TH)
0
115V
230V
I
Reset
Printer
RS232 interface 2
Balance
Fig. 24: Connection possibilities for the RS232 interfaces
3.12.1 Connection of a PC
IBM-compatible PCs are connected to the 746 VA Trace Analyzer via RS232 inter-
face 1 (remote keyboard function possible) or via RS232 interface 2 (remote key-
board function not possible, see Fig. 24). The following table provides information
on the connection of PCs. It lists the required cables and details on the configura-
tion of the 746 VA Trace Analyzer and PC.
PC Cable Settings on 746 VA Trace Analyzer Settings on PC
PC with 25-pin 6.2125.060 RS232 settings Ifc.1/2

RS232 connector Baud rate
Data bits Settings
Stop bit(s) same as
Parity on PC setting of the RS
Handshake parameters
Receive mode on/off depends on
PC with 9-pin 6.2125.060 Balance type none control program
RS232 connector + Printer type none
6.2125.010 Printer width
Remote keyboard off/send/
receive

3 Installation
3.12.2 Connection of a printer

External printers with a serial interface can be attached to the two RS232 interfaces
of the 746 VA Trace Analyzer. For several printers, connecting cables are available
as an option (see section 9.5). The type of the printer is selected on dialog page
"VA TRACE ANALYZER". The following printer drivers are available (see also section
5.3.1):
HP Deskjet HP printers (HP DeskJet, HP LaserJet) and printers
with HP PCL3 emulation
If you connect other printers, ensure that these emulate a printer mode supported
by the 746 VA Trace Analyzer. In some cases, a reset on the printer may be neces-
sary before the printer works properly (see printer manual).
If a balance is attached to the RS232 interface at the same time as a printer, the
6.2125.030 Socket-outlet adapter must be used. The printer must be connected to
the data out port of the socket-outlet adapter. It can be operated only with the
simple hardware handshake HWshort or without handshake. The settings of the RS
parameters may possibly have to be matched to those of the balance (e.g. baud
rate). Attachment of a balance and a printer together functions perfectly only with
balances with 8-bit data capacity. Balances with 7-bit data capacity can be oper-
ated in this manner only when a parity space is set on the balance, whereas
printer and VA Trace Analyzer operate with 8-bits, no parity.

3.12.3 Connection of a balance
The balances listed below can be attached to RS232 interface 2 of the 746 VA
Trace Analyzer. The settings of the RS232 parameters on the 746 VA Trace Ana-
lyzer depend on the settings of the balance, Receive mode must be set to on.
Balance Cable Settings on 746 VA Trace Analyzer
Sartorius MP8, MC1 6.2125.070 Balance type Sartorius
Mettler AB, AG (LC-RS25) cable from Mettler Balance type Mettler
Mettler AM, PM ME 33995 from Mettler: Balance type Mettler

green lead to pin 2,
brown to 3, white to 7,
yellow to 20 of the 25-
pin connector
Mettler with interface 016 cable from Mettler: Balance type Mettler
red lead to pin 3, white
to 7 of the 25-pin
connector
Mettler with interface 011 6.2125.020 Balance type Mettler

or 012
Mettler AT ME 33995 from Mettler: Balance type Mettler AT

green lead to pin 2,
brown to 3, white to 7,
yellow to 20 of the 25-
pin connector
Precisa
Balances with RS232 6.2125.080 Balance type Precisa
interface
AND
ER-60, 120, 180, 182 6.2125.020 Balance type AND
FR-200, 300 6.2125.020 Balance type AND
FX-200, 300, 320 with 6.2125.020 Balance type AND
RS232 interface (OP-03)
A balance and a printer can be attached to RS232 interface 2 at the same time with
the aid of the 6.2125.030 Socket-outlet adapter. The balance must then be plugged
into the data in port of the socket-outlet adapter.
The initial mass is transferred as a number with up to 6 digits, sign and decimal
point. Units and control characters sent by the balance are not transferred. With the
aid of a special input device supplied by the balance manufacturer, not only the ini-
tial mass but also sample identifications and methods can be put in from the bal-
ance. The addresses of the identification or method must be preselected on the in-
put device:
Balance Method Id#1 Id#2 Id#3
Sartorius METH or 27 ID.1 or 26 ID.2 or 24 C-20 or 23
Mettler (AT) D (Mthd) C (ID#1) B (ID#2) A (c20)

3 Installation
3.13 Connection of devices via remote interface
The 746 VA Trace Analyzer is fitted with a 25-pin remote interface (connection 23
Control Lines) with a total of 16 control lines. Any external device can be attached
to the 8 inputs (scan) and 8 outputs (set) and can be scanned or set via these lines.
The current status of the control lines at the 746 VA Trace Analyzer is shown on the
VA TRACE ANALYZER page as follows (see section 5.3.1):
Numbering of the input and

output control lines (1...8)
Ctrl.lines # 87654321
Inputs 0 = inactive, off 5V
Scan 01001111 1 = active, on 0V
Set 00011001
Outputs 0 = inactive, off 5V
1 = active, on open
The instruction SCANCTRL is used to scan the input lines within programs, whereas
the SETCTRL instruction (see section 5.7) serves to set the output lines.
The pin assignment of the remote interface, the pin functions and the electrical
conditions and statuses are shown in the Table on page 3-56.
The following Table shows which input and output lines are used for the external
start/stop function, the pipetting handle and the cables for the 708 Sampling Unit
and 683 Pump Units.
Input Output
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
External start l
External stop l
6.1562.040 Pipetting handle l l
6.2143.100 Cable (1 708) l l l
6.2143.110 Cable (2 708) l l l l l l
6.2143.120 Cable (1 708, 4 683) l l l l l l l
The output line 8 can be used only for the 6.1562.040 Pipetting
handle.

3.13 Connection of devices via remote interface
746
Printer
230V
External device Control Lines
2A(TH)
0
115V
230V
I
Reset
Remote cable
Fig. 25: Connection of external devices to the remote interface
746 VA Trace Analyzer external
Inputs
Pin Func-
tion
+5V 21 input 1
9 input 2 Voltage Scan
at input status
22 input 3 0V 1 (on)
10 input 4 5V 0 (off)
23 input 5
11 input 6
24 input 7
12 input 8
Outputs
Pin Func-
tion External device
5 output 1 VCEO 40 V
18 output 2 IC 20 mA
4 output 3
Voltage Scan
17 output 4 at input status
3 output 5 0V 1 (on)
16 output 6 open 0 (off)
1 output 7
2 output 8
Voltages
Pin Function
+5V
15 5 V: inactive, High (H) I 40 mA
0V 14 0 V: active, Low (L) Ri 12
25 0 V: active, Low (L)
Contact arrangement at socket

"Control Lines" (female)
13 1 Connecting cables to external devices must have an
appropriate 25-pin connector (male). Metrohm offers
connector sockets (K.210.9060) and the associated
housing (K.210.0002) as an option for the prepara-
tion of such cables.
25 14
No liability whatsoever will be accepted for damage arising from improper connection of devices.

3 Installation

4.1 Preparations
4 Introduction to the
operation
This section uses simple examples to introduce you to the operation

of the 746 VA Trace Analyzer and the 747 VA Stand. These examples
have been so selected that both the routine operation and the most
important instrument possibilities are demonstrated. You will find
general, more detailed explanations and information in framed, itali-
cized text blocks.
The illustrative methods can also be used as starting methods for
concrete, analytical determinations. For deeper explanations of the
operation, please refer to section 5, which describes the individual
dialog pages and program instructions.

4 Introduction to the operation
4.1 Preparations
In order to be able to perform the illustrative methods described in section 4.2 ff,
you must first put the 746 VA Trace Analyzer and 747 VA Stand into operation in a
proper manner. Proceed as described in section 4.1.1 and section 4.1.2 (you will
find information regarding the installation in the specified subsections of section 3).
Additional preparations required involve several instrument settings for the 746 VA
Trace Analyzer (section 4.1.3) and various tests for checking the 747 VA Stand
(section 4.1.4).
4.1.1 Installation of the 746 VA Trace Analyzer
When putting the 746 VA Trace Analyzer into operation for the first time, please pro-
ceed in the following sequence:
1 Setting up the instrument Section 3.1
2 Setting the mains voltage Section 3.2.1
3 Checking the fuses Section 3.2.2
4 Mains connection Section 3.2.3
5 Inserting paper Section 3.2.5
4.1.2 Installation of the 747 VA Stand
When putting the 747 VA Stand into operation for the first time, please proceed in
the following sequence:
1 Setting up the instrument Section 3.1
2 Attachment to 746 VA Trace Analyzer Section 3.3.1
3 Inserting dummy stoppers Section 3.3.2

Inserting dummy stoppers in measuring head
4 Assembling stirrer Section 3.8

Assembling stirrer and inserting in measuring head
5 Filling reference electrode Section 3.5

Filling reference electrode with internal and bridging
electrolyte and screwing together
Internal electrolyte: KCl 3 mol/L (6.2308.020)
Bridging electrolyte: KCl 3 mol/L (6.2308.020)

4.1 Preparations
6 Inserting reference electrode Section 3.3.2

Inserting reference electrode in measuring head
and connecting
7 Inserting Pt auxiliary electrode Section 3.3.2

Inserting Pt auxiliary electrode in measuring head
and connecting
8 Filling MME Section 3.4

Filling multi-mode electrode (MME) with mercury,
mounting capillary and filling
9 Inserting MME Section 3.3.2

Inserting multi-mode electrode (MME) in measuring
head and connecting
10 Filling measuring vessel Section 3.3.2

Filling measuring vessel with ca. 20 mL dist. H2O and
inserting
11 Connecting inert gas Section 3.3.3
4.1.3 Settings on the "VA TRACE ANALYZER" page
The settings necessary for startup of the 746 VA Trace Analyzer include setting the
date and time and contrast adjustment of the LCD. Proceed as follows:
1 Switch on instrument
Switch on the 746 VA Trace Analyzer with mains switch 11 at the rear of
the instrument. The instrument is initialized. If all is in order and the 747
VA Stand is attached properly, the dialog page "MONITORING" appears
after a few seconds.
The 746 VA Trace Analyzer has a total of 17 different dialog pages which can all be
selected directly using the yellow keys of the same name. The dialog keys are divided
into four groups and can also contain additional subpages. You will find an overview of
the dialog keys in section 5.1.3 and details of the individual pages in sections 5.35.6.
2 Switch to dialog page "VA TRACE ANALYZER"

Press the yellow <VA TRACE ANALYZER> key. The "VA TRACE ANA-
LYZER" dialog page appears:

746 VA TRACE ANALYZER

Program 5.746.0101
Date 1997-03-20 RS232 settings Ifc.1 Ifc.2

Time 10:41:15
Beeper on Baud rate 9600 9600
Data bits 8 8
Display Stop bit(s) 1 1
Parity none none
Switchoff time 30 min Handshake Hwshort Hwshort
Contrast 106 Receive mode off off
Configuration Address Balance type none

Printer type none none
VA stand 1 Printer width 1.00 1.00
Remote keyboard off
Ctrl.lines # 87654321 Printer

Scan 00000000 Type Metrohm
Set 00000000
Ext. Start off
Modify Set Ctrl Contrast Contrast Reset Reset Save Diagn.

column lines up down Ifc.1 Ifc.2 Ifc.par.
Dialog pages are divided into three parts:

The header contains the page title and further details regarding the dialog page (here the
program number).
The largest part of the dialog page is taken up with the page parameters. All editable pa-
rameters have not only a parameter name but also a gray-backed entry field in which a nu-
meric value or text expression can be entered. The individual entry fields can be selected in the
navigation mode (see section 5.2.2) using the cursor keys (arrow keys) with the current posi-
tion of the field cursor being marked by the black-backed entry field.
The bottom part of each dialog page contains the softkey bar in which the functions for the 8
softkeys F1...F8 are displayed.
You will find further information regarding the layout of the dialog pages in section 5.2.1.
3 Setting the date

After selection of the "VA TRACE ANALYZER" dialog page the field cursor
is already located in the entry field Date, which is black-backed.
If you wish to change the displayed date, first press the space bar to
change from the navigation mode to the edit mode. The whole field is
now no longer black-backed, but only the first flashing digit, at the same
time all displays in the softkey bar except for the softkey function <Help>
have disappeared.
Entry into the edit mode to change a parameter can be effected not only with the
space bar, but also with the <CLEAR> key, with the softkeys <Modify column>
and <Modify line> as well as by pressing all alphanumeric keys which are not in
simultaneous use as dialog keys (for details, see section 5.2.3).
Press the softkey <Help>. A help message for the Date parameter
appears in the HELP WINDOW with details of the entry format and the pos-
sible entry values. Close this window by pressing the <ENTER> key
again.

4.1 Preparations
In addition to the softkey <Help>, with parameters for which only certain numeric
values or text expressions can be entered, further softkeys with these numbers or texts
appear as keying-in aids. By pressing these softkeys, the corresponding expression is
entered directly in the entry field and the field closed.
Enter the desired date in the order year month day in the format
YYYY-MM-DD and confirm the entry by pressing the <ENTER> key. The
instrument then returns to the navigation mode.
During the entry of parameters in the edit mode, you have the following possibilities
available, among others:
Clearing entire field contents with the <CLEAR> key.
Resetting field contents to the original value with the <ESC> key.
Shifting the character cursor to the right or left with the <> or <> key.
Deleting individual characters with the <BACK SPACE> or <DELETE> key.
Switching between entry mode (cursor fixed) and overwrite mode (cursor flashes)
with the <INSERT> key.
You will find further information regarding the entry of numbers and characters in section
5.2.3.
4 Setting the time

Use the cursor key <> to select the entry field Time, which then be-
comes black-backed.
If you wish to change the displayed time, follow the same sequence as
described in point 3:
Press the space bar to enter the edit mode.
If need be, press the softkey <Help> to display the help message
for the Time parameter. Close this window by pressing the
<ENTER> key.
Enter the desired time in the order hours minutes seconds in the
format hh-mm-ss and confirm the entry by pressing the <ENTER>
key. The instrument then returns to the navigation mode.
5 Setting the screen contrast

The contrast of the LCD can be set in steps from completely dark (value
0) to extremely bright (value 250); the set contrast value is displayed in
the Contrast parameter.
If you wish to increase the current contrast, press the softkey
<Contrast up> repeatedly until the desired condition is reached.
If you wish to lower the current contrast, press the softkey <Contrast
down> repeatedly until the desired contrast is reached.
There is another possibility to set the screen contrast:

Press the <SHIFT> and <> keys simultaneously to increase the contrast continu-
ously, press the <SHIFT> and <> keys simultaneously to lower the contrast con-
tinuously.

4.1.4 Tests to check the 747 VA Stand
The tests described below are used to check the functions of the 747 VA Stand
such as purging, stirrer, DME and HMDE required for the illustrative methods. Per-
form the tests as follows (if the 746 VA Trace Analyzer is switched on, you can start
directly with point 2):
2 Switch to dialog page "STAND"

Press the yellow <STAND> key. The "STAND" dialog page appears:
747 VA STAND
Manual Address 1
Switches Settings States

Pressure off U.standby --- mV
Purging off
Stirrer off Rot.speed 2000 /min
DME off
HMDE off Drop size 5
SMDE off Drop size 5
RDE off Rot.speed 2000 /min
V.meas max 80 mL
Pressure Purging Stirrer DME HMDE SMDE RDE >>

Settings
3 Testing purging
To check the inert gas purging at the 747 VA Stand, the measuring
vessel must be filled with ca. 20 mL dist. water.
Press the softkey <Purging>. The inert gas purging is switched on, at
the same time the displays for Pressure and Purging switch to on and
an asterisk * appears in the two softkeys of the same name.
Check whether the purging of the analysis solution functions properly. If
so, you can switch off the purging by pressing the two softkeys
<Purging> and <Pressure>.
If the purging does not function properly, check the inert gas connection
as described in section 3.3.3 and then repeat the test.
The purging with inert gas (e.g. N2) serves to remove any electrochemically active
and hence interfering atmospheric oxygen in aqueous solutions. In determinations, the
instructions PURGE or TPURGE are used for this with a purging time of 35 min
generally sufficing (see section 5.7.3).

4.1 Preparations
4 Testing stirrer
Press the softkey <Stirrer>. The stirrer is switched on, at the same
time the display for Stirrer switches to on and an asterisk * appears
in the softkey of the same name.
Check whether the stirrer functions properly. If so, you can switch off
the stirrer by pressing the softkey <Stirrer>.
If the stirrer does not function properly, check its installation as described
in section 3.8 and then repeat the test.
Stirring serves to mix the analysis solution thoroughly. In determinations, the instruc-
tions STIR or TSTIR are used for this (see section 5.7.3).
5 Testing DME
Press the softkey <DME>. The dropping mercury electrode DME is
switched on, at the same time the display for DME switches to on.dt
and an asterisk * appears in the softkey of the same name.
Check whether the DME functions properly. The mercury must flow
slowly out of the capillary of the MME and the drop time be ca. 3 s. If this
is the case, you can switch off the DME by pressing the softkey <DME>.
If the DME does not function properly, check the installation of the MME
as described in section 3.4 and then repeat the test.
You will find further information regarding the DME under the instruction DME in section
5.7.3.
6 Testing HMDE
Press the softkey <HMDE>. The hanging mercury drop electrode HMDE is
switched on, at the same time the display for HMDE switches briefly to on
and an asterisk * appears in the softkey of the same name.
Check whether the HMDE functions properly. Each time the softkey
<HMDE> is pressed, a mercury drop should be formed. Dislodge the mer-
cury drop formed by lightly tapping the MME with your finger and check
that the mercury ceases to flow.
If the HMDE does not function properly, check the installation of the
MME as described in section 3.4 and then repeat the test.
You will find further information regarding the HMDE under the instruction HMDE in
section 5.7.3.
7 Switch to subpage "Settings"

Press the softkey <Settings>. The top part of the "STAND" dialog page
remains the same, but different softkeys appear:

747 VA STAND
Manual Address 1

Pressure off U.standby --- mV
Purging off
Stirrer off Rot.speed 2000 /min
DME off
HMDE off Drop size 5
SMDE off Drop size 5
RDE off Rot.speed 2000 /min
V.meas max 80 mL
VA Stand VA Stand 695 Auto 717 Smpl Rinsing Electr. Default >>
1 2 sampler Changer Dosinos test values Switches
8 Electrode test of the DME

Press the softkey <Electr. test>. The four softkeys <DME>, <HMDE>,
<SMDE> and <RDE> appear in the softkey bar.
Press the softkey <DME>. The message Connect Dummy Cell or
electrodes appears.
Press <ENTER> to start the test. The DME is tested, the message
Testing electrodes appears. On successful completion of the test, the
message DME test ok appears in the system window. Press the
<ESC> key to close the system window.
If the DME test was not successful, an error message appears (see
section 7.3.2). Check the installation of the MME as described in section
3.4 and then repeat the test.
You will find further information regarding the DME under the instruction DME in section
5.7.3.
9 Electrode test of the HMDE

Press the softkey <Electr. test>. The four softkeys <DME>, <HMDE>,
<SMDE> and <RDE> appear in the softkey bar.
Press the softkey <HMDE>. The message Connect Dummy Cell or
electrodes appears.
Press <ENTER> to start the test. The HMDE is tested, the message
Testing electrodes appears. On successful completion of the test, the
message HMDE test ok appears in the system window. Press the
<ESC> key to close the system window.
If the HMDE test was not successful, an error message appears (see
section 7.3.2). Check the installation of the MME as described in section
3.4 and then repeat the test.
You will find further information regarding the HMDE under the instruction HMDE in
section 5.7.3.

4.2 Lead determination with standard addition
With the aid of this illustrative method for the determination of lead in
the ion standard solution supplied, you can easily check whether the
746 VA Trace Analyzer and the 747 VA Stand are functioning properly.
At the same time, you will learn how to set up a method with standard
addition and will be introduced to the basic operation of the 746 VA
Trace Analyzer.
Before you can perform this illustrative method, you must first prepare
the instruments as described in section 4.1.
4.2.1 Reagents
The following solutions are needed to perform the method TESTPb.mth:
Potassium chloride solution, c(KCl) = 3 mol/L (Metrohm No.
6.2308.020)
Lead ion standard solution, (Pb2+) = 1 g/L (Metrohm No. 6.2301.100)
Dist. or deion. water
4.2.2 Loading the method TESTPb.mth

To load the method TESTPb.mth from the method memory into the working stor-
age, the following steps are necessary:
2 Switch to dialog page "METHODS"

Press the yellow <METHODS> key. The "METHODS" dialog page ap-
pears showing the methods stored in the instrument:
Files : 39 of 256 METHODS

Available: 1353520 Bytes
File

*#NEW.mth *AB110.mth *AB116_1.mth *AB116_2.mth
*AB116_3.mth *AB117.mth *AB123_1.mth *AB123_2.mth
*AB131.mth *AB146.mth *AB176_2.mth *AB186.mth
*AB196_1.mth *AB196_2.mth *AB199_1.mth *AB199_2.mth
*AB220.mth *AB226.mth *AB226_2.mth *AB231_1.mth
*AB231_2.mth *AB241.mth *AB243.mth *AB254.mth
*AB74_1.mth *AB74_2A.mth *AB74_2B.mth *AB74_3.mth
*AB76.mth *AB96.mth *AB96_2.mth *AB97.mth
*AB98.mth *ASV.mth *CALCRV.mth *INTSTD.mth
*POL.mth *TEST747.mth *TESTPb.mth
Modify Modify Delete Copy Copy Unselect Change >>

column line file(s) to from file(s) display

The header of dialog page "METHODS" contains details of the number of stored
methods and the available storage space. This is followed by the names of all stored
methods displayed in 4 columns.
You obtain a different type of display if you press the softkeyy <Change display>. In
addition to the name of the method, its content (method title) and memory requirements
are shown.
You will find further information regarding the dialog page "METHODS" in section 5.4.1.
3 Selection of the method TESTPb.mth

Use the cursor keys to select the method TESTPb.mth, which then
becomes black-backed.
4 Copying the method TESTPb.mth to the working storage

Press the softkey <Copy to>. The softkey bar changes and presents the
destinations for copying the selected method.
Press the softkey <Working storage>. The method TESTPb.mth is
copied to the working storage.
4.2.3 Method specifications of the method TESTPb.mth
In this section the 5 dialog pages of the group "Method Specifications" associated
with the loaded method TESTPb.mth will be explained in detail. If you are interested
only in a rapid lead measurement, you can proceed directly to section 4.2.4.
1 Switch to dialog page "OPERATION SEQUENCE"

Press the yellow <OP. SEQUENCE> key. The dialog page "OPERATION
SEQUENCE" appears with the main program for the lead determination:
Method: TESTPb .mth OPERATION SEQUENCE

Title : Pb determination in ion standard solution
Instructions t/s Main parameters Auxiliary parameters

1 DOS/M V.added 20.500 mL
2 REM 20 mL distilled water + 0.5 mL KCl 3 mol/L
3 SMPL/M V.fraction mL V.total L
4 REM 100 uL Pb ion standard 1 g/L
5 PURGE
6 STIR 300.0 Rot.speed 2000 /min
7 (ADD
8 PURGE
10 PURGE
11 STIR 5.0
12 (REP
13 SEGMENT Segm.name SegPb
14 REP)2
15 ADD>M Soln.name PbStd V.add 0.100 mL
16 ADD)2
17 END
Modify Modify Delete Insert Method

column line instr. instr. labels

The dialog page "OPERATION SEQUENCE" contains a sequence of program

instructions which can be freely combined. Most of the instructions also have certain
main and auxiliary parameters as well as optional entry of a line time. A total of 88
different program instructions can be used to program any type of determination.
You will find further information regarding this dialog page in section 5.6.1 and a
detailed description of all program instructions in section 5.7.3.
The following is a brief explanation of the main program sequence:

Line 2
1 Addition of 20 mL dist. water and 0.5 mL KCl 3 mol/L
Line 4
3 Addition of sample: 100 L Pb ion standard 1 g/L
Line 6
5 Purging and stirring of the analysis solution for 5 min
Line 16
7 Loop for double standard addition
Line 9
8 Purging and stirring of the analysis solution for 30 s
11
Line 10 Switch off purging and stirring, stabilization of the
analysis solution for 5 s
14
Line 12 Loop for duplicate replication of the segment
Line 13 Call up of the segment SegPb for lead determination
Line 15 Addition of standard addition solution:
100 L Pb ion standard 1 g/L
Line 17 End of main program
2 Switch to dialog page "SEGMENT"

Press the yellow <SEGMENTS> key. The dialog page "SEGMENT"
appears with the program for measured value acquisition:
Method: TESTPb SEGMENT

SegPb

1 DME
2 DPMODE U.ampl -50 mV t.meas 20.0 ms
t.step 0.40 s t.pulse 40.0 ms
3 SWEEP 24.8 U.start -200 mV U.step 6 mV
U.end -550 mV Sweep rate 15 mV/s
4 MEAS U.standby mV
5 END
Modify Modify Delete Insert Select Delete Plot Segment

column line instr. instr. segment segment param. name
The dialog page "SEGMENT" also contains a freely combinable sequence of program
instructions with associated parameters and an optional line time. A segment is used
primarily for the programming of the measured value acquisition (sweep) and is called
up in the main program with the SEGMENT instruction. Per method max. 8 different
segments can be defined, but only 1 sweep is admissible per segment.
You will find further information regarding this dialog page in section 5.6.2 and a
detailed description of all program instructions in section 5.7.3.

The sequence of the segment SegPb is explained in brief in what follows:

Line 1 Switching on the DME (dropping mercury electrode)
Line 2 Selection of the measurement mode DP (differential pulse)
with voltage amplitude 50 mV, voltage step 0.4 s, meas-
urement time 20 ms and pulse time 40 ms
Line 3 Voltage sweep of 200 mV ... 550 mV with a
voltage step of 6 mV
Line 4 Switch off voltage, current measurement and DME
Line 5 End of the segment (return to main program)
3 Switch to dialog page "SUBSTANCES"

Press the yellow <SUBSTANCES> key. The dialog page "SUBSTAN-
CES" appears with the parameters for evaluation of the substance lead:
Method: TESTPb SUBSTANCES

Pb - SegPb
Recognition Display / Plot

U.verify -380 mV I.scale auto
U.tol (+/-) 40 mV U.div 50.00 mV/cm
U.width min 25 mV U.begin mV
U.width max 120 mV U.end mV
I.threshold 200 pA
Baseline Evaluation

Type linear Mode VA
Scope whole Quantity I.peak
dU.front auto Sign. digits 4
S.front auto
dU.rear auto
S.rear auto
Modify Modify Select Link to Delete Subst. >>

column line subst. segment subst. name
The header of the dialog page "SUBSTANCES" contains the name of the substance
Pb and the segment SegPb linked with this substance. This is followed by the
parameters for substance recognition (Recognition), baseline calculation (Baseline),
evaluation quantity (evaluation) and curve representation (Display/Plot).
You will find further information regarding this dialog page in section 5.6.3.
The following is a brief explanation of the most important parameters:

U.verify Characteristic voltage for lead: 380 mV
U.tol Tolerance for characteristic voltage: only peaks with
a peak voltage of 380 V 40 mV are recognized
U.width min Minimum peak width: only peaks with a
peak width > 25 mV will be recognized
U.width max Maximum peak width: only peaks with a
peak width < 120 mV will be recognized
Type Baseline type: linear (tangent)
Scope Baseline range: entire curve

dU.front/dU.rear Determination of base points: automatic

S.front/S.rear Determination of the slopes at the base points:
automatic
I.scale Scaling of the current axis: automatic
U.div Division of the voltage axis for printout
Quantity Evaluation quantity: peak height
Press the softkey < >> >. The subpage of "SUBSTANCES" appears with
the parameters for calibration of the substance lead:
Method: TESTPb SUBSTANCES

Pb - SegPb
Calibration 1997-03-20 16:23 Coefficients

Technique std.add Y.reg -1.957e-07
Curve type linear Slope -3.907e-05
Nonlin.
Mean dev. 2.137e-09
Additions

Soln.name PbStd

Mass conc. 1 g/L g/L g/L g/L
Range min g/L g/L g/L g/L
Range max g/L g/L g/L g/L
M.conc./cm g/L g/L g/L g/L

The dialog page "SUBSTANCES" contains a subpage with the parameters for the
calibration. Here, the type of calibration (standard addition, calibration curve or internal
standard) and the required solutions are defined, in addition the results of the last
calibration are displayed.

Technique Calibration technique: standard addition
Curve type Curve type for calculation of the standard addition:
linear
Soln.name Name of the standard addition solution PbStd
called up in the instruction ADD>M
Mass conc. Mass concentration of the standard addition solution:
1 g/L
4 Switch to dialog page "CALCULATION"

Press the yellow <CALCULATION> key. The dialog page
"CALCULATION" appears for calculation of the final results:

Method: TESTPb CALCULATION

max. 15 lines
Quantity Formula (R##, C##, A##) Res.unit Sig.dig.

Pb R1000=MC:Pb #g/L 4
Modify Modify Delete Insert New Upd.from Syntax

column line line line calcul. method check
On the dialog page "CALCULATION", maximum 15 formulae for the calculation of the
final results as well as the designations of the result quantities and units can be entered.
In the present example, the standard formula for lead is entered. As the
result, the mass concentration of lead (MC:Pb) determined using the
standard addition is outputted in g/L with 4 significant figures.
5 Switch to dialog page "DOCUMENTATION"

Press the yellow <DOCUMENTATION> key. The dialog page "DOCU-
MENTATION" appears for the automatic output of reports and curves:
Method: TESTPb DOCUMENTATION

Output
Auto form feed no Auto error printing no
COPY Reports, Curves TO Destination

Report Full Printer
Curve Smth Sbst:Pb VR:** Printer
Curve Cal Sbst:Pb Printer
Modify Modify Delete Insert Exec. Exec. >>

column line line line line all Comment

The dialog page "DOCUMENTATION" can be used for the entry of reports and curves
which should be put out automatically to the specified destination at the end of the
determination. A single line or all these lines can also be executed later using the
softkeyy <Exec. line> or <Exec. all>.
The three lines entered in the present example have the following mean-
ing:
Report Full Printout of the full result report on the
built-in or connected printer
Curve Smth Sbst:Pb VR:** Printout of all smoothed substance
curves on the built-in or connected printer
Curve Cal Sbst:Pb Printout of the calibration curve (graphical
representation of the standard addition)
on the built-in or connected printer
If you do not desire an automatic printout in the subsequent lead deter-

mination, you can either delete the three entered lines with the softkey
<Delete line> or clear the output destination Printer for each line with
the <CLEAR> key.
Press the softkey <Comment>. The subpage of "DOCUMENTATION"
appears with the method comment:
Method: XXXXXXXX DOCUMENTATION

Comment
Method: - Pb determination with DP polarography from -200 mV to -550 mV.
- This method can be used as a first test after installing the
746 VA Trace Analyzer and the 747 VA Stand or can be used as
standard operating procedure (SOP) for a GLP test of 746/747.
- For detailed information see instruction manual.
Electrodes: - Multi-Mode electrode

- Ag/AgCl reference electrode with KCl 3 mol/L
- Pt auxiliary electrode
Reagents: - KCl 3 mol/L (6.2308.020)

- Pb ion standard 1 g/L (6.2301.100)
- dist. or deion. water
Procedure: - Add 20 mL of water, 0.5 mL of KCl 3 mol/L and 100 L of

Pb ion standard 1 g/L (that means 100 g Pb)
into the well rinsed measuring vessel.
- Enter '100 uL' for 'Sample size/S0' on MONITORING page.
- Start determination.
- Add 2 * 100 L of Pb ion standard 1 g/L (standard addition).
Help Delete Insert Get Put >>

line line line line Output
The dialog page "DOCUMENTATION" includes a subpage on which maximum 20

lines of free text can be entered as a comment on the method.
In the present example, details of the method, the electrodes and rea-
gents to be used and the procedure used in the lead determination are
entered.
Finally press the <ESC> key to return to the main page of "DOCUMEN-
TATION".

4.2.4 Preparing the sample solution

The sample solution for the lead determination is prepared as follows:
1 Addition of 20 mL dist. water

Add 20 mL dist. or deion. water to the measuring vessel.
2 Addition of 0.5 mL KCl 3 mol/L

Add 0.5 mL potassium chloride c(KCl) = 3 mol/L to the measuring
vessel.
3 Addition of 100 L Pb ion standard solution

Add 100 L Pb ion standard solution (Pb) = 1 g/L to the measuring
vessel (this results in 100 g Pb in the measuring vessel).
4.2.5 Settings on the "MONITORING" page

Before the start of the loaded method, the sample volume must be entered on the
"MONITORING" page. Proceed as follows:
1 Switch to dialog page "MONITORING"

Press the yellow <MONITORING> key. The dialog page "MONITORING"
appears:
Method: TESTPb MONITORING * READY *

Remark 1
Remark 2
Run mode determination Run 0

User name Stand address 1
Auto.samples off 0 of 160 Determination .dtm

Auto.batch off 0 of *
Start interval 0.0 h Modified no
Det.storage off 93.7 % free Sample table -
Pos. Ident.1/S1 Ident.2/S2 Ident.3/S3 Method.call Sample size/S0
Modify Modify Recalc. Check System Error Live

column line method window window display
For the determination using the method TESTPb, the adjustable pa-
rameters Run mode, Auto.samples, Auto.batch, Start interval and
Det.storage must have the values shown here. If this is not the case,
they must be changed accordingly.
The dialog page "MONITORING" is used to monitor the operation. Here, various
settings and entries for subsequent determinations can be defined. You will find a
detailed description of this dialog page in section 5.5.1.

2 Entry of the sample volume

Enter the sample volume as follows:
Use the cursor keys to select the first field below the title Sample
size/S0.
Press the space bar to enter the edit mode (this step can be omitted as
the entry of a number switches directly to the edit mode).
Enter 0.1 mL and confirm this entry with the <ENTER> key.
In addition to the obligatory entry of the sample volume, you can make additional entries
on this dialog page which are then stored in the determination. These are the two lines
Remark 1 and Remark 2 for general comments, the user name User name and
the 3 sample identifications Ident 1,, Ident 2 and Ident 3.
4.2.6 Performing the determination

To perform the lead determination in the prepared sample solution, the following
steps are necessary:
1 Start the determination

Press the red <START> key.
The status display in the header of the dialog page "MONITORING"
switches to * BUSY *, the start time of the measurement is entered un-
der Determination and the determination is given a standard name,
also formed from the start time. Further, during the measurement the
measurement window is superimposed which shows the current pro-
gram line being executed and the remaining line time:
Method: TESTPb MONITORING * BUSY *

Remark 1
Remark 2
Run mode determination Run 1

User name Stand address 1
Auto.samples off 0 of 160 Determination 03201614.dtm

Auto.batch off 0 of * 1997-03-20 16:14:53
Start interval 0.0 h Modified no
Det.storage off 93.7 % free Sample table -

0.1 mL
Segment: 6 STIR 263 s

VR: 00

During the ongoing determination, you have the following main function keys available:
<BREAK> Immediate abort of the determination
<HOLD> Interruption (continue with <(CONT)> or <(STEP)>)
<ABBREV> Truncation of the current instruction (line time set to 0)

Further, you can also select all dialog pages with the exception of "STAND" and
"CURVES" and make changes to them. But be careful when making such changes as
they immediately become effective and could lead to uncontrollable conditions for the
active program.
2 Measurement of the sample solution

The first part of the lead determination involves the measurement of the
sample solution. It runs as follows (see also the description of the pages
"OP. SEQUENCE" and "SEGMENTS" in section 4.2.3):
Purging and stirring for 330 s
Wait time 5 s to stabilize the analysis solution
Call-up of the segment SegPb three times for measured value
acquisition. The lead in the solution is reduced at the dropping
mercury electrode (DME). The selected measurement mode DP
leads to a current peak with a maximum at ca. 380 mV.
During the voltage sweep the measurement window shows a continuous
display of the current measured values for voltage (U) and current (I):
Segment: SegPb 3 SWEEP 29 s U = -0.2548 V

VR: 00 I = -1.961e-08 A
In addition, the name of the segment (SegPb) and the current VR number,
which is composed of the number of the variation (V) and replication (R),
are specified. In the present example, in this first phase (variation 0)
three measurements are performed and are numbered as follows:
00 1st measurement of the sample solution
01 2nd measurement of the sample solution (1st repetition)
02 3rd measurement of the sample solution (2nd repetition)
Each single measurement recorded in a segment is consecutively numbered using

variation and replication, each from 0...8. The resulting VR number is used to identify the
individual results and curves on the dialog pages "RESULTS" and "CURVES" and for the
selective call-up of reports and curves on the "DOCUMENTATION" page.
During an ongoing determination, you have the possibility to display the

live curve by pressing the softkey <Live display>.
Instead of the "MONITORING" page, the graphical representation of the
measured current values (y axis) appears as a function of the voltage
values (x axis) with the current axis being automatically adjusted to the
measured values. The measurement window with the current experi-
mental data continues to be shown below the live curve.
If you do not desire automatic switching of the current axis in the display of the live
curve, you can fix this by changing the plot parameters for the segment to preset values
(see dialog page "SEGMENTS", section 5.6.2).
To return to the "MONITORING" page from the display of the live curve,
you must press either the <ESC> or the <MONITORING> key.
On completion of the 3rd measurement of the sample solution, the pro-
gram is interrupted. The screen shows the prompt to add 100 L of the
standard addition solution PbStd to the measuring vessel:

MEAS.TASK MESSAGE

ADD PbStd 100.000 uL > M
press <Esc> to break
<Enter>: continue

3 1st standard addition

Remove stopper 25 and use a pipette to add 100 L lead ion standard
solution to the measuring vessel through the pipetting opening. Then
close the pipetting opening with stopper 25 and press the <ENTER>
key.
The sample solution spiked with standard addition solution is then
measured:
acquisition. The three individual measurements are given the VR
numbers 10, 11 and 12.
On completion of the 3rd measurement of the sample solution, the pro-
gram is interrupted. The screen again shows the prompt to add 100 L
of the standard addition solution PbStd to the measuring vessel:
MEAS.TASK MESSAGE

ADD PbStd 100.000 uL > M
<Enter>: continue

4 2nd standard addition

Remove stopper 25 and use a pipette to add 100 L lead ion standard
solution to the measuring vessel through the pipetting opening. Then
key.
The sample solution spiked with standard addition solution is then
measured:
acquisition. The three individual measurements are given the VR
numbers 20, 21 and 22.
On completion of the 3rd measurement and calculation of the results, the
program is ended. The status display in the header of the "MONITO-
RING" dialog page switches back to * READY *, the instrument is ready
for a new determination.
5 Printout of reports and curves

On completion of the program, the reports and curves entered on the
"DOCUMENTATION" page are put out on the printer.
The printout of reports and curves can be stopped at any time by simultaneously
pressing the <SHIFT> and <PRINT STOP> keys.

First the full report Report Full is printed out with all results:
================== METROHM 746 VA TRACE ANALYZER (5.746.0101) ==================

Determ. : 03201614 User: Date: 1997-03-20
1 Modified : no Run : 1 Time: 16:14:53
Sample table: -
--------------------------------------------------------------------------------
2 0.1 mL
--------------------------------------------------------------------------------
Method : TESTPb
3 Title : Pb determination in ion standard solution
Remark1 :
Remark2 :
--------------------------------------------------------------------------------
Substance : Pb Comments
4 Mass conc.: 1.032 g/L Mass : 103.2 ug
MC.dev. : 0.011 g/L (1.05%) Add.mass : 100 ug
Cal.dev. : - V0.sample: 100 uL
VR U/mV I/nA I.mean Std.dev. I.delta Comments

5
00 -355 -195.9 -194.7 1.569
01 -355 -195.3
02 -355 -192.9
10 -356 -385.2 -385.5 0.4942 -190.8
11 -356 -386.1
12 -356 -385.3
20 -357 -568.1 -568.5 1.968 -182.9
21 -357 -566.7
22 -357 -570.6
Substance Techn. Y.reg/offset Slope Nonlin. Mean deviat.

6
Pb std.add. -1.957e-07 -3.907e-05 2.137e-09
C# Workg.com.var Remark
7
Final results +/- Res.dev. % Comments

8
Pb = 1.032 g/L 0.011 1.05
The full report comprises the following parts:

1 Data of determination Name, date and time, user, run number, etc.
2 Data of sample Sample identification, sample size
3 Data of method Name, title, remarks
4 Data of substance Substance name, mass concentration found and
evaluation its absolute and relative total deviation, substance
mass found in measuring vessel, standard addition
mass and sample volume in the measuring vessel
5 Data of peak evaluation Overview of the 9 individual measurements with
the following results: peak voltage U, peak current
I, mean value of the peak current I.mean with
associated standard deviation Std.dev. and
difference between the peak currents I.delta
6 Data for standard Current value Y.reg for the sample calculated
addition from the standard addition curve, slope and mean
deviation of standard addition curve
7 Common variables not used in this example
8 Final results Final result with formula calculation
You will find further information regarding the report in section 5.5.2
"RESULTS" and section 5.6.5 "DOCUMENTATION".

Next, all smoothed experimental curves are printed out. Here, all single
curves are put out superimposed.

Method : TESTPb User : Date : 1997-03-20
1 Mode : DPMODE Determ. : 03201614 Time : 16:14:53
Run : 1
Curve : smoothed Segment : SegPb V R : * *
3 Substance : Pb U = -355 mV I = -195.871 nA
The printout of a curve comparison comprises the following parts:

1 Data of determination Name of the method, user, date and time of the
recording, measurement mode, name of the
determination, run number, curve type, name of
the segment, VR number
2 Curves Experimental curves, calculated baseline (dashed),
peak voltage, base points, current and voltage axis
3 Results Name of the substance, peak voltage and peak
current for the sample (VR = 00)
You will find further information regarding the curve printout in section
5.5.3 "CURVES" and section 5.6.5 "DOCUMENTATION".

The last curve to be printed out is the calibration curve for the standard
addition:

Method : TESTPb User : Date : 1997-03-20
1 Mode : DPMODE Determ. : 03201614 Time : 16:14:53
Run : 1 Sample :
Standard addition curve

2 Curve type : lin Slope : -3.907e-05 Mean.dev. : 2.137e-09
Mode : const Y.reg : -1.957e-07
4 Substance : Pb
The printout of the standard addition curve comprises the following

parts:
1 Data of determination Name of the method, user, date and time of the
recording, measurement mode, name of the
determination, run number, sample identification
2 Data of standard addition Curve type, addition mode, slope of the standard
addition curve, current value Y.reg for the
sample calculated from the standard addition
curve, mean deviation Mean.dev. of the
measured values about the standard addition
curve
3 Standard addition curve Measured points (mean value of the measured
peak currents), calculated standard addition curve,
current axis, axis for effective mass concentration
in the measuring vessel
4 Substance Name of substance
You will find further information regarding the printout of the standard
addition curves in section 5.5.3 "CURVES" and section 5.6.5 "DOCU-
MENTATION".
This concludes the lead determination. In the following sections you will
learn how you can subsequently store the recorded determination
(section 4.2.7) and what possibilities you have available to view and
process the measured data on the dialog pages "RESULTS" (section
4.2.8) and "CURVES" (section 4.2.9).

4.2.7 Storing the determination

The lead determination you have just performed remains in the working storage un-
til you start a new determination or load a different determination into the working
storage. For permanent storage of the recorded determination, you have the fol-
lowing three possibilities available:
1 Storage in determination memory

Press the yellow <DETERMINATIONS> key. The dialog page "DETER-
MINATIONS" appears showing the determinations stored in the instru-
ment:
Files : 0 of 256 DETERMINATIONS

Available: 1353520 Bytes Full condition: stop
File


The header of the dialog page "DETERMINATIONS" contains information on the

number of stored determinations and the available storage space. This is followed by
the names of all stored determinations displayed in 4 columns.
Press the softkey <Copy from>. The softkey bar changes and presents
the sources for copying a determination to the determination memory.
Press the softkey <Working storage>. The determination loaded in the
working storage is copied to the determination memory, the file name (in
this example 03201614.dtm) appears in the first column under the title
File.
Press the softkey <Change display>. The type of display changes, in
addition to the name of the determination a field for content information
and the storage space needed for the determination in bytes appear.
Both file name and content information can be changed for improved
documentation. To do this, press the softkey <Modify line> to enter the
edit mode. The first 8 characters of the determination name can now be
changed in any way (the extension .dtm must be retained). Now press
the <ENTER> key and enter any comment in the Content field for the
determination (e.g. Lead determination with method TESTPb of
20.03.1997). After confirmation with the <ENTER> key, you are again in
the navigation mode.

2 Storage on the data card

A data card is included in the standard equipment of the 746 VA Trace
Analyzer for the storage of methods and determinations. Before first-time
use in the 746 VA Trace Analyzer, this data card must first be prepared.
The steps required for this (insertion of the battery, affixing the label, for-
matting, plugging in) are described in section 3.2.6.
Insert the prepared and formatted data card in the 746 VA Trace Ana-
lyzer and press the yellow <DATA CARD> key. The dialog page "DATA
CARD" appears showing the methods and determinations stored on the
card:
Files : 0 of 256 DATA CARD Capacity: 131072 Bytes

Available: 1353520 Bytes Label :
File


The header of the dialog page "DATA CARD" contains information on the number of
files stored and the available storage space. This is followed by the names of all stored
files displayed in 4 columns.
Press the softkey <Copy from>. The softkey bar changes and presents
the sources for copying a method or determination to the data card.
Press the softkey <Working storage> (determination in the working
storage). The determination loaded in the working storage is copied to
the data card, the file name (in this example 03201614.dtm) appears in
the first column under the title File.
Press the softkey <Change display>. The type of display changes, in
addition to the name of the determination a field for content information
and the storage space needed for the determination in bytes appear.
Both file name and content information can be changed for improved
documentation. To do this, press the softkey <Modify line> to enter the
edit mode. The first 8 characters of the determination name can now be
changed in any way (the extension .dtm must be retained). Now press
the <ENTER> key and enter any comment in the Content field for the
determination (e.g. Lead determination with method TESTPb of
20.03.1997). After confirmation with the <ENTER> key, you are again in
the navigation mode.

3 Storage on a PC
For the permanent storage of methods and determinations we recom-
mend you copy these to a PC via the RS232 interface. For this purpose,
the 6.6017.000 PC Program Metrodata VA Back Up is enclosed with
the VA Trace Analyzer which allows data to be interchanged between the
746 VA Trace Analyzer and an IBM-compatible PC (with Windows 3.1 or
Windows 95). The exact procedure is described in the Instructions for
Use enclosed with the program.
A further possibility to store methods and determinations on a PC in-
volves the 6.6016.113 PC Program Metrodata VA Database 2.1
available as an option which allows not only data transfer between the
746 VA Trace Analyzer and an IBM-compatible PC (with Windows 95 or
Windows NT) but also the viewing of curves and results on the PC and
includes a special report generator with filter functions. Operation of this
program is described in the Instructions for Use enclosed with the pro-
gram.
4.2.8 Display of the results

The results obtained in the recorded lead determination can not only be printed out,
but also shown on the screen. Proceed as follows:
1 Switch to dialog page "RESULTS/Calculation"

Press the yellow <RESULTS> key. The dialog page "RESULTS" appears
with the subpage "Calculations" showing the final results of the determi-
nation loaded in the working storage:
Method : TESTPb RESULTS

Determ.: 03201614 Calculations

Pb = 1.032 g/L 0.011 1.05
>> >>
Eval. Calibr.
On the dialog page "RESULTS" the results of the determination loaded in the working
storage are displayed on the three subpages "Calculations" (final results), "Evaluations"
(substance and peak evaluations) and "Calibrations" (calibration data).

2 Switch to dialog page "RESULTS/Evaluation"

Press the softkey <Eval.>. The dialog page "RESULTS" with the sub-
page "Evaluations" appears showing an overview of the substance and
peak evaluations of the determination loaded in the working storage:

Determ.: 03201614 Evaluations
Mass conc.: 1.032 g/L Mass : 103.2 ug
MC.dev. : 0.011 g/L (1.05%) Add.mass : 100 ug
Cal.dev. : - V0.sample: 100 uL

00 -355 -195.9 -194.7 1.569
01 -355 -195.3
02 -355 -192.9
10 -356 -385.2 -385.5 0.4942 -190.8
11 -356 -386.1
12 -356 -385.3
20 -357 -568.1 -568.5 1.968 -182.9
21 -357 -566.7
22 -357 -570.6
Select Suspend/ New >> >>

subst. activate calcul. Calcul. Calibr.
You will find a brief explanation of the result data shown here in the
description of the full report in section 4.2.6.
On this subpage you have the possibility to ignore undesired peak
results (e.g. spikes) for subsequent calculations. Proceed as follows:
Use the cursor keys to select the desired result by its VR num-
ber.
Press the softkey <Suspend/activate>. In addition to the VR
number, the marking ! appears to show that this peak result will
be ignored in subsequent calculations (this marking can also be
canceled using the same softkey).
Press the softkey <New calcul.>. This initiates a new calculation
whose effects on the substance evaluation are immediately ap-
parent on this page.
3 Switch to dialog page "RESULTS/Calibration"

Press the softkey <Calibr.>. The dialog page "RESULTS" with the
subpage "Calibration" appears showing the results of the substance cali-
brations:


Determ.: 03201614 Calibrations
Substance Techn. Y.reg/offset Slope Nonlin. Mean.deviat.

Pb std.add. -1.957e-07 -3.907e-05 2.137e-09
>> >>
Calcul. Eval.
You will find a brief explanation of the result data shown here in the
description of the full report in section 4.2.6.
4.2.9 Display of the curves

The curves obtained in the recorded lead determination can not only be printed out,
but also shown on the screen. Proceed as follows:
1 Switch to dialog page "CURVES"

Press the yellow <CURVES> key. The dialog page "CURVES" appears
showing three smoothed curves of the lead determination loaded in the
working storage:

On the dialog page "CURVES" various experimental curves can be displayed for both
individual substances and segments. Moreover, parameters for the scaling, the sub-
stance recognition and the baseline calculation can be changed interactively and
measured spike values removed manually.
The curves which are shown can be seen from the title line. The curve
displayed in black is the smoothed curve of the substance lead with VR
number 00 (Pb-00-smoothed). In addition, the curves 10 and 20 are
shown in gray (grouped VR: *0). The calculated baseline for the curve
00, the peak voltage and the two base points of the lead curve are also
drawn in.
Below the curves is a list of the results of the peak evaluation for the
curve 00: peak voltage U.peak, peak current I.peak, peak area P.peak,
peak width U.width and the two voltage differences to the front base
point dU.front and the rear base point dU.rear.
This dialog page offers you extensive possibilities with the aid of the
softkeys:
Display Display of segment associated with the substance with
segment
the possibility to eliminate measured spike values.
Select Selection of substance and VR number for the display.

segment
Select Selection of curve type for the display. Possible are:

curve
Original Curve of the original measured values
Processed Curve of the measured values after
automatic spike elimination
Smoothed Smoothed curve
Derived Derived curve
Subtracted Subtracted curve (baseline subtracted
from the smoothed curve)
Calibr. Calibration curve
Next Display next curve

VR
Prev. Display previous curve

VR
Scale New axis scaling for the substance curves

The temporary changes made here to the "Display/Plot"
parameters can also be incorporated permanently in the
method with the softkey <Save param.>.
Modify Modify parameters for substance recognition

recogn.
The temporary changes made here to the "Recognition"
Modify Modify baseline parameters

baseline
The temporary changes made here to the "Baseline"

4.3 Lead determination with calibration curve
The usual calibration procedure for the majority of the determinations

possible with the 746 VA Trace Analyzer is standard addition
(example, see section 4.2). However, the mass concentration of a
substance can also be calculated using a calibration curve deter-
mined beforehand by measurement of different reference solutions.
Result determination with the aid of a calibration curve saves time
compared with standard additions, but is admissible only when
the matrix of all samples and calibration solutions is identi-
cal or has no influence on the measurement,
all measurement parameters (capillary, temperature, etc.)
remain unchanged in the measurements, and
the accuracy of the results obtained is regularly checked
using the standard addition method.
In the present example, a lead determination in drinking water is used
to show you how a method with calibration curve is programmed and
performed.
You must first prepare the 746 VA Trace Analyzer and 747 VA Stand as
described in section 4.1 before you can perform this example.
4.3.1 Reagents and accessories

To perform the method CALCRV.mth, the following solutions are needed:
1 Acetate buffer 1 mol/L, pH 4.6
2 Lead ion standard solution, (Pb2+) = 1 g/L

Lead ion standard solution (Metrohm No. 6.2301.100) for preparation of the
following calibration solutions:
Calibration solution Pb-1 (Pb2+) = 2.5 g/L
Calibration solution Pb-2 (Pb2+) = 5 g/L
3 Conc. hydrochloric acid Suprapur, w(HCl) = 0.3 (30%)
4 Drinking water
Water that has been in the supply system for a lengthy period of time
absorbs metals from the pipe and fittings materials and thus falsifies the
analysis results. Hence, before taking the water sample allow the water
to run out of the tap in a powerful stream for several minutes.

The drinking water sample should be acidified immediately after the

sample has been taken by adding 10 L conc. hydrochloric acid per
10 mL drinking water.
Owing to the large temperature dependence of the measured values ( 2%/C), we

recommend you to use the 6.1418.220 Thermostatable measuring vessel with the
calibration curve method.
4.3.2 Loading the method CALCRV.mth

To load the method CALCRV.mth from the method memory into the working stor-
the instrument. The instrument is initialized. If all is in order, the dialog
page "MONITORING" appears after a few seconds.

pears showing the methods stored in the instrument.
3 Selection of the method CALCRV.mth

Use the cursor keys to select the method CALCRV.mth, which then
4 Copying the method CALCRV.mth to the working storage

Press the softkey <Working storage>. The method CALCRV.mth is

4.3.3 Method specifications of the method CALCRV.mth
with the loaded method CALCRV.mth will be explained in detail. If you are interested

Method: CALCRV .mth OPERATION SEQUENCE

Title : Pb determination with calibration curve

1 D SMPL>M V.fraction mL V.total L
2 C (CAL
3 C CSOLN>M addition into MEAS
4 DOS>M Soln.name Acetate V.add 1.000 mL
5 PURGE
7 PURGE
8 (REP
10 SEGMENT Segm.name DPASV
11 REP)2
12 C RINSE Cycles 1 V.rinse mL
13 C CAL)3
14 END


Line 1 Addition of sample: 10 mL
Line 2 13 Loop for recording the calibration curve (4 calibration solutions)
Line 3 Addition of calibration solution to measuring vessel: 10 mL
Line 4 Addition of acetate buffer to measuring vessel: 1 mL
Line 5 6 Purging and stirring of the analysis solution for 3 min
Line 7 Switching off the purging
Line 8 11 Loop for double replication of the segment
Line 9 Stirring of the analysis solution for 5 s
Line 10 Call-up of the segment DPASV for lead determination
Line 12 Resetting of the volume bookkeeping to 0 for solution change
(new calibration solution)
The sequence of the main program depends on the selected mode for
the program run Run mode on the "MONITORING" page:
In the program run mode calibration, all instructions marked with
D are ignored. 4 calibration solutions are measured in turn and the
coefficients of the calibration curve determined.
In the program run mode determination, on the other hand, all in-
structions marked with C are ignored. The sample is measured and
its mass concentration then determined using the calibration curve
recorded earlier.


Method: CALCRV SEGMENT

DPASV

1 HMDE Drop size 4 Meas.cell normal
2 DPMODE U.ampl 50 mV t.meas 20.0 ms
3 MEAS 90.0 U.meas -600 mV
4 STIR 5.0
6 MEAS U.standby mV
7 END

The sequence of the segment DPASV is explained in brief in what follows:

Line 1 Switching on the HMDE (hanging mercury drop electrode)
with voltage amplitude 50 mV, voltage step 0.1 s,
measurement time 20 ms and pulse time 40 ms
Line 3 Application of a measurement voltage of 600 mV for 90 s
for the enrichment of lead at the hanging mercury drop
Line 4 Switching off the stirrer and stabilization of the analysis
solution for 5 s
Line 6 Switch off voltage and current measurement

CES" appears with the parameters for evaluation of the substance lead.
Except for the characteristic voltage U.verify (400 mV), these are
identical to those of the TESTPb.mth method and are not explained fur-
ther here (see section 4.2.3).

Method: CALCRV SUBSTANCES

Pb - DPASV

Technique cal.crv. Y.offset -8.183e-10
Curve type linear Slope 0.002712
Temperature 20.0 C Nonlin
Mean dev. 1.113e-09
Range min g/L # CSoln.name Mass conc.

Range max g/L
0 Pb-1 2.5 ug/L
M.conc./cm g/L 1 Pb-2 5 ug/L
M.conc.begin zero 2 Pb-3 10 ug/L
3 Pb-4 20 ug/L
V0.CSoln. 10.000 mL 4 g/L
5 g/L
6 g/L
7 g/L
8 g/L
9 g/L


Technique Calibration technique: calibration curve
Curve type Curve type for calculation of the calibration curve:
linear
Temperature Temperature of the analysis solution
V0.CSoln. Volume added of every calibration solution
Y.offset Offset of the calibration curve
Slope Slope of the calibration curve
Mean dev. Mean deviation of the calibration curve
CSoln.name Name of the calibration solutions
Mass conc. Mass concentration of the calibration solutions

Press the yellow <CALCULATION> key. The dialog page "CALCU-
LATION" appears for calculation of the final results. The mass concen-
tration of lead (MC:Pb) determined using the calibration curve is put out
as the result in g/L with 4 significant figures.

MENTATION" appears for the automatic output of reports and curves.
The two lines entered in the example have the following meaning:
Report Full Printout of the full result report on the printer
Curve Cal Sbst:Pb Printout of the calibration curve on the printer

appears with the method comment describing, among other things, the
procedure used in the calibration and determination.
Finally press the <ESC> key to return to the main page of
"DOCUMENTATION".

4.3.4 Recording the calibration curve

Recording of the calibration curve involves the following steps:

whose header shows the loaded method CALCRV appears.
2 Switch the program run mode to calibration

If the parameter Run mode is set to determination, proceed as follows:
Use the cursor keys to select the field Run mode.
Press the softkey <calibr.> and confirm this entry with the <ENTER>
key.

size/S0.
Enter either * or 10 mL (as preparation for performance of the determi-
nation in section 4.3.5) and confirm this entry with the <ENTER> key.
Although the sample volume for recording the calibration curve is not needed (the
volume of the calibration solutions is defined in the parameter V0.CSoln), the
Sample size/S0 field must not be empty.

gram line being executed and the remaining line time.
Shortly after the start of the determination, the prompt to add 10 mL of
calibration solution Pb-1 to the measuring vessel appears on the
screen:
MEAS.TASK MESSAGE

CSOLN Pb-1 10.000 mL > M

<Enter>: continue

5 Addition of 1st calibration solution

Remove stopper 25 and use a pipette to add 10 mL of calibration
solution Pb-1 with a mass concentration of 2.5 g/L to the measuring
vessel through the pipetting opening. Press the <ENTER> key.
The screen shows the prompt to add 1 mL acetate buffer to the measur-
ing vessel:

MEAS.TASK MESSAGE

DOS Acetate 1.000 mL > M
<Enter>: continue

6 Addition of acetate buffer

Use a pipette to add 1 mL acetate buffer (1 mol/L, pH 4.6) to the
measuring vessel through the pipetting opening. Then close the pipet-
ting opening using stopper 25 and press the <ENTER> key.
7 Measurement of the 1st calibration solution

Measurement of the 1st calibration runs as follows (see also section
4.3.3):
Purging and stirring for 180 s.
Call-up of the segment DPASV for measured value recording. The
lead present in the solution is enriched at the hanging mercury
drop with stirring at a measurement voltage of 600 mV and then
determined anodically without stirring from 600 200 mV. The
selected measurement mode DP leads to a current peak whose
maximum lies at ca. 400 mV.
The DPASV segment is then repeated twice. The three single
measurements are allocated the VR numbers 00, 01 and 02.
After the 3rd measurement, the program is interrupted. The screen shows
the prompt to change the measuring vessel:
MEAS.TASK MESSAGE

Change measuring vessel

<Enter>: continue

8 Empty the measuring vessel

Empty the measuring vessel, rinse it thoroughly with dist. water and
replace it in the 747 VA Stand.
The measuring vessel contains mercury, which must be disposed of in

the proper manner (see section 7.2.3).
9 Measurement of the 2nd calibration solution

Repeat steps 5 8 with 10 mL of calibration solution Pb-2 with a
mass concentration of 5 g/L. You obtain three single measurements
with the VR numbers 10, 11 and 12.
10 Measurement of the 3rd calibration solution


11 Measurement of the 4th calibration solution

On completion of the last measurement, the results for the coefficients of
the calibration curve are calculated and entered in the dialog page
"SUBSTANCES/Calibration" together with the date and time of the cali-
bration.
The program is now at an end. The status display in the header of the
dialog page "MONITORING" switches back to * READY *, the instrument
is now ready for a new determination.

On completion of the program, the full report of the calibration is put out
on the printer.

Determ. : 12151548 User: Date: 1996-12-15
Modified : no Run : 2 Time: 15:48:08
Sample table: -
--------------------------------------------------------------------------------
10 mL
--------------------------------------------------------------------------------
Method : CALCRV
Remark1 :
Remark2 :
--------------------------------------------------------------------------------
1 Mass conc.: - Mass : -
MC.dev. : - Add.mass : -
Cal.dev. : - V0.sample: -

00 -408 3.351 3.358 0.0853
01 -409 3.447
02 -409 3.277
10 -408 7.286 7.190 0.2184 3.832
11 -409 7.344
12 -410 6.940
20 -408 14.42 14.26 0.1894 7.072
21 -409 14.05
22 -409 14.31
30 -408 25.69 25.83 0.3866 11.57
31 -409 25.53
32 -409 26.26

2
Pb cal.crv. 5.489e-10 0.001438 5.933e-10


3
Pb = 0.000 g/L 0.000 - var. not found

The full report Full report essentially contains the same parts as that
of the TESTPb.mth method with standard addition (see section 4.2.6).
However, the following sections are different:
1 Data for substance Only the substance name Pb is given, the other
evaluation parameters remain blank as they are not calcula-
ted when the calibration curve is recorded.
2 Data for calibration Offset Y.offset and slope Slope of the
curve calibration curve.
3 Final results The final result is not calculated as the variable
MC:Pb is not calculated when the calibration
curve is recorded.
Finally, the calibration curve is printed out:

Method : CALCRV User : Date : 1996-12-15
Mode : DPMODE Determ. : 12151548 Time : 15:48:08
Run : 2 Sample :
Calibration curve
1 Curve type : lin Slope : 1.438e-03 Mean.dev. : 5.933e-10
Y.reg : 5.489e-10
Substance : Pb
The printout of the calibration curve essentially contains the same parts
as the TESTPb.mth method with standard addition (see section 4.2.6).
1 Data for calibration curve Curve type, addition mode, slope of the calibration
curve, offset Y.offset of the calibration curve,
mean deviation of the measured values about the
calibration curve.
2 Calibration curve Measured points (mean values of the measured
peak currents for the calibration solutions),
calculated calibration curve, current axis, axis for
effective mass concentration in the measuring
vessel.

13 Storing the calibration data in the method

The recalculated coefficients of the calibration curve are first stored only
in the method loaded in the working storage. To store these data perma-
nently, this method must be copied to the method memory. Proceed as
follows:
Press the yellow <METHODS> key. The dialog page "METHODS"
appears showing the methods stored in the instrument.
If the CALCRV.mth method is secured (an * is shown on the left
of the file name), it must first be unsecured. For this, select the
CALCRV.mth method with the cursor keys. Press the softkey
< >> > and then the softkey <Secure/Unsecure>. The asterisk
next to the file name disappears, the method is unsecured. Then
press the softkey < >> > again.
Press the softkey <Copy from>. The softkey bar changes and
presents the sources for copying a method.
Press the softkey <Working storage>. The CALCRV.mth method
is copied from the working storage to the method memory; the
method of the same name containing the old calibration data will
be overwritten.

To perform the lead determination using the calibration curve previously recorded,
the following steps are necessary:

whose header shows the loaded method CALCRV appears.
2 Switch the program run mode to determination

If the parameter Run mode is set to calibration, proceed as follows:
Press the softkey <determ.> and confirm this entry with the <ENTER>
key.

size/S0.
Enter 10 mL and confirm this entry with the <ENTER> key.


Shortly after the start of the determination, the screen shows the prompt
to add 10 mL sample to the measuring vessel:
MEAS.TASK MESSAGE

SMPL 10.000 mL > M

<Enter>: continue

5 Addition of sample
Remove stopper 25 on 747 VA Stand and use a pipette to add 10 mL of
drinking water to the measuring vessel through the pipetting opening.
Press the <ENTER> key.
ing vessel:
MEAS.TASK MESSAGE

<Enter>: continue



Measurement of the sample solution runs as follows (see also section
4.3.3):
Call-up of the segment DPASV for measured value recording. The
lead present in the solution is enriched at the hanging mercury
drop with stirring at a measurement voltage of 600 mV and then
determined anodically without stirring from 600 200 mV. The
selected measurement mode DP leads to a current peak whose
maximum lies at ca. 400 mV.
The DPASV segment is then repeated twice. The three single
measurements are allocated the VR numbers 00, 01 and 02.
On completion of the last measurement, the lead mass concentration is
calculated using the coefficients of the calibration curve stored in the
method. The program is now at an end. The status display in the header
of the dialog page "MONITORING" switches back to * READY *, the in-
strument is ready for a new determination.


"DOCUMENTATION" page are put out on the printer:

Determ. : 12160827 User: Date: 1996-12-16
Sample table: -
--------------------------------------------------------------------------------
Drink water 10 mL
--------------------------------------------------------------------------------
Method : CALCRV
Remark1 :
Remark2 :
--------------------------------------------------------------------------------
1 Mass conc.: 12.48 ug/L Mass : 124.8 ng
MC.dev. : 0.344 ug/L (2.76%) Add.mass : - dev. estimated
Cal.dev. : 0.195 ug/L (1.57%) V0.sample: 10 mL

00 -409 16.57 16.86 0.2620
01 -409 16.96
02 -410 17.06

2
Pb cal.crv. 5.489e-10 0.001438 5.933e-10


3
Pb = 12.48 ug/L 0.344 2.76 see Evaluations
The full report Full report essentially contains the same parts as that
of the TESTPb.mth method with standard addition (see section 4.2.6).
1 Data for substance Substance name, mass concentration Mass
evaluation conc. found and its absolute and relative total
deviation MC.dev., the deviation due to the
calibration Cal.dev., substance mass Mass
found in the measuring vessel and sample volume
V0.sample in the measuring vessel.
2 Data for calibration Offset Y.offset and slope Slope of the
curve calibration curve used for the calculation.
3 Final results Final result with formula calculation.

Finally, the calibration curve is printed out; it essentially contains the

same parts as the TESTPb.mth method with standard addition (see sec-
tion 4.2.6). However, there is a difference in the curve representation. The
plot shows not only the calibration curve but also the current value
measured for the sample and the associated calculated value for eff
(effective lead mass concentration in the measuring vessel):

Method : CALCRV User : Date : 1996-12-16
Run : 3 Sample : Drink water
Calibration curve
Curve type : lin Slope : 1.438e-03 Mean.dev. : 5.933e-10
Y.reg : 5.489e-10
Substance : Pb

4.4 Lead determination with internal standard
The usual calibration procedure for the majority of the determinations

possible with the 746 VA Trace Analyzer is standard addition
(example, see section 4.2). However, the mass concentration of a
substance can also be calculated using the method of internal stan-
dards. With this calibration procedure, a known quantity of a reference
substance (internal standard) is added to the analysis solution. The
mass concentration of the analyte is calculated from the ratio of the
evaluation quantities of this substance and those of the internal stan-
dard using a proportionality factor determined earlier by measuring
different reference solutions.
Result determination with the aid of the internal standard saves time
compared with standard additions (particularly if several substances
are determined using the same internal standard), but is admissible
only if
the requirement of a linear relation between analyte and
reference substance holds,
the matrix of all samples and calibration solutions is identi-
cal or has no influence on the measurement,
all measurement parameters (capillary, temperature, etc.)
remain unchanged in the measurements, and
the accuracy of the results obtained is regularly checked
using the standard addition method.
The present example shows you how this procedure is programmed
and performed using cadmium as an internal standard in the determi-
nation of lead in drinking water.
You must first prepare the 746 VA Trace Analyzer and 747 VA Stand as
described in section 4.1 before you can perform this example.
4.4.1 Reagents and accessories

To perform the method INTSTD.mth, the following solutions are needed:
2 Lead ion standard solution, (Pb2+) = 1 g/L

Lead ion standard solution (Metrohm No. 6.2301.100) for preparation of the
following calibration solutions:
Calibration solution Pb-1 (Pb2+) = 2.5 g/L
3 Cadmium standard solution, (Cd2+) = 1 mg/L
4 Conc. hydrochloric acid Suprapur, w(HCl) = 0.3 (30%)

5 Drinking water
Water that has been in the supply system for a lengthy period of time
absorbs metals from the pipe and fittings materials and thus falsifies the
analysis results. Hence, before taking the water sample allow the water
to run out of the tap in a powerful stream for several minutes.
The drinking water sample should be acidified immediately after the
sample has been taken by adding 10 L conc. hydrochloric acid per
10 mL drinking water.
Owing to the large temperature dependence of the measured values ( 2%/C), we

recommend you to use the 6.1418.220 Thermostatable measuring vessel with
the internal standard method.
4.4.2 Loading the method INTSTD.mth

To load the method INTSTD.mth from the method memory into the working stor-

3 Selection of the method INTSTD.mth

Use the cursor keys to select the method INTSTD.mth, which then
4 Copying the method INTSTD.mth to the working storage

Press the softkey <Working storage>. The method INTSTD.mth is
4.4.3 Method specifications of the method INTSTD.mth
with the loaded method INTSTD.mth will be explained in detail. If you are interested


Method: INTSTD .mth OPERATION SEQUENCE

Title : Pb determination with internal standard (Cd)

2 C (CAL
5 RADD>M Soln.name CdRefSol V.add 0.100 mL
6 PURGE
8 PURGE
9 (REP
12 REP)2
13 C RINSE Cycles 1 V.rinse mL
14 C CAL)3
15 END


Line 1 Addition of sample: 10 mL
Line 2 14 Loop for recording the calibration curve (4 calibration solutions)
Line 3 Addition of calibration solution to measuring vessel: 10 mL
Line 4 Addition of acetate buffer to measuring vessel: 1 mL
Line 5 Addition of the internal standard to the measuring vessel:
0.1 mL Cd standard solution 1 mg/L
Line 6 7 Purging and stirring of the analysis solution for 3 min
Line 9 12 Loop for double replication of the segment
Line 11 Call-up of the segment DPASV for lead determination
Line 13 Resetting of the volume bookkeeping to 0 for solution change
(new calibration solution)
The sequence of the main program depends on the selected mode for
the program run Run mode on the "MONITORING" page:
In the program run mode calibration, all instructions marked with
D are ignored. Internal standard is added to 4 calibration solutions in
turn and lead and cadmium measured each time. The proportional-
ity factor between lead and cadmium is determined from the re-
corded calibration curve.
In the program run mode determination, on the other hand, all in-
structions marked with C are ignored. Internal standard is added to
the sample and then lead and cadmium measured. The lead mass
concentration is calculated using the proportionality factor deter-
mined beforehand.


appears with the program for measured value acquisition. The segment
DPASV is virtually identical to the segment of the same name of the
CALCRV.mth method (explanation, see section 4.3.3), except the enrich-
ment and start voltage is 800 mV instead of 600 mV.

CES" appears with the parameters for evaluation of the substance lead.
Except for the characteristic voltage U.verify (400 mV), these are
identical to those of the TESTPb.mth method and are not explained fur-
ther here (see section 4.2.3).
Method: INTSTD SUBSTANCES

Pb - DPASV

Technique int std. Prop.fact. 0.5699
Mode analyte Mean dev. 0.03553
Ref.subst. CdRef
Temperature 20.0 C
# CSoln.name Mass conc.

Range min g/L
Range max g/L 0 Pb-1 2.5 ug/L
1 Pb-2 5 ug/L
M.conc./cm g/L 2 Pb-3 10 ug/L
M.conc.begin zero 3 Pb-4 20 ug/L
4 g/L
V0.CSoln. 10.000 mL 5 g/L
6 g/L
7 g/L
8 g/L
9 g/L


Technique Calibration technique: internal standard
Mode Mode for parameter display: analyte
Ref.subst. Name of reference substance: CdRef
Temperature Temperature of the analysis solution: 20C
V0.CSoln. Volume added of every calibration solution: 10 mL
Prop.fact. Proportionality factor between analyte and reference
substance
Mean dev. Mean deviation of the calibration curve

Press the softkey < >> > to switch to the main page "Substance pa-
rameters". Then press the softkey <Select subst.>. The two substances
Pb and CdRef are shown on the softkeys.
Press the softkey <CdRef> to select the internal standard cadmium. The
dialog page "SUBSTANCES" appears with the parameters for evaluation
of the reference substance cadmium. It is identical to that of the
TESTPb.mth method except for the characteristic voltage U.verify
(580 mV) and will thus not be discussed further here (see section 4.2.3).
Press the softkey < >> >. The subpage with the parameters for the
reference substance cadmium appears:
Method: INTSTD SUBSTANCES

CdRef - DPASV
Calibration 1996-12-16 14:23

Technique int std.
Mode referen.
Temperature 20.0 C
Soln.name CdRefSol
Mass.conc. 1 mg/L


Technique Calibration technique: internal standard
Mode Mode for parameter display: reference (internal standard)
Temperature Temperature of the analysis solution: 20C
Soln.name Name of the solution with the internal standard: CdRefSol
Mass conc. Mass concentration of the solution with the internal
standard: 1 mg/L

LATION" appears for calculation of the final results. The mass concen-
tration of lead (MC:Pb) determined using the internal standard method is
put out as the result in g/L with 4 significant figures.

The two lines entered in the example have the following meaning:

Report Full Printout of the full result report on the printer

Curve Cal Sbst:Pb Printout of the calibration curve on the printer

procedure used in the calibration method with the internal standard.
TATION".
4.4.4 Recording the calibration curve

To be able to perform a determination with the internal standard, the proportionality
factor must first be determined using a calibration curve. The following steps are
necessary for this:

whose header shows the loaded method INTSTD appears.
2 Switch the program run mode to calibration

If the parameter Run mode is set to determination, proceed as follows:
Press the softkey <calibr.> and confirm this entry with the <ENTER>
key.

size/S0.
Enter either * or 10 mL (as preparation for performance of the determi-
nation in section 4.4.5) and confirm this entry with the <ENTER> key.
Although the sample volume for recording the calibration curve is not needed (the
volume of the calibration solutions is defined in the parameter V0.CSoln), the
Sample size/S0 field must not be empty.


Shortly after the start of the determination, the prompt to add 10 mL of

calibration solution Pb-1 to the measuring vessel appears on the
screen:
MEAS.TASK MESSAGE

CSOLN Pb-1 10.000 mL > M

<Enter>: continue

5 Addition of 1st calibration solution

Remove stopper 25 and use a pipette to add 10 mL of calibration
solution Pb-1 with a mass concentration of 2.5 g/L to the measuring
vessel through the pipetting opening. Press the <ENTER> key.
ing vessel:
MEAS.TASK MESSAGE

<Enter>: continue


The screen shows the prompt to add 100 L of the solution CdRefSol
with the internal standard to the measuring vessel:
MEAS.TASK MESSAGE

ADD CdRefSol 100.000 uL > M
<Enter>: continue

7 Addition of the internal standard

Use a pipette to add 100 L of the cadmium standard solution with a
mass concentration of 1 mg/L to the measuring vessel through the pi-
petting opening. Then close the pipetting opening using stopper 25 and
press the <ENTER> key.
8 Measurement of the 1st calibration solution

Measurement of the 1st calibration runs as follows (see also section
4.4.3):
Call-up of the segment DPASV for measured value recording.
Lead and cadmium are enriched with stirring at the hanging mer-
cury drop at a measurement voltage of 800 mV and then deter-
mined anodically without stirring from 800 ... 200 mV. The se-
lected measurement mode DP leads to a current peak for lead
whose maximum lies at ca. 400 mV and a current peak for cad-
mium with a maximum at ca. 580 mV.
The DPASV segment is then repeated twice. Both the three single
measurements for the substance lead and also the three single

measurements for cadmium are allocated the VR numbers 00,

01 and 02.
After the 3rd measurement, the program is interrupted. The screen shows
the prompt to change the measuring vessel:
MEAS.TASK MESSAGE

Change measuring vessel

<Enter>: continue

9 Empty the measuring vessel

Empty the measuring vessel, rinse it thoroughly with dist. water and
replace it in the 747 VA Stand.
The measuring vessel contains mercury, which must be disposed of in

the proper manner (see section 7.2.3).
10 Measurement of the 2nd calibration solution

11 Measurement of the 3rd calibration solution

12 Measurement of the 4th calibration solution

On completion of the last measurement, the proportionality factor is
calculated from the recorded calibration curve and entered in the dialog
page "SUBSTANCES/Calibration" together with the date and time of the
calibration.
The program is now at an end. The status display in the header of the
dialog page "MONITORING" switches back to * READY *, the instrument
is now ready for a new determination.

On completion of the program, the full report of the calibration is put out
on the printer:


Determ. : 12161422 User: Date: 1996-12-16
Sample table: -
--------------------------------------------------------------------------------
10 mL
--------------------------------------------------------------------------------
Method : INTSTD
Title : Pb determination with internal standard (Cd)
Remark1 :
Remark2 :
--------------------------------------------------------------------------------

00 -407 3.664 3.721 0.0523
01 -408 3.767
02 -408 3.732
10 -408 7.289 7.134 0.1342 3.413
11 -407 7.056
12 -407 7.057
20 -408 13.30 14.14 1.095 7.010
21 -408 15.38
22 -408 13.75
30 -408 28.18 27.12 0.9354 12.97
31 -408 26.77
32 -408 26.41
2 Substance : CdRef Comments

Mass conc.: - Mass : -

00 -583 24.47 24.73 0.2262
01 -583 24.89
02 -583 24.82
10 -583 25.55 25.04 0.4501 0.3084
11 -583 24.73
12 -583 24.82
20 -582 22.60 23.77 1.480 -1.268
21 -582 25.43
22 -583 23.27
30 -583 25.53 24.80 0.6384 1.029
31 -583 24.51
32 -583 24.35

3
Pb int.std. 0.5699 0.03553
CdRef int.std.


4
Pb = 0.0000 g/L 0.000 - var. not found

The full report Full report contains not only the usual header (see
section 4.2.6), but also the following important sections:
1 Data for substance Only the substance name Pb is given, the other
evaluation of Pb parameters remain blank as they are not calcula-
ted when the calibration curve is recorded.
2 Data for substance Only the substance name CdRef is given, the
evaluation of Cd other parameters remain blank as they are not
calculated when the calibration curve is recorded.
3 Data for calibration Only the proportionality factor is given.
4 Final results The final result is not calculated as the variable
MC:Pb is not calculated when the calibration
curve is recorded.
Finally, the calibration curve is printed out:

Method : INTSTD User : Date : 1996-12-16
Run : 4 Sample :
Internal standard calibration curve

1 Curve type : 0/lin Slope : 5.699e-01 Mean.dev. : 3.553e-02
Substance : Pb
The calibration curve contains the usual header (see section 4.2.6) and
the following important sections:
1 Data for calibration curve Curve type, proportionality factor Slope, mean
deviation of the measured values about the
calibration curve.
2 Calibration curve Measured points (mean values of the measured
peak currents for the calibration solutions),
calculated calibration curve, current axis, axis for
effective mass concentrations of analyte and
reference substance in the measuring vessel.

14 Storing the calibration data in the method

The proportionality factor Prop.fact. calculated from the calibration
curve as well as the mean deviation Mean.dev. are first stored only in
the method loaded in the working storage. To store these data perma-
nently, this method must be copied to the method memory. Proceed as
follows:
Press the yellow <METHODS> key. The dialog page "METHODS"
If the INTSTD.mth method is secured (an * is shown on the left
of the file name), it must first be unsecured. For this, select the
INTSTD.mth method with the cursor keys. Press the softkey
< >> > and then the softkey <Secure/Unsecure>. The asterisk
next to the file name disappears, the method is unsecured. Then
press the softkey < >> > again.
Press the softkey <Copy from>. The softkey bar changes and
presents the sources for copying a method.
Press the softkey <Working storage>. The INTSTD.mth method
is copied from the working storage to the method memory; the
method of the same name containing the old calibration data will
be overwritten.

To perform the lead determination using an internal standard with the aid of the re-
corded calibration curve, the following steps are necessary:

whose header shows the loaded method INTSTD appears.

key.

size/S0.



to add 10 mL sample to the measuring vessel.
ing vessel.

The screen shows the prompt to add 100 L of the solution CdRefSol
with the internal standard to the measuring vessel.
7 Addition of the internal standard

Use a pipette to add 100 L of the cadmium standard solution with a
mass concentration of 1 mg/L to the measuring vessel through the pi-
petting opening. Then close the pipetting opening using stopper 25 and
press the <ENTER> key.

4.4.3):
Call-up of the segment DPASV for measured value recording.
Lead and cadmium are enriched with stirring at the hanging mer-
cury drop at a measurement voltage of 800 mV and then deter-
mined anodically without stirring from 800 ... 200 mV. The se-
lected measurement mode DP leads to a current peak for lead
whose maximum lies at ca. 400 mV and a current peak for cad-
mium with a maximum at ca. 580 mV.
The DPASV segment is then repeated twice. Both the three single
measurements for the substance lead and also the three single
measurements for cadmium are allocated the VR numbers 00,
01 and 02.
On completion of the last measurement, the lead mass concentration is
calculated using the proportionality factor stored in the method. The pro-
gram is now at an end. The status display in the header of the dialog
page "MONITORING" switches back to * READY *, the instrument is
ready for a new determination.


"DOCUMENTATION" page are put out on the printer:

Determ. : 12161627 User: Date: 1996-12-16
Sample table: -
--------------------------------------------------------------------------------
Drink water 10 mL
--------------------------------------------------------------------------------
Method : INTSTD
Remark1 :
Remark2 :
--------------------------------------------------------------------------------
1 Mass conc.: 13.02 ug/L Mass : 130.2 ng
MC.dev. : 0.603 ug/L (4.63%) Add.mass : - dev. estimated
Cal.dev. : 0.326 ug/L (2.5%) V0.sample: 10 mL

00 -409 17.66 17.74 0.1623
01 -409 17.92
02 -409 17.63
Substance : CdRef Comments


00 -583 23.78 23.90 0.1073
01 -583 24.00
02 -584 23.92

3
Pb int.std. 0.5699 0.03553
CdRef int.std.


4
Pb = 13.02 ug/L 0.603 4.63 see Evaluations
The full report Full report contains not only the usual header (see
section 4.2.6), but also the following important sections:
1 Data for substance Results of peak evaluations and result for Pb mass
evaluation of Pb concentration.
2 Data for substance Only the substance name CdRef is given, the
evaluation of Cd other parameters remain blank as they are not
calculated when the calibration curve is recorded.
3 Data for calibration The proportionality factor determined from the
calibration curve is given.
4 Final results Final result with formula calculation.

Finally, the calibration curve is printed out; it essentially contains the

same parts as the recorded calibration curve (see section 4.4.4). How-
ever, there is a difference in the curve representation. The plot shows not
only the calibration curve, but also the current value measured for the
sample and the calculated ratio of the effective mass concentrations of
lead and cadmium.

Method : INTSTD User : Date : 1996-12-16
Run : 5 Sample : Drink water
Calibration curve
Curve type : 0/lin Slope : 5.699e-01 Mean.dev. : 3.553e-02
Substance : Pb

4.5 Basic method for DP polarography
This illustrative method can be used to investigate a sample for sub-

stances which can be determined with differential pulse polarography
at the dropping mercury electrode (DME). The basic structure for DP
polarography contained in the method can then be modified and
expanded in any way whatever for the specific determination of one or
more substances.
So that you can perform this example, first the 746 VA Trace Analyzer
and 747 VA Stand must have been prepared as described in section
4.1.
4.5.1 Reagents
The following solutions are needed to perform the method POL.mth:
4.5.2 Loading the method POL.mth

To load the method POL.mth from the method memory into the working storage,

3 Selection of the method POL.mth

Use the cursor keys to select the method POL.mth, which then be-
comes black-backed.
4 Copying the method POL.mth to the working storage

Press the softkey <Working storage>. The method POL.mth is copied to
the working storage.

4.5.3 Method specifications of the method POL.mth
with the loaded method POL.mth will be explained in detail. If you are interested

SEQUENCE" appears with the main program:
Method: POL .mth OPERATION SEQUENCE

Title : Polarographic method / DP / 150 mV -> -1150 mV

1 SMPL>M V.fraction mL V.total L
3 PURGE
5 ! (ADD
6 PURGE
7 TSTIR 30.0 Rot.speed 2000 /min
8 PURGE 5.0
9 (REP
10 SEGMENT Segm.name polaro
11 REP)0
12 ! ADD>M Soln.name V.add 0.100 mL
13 ! ADD)0
14 END


Line 1 Addition of 10 mL sample
Line 2 Addition of 1 mL acetate buffer 1mol/L pH 4.6
Line 3....4 Purging and stirring of the analysis solution for 5 min
Line 5...13 Prepared loop for standard addition (inactive)
Line 6....7 Purging and stirring of the analysis solution for 30 s
Line 8 Switching off the purging. Stabilization time 5 s
Line 9...11 Prepared loop for replication of the segment
Line 10 Call-up of the segment polaro
Line 12 Prepared instruction for addition of the standard
addition solution (inactive)


Method: POL SEGMENT

polaro

1 DME
2 DPMODE U.ampl -50 mV t.meas 20.0 ms
3 SWEEP 87.6 U.start 150 mV U.step 6 mV
4 MEAS U.standby mV
5 END

The sequence of the segment polaro is explained in brief in what

follows:
Line 1 Switching on the DME (dropping mercury electrode)
Line 4 Switch off voltage, current measurement and DME

CES" appears with the parameters for evaluation of substances. Only
one substance Subst1 with standard parameters without an entry for the
characteristic voltage U.verify is defined).
the parameters for calibration. There is no calibration for the substance
Subst1 (Technique = none).

LATION" appears for calculation of the final results. No formulae are en-
tered.

The line entered here has the following meaning:
Curve Smth Sgmt:polaro VR:00 Printout of the smoothed segment
curve 00 on the printer

If you do not want an automatic printout in the following determination,

you can either delete this line with the softkey <Delete line> or clear
the output destination Printer for the line with the <CLEAR> key.
procedure used in the determination.
TATION".

To perform the determination, the following steps are necessary:

whose header shows the loaded method POL appears.

key.

size/S0.

ing vessel.



4.5.3):
Wait time 5 s to stabilize the analysis solution.
Call-up of the segment polaro for measured value recording.
The single measurement is allocated the VR number 00.
On completion of the measurement, the program is at an end. The status
display in the header of the dialog page "MONITORING" switches back
to * READY *, the instrument is ready for a new determination.
8 Printout of the segment curve

On completion of the program, the smoothed segment curve entered on
the "DOCUMENTATION" page is put out on the printer. The following ex-
ample shows a determination with drinking water as sample:

Method : POL User : Date: 1996-12-10
Mode : DPMODE Determ. : 12101420 Time: 14:20:12
Run : 6
Curve : smoothed Segment : polaro V R : 0 0

4.6 Basic method for DPASV
This illustrative method can be used to investigate a sample for sub-

stances which can be determined with DPASV (Differential Pulse
Anodic Stripping Voltammetry) at the hanging mercury drop electrode
(HMDE). The basic structure for DPASV contained in the method can
then be modified and expanded in any way whatever for the specific
determination of one or more substances.
So that you can perform this example, first the 746 VA Trace Analyzer
and 747 VA Stand must have been prepared as described in section
4.1.
4.6.1 Reagents
The following solutions are needed to perform the method ASV.mth:
4.6.2 Loading the method ASV.mth

To load the method ASV.mth from the method memory into the working storage,

3 Selection of the method ASV.mth

Use the cursor keys to select the method ASV.mth, which then be-
comes black-backed.
4 Copying the method ASV.mth to the working storage

Press the softkey <Working storage>. The method ASV.mth is copied to
the working storage.

4.6.3 Method specifications of the method ASV.mth
with the loaded method ASV.mth will be explained in detail. If you are interested

SEQUENCE" appears with the main program:
Method: ASV .mth OPERATION SEQUENCE

Title : Anodic stripping voltammetry / -1150 mV -> 150 mV

3 PURGE
5 ! (ADD
6 PURGE
8 PURGE
9 (REP
10 SEGMENT Segm.name ASV
11 REP)0
12 ! ADD>M Soln.name V.add 0.100 mL
13 ! ADD)0
14 END


Line 1 Addition of 10 mL sample
Line 2 Addition of 1 mL acetate buffer 1mol/L pH 4.6
Line 3....4 Purging and stirring of the analysis solution for 5 min
Line 5...13 Prepared loop for standard addition (inactive)
Line 6....7 Purging and stirring of the analysis solution for 30 s
Line 9...11 Prepared loop for replication of the segment
Line 10 Call-up of the segment ASV
Line 12 Prepared instruction for addition of the standard
addition solution (inactive)


Method: ASV SEGMENT

ASV

5 STIR 5.0
U.end 150 mV Sweep rate 60 mV/s
7 MEAS U.standby mV
8 END

The sequence of the segment ASV is explained in brief in what follows:

Line 2 Switching on the HMDE (hanging mercury drop electrode)
Line 4 Application of a measurement voltage of 1150 mV for
90 s for the enrichment at the hanging mercury drop
Line 5 Switching off the stirrer and stabilization of the analysis
solution for 5 s
Line 6 Voltage sweep from 1150 mV ... 150 mV with a voltage
step of 6 mV
Line 7 Switch off voltage and current measurement
Line 8 End of segment (return to main program)

CES" appears with the parameters for evaluation of substances. Only
one substance Subst1 with standard parameters without an entry for the
characteristic voltage U.verify is defined.
the parameters for calibration. There is no calibration for the substance
Subst1 (Technique = none).

Press the yellow <CALCULATION> key. The dialog page "CALCULA-
TION" appears for calculation of the final results. No formulae are en-
tered.


The line entered here has the following meaning:
Curve Smth Sgmt:ASV VR:00 Printout of the smoothed segment curve
00 on the printer
If you do not want an automatic printout in the following determination,

you can either delete this line with the softkey <Delete line> or clear
the output destination Printer for the line with the <CLEAR> key.
procedure used in the determination.
TATION".

To perform the determination, the following steps are necessary:

whose header shows the loaded method ASV appears.

key.

size/S0.


ing vessel.


4.5.3):
Call-up of the segment ASV for measured value recording. The
substances present in the sample solution are enriched at the
hanging mercury drop with stirring at a measurement voltage of
1150 mV and then determined anodically without stirring from
1150 ... 150 mV. The single measurement is allocated the VR
number 00.
On completion of the measurement, the program is at an end. The status
display in the header of the dialog page "MONITORING" switches back
to * READY *, the instrument is ready for a new determination.
8 Printout of the segment curve

On completion of the program, the smoothed segment curve entered on
the "DOCUMENTATION" page is put out on the printer. The following ex-
ample shows a determination with drinking water as sample:


Method : ASV User : Date: 1996-12-10
Mode : DPMODE Determ. : 12101407 Time: 14:07:43
Run : 7
Curve : smoothed Segment : ASV V R : 0 0

5.1 The keys and their functions
5 Operation
This section provides a detailed description of the operation of the

746 VA Trace Analyzer, 747 VA Stand and 695 Autosampler using the
keypad and screen dialog. Particular attention is given to descriptions
of
all key functions
the layout of the screen dialog
all parameters and softkeys of the 17 dialog
pages and their subpages
all program instructions.

5 Operation
5.1.1 Key categories
The keypad 5 of the 746 VA Trace Analyzer is a splash-waterproof piezoelectric

keypad whose keys react to even slight pressure. The total of 76 keys can be
distinguished by their shape and color as follows:
Shape Color Key category
Yellow Dialog keys

U
MONI-
TORING
START ENTER
Red or orange Main function keys
(CONT)
Light gray Auxiliary function keys, numeric keys,

# D
ESC 3
letter and character keys
DELETE
Dark gray Cursor keys, auxiliary function keys
F5
Blue Softkeys
FORM FEED PRINT STOP
ESC LINE FEED

PRINT
SCREEN F1 F2 F3 F4 F5 F6 F7 F8 START
(CONT)
METHOD
SET UP STORAGES OPERATION SPECIFICATIONS
Q W E R T Y U I O P + & * (
= 7 8 9
VA TRACE MONI- OP. SUB- BACK
STAND METHODS SAMPLES INSERT HOME BREAK
ANALYZER TORING SEQUENCE STANCES SPACE
A S D F G H J K L
;
:
" PG UP $ % ^
4 5 6
DETERMI- COMMON DELAY
DOSIMATS SOLUTIONS
NATIONS VARIABLES
RESULTS SEGMENTS CALCU-
LATION ' CLEAR DELETE PG DN
STOP
Z X C V B N M < > ? _ ! @ #
.
DATA
, / 1 2 3
CARD
CURVES DOCUMEN-
TATION - ABBREV
0 . -
HOLD
CAPS SHIFT SHIFT ENTER
(STEP)

5.1.2 Alphanumeric keys
The following enframed keys are available for the entry of alphanumeric characters:
ESC LINE FEED

PRINT
(CONT)
METHOD
Q W E R T Y U I O P + & * (
= 7 8 9
A S D F G H J K L
;
:
" PG UP $ % ^
4 5 6
DOSIMATS SOLUTIONS
NATIONS VARIABLES
STOP
Z X C V B N M < > ? _ ! @ #
.
DATA
, / 1 2 3
CARD
CURVES DOCUMEN-
TATION - ABBREV
0 . -
HOLD
(STEP)
In entries in the edit mode (see section 5.2.3), these keys have the following
meaning:
Key Meaning
A D Letter keys
without <SHIFT>: lowercase letter (e.g. a, d)
DOSIMATS with <SHIFT>: uppercase letter (e.g. A, D)
: + Character keys
; without <SHIFT>: character in lower field (e.g. ;, =)
CALCU-
LATION
= with <SHIFT>: character in upper field (e.g. :, +)
! Numeric keys
without <SHIFT>: number (e.g. 1)
1 with <SHIFT>: character in upper field (e.g. !)
Caps lock key

Switching to uppercase letters;
CAPS return to normal mode by pressing this key again.
Shift key
By pressing this key and a letter, character or numeric key
SHIFT at the same time, the character in the upper key field is put
out.
Space bar
This bar has three action points in the middle of the bar. In
contrast to the other keys listed here, it is repetitive.

5 Operation
5.1.3 Dialog keys
On the keypad of the 746 Trace Analyzer you will find a total of 17 yellow dialog
keys divided into the following four groups:
Set Up
Storages
Operation
Method Specifications
ESC LINE FEED

PRINT
(CONT)
METHOD
Q W E R T Y U I O P + & * (
= 7 8 9
A S D F G H J K L
;
:
" PG UP $ % ^
4 5 6
DOSIMATS SOLUTIONS
NATIONS VARIABLES
STOP
Z X C V B N M < > ? _ ! @ #
.
DATA
, / 1 2 3
CARD
CURVES DOCUMEN-
TATION - ABBREV
0 . -
HOLD
(STEP)
The dialog keys are used for fast and direct selection of the corresponding dialog
pages. In what follows, you will find a brief overview of the most important functions
of these keys. For a detailed description of the individual dialog pages and their
parameters, please refer to sections 5.3 5.6.
Set Up
Q Settings and manual W Settings of 746 VA Trace

operation of 747 VA Stand VA TRACE Analyzer
STAND and 695 Autosampler Date/time
ANALYZER
Inert gas pressure Screen
Purging Peripheral units
Stirrer RS232 settings
Electrodes Balance selection
Sample changer functions Printer selection
Rack definition Remote control
Control lines
A Settings and handling of S Entry of standard addition

Dosimats/Dosinos and auxiliary solutions
DOSIMATS Filling rate SOLUTIONS Solution name
Dispensing rate Position
Manual filling Substance name
Manual dispensing Mass concentration
Preparing dilutions

Storages
R Methods T Sample data

Display Sample size
METHODS SAMPLES
Copy to/from 3 sample identifications
Delete Automatic method call
Secure
Sort
Rename
F Determinations G Common variables

DETERMI- Display COMMON 18 resident variables
NATIONS Copy to/from VARIABLES 18 common variables in
Delete working memory
Secure Input
Sort Delete
Rename Take over from method
Transfer to method
V Data card
DATA Display
CARD Copy to/from
Delete
Secure
Sort
Rename
Format
Operation
U Operation monitoring J Results

MONI- Display of instrument status Final results
RESULTS
TORING Display of loaded methods Intermediate results
Selection of operation Spike elimination
mode Calibration results
Selection of Stand
Display of current
determination M Curves
Display/entry of sample Display of substance and
CURVES
data segment curves
Display of current program Scaling
line and measurement Changing parameters for
values substance recognition
Switching to automatic Baseline matching
curve representation

5 Operation
Method Specifications
O Operation sequence P Substance data

OP. Programming: SUB- Recognition
SEQUENCE instructions with modifiable STANCES Baseline
parameters
Display/Plot parameters
Insertion of segments
Evaluation
Standard addition
Calibration curve
Internal standard
L Segments : Calculations/Formulae
Programming of sweeps ; Designations for result
SEGMENTS CALCU-
Programming of macros quantities
LATION
Designations for result
units
Formulae
> Documentation
. Automatic output of reports,
DOCUMEN-
curves and measurement
TATION
values
Selection of output
destinations: printer,
RS232 interface 1 or 2
Entry of comment

5.1.4 Main function keys
The following 6 red and orange keys constitute the main function keys on the key-
pad of the 746 Trace Analyzer:
ESC LINE FEED

PRINT
(CONT)
METHOD
Q W E R T Y U I O P + & * (
= 7 8 9
A S D F G H J K L
;
:
" PG UP $ % ^
4 5 6
DOSIMATS SOLUTIONS
NATIONS VARIABLES
STOP
Z X C V B N M < > ? _ ! @ #
.
DATA
, / 1 2 3
CARD
CURVES DOCUMEN-
TATION - ABBREV
0 . -
HOLD
(STEP)
These keys have the following meaning:
Key Meaning
Start = Program start

The program loaded in the working memory is started. The display
START * BUSY * then appears on the "MONITORING" page instead of
(CONT) * READY *. Starting the program with this key is possible from all dialog
pages with the exception of "STAND" and "CURVES".
(Cont) = Continue interrupted program
The program interrupted with <HOLD> is continued. The display
* BUSY * then appears on the "MONITORING" page instead of
* BUSY (HOLD) *.
Immediate program stop

The active program or one interrupted with <HOLD> is immediately
BREAK stopped. The display * READY * then appears on the "MONITORING"
page instead of * BUSY * or * BUSY (HOLD) *.
Some functions with the 685 Dosimats, 700 Dosinos or 695 Autosam-
pler must be carried out completely before the program can be stopped
definitely. In this case, * BUSY (BREAK) * appears on the "MONITO-
RING" page.
Reset possibility
In the instrument standby mode (* READY *), you have the possibility to
initiate a normal reset through pressing this key (see section 7.3.3) and
responding to the subsequent inquiry Do you really want to reset ?
by pressing the <ENTER> key (abort by pressing <ESC>).
Delayed program stop

The active program is run to completion for the current sample, but the
DELAY
sample series is then stopped. Until the stop, the display * BUSY
STOP (DSTOP) * appears on the "MONITORING" page followed by
* READY *. This key is of practical importance only for ongoing sample
series (Auto.batch = on).

5 Operation
Key Meaning
Abbreviate current instruction

The line time of the current program instruction is set to 0 s and the next
ABBREV instruction is started.
Exception: With the SWEEP instructions the line time is also
set to 0, but the sweep is run to completion.
Hold = Program interruption

The current program instruction is stopped. The display * BUSY (HOLD)
HOLD
* then appears on the "MONITORING" page instead of * BUSY *. The
(STEP) program can be continued by pressing the <(CONT)> key at the
location where it was interrupted.
(Step) = Skip to next instruction
The program instruction interrupted with <HOLD> is run to completion
and a skip then made to the next instruction. This instruction is exe-
cuted (without processing of the line time) and the program is then
interrupted again.
Enter key
This key is used to close every field entry and confirm the current
ENTER parameter value.

5.1.5 Auxiliary function keys and softkeys
The keypad of the 746 Trace Analyzer includes 13 gray auxiliary keys and 8 blue
function keys positioned below the screen, the so-called softkeys, whose meaning
is shown on the individual dialog pages:
ESC LINE FEED

PRINT
(CONT)
METHOD
Q W E R T Y U I O P + & * (
= 7 8 9
A S D F G H J K L
;
:
" PG UP $ % ^
4 5 6
DOSIMATS SOLUTIONS
NATIONS VARIABLES
STOP
Z X C V B N M < > ? _ ! @ #
.
DATA
, / 1 2 3
CARD
CURVES DOCUMEN-
TATION - ABBREV
0 . -
HOLD
(STEP)
These keys have the following meaning:
Key Meaning
Escape
Pressing this key in the navigation mode (see section 5.2.2) switches
ESC directly to the "MONITORING" dialog page.
In the edit mode (see section 5.2.3), this key is used to exit the editing
of a parameter field. The field contents are reset to the value or expres-
sion originally in this field before the start of editing.
FORM FEED Line Feed

Pressing this key initiates a line feed on the printer. This key is not
LINE FEED repetitive, i.e. it must be pressed several times in succession to initiate
a multiple line feed.
Form Feed
Pressing this key together with the <SHIFT> key initiates a page
advance on the printer to the start of the next page.
PRINT STOP Print screen contents

Pressing this key initiates a printout of the current screen contents on
PRINT
the printer.
SCREEN
Immediate stop of printing
When this key is pressed together with the <SHIFT> key, no more data
are sent to the printer. With the built-in thermoprinter, any printing
operation in progress will be immediately stopped. With external print-
ers, the printing is stopped as soon as the internal buffer of the printer is
empty.
Softkeys
The meaning of these keys is shown in the softkey bar which appears
F1 on the individual dialog pages. In the navigation mode (see section
5.2.2), softkeys can be used to initiate functions specific to the page; in
the edit mode (see section 5.2.3) they offer keying aids if possible.

5 Operation
Key Meaning
Backspace key
The character immediately to the left of the current cursor position is
BACK
deleted, the cursor moves to this position.
SPACE
Clear field contents

The contents of the current parameter field are cleared. This key func-
CLEAR tions in both the navigation and edit modes (see section 5.2). In the
navigation mode, a direct switch is made to the edit mode after the field
contents have been cleared.
Switch between insert/overwrite mode

This key is used to switch between the insert and overwrite modes. The
INSERT current mode can be seen from the nature of the cursor with existing
characters:
Insert mode: Non-flashing cursor
Overwrite mode: Flashing cursor
When the instrument is switched on, the overwrite mode is always
active.
Delete character key

The character at the current cursor position is deleted.
DELETE
Return to start position

In the navigation mode this key is used to reset the field cursor to the
HOME start of the page or list. This key has no meaning in the edit mode.
PG UP Page Down
Pressing this key scrolls dialogue pages with lists (e.g. "SAMPLES",
PG DN "METHODS") downward block-by-block.
Page Up
Pressing this key together with the <SHIFT> key scrolls dialog pages
with lists (e.g. "SAMPLES", "METHODS") upward block-by-block.
Cursor keys
In the navigation mode (see section 5.2.2), the
cursor keys are used to move the field cursor
or for special functions specific to a page.
In the edit mode (see section 5.2.3), the
character cursor can be moved with the two
keys <> and <>.

5.2 Screen dialog
5.2 Screen dialog
5.2.1 Layout of the dialog pages
The 17 dialog pages of the 746 VA Trace Analyzer are all divided into the same
three areas header, page parameters and softkey bar. The schematic layout has
the following appearance:
Header
page title, method name, determi-
nation name, status messages, etc.
Page parameters
not backed: display only
gray-backed: modifiable
black-backed: modifiable, position
of the field cursor
Display of the softkey functions
black: active
gray: inactive
Headers
The header line area of the dialog pages comprises 2 lines and is separated from
the area of the page parameters by a double line. The most important elements of
the headers are:
Page title Name of the dialog page in uppercase letters,
including (if applicable) name of the subpage
Method Name of method loaded in the working mem-
ory
Determ. Name of determination loaded in the working
memory
Files Display of number of stored files
Available Display of free memory space
Line Display of current line number
Status messages * READY * instrument standby
* BUSY * program running
* BUSY (BREAK) * program going to be stopped
* BUSY (HOLD) * program interrupted
* BUSY (DSTOP) * delayed program stop
Other displays and parameters in the header lines are explained in the description
of the individual dialog pages in sections 5.3 5.6.
Page parameters
In the area of the page parameters you will always find three different forms of dis-
plays:
Not backed all parameter names, the column title and the
nonmodifiable parameters
Gray-backed all modifiable parameters
Black-backed the current position of the field cursor

5 Operation
Softkey bar
The functions for the 8 softkeys <F1>...<F8> located below the screen can be
found at the very bottom of the dialog page. The following four categories of soft-
keys can be distinguished:
XXXXXX Initiation of a function (in the navigation mode)
XXXX
>> Selection of a subpage (in the navigation mode)
Help Display of a help message for the selected

parameter (in the edit mode)
XXXXXX Keying aid for the selected parameter (in the edit
--------
mode)
All softkeys shown in black are active, the gray-backed softkeys have no function.
5.2.2 Navigation mode
The navigation mode is the basic mode of the 746 VA Trace Analyzer and is auto-
matically activated when the instrument is switched on. The most important func-
tions which can be initiated using the keypad are listed in the illustration on page
5-14. The following additional functions are also possible:
Initiation of functions via softkeys (e.g. <Copy to>, <Insert line>, etc.)
Initiation of the main functions <START>, <BREAK>, <DELAY STOP>,
<ABBREV>, <HOLD> (see section 5.1.4)
Initiation of the auxiliary functions <FORM FEED>, <LINE FEED>,
<PRINT SCREEN>, <PRINT STOP>(see section 5.1.5)
5.2.3 Edit mode
The edit mode is used to change the gray-backed parameter fields on the dialog
pages. It is activated with the following keys:
Space bar Edit field, on closure with <ENTER> return to

navigation mode
Clear field contents, edit field, on closure with

CLEAR <ENTER> return to navigation mode
Modify Edit field, on closure with <ENTER> jump to next

column
field in the same column
Modify Edit field, on closure with <ENTER> jump to next
line
field on the same line
D ! The character or number keyed in is written into the
1 field directly (possible only with keys which are not
currently in use as dialog keys). Then edit field, on
closure with <ENTER> return to navigation mode.

5.2 Screen dialog
The most important functions which can be initiated using the keypad are listed on
page 5-14. The following additional functions are also possible:
Initiation of the main functions <BREAK>, <DELAY STOP>,
<ABBREV>, <HOLD> (see section 5.1.4)
Initiation of the auxiliary functions <FORM FEED>, <LINE FEED>,
<PRINT SCREEN>, <PRINT STOP> (see section 5.1.5)
Entry in numeric fields

For the entry of numbers in numeric fields, the following rules apply:
The period "." is used as a decimal point, a preceding 0 need not be entered
(Examples: -678.98 -678.98; 0.3600 0.3600; .3 0.3).
Numbers in exponential format are entered with the character e or E
(Examples: 1e20 1e+20, 5.89E-08 5.89e-08, 345.7e12 3.457e+14).
With numeric fields without a value range, numbers from -3.7e+33-1.7e-33
and 1.7e-333.7e+33 can be entered.
With numeric fields with a value range, the maximum and minimum values
are entered in case the upper or lower limit of this range is violated.
Entry in selection fields

Only predetermined expressions can be entered in selection fields. It is an advan-
tage to use the keying aids offered by the softkeys here.
Entry in character fields

All numbers, letters and characters offered by the keypad can be entered in char-
acter fields. In addition, the entry of all ASCII characters with decimal code
032255 from the IBM character set 437 is also possible (see below table). Entry is
effected with the aid of the <^> key (<SHIFT><6>) followed by the three-digit
decimal code.
Examples: ^064 = @; ^132 = ; ^237 =
To output the ^ character, it must be entered twice in succession (^^). With the ex-
ception of 010 (LF), the special characters with decimal code 000031 are shown
on the screen, but can not be printed out as they are used as control characters for
the printer.
032 048 0 064 @ 080 P 096 ` 112 p 128 144 160 176 192 208 224 240
033 ! 049 1 065 A 081 Q 097 a 113 q 129 145 161 177 193 209 225 241
034 " 050 2 066 B 082 R 098 b 114 r 130 146 162 178 194 210 226 242
035 # 051 3 067 C 083 S 099 c 115 s 131 147 163 179 195 211 227 243
036 $ 052 4 068 D 084 T 100 d 116 t 132 148 164 180 196 212 228 244
037 % 053 5 069 E 085 U 101 e 117 u 133 149 165 181 197 213 229 245
038 & 054 6 070 F 086 V 102 f 118 v 134 150 166 182 198 214 230 246
039 ' 055 7 071 G 087 W 103 g 119 w 135 151 167 183 199 215 231 247
040 ( 056 8 072 H 088 X 104 h 120 x 136 152 168 184 200 216 232 248
041 ) 057 9 073 I 089 Y 105 i 121 y 137 153 169 185 201 217 233 249
042 * 058 : 074 J 090 Z 106 j 122 z 138 154 170 186 202 218 234 250
043 + 059 ; 075 K 091 [ 107 k 123 { 139 155 171 187 203 219 235 251
044 , 060 < 076 L 092 \ 108 l 124 | 140 156 172 188 204 220 236 252
045 - 061 = 077 M 093 ] 109 m 125 } 141 157 173 189 205 221 237 253
046 . 062 > 078 N 094 ^ 110 n 126 ~ 142 158 174 190 206 222 238 254
047 / 063 ? 079 O 095 _ 111 o 127 - 143 159 175 191 207 223 239 255

5 Operation
Navigation mode
Change to
other dialog
pages
Move field
cursor
Return to start of
HOME page or list
Scroll upward
block-by-block
PG UP
PG DN
Scroll downward
block-by-block
>>
Modify
line
Select subpage
Modify Modify
column line Space CLEAR
Edit Edit Edit Clear field con-

parameters parameters parameters tents, edit pa-
by column by line by field rameters by field
Edit mode
ESC
Reset field
contents
ENTER
Accept field
contents Switch between
insert mode (solid
INSERT
cursor) and
overwrite mode
(flashing cursor)
Help xxxxxx
--------
Delete character on
BACK the left and move
SPACE
CLEAR back 1 position
Help Keying
message for aids
parameter Delete character at
Move character Clear field
DELETE
the cursor position
cursor contents

5.3.1 VA TRACE ANALYZER
5.3 Set Up
Under the title "SET UP", the keypad contains 4 yellow dialog keys for the parameter
settings and manual operation of the 746 VA Trace Analyzer and the attached de-
vices. These are described in detail in the following sections.
SET UP
Q W
VA TRACE
STAND
ANALYZER
A S
DOSIMATS SOLUTIONS

5.3 Set Up
W This dialog page is used to set the instrument parameters of the

VA TRACE 746 VA Trace Analyzer, the parameters of the RS232 interfaces
ANALYZER and those of the output control lines.
746 VA TRACE ANALYZER

Program 5.746.0101
Date ....:..:.. RS232 settings Ifc.1 Ifc.2

Time ..:..:..
Beeper ... Baud rate .... ....
Data bits .. ..
Display Stop bit(s) .. ..
Parity ..... .....
Switchoff time ... min Handshake ........ ........
Contrast XXX Receive mode ... ...
Configuration Address Balance type ............

Printer type ............ ............
XXXXXXXXXXXXXXXXXXX X Printer width ........ ........
XXXXXXXXXXXXXXXXXXX X Remote keyboard ........
XXXXXXXXXXXXXXXXXXX X
XXXXXXXXXXXXXXXXXXX X Ctrl.lines # 87654321 Printer
XXXXXXXXXXXXXXXXXXX X
Scan XXXXXXXX Type ............
Set ........
Ext. start ...
Modify Set Ctrl Contrast Contrast Reset Reset Save Diagn.

column lines up down Ifc.1 Ifc.2 Ifc.par.
Softkeys Meaning
Modify Modify parameters column-by-column

column
Set Ctrl Commands for 708 Sampling Unit

lines
For manual operation via control lines of the 708 Sampling Unit
connected to the 746 VA Trace Analyzer with a 6.2143.100 or
6.2143.110 cable, the following commands are available, which
change the last three digits of the parameter Set simultaneously:
FILL Set injection valve to "FILL", switch pump on (Set = *****101)

PUMP ON
FILL Set injection valve to "FILL", switch pump off (Set = *****100)
PUMP OFF
INJECT Set injection valve to "INJECT", switch pump on (Set = *****011)

PUMP ON
INJECT Set injection valve to "INJECT", switch pump off (Set = *****010)
PUMP OFF
Contrast Increase screen contrast

up
The screen is set one level brighter (+2). The current contrast value is
displayed in the Contrast parameter.
Continuous brightening can be achieved by pressing the keys
<SHIFT> and <> simultaneously.

Softkeys Meaning
Contrast Decrease screen contrast

down
The screen is set one level darker (2). The current contrast value is
displayed in the Contrast parameter.
Continuous darkening can be achieved by pressing the keys
<SHIFT> and <> simultaneously.
Reset Reset RS interface 1

Ifc.1
RS232 interface 1 is reinitialized. This may be necessary with certain
disturbances in data communication traffic via the RS interface (see
Error messages, section 7.3.2).
Reset Reset RS interface 2

Ifc.2
RS232 interface 2 is reinitialized. This may be necessary with certain
disturbances in data communication traffic via the RS interface (see
Error messages, section 7.3.2).
Save Storage of RS232 parameters

Ifc.par.
For both RS interfaces, the five RS232 parameters Baud rate, Data
bits, Stop bits, Parity and Handshake are not stored definitively
until this softkey has been pressed.
Diagn. Diagnostic routine

Enter the instrument diagnostic routine (see section 7.6).
Parameter Range; Default value / Meaning

Program display only
Program version number
Date YYYY-MM-DD;
Date
Date in the format year month day.
Time hh:mm:ss;
Time
Time in the format hours minutes seconds.
Beeper on, off; on
Beeper
General switching on/off of the beeper (with Beeper = off an audio
signal is put out only with errors occurring during program execution
or with the BEEP command).
Display display only
Screen
Title for those parameters which affect the screen settings.
Switch-off time 15...999 min; 30 min
Switch-off time
Time interval without keypad entry after which the screen will be
automatically blanked.

5.3 Set Up

Contrast display only
Screen contrast
Display of the contrast value between 0 (completely dark) and 250
(extremely bright). Under normal room lighting conditions, it is advis-
able to set a contrast value of ca. 90...110 using the softkeys
<Contrast up> or <Contrast down>.
Configuration display only
Instrument configuration
Display of the attached devices.
Address display only
Address numbers
Display of the address numbers of the attached devices.
RS232 settings display only
RS232 settings
Title for those parameters which affect the settings of the two RS232
interfaces Ifc.1 and Ifc.2.
If the RS interface is in use (sending or receiving), the display busy
flashes next to Ifc.1 or Ifc.2.
Baud rate 300, 600, 1200, 2400, 4800, 9600; 9600
Date transfer rate

Baud rate in bits for data interchange via RS232 interface. If this
parameter is changed, the change does not become effective until the
softkey <Save Ifc.par.> has been pressed.
Data bits 7, 8; 8
Data bits
Data bits (7-bit or 8-bit) for data interchange via RS232 interface. If
this parameter is changed, the change does not become effective
until the softkey <Save Ifc.par.> has been pressed.
Stop bit(s) 1, 2; 1
Stop bits
Stop bits (1 or 2) for data interchange via RS232 interface. If this
parameter is changed, the change does not become effective until the
softkey <Save Ifc.par.> has been pressed.
Parity none, even, odd; none
Parity
Parity (none, even, odd) for data interchange via RS232 interface. If
this parameter is changed, the change does not become effective
Handshake HWshort, HWfull, SWchar, SWline, none; HWshort
Handshake
Handshake for data interchange via RS232 interface (hardware short,
hardware full, software character, software line, none). For more
detailed information on the individual handshake possibilities, please
see section 8.3.5.
If this parameter is changed, the change does not become effective


Receive mode on, off; off
Receive mode
Receive mode for RS232 interface (on, off). off means that the
receipt of data via the interface is blocked, but data output is possible
(details, see section 8.3).
Balance type none, Mettler, Mettler AT, Sartorius, Precisa, AND; none
Balance type
Selection of the balance type for RS232 interface 2 (manufacturer and
model). You will find further details on the attachment of balances and
the required settings in section 3.12.3.
Printer type none, IBM Propr., Epson 80*60, Epson 60*72, HP Deskjet,
HP Thinkjet, HP Thinkj.E; none
Printer type
Selection of the printer driver for the external printer attached to RS232
interface 1 or 2.
none no printer attached
Epson 80*60 EPSON printers and printers with EPSON emu-
lation with 80 60 dpi graphics resolution (24-
pin dot matrix, ink jet and laser printers)
lation with 60 72 dpi graphics resolution (9-pin
dot matrix, ink jet and laser printers)
HP Deskjet HP printers (HP DeskJet, HP LaserJet) and
printers with HP PCL3 emulation

You will find further details on the attachment of printers and the
required settings in section 3.12.2.
Printer width 0.10...1.00; 1.00
Printing width
Selection of the printing width for the graphics printout. The normal
printing width (1.00) can be reduced by up to a factor of 10 if need be.
Remote keyboard off, send, receive; off
Remote keypad mode

The key code of the 746 VA Trace Analyzer can be sent to RS232
interface 1 or received from there. This allows, e.g. remote control of
the VA Trace Analyzer by a PC by sending directly keyed in or stored
key entries to the VA Trace Analyzer.
off off
send send key code
receive receive key code
(Receive mode must be set to on for this)
Ctrl.lines display only

# 87654321
Control lines 1...8
Title for the 8 input and 8 output control lines of the remote interface.

5.3 Set Up

Scan display only
Input control lines 1...8

Status display of the input control lines 1...8:
0 off, inactive (5 V)
1 on, active (0 V)
You will find further details on the control lines in section 3.13.
Set 0,1; 0
Output control lines 1...8

Here, the output control lines 1...8 can be set manually:
0 off, inactive (open)
1 on, active (0 V)
Ext. start on, off; off
External start via remote interface

Enable/disable external start via input control lines 1 and 2 of the
remote interface:
on External start/stop enabled:
Input control line 1 = on <START>
Input control line 2 = on <BREAK>
off External start/stop disabled
Printer display only
Printer at parallel interface

Title for the printer connected to the 746 VA Trace Analyzer.
Type Metrohm, IBM Propr., Epson 80*60, Epson 60*72, HP Deskjet,

HP Thinkjet, HP Thinkj.E; none
Printer type
Selection of the printer driver for the external printer attached to the
parallel interface (only for 746.0010 version without built-in printer).
Metrohm Built-in thermal printer
(only with 746.0020 version)

lation with 80 60 dpi graphics resolution (24-
pin dot matrix, ink jet and laser printers)
lation with 60 72 dpi graphics resolution (9-pin
dot matrix, ink jet and laser printers)
HP Deskjet HP printers (HP DeskJet, HP LaserJet) and
printers with HP PCL3 emulation
You will find further details on the attachment of printers and the
required settings in section 3.11.

5.3.2 STAND
5.3.2 STAND
Q This dialog page is used for manual operation of the 747 VA

Stand(s) attached to the 746 VA Trace Analyzer and of the 695
STAND Autosampler. It is accessible only in the instrument mode
* READY *.
747 VA STAND
1 Manual Address 1

Pressure .... U.standby --- mV
Purging ....
Stirrer .... Rot.speed ..... /min Rinse unit pos. XXXXX
DME ....
HMDE .... Drop size .....
SMDE .... Drop size .....
RDE .... Rot.speed ..... /min
V.meas max ..... mL

V.rinse ..... mL
V.standby ..... mL
Pressure Purging Stirrer DME HMDE SMDE RDE >>

Settings
VA Stand VA Stand 695 Auto 717 Smpl Rinsing Electr. Default >>
1 2 sampler Changer Dosinos test values Switches
Softkeys Meaning
Pressure Switch inert gas pressure on/off

The inert gas pressure needed for operation of the MME and for
purging is switched on or off. The current status is shown in the
Pressure parameter.
Even when the "STAND" page is quit, the inert gas pressure remains
switched on until it is switched off manually or automatically (by a
program start).
Purging Switch inert gas purging on/off

Purging of the analyte solution is switched on or off. The current status
is shown in the Purging parameter.
Even when the "STAND" page is quit, purging remains switched on
until it is switched off manually or automatically (by a program start).

5.3 Set Up
Softkeys Meaning
Stirrer Switch stirrer on/off

The stirrer is switched on or off. The current status is shown in the
Stirrer parameter.
Even when the "STAND" page is quit, the stirrer remains switched on
until it is switched off manually or automatically (by a program start).
DME Switch DME (Dropping Mercury Electrode) on/off

The DME is switched on or off. After switching on, the mercury drops
freely from the MME for ca. 1 min. This is shown in the DME parameter
by on.dt.
After the "STAND" page has been quit or on change to another type of
electrode, a DME which is switched on is automatically switched off.
HMDE Switch HMDE (Hanging Mercury Drop Electrode) on/off

The HMDE is switched on or off. On switching on, a new mercury drop
is formed at the MME. This is briefly shown in the HMDE parameter by
on.
The size of the mercury drop can be set with the Drop size parame-
ter.
SMDE Switch SMDE (Static Mercury Drop Electrode) on/off

The SMDE is switched on or off. After switching on, mercury drops
from the MME in a controlled manner for ca. 1 min. This is shown in
the SMDE parameter by on.dt.
The size of the mercury drop can be set with the Drop size parame-
ter.
RDE Switch RDE (Rotating Disk Electrode) on/off

The RDE is switched on or off. The current status is shown in the RDE
parameter.
>> Switch to Settings

Settings
Switches the softkey bar to the settings parameters and other func-
tions.
VA Stand Switch to VA Stand 1

1
Maximum three 747 VA stands can be attached to the 746 VA Trace
Analyzer. This softkey is used to switch to the VA Stand with stand
address 1.
The stand currently selected is displayed in the title line:
Manual Address 1 VA Stand with address 1
Automatic Address 3 VA Stand for Autosampler with address 3
VA Stand Switch to VA Stand 2

2
Maximum three 747 VA stands can be attached to the 746 VA Trace
Analyzer. This softkey is used to switch to the VA Stand with stand
address 2.

5.3.2 STAND
Softkeys Meaning
695 Auto Switch to 695 Autosampler and VA Stand 3

sampler
For operation of a 695 Autosampler with the 746 VA Trace Analyzer, a
747 VA Stand with stand address 3 is needed. This softkey is used to
switch to the 695 Autosampler and to the VA Stand with address 3.

2
717 Smpl Switch to 717 Sample Changer
Changer
Reserved for future applications. This softkey will be used to switch to
the initialization and manual operation of the 717 Sample Changer via
746 VA Trace Analyzer.
Rinsing Switch to rinsing Dosinos

Dosinos
The measuring vessel at the 747 VA Stand can be rinsed by means of
two 700 Dosinos with 50 mL dosing units screwed to supply contain-
ers, one of which adds the rinsing solution while the other siphons off
the wash solution into the waste container. The rinsing Dosinos must
be attached to the 746 VA Trace Analyzer and initialized according to
section 3.10.5. This softkey is used to switch to the manual operation
of the two rinsing Dosinos. The following functions are available:
Rinse Rinse measuring vessel
meas.v.
After this softkey has been pressed, the measuring vessel is auto-
matically rinsed as follows:
The solution in the measuring vessel is siphoned off.
The measuring vessel is filled with the volume of rinsing solu-
tion defined as V.rinse.
The rinsing solution is siphoned off.
tion defined as V.standby (conditioning solution).
Prime Initialize rinsing Dosinos
Dosinos
The burette cylinders of the rinsing Dosinos and all connecting tubing
up to the measuring vessel are automatically filled with rinsing solu-
tion.
Empty Empty rinsing Dosinos

Dosinos
up to the measuring vessel are emptied.
Exchange Switch rinsing Dosinos to exchange position

position
The current position of the two rinsing Dosinos is shown in the pa-
rameter Rinse unit pos.:
exch. Exchange position (dosing unit can be changed)
rinse Rinse position
To fill or empty the containers or to remove the dosing units from the
Dosinos, the Dosinos must be in the exch. position. If the Dosinos
are in the rinse position, they have to be switched to the exchange
position by pressing <Exchange position>.

5.3 Set Up
Softkeys Meaning
After the solutions or the dosing units have been changed, the Dosi-
nos must be initialized by pressing <Prime Dosinos>. All connecting
tubing up to the measuring vessel are automatically filled with rinsing
solution.
Electr. Electrode test

test
The electrode (MME or RDE) used in the 747 VA Stand is tested. The
electrode type must be specified for this:
DME DME (Dropping Mercury Electrode)
HMDE HMDE (Hanging Drop Mercury Electrode)
SMDE SMDE (Static Mercury Drop Electrode)
RDE RDE (Rotating Disk Electrode)
On successful completion of the test, the message Electrode test

ok appears in the system window, if any type of malfunction is found
the appropriate error message is shown (see section 7.3.2).
Default Reset parameters to default values

values
The parameters under Settings are reset to their default values.
>> Switch to "Switches"

Switches
Switches the softkey bar to the setting of inert gas pressure, purging,
stirrer and electrodes.

5.3.2 STAND

Pressure on, off; off
Inert gas pressure (see <Pressure>)
Purging on, off; off
Purging (see <Purging>)
Stirrer on, off; off
Stirrer (see <Stirrer>)
DME on.dt, off; off
DME (Dropping Mercury Electrode) (see <DME>)
HMDE on, off; off
HMDE (Hanging Mercury Drop Electrode) (see <HMDE>)
SMDE on.dt, off; off
SMDE (Static Mercury Drop Electrode) (see <SMDE>)
RDE on, off; off
RDE (Rotating Disk Electrode) (see <RDE>)
Rot.speed 0, 200, 400, ..., 3000 /min; 2000 /min
Rotational speed of stirrer

Setting of the rotational speed of the stirrer for manual operation
(revolutions/min).
Drop size 1...9; 5
Drop size of the HMDE

Setting of the drop size of the HMDE (Hanging Mercury Drop Elec-
trode) for manual operation.
2
The surface area of the mercury drop is 0.15...0.60 mm , depending
on the setting.
Drop size 1...9; 5
Drop size of the SMDE

Setting of the drop size of the SMDE (Static Mercury Drop Electrode)
for manual operation.
2
on the setting.
The time for formation of the drop is:
Drop time t.drop = Drop size 40 ms
Rot.speed 0, 200, 400, ..., 3000 /min; 2000 /min
Rotational speed of RDE

Setting of the rotational speed of the RDE (Rotating Disk Electrode) for
manual operation (revolutions/min).

5.3 Set Up

V.meas max 1...999 mL; 80 mL
Maximum fill volume

Setting of the maximum fill volume for the measuring vessel of the 747
VA Stand. It must be ensured here that the measuring vessel is not
overfilled. In dispensing operations which would lead to this volume
being exceeded, an error message appears.
The following settings are recommended:
Measuring vessel V.meas max Measuring vessel V.meas max
6.1415.210 80 mL 6.1450.210 80 mL
6.1415.150 70 mL 6.1456.210 80 mL
6.1418.220 70 mL 6.1457.210 80 mL
V.rinse 1...999 mL; 8 mL
Rinse volume
Setting of the rinse volume for manual rinsing of the measuring vessel
triggered by the softkey <Rinse meas.v.>.
This parameter is displayed only if two rinsing Dosinos are attached to
the 746 VA Trace Analyzer.
V.standby 1...999 mL; 0 mL
Standby volume
Setting of the volume of rinsing solution which is filled into the meas-
uring vessel after manual rinsing triggered by the softkey <Rinse
meas.v.>. This volume can be used as conditioning solution for the
electrodes.
U.standby display only
Standby voltage at electrodes

Display of the polarization voltage set to the electrodes at the end of
the determination (U.standby is set with the MEAS command).
Rinse unit pos. exch., rinse; exch.
Position of the rinsing Dosinos

Display of the current position of the two rinsing Dosinos used for
rinsing the measuring vessel and siphoning off solution:

5.3.2 STAND
747 VA STAND / 695 AUTOSAMPLER

2 Automatic Address 3

Pressure XXXX U.standby XXXXX mV
Purging XXXX
Stirrer XXXX Rot.speed ..... /min Rinse unit pos. XXXXX
DME XXXX Racks AXX BXX SXX

HMDE XXXX Drop size .....
SMDE XXXX Drop size .....
RDE XXXX Rot.speed ..... /min
V.meas max ..... mL

V.rinse ..... mL
V.standby ..... mL
Move Rinse Prime Cond. Rinsing Electr. >> >>

needle needle tube tube Dosinos test Rack def Switches
3 1
Softkeys Meaning
Move Move transfer needle to selected position

needle
The transfer needle can be moved to the following positions:
Wipe Wipe position for cleaning the transfer needle, for unscrewing the
position
transfer needle and for changing the transfer tubing (see 695 Instruc-
tions for use).
Waste Waste position for expelling solution into the waste (normal position of
position
the transfer needle when instrument switched on).
Wash Wash position on the wash station of the 695 Autosampler.

position
Measure Measure position (x and y position) above the measuring vessel on

position
the 747 VA Stand.
Home Home position 0,0 (extreme right rear).

position
Rinse Rinse transfer needle

needle
After this softkey has been pressed, the transfer needle is automati-
cally rinsed as follows:
Ca. 5 mL hydraulic solution are expelled through the transfer
needle into the waste.
The transfer needle is washed in the rinsing solution.

5.3 Set Up
Softkeys Meaning
Prime Fill transfer tubing

tube
By pressing this softkey the transfer tubing is automatically refilled
with hydraulic solution. This may be necessary in two cases:
For filling empty transfer tubing.
For expelling interfering air bubbles.
For further details, please see the 695 Instructions for use.
Cond. Clean transfer tubing

tube
Contamination of the transfer tubing is normally shown by breaking up
of the air bubbles used to separate the solutions, i.e. they are no
longer durable. In this case, an attempt can be made to free the
transfer tubing from contamination using a cleaning solution, prefera-
bly Javelle water (hypochlorite solution). Proceed as follows:
Press <Cond. tube>. The transfer needle is moved to a posi-
tion in front of the 747 VA Stand, at the same time the prompt
Put solution on cond. position appears.
Position a vessel containing sufficient Javelle water below the
transfer needle.
Press <ENTER>. The transfer tubing is filled with Javelle
water. After a wait of 1 min., the transfer needle is moved to
the waste position and the solution expelled
Repeat the entire procedure once more.
For further details, please see the 695 Instructions for use.
Rinsing Switch to Rinsing Dosinos

Dosinos
The measuring vessel at the 747 VA Stand are rinsed by means of two
700 Dosinos with 50 mL dosing units screwed to supply containers,
one of which adds the rinsing solution while the other siphons off any
wash solutions into the waste container. This softkey is used to switch
to the manual operation of the two rinsing Dosinos. The following
functions are available:
Rinse Rinse measuring vessel
meas.v.
After this softkey has been pressed, the measuring vessel is auto-
matically rinsed as follows:
The solution in the measuring vessel is siphoned off.
tion defined as V.rinse.
The rinsing solution is siphoned off.
tion defined as V.standby (conditioning solution).
Prime Initialize rinsing Dosinos
Dosinos
up to the measuring vessel and the wash station are automatically
filled with rinsing solution.
Empty Empty Dosinos

Dosinos
The burette cylinders of the rinsing Dosinos, the wash station and all
connecting tubing up to the measuring vessel and the wash station
are emptied.

5.3.2 STAND
Softkeys Meaning
Exchange Switch rinsing Dosinos to exchange position

position
The current position of the two rinsing Dosinos is shown in the pa-
rameter Rinse unit pos.:
After the solutions or the dosing units have been changed, the Dosi-
nos must be initialized by pressing <Prime Dosinos>. All connecting
tubing up to the measuring vessel and the wash station are automati-
cally filled with rinsing solution.
Electr. Electrode test

test
The electrode (MME or RDE) used in the 747 VA Stand is tested. The
electrode type must be specified for this:
DME DME (Dropping Mercury Electrode)
HMDE HMDE (Hanging Drop Mercury Electrode)
SMDE SMDE (Static Mercury Drop Electrode)
RDE RDE (Rotating Disk Electrode)
On successful completion of the test, the message Electrode test

ok appears in the system window, if any type of malfunction is found
the appropriate error message is shown (see section 7.3.2).
>> Switch to "Rack definition"

Rack def
Switches to subpage "Rack definition" for setting the rack positions.
>> Switch to "Switches"

Switches
Switches the softkey bar to the setting of inert gas pressure, purging,
stirrer and electrodes.
1

5.3 Set Up

Rot.speed 0, 200, 400, ..., 3000 /min; 2000 /min
Rotational speed of stirrer

Setting of the rotational speed of the stirrer for manual operation
(revolutions/min).
Drop size 1...9; 5
Drop size of the HMDE

Setting of the drop size of the HMDE (Hanging Mercury Drop Elec-
trode) for manual operation.
2
on the setting.
Drop size 1...9; 5
Drop size of the SMDE

Setting of the drop size of the SMDE (Static Mercury Drop Electrode)
for manual operation.
2
on the setting.
The time for formation of the drop is:
Drop time t.drop = Drop size 40 ms
Rot.speed 0, 200, 400, ..., 3000 /min; 2000 /min
Rotational speed of RDE

Setting of the rotational speed of the RDE (Rotating Disk Electrode) for
manual operation (revolutions/min).
V.meas max 1...999 mL; 80 mL
Maximum fill volume

Setting of the maximum fill volume for the measuring vessel of the 747
VA Stand. It must be ensured here that the measuring vessel is not
overfilled. In dispensing operations which would lead to this volume
being exceeded, an error message appears.
The following settings are recommended:
Measuring vessel V.meas max Measuring vessel V.meas max
6.1415.210 80 mL 6.1450.210 80 mL
6.1415.150 70 mL 6.1456.210 80 mL
6.1418.220 70 mL 6.1457.210 80 mL
V.rinse 1...999 mL; 8 mL
Rinse volume
Setting of the rinse volume for manual rinsing of the measuring vessel
triggered by the softkey <Rinse meas.v.>.
V.standby 1...999 mL; 0 mL
Standby volume
Setting of the volume of rinsing solution which is filled into the meas-
uring vessel after manual rinsing triggered by the softkey <Rinse
meas.v.> or at the end of a determination containing a RINSE com-
mand. This volume can be used as conditioning solution for the
electrodes.

5.3.2 STAND
Softkeys Meaning
U.standby display only
Standby voltage at electrodes

Display of the polarization voltage set to the electrodes at the end of
the determination (U.standby is set with the MEAS command).
Rinse unit pos. exch., rinse; exch.
Position of the rinsing Dosinos

Display of the current position of the two rinsing Dosinos used for
rinsing the measuring vessel and siphoning off solution:
Racks display only
Mounted racks
Display of the racks mounted on the 695 Autosampler:
S## Sample rack, e.g. S05 (6.2041.060 for 80 samples)
S10 (6.2041.070 for 40 samples)
S03 (6.2041.100 for 24 samples)
S12 (6.2041.110 for 32 samples)
A## Standard rack, e.g. A01 (6.2041.080 for 16 standards)
B## Standard rack, e.g. B01 (6.2041.090 for 10 standards)

5.3 Set Up
Rack name: ........ 695 AUTOSAMPLER Valid entries: XXX

3 Rack type: ........ Rack definition V.sample max : ..... mL
Rack pos. X-pos./mm Y-pos./mm Z-pos./mm Speed

XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
ESC XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
XXX ....... ....... ....... .......
1 XXX
XXX
.......
.......
.......
.......
.......
.......
.......
.......
Modify Modify Copy Teach Copy to Load Store Rack

column line prev. mode Data Cd. from 695 to 695 param.
Keys Meaning
Insert line
INSERT A blank line is inserted above the line selected with the field cursor.
Delete line
DELETE The line selected with the field cursor is deleted.
Softkeys Meaning

column
Modify Modify parameters line-by-line

line
Copy Copy previous line

prev.
The contents of the preceding line are copied into the line selected
with the field cursor (any existing entries will be overwritten).
Teach Switch to teach mode

mode
Switching to teach mode for adoption of rack positions.

5.3.2 STAND
Softkeys Meaning
Copy to Copy rack data to data card

Data Cd.
The put in rack data are copied to the data card; the name entered
under Rack name is used as file name and automatically assigned the
extension aut.
Load Load rack data from 695 Autosampler

from 695
The rack data stored in the 695 Autosampler for the rack selected
under Rack type are loaded into the working memory.
Data in the 695 Autosampler for the following sample and standard
racks as well as special positions are loaded as standard:
S01, S02, S03, S04, S05, S08, S10, S12, A01, B01
Homepos., Measpos., Washpos., Wastepo.
Store Store rack data in 695 Autosampler

to 695
The put in rack data are permanently stored in the autosampler under
the address selected with Rack type.
To avoid inadvertent losses of the rack data stored in the Autosampler
as standard, we advise you to use the softkey <Copy to Data Cd.> to
make a backup copy on the data card of the following rack data:
S01, S02, S03, S04, S05, S08, S10, S12, A01, B01
Homepos., Measpos., Washpos., Wastepo.
Rack Modify rack parameters in header lines

param.
Pressing this softkey allows modification of the parameters Rack
name, Rack type and V.sample max in succession. Below the header
lines, the window Rack definitions containing the rack types and
rack names stored on the 695 Autosampler is displayed.

Rack name 8 characters;
Rack name
Freely selectable name for rack. The name entered here will be used
as a file name and automatically given the extension .aut when
stored on the data card with <Copy to Data Cd.>.
Rack type S01...S31, A01...A07, B01...B07, Homepos., Measpos., Washpos.,

Wastepo.;
Rack type or special needle position

Selection of the rack type or the special needle position for the display
or entry of rack data:
Sample rack Sample holder Samples
S05 6.2041.060 80
S10 6.2041.070 40
S01 6.2041.100 1 6.2041.040 (left) 12
S02 6.2041.100 1 6.2041.040 (right) 12
S03 6.2041.100 2 6.2041.040 24
S04 6.2041.110 1 6.2041.050 (left) 16
S08 6.2041.110 1 6.2041.050 (right) 16
S12 6.2041.110 2 6.2041.050 32
A01 6.2041.080 16
B01 6.2041.090 10

5.3 Set Up
S## User-defined sample rack

A## User-defined standard rack
B## User-defined standard rack
Homepos. Home position (position 0,0 at extreme right rear)
Measpos. Measurement position, position of the needle in the
measuring vessel
Washpos. Wash position, position of the needle during washing
Wastepo. Waste position, position of the needle when solution is
expelled
Valid entries display only
Number of rack positions

Display of the number of rack positions entered for the selected rack.
V.sample max 1...999 mL; 10 mL
Maximum sample volume

Maximum volume of the sample vessels for the selected rack.
Rack pos. display only
Rack position
Display of the position number (consecutive numbering).
X-pos./mm 0...337.5 mm; 0 mm
X position
Needle position in the x direction in mm (resolution 0.125 mm).
This is the distance which the needle has to travel from the home
position to the center of the sample vessel or to the special position in
the x direction.
Y-pos./mm 0...225 mm; 0 mm
Y position
Needle position in the y direction in mm (resolution 0.125 mm).
This is the distance which the needle has to travel from the home
position to the center of the sample vessel or to the special position in
the y direction.
Z-pos./mm 0...128.5 mm; 0 mm
Z position
Needle position in the z direction in mm (resolution 0.05 mm).
This is the maximum distance which the needle may travel from the
home position to the bottom of the sample vessel in the z direction.
Speed slow, medium, fast; slow
Transfer speed
Speed at which the solution is transferred at the selected position with
the large syringe (siphoning off or addition).
slow 9 mL/min for viscous or surfactant-containing
solutions
medium 22 mL/min for aqueous solutions
fast 50 mL/min suitable only for waste position
Wastepo.

5.3.2 STAND
Rack name: XXXXXXXX 695 AUTOSAMPLER Valid entries: XXX

4 Rack type: XXXXXXXX Rack definition V.sample max : XXXXX mL
Rack pos.
Wait
X-pos./mm Y-pos./mm Z-pos./mm Speed

XXX Learning position: XXXXXXX
XXXXXXX XXX XXXXXXX XXXXXXX
XXX X=XXXXXX Y=XXXXXX Z=XXXXXX
XXXXXXX XXXXXXX XXXXXXX XXXXXXX
XXX

XXXXXXX XXXXXXX XXXXXXX XXXXXXX
XXX XXXXXXX XXXXXXX XXXXXXX XXXXXXX
ESC XXX XXXXXXX XXXXXXX XXXXXXX XXXXXXX
3 XXX
XXX
XXXXXXX
XXXXXXX
XXXXXXX
XXXXXXX
XXXXXXX
XXXXXXX
XXXXXXX
XXXXXXX
Up Down
Specifying positions in the teach mode
Move position in x direction

The needle tip is moved to the desired x position using the cursor
keys <> or <>. The current x position is shown in the
window.
Move position in y direction

The needle tip is moved to the desired x position using the cursor
keys <> or <>. The current y position is shown in the win-
dow.
Up Move position in z direction

The needle tip is moved to the desired z position using these two
Down
softkeys. The current z position is shown in the window.
When shifting the position with the cursor keys or the softkeys
<Up> and <Down>, the following applies:
Each time these keys are pressed, the needle position is
shifted by 0.125 mm (x and y axis) or 0.05 mm (z axis) in
the selected direction. In contrast to the softkeys, the cur-
sor keys are repetitive, i.e. the longer the cursor key is
pressed, the further the needle is shifted.
Adopt position
ENTER When the desired position is reached, it is adopted definitively by
pressing the <ENTER> key. The needle is then automatically
raised to the position z = 0 mm.

5.3 Set Up

Rack name display only
Rack name
Display of rack name.
Rack type display only
Rack type or special needle position

Display of the rack type or of the special needle position for which
rack positions have been entered in the teach mode.
Valid entries display only
Number of rack positions

Display of the number of rack positions entered for the selected rack.
V.sample max display only
Maximum sample volume

Display of the maximum volume of the sample vessels for the se-
lected rack.
Learning display only

position
Current rack position for teach mode
Display of the number of the current position; this position can be
changed using the cursor keys and softkeys.
X= display only
Current x position
Display of the current needle position in the x direction in mm
(resolution 0.125 mm).
Y= display only
Current y position
Display of the current needle position in the y direction in mm
Z= display only
Current z position
Display of the current needle position in the z direction in mm

5.3.3 DOSIMATS
5.3.3 DOSIMATS
A This dialog page is used for manual operation of the 685

Dosimats and 700 Dosinos attached to the 746 VA Trace
DOSIMATS Analyzer.
If two rinsing Dosinos are attached to the 746 VA Trace Analyzer
(see section 3.10.5 and section 3.5.4), the Dosinos #3 and #4 will
not be displayed on this page.
If one of the Dosimats/Dosinos is active, the status message
* BUSY * appears in the title line.
DOSIMATS
Dosimat/Dosino #1 #2 #3 #4

V.display XXXXXX mL XXXXXX mL XXXXXX mL XXXXXX mL
V.burette XX mL XX mL XX mL XX mL
Type XXX XXX XXX XXX
Position XXXXXXXX XXXXXXXX XXXXXXXX XXXXXXXX
Gen.settings

Dosing rate ........L/min ........L/min ........L/min ........L/min
Filling rate ........L/min ........L/min ........L/min ........L/min
V.init ...... mL ...... mL ...... mL ...... mL
V.tube in ...... mL ...... mL ...... mL ...... mL
V.tube out ...... mL ...... mL ...... mL ...... mL
Dil.settings

C.init std ........g/L ........g/L ........g/L ........g/L
C.end dilution ........g/L ........g/L ........g/L ........g/L
V.end dilution ...... mL ...... mL ...... mL ...... mL
Modify Modify Empty Dos Exchange Prime Fill >>

column line Dosimat V.init position Dosimat Dosimat
Modify Modify Default Start Exchange Prime Fill >>

column line values dilution all all all
Softkeys Meaning

column

line
Empty Empty 700 Dosino

Dosimat
The burette cylinder of the selected Dosino and all connecting tubing
up to the measuring vessel are emptied.
This softkey has no function with 685 Dosimats.

5.3 Set Up
Softkeys Meaning
Dos Dispense initial volume

V.init
After pressing this softkey, the selected Dosimat/Dosino (position of
the field cursor) dispenses the volume V.init at the set Dosing rate
The total dispensed volume is displayed under V.display.
Exchange Switch Dosimat/Dosino to exchange position

position
In order to change the exchange or dosing unit, the 685 Dosimat or
700 Dosino must be in the exchange position. If the Dosimat/Dosino
is in the dosing position, it has to be switched to the exchange
position by pressing <Exchange position> or <Exchange all>.
After the exchange or dosing unit has been changed, the Dosi-
mat/Dosino must be initialized by pressing <Prime Dosimat> or
<Prime all>.
Prime Initialize Dosimat/Dosino

Dosimat
The burette cylinder of the selected Dosimat/Dosino and all connect-
ing tubing up to the measuring vessel are automatically filled. Excess
solution is expelled to the measuring vessel.
Should the filling take longer than 30 s, the message This operation
takes x.x minutes appears. The filling operation can then be started
with <r> or aborted with <a> to increase the filling rate. Once a filling
operation has been started, it can no longer be aborted.
After the filling, the initial volume V.init is automatically delivered to
the measuring vessel. With V.init > 0 uL, the Dosimat/Dosino is
then in the dosing position and is ready for dispensing. With V.init
= 0 uL, the exchange position is retained, the Dosimat/Dosino is
ready for both dispensing and replacement of the exchange or dosing
unit.
To ensure the correct initializing of 700 Dosinos, the volume V.tube

in of the tubing from the supply bottle to the Dosino and V.tube out
of the tubing from the Dosino to the measuring vessel must be set.
To ensure the correct initializing of 685 Dosimats, the volumes V.tube

in and V.tube out must be set equal to the burette volume, so that
the burette cylinder is filled three times.
Fill Fill Dosimat/Dosino

Dosimat
The burette cylinder of the selected Dosimat/Dosino (position of the
field cursor) is filled at the set Filling rate.
the measuring vessel.
>> Switch to additional softkeys
Default Reset parameters to default values

values
The parameters under Gen.settings and Dil.settings are reset to
their default values.

5.3.3 DOSIMATS
Softkeys Meaning
Start Start dilution operation

dilution
With this softkey the dilution operation for preparing standard solu-
tions at the selected Dosimat/Dosino is started. For this operation, the
6.5611.010 pipetting equipment must have been installed at the
Dosimat/Dosino and connected to the remote interface of the 746 VA
Trace Analyzer (see section 3.10.6).
To prepare a solution with the volume V.end dilution and the
concentration C.end dilution out of a standard with the concentra-
tion C.init std proceed as follows:
Select the Dosimat/Dosino with the mounted pipetting equipment
and press the softkey <Prime Dosimat> for initializing the Dosi-
mat/Dosino and fill the transfer tubing.
Press the softkey <Start dilution>. The message Preparing
Dosimat #X appears.
Put the pipetting tip into a waste container at about the same level
as the container with the standard solution and press the button on
the pipetting tip. After aspiration of the dilution solution the mes-
sage Aspirating standard appears.
Put the pipetting tip into the standard solution and press the button
on the pipetting tip. After aspiration of the standard solution the
message Dispensing solution appears.
Put the pipetting tip into the desired void container and press the
button on the pipetting tip. Standard and dilution solution are dis-
pensed into the void container. Afterwards the message Next
operation / press <ESC> to break appears.
If you press <ENTER>, the Dosimat/Dosino will be ready for
another dilution, if you press <ESC>, the Dosimat/Dosino is
switched to the exchange position.
Exchange Switch all Dosimats/Dosinos to exchange position

all
In order to change the exchange or dosing unit, the 685 Dosimats or
700 Dosinos must be in the exchange position. If the Dosi-
mats/Dosinos are in the dosing position, they have to be switched to
the exchange position by pressing <Exchange position> or
<Exchange all>.
After the exchange or dosing units have been changed, the Dosi-
mats/Dosinos must be initialized by pressing <Prime Dosimat> or
<Prime all>.
Prime Initialize all Dosimats/Dosinos

all
The burette cylinders of all Dosimats/Dosinos and all connecting
tubing up to the measuring vessel are automatically filled. Excess
solution is expelled to the measuring vessel.
the measuring vessel. With V.init > 0 uL, the Dosimat/Dosino is
then in the dosing position and is ready for dispensing. With V.init
= 0 uL, the exchange position is retained, the Dosimat/Dosino is
ready for both dispensing and replacement of the exchange or dosing
unit.

5.3 Set Up
Softkeys Meaning
To ensure the correct initializing of 700 Dosinos, the volume V.tube

in of the tubing from the supply bottle to the Dosino and V.tube out
of the tubing from the Dosino to the measuring vessel must be set.
To ensure the correct initializing of 685 Dosimats, the volumes V.tube

in and V.tube out must be set equal to the burette volume, so that
the burette cylinder is filled three times.
Fill Fill all Dosimats/Dosinos

all
The burette cylinders of all Dosimats/Dosinos are filled at the set
Filling rate.
the measuring vessel.

V.display display only
Dispensed volume
Display in mL of the volume dispensed with the Dosimat/Dosino.
V.burette display only
Burette volume
Display in mL of the burette volume of the exchange or dosing unit
mounted on the Dosimat/Dosino.
Type display only
Dosimat type
Display of the attached Dosimat type:
685 685 Dosimat
700 700 Dosino
Position dosing, exchange; dosing
Position of the Dosimat/Dosino

Display of the current position of the Dosimat/Dosino:
dosing Dispensing position
exchange Exchange position (exchange unit or dosing unit
can be changed)
If the Dosimat/Dosino is in the dosing position, it can be switched to
the exchange position by pressing <Exchange position>.
Gen.settings display only
General settings
Title for the general parameters of the Dosimats/Dosinos.

5.3.3 DOSIMATS

Dosing rate 0.001...3.333*(V.burette) L...L/min; 2.00 mL/min
Dosing rate
Discharge rate of the Dosimat/Dosino. The maximum rate which can
be set depends on the burette volume of the mounted exchange or
dosing unit.
If the 4-way microtip 47 or another microcapillary tubing is used for the

addition of solutions from the Dosimat/Dosino to the measuring vessel,
the Dosing rate must be set to 2 mL/min .
Filling rate 0.001...3.333*(V.burette) L...L/min; 3.0*(V.burette) mL/min
Filling rate
Filling rate of the Dosimat/Dosino. The maximum rate which can be
set depends on the burette volume of the mounted exchange or
dosing unit.
At the end of a determination, the burette is automatically filled at this
filling rate.
V.init 0.00...2.00 mL; 0.00 mL
Initial volume
The initial volume V.init is the volume that is automatically dis-
pensed after filling of the burette cylinder. The purpose of this auto-
matic volume addition is to enlarge the accuracy of the first dispens-
ing operation following filling for the addition of small volumes.
For dispensing volumes 50 L, we advise working with an initial

volume of at least 50 L as without this automatic addition the first
dispensing operation following filling would be inexact.
V.tube in 0.0...(V.burette) mL; 0.7 mL
Volume of filling tube

The volume V.tube in is the volume of the tubing from the supply
bottle to the Dosimat/Dosino. To ensure an air-free filling of the tubing,
this volume must be determined and entered. For the standard
accessories of the Dosimat/Dosino, the following volumes should be
entered:
6.3014.XXX Exchange unit for 685 Dosimat: 1.7 mL
6.3030.XXX Dosing unit for 700 Dosino: 0.7 mL
V.tube out 0.0...999.9 mL; 0.2 mL
Volume of dosing tube

The volume V.tube out is the volume of the tubing from the Dosi-
mat/Dosino to the measuring vessel. To ensure an air-free filling of the
tubing, this volume must be determined and entered. With normally
used accessories for addition of standard or auxiliary solutions and
preparation of standard solutions using the pipetting equipment the
following volumes should be entered:
Addition of standard solutions with
6.1624.000 4-way microtip: 0.2 mL
Addition of auxiliary solutions
(see sections 3.9.3/4, 3.10.3/4) 3.0 mL
6.1562.050 pipetting tube: 4.8 mL

5.3 Set Up

Dil.settings display only
Dilution settings
Title for the dilution parameters of the Dosimats/Dosinos. With the aid
of these parameters and the softkey <Start dilution> standard
solutions can be prepared. For this operation, the 6.5611.010 pipet-
ting equipment must have been installed at the Dosimat/Dosino and
connected to the remote interface of the 746 VA Trace Analyzer (see
section 3.10.6).
The initial volume V.init std needed for the dilution is automatically
calculated according to the formula
V.init std = V.end dilution * C.end dilution / C.init std
If the initial volume V.init std is smaller than 10 L, the error mes-
sage DOSIMAT ERROR 11: Illegal Dilution settings appears.
We recommend to make only dilutions with an initial volume
V.init std 20 L.
C.init std 0.001...999.9 ug...kg/L; 1.00 g/L
Initial standard concentration

Initial concentration of the standard used for the preparation of new
standard solutions.
The initial standard concentration C.init std must be 2 times the
desired end concentration C.end dilution.
C.end dilution 0.001...999.9 ng...g/L; 10.00 mg/L
End concentration
Desired end concentration of the new standard solution to be pre-
pared.
The end concentration C.end dilution must be 0.5 times the initial
standard concentration C.init std.
V.end dilution 0.1...999.9 mL; 10 mL
End volume
Desired end volume of the new standard solution to be prepared.

5.3.4 SOLUTIONS
5.3.4 SOLUTIONS
S This dialog page is used for entry of the standard addition and
auxiliary solutions which should be added automatically either
SOLUTIONS with the aid of Dosimats/Dosinos or with the 695 Autosampler.
Before a method is started, ensure that all these solutions are
entered here and that the right solutions are installed in the right
position.
If no 685 Dosimat, 700 Dosino or 695 Autosampler are connected to

the 746 VA Trace Analyzer, we recommend not to make any inputs on
this dialog page.
SOLUTIONS
Line: XX
Soln.name Pos. Std.subst. Mass conc. Remark

........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
........ .... ........ ............. .........................
Modify Modify Delete Check Sort by Sort by Print Upd.from
column line line soln.s name position all method
Softkeys Meaning

column

line
Delete Delete line

line
The line selected with the field cursor is deleted.
Check Check solutions

soln.s
The solutions entered in the table are checked to see whether their
mass concentrations match the mass concentrations of the solutions
with the same name defined in the loaded method. Any errors will be
displayed with specification of the line number.

5.3 Set Up
Softkeys Meaning
Sort by Sort by name

name
The solutions are sorted alphabetically by name Soln.name.
Sort by Sort by position

position
The solutions are sorted by their position Pos..
Print Print list of all solutions

all
The "SOLUTIONS" page is printed out with all solution entries.
Upd.from Takeover solutions from method

method
The auxiliary solutions defined in the loaded method on the dialog
pages "OP.SEQUENCE", "SEGMENTS" or "SUBSTANCES" are auto-
matically transferred to the solution list. Depending on the place of
origin, the following entries are made in the Remarks column:
from: <Subst.> Solution from subpage "Calibrations" of
the substance with the name <Subst.>
Command from: Op.Seq. Solution from dispensing instruction on
the "OP.SEQUENCE" page
Command from: <Segm.> Solution from dispensing instruction in
the segment with the name <Segment>

Soln.name 8 characters;
Solution name
The entry of a solution on this page is required only if this has to be
dispensed automatically with a 685 Dosimat, a 700 Dosino or the 695
Autosampler. In this case, the name entered here must be identical
with the solution name Soln.name of the dispensing instruction in
question.
We recommend not to put in the solution names via keypad but to

takeover the solution names defined in the current method by pressing
the softkey Upd.from method .
If work is carried out with a single mixed solution for standard addi-
tions of several substances, a separate line with the solution name
and the position of the mixed solution must be entered for each
substance.
Rinsing Dosinos
It is possible to rinse the measuring vessel at the 747 VA Stand manually
via dialog page "STAND" or with the RINSE command by means of two
700 Dosinos with 50 mL dosing units attached to the "Dos. 3" and
"Dos. 4" connections of the 746 VA Trace Analyzer (see section 3.10.5).
To make possible this rinsing, a solution with the solution name
Soln.name = RINSE (upper case letters) and the position Pos. = Dos.3
has to be entered.

5.3.4 SOLUTIONS

Pos. Do.1...4, R, H, A01...A44, B01...B44, -; -
Position of solution
For automatic dispensing operations, the solution can be assigned as
follows:
Do.1...4 Dosimat/Dosino 1...4
(attached to 746 VA Trace Analyzer)
R Rinsing solution
(possible only with Rinsing Dosinos)
H Hydraulic solution
(possible only with 695 Autosampler)
A01...A44 Standard rack A with position 1...44
B01...B44 Standard rack B with position 1...44
With no assignment (-) or if no Dosimat/Dosino is attached, manual

dispensing must be performed (the appropriate prompt for this
appears during the program).
Std.subst. 8 characters; -
Name of standard substance

For automatic dispensing operations with ADD instructions, here it is
mandatory to enter the name of the relevant substance and this must
match the substance name on the "SUBSTANCES" page. Without
specification of a name (-), manual dispensing must be performed
(the appropriate prompt for this appears during the program).
With auxiliary solutions which should be dispensed automatically, this
column must remain empty (-).
Mass conc. 0.100...999.999 ng/L...kg/L;
Mass concentration of solution

For automatic dispensing operations with ADD instructions, here it is
mandatory to enter the mass concentration of the standard addition
solution and this must match the mass concentration entered on the
"SUBSTANCES" page.
Remark 25 characters;
Remarks regarding solution

Free alphanumeric entry.
With solutions which are transferred automatically by pressing the
softkey <Upd. from method>, the place of origin is entered in this
column (see <Upd. from method>).

5.4 Storages
5.4 Storages
Under the title "STORAGES" the keypad has 5 yellow dialog keys for selection of the
lists of methods and determinations as well as the sample data and instrument
variables stored in the instrument or on the data card. These are described in detail
in what follows.
STORAGES
R T
METHODS SAMPLES
F G
DETERMI- COMMON
NATIONS VARIABLES
V
DATA
CARD

5.4.1 METHODS
5.4.1 METHODS
R This dialog page shows the methods stored in the instrument.

They can be copied, deleted, secured and sorted.
METHODS
Files : XXX of 256 METHODS

Available: XXXXXXX Bytes
File Content Size

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............ .................................................. XXXXX
............ .................................................. XXXXX

Print Select Secure/ Sort >>

all all Unsecure
Marking of files
For the delete and copy functions of files, several method files can first be selected and
marked by an arrow >. Single files are selected with the <ENTER> key, all files with the
softkey <Select all>. Pressing the two keys <SHIFT> and <> marks files in succes-
sion.
Softkeys Meaning

column
Secured methods (*) must first be unsecured with <Unsecure> before
they can be modified.

line

5.4 Storages
Softkeys Meaning
Delete Delete selected methods

file(s)
The methods marked by an arrow > (if no methods are marked, the
method selected with the cursor) are deleted after confirmation with y.
Copy Copy selected methods to selected destination

to
The methods marked by an arrow > (if no methods are marked, the
method selected with the cursor) are copied to the selected destina-
tion. The following destinations are available:
Working Working storage (only the method selected with the cursor is copied;
storage
the loaded method will be overwritten)
Method Method storage "METHODS" (a new name must be entered for the
storage
copied method)
Data Data card (an unsecured method with the same name will be over-
card
written)
RS232 RS232 interface 1, i.e. the PC connected to it

Ifc.1

Ifc.2
Copy Copy method from selected source

from
The method is copied from the selected source to the method list. The
following sources can be selected:
Working Working storage (an unsecured method with the same name will be
storage
overwritten)

Ifc.1

Ifc.2
Unselect Cancel selection

file(s)
The selection of the methods marked by an arrow > is canceled.
Change Change display type

display
Switching between the space-saving display mode with method
names in 4 columns and the display mode with name, contents and
memory size.
Print Print list of all methods

all
The "METHODS" page is printed out with all method entries.
Select Select all methods

all
All methods on the page are selected and marked by an arrow >.

5.4.1 METHODS
Softkeys Meaning
Secure/ Secure/unsecure selected method

Unsecure
The method selected with the cursor is secured (marking * appears
on the left next to the method name) or unsecured (marking * is
deleted).
Secured methods can not be deleted or overwritten.
Sort Sort methods alphabetically

The methods are sorted alphabetically. Here, numbers take prece-
dence over letters, uppercase letters precedence over lowercase
letters.

Files display only
Number of files
Display of the number of stored methods (maximum 256 methods can
be stored).
Available display only
Free storage space

Display of the free storage space in bytes.
File 8 characters;
Method name
In copying a method from the working memory, the method name
Method entered on the "OP.SEQUENCE" page is automatically given
the extension .mth. The first 8-character part of the method name can
be changed, however the extension .mth must be retained as it
characterizes method files.
their name can be changed.
For the method name all characters are allowed with the exception of
the character ".".
Content 50 characters;
Method title
In copying a method from the working memory, the method title Title
entered on the "OP.SEQUENCE" page is entered in this column. This
50-character title can be changed.
their title can be changed.
Size display only
Memory size
Display of the memory requirements of the method in bytes.

5.4 Storages
Methods stored as standard
The following methods are stored as standard in the method memory:

#New Basic method without program
TEST747 Test method for checking the 747 VA Stand (see section 7.6)
TESTPb Lead determination with standard addition (see sections 4.2
and 7.7)
CALCRV Lead determination with calibration curve (see section 4.3)
INTSTD Lead determination with internal standard (see section 4.4)
POL Basic method for DP polarography (see section 4.5)
ASV Basic method for DPASV (see section 4.5)
AB..... Various methods described in detail in Application Bulletins.
The corresponding Application Bulletins 74, 76, 96, 97, 98,
110, 116, 117, 123, 131, 146, 176, 186, 196, 199, 220, 226,
231, 241, 243, 254 and 266 are available free of charge from
your Metrohm representative.

5.4.2 DETERMINATIONS
F This dialog page is used for display of the determinations stored

DETERMI- in the instrument. They can be copied, deleted, secured and
NATIONS sorted.
Files : XXX of 256 DETERMINATIONS

Available: XXXXXXX Bytes Full condition: .......
File Content Size

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............ .................................................. XXXXX
............ .................................................. XXXXX
............ .................................................. XXXXX
............ .................................................. XXXXX
............ .................................................. XXXXX

Print Select Recalc. Secure/ Change Sort >>

all all file(s) Unsecure full cd.
Marking of files
For the delete and copy functions of files, several determination files can first be selected
and marked by an arrow >. Single files are selected with the <ENTER> key, all files with
the softkey <Select all>. Pressing the two keys <SHIFT> and <> marks files in
succession.

5.4 Storages
Softkeys Meaning

column
Secured determinations (*) must first be unsecured with <Unsecure>
before they can be modified.

line
Delete Delete selected determinations

file(s)
The determinations marked by an arrow > (if no determinations are
marked, the determination selected with the cursor) are deleted after
confirmation with y.
Copy Copy selected determinations to selected destination

to
The determinations marked by an arrow > (if no determinations are
marked, the determination selected with the cursor) are copied to the
selected destination. The following destinations are available:
Working Working storage (only the determination selected with the cursor is
storage
copied; the loaded determination will be overwritten)
Determ. Determination storage "DETERMINATIONS" (a new name must be

storage
entered for the copied determination)
Data Data card (an unsecured determination with the same name will be
card
overwritten)

Ifc.1

Ifc.2
Copy Copy determination from selected source

from
The determination is copied from the selected source to the determi-
nation list. The following sources can be selected:
Working Working storage (an unsecured determination with the same name will
storage
be overwritten)

Ifc.1

Ifc.2

file(s)
The selection of the determinations marked by an arrow > is can-
celed.

display
Switching between the space-saving display mode with determination
names in 4 columns and the display mode with name, contents and
memory size.

Softkeys Meaning
Print Print list of all determinations

all
The " DETERMINATIONS" page is printed out with all determination
entries.
Select Select all determinations

all
All determinations on the page are selected and marked by an arrow
>.
Recalc. Recalculate selected file(s)

file(s)
All determinations selected and marked by an arrow > are recalcu-
lated with the method currently loaded in the working storage. For
each of the selected determinations, a recalculation from original
and a recalculation from Op. Sequence (see softkey <Recalc.> on
the "MONITORING" page, section 5.5.1) using the originally recorded
experimental data and the modified method parameters is performed.
The result of the recalculation is seen on the reports and/or curves
defined on the "DOCUMENTATION" page which are automatically put
out to the printer or RS interfaces.
Make sure that only determinations are selected for recalculation which
were recorded with a method whose name Method is identical to the
method name of the method currently loaded in the working storage.
The result of the recalculation is not stored automatically in the deter-
mination file.
Secure/ Secure/unsecure selected determination

Unsecure
The determination selected with the cursor is secured (marking *
appears on the left next to the determination name) or unsecured
(marking * is deleted).
Secured determinations can not be deleted or overwritten.
Change Specify mode when memory full

full cd.
This softkey can be used to switch between the two possibilities push
out or stop for the Full condition parameter (see under Parame-
ters).
Sort Sort determinations alphabetically

The determinations are sorted alphabetically. Here, numbers take
precedence over letters, uppercase letters precedence over lower-
case letters.

5.4 Storages

Files display only
Number of files
Display of the number of stored determinations (maximum 256
determinations can be stored).
Free storage space

File 8 characters;
Determination name
In copying a determination from the working memory to the determi-
nation list, the name MMDDhhmm.dtm is allocated automatically and
comprises the month (MM) day (DD) hours (hh) minutes (mm) when
the determination was recorded and the extension .dtm. The first 8-
digit part of the determination name can be changed, however the
extension .dtm must be retained as it characterizes determination
files.
before their name can be changed.
For the determination name all characters are allowed with the excep-
tion of the character ".".
Content information for determination

nation list, the three parameters Sample table, S1 and Method call
are entered automatically if they were available on the "MONITORING"
or "SAMPLES" page at the time of recording.
This 50-character content information can be changed at will and is
retained in direct copying to the data card or the RS interfaces.
However, if the determination is loaded in the working memory and
then copied from there to another destination, this content information
will be lost.
their title can be changed.
Size display only
Memory size
Display of the memory requirements of the determination in bytes.
Full condition push out, stop; stop
Mode when memory full

Specification of what should happen when the automatic storage is
switched on (Det.storage = on on the "MONITORING" page), but the
determination memory is full:
push out Create space by deleting the oldest
determination(s)
stop Discontinue determination series
The mode can be switched with the softkey <Change full cd.>.

5.4.3 DATA CARD
5.4.3 DATA CARD
V This dialog page is used to access the data card. Methods and
DATA determinations can be copied, deleted, secured and sorted. You
CARD
will find further details on the data card (types to be used, battery
change, etc.) in section 3.2.6.
Files : XXX of 256 DATA CARD Capacity: XXXXXX Bytes

Available: XXXXXXX Bytes Label : XXXXXXXXXXXXXXXXXXX
File Content Size

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Print Select Recalc. Secure/ Format Sort >>

all all file(s) Unsecure card
Marking of files
For the delete and copy functions of files, several files can first be selected and marked by
an arrow >. Single files are selected with the <ENTER> key, all files with the softkey
<Select all>. Pressing the two keys <SHIFT> and <> marks files in succession.

5.4 Storages
Softkeys Meaning

column
Secured files (*) must first be unsecured with <Unsecure> before they
can be modified.

line
can be modified.
Delete Delete selected files

file(s)
The files marked by an arrow > (if no files are marked, the file se-
lected with the cursor) are deleted after confirmation with y.
can be modified.
Copy Copy selected files to selected destination

to
The files marked by an arrow > (if no files are marked, the file se-
lected with the cursor) are copied to the selected destination. The
following destinations are available:
Working Working storage (only the file selected with the cursor is copied).
storage
The following files can be copied:
XXXXXXXX.mth Method files (the loaded method will be over-
written)
XXXXXXXX.dtm Determination files (the loaded determination
and the method will be overwritten)
XXXXXXXX.smp Sample data files (the sample data table on the
"SAMPLES" page will be overwritten)
XXXXXXXX.aut Rack data files (the rack data table on the sub-
page Rack definition of the "STAND" page
will be overwritten)
Method Method storage "METHODS" (only the method files with the extension
storage
.mth can be copied; an unsecured method with the same name will
be overwritten)
Determ. Determination storage "DETERMINATIONS" (only the determination

storage
files with the extension .dtm can be copied; an unsecured determi-
nation with the same name will be overwritten)
Data Data card (a new name must be entered for the copied file)
card

Ifc.1

Ifc.2
Copy Copy files from selected source

from
The files are copied from the selected source to the data card. The
following sources can be selected:
Working Method from the working memory (an unsecured method with the
method
same name will be overwritten)

5.4.3 DATA CARD
Softkeys Meaning
Working Determination from the working memory (an unsecured determination

determ.
with the same name will be overwritten)
Ifc.1

Ifc.2

file(s)
The selection of the files marked by an arrow > is canceled.

display
Switching between the space-saving display mode with file names in
4 columns and the display mode with name, contents and size.
Print Print list of all files

all
The " DATA CARD" page is printed out with all file entries.
Select Select all files

all
All files on the page are selected and marked by an arrow >.
Recalc. Recalculate selected file(s)

file(s)
All determinations selected and marked by an arrow > are recalcu-
lated with the method currently loaded in the working storage. For
each of the selected determinations, a recalculation from original
and a recalculation from Op. Sequence (see softkey <Recalc.> on
the "MONITORING" page, section 5.5.1) using the originally recorded
experimental data and the modified method parameters is performed.
The result of the recalculation is seen on the reports and/or curves
defined on the "DOCUMENTATION" page which are automatically
outputted to the printer or RS interfaces.
Make sure that only determinations are selected for recalculation which
were recorded with a method whose name Method is identical to the
method name of the method currently loaded in the working storage.
The result of the recalculation is not stored automatically in the deter-
mination file.
Secure/ Secure/unsecure selected file

Unsecure
The file selected with the cursor is secured (marking * appears on
the left next to the file name) or unsecured (marking * is deleted).
Secured files can not be deleted or overwritten.
Format Reformat data card

card
The data card is reformatted, all existing data will be lost. After confir-
mation with y, an inquiry concerning the card title Label of this Data
card ? appears. A title of max. length 20 characters can be entered
and will henceforth be displayed under the Label parameter.
Sort Sort files alphabetically

The files are sorted alphabetically. Here, numbers take precedence
over letters, uppercase letters precedence over lowercase letters.

5.4 Storages

Files display only
Number of files
Display of the number of stored files (maximum 256 files can be
stored).
Free storage space

Capacity display only
Storage capacity of data card

Display of the storage capacity of the data card in bytes.
Label display only
Title of data card

Display of the card title entered during formatting.
File 8 characters;
File name
In copying a file from the working memory to the data card, the
extension .mth (methods), .dtm (determinations), .smp (sample
data) or .aut (rack data) is appended automatically, depending on
the type of file copied. The first 8-character part of the file name can
be changed, however the extension must be retained as it character-
izes the type of file.
Secured files (*) must first be unsecured with <Unsecure> before their
name can be changed.
For the file name all characters are allowed with the exception of the
character ".".
Content information for file

In copying a method from the working memory to the data card, the
method title Title entered on the "OP.SEQUENCE" page is entered
in this column.
nation list, the three parameters Sample table, S1 and Method call
are entered automatically if they were available on the "MONITORING"
or "SAMPLES" page at the time of recording.
This 50-character content information can be changed at will and is
retained in direct copying to the data card or the RS interfaces.
However, if the file is loaded in the working memory and then copied
from there to another destination, this content information will be lost.
Secured files (*) must first be unsecured with <Unsecure> before their
title can be changed.
Size display only
Memory size
Display of the memory requirements of the file in bytes.

5.4.4 SAMPLES
5.4.4 SAMPLES
T This dialog page is used for the entry of sample-specific data for
maximum 160 samples. These data are transferred automatically
SAMPLES line-by-line to the sample data line on the "MONITORING" page
and used for the next determination if Auto.samples = on has
been set. The entire sample data table can be stored on the data
card or a PC and also reloaded from these sources.
Name: .........smp SAMPLES Autoincrement: .

Line: XXX XXX of 160 Balance input: ...

.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
.... ............ ............ ............ ............ ..............
Modify Modify Delete Insert Copy Check Rename >>
column line line line prev. samples table
Print Copy to Copy to Copy fr. Change Balance >>

all Data Cd. RS Ifc.1 RS Ifc.1 Autoinc. on / off
Softkeys Meaning

column

line
Delete Delete line

line
Insert Insert empty line

line
A blank line is inserted above the line selected with the field cursor.

5.4 Storages
Softkeys Meaning
Copy Copy previous line

prev.
The contents of the preceding line are copied into the line selected
with the field cursor (any existing entries will be overwritten).
The number in the Pos. field is incremented automatically by the
value defined in the parameter Autoincrement.
Check Check sample data

samples
The sample data entered in the table are checked. Any errors will be
displayed.
Rename Change name of sample data table

table
Possibility to change the name of the sample data table (see pa-
rameter Name).
Print Print list of all samples

all
The "SAMPLES" page is printed with all sample data entries.
Copy to Copy sample data to data card

Data Cd.
The sample data entered on this page are copied to the data card; the
file name entered under Name is automatically assigned the extension
.smp.
To reload a sample data file stored on the data card in this manner, it
must be copied to the working memory on the "DATA CARD" page
using the softkeys <Copy to> <Working storage>.
Copy to Copy sample data to RS interface 1

RS Ifc.1
The sample data entered on this page are copied to RS232 interface
1, i.e. to the PC connected to it; the file name entered under Name is
automatically assigned the extension .smp.
Copy fr. Copy sample data from RS interface 1 to working memory

RS Ifc.1
The sample data are copied from RS232 interface 1, i.e. from the PC
connected to it to the sample data table on this page; existing data
will be overwritten.
Change Change increment for automatic numbering

Autoinc.
Possibility to change the increment for the automatic numbering in the
Pos. column (see parameter Autoincrement).
Balance Switch data input from balance on/off

on / off
On/off switching of the automatic data input from a balance attached
to RS232 interface 2. Whether the data receipt is switched on or off is
shown by the Balance input parameter.
For the attachment of balances, see section 3.12.3.

5.4.4 SAMPLES

Name 8 characters;
Name of sample data table

Name of the sample data table which is used as file name together
with the automatic extension .smp in storage of the sample data on
the data card or RS interface. The softkey <Rename table> must be
pressed to change the name.
For the name of the sample table all characters are allowed with the
exception of the character ".".
Line display only
Line number
Number of the sample data line on which the field cursor is posi-
tioned.
Autoincrement 1,2; 1
Increment for automatic position numbering

Increment for the automatic numbering of the Pos. column during
filling in of the sample data table (effective if a position number is
entered in the previous line):
1 continuous increase in the position number by +1
2 continuous increase in the position number by +2
(useful if an auxiliary vessel AUX is used after every
sample vessel FEED on the Autosampler).
The parameter Autoincrement is changed with <Change Autoinc.>.
Balance input on, off; off
Data receipt from balance

The data receipt from a balance attached to RS232 interface 2 can be
switched on or off using the softkey <Balance on/off>. When the data
receipt is switched on, the data sent by the balance are written into
the next blank line.
For the attachment of balances, see section 3.12.3.
Pos. 1...160;
Position number
Position number on the sample rack of the 695 Autosampler (without
695 Autosampler this column has no meaning, however it can be
used for simple sample numbering).
The following rules apply to the position numbering:
All instructions concerning the sample vessel (FEED) (e.g.
SMPL/F, CSOLN/F, F>M, DOS>F, etc.) are referred to the vessel at
the rack position Pos. defined by the position number.
All instructions concerning the auxiliary vessel (AUX) (e.g. F>A,
DOS>A, etc.) are referred to the vessel which immediately follows
the sample vessel defined by the position number (rack position
Pos. + 1).
The sequence of the positions can be freely selected for sample
solutions, but the same position number can be entered only
once.

5.4 Storages
With calibration solutions, all solutions must be entered in imme-

diate succession, however, the position numbers themselves can
be selected at random.
With the UV sample racks, the position numbers on the sample
holders are defined as follows:
6.2041.100 Sample Rack: Sample holder left 1...12
Sample holder right 13...24
Ident.1/S1 12 characters;
Sample identification 1 / Variable S1

This column can be used for optional entry of either the alphanumeric
sample identification 1 or the numeric variable S1. The following rules
hold for the entry:
If the first character is not a number, the entire entry is interpreted
as alphanumeric sample identification 1 (e.g. Sample 456, B-56-
234-199).
If the first character is a number or a period (point), the entire
entry is interpreted as numeric variable S1 (e.g. 125.849, 4.629e-
08). Subsequent entry of letters or special characters is no longer
possible. If you wish to enter a sample identification starting with
a number, you must thus precede the number by a non-numeric
character (e.g. #).
The sample-specific variable S1 can be used in formulae (see section
5.6.4).

sample identification 2 or the numeric variable S2. The same rules as
for Ident.1/S1 apply to the entry.
If the sample size Sample size/S0 is entered as a weight, S2 must
be entered as a density in g/mL (without manual entry the default
value 1.0000 is automatically entered).
5.6.4). If S2 has been entered as a density in g/mL, this numeric value
must be multiplied by the factor 1000 in formula calculations as all
other variables are based on the base units g or L.

5.6.4).

5.4.4 SAMPLES

Method.call 11 characters;
Method call
For automatic call-up of a method, method name, stand number and
program run mode can be entered here. The entry must have the
following format:
xxxxxxxx.SR xxxxxxxx = Method name
S = Stand address (1...3)
R = Run mode (C,D,T)
(Calibration/Determination/
Test)
With this entry, all methods loaded in the method memory are dis-
played in the softkeys and can thus be taken over directly.
XXXXXXXX Method name XXXXXXXX is copied to the field Method.call.
--------
Without entry of a stand number, the VA Stand set in the parameter
Stand address on the "MONITORING" page is used as default.
Without entry of the run mode, the program run mode set in the
parameter Run mode on the "MONITORING" page is used as default.
The automatic method call functions only when the specified method
is present in the working memory.
Sample size/S0 1.0...9999.9 uL...L / ug...kg; - L
Sample size
Entry of the sample size (variable S0) in this column as either a volume
or weight is mandatory, otherwise the determination can not be
started (error message Missing sample). Entry of an asterisk * is also
possible, but only
if no concentrations or dispensed volumes based on S0 need be
calculated, or
if the instruction SMPL/F is used with the 695 Autosampler with
subsequent solution transfer to the auxiliary or measuring vessel,
or
if the instruction CSOLN>M or CSOLN/F for calibration solutions is
used with the 695 Autosampler.
The use of S0 depends on whether work is performed with undiluted
or diluted samples:
Undiluted sample, entry as volume
The entered sample size S0 (in L, mL or L) is used as addition
volume for the SMPL instructions. The substance content in g/L is
identical to the calculated mass concentration s (Mass. conc.,
see section 5.5.2).
Undiluted sample, entry as weight
If the sample size is entered as a weight, the density must be
entered under S2 in g/mL (with no entry, S2 = 1.000 is set
automatically). For calculation of the addition volume for the
SMPL instructions, the entered sample size S0 in g is divided by
the density S2*1000 in g/L. To obtain the substance content in
g/g, the calculated mass concentration s (Mass. conc., see sec-
tion 5.5.2) is divided by S2*1000 (see section 5.6.4).

5.4 Storages
Diluted sample, entry as volume or weight

The volume fraction V.fraction entered in the SMPL instruction
is used as addition volume for the SMPL instructions irrespective
of S0. To obtain the substance content in g/L or g/g for the origi-
nal sample size S0, the calculated mass concentration s (Mass.
conc., see section 5.5.2) is multiplied by the factor V.total/S0
(see section 5.6.4).
The following is an overview of the various possibilities for the entry of
S0 and the parameters of the SMPL instructions:
S0 S2 V.fraction V.total Vol. for SMPL Formula for Result

instruction final result unit
L S0 MC:<subst> g/L
g d S0/S2 MC:<subst>/ g/g
(S2*1000)
L V.fraction V.total V.fraction MC:<subst>* g/L

(V.total/S0)
g V.fraction V.total V.fraction MC:<subst>* g/g

(V.total/S0)
The following should be noted in connection with the sample quantity

S0:
The terms "undiluted sample" and "diluted sample" in the pre-

ceding section refer only to dilutions during the sample prepara-
tion which have not been defined on the "OP.SEQUENCE" or
"SEGMENT" page.
Dilutions initiated during the program by DOS or transfer instruc-
tions (e.g. addition of auxiliary solutions or pipetting operations
on the Autosampler) are automatically taken into consideration in
the volume bookkeeping (see section 6.9.2). Irrespective of these
dilutions, the calculated mass concentration s of the investigated
substance always refers to the addition volume defined for the
SMPL instruction (that is, depending on the entry, to S0,
S0/(S2*1000) or V.fraction).
The effective mass concentration eff,s of the investigated sub-
stance in the measuring vessel, referred to the total solution vol-
ume Veff which it contains at the start of the first measurement, is
reported only in the graphical representation of the calibration
curve.
The amount of the original addition volume of the SMPL instruc-
tion which is actually present in the measuring vessel at the start
of the measurement is shown in the parameter V0.sample on the
"RESULTS" dialog page (see section 5.5.2). This page also
shows the Mass of the investigated substance found in the
measuring vessel as well as its mass concentration Mass conc..
The following relation holds:
Mass conc. = Mass / V0.sample

5.4.4 SAMPLES
The following numeric examples are intended to clarify these points:
Example S0 Program Veff V0.sample Mass Mass.conc. eff,s

1 10 mL SMPL>M (10 mL) 10 mL 10 mL 1 g 100 g/L 100 g/L
2 10 mL SMPL>M (10 mL) 20 mL 10 mL 1 g 100 g/L 50 g/L

DOS>M 10 mL
3 10 mL SMPL/F (10 mL) 10 mL 5 mL 0.5 g 100 g/L 50 g/L

DOS>F 10 mL
F>M 10 mL
4 10 mL SMPL/F (10 mL) 20 mL 5 mL 0.5 g 100 g/L 25 g/L

DOS>F 10 mL
F>M 10 mL
DOS>M 10 mL
Example 1: undiluted sample

Example 2: dilution in the measuring vessel
Example 3: dilution of the sample on the Autosampler,
transfer of half to measuring vessel
Example 4: as Example 3, followed by dilution in the meas-
uring vessel
Sample 10 mL, concentration 100 g/L (for all examples)
Veff Volume in the measuring vessel at start of
measurement (first sweep)
V0.sample Sample volume in the measuring vessel
Mass Substance mass found in the measuring vessel
Mass conc. Calculated mass concentration s of the sub-
stance for the sample
eff,s Effective mass concentration of the substance in
the measuring vessel (displayed on calibration
curve)

5.4 Storages
5.4.5 COMMON VARIABLES
G This dialog page is used for the entry of variables common to

COMMON different methods (so-called common variables). The page is
VARIABLES divided into two sections, each with 18 lines:
Resid.com.var Instrument-resident common variables
The common variables in this section remain
permanently stored. If need be, they can be
loaded in the working memory with <Load all>
or copied from the working memory with
<Save all>.
Workg.com.var Common variables in working memory

This are common variables applicable to a
determination and can be used for formulae.
Both the reading in of existing common vari-
ables and the writing of new ones is possible
On loading a determination stored in the
determination memory or on the data card
into the working memory, this area is auto-
matically overwritten with the common vari-
ables current at the time of recording. To re-
tain the common variables in force before the
determination was loaded, these must first be
stored with <Save all> in the area of the in-
strument-resident common variables.
Before using a method in which common variables are employed
on the "CALCULATIONS" page, ensure that these common
variables are loaded in the right half of this page under
Workg.com.var.
COMMON VARIABLES
max. 18
C# Resid.com.var Remark C# Workg.com.var Remark

01 ............. ................ 01 ............. ................
02 ............. ................ 02 ............. ................
03 ............. ................ 03 ............. ................
04 ............. ................ 04 ............. ................
05 ............. ................ 05 ............. ................
06 ............. ................ 06 ............. ................
07 ............. ................ 07 ............. ................
08 ............. ................ 08 ............. ................
09 ............. ................ 09 ............. ................
10 ............. ................ 10 ............. ................
11 ............. ................ 11 ............. ................
12 ............. ................ 12 ............. ................
13 ............. ................ 13 ............. ................
14 ............. ................ 14 ............. ................
15 ............. ................ 15 ............. ................
16 ............. ................ 16 ............. ................
17 ............. ................ 17 ............. ................
18 ............. ................ 18 ............. ................
Modify Modify Delete Load all Save all Delete Delete

column line line ---> <--- Resid.CV Workg.CV

5.4.5 COMMON VARIABLES
Softkeys Meaning

column

line
Delete Delete line

line
The line selected with the field cursor is deleted. The two fields
Resid.com.var and Remark or Workg.com.var and Remark are
considered as lines here.
Load all Load common variables into working memory

--->
The common variables permanently stored in the instrument are
loaded into the working memory where they can be used for formulae.
Save all Save common variables from the working memory

<---
The common variables loaded in the working memory are perma-
nently stored in the instrument as Resid.com.var. This is particularly
advisable before loading an old determination as this area is then
overwritten with the common variables valid for this determination.
Delete Delete all instrument-resident common variables

Resid.CV
Delete Delete all common variables in working memory

Workg.CV

Resid.com.var -3.7e+33...-1.7e-33, 1.7e-33...3.7e+33;
Instrument-resident common variables C01...C18

Numeric variables common to different methods permanently stored
in the instrument.
Comment on common variable

Workg.com.var -3.7e+33...-1.7e-33, 1.7e-33...3.7e+33;
Common variables C01...C18 in working memory

Numeric variables common to different methods stored in the working
memory.
Comment on common variable


5.5 Operation
5.5 Operation
The keypad contains 3 yellow dialog pages under the title "OPERATION" for selec-
tion of the operation monitoring, the display of the current results and the display
and interactive processing of the curves of the determination loaded in the working
memory.
OPERATION
U
MONI-
TORING
RESULTS
CURVES

5.5.1 MONITORING
5.5.1 MONITORING
U This dialog page is used to monitor the operation and for entry of
MONI- various parameters of general validity for subsequent determina-
TORING tions. It shows the method, determination and sample data
currently loaded in the working memory and the current instru-
ment status. Further, following the start of a measurement, the
current program data and measured values are shown in a
window.
Method: XXXXXXXX MONITORING * BUSY *

Title : XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX
Remark 1 ............................................................
Remark 2 ............................................................
Run mode .............. Run XXX

User name .............. Stand address ...
Auto.samples ..... XXX of 160 Determination XXXXXXXX.dtm

Auto.batch ..... XXX of ... xxxx-xx-xx xx:xx:xx
Start interval .....h Modified xxxx-xx-xx xx:xx:xx
Det.storage ..... XXXXX % free Sample table XXXXXXXX

... ............ ............ ............ ............ ..............
... ............ ............ ............ ............ ..............
Segment: XXXXXXXX XX XXXXXXXXXXXXX XXXX s U = XXXXX V

VR: XX I = XXXXXXXXX A

Softkeys Meaning

column

line
Recalc. Start recalculation

If experimental data or method parameters which affect the evaluation
are subsequently changed for a loaded determination, these changes
do not become effective until a recalculation has been performed.
There are four different possibilities for a recalculation (see below
Table):
from Recalculation using original experimental data (original). The deter-
original
mination is reevaluated using the originally recorded experimental
data and the modified method parameters.

5.5 Operation
Softkeys Meaning
from Recalculation using manually modified experimental data (processed).

proc.
The determination is reevaluated with the aid of the experimental data
modified by spike elimination and the modified method parameters.
from New content and formula calculation using evaluation values of

eval.
substances (EV values).
from Op. New content and formula calculation with modified method parame-
sequence
ters referring to sample quantity, dispensed volumes or concentra-
tions of solutions.
The following should be noted with regard to the different types of
recalculation:
A recalculation from orig. or from proc. must always be
initiated if method parameters have been modified which affect
the determination of the EV values (e.g. Recognition, Baseline,
Evaluation).
A recalculation from Op.sequence must always be initiated when
the dilution calculation should be redone owing to modified
method parameters.
A recalculation from eval. is advisable if only certain EV values
have been suspended or formulae changed.
Storage of recalculated determinations

Recalculated determinations are not stored automatically. To store a
recalculated determination with its modified method, it must be copied
to the determination storage or to the data card.
Dilution recalculation with Dosimats/Dosinos
Before starting a recalculation from Op.sequence with modified pa-
rameters affecting the dispensing operations with 685 Dosimats/700
Dosinos make sure that the same Dosimats/Dosinos with the same
Exchange/Dosing units are attached to the 746 VA Trace Analyzer as in
the original determination, otherwise deviations in the result calculation
could arise.
Recalculation of determinations from older software versions
Because of a modified smoothing procedure the recalculation of
determinations from the 693 VA Processor with a program version
5.693.0021 may lead to peak evaluation values which differ by 5%.
Data processing Determi- Recalculation

nation from from from from
orig. proc. eval. Op.seq.
1. Data acquisition original l
2. Spike elimination processed l l
3. Smoothing smoothed l l l
4. Recognition l l l
5. Baseline calculation subtracted l l l
6. Height/area calculation EV values l l l
7. Dilution calculation l l
8. Calibration MC values l l l l l
9. Formula calculation final results l l l l l

5.5.1 MONITORING
Softkeys Meaning
Check Method test

method
The method loaded in the working memory is tested:
If no error is found, the message no errors found appears in
the system window.
If errors are found, the appropriate error messages are displayed
in the error window (see list of error messages in section 7.3.2).
System Display of system window

window
SYSTEM WINDOW

<Esc>: continue

The last 4 lines of the system window are displayed. The system
window successively stores all system messages (warnings, confir-
mations, etc.) which appear during determinations or in work with the
746 VA Trace Analyzer.
To display the entire system window, the following softkey is used:
Zoom Display of the entire system window (18 lines)
Error Display of error window

window
ERROR WINDOW

<Esc>: continue

The last 4 lines of the error window are displayed. The error window
successively stores all error messages which appear during determi-
nations or in work with the 746 VA Trace Analyzer. The error messages
contain the date and time of occurrence of the error.
To display the entire error window, the following softkey is used:
Zoom Display of the entire error window (18 lines)
Live Display of live curve

display
Pressing this softkey during an ongoing determination switches to the
display of the live curve. The measured current (y axis) is shown
continuously as a function of the voltage (x axis) for each segment.
For representation of the live curve, the plot parameters of the seg-
ment are used (see section 5.6.2). In the default setting I.scale =
auto, the current axis is automatically adjusted, with I.scale = fixed
the specified limits for the current axis are used.
The current experimental data are shown below the curve (for details,
see measurement window).
For segments with the measurement mode CYCMODE or PSAMODE,

the live curve can not be displayed for technical reasons.

5.5 Operation
Measurement window
During an ongoing measurement, the measurement window is shown with the following
current data:
Segment: XXXXXXXX XX XXXXXXXXXXXXX XXXX s U = XXXXX V

VR: XX I = XXXXXXXXX A
Segment name Program line with line Measured values,

Variation (V) number, program voltage (U) and
Replication (R) instruction and line time current (I)
Status Meaning
* READY * Ready
The instrument is in the standby mode, all dialog pages can be
selected. A new measurement or measurement series (with
Auto.batch = on) must be started with the <START> key.
* BUSY * Program running

The program loaded in the working memory that has been started with
the <START> key or automatically (with Auto.batch = on) is running.
In this instrument mode, the following limitations apply to the screen
dialog:
The two dialog pages "STAND" and "CURVES" can not be se-
lected.
st
The entry of sample data in the 1 input line of the
"MONITORING" page is not possible (see section 5.5.1). With
programs for the 695 Autosampler with preparation cycles, this
nd
also applies to the 2 input line.
Changes to the program loaded in the working memory
("OP.SEQUENCE" or "SEGMENTS") or to any parameters on the
other dialog pages are immediately effective for the current de-
termination. However, care should be exercised when making
such changes as uncontrolled program status conditions could
easily be produced.
During the measurement, either the measurement window (see
above) or, after switching with the softkey <Live display>, the current
experimental curve is shown.
In the instrument status * BUSY *, the following main function keys
are active (for details, see section 5.1.4):
<BREAK> Active program aborted immediately
<DELAY STOP> Sample series stopped on completion of the
ongoing determination
<ABBREV> Abbreviation of the current instruction
Exception: SWEEP instructions can not be
abbreviated with the <ABBREV> key. How-
ever, it is possible to change the SWEEP
parameter U.end at any time.
<HOLD> The program is interrupted

5.5.1 MONITORING
Status Meaning
* BUSY (BREAK) * Program stopped

The active program has been stopped with the <BREAK> key, but
some functions with the 685 Dosimats, 700 Dosinos or 695 Autosam-
pler must be carried out completely before the program is aborted
definitively.
* BUSY (HOLD) * Hold program

The active program has been interrupted with the <HOLD> key. In
the instrument status * BUSY (HOLD) * , the following main function
keys are active (for details, see section 5.1.4):
<(CONT)> Continue interrupted program
<(STEP)> Jump to next instruction
* BUSY (DSTOP) * Program running, the sample series will be stopped on

completion of the current determination
With an ongoing sample series (Auto.batch = on), the <DELAY
STOP> key has been pressed. The current determination will be run
to completion and the sample series then stopped.
In the instrument status * BUSY (DSTOP) *, the following main func-
tion keys are active (for details, see section 5.1.4):
<ABBREV> Abbreviation of current instruction
<HOLD> The program still running is interrupted.
The delayed program stop is deactivated and
* BUSY (HOLD) * appears instead of the display
* BUSY (DSTOP) * (see above). To achieve a
delayed program stop again, the <DELAY
STOP> key must be pressed once more.

Method display only
Method name
Name of the method loaded in the working memory.
The method name can be changed on the "OP.SEQUENCE" page
The method name of stored methods can also be changed later on
the "METHODS" or "DATA CARD" page (see chapters 5.4.1 and 5.4.3).
Title display only
Method title
Title of the method loaded in the working memory.
The method title can be changed on the "OP.SEQUENCE" page (see
section 5.6.1).
The method title of stored methods can also be changed later on the
"METHODS" or "DATA CARD" page (see chapters 5.4.1 and 5.4.3).

5.5 Operation

Remark 1 60 characters;
Remark 1 regarding method

Comment 1 entered here is part of the loaded method and will be put
out with all result reports together with the method name and title.
When a method is copied from the working memory, the remark will
be stored with the method. If a new method is loaded (with or without
determination), this parameter will be overwritten.
Remark 2 60 characters;
Remark 2 regarding method

Comment 2 entered here is part of the loaded method and will be put
out with all result reports together with the method name and title.
When a method is copied from the working memory, the remark will
be stored with the method. If a new method is loaded (with or without
determination), this parameter will be overwritten.
Run mode determination, calibration, test; determination
Mode for program execution

The following three modes exist for running programs:
determination Determination
Normal mode for all determinations with stan-
dard addition, calibration curve and internal
standard. Commands marked by C, calibration
loops and CSOLN instructions are ignored.
calibration Calibration
Mode for recording calibration curves. Com-
mands marked by D and SMPL instructions are
ignored. With Auto.batch = on, an unsecured
method with the same name in the method
memory is automatically overwritten and the
current calibration data stored.
test Test
Mode for program test run. All replications and
dispensing operations are suppressed.
For subsequent measurements the set mode remains in force until it
is changed manually or by automatic method call-up with specifica-
tion of the run mode (C, D, T).
When a stored determination is loaded in the working memory, the

mode originally selected for this determination is set automatically.
User name 14 characters;
User name
The user name is put out with all result records and curve printouts.

5.5.1 MONITORING

Run display only
Run number
This counter is incremented by one on completion of every determi-
nation.
The run number is reset when the instrument is switched on and on
reset to 0.
The run number is put out with all result reports and curve printouts.
Stand address 1, 2, 3; 1
Stand address
Address number of the 747 VA Stand set using rotary switch 35 (see
section 3.3.1).
Maximum three 747 VA Stands can be attached to the 746 VA Trace
Analyzer, but only one can be active at the same time. The parameter
Stand address is used to switch between the different stands.
For subsequent measurements, the set stand address remains in

force until it is changed by manual entry or by automatic method call-
up with specification of the stand address (1, 2, 3).
Auto.samples on, off; off
Automatic transfer of sample data

The automatic transfer of the samples entered on the "SAMPLES"
page can be switched on or off here.
on On start of a determination, the data in the top line on
st
the "SAMPLES" page are transferred to the 1 sample
data line on the "MONITORING" page and used for the
determination.
off On start of a determination, the current data in the
sample data lines on the "MONITORING" page are
used.
XXX of 160 In addition to the input field, the number of remaining sample data
lines on the "SAMPLES" page is displayed (max. 160).
Auto.batch off, on, reset; off
Automatic series determination

The automatic processing of sample series for the specified number
of samples (see below) can be switched on or off here.
on On start of the first determination with <START>, fur-
ther determinations are performed automatically and
the sample counter incremented by 1 each time until
the specified number of samples has been reached (or
until a stop using the <BREAK> or <DELAY STOP>
keys if * is set).
The type of transfer of sample data depends on the
setting of the parameter Auto.samples (see also 1st
sample data line).

5.5 Operation

Auto.samples = on
At the start of every determination, the data in the top
st
line on the "SAMPLES" page are transferred to the 1
sample data line on the "MONITORING" page and
used for the determination.
With methods for the 695 Autosampler with preparation
blocks (PREP...PREP), the sample data of the sample
in question are already transferred during the prepara-
nd
tion time to the 2 sample data line on the
"MONITORING" page. On completion of the preceding
st
determination, these data are transferred to the 1
sample data line.
Auto.samples = off
The data of the two sample data lines on the "MONI-
TORING" page are used for every determination. If
nd
data have been entered in the 2 sample data line,
st
these are transferred to the 1 line for the next deter-
st
mination; if the second line is blank, the data in the 1
line are retained.
The 695 Autosampler processes the samples in se-
quence. If a position number is entered in the sample
data line, a start is made at this rack position (with no
st
entry, start at 1 position). If A-instructions (e.g. F>A)
nd
are used in the program, every 2 position is defined
as a sample vessel. During the series determination,
the position number of the current sample is shown in
st
the parameter Pos. on the 1 sample data line.
In work with Auto.batch = on, the volume book-

keeping is not automatically reset to 0 on completion of
the program. If this is desired, the instruction RINSE
must be inserted before the end of the program.
off The automatic processing of sample series is switched

off, when the <START> key is pressed only a single
determination is performed. The data of the two sam-
ple data lines on the "MONITORING" page are used. If
nd
data have been entered in the 2 line, these are
st
transferred to the 1 line for the next determination; if
st
the second line is blank, the data in the 1 line are re-
tained. If this is also blank, the error message Missing
sample appears.
reset The sample counter is reset to 0.
Auto.batch XXX 1...160, *; *

of ...
Number of samples for series determination
Number of samples which should be determined automatically.
The entry of * means "infinite", i.e. the automatic series determination
is performed until it is stopped by pressing <BREAK> or <DELAY
STOP>.

5.5.1 MONITORING

Start interval 0.0...99.9 h; 0.0 h
Time interval for automatic determination start

This parameter enables the automatic start of determinations at
regular time intervals for automatic series determinations with
Auto.batch = on (e.g. for online analysis).
The time interval set must be > the time needed for the whole deter-
mination, otherwise the next determination is started immediately.
Det.storage on, off; off
Automatic storage of determinations

The automatic storage of determinations in the determination memory
"DETERMINATIONS" can be switched on or off here.
on The determinations are automatically transferred to the
determination memory. If the memory is full, the pro-
cedure depends on the setting of the parameter Full
condition whereby either the oldest determinations
are deleted (Full condition = push out) or the de-
termination series is stopped (Full condition = stop,
see section 5.4.2).
off The determination data are not stored.
Determination display only
Loaded determination
Name of the determination currently loaded in the working memory or
currently running. A name is given to each determination when it is
recorded and comprises the current time on method start and the
extension.dtm:
MMDDhhmm.dtm MM = month hh = hour
DD = day mm = minutes
The first, 8-digit part of the name can be modified on these dialog
pages after copying to the determination memory or the data card,
but the extension .dtm must be retained as it characterizes the
determination files.
xxxx-xx-xx Below the determination name, the exact time when the determination
xx:xx:xx was started is displayed.
Modified display only
Subsequent modification
Date and time when the determination loaded in the working memory
was subsequently modified for the first time (later modifications are
not displayed). The modification date is set only in the case of modifi-
cations on the following dialog pages:
COMMON VARIABLES Changes to Workg.com.var and the
associated Remarks
OP.SEQUENCE All changes
SEGMENTS All changes
st
MONITORING Modification of the parameters in the 1
sample data line, recalculation with soft-
key <Recalc. from Op.Sequence>).

5.5 Operation

The display of no means that the determination has not been
changed.
Once a determination has been modified, it can no longer be forced to

the unmodified condition no. If you wish to keep the determination in
the unmodified condition, it must be stored in the "DETERMINATIONS"
memory or on the "DATA CARD" before the change.
Sample table display only
Name of the sample data table

Name of the sample data table from which the sample data of the
determination loaded in the working memory have been automatically
fetched (Auto.samples = on).
The display of means that the sample data have not been fetched
from a sample data table (Auto.samples = off).
1st sample data Input possibilities, see under the individual parameters
line
Sample data of current sample
Display of the current sample data. The layout of this line is identical
to that of the lines on the "SAMPLES" page (see section 5.4.4). The
meaning of the displayed data and the input possibilities depend on
the instrument status:
In the standby mode * READY *, data specific to the sample can
be entered here and can be used for the next determination in
certain cases (see Table).
During an ongoing determination (* BUSY * status), the data of
the current sample are displayed and can not be modified at this
time.
What happens to the sample data entered in this line when <START>
nd
is pressed depends on possible entries in the 2 sample data line as
well as on the setting of the two parameters Auto.samples and
Auto.batch:
st nd
1 line 2 line Auto.samples Auto.batch Determination
filled blank off off Single determination with

st
sample data of the 1 line
filled or filled off off Single determination with
nd
blank sample data of the 2 line
filled blank off on Series determination with
st
sample data of the 1 line
filled or filled off on Series determination with
nd
blank sample data of the 2 line
filled or filled or on off Single determination with
blank blank automatic sample data
transfer from "SAMPLES"
filled or filled or on on Series determination with
blank blank automatic sample data
transfer from "SAMPLES"

5.5.1 MONITORING

st
In summary, the data entered in the 1 sample data line are used only
for the next determination
if the automatic sample data transfer is switched off
(Auto.samples = off), and
nd
if no sample data are entered in the 2 line.
2nd sample data Input possibilities, see under the individual parameters
line
Sample data of sample being prepared
The layout of this line is identical to that of the lines on the "SAMPLES"
page (see section 5.4.4). The meaning of the displayed data and the
input possibilities depend on various factors:
With methods without sample preparation cycles, here both in the
standby mode * READY * and during an ongoing determination
(* BUSY * status) data specific to samples can be entered and
used for the next determination (see Table) when the automatic
sample data transfer (Auto.samples = off) is switched off.
In the case of methods with sample preparation cycles (possible
only with 695 Autosampler and Auto.batch = on), here the data
of the sample being prepared are shown and can not be
changed.
Pos. 1...160;
Position number
Position number on the sample rack of the 695 Autosampler (without
695 Autosampler this column has no meaning, however it can be
used for simple sample numbering).
The following rules apply to the position numbering:
All instructions concerning the sample vessel (FEED) (e.g.
SMPL/F, CSOLN/F, F>M, DOS>F, etc.) are referred to the vessel at
the rack position Pos. defined by the position number.
All instructions concerning the auxiliary vessel (AUX) (e.g. F>A,
DOS>A, etc.) are referred to the vessel which immediately follows
the sample vessel defined by the position number (rack position
Pos. + 1).
The sequence of the positions can be freely selected for sample
solutions, but the same position number can only be entered
once.
With calibration solutions, all solutions must be entered in imme-
diate succession, however, the position numbers themselves can
be selected at random.
During series determinations without automatic transfer of sample
data Auto.samples = off, the position number of the current
st
sample is shown on the 1 sample data line in the parameter
Pos..
With the UV sample racks, the position numbers on the sample
holders are defined as follows:

5.5 Operation


sample identification 1 or the numeric variable S1. The following rules
hold for the entry:
If the first character is not a number, the entire entry is interpreted
as alphanumeric sample identification 1 (e.g. Sample 456, B-56-
234-199).
If the first character is a number or a period (point), the entire
entry is interpreted as numeric variable S1 (e.g. 125.849, 4.629e-
08). Subsequent entry of letters or special characters is no longer
possible. If you wish to enter a sample identification starting with
a number, you must thus precede the number by a non-numeric
character (e.g. #).
5.6.4).

If the sample size Sample size/S0 is entered as a weight, S2 must
be entered as a density in g/mL (without manual entry the default
value 1.000 is automatically entered).
5.6.4). If S2 has been entered as a density in g/mL, this numeric value
must be multiplied by the factor 1000 in formula calculations as all
other variables are based on the base units g or L.

5.6.4).
Method.call 11 characters;
Method call
For automatic call-up of a method, method name, stand number and
program run mode can be entered here. The entry must have the
following format:
xxxxxxxx.SR xxxxxxxx = Method name
S = Stand address (1...3)
R = Run mode (C,D,T)
(Calibration/Determination/
Test)
With this entry, all methods loaded in the method memory are dis-
played in the softkeys and can thus be taken over directly.

5.5.1 MONITORING
XXXXXXXX Method name XXXXXXXX is copied to the field Method.call.

--------
Without entry of a stand number, the VA Stand set in the parameter
Stand address on the "MONITORING" page is used as default.
Without entry of the run mode, the program run mode set in the
parameter Run mode on the "MONITORING" page is used as default.
The automatic method call functions only when the specified method
is present in the working memory.
Sample size/S0 1.0...9999.9 uL...L / ug...kg; - L
Sample size
Entry of the sample size (variable S0) in this column as either a volume
or weight is mandatory, otherwise the determination can not be
started (error message Missing sample). Entry of an asterisk * is also
possible, but only
if no concentrations or dispensed volumes based on S0 need be
calculated, or
if the instruction SMPL/F is used with the 695 Autosampler with
subsequent solution transfer to the auxiliary or measuring vessel,
or
if the instruction CSOLN>M or CSOLN/F for calibration solutions is
used with the 695 Autosampler.
You will find a detailed description of the Sample size/S0 parameter
in section 5.4.4 "SAMPLES".

5.5 Operation
5.5.2 RESULTS
J This dialog page allows the three following subpages to be

selected which display the results of the determination loaded in
RESULTS the working memory.
"Calculations" Final results with formula calculation
"Evaluations" Detailed overview of substance and peak/wave
evaluations. In the instrument mode * BUSY *
the displayed results are continuously updated.
"Calibrations" Results of the substance calibrations
Changes to the method which affect the evaluation and result calcula-
tion do not become effective until a recalculation of the loaded deter-
mination, which must be started on the "MONITORING" page with
<Recalc.> (see section 5.5.1), has been performed.
Method : XXXXXXXX RESULTS

5 Determ.: XXXXXXXX Calculations

XXXXXXXXXXXX = XXXXXXXXXX XXXXXXXX XXXXXXXXXX XXXXX XXXXXXXXXXXXXXXXXX
>> >>
Eval. Calibr.
6 7
Softkeys Meaning
>> Evaluations
Eval.
Switching to the subpage "Evaluations" with an overview of all sub-
stance and peak/wave evaluations.
6
>> Calibrations
Calibr.
Switching to the subpage "Calibrations" with the results of the sub-
stance calibrations.
7

5.5.2 RESULTS

Method display only
Method name
Name of the method loaded in the working memory (file name without
extension .mth).
Determ. display only
Determination name
Name of the determination loaded in the working memory (file name
without extension .dtm).
Final results display only
Final results
Calculated results for the calculation formulae defined on the
"CALCULATION" dialog page (see section 5.6.4).
Quantity = formula value * Res.unit
Res.dev. display only
Result deviation
Deviation in the final results calculated using the error propagation
rules (see section 6.10).
If the quantity MC:<subst> is used in the calculation formula, the result
deviation Res.dev. is used to determine the range Result
Res.dev. in which a final result may be expected with a probability of
68.3%.
The absolute error (in the same unit as the final result) and the relative
error (in %) are displayed.
Comments display only
Comments
Display of comments if any type of error or difficulties appeared in the
evaluation.
The following comments are possible:
see Evaluations The "RESULTS/Evaluation" page contains com-
ments on single results which must be heeded.
var. not found No result, as a variable is used in the formula for
which no value is available.
div. by zero No result, as division by 0 occurs in the formula.
range violat. No result as the admissible numeric range has
been violated in the formula calculation.
Admissible range:
-3.7e+33...-1.7e-33, 0, 1.7e-33...3.7e+33

5.5 Operation

6 Determ.: XXXXXXXX Evaluations
Substance : XXXXXXXX Comments

Mass conc.: XXXXXXXX XXXX Mass : XXXXX xg
MC.dev. : XXXXXXXX XXXX (XXXX%) Add.mass : XXXXX xg XXXXXXXXXXXXXXXXXX
Cal.dev. : XXXXXXXX XXXX (XXXX%) V0.sample: XXXXX xL XXXXXXXXXXXXXXXXXX
VR U/mV I/xA I.mean Std.dev. I.delta Comments

XX. XXXXX XXXXXX XXXXXX XXXXXX XXXXXXXXXXXXXXXXXX
XX. XXXXX XXXXXX
XX. XXXXX XXXXXX XXXXXX XXXXXX XXXXXX XXXXXXXXXXXXXXXXXX
XX. XXXXX XXXXXX
XX. XXXXX XXXXXX XXXXXX XXXXXX XXXXXX XXXXXXXXXXXXXXXXXX
Select Suspend/ New >> >>

subst. activate calcul. Calcul. Calibr.
5 7
Softkeys Meaning
Select Select substance

subst.
The available substances can be selected using the softkeys carrying
the substance name and segment name:
Subst.# Selection of the substance Subst.# assigned to the segment
Segment#
Segment#.
Suspend/ Suspend/activate single measurements

activate
The single measurement VR selected with the field cursor is sus-
pended for subsequent calculations (marking !) or reactivated (no
marking).
New Recalculation
calcul.
The content and formula calculation from evaluation values of the
substances (EV values) is restarted (corresponds to the softkey
<Recalc. from eval.> on the "MONITORING" page).
>> Calculations
Calcul.
Switching to the subpage "Calculations" with an overview of the final
results.
5
>> Calibrations
Calibr.
Switching to the subpage "Calibrations" with the results of the sub-
stance calibrations.
7

5.5.2 RESULTS

Method display only
Method name
extension .mth).
Determination name
Substance display only
Substance name
Name of the selected substance. Additional substances can be
selected with the softkey <Select subst.>.
Mass conc. display only
Mass concentration s (variable MC:<subst>)

The mass concentration in the sample s for the selected substance
with numeric value and unit (g/L, mg/L, g/L, etc.) determined using
the selected calibration (see section 6.9).
The mass concentration s can be used in formulae as MC:<subst>
(<subst> = substance name) for further calculations. It should be
noted that this value is put out in such cases in the base unit g/L
without prefix (see section 5.6.4).
The mass concentration s of the substance always refers to the
addition volume V.sample defined for the SMPL instruction (in other
words, depending on the entry to S0, S0/S2 or V.fraction). The
effective mass concentration eff,s of the investigated substance in the
measuring vessel, referred to the total solution volume Veff it contains
at the start of the first measurement, is reported only in the graphical
representation of the calibration curve (cf. here the remarks on Sample
size/S0 in section 5.4.4).
This field remains empty () if no calibration technique has been

selected (Technique = none) or no result has been found.
MC.dev. display only
Total deviation for mass concentration s of the substance

(variable MD:<subst>)
Absolute total deviation of the mass concentration s of the substance
with numeric value and unit as well as, in brackets, the relative total
deviation in % (for further details, see section 6.9.3).
The total deviation of the mass concentration s of the substance can
be used in formulae as MD:<subst> (<subst> = substance name) for
further calculations. It should be noted that this value is put out in
such cases in the base unit g/L without prefix (see section 5.6.4).
The total deviation MC.dev. defines the range Mass conc. MC.dev.
in which the mass concentration s of the substance may be expected
with a probability of 68.3% (see section 6.9.3).

5.5 Operation

In evaluations with standard addition (see section 6.9.4), MC.dev. is
calculated directly from the measured values of the sample and
standard additions. In evaluations with a calibration curve (see section
6.9.5) or internal standard (see section 6.9.6), MC.dev. comprises the
deviation component of the calibration Cal.dev. and that of the
measurement Meas.dev. as follows:
MC.dev. = (Cal.dev.)2 + (Meas.dev.)2
Cal.dev. display only
Deviation due to calibration (variable ML:<subst>)

Deviation of the mass concentration s of the substance due to the
calibration (calibration curve or internal standard) (see also MC.dev.).
The absolute value with numeric value and unit together with, in
brackets, the relative value in % is shown (for further details, see
section 6.9).
The deviation of the mass concentration s of the substance due to
the calibration can be used in formulae as ML:<subst> (<subst> =
substance name) for further calculations. It should be noted that this
value is put out in such cases in the base unit g/L without prefix (see
section 5.6.4).
This field remains empty () if standard addition has been selected as
the calibration technique (Technique = std.add.) or no result has
been found.
Mass display only
Substance mass in measuring vessel (variable MS:<subst>)

Absolute mass of the selected substance in the measuring vessel with
numeric value and unit (g, mg, g, etc.) determined with the aid of the
selected calibration (std.add., cal.crv., int.std.).
The absolute mass of the substance in the measuring vessel can be
used in formulae as MS:<subst> (<subst> = substance name) for
further calculations. It should be noted that this value is put out in
such cases in the base unit g without prefix (see section 5.6.4).
The relation between Mass and Mass conc. is given by
Mass conc. = Mass / V0.sample
This field remains empty (-) if no calibration technique has been

selected (Technique = none) or no result has been found.
Add.mass display only
Standard addition mass (variable MA:<subst>)

Mass of the selected substance with numeric value and unit (g, mg,
g, etc.) added in every standard addition.
The standard addition mass can be used in formulae as MA:<subst>
(<subst> = substance name) for further calculations. It should be
noted that this value is put out in such cases in the base unit g without
prefix (see section 5.6.4).
This value can be used to asses whether the standard addition ratio
has been correctly selected (cf. remarks on std.add. in section
5.6.3).
This field remains empty () if standard addition has not been se-
lected as the calibration technique (Technique std.add.).

5.5.2 RESULTS

V0.sample display only
Sample volume in measuring vessel (variable V0)

Display of the sample volume in the measuring vessel at the start of
measurement with numeric value and unit (L, mL, L, etc.).
The sample volume in the measuring vessel can be used in formulae
as VO for further calculations. It should be noted that this value is put
out in such cases in the base unit L without prefix (see section 5.6.4).
This field remains empty () if no calibration technique has been
selected (Technique = none).
The nature of the sample volume display depends on whether
Sample size/S0 has been entered as a volume or a weight (see
section 5.4.4),
work has been performed with undiluted (V.fraction = empty)
or diluted (V.fraction not empty) samples (see section 5.4.4),
only part of the sample quantity defined by Sample size/S0 or
V.fraction has been transferred to the measuring vessel on the
695 Autosampler (dilution factor fAS).
The dependency of V0.sample on these factors is shown in the
following Table:
S0 S2 V.fraction V.total V0.sample without V0.sample with

Autosampler Autosampler
L S0 S0 * fAS
g d S0/S2 S0/S2 * fAS
L V.fraction V.total V.fraction V.fraction * fAS
g V.fraction V.total V.fraction V.fraction * fAS
You will find several numeric examples to clarify this table in the
explanation of the parameter Sample size/S0 on the "SAMPLES"
page (see section 5.4.4).
Comments
determination of the mass concentration s of the substance.
conc. out of range The mass concentration s of the substance
Mass conc. is outside the working range
Range min...Range max defined on the
"SUBSTANCES" page.
dev.estimated The total deviation MC.dev. could only be
estimated (see sections 6.9.5/6.9.6).
no cal.deviation Calculation of the calibration deviation
Cal.dev. is not possible as insufficient cali-
bration points are available (see sections
6.9.5/6.9.6).
no meas.deviation The determination of the measurement de-
viation Meas.dev. is not possible as only 1
measured point is available (see section
6.9.4).

5.5 Operation

red. fitting prec. Unsatisfactory matching of the non-linear
calibration curve.
VR. display only
Variation and replication

Per variation and replication, all single measurements are numbered
consecutively from 0...8 (std.add.) or 09 (cal.crv.):
V Variation (standard addition or parameter variation)
R Replication (repeat)
Each single measurement can be suspended or reactivated for
subsequent calculations with the softkey <Suspend/activate>.
Suspended measurements are marked by the character ! positioned
next to the VR number.
U/mV display only
Peak voltage or half-wave voltage (variable EU:<subst>:<V>)

Peak voltage U.peak determined for the single measurement in mV.
With measurements recorded with DCTMODE (SWEEP) or
AC2MODE, the half-wave voltage U/2 is shown here in mV.
The mean value of the peak voltages for all replications of a variation
can be used in formulae as EU:<subst>:<V> (<subst> = substance
name; <V> = variation) for further calculations. It should be noted that
this value is put out in such cases in the base unit V without prefix
I/xA, P/xW, display only

t/xs
Evaluation quantity
Evaluation quantity determined for single measurement with unit (A,
W, s). Depending on the selection of the measurement mode and
Quantity on the "SUBSTANCES" page, the following is shown here:
I/xA Peak current I.peak for DPMODE, SQWMODE,
AC1MODE, AC2MODE, DCTMODE (SSWEEP) with
Quantity = I.peak, or wave current I.wave for
DCTMODE (SWEEP) (in A, mA, A, nA, etc.)
P/xW Peak area P.peak for DPMODE, SQWMODE, AC1MODE,
DCTMODE (SSWEEP) with Quantity = P.peak (in W,
mW, W, nW, etc.)
t/xs Peak area t.peak for PSAMODE (in s, ms, s, etc.)
I.mean, P.mean, display only

t.mean
Mean value of evaluation quantities (variable EV:<subst>:<V>)
Mean value of the evaluation quantities of the single measurements in
replications. Depending on the selection of the measurement mode
and Quantity on the "SUBSTANCES" page, the following is shown
here:
I.mean Mean value of the peak current I.peak for DPMODE,
SQWMODE, AC1MODE, AC2MODE, DCTMODE
(SSWEEP) with Quantity = I.peak, or mean value of the
wave current I.wave for DCTMODE (SWEEP) (in the
same unit as for I)
P.mean Mean value of the peak area P.peak for DPMODE,
SQWMODE, AC1MODE, DCTMODE (SSWEEP) with
Quantity = P.peak (in the same unit as for P)

5.5.2 RESULTS

t.mean Mean value of the peak area t.peak for PSAMODE
(in the same unit as for t)
The mean value of the evaluation quantities for a variation V can be
used in formulae as EV:<subst>:<V> (<subst> = substance name;
<V> = variation) for further calculations. It should be noted that this
value is put out in such cases in the base units A, W or s without prefix
Std.dev. display only
Standard deviation of evaluation quantities

(variable ES:<subst>:<V>)
Standard deviation of the individual value of the evaluation quantities
in replications (see section 6.9.3). It is displayed in the same unit as
the mean value I.mean, P.mean or t.mean and is calculated only if
more than one evaluation quantity is available.
The mean value of standard deviations for a variation V can be used in
formulae as ES:<subst>:<V> (<subst> = substance name; <V> =
variation) for further calculations. It should be noted that this value is
put out in such cases in the base units A, W or s without prefix (see
section 5.6.4).
I.delta, display only

P.delta,
t.delta Difference in evaluation quantities in variations
(variable ED:<subst>:<V>)
Difference in the evaluation quantities (or difference in the mean
values in replications) between two successive measurements with
different variation (e.g. standard additions). Analogous to the mean
values of the evaluation quantities, depending on the selection of the
measurement mode and of Quantity on the "SUBSTANCES" page,
the following is displayed here:
I.delta Difference in the peak currents I.peak or wave currents
I.wave (in the same unit as for I).
P.delta Difference in the peak areas P.peak
(in the same unit as for P)
t.delta Difference in the peak areas t.peak
(in the same unit as for t)
The difference in the evaluation quantities for a variation V (V > 0) can
be used in formulae as ED:<subst>:<V> (<subst> = substance name;
<V> = variation) for further calculations. It should be noted that this
value is put out in such cases in the base units A, W or s without prefix
Comments
determination of the peak or wave evaluation.
approx.peak<thresh No result, as the peak height approximated
in the first approximation is less than the limit
value I.threshold or t.threshold entered
on the "SUBSTANCES" page (see section
5.6.3). If desired, this limit value can be sub-
sequently lowered.

5.5 Operation
With non-gaussian shaped peaks, the approximated peak

height can differ greatly from the actual peak height I.peak
or t.peak. To ensure that the results are still displayed or
suppressed as desired, I.threshold or t.threshold
must be adjusted if need be.
bad U.peak interp. No result, as the interpolation of the peak
voltage U.peak is not possible (see section
6.6). It is advisable to start a new measure-
ment.
basel.type error In a double peak evaluation, both peaks
must have the same baseline type (linear,
polynom, expon.; see section 6.7.3).
crit.basept.interp. Critical base point interpolation (see section

6.6), the base point was simulated. If de-
sired, the base point can be subsequently
changed manually (see section 5.5.3).
crit. front ovlp. Critical overlapping at the peak front half, the
overlapping is 10...40%, A switch to r.half
or r.double is advisable (see section 6.7.1).
crit. rear ovlp. Critical overlapping at the peak rear half, the
overlapping is 10...40%, A switch to f.half
or f.double is advisable (see section 6.7.1).
eval. impossible An evaluation is not possible (e.g. for
CYCMODE).
front overlapping Admissible overlapping at the peak front half

(<10%, see section 6.7.1).
illegal basel.type The evaluation with exponential baseline
expon. is not possible. The baseline must
be set to linear or polynom (see section
6.7.3).
illeg. basel.scope The evaluation with f.half or r.half is not
possible with the selected baseline type (see
section 6.7.1).
illeg. front ovlp. Inadmissible overlapping at the peak front
half (>40%, see section 6.7.1).
illeg. rear ovlp. Inadmissible overlapping at the peak rear
half (>40%, see section 6.7.1).
illegal U.width The determined peak width U.width is out-
side the admissible range U.width
min...U.width max defined on the
"SUBSTANCES" page (see section 6.6).
missing front peak Missing front peak for rear peak evaluation of
a double peak (see section 6.7.3).
missing rear peak Missing rear peak for front peak evaluation of
a double peak (see section 6.7.3).
rear overlapping Admissible overlapping at the peak rear
edge (<10%, see section 6.7.1).

5.5.2 RESULTS

7 Determ.: XXXXXXXX Calibrations

XXXXXXXX XXXXXXXX XXXXXXXXXXXX XXXXXXXXXX XXXXXXXXXX XXXXXXXXX
>> >>
Calcul. Eval.
5 6
Softkeys Meaning
>> Calculations
Calcul.
Switching to the subpage "Calculations" with an overview of the final
results.
5
>> Evaluations
Eval.
Switching to the subpage "Evaluations" with the results of all sub-
stance and peak/wave evaluations.
6

Method display only
Method name
extension .mth).
Determination name
Substance display only
Substance name
Name of the evaluated substance.

5.5 Operation

Techn. display only
Calibration technique
Calibration technique selected for the evaluation of the substance
(see sections 5.6.3 and 6.9):
std.add. Standard addition
cal.crv. Calibration curve
int.std. Internal standard
Y.reg/offset display only
Regression value or intercept (variable KY:<subst>)

Depending on the calibration technique selected, the following is
shown under this parameter (see sections 5.6.3 and 6.9):
std.add. Current or area value for the sample in A, W or s cal-
culated from the standard addition curve
cal.crv. Intercept of the calibration curve
int.std. No display
This value can be used in formulae as KY:<subst> (<subst> =
substance name) for further calculations. It is put out in such cases in
the base units A, W or s without prefix (see section 5.6.4).
Slope display only
Slope or proportionality factor (variable KS:<subst>)

Depending on the calibration technique selected, the following is
shown under this parameter (see sections 5.6.3 and 6.9):
std.add. Slope of the standard addition curve
(in AL/g, WL/g or sL/g)
cal.crv. Slope of the calibration curve (in AL/g, WL/g or sL/g)
int.std. Proportionality factor between analyte and reference
substance (in AL/g, WL/g or sL/g)
This value can be used in formulae as KS:<subst> (<subst> =
the base units AL/g, WL/g or sL/g without prefix (see section 5.6.4).
Nonlin. display only
Non-linearity factor (variable KN:<subst>)

Non-linearity factor of the calibration curve or the standard addition
4 4 4
curve (in [AL/g] , [WL/g] or [sL/g] , see sections 5.6.3 and 6.9).
This value can be used in formulae as KN:<subst> (<subst> =
the base units without prefix (see section 5.6.4).
Mean deviat. display only
Mean deviation of standard addition or calibration curve

(variable KD:<subst>)
Calculated mean deviation of the measured values about the standard
addition or calibration curve in A, W or s.
The size of Mean deviat. can be used as a measure of the quality of
a standard addition or calibration curve.
This value can be used in formulae as KD:<subst> (<subst> =
the base units A, W or s without prefix (see section 5.6.4).

5.5.3 CURVES
5.5.3 CURVES
M This dialog page is used to display curves of the determination

loaded in the working memory. It is accessible only in the
CURVES instrument mode * READY *.
In addition to the display of the various types of curves for the
individual substances or segments, here interactive parameters
for scaling, substance recognition and the baseline calculation
can be changed and spikes eliminated manually.
In the selection of this dialog page, the following rules apply:

When the "CURVES" page is selected for the first time, the first
substance is displayed on this page, with later selections the
last selected substance.
Without special entry for the VR value, the smoothed curves of
all variations with replication 0 are shown for the selected
substance (Substance-*0-smoothed).
Simultaneous pressing of the keys <SHIFT> and
<CURVES> displays the original curve with VR = 00 for the
first segment directly (Segment-00-original).
If no substance has been defined, following a warning the
original curve with VR = 00 for the first segment is shown
(Segment-00-original).
With parameter changes, the following must be noted:

Changes in the display/plot, recognition or baseline parame-
ters lead to a recalculation and updated display of the curve.
These changes are temporary, i.e. they are canceled after exit
with <ESC>.
Parameter changes are permanently incorporated in the
method only if they are stored with <Save param.>. To ensure
that these changes are also effective for the calculation of all
peak and wave results, a recalculation must be initiated with
<Recalc.> on the "MONITORING" page (see section 5.5.1).
In the manual elimination of spikes, the following holds:

After closure with <ENTER>, the spike elimination automati-
cally initiates a recalculation with the changed measured
values. In order to access the original experimental data, the
softkey <Recalc. from orig.> on the "MONITORING" page
must be pressed.
In storage of a determination in the determination memory or
on the data card, the original experimental data (original) are
retained, but not those measured values changed with the
manual spike elimination (processed).
Before any type of parameter changes, it is advisable to store the

determination in the determination memory or on a data card to be
able to fall back on the unchanged determination and method in an
emergency.

5.5 Operation
Substance-VR-Curve: XXXXXXXX-XX-smoothed
8
U.peak : XXXXXX mV dU.front: XXXXXX mV dU.rear: XXXXXX mV

I.peak : XXXXXX xA S.front: XXXXXX S.rear: XXXXXX
P.peak : XXXXXX xW
U.width: XXXXXX mV
Display Select Select Next Prev. Scale Modify Modify
segment subst. curve VR VR recogn. baseline
12 with cyclic
9 10 11
curves 15
Curve display
The representation of the substance curve as well the display of the peak/wave results
depends on the measurement mode selected:
Measurement mode y axis x axis Results
DPMODE, SQWMODE, AC1MODE I/xA U/mV U.peak

DCTMODE with SSWEEP (peaks) I.peak
CYCMODE with only 1 ramp (RAMP) P.peak
U.width
DCTMODE with SWEEP (waves) I/xA U/mV U / 2

I.wave
U.width
AC2MODE with evaluation AC2 abs. I/xA U/mV U / 2

I.abs
AC2MODE with evaluation AC2 rel. I/xA U/mV U / 2

I.rel
PSAMODE with PSWEEP t/U / s/V U/mV U.peak

t.peak
U.width
In what follows, a substance peak recorded with DPMODE will be used as a curve exam-
ple. However, in most cases the listed functions of the softkeys and the meaning of the
parameters apply to not just this example but also curves with other measurement modes.
Any differences which appear are listed specifically under "Softkeys" or "Parameter".

5.5.3 CURVES
Softkeys Meaning
Display Display segment

segment
Switching to the display of the segment associated with the selected
substance.
12
Select Select substance curves

subst.
The selection of substance and VR numbers determines what sub-
stance curves are displayed. First, the softkeys carrying the substance
name and segment name must be used to select the substance:
Subst.# Selection of the substance Subst.# allocated to the segment
Segment#
Segment#.
This is followed by entry of the numbers for variation V and replication

R. For this, the system window shows the message:
VR max: ## Maximum selectable VR values
Enter VR: [*0] Entry of VR
The following possibilities are available for the entry of VR:
## Entry of two numbers ## for the display of a single
curve.
*# Entry of an asterisk * and a number # for the display
of all variations with the same replication (shown by
(grouped VR: *#) in the title line).
#* Entry of a number # and an asterisk * for the display
of all replications of the same variation (shown by
(grouped VR: #*) in the title line).
** Entry of two asterisks ** for the display of all curves
(shown by (grouped VR: **) in the title line).
Some of the possible entries can be selected directly by pressing the
appropriate softkeys. Without entry of VR, the default value *0 is
effective for all variations with replication 0 as standard.
Select Select curve

curve
The following curves can be selected for each substance using the
softkeys:
Original Display of the original curve (original measured values)

Valid measured values
k Recognized spikes
Invalid measured values (overflow)
k
In determinations with
k PSAMODE, the original
k curve can not be dis-
played.
U

5.5 Operation
Softkeys Meaning
Pro- Display of the processed curve (measured values after spike elimi-
cessed
nation and possible background compensation):
k Spikes still present (can be removed manually in the
segment if need be)
Invalid measured values (overflow) (can be removed
manually in the segment if need be)
k
PSAMODE, the proc-
essed curve can not be
displayed.
U
Smoothed Display of the smoothed curve (smoothing of the processed meas-

ured values), the calculated baseline and the results of the peak or
wave evaluation.
I In a group of curves
the selected curve is
black, the remaining
curves are gray. The
displayed baseline
refers to the selected
curve.
U
st
Derived Display of the derived curve (1 derivative of the processed meas-
ured values). A relative scaling in % is specified for the y axis.
dI/dU
PSAMODE, the derived
curve can not be dis-
played.
U
Subtrac. Display of the subtracted curve in addition to the smoothed curve

(the baseline is subtracted from the measured value curve).

5.5.3 CURVES
Softkeys Meaning
Calibr. Display of the calibration curve and the mass concentration of the
substance calculated from it for the sample. The axes for standard
addition and calibration curve have the following meaning:
EV Evaluation value (current I, power P or time t)
eff Effective mass concentration of the selected sub-
stance in the measuring vessel
With the internal standard, the following axes are shown:
EVa/EVr Ratio of the evaluation values of analyte (a = analyte)
and reference substance (r = reference)
a/
r Ratio of the effective mass concentrations of analyte
(a = analyte) and reference substance (r = refer-
ence) in the measuring vessel
The curve representation depends on the selected calibration tech-
nique Technique and the run mode Run mode:
Standard addition (see also section 6.9.4):
EV std.add., determ.
Sample
Standard additions
Standard deviation
(if available)
eff
Calibration curve (see also section 6.9.5):
EV cal.crv., calibr. EV cal.crv., determ.
eff eff
Calibration points The measured value is

Standard deviation plotted.
Internal standard (see also section 6.9.6):
EVa/EVr int.std., calibr. EVa/EVr int.std., determ.
a / r a / r
Calibration points The measured value is

Deviation plotted.
The results of the calibration are also shown for all curves (for details,
see under Coefficients on the "SUBSTANCES/Calibration" page,
section 5.6.3).

5.5 Operation
Softkeys Meaning

VR
Switch to next single curve VR (the current VR number is shown in the
title line). The same function can also be initiated with the cursor key
<>.
In the display of several curves, the current curve is shown in black,
the remaining curves in gray. The selection of VR determines what
curve is switched to with <Next VR>:
*# Switching of the variation has precedence
(e.g. 00 10 20 01 11 21 02 12 22)
#* and ** Switching of the replication has precedence
(e.g. 00 01 02 10 11 12 20 21 22)
Once the last curve has been reached, the warning last VR: XX of
this segment reached appears in the system window.

VR
Switch to the preceding single curve VR (the current VR number is
shown in the title line). The same function can also be initiated with the
cursor key <>.
curve is switched to with <Prev. VR>:
(e.g. 22 12 02 21 11 01 20 10 00)
(e.g. 22 21 20 12 11 10 02 01 00)
Once the first single curve has been reached, the warning first VR:
XX of this segment reached appears in the system window.
Scale Axis scaling

Possibility for interactive modification of the parameters for the axis
scaling of the substance curves (display/plot parameters of the
substances, see also section 5.6.3).
9
Modify Modify the parameters for substance recognition

recogn.
Possibility for interactive modification of the parameters for the recog-
nition of the substances (recognition parameters of the substances,
see also section 5.6.3).
10
Modify Modify the baseline parameters

baseline
Possibility for interactive modification of the parameters for the calcu-
lation of the baseline (baseline parameters of the substance, see also
section 5.6.3).
12
This softkey is not available for curves recorded with
PSAMODE.

5.5.3 CURVES

Substance-VR- display only
Curve
Identification of selected curve
Substance Name of selected curve
VR Variation and replication number of selected single
curve (shown in black)
Curve
original Original curve
processed Processed curve
smoothed Smoothed and evaluated curve with baseline
st
derived Derived curve (1 derivative)
subtracted Subtracted curve
calibr Calibration curve
grouped VR: Display of the grouping with several curves:
*# All variations with replication #
#* All replications of the variation #
** All variations and replications
U.peak display only
Peak voltage
Determined peak voltage in mV.
U.peakis shown for curves recorded with one of the following meas-
urement modes:
DPMODE, SQWMODE, AC1MODE
DCTMODE with SSWEEP (peaks)
PSAMODE
CYCMODE with only 1 ramp
U.peak U
U / 2 display only
Half-wave voltage
Determined half-wave voltage in mV.
U/2 is shown for curves recorded with one of the following meas-
urement modes:
DCTMODE with SWEEP (peaks)
AC2MODE
DCTMODE AC2MODE
I I
U/2 U U/2 U

5.5 Operation

I.peak display only
Peak height
Determined peak height in A.
I.peakis shown for curves recorded with one of the following meas-
urement modes:
I
I.peak
I.wave display only
Wave height
Determined wave height in A.
I.waveis shown for curves recorded with one of the following meas-
urement mode DCTMODE and SWEEP (for waves).
I
I.wave
I.abs, I.rel display only
Current evaluation quantity for AC2 curves

Determined current evaluation quantity in A.
I.absor I.rel is shown for curves recorded with the measurement
mode AC2MODE.
Type = AC2 abs. Type = AC2 rel.

I I I.rel = If + Ir
I.abs Ir
If
U U
P.peak display only
Peak area
Determined peak area in W.
P.peakis shown for curves recorded with one of the following meas-
urement modes:
In an evaluation with Scope = f.half or Scope = r.half, the area up
to the peak maximum is shown here.

5.5.3 CURVES
Scope = whole Scope = f.half Scope = r.half

I
P.peak
t.peak display only
Current evaluation quantity for PSA curves

Determined peak area in s.
is shown for curves recorded with the measurement mode
t.peak
PSAMODE.
t/U
t.peak
U.width display only
Peak or wave width

Peak or wave width determined between the inflection points of the
peak or the derived wave in mV.
U.widthis shown for curves recorded with one of the following
measurement modes:
DCTMODE
PSAMODE
U.width
I
U
dI/dU
dU.front display only
Voltage difference to front base point

Absolute voltage difference determined between the base point at the
peak/wave front half and the peak voltage U.peak or the half-wave
potential U/2 in mV.

5.5 Operation

dU.rear display only
Voltage difference to rear base point

Absolute voltage difference determined between the base point at the
peak/wave rear half and the peak voltage U.peak or the half-wave
potential U/2 in mV.
S.front display only
Slope of baseline at front base point

Slope of the baseline determined at the base point at the peak/wave
front half.
With peaks with a baseline of the linear type, this parameter is not
shown.
S.rear display only
Slope of baseline at rear base point

Slope of the baseline determined at the base point at the peak/wave
front half.
With peaks with a baseline of the linear type, this parameter is not
shown.
linear, whole linear, DCT

dU.frontdU.rear dU.frontdU.rear
S.rear
S.front
polynom, whole expon., whole

dU.frontdU.rear dU.frontdU.rear
S.rear
S.front S.rear
S.front

5.5.3 CURVES
9
Display / Plot

I.scale ........
I.begin ........A
I.end ........A
U.div ........V/cm
U.begin ........V
U.end ........V
ESC

8 I.peak : XXXXXX xA S.front: XXXXXX S.rear: XXXXXX
P.peak : XXXXXX xW
U.width: XXXXXX mV
Modify Start New Reset Save
column zoom display param. param.
Softkeys Meaning
Modify Modify display/plot parameters column-by-column

column
Modification of the parameters for the axis scaling. For details of the
display/plot parameters, see section 5.6.3.
Modifications made here initiate a recalculation and curve display on
closure of the entry. These changes are temporary, they are canceled
with <Reset param.> or after exit with <ESC>.
The changes are permanently incorporated in the method only if they
are stored with <Save param.> before exiting.
Start Select zoom range

zoom
This softkey starts the selection of the zoom region (curve section
which should be enlarged).
First, the cursor keys <>, <>, <> and <> must be used
to define the top left corner point of the zoom region (marked by a
cross) as follows:
Each time these keys are pressed, the corner point moves in the
selected direction by 5 pixels. A finer shift of 1 pixel can be
achieved when the <SHIFT> key is pressed at the same time. In
both cases, the cursor keys are repetitive, i.e. the longer the cur-
sor key is pressed, the further the corner point is shifted.
Uppr/lft Once the top left corner point is in the desired position, it must be
corner
fixed by pressing the softkey <Uppr/lft corner> or the <ENTER>
key. Next, the bottom right corner point of the zoom region is also
defined using the cursor keys. This automatically opens a frame
encompassing the region to be enlarged.

5.5 Operation
Softkeys Meaning
Lwr/rght Once the bottom right corner point is in the desired position, it must
corner
be fixed by pressing the softkey <Lwr/rght corner> or the
<ENTER> key. Next, the selected zoom region is shown full screen
and the parameters in the display/plot window updated appropriately.
These changes are temporary, they are canceled with <Reset
param.> or after exit with <ESC>.
The changes in the display/plot parameters are permanently incorpo-

rated in the method only if they are stored with <Save param.> before
exiting.
The procedure described for selection of the zoom region can be
repeated several times in succession.
New Redisplay curve

display
This softkey is used for manual initiation of a recalculation and curve
display (this normally runs automatically each time the parameter
modification is closed).
Reset Reset display/plot parameters

param.
The parameters appearing in the window are reset to the values
entered on the "SUBSTANCES" page.
Save Store display/plot parameters

param.
The parameters appearing in the window are transferred to the
"SUBSTANCES" page and hence stored in the method.

5.5.3 CURVES
10
Recognition

U.verify ........mV
U.tol (+/-) ........mV
U.width min ........mV
U.width max ........mV
I.threshold ........pA
ESC

P.peak : XXXXXX xW
U.width: XXXXXX mV
Modify New Reset Save
column display param. param.
Softkeys Meaning
Modify Modify recognition parameters column-by-column

column
Modification of the parameters for the substance recognition. For
details of the recognition parameters, see section 5.6.3.
are stored with <Save param.> before exiting. To ensure they are also
effective for the result calculation, a recalculation must be initiated on
the "MONITORING" page with <Recalc. from proc.>.
New Redisplay curve

display
Reset Reset recognition parameters

param.
Save Store recognition parameters

param.

5.5 Operation
11
Baseline

Type ........
Scope ........
dU.front ........
S.front ........
dU.rear ........
S.rear ........
ESC

P.peak : XXXXXX xW
U.width: XXXXXX mV
Modify Start Modify Modify New Reset Save
column zoom dU.front dU.rear display param. param.
Softkeys Meaning
Modify Modify baseline parameters column-by-column

column
Modification of the parameters for calculation of the baseline (not
possible for curves recorded with PSAMODE). For details of the
baseline parameters, see section 5.6.3.
Modifications made here initiate a recalculation and baseline display
on closure of the entry. These changes are temporary, they are
canceled with <Reset param.> or after exit with <ESC>.
are stored with <Save param.> before exiting. To ensure they are also
effective for the result calculation, a recalculation must be initiated on
the "MONITORING" page with <Recalc. from proc.>.

zoom
cross) as follows:
corner

5.5.3 CURVES
Softkeys Meaning
corner
<ENTER> key. The selected zoom region is then shown full screen.
repeated several times in succession. The enlarged display of the
curve remains active until the baseline modification is quit by pressing
the <ESC> key.
Modify Activate front base point shift

dU.front
The base point at the front half of the peak or wave is marked by a
double dash and can be shifted to the right or left using the cursor
keys <> and <>. The following should be noted here:
Each time these keys are pressed, the base point moves in the
On completion of the shift, the curve is automatically recalculated and
displayed. The current value for dU.front appears in the baseline
window. Alternatively, dU.front (just like the slope S.front) can also
be changed numerically directly in the baseline window.
Modify Activate rear base point shift

dU.rear
The base point at the rear half of the peak or wave is marked by a
double dash and can be shifted to the right or left using the cursor
keys <> and <> in the manner described under <Modify
dU.front>.
On completion of the shift, the curve is automatically recalculated and

displayed. The current value for dU.rear appears in the baseline
window. Alternatively, dU.rear (just like the slope S.rear) can also be
changed numerically directly in the baseline window.
New Redisplay curve

display
Reset Reset baseline parameters

param.
Save Store baseline parameters

param.

5.5 Operation
Segment-VR-Curve: XXXXXXXX-XX-original
12
Display Select Select Next Prev. Scale Unlinked Spike

subst. segment curve VR VR peaks elimin.
8 13 14
Curve display
The representation of the segment curve depends on the selected sweep:
Sweep y axis x axis
SWEEP, FSWEEP, SSWEEP I/xA U/mV
PSWEEP U/mV t/xs
TSWEEP I/xA t/xs
In what follows, a segment recorded with SWEEP will be used as a curve example. How-
ever, in most cases the listed functions of the softkeys and the meaning of the parameters
apply to not just this example but also curves with other sweeps. Any differences which
appear are listed specifically under "Softkeys" or "Parameter".

5.5.3 CURVES
Softkeys Meaning
Display Display substance

subst.
Switching to the display of the first substance of the selected seg-
ment.
8
Select Select segment

segment
The selection of segment and VR numbers determines what segment
curve is displayed (the simultaneous display of several segment
curves is not possible). First, the softkeys carrying the segment
names must be used to select the desired segment:
Segment# Selection of the segment Segment#.
Enter VR: [00] Entry of VR
For VR the numbers for the desired variation or replication must be
entered (the entry of * is not allowed). Without entry of VR, the default
value 00 is effective for the variation 0 with replication 0 as standard.
In determinations with background compensation

(BACKGDN instructions), the background curve
Segment-Curve-00-backgnd is shown when VR = 00 is
selected. The normal curve Segment-Curve-00 is
reached by pressing the softkey <Next VR>.
Select Select curve

curve
The following curves can be selected for each segment using the
softkeys:
Original Display of the original curve (original measured values)

k Recognized spikes
k
k PSAMODE, the original
k curve can not be dis-
played.
U
Pro- Display of the processed curve (measured values after spike elimi-
cessed
nation and possible background compensation):
k Spikes still present
(can be removed manually if need be)
(can be removed manually if need be)

5.5 Operation
Softkeys Meaning
k In determinations with
PSAMODE, the proc-
essed curve can not be
displayed.
U
Smoothed Display of the smoothed curve (smoothing of the processed meas-

ured values).
st
Derived Display of the derived curve (1 derivative of the processed meas-
ured values). A relative scaling in % is specified for the y axis.
dI/dU
PSAMODE, the derived
curve can not be dis-
played.
U

VR
Switch to next single curve VR (the current VR number is shown in the
title line). The same function can also be initiated with the cursor key
<>.
First the replication (R) is switched, then the variation (V),
e.g. 00-backgnd 00 01 02 10 11 12 20 21 22.
Once the last curve has been reached, the warning last VR: XX of
this segment reached appears in the system window.

VR
Switch to the preceding single curve VR (the current VR number is
shown in the title line). The same function can also be initiated with the
cursor key <>.
First the replication (R) is switched, then the variation (V),
e.g. 22 21 20 12 11 10 02 01 00 00-backgnd.
Once the first single curve has been reached, the warning first VR:
XX of this segment reached appears in the system window.

5.5.3 CURVES
Softkeys Meaning
Scale Axis scaling

scaling of the segment curves (display/plot parameters of the seg-
ments, see also section 5.6.2).
13
Unlinked Non-assigned peaks

peaks
Display of all peak and wave voltages U.ver/mV found for the se-
lected segment but not linked to a substance.
Spike Spike elimination

elimin.
Possibility for interactive modification of spike measured values.
14
This softkey is not available for curves recorded with
PSAMODE.

Segment-VR- display only
Curve
Identification of selected curve
Segment Name of selected segment
VR Variation and replication number of the selected
segment
Curve
original Original curve
processed Processed curve
smoothed Smoothed and evaluated curve with baseline
st
derived Derived curve (1 derivative)
-backgnd Background curve (only with determinations with
BACKGND instructions, possible for all four curve
types)

5.5 Operation
Segment-VR-Curve: XXXXXXXX-XX-original
13
Display / Plot

I.scale ........
I.begin ........A
I.end ........A
U.div ........V/cm
ESC
12

Softkeys Meaning

column
Modification of the parameters for the axis scaling of the selected
segment. For details of the display/plot parameters, see section 5.6.2.

zoom
A segment curve can be zoomed only in the y direction,

the x axis is always shown full scale (limit values U.start
and U.end of the segment).
cross) as follows:

5.5.3 CURVES
Softkeys Meaning
corner
corner

exiting.
New Redisplay curve

display

param.
entered on the "SEGMENTS" page.

param.
"SEGMENTS" page and hence stored in the method.

5.5 Operation
Segment-VR-Curve: XXXXXXXX-XX-processed
14
ESC
Meas.point
12
U : XXXXXX mV
I : XXXXXX nA
Start
zoom
Softkeys Meaning

zoom
cross) as follows:
Each time these keys are pressed, the corner point moves
in the selected direction by 5 pixels. A finer shift of 1 pixel
can be achieved when the <SHIFT> key is pressed at the
same time. In both cases, the cursor keys are repetitive, i.e.
the longer the cursor key is pressed, the further the corner
point is shifted.
corner
corner
repeated several times in succession. The enlarged curve display
remains active until the spike elimination is exited by pressing the
<ESC> key.

5.5.3 CURVES
Manual modification of spike measured values
Notes on spike elimination (see also section 6.4)

When the measured values are recorded, spikes are recognized automatically and
marked in the original curve by an asterisk (k) or a circle ( = overflow). The subse-
quent measured value processing eliminates these points if possible automatically and
provides the processed curve. The measured values of this curve and hence any spikes
still present can be changed manually with the aid of the spike elimination. Here, the
following must be noted:
On closure with <ENTER>, the spike elimination automatically initiates a recal-
culation with both modified and unmodified measured values (spikes can thus
also disappear without manual change of the measured values). In order to ac-
cess the original experimental data again, the softkey <Recalc. from orig.> on
the "MONITORING" page must be pressed.
On storage of a determination in the determination memory or on the data card,
the original experimental data are retained, but not the processed measured
values changed with the spike elimination.
Proceed as follows in manual modification of the measured values:
Select measured value

The desired measured value is selected using the cursor keys <>
or <>. The current measured value is marked by a cross, further
the numeric data voltage U and current I are shown below the curve.
The following applies to selection with the cursor keys:
Each time these keys are pressed, the cursor moves by 1 meas-
ured point in the selected direction. A greater shift by 4 meas-
ured points can be achieved by pressing the <SHIFT> key at
the same time. In both cases the cursor keys are repetitive, i.e.
the longer the cursor key is pressed, the greater the cursor shift.
Shift measured values

Once the desired measured value has been selected, it can be
changed using the cursor keys <> or <>. The current measured
value is marked by a cross, further the numeric data voltage U and
current I are shown below the curve.
The following applies to selection with the cursor keys:
Each time these keys are pressed, the cursor moves by 1 pixel in
the selected direction. A greater shift by 4 pixels can be
achieved by pressing the <SHIFT> key at the same time. In
both cases the cursor keys are repetitive, i.e. the longer the cur-
sor key is pressed, the greater the shift in the measurement
point.
Adopt measured value

When the measured value is in the desired position, it is adopted
ENTER
definitively by pressing the <ENTER>, <> or <> keys.

5.5 Operation
Cyclic Segment-VR-Curve: XXXXXXXX-XX-original

15
Select Start Reset Next Prev. Scale

segment zoom zoom VR VR
16
Softkeys Meaning
Select Select segment curves

segment
The selection of segment and VR numbers determines what cyclic
curves are displayed. A cyclic segment curve always includes all of
the maximum 5 ramps which have the same VR number (the display
of individual ramps is not possible). First, the softkeys carrying the
segment names must be used to select the desired cyclic segment:
Enter VR: [0*] Entry of VR
The following possibilities are available for the entry of VR:
## Entry of two numbers ## for the display of a single cy-
clic curve with all ramps of the same measurement cy-
cle (measurement cycles = replications).
*# Entry of an asterisk * and a number # for the display
of all variations with the same replication (shown by
(grouped VR: *#) in the title line).
#* Entry of a number # and an asterisk * for the display
of all cyclic curves of the same variation (shown by
(grouped VR: #*) in the title line.
** Entry of two asterisks ** for the display of all cyclic
curves (shown by (grouped VR: **) in the title line).
Without entry of VR, the default value 0* is effective for variation 0
with all replications as standard.

5.5.3 CURVES
Softkeys Meaning

zoom
cross) as follows:
Each time these keys are pressed, the corner point moves
in the selected direction by 5 pixels. A finer shift of 1 pixel
can be achieved when the <SHIFT> key is pressed at the
same time. In both cases, the cursor keys are repetitive, i.e.
the longer the cursor key is pressed, the further the corner
point is shifted.
corner
corner
repeated several times in succession. The enlarged curve display
remains active until the <ESC> key or the softkey <Reset zoom> is
pressed.
Reset Reset zoom range

zoom
For the display of the cyclic curve the axis scalings of the display/plot
parameters are again used.

VR
Switch to the next cyclic curve VR (the current VR number is shown in
the title line). The same function can also be initiated with the cursor
key <>.
When several curves are displayed, the current curve is shown in
black, the remaining curves in gray. The selection of VR determines
what curve is switched to with <Next VR>.
(e.g. 00 10 20 01 11 21 02 12 22)
(e.g. 00 01 02 10 11 12 20 21 22)
Once the last cyclic curve has been reached, the warning last
cyclic replication reached appears in the system window.

5.5 Operation
Softkeys Meaning

VR
Switch to the preceding cyclic curve VR with all ramps (the current VR
number is shown in the title line). The same function can also be
initiated with the cursor key <>.
curve is switched to with <Prev. VR>:
(e.g. 22 12 02 21 11 01 20 10 00)
(e.g. 22 21 20 12 11 10 02 01 00)
Once the first cyclic curve has been reached, the warning first
cyclic replication reached appears in the system window.
Scale Axis scaling

scaling of the cyclic curves (display/plot parameters of the sub-
stances, see also section 5.6.2).
16

5.5.3 CURVES
Cyclic Segment-VR-Curve: XXXXXXXX-XX-original

16
Display / Plot: I = f(U)

I.scale ........
I.begin ........A
I.end ........A
U.div ........V/cm
ESC
15

Softkeys Meaning

column
Modification of the parameters for the axis scaling of the selected
cyclic segment. For details of the display/plot parameters, see section
5.6.2.

zoom
A segment curve can be zoomed only in the y direction,

the x axis is always shown full scale (limit values U.start
and U.end of the segment).
cross) as follows:

5.5 Operation
Softkeys Meaning
corner
corner

exiting.
New Redisplay curve

display

param.
entered on the "SEGMENT" page.

param.
"SEGMENT" page and hence stored in the method.

5.6.1 OPERATION SEQUENCE
5.6 Method Specifications

The keypad contains 5 yellow dialog keys under the title "METHOD SPECIFICA-
TIONS" for selection of the main program, the segment programs, the substance
data, the formula calculations and the documentation.
METHOD
SPECIFICATIONS
O P
OP. SUB-
SEQUENCE STANCES
L :
;
SEGMENTS CALCU-
LATION
>
.
DOCUMEN-
TATION

O This dialog page is used for the display and entry of the main
OP. program. Program instructions (see section 5.7), the associated
SEQUENCE parameters and the freely adjustable line time are used to
determine the sequence of the sample determination.
Method: .........mth OPERATION SEQUENCE

Title : ..................................................

## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................

Softkeys Meaning

column

line
Delete Delete program instruction

instr.
Insert Insert program instruction

instr.
Method Change method name and method title

labels
Keys Meaning
Program test
ENTER
By pressing the <ENTER> key in the navigation mode the program
on this dialog page is tested:
If no error is found, no action occurs.
in the error window (see section 7.3.2).


Method 8 characters;
Method name
For the method name all characters are allowed with the exception of
the character ".".
Title 50 characters;
Method title
Title of the method loaded in the working memory.
## display only
Line number
Automatic numbering of the instruction lines (max. 99 instruction lines
can be entered).
Attribute C, D, !, @;
Line attribute
Optional marking of the instruction lines with the following attributes:
C Calibration; the marked instruction line is executed only
if Run mode = calibration.
D Determination; the marked instruction line is executed
only if Run mode = determination.
! Inactive line; this line will not be executed.
@..@ Inactive range; the range between the two lines marked
by @ will not be executed.
Combinations of line attributes are also possible (e.g. C!, D@).
Instructions Instructions;
Program instructions
Entry of program instructions (see section 5.7). The associated
parameters are entered automatically.
In the entry, all possible instructions on this dialog page are displayed
in alphabetical order on the softkeys and can thus be incorporated
directly:
XXXXXXXX Instruction XXXXXXXX is copied to the Instructions field.
--------
t/s 0.1...999.9 s;
Line time
Optional entry of a wait time for the instruction line. When the program
is running, this line time will be allowed to elapse before the next
instruction is executed. The time counter is started at the moment the
program instruction is started.
With SWEEP instructions, the line time is calculated automatically and
can not be changed.
Main parameters Parameter;
Main parameters
Main parameters for program instruction (see section 5.7.3).
Auxiliary Parameter;
parameters
Auxiliary parameters
Auxiliary parameters for program instruction (see section 5.7.3).

5.6.2 SEGMENTS
L This dialog page is employed for the display and entry of the
segment programs (max. 8 segments). Program instructions (see
SEGMENTS section 5.7), the associated parameters and the freely adjustable
line time are used to determine the sequence of the segments,
which are called up with the instruction SEGMENT in the main
program ("OPERATION SEQUENCE").
The segments are primarily used for programming of the
measured value recording using the SWEEP instructions with one
sweep being allowed per segment. However, the segments can
also be used for the programming of macros with any other
instructions.
17 Method: XXXXXXXX SEGMENT

........

## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................

18
Softkeys Meaning

column

line
Delete Delete program instruction

instr.
Insert Insert program instruction

instr.

5.6.2 SEGMENTS
Softkeys Meaning
Select Select segment

segment
The existing segments and those still free can be selected with the
softkeys carrying the segment names or -----:
Delete Delete segment

segment
The displayed segment is deleted after confirmation with y.
Plot Axis scaling

param.
Possibility to display and modify the parameters for the axis scaling of
the segment curves (display/plot parameters of the segments).
18
Segment Change segment name
name
Possibility to enter the segment name. Segment names already
defined with the instruction SEGMENT on the "OPERATION
SEQUENCE" page are displayed on the softkeys and can be adopted
directly:
Segment# Adoption of the segment name Segment#.
Keys Meaning
Program test
ENTER
By pressing the <ENTER> key in the navigation mode the program
on this dialog page is tested:

Method display only
Method name
For the method name, all characters are allowed with the exception of
the character ".".
SEGMENT 8 characters;
Segment name
Name of the displayed segment. To change this, the softkey <Segment
name> must be pressed.
For the segment name, no brackets "(" or ")" are allowed.


## display only
Line number
Automatic numbering of the instruction lines (max. 29 instruction lines
can be entered).
Attribute C, D, !, @;
Line attribute
Optional marking of the instruction lines with the following attributes:
if Run mode = calibration.
only if Run mode = determination.
! Inactive line; this line will not be executed.
@..@ Inactive range; the range between the two lines marked
by @ will not be executed.
Combinations of line attributes are also possible (e.g. C!, D@).
Instructions Instructions;
Program instructions
Entry of program instructions (see section 5.7). The associated
parameters are entered automatically.
In the entry, all possible instructions on this dialog page are displayed
in alphabetical order on the softkeys and can thus be incorporated
directly:
XXXXXXXX Instruction XXXXXXXX is copied to the Instructions field.

--------
t/s 0.1...999.9 s;
Line time
Optional entry of a wait time for the instruction line. When the program
is running, this line time will be allowed to elapse before the next
instruction is executed. The time counter is started at the moment the
program instruction is started.
With SWEEP instructions, the line time is calculated automatically and
can not be changed.
Main parameters Parameter;
Main parameters
Main parameters for program instruction (see section 5.7.3).
Auxiliary Parameter;
parameters
Auxiliary parameters
Auxiliary parameters for program instruction (see section 5.7.3).

5.6.2 SEGMENTS
18 Method: XXXXXXXX SEGMENT

........

## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................

I.scale
## .. ............. ..... ......................... ........
.........................

I.begin
## .. ............. ..... ......................... ........A
.........................
I.end
## .. ............. ..... ......................... ........A
.........................
U.div
## .. ............. ..... ......................... ........V/cm
.........................
<Esc>
/ <Enter>

## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................

## .. .............
..... .........................
.........................
Display
## .. ............. ..... / .........................
Plot: I = f(t) Display / Plot: U = f(t)
.........................
ESC
## .. .............
I.scale ........

..... .........................
.........................
U.scale ........
## .. ............. .....
I.begin .........................
........A U.end.........................
........V
## .. ............. .....
I.end .........................
........A t.div.........................
........s/cm
## .. ............. .....
t.div .........................
........s/cm .........................

## .. .............
...../ <Enter>
<Esc> .........................
.........................
<Esc> / <Enter>

## .. ............. ..... ......................... .........................
17 ## .. ............. ..... ......................... .........................
## .. ............. ..... ......................... .........................
Modify
column
Softkeys Meaning

column
Modification of the display/plot parameters for scaling the axes of the
selected segment.
Which of the above three parameter windows is displayed depends
on the SWEEP instructions in the segment. With PSWEEP (PSA mode),
the window with U = f(t) appears, with TSWEEP, the window with
I = f(t) appears, with all other SWEEPS the window with I = f(U)
appears.

I.scale auto, fixed; auto
Scaling of the current axis

Specification whether the current axis for the segment should be
scaled automatically (auto) or with the preset fixed values I.begin
and I.end.
The type of scaling specified here applies to both the display of the
live curve during the measurement and the plot of segment curves.
If all measurement values of a segment are outside the current axis

fixed with I.scale, the current axis for printing the segment curve is
scaled automatically. In this case, the message scale auto is printed
in the header line.


I.begin -999.99...999.99 nA...A;
Initial value for current axis

Entry of an initial current value for scaling of the current axis. In the
absence of an entry, the initial value will be selected automatically.
This parameter appears only if I.scale = fixed is selected.
I.end -999.99...999.99 nA...A;
Final value for current axis

Entry of the final current value for scaling of the current axis. In the
absence of an entry, the final value will be selected automatically.
This parameter appears only if I.scale = fixed is selected.
U.div 10 mV/cm...5 V/cm; 50 mV/cm
Division of the voltage axis per cm

Entry of the mV difference per cm for scaling of the voltage axis
(effective only for the plot).
U.scale auto, fixed; auto
Scaling of the voltage axis for PSA segments

Specification whether the voltage axis for the PSA segment should be
scaled automatically (auto) or with the preset fixed value U.end (the
initial voltage U.begin can not be changed).
The type of scaling specified here applies to the plot of segment
curves.
U.end -3000...3000 mV;
Final value for the voltage axis of PSA segments

Entry of the final voltage value for scaling of the voltage axis with PSA
segments. In the absence of an entry, the final value will be selected
automatically.
This parameter appears only if U.scale = fixed is selected.
t.div 10 ms/cm...5 s/cm; 50 ms/cm
Division of the time axis per cm

Entry of the time difference per cm for the scaling of the time axis of
PSA segments or segments with TSWEEP (effective only for the
printout).

5.6.3 SUBSTANCES
5.6.3 SUBSTANCES
P On this dialog page you will find all parameters and data for the
SUB- evaluation, calibration and representation of max. 8 substances.
STANCES The parameters which are displayed are different for Mode = VA
and Mode = PSA.
19 Method: XXXXXXXX SUBSTANCES

........ - XXXXXXXX

U.verify ........mV I.scale ........
U.tol (+/-) ........mV I.begin ........A
U.width min ........mV I.end ........A
U.width max ........mV U.div .......mV/cm
I.threshold ........pA U.begin .......mV
U.end .......mV
Baseline Evaluation

Type ........ Mode VA
Scope ........ Quantity ........
dU.front ........ Sign. digits ........
S.front ........
dU.rear ........
S.rear ........

21

........ - XXXXXXXX

U.verify ........mV t/U.scale ........
U.tol (+/-) ........mV t/U.begin ........s/V
U.width min ........mV t/U.end ........s/V
U.width max ........mV U.div .......mV/cm
t.threshold ........ms U.begin .......mV
U.end .......mV
Evaluation

Mode PSA
Sign. digits ........

21

Softkeys Meaning

column

line
Select Select substance

subst.
The existing substances and those still free can be selected with the
softkeys:
Subst.# Selection of a substance Subst.# already linked to the segment
Segment#
Segment#
Subst.# Selection of a substance Subst.# not linked to a segment
-------- Selection of a substance still free. The substance is automatically

given the standard name Subst#, which can later be changed with the
softkey <Subst. name>.
Link to Link substance to segment

segment
Substances can be evaluated only if they are linked to a predefined
segment. This is accomplished using the softkeys which display all
segments defined on the "SEGMENTS" page.
Segment# Linkage of the selected substance to the segment Segment#. Follow-
ing the linkage, the segment name is shown with the substance name
in the title line.
Delete Delete substance

subst.
The selected substance will be deleted directly without any warning.
Subst. Change substance name

name
Possibility to change the substance name Subst# allocated as
standard.
For the substance name, no brackets "(" or ")" are allowed.
>> Switching to subpage "Calibration"

Switching to the subpage "Calibration" with details of the substance
calibration.
21
Keys Meaning
Substance parameter test

ENTER
By pressing the <ENTER> key in the navigation mode the parame-
ters on the "SUBSTANCES" page are tested:

5.6.3 SUBSTANCES

Method display only
Method name
Subst# - 8 characters;
Segment#
Substance name and segment name
Name of the displayed substance and the associated segment. To
change the substance name, the softkey <Subst. name> must be
pressed.
The segment name is shown only if the substance has first been
linked to a segment using the softkey <Link to segment>.
Recognition display only
Substance recognition
Title for those parameters which concern recognition of the sub-
stance.
U.verify -3000...3000 mV;
Characteristic voltage
Verification voltage for the assignment of a peak or a wave to a
substance. The voltage aU.peak or aU/2 estimated in a first ap-
proximation must be within the range U.verify U.tol for the
substance to be recognized (see adjacent diagram and section 6.6).
If the characteristic voltage is not known before the first measurement,
this field (or with several substances, these fields) can be left blank.
The first peak or wave found in the segment is then assigned to the
first substance allocated to this segment, the second to the second,
etc.
Following the first measurement, the voltages U.peak or U/2 of the
peaks/waves found in the segment are shown on the softkeys when
the U.verify field is edited and can hence be adopted directly:
XXXXXXXX The displayed voltage XXXXXXXX is copied to the U.verify field.

--------
U.tol (+/-) 1...150 mV; 30 mV
Tolerance for characteristic voltage

Tolerance of the verification voltage for the assignment of a peak or
wave to a substance. The voltage aU.peak or aU/2 estimated in a
first approximation must be within the range U.verify U.tol for the
substance to be recognized (see adjacent diagram and section 6.6).
With peaks that are close together, it is advisable to choose toler-
ances which are not too large, otherwise an unambiguous assignment
to the substances can no longer be assured owing to the overlapping
ranges.
U.width min 1...(U.width max) mV; 10 mV
Minimum peak width

Minimum peak width for the assignment of a peak or a wave to a
substance. The peak width aU.width estimated in a first approxima-
tion must be larger than U.width min for the substance to be recog-
nized (see adjacent diagram and section 6.6).


U.width max (U.width min)...400 mV; 200 mV
Maximum peak width

Maximum peak width for the assignment of a peak or a wave to a
substance. The peak width aU.width estimated in a first approxima-
tion must be smaller than U.width max for the substance to be
recognized (see adjacent diagram and section 6.6).
I.threshold 100...5000 pA; 200 pA
Limiting current value

Limiting current value for the assignment of a peak or wave to a
substance (for all measurement modes with the exception of
st
PSAMODE). With the aid of the 1 derivative of the peak curve (or the
nd
2 derivative of the wave curve), the difference minmax is multiplied
with an empirical factor fMM dependent on the measurement mode to
determine the estimated peak height approx.peak. This estimated
value must be larger than I.threshold for the substance to be
recognized (see also section 6.6).
With non-gaussian shaped peaks, the peak height approx.

peak estimated from the derivative can differ greatly from
the actual peak height I.peak. It may be necessary to
modify I.threshold for the results to be displayed or
suppressed in the desired manner.
The substance recognition is

U.width max
I based on the recognition
aU.width
estimated U.width min parameters specified for the
gaussian approx.peak = individual substances. The
peak minmax fMM following conditions must be
I.threshold met for a detected peak to
be assigned to a substance:
1. aU.peak =
U
U.verify U.tol
U.verify U.tol
2. aU.width > U.width min
aU.width < U.width max
dI/dU minmax
3. approx.peak >
I.threshold
aU.max aU.min U
aU.peak

5.6.3 SUBSTANCES

t.threshold 0.100...9.99 ms; 4.0 ms
Time limit value

Minimum time limit (peak area) for the assignment of a peak to a
st
substance (for measurement mode PSAMODE). With the aid of the 1
derivative of the peak curve, the difference minmax is multiplied by the
empirical factor fMM valid for the PSAMODE to determine the esti-
mated peak area approx.peak. This estimated value must be larger
than t.threshold for the substance to be recognized (see also
section 6.6).
With non-gaussian shaped peaks, the peak height approx.

peak estimated from the derivative can differ greatly from
the actual peak height t.peak. It may be necessary to
modify t.threshold for the results to be displayed or
suppressed in the desired manner.
The substance recognition is

t/U U.width max
aU.width
based on the recognition
estimated U.width min parameters specified for the
gaussian approx.peak = individual substances. The
peak minmax fMM following conditions must be
met for a detected peak to
be assigned to a substance:
1. aU.peak =
U
U.verify U.tol
U.verify U.tol
2. aU.width > U.width min
aU.width < U.width max
d(t/U)/dU minmax
3. approx.peak >
t.threshold
aU.max aU.min U
aU.peak


Display / Plot display only
Display/plot (for all measurement modes except PSAMODE)

Title for those parameters which concern the display and plotting of
substance curves recorded with the measurement modes DCTMODE,
DPMODE, SQWMODE, AC1MODE or AC2MODE.
I.scale auto, fixed; auto
Scaling of the current axis

The following two possibilities are available for scaling of the current
axis for the display and plotting of substance curves:
auto Automatic scaling with matching to the measured
experimental values
fixed Fixed scaling with the preset values I.begin and
I.end
If all measurement values are outside the current axis fixed with
I.scale, the current axis for printing the substance curve is scaled
automatically. In this case, the message scale auto is printed in the
header line.
I.begin -999.99...999.99 nA...A;
Initial value for scaling of current axis

This parameter appears only if I.scale = fixed has been selected.
If no value is entered for I.begin, the initial value is determined
automatically.
I.end -999.99...999.99 nA...A;
Final value for scaling of current axis

This parameter appears only if I.scale = fixed has been selected.
If no value is entered for I.end, the final value is determined auto-
matically.
Division of the voltage axis

Division of the voltage axis in mV/cm for the plotting of substance
curves (not effective in display of the curves).
U.begin -3000...3000 mV;
Initial value for scaling of voltage axis

If no value is entered for U.begin, the initial voltage U.start of the
sweep is taken as the initial value.
U.end -3000...3000 mV;
Final value for scaling of voltage axis

If no value is entered for U.end, the final voltage U.end of the sweep
is taken as the final value.
I.end
I.begin
U.begin U.end

5.6.3 SUBSTANCES

Display / Plot display only
Display/plot (for measurement mode PSAMODE)

Title for those parameters which concern the display and plotting of
substance curves recorded with the measurement mode PSAMODE.
t/U.scale auto, fixed; auto
Scaling of the y axis of PSA curves

The following two possibilities are available for scaling of the y axis of
PSA curves for the display and plotting of substance curves:
auto Automatic scaling with matching to the measured
experimental values
fixed Fixed scaling with the preset values t/U.begin and
t/U.end
If all measurement values are outside the y axis fixed with t/U.scale,
the y axis for printing the substance curve is scaled automatically. In
this case, the message scale auto is printed in the header line.
t/U.begin -999.99...999.99 ns/V...s/V;
Initial value for scaling of the y axis of PSA curves

This parameter appears only if t/U.scale = fixed has been se-
lected.
If no value is entered for t/U.begin, the initial value is determined
automatically.
t/U.end -999.99...999.99 ns/V...s/V;
Final value for scaling of the y axis of PSA curves

This parameter appears only if t/U.scale = fixed has been se-
lected.
If no value is entered for t/U.end, the final value is determined auto-
matically.
Division of the voltage axis

Division of the voltage axis in mV/cm for the plotting of substance
curves (not effective in display of the curves).
U.begin -3000...3000 mV;
Initial value for scaling of voltage axis

If no value is entered for U.begin, the initial voltage U.start of the
sweep is taken as the initial value.
U.end -3000...3000 mV;
Final value for scaling of voltage axis

If no value is entered for U.end, the final voltage U.end of the sweep
is taken as the final value.
t/U.end
t/U.begin
U.begin U.end


Baseline display only
Baseline
Title for those parameters which concern calculation of the baseline.
These parameters are not displayed for substances recorded with
measurement mode PSAMODE.
Type linear, polynom, expon., AC2 rel., AC2 abs.; linear
Baseline type
The following possibilities are available for approximation of the
baseline and the evaluation of peaks/waves (see also section 6.7):
linear Linear baseline with DPMODE, SQWMODE, AC1MODE,
DCTMODE (with SSWEEP):
The linear type baseline is determined using the tangent
method. After definition of the peak base points dU.front
and dU.rear (automatically or by manual entry), starting
from the base points an iterative search within a fixed
range (inward: up to 1 point before the peak maximum;
outward: ca. 20 mV) is made for a common slope. The
two points of tangency are connected to produce the lin-
ear baseline.
If no common slope is found, the linear baseline is drawn
directly through the two base points.
linear, whole
dU.front dU.rear
Base point Base point

(front) (rear)
Point of tangency
(front)
Point of tangency
(rear)
Range for Range for

tangent search tangent search
Linear baseline with DCTMODE (with SWEEP):

Wave-shaped curves recorded with DCTMODE are al-
ways evaluated with the tangent method Type = linear.
The base points dU.front and dU.rear and the associ-
ated slopes S.front and S.rear can be determined
automatically or entered manually. In contrast to peaks
with a linear baseline, the slopes may be different.
linear, whole (DCT)
dU.front dU.rear
Base point
(rear)
S.rear
Base point I.wave

(front)
S.front
U.wave

5.6.3 SUBSTANCES

polynom Polynomial baseline with DPMODE, SQWMODE,
AC1MODE, DCTMODE (with SSWEEP):
With a baseline of the polynom type, the curvature of the
peak baseline is approximated by a polynomial curve.
After definition of the peak base points dU.front and
dU.rear and the associated slopes S.front and
S.rear (automatically or by manual entry), the curved
baseline is determined by calculation.
polynom, whole
dU.front dU.rear

(front) (rear)
S.front S.rear
expon. Exponential baseline with DPMODE, SQWMODE,

AC1MODE, DCTMODE (with SSWEEP):
The expon. type baseline is suitable for peaks which lie
on an exponentially ascending or descending baseline.
After definition of the peak base points dU.front and
dU.rear and the associated slopes S.front and
S.rear (automatically or by manual entry), the exponen-
tial baseline is determined by calculation.
expon., whole
dU.front dU.rear

(front) (rear)
S.rear
S.front
AC2 rel. Linear baseline with relative evaluation with AC2MODE:

Curves recorded with AC2MODE are always evaluated
with a linear baseline. The base points dU.front and
dU.rear can be determined automatically or entered
manually, the slopes S.front and S.rear have no
meaning here.
In the relative evaluation, the two peak heights If and Ir
are determined relative to the linear baseline and added
to give the result I.rel.
AC2 rel. dU.front dU.rear
I.rel = If + Ir
If
Ir
U/2


AC2 abs. Linear baseline with absolute evaluation with AC2MODE:
Curves recorded with AC2MODE are always evaluated
with a linear baseline. The base points dU.front and
dU.rear can be determined automatically or entered
manually, the slopes S.front and S.rear have no
meaning here.
In the absolute evaluation, the total peak height I.abs is
determined and put out as the result.
In place of AC2 abs., linear can be entered under
Type.
AC2 abs. dU.front dU.rear
I.abs
U/2
Scope whole, f.half, r.half, f.double, r.double; whole
Baseline range
The following possibilities exist to define the range over which the
baseline should be calculated:
whole Calculation of the baseline for the whole curve.
whole
f.half Calculation of the baseline starting from peak front half

(possible only with Type = linear).
r.half Calculation of the baseline starting from peak rear half
(possible only with Type = linear).
With f.half and r.half is recommended to set
S.front and S.rear from auto to 0.000 (zero).
linear, f.half linear, r.half
f.double Calculation of the baseline for the first peak of a double

peak (possible only with Type = linear, Type =
polynom and Type = expon.). The second peak must be
evaluated with the same Type.
r.double Calculation of the baseline for the second peak of a
double peak (possible only with Type = linear, Type =
polynom and Type = expon.). The first peak must be
evaluated with the same Type.

5.6.3 SUBSTANCES
f.double r.double
Wave-shaped curves recorded with DCTMODE are evalu-

ated only with Scope = whole.
dU.front auto, 10...500 mV; auto
Difference to front base point

Absolute voltage difference between base point at the peak/wave front
half and the peak voltage U.peak or halfwave voltage U/2.
With dU.front = auto, the difference is determined automatically
(default setting).
S.front auto, -99.99...99.99; auto
Slope at front base point

Slope of the baseline at its start point.
With S.front = auto, the slope is determined automatically (default
setting).
For peak baselines of the linear type, the slope is always calculated
automatically, any numeric entry is ignored.
For baselines of the AC2 rel. and AC2 abs. types, the slope is not
needed, any numeric entry is ignored.
dU.rear auto, 10...500 mV; auto
Difference to rear base point

Absolute voltage difference between base point at the peak/wave rear
half and the peak voltage U.peak or half-wave voltage U/2.
With dU.rear = auto, the difference is determined automatically
(default setting).
S.rear auto, -99.99...99.99; auto
Slope at rear base point

Slope of the baseline at its end point.
With S.rear = auto, the slope is determined automatically (default
setting).
For peak baselines of the linear type with Scope = whole or Scope =
f.double/r.double, the slope is always calculated automatically, any
numeric entry is ignored.
For baselines of the AC2 rel. and AC2 abs. types, the slope is not
needed, any numeric entry is ignored.
dU.front dU.rear

(front) (rear)
S.front S.rear


Evaluation display only
Evaluation
Title for those parameters which concern the evaluation of sub-
stances.
Mode VA, PSA; VA
Evaluation mode
Selection between evaluation mode for measurements with
PSAMODE (PSA) and those for all other VA measurement modes (VA).
Substances can be evaluated only if all substance pa-

rameters and program instructions correspond to the
selected evaluation mode.
Quantity I.peak, P.peak; I.peak
Evaluation quantity
Whereas only the wave height I.wave can be determined with waves
(DCTMODE with SWEEP), there are two different evaluation quantities
with peaks:
I.peak Peak height (current I in A)
P.peak Peak area (power P in W)
In the case of a linear baseline with Scope = f.half or
Scope = r.half, only the area up to the peak maximum
is taken as the evaluation quantity.
I.peak
I.wave
P.peak
Scope = whole Scope = f.half Scope = r.half
This parameter is not displayed for substances recorded with meas-

urement mode PSAMODE.
Sign. digits 1...5; 4
Significant digits
Number of significant figures for the calculated mass concentration
Mass. conc. on the "RESULTS/Evaluations" page.

5.6.3 SUBSTANCES

........ - XXXXXXXX
Calibration XXXX-XX-XX XX:XX

Technique none

19 20
Softkeys Meaning
Meaning of the softkeys F1...F7, see page 130
>> Switching to subpage "Substance parameters"

Switching to the subpage "Substance parameters" with the parame-
ters for substance recognition, baseline calculation, scaling and
evaluation.
19 20

Technique none, std.add., cal.crv., int.std.; none
Calibration technique
In order to determine the sample content (mass concentration) from
the measured current or area values for the substances EV:<subst.>,
a calibration is required (see section 6.9). One of the following calibra-
tion techniques can be selected for this (with none, no calculation is
performed):
none None
std.add. Standard addition 22

cal.crv. Calibration curve 23
int.std. Internal standard 24


........ - XXXXXXXX
Calibration XXXX-XX-XX XX:XX Coefficients

Technique std.add. Y.reg XXXXXXXXXX
Curve type ......... Slope XXXXXXXXXX
Nonlin. XXXXXXXXXX
Mean dev. XXXXXXXXXX
Additions

Soln.name ........ ........ ........ ........

Mass conc. .........g/L .........g/L .........g/L .........g/L
Range min .........g/L .........g/L .........g/L .........g/L
Range max .........g/L .........g/L .........g/L .........g/L
M.conc./cm .........g/L .........g/L .........g/L .........g/L

19 20
Softkeys Meaning

evaluation.
19 20

Calibration display only
XXXX-XX-XX
XX:XX Date of calibration
Date and time of the calculation of the standard addition.
Calibration technique = Standard addition (std.add.)

With the standard addition method, a known quantity of the substance
under investigation is added to the sample one or more times (see
section 6.9.4). The addition can be performed manually with a pipette
or the 6.5611.010 pipetting equipment, automatically with a 685
Dosimat or 700 Dosino attached to the 746 VA Trace Analyzer or with
the 695 Autosampler. There are two types of instructions for this
addition:

5.6.3 SUBSTANCES

ADD... Standard addition with the constant, preset volume
V.add.
PADD... Standard addition with a volume that is proportional to a
signal (EV:<subst.>) measured in the original sample,
which originates from any substance present in the
sample.
A standard addition is normally programmed with the following basic
structure:
:
SMPL>M or SMPL/M Sample addition to measuring vessel
(ADD Loop start for standard additions
(REP Loop start for replication
SEGMENT Call-up of segment (measurement)
REP)n Loop end, n = number of replications
ADD>M or PADD>M Constant or proportional standard addition
ADD)n Loop end, n = number of standard additions
:
Standard addition is the usual calibration method for the majority of

the applications possible with the 746 VA Trace Analyzer. Its advan-
tage lies in its high level of reliability as the calibration is performed in
the sample under real matrix conditions and all measurement pa-
rameters remain unchanged.
With regard to optimum accuracy and deviation, a number of rules
must be observed in standard additions:
Check linearity range
In development of the method, the linearity range should be
checked for each substance. This involves performing several
standard additions over a wide concentration range. Using the
calibration curve shown on the "CURVES" page, you can then
determine the region in which the standard addition is linear and
that in which it is non-linear (see also Curve type).
Working in the linear range
If the substance content lies in the linear range, multiple standard
addition is meaningful only if you wish to check the linearity in
every determination. To reduce the deviation, it is better to spike
the solution once only and to choose as many replications as
possible.
Working in the non-linear range
If the substance content is in the non-linear range, several stan-
dard additions have to be performed to determine the nonlinear
curve shape exactly.
Standard addition ratio 1:2 to 1:5
The optimum standard addition ratio for the entire standard addi-
tion lies between 1:2 and 1:5, i.e. the sum of all standard addition
amounts should be 2 to 5 times greater than the amount of sam-
ple in the measuring vessel. This can be easily checked later us-
ing the parameters Mass and Add.mass put out on the dialog
page "RESULTS/Evaluations".
Consideration of blank values
Any blank values must be determined separately and subtracted
in the formula calculation on the dialog page "CALCULATIONS".


Curve type linear, nonlin; linear
Curve type for standard addition

The measured values obtained in the standard addition can be
evaluated with a linear or a non-linear function (see also section
6.9.4):
linear Straight line of type y = bx
Calculation by weighted linear regression
y: EV Evaluation value (A, W or s)
x: eff Effective mass concentration in the
analysis solution
b: Slope Slope of the line
Y.reg Estimated EV value for sample con-
centration eff,s
std.add., linear
EV
3rd standard addition
Slope
2nd standard addition
Sample 1st standard addition
Y.reg
0
0 eff
4
nonlin Curve of type y = bx + cx
Calculation by weighted curve matching
analysis solution
b: Slope Slope of the line in the linear region
c: Nonlin. Non-linearity factor
Y.reg Estimated EV value for sample con-
centration eff,s
std.add., nonlin
EV
3rd standard addition

2nd standard addition
Sample
Slope 1st standard addition
Y.reg
0
0 eff

5.6.3 SUBSTANCES

Coefficients display only
Coefficients
Title for coefficients of the standard addition calculation.
Y.reg display only
Regression value calculated for sample

Display of the value Y.reg in A, W or s.
Y.reg is the evaluation quantity (current or area) for the sample
concentration eff,s calculated from the standard addition curve (see
also Curve type).
This value can be used in formulae as KY:<subst> (<subst> = sub-
stance name) for further calculations.
Slope display only
Slope of standard addition curve

Display of the slope in AL/g, WL/g or sL/g.
With non-linear curves Slope represents the slope in the linear region
(see also Curve type).
This value can be used in formulae as KS:<subst> (<subst> = sub-
Nonlin. display only
Non-linearity factor
Display of the non-linearity factor for a non-linear standard addition
4 4 4
curve in [Al/g] , [WL/g] or [sL/g] (see also Curve type).
This value can be used in formulae as KN:<subst> (<subst> = sub-
Mean dev. display only
Mean deviation of standard addition curve

Display of the calculated, mean deviation of the measured values
about the standard addition curve in A, W or s.
The size of Mean dev. can be used as a measure of the quality of a
standard addition.
This value can be used in formulae as KD:<subst> (<subst> = sub-
Additions display only
Additions
Title for the standard addition solutions. In conjunction with CASE
instructions, maximum 4 different standard addition solutions can be
defined.


Name of standard addition solution

The name of the standard addition solution must be identical with the
name entered under Soln.name with an ADD or PADD instruction.
If the standard addition solution has to be added automatically, this
solution must be entered on the "SOLUTIONS" page and assigned a
position Pos. (see section 5.3.4). The standard addition solutions
entered on the "SUBSTANCES" page can here be automatically
copied to the solution list with the softkey <Upd.from method>.
XXXXXXXX If already standard addition solutions have been entered on the "OP.
--------
SEQUENCE" page, these names are displayed on the softkeys and
can be incorporated directly.
Mass conc. 0.001...999.99 ng...kg/L;
Mass concentration std of standard addition solution

If the standard addition solution has to be added automatically, the
mass concentration must also be entered on the "SOLUTIONS" page
Range min 0.001...999.99 ng...kg/L;
Lower limit of working range

Here, a lower limit can be optionally defined for the working range in
the standard addition. If a mass concentration Mass conc. less than
the value entered here is found for the substance, an error message is
put out and the remark conc. out of range displayed on the
"RESULTS" page.
The lower limit of the working range (in terms of the effective mass
concentration eff) is marked by a vertical line in the display and on the
plot of the calibration curve.
Range max 0.001...999.99 ng...kg/L;
Upper limit of working range

Here, an upper limit can be optionally defined for the working range in
the standard addition. If a mass concentration Mass conc. greater
than the value entered here is found for the substance, an error
message is put out and the remark conc. out of range displayed on
the "RESULTS" page.
The upper limit of the working range (in terms of the effective mass
M.conc./cm 0.001...999.99 ng...kg/L;
Axis scaling for plot of standard addition curve

Here, the scale in g/L per cm for the plot of the x axis of the standard
addition curve (eff) can be entered. In the absence of an entry, the
entire curve is plotted within 10 cm.

5.6.3 SUBSTANCES

........ - XXXXXXXX

Technique cal.crv. Y.offset ..........
Curve type ......... Slope ..........
Temperature .........C Nonlin. ..........
Mean dev. ..........
Range min .........g/L # CSoln.name Mass conc.

Range max .........g/L
0 ........ .........g/L
M.conc./cm .........g/L 1 ........ .........g/L
M.conc.begin ......... 2 ........ .........g/L
3 ........ .........g/L
V0.CSoln. .........mL 4 ........ .........g/L
5 ........ .........g/L
6 ........ .........g/L
7 ........ .........g/L
8 ........ .........g/L
9 ........ .........g/L

19 20
Softkeys Meaning

evaluation.
19 20

XX-XX-XX XX:XX
Date of calibration
Date and time of the calculation of the calibration curve.
Calibration technique = Calibration curve (cal.crv.)

The relation between the mass concentration Mass conc. of a sub-
stance and the evaluation value EV is determined by a calibration
curve established by measurement of different standard solutions

Determinations with the aid of a calibration curve are normally pro-

grammed with the following basic structure:
:
D SMPL>M or SMPL/M Sample addition to measuring vessel
C (CAL Loop start for calibration
C CSOLN>M Addition of calibration solution to measuring vessel
SEGMENT Call-up of segment (with sweep)
MEAS Switch off voltage (solution change)
C RINSE Resetting of the volume bookkeeping to 0
C CAL)n Loop end, n = number of calibration solutions 1
:
First, this program must be used to record the calibration curve. For
this, Run mode = calibration must be set on the "MONITORING"
page. The instructions marked by D are ignored. The calibration
solutions (max. 10) are measured in sequence and the coefficients of
the calibration curve determined. To store these permanently, the
method must then be copied from the working memory into the
method memory. This occurs automatically with Auto.batch = on; an
unsecured method with the same name in the method memory will be
overwritten. A switch is then made to Run mode = determination and
the sample measured. Instructions marked by C are ignored.
The result determination with the aid of a calibration curve saves time
compared with standard additions, but is reliable only
if the matrix of all samples and calibration solutions is identical or
has no influence on the measurement
if all measurement parameters (capillary, temperature, etc.) re-
main unchanged during measurements
if the accuracy of the results obtained is checked regularly with
the standard addition method.

must be observed with calibration curves (see also section 6.9.5):
Check the linearity range of the calibration curve for each sub-
stance.
In determinations in the linear range, calibration must be per-
formed above all in the upper and lower parts of this range and
as large a number of replications as possible chosen.
Working in the non-linear range
In determinations in the non-linear range, as many calibration
solutions as possible with concentrations evenly distributed
throughout the entire range must be recorded.
Checking the offset
With curves, check with linear or nonlin whether the offset
Y.offset may be neglected. The size of the offset provides in-
formation on a possible systematic error or blank value.

5.6.3 SUBSTANCES
Determining working range

Extrapolations above the range determined with calibration solu-
tions are not allowed. Thus, enter the maximum admissible
working range on the dialog page "SUBSTANCES".
Keep temperature constant
Owing to the large temperature dependence of the measured
values ( 2%/C), it is advisable to work with the 6.1418.220 ther-
mostatted measuring vessel.
Curve type linear, 0/linear, nonlin, 0/nonlin; linear
Curve type for calibration curve

The calibration curve can be determined with linear or nonlinear
functions:
linear Straight line of type y = a + bx
Calculation by weighted linear regression.
Minimum number of calibration solutions: 2
0/linear Straight line of type y = bx

Calculation by weighted linear regression, the line is
passed through the origin.
4
nonlin Curve of type y = a + bx + cx
Calculation by weighted curve matching.
4
0/nonlin Curve of type y = bx + cx
Calculation by weighted curve matching, the curve is
passed through the origin.

analysis solution (g/L)
a: Y.offset Intercept
b: Slope Slope of the line or slope of the curve

in the linear region
c: Nonlin. Non-linearity factor

EV linear
nonlinear
Slope
Y.offset
eff
EV
0/linear
0/nonlinear
Slope
0
0 eff
Temperature 0.0...99.9 C; 25.0 C
Measurement temperature
Measurement temperature for calibration and measurement.
Owing to the large temperature dependence of the measured values
( 2%/C), it is advisable to work with the 6.1418.220 thermostatted
measuring vessel and to enter the set temperature here.
Range min 0.001...999.99 ng...kg/L;

Here, a lower limit can be optionally defined for the working range with
the calibration curve. If a mass concentration Mass conc. less than
the value entered here is found for the substance, an error message is
put out and the remark conc. out of range displayed on the
"RESULTS" page.
The lower limit of the working range (in terms of the effective mass
Range max 0.001...999.99 ng...kg/L;

Here, an upper limit can be optionally defined for the working range
with the calibration curve. If a mass concentration Mass conc. greater
than the value entered here is found for the substance, an error
message is put out and the remark conc. out of range displayed on
the "RESULTS" page.
The upper limit of the working range (in terms of the effective mass

5.6.3 SUBSTANCES

M.conc./cm 0.001...999.99 ng...kg/L;
Axis scaling for plot of calibration curve

Here, the scale in g/L per cm for the plot of the x axis of the calibration
curve (eff) can be entered. In the absence of an entry, the entire curve
is plotted within 10 cm.
M.conc.begin auto, zero; auto
Begin of x axis for plot of calibration curve

Selection of the begin of the x axis (mass concentration) for the plot of
the calibration curve:
auto Automatic selection of the begin
zero Begin fixed to 0 g/L
V0.CSoln. 0.1...50.0 mL; 5.000 mL
Addition volume of calibration solutions

Volume of every calibration solution that must be added to the meas-
uring vessel.
If work is performed with the 695 Autosampler, an asterisk * can be
entered here in place of a volume. However, this is admissible only if
the instruction CSOLN/F with subsequent solution transfer to the
auxiliary or measuring vessel is used.
If calibration curves of several substances are recorded simultane-
ously, V0.CSoln. must be the same for every substance.
Coefficients
Title for coefficients of the calibration curve.
Y.offset -999.9...999.9 e-20...e+20;
Intercept of calibration curve

Display of the intercept of the calculated calibration function of type
linear or nonlin in A, W or s. This value can be changed manually.
This value can be used in formulae as KY:<subst> (<subst> = sub-

Slope -999.9...999.9 e-20...e+20;
Slope of calibration curve

Display of the slope of the calculated calibration function in AL/g,
WL/g or sL/g. This value can be changed manually.
With non-linear curves, Slope represents the slope in the linear region
(see also Curve type).
Nonlin. -999.9...999.9 e-20...e+20;
Non-linearity factor
Display of the non-linearity factor of the calculated nonlinear calibra-
4 4 4
tion function in [Al/g] , [WL/g] or [sL/g] (see also Curve type). This
value can be changed manually.
This value can be used in formulae as KN:<subst> (<subst> = sub-


Mean dev. -999.9...999.9 e-20...e+20;
Mean deviation of calibration curve

about the calibration curve in A, W or s. This value can be changed
manually.
The size of Mean dev. can be used as a measure of the quality of a
calibration curve.
CSoln.name 8 characters;
Name of calibration solutions

The entry of a name for the calibration solutions is optional. The
names are used as follows:
Without 695 Autosampler, before every manual addition of a
calibration solution to the measuring vessel the message Next
Standard, CSOLN 'CSOLN.name''Mass conc.' > M appears with
details of the name and the mass concentration of the calibration
solution.
If work is performed with the 695 Autosampler with Auto.samples
= on, all calibration solutions must be entered on the "SAMPLES"
page. We advise you to enter the names CSoln.name there as
sample identification.
Mass conc. 0.001...999.99 ng...kg/L;
Mass concentration n of calibration solutions

The mass concentration must be specified for all n calibration solu-
tions defined by the instruction CAL)n.

5.6.3 SUBSTANCES

........ - XXXXXXXX

Technique int.std. Prop.fact. ..........
Mode analyte Mean dev. ..........
Ref.subst. ........
Temperature .........C
# CSoln.name Mass conc.

Range min .........g/L
Range max .........g/L 0 ........ .........g/L
1 ........ .........g/L
M.conc./cm .........g/L 2 ........ .........g/L
M.conc.begin ......... 3 ........ .........g/L
4 ........ .........g/L
V0.CSoln. .........mL 5 ........ .........g/L
6 ........ .........g/L
7 ........ .........g/L
8 ........ .........g/L
9 ........ .........g/L

19 20
Softkeys Meaning

evaluation.
19 20

XXXX-XX-XX
Date and time of the calculation of the calibration curve for the internal
standard.
Calibration technique = Internal standard (int.std.)

With the internal standard method, a known quantity of a reference
substance (r) is added to the analysis solution (see section 6.9.6). The
mass concentration a = Mass conc. of the analyte (a) is calculated
as follows from the ratio of the two evaluation values EVa / EVr and the
proportionality factor Prop.fact. determined beforehand by meas-
urement of various standard solutions:
a = r EVa / EVr 1 / Prop.fact.

The proportionality factor is determined by means of a linear function

of type 0/linear, i.e. a straight line of type y = bx passed through the
origin, where
y: EVa / EVr Ratio of the evaluation values of analyte
and reference substance
x: eff,a / eff,r Ratio of the effective mass concentrations
of analyte and reference substance in the
analysis solution
b: Prop.fact. Proportionality factor
The curve "EVa / EVr" vs "eff,a / eff,r" is displayed and plotted.
int.std.
EVa / EVr
0/linear
Slope = Prop.fact.
0
0 eff,a / eff,r
Determinations with the aid of an internal standard are normally

programmed with the following basic structure:
:
C CSOLN>M Addition of calibration solution to meas. vessel
RADD>M Addition of internal standard to meas. vessel
SEGMENT Call-up of segment (with sweep)
MEAS Switch off voltage (solution change)
C RINSE Resetting of the volume bookkeeping to 0
:
First, this program is used to record a calibration curve for determina-

tion of the proportionality factor. For this, the run mode on the
"MONITORING" page must be set to Run mode = calibration.
Instructions marked by D are ignored. Internal standard is added to
the calibration solutions (max. 10) in sequence and the measure-
ments performed.
To store the proportionality factor calculated from the calibration curve
permanently in the method, the method must then be copied from the
working memory into the method memory. This occurs automatically
with Auto.batch = on; an unsecured method with the same name in
the method memory will be overwritten.
The run mode is then switched to Run mode = determination. In-
structions marked by C are ignored. Internal standard is added to the
analysis solution and the measurement performed.

5.6.3 SUBSTANCES

The result determination with the aid of an internal standard saves
time compared with standard additions (particularly when several
substances are determined with the aid of the same internal stan-
dard), but is reliable only
if analyte and reference substance can be measured in
the same segment
if the requirement of a linear relation between analyte
and reference substance is met
if the matrix of all samples and calibration solutions is
identical or has no influence on the measurement, or if
the influence of the matrix is the same for all substances
(reference and analyte)
if all measurement parameters (capillary, temperature,
etc.) remain unchanged during measurements
if the accuracy of the results obtained is checked regu-
larly with the standard addition method.

must be observed with the internal standard method (see also section
6.9.6):
Check the linearity range of the calibration curve for each sub-
stance.
In determinations in the linear range, calibration must be per-
formed above all in the upper and lower parts of this range and
as large a number of replications as possible chosen.
Determining working range

Extrapolations above the range determined with calibration solu-
tions are not allowed. Thus, enter the maximum admissible
working range on the dialog page "SUBSTANCES".
Owing to the large temperature dependence of the measured
values ( 2%/C), it is advisable to work with the 6.1418.220 ther-
mostatted measuring vessel.
Mode analyte, referen.; analyte
Mode for parameter display

Selection of the parameter display for the measured substance or the
reference substance:
analyte Measured substance (analyte)
referen. Reference substance
(internal standard) 25
Analyte and reference substance must be assigned to the

same segment.


Ref.subst. 8 characters;
Name of reference substance

Here the name of the substance used as the reference substance
(internal standard) must be specified.
Range min 0.001...999.99 ng...kg/L;

Here, a lower limit can be optionally defined for the working range in
the evaluation with an internal standard. If a mass concentration Mass
conc. less than the value entered here is found for the substance, an
error message is put out and the remark conc. out of range dis-
played on the "RESULTS" page.
The lower limit of the working range (in terms of the ratio of the effec-
tive mass concentrations eff,a / eff,r) is marked by a vertical line in the
display and on the plot of the calibration curve.
Range max 0.001...999.99 ng...kg/L;

Here, an upper limit can be optionally defined for the working range in
the evaluation with an internal standard. If a mass concentration Mass
conc. greater than the value entered here is found for the substance,
an error message is put out and the remark conc. out of range
displayed on the "RESULTS" page.
The upper limit of the working range (in terms of the ratio of the
effective mass concentrations eff,a / eff,r) is marked by a vertical line
in the display and on the plot of the calibration curve.
M.conc./cm 0.001...999.99 ng...kg/L;
Axis scaling for plot of calibration curve

The dimensionless ratio of the effective mass concentrations
eff,a / eff,r is plotted on the x axis of the calibration curve. As a meas-
ure for the scaling of the x axis, the mass concentration a can be
entered here in g/L per cm. To obtain the actual scale of eff,a / eff,r ,
a must thus be divided by r and also any dilution taken into account.
In the absence of an entry, the entire curve is plotted within 10 cm.
M.conc.begin auto, zero; auto
Begin of x axis for plot of calibration curve

Selection of the begin of the x axis (mass concentration) for the plot of
the calibration curve:
auto Automatic selection of the begin
zero Begin fixed to zero on x axis

5.6.3 SUBSTANCES

V0.CSoln. 0.1...50.0 mL; 5.000 mL
Addition volume of calibration solutions

Volume of every calibration solution that must be added to the meas-
uring vessel.
If work is performed with the 695 Autosampler, an asterisk * can be
entered here in place of a volume. However, this is admissible only if
the instruction CSOLN/F with subsequent solution transfer to the
auxiliary or measuring vessel is used.
If calibration curves of several substances are recorded simultane-
ously, V0.CSoln. must be the same for every substance.
Coefficients
Title for the calculated coefficients of the calibration curve for the
internal standard.
Prop.fact. -999.9...999.9 e-20...e+20;
Proportionality factor
Display of the proportionality factor between analyte and reference
substance. The proportionality factor is identical with the slope calcu-
lated from the calibration lines. This value can also be entered or
changed manually.
Mean dev. -999.9...999.9 e-20...e+20;
Mean deviation of calibration curve for internal standard

about the calibration curve. This value can be changed manually.
The size of Mean dev. can be used as a measure of the quality of the
calibration curve for the internal standard.
CSoln.name 8 characters;
Name of calibration solutions

The entry of a name for the calibration solutions is optional. The
names are used as follows:
Without 695 Autosampler, before every manual addition of a
calibration solution to the measuring vessel the message Next
Standard, CSOLN 'CSOLN.name''Mass conc.' > M appears with
details of the name and the mass concentration of the calibration
solution.
If work is performed with the 695 Autosampler with Auto.samples
= on, all calibration solutions must be entered on the "SAMPLES"
page. We advise you to enter the names CSoln.name there as
sample identification.
Mass conc. 0.001...999.99 ng...kg/L;
Mass concentration a,n of calibration solutions

The mass concentration must be specified for all n calibration solu-
tions defined by the instruction CAL)n.


........ - XXXXXXXX
Calibration XXXX-XX-XX XX:XX

Technique int.std.
Mode referen.
Temperature .........C
Soln.name ........
Mass conc. .........g/L

19 20
Softkeys Meaning

evaluation.
19 20

XXXX-XX-XX
Date and time of the calculation of the calibration curve for the internal
standard.
Mode analyte, referen.; analyte
Mode for parameter display

Selection of the parameter display for the measured substance or the
reference substance:
analyte Measured substance (analyte) 24
referen. Reference substance
(internal standard)
Analyte and reference substance must be assigned to the

same segment.

5.6.3 SUBSTANCES

Name of solution with internal standard

The name of the solution which contains the internal standard must be
identical with the name entered in the instruction RADD>M under
Soln.name.
If the solution with the internal standard has to be added automati-

cally, this solution must be entered on the "SOLUTIONS" page and
assigned a position Pos. (see section 5.3.4). This solution entered on
the "SUBSTANCES" page can be automatically copied to the solution
list with the softkey <Upd.from method>.
Mass conc. 0.001...999.99 ng...kg/L;
Mass concentration r of solution with internal standard

If the solution with the internal standard has to be added automati-
cally, the mass concentration must also be entered on the
"SOLUTIONS" page (see section 5.3.4).

5.6.4 CALCULATION
: This dialog page is employed for the entry of calculation formulae

; and designations of the result quantities and units. Variables and
CALCU- operators can be used for free definition of the "Final results" put
LATION
out on the "RESULTS" page.
Method: XXXXXXXX CALCULATION

max. 15 lines

............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
............ ........................................ ........ ........
Modify Modify Delete Insert New Upd.from Syntax

column line line line calcul. method check
Softkeys Meaning

column

line
Delete Delete line

line
Insert Insert line

line
New Recalculation
calcul.
The content and formula calculation from the evaluation results of the
substances (EV values) is restarted.
Upd.from Transfer of standard formulae from method

method
For all substances defined in the method, standard formulae for the
mass concentration are entered and provide the results in g/L or g/g,
depending on the SMPL command and the sample size S0.
Sytax Syntax test

check
The put in formulae are checked for proper syntax. Any errors are
displayed.

5.6.4 CALCULATION

Method display only
Method name
Quantity 12 characters;
Result quantity
Designation of the result quantity (text-only entry).
On the transfer of standard formulae with the softkey <Upd. from
method>, the substance name is entered in this field.
If this field is left blank in a calculation formula, the result designation

(e.g. R1, A23) appears in the final formula.
Formula Formula expressions;
Calculation formulae
Display and entry of calculation formulae comprising value assign-
ments with the aid of instrument variables, freely definable variables,
constants and operators.
Value assignments
Value assignments are processed in the order of their entry. The
following four types of assignments are possible:
R..........= Value assignment for final result that is dis-
played and printed. The variable name must
start with an uppercase R and can then contain
max. 10 arbitrary characters (numbers or let-
ters).
A##= Value assignment for alternative result, which is
then displayed and printed only if it is set active
in CASE instructions. The variable name must
start with an uppercase A and can then contain
one of the numbers 01...15. Alternative result
formulae set active are marked by an asterisk *.
........= Value assignment to any variable for intermedi-
ate result (not displayed). The variable name
must start with a lowercase letter and can then
contain max. 7 arbitrary characters (numbers or
letters).
C##= Value assignment to common variable. The
variable name must start with an uppercase C
and can then contain one of the numbers
01...18.
Freely definable variables

The following variables must first be defined in value assignments and
can then be used as often as liked in other formulae:
R.......... Result
A## Alternative result
........ Intermediate result

Instrument variables
The following instrument variables can be used in formulae:
C## Common variable C01...C18 from the working
memory (see section 5.4.5). The common vari-
ables can be used to exchange results between
different determinations.
ED:<subst>:<V> Difference of the mean values of the evaluation
quantities (I.delta, P.delta or t.delta) for the
specified substance <subst> and variation <V>.
The numeric value put out refers to the basic
unit A, W or s.
ES:<subst>:<V> Standard deviation of evaluation quantities
(Std.dev.) for the specified substance <subst>
and variation <V>. The numeric value put out
refers to the basic unit A, W or s.
EU:<subst>:<V> Mean value of peak voltages (U) or half-wave
voltages (U/2) for the specified substance
<subst> and variation <V>. The numeric value
put out refers to the basic unit V.
EV:<subst>:<V> Mean value of evaluation quantities (I.mean,
P.mean or t.mean) for the specified substance
<subst> and variation <V>. The numeric value
put out refers to the basic unit A, W or s.
MA:<subst> Standard addition mass (Add.mass) for the
specified substance <subst>. The numeric
value put out refers to the basic unit g.
MC:<subst> Mass concentration s (Mass conc.) for the
specified substance <subst>. The numeric
value put out refers to the basic unit g/L.
MD:<subst> Total scatter (MC.dev.) of mass concentration s
for the specified substance <subst>. The nu-
meric value put out refers to the basic unit g/L.
ML:<subst> Scatter due to calibration (Cal.dev.) of mass
concentration s for the specified substance
<subst>. The numeric value put out refers to the
basic unit g/L.
MS:<subst> Substance mass (Mass) in the measuring vessel
for the specified substance <subst>. The nu-
meric value put out refers to the basic unit g.
KD:<subst> Mean scatter (Mean deviat.) for calibration and
standard addition curve of the specified sub-
stance <subst>. The numeric value put out re-
fers to the basic unit A, W or s.
KN:<subst> Non-linearity factor (Nonlin.) for calibration and
standard addition curve of the specified sub-
stance <subst>. The numeric value put out re-
4 4
fers to the basic unit [AL/g] , [WL/g] or
4
[sL/g] .

5.6.4 CALCULATION
KS:<subst> Slope (Slope) for calibration and standard addi-

tion curve or proportionality factor (Prop. fact.)
for internal standard of the specified substance
<subst>. The numeric value put out refers to the
basic unit AL/g, WL/g or sL/g.
KY:<subst> Intercept (Y.offset) for the calibration curve or
regression value (Y.reg) for standard additions
of the specified substance <subst>. The nu-
meric value put out refers to the basic unit A, W
or s.
S0 Sample size S0 entered on the "MONITORING
"page (see section 5.5.1). The numeric value put
out as S0 refers to the basic unit L or g.
S1 Sample-specific variable S1 entered on the
"MONITORING" page (see section 5.5.1). S1 is
put out as a numeric value.
put out as a numeric value. If S2 is used as a
density, the put out numeric value refers to the
unit g/mL.
put out as a numeric value.
V0 Sample volume (V0.sample) in the measuring
vessel at the start of the measuring. V0 refers to
the basic unit L.
Vfrac Fractional volume (V.fraction) with diluted
samples (volume fraction of the total volume
V.total which has been added to the measur-
ing vessel). Vfrac refers to the basic unit L.
Vmeas Volume of measuring solution in the measuring
vessel at the start of the first sweep. Vmeas re-
fers to the basic unit L.
Vtot Total volume (V.total) with diluted samples
(volume of sample S0 and dilution solution).
Vtot refers to the basic unit L.
Constants
Constants are put in as numeric values. They can cover the range
33 33 33 33
3.710 ... 1.710 / 0 / 1.710 ... 3.710 (input of the
exponential format with e or E, e.g. 2.378e-12).

Operators
The operators are processed from left to right. With nested expres-
sions, multiplication and division have precedence over addition and
subtraction.
= Equals (value assignment)
+ Addition
Subtraction
* Multiplication
/ Division
( ) Brackets
Max. 4 pairs of brackets can be nested.
Standard formulae
Pressing the softkey <Upd. from method> enters standard formulae in
this field which provide the mass concentration of the substances
referred to the sample size S0 as a final result in g/L or g/g.
Automatic entry of the standard formulae depends on whether the
sample size has been entered as a weight or volume and whether
diluted or undiluted samples have been used (see also section 5.4.4).
The dependence of the put in sample size S0 and the parameters of
the SMPL instructions is as follows:
S0 S2 V.fraction V.total Standard formula for final Result

result unit
L MC:<subst> g/L
g d MC:<subst> / (S2 * 1000) g/g
L V.fraction V.total MC:<subst> * V.tot / S0 g/L
g V.fraction V.total MC:<subst> * V.tot / S0 g/g
The standard formulae listed above refer to the basic quantities g and
L, but the results are automatically supplied with the appropriate prefix
by the simultaneous entry of #g/L or #g/g in the field Res.unit (see
Res.unit).
Standard formulae can be altered at a later date to specify the result in

another unit (e.g. ppm) or for further calculation.
In the case of modifications to the method which also

influence the standard formulae, any existing standard
formulae must be deleted and then regenerated with the
softkey <Upd. from method>).

5.6.4 CALCULATION
Conversions of standard formulae

The following table shows a few examples for the conversion of the
four possible standard formulae (see above):
S0 Desired result unit Formula Res.unit
L g/L with automatic prefix Standard formula #g/L

mg/L Standard formula * 1e+03 mg/L
g/L Standard formula * 1e+06 ug/L
ng/L Standard formula * 1e+09 ng/L
volume ppm Standard formula * 1e+03 ppm
volume ppb Standard formula * 1e+06 ppb
g g/g with automatic prefix Standard formula #g/g

mg/g Standard formula * 1e+03 mg/g
g/g Standard formula * 1e+06 ug/g
ng/g Standard formula * 1e+09 ng/g
weight ppm Standard formula * 1e+06 ppm
weight ppb Standard formula * 1e+09 ppb
Res.unit 8 characters;
Result unit
Designation of the result unit for final result (text-only entry).
If # is entered as the first character, the result calculated with the
formula is automatically provided with a prefix (m, , n, etc.)
6
(e.g. 5.64 g/L for 5.6410 g/L).
On the transfer of standard formulae with the softkey <Upd. from
method>, either #g/L or #g/g is entered in this field, depending on the
entry of S0 (see Standard formulae).
Sign.dig. 1...5; 5
Significant digits
Number of significant figures for the final result.

5.6.5 DOCUMENTATION
> This dialog page can be used for definition of the automatic
. output of reports and curves to the printer or the RS interfaces.
DOCUMEN- There is also the possibility to enter a detailed comment on the
TATION
method.
26 Method: XXXXXXXX DOCUMENTATION

Output
Auto form feed .... Auto error printing ....

.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
.................................................. ....................
Modify Modify Delete Insert Exec. Exec. >>

column line line line line all Comment
27
Softkeys Meaning

column

line
Delete Delete line

line
Insert Insert line

line
Exec. Execute selected line

line
The line selected with the field cursor is executed.
Exec. Execute all lines

all
All put in lines are executed.
>> Comment
Comment
Switching to the subpage "Comment" for entry of a comment on the
method.
27

5.6.5 DOCUMENTATION

Method display only
Method name
Auto form feed no, yes; no
Automatic page advance

The automatic page advance before every report and curve printout
can be switched on or off here.
no No automatic page advance, printing is continuous
and without regard to perforation.
yes Automatic page advance before every report and
curve printout.
Auto error no, yes; no

printing
Automatic error printing
The automatic printing of error messages during program execution
can be switched on or off here.
no No automatic printing of error messages.
yes The error messages occurring during program execu-
tion (status * BUSY *) are continuously printed out
(together with date and time of occurrence) on the
printer..
COPY Report ...,Curve ...;
Selection of objects for automatic output

These lines can be used for entry of the objects (reports or curves)
which are put out automatically at the specified destination after every
determination. Each step in the entry is supported by softkeys which
offer the current selection possibilities for direct incorporation.
Reports
All reports with the exception of MethSpc and Mpts start with the
same preamble containing the following details:
METROHM Name of manufacturer
746 VA TRACE ANALYZER Instrument designation
(5.746.0101) Program number
Determ. Name of determination

Modified Modification time (no = unchanged)
Sample table Name of sample table (if sample data
transferred from sample table)
User User name
Run Run number
Date Date of recording
Time Time of recording
Pos. Position number of sample on sample

rack (with 695 Autosampler)
Ident.1/S1 Sample identification 1 or S1
Method.call Method call-up
Sample size/S0 Sample size

Method Method name

Title Method title
Remark 1 Remark 1 regarding method
Remark 2 Remark 2 regarding method
The following reports can be selected:

Report Short Short report with Final results which have
been defined on the "CALCULATIONS" page. This
report is identical with the subpage "Calculations"
Report Eval Evaluation report with detailed results of the peak

or wave evaluation for all substances. This report
is identical with the subpage "Evaluations" (see
section 5.5.2).
Report Full Full report with the following outputs:

Detailed results of the peak or wave evaluation
for all substances (subpage "Evaluations", see
section 5.5.2)
Results of all substance calibrations (subpage
"Calibrations", see section 5.5.2)
Solutions (dialog page "SOLUTIONS", see
section 5.3.4)
Common variables (dialog page "COMMON
VARIABLES", see section 5.4.5)
Final results (subpage "Calculations", see sec-
tion 5.5.2)
Report MethSpc Method report with output of all dialog pages of

the group "Method Specifications":
Dialog page "OPERATION SEQUENCE"
Dialog page "SEGMENTS" (all segments)
Dialog page "DOCUMENTATION"
Dialog page "SUBSTANCES" (all substances)
Dialog page "CALCULATION"
Report Mpts Measured point report with output of the list of

measured points of segments. It is necessary to
enter the name of the substance or segment and
the VR number:
Sbst:<subst> Output of the original measured values of the
segment associated with the specified substance.
Sgmt:<segm> Output of the original measured values of the
specified segment.
VR: xx Selection of the single measurement whose list of
measured points should be put out by specifica-
tion of the VR number (V = variation, R = replica-
tion). On entry of *, all variations or replications
are put out.

5.6.5 DOCUMENTATION
Report Comment Comment report with output of the method com-

ment entered on the subpage "Comment".
Report ActDetm Full report of the determination including determi-

nation file for output to a PC via RS interface for
further processing with the PC Windows pro-
grams "VA Back Up" and "VA Database". The re-
port contains an ASCII part and finally the binary
file. It has the following layout:
XXXXXXXX.dtm File name of determination
A-Fullreport, esize: Identification for full report and
details of file size in bytes
Report Full Full report (see above)
A-Meth.spec Identification for method report
Report MethSpc Method report (see above)
A-Sweeps (smooth) Identification for report of
smoothed measured points
Report Mpts List of smoothed measured
points for all segments (see
above)
A-Baselines Identification for report of base-
lines
Report Mpts List of baseline points for all sub-
stances
A-Calibrations Identification for report of calibra-
tion curves
Report Mpts List of calibration points for all
substances
B-File Identification for binary file
XXXXXXXX.dtm Determination file (binary file)
Report ActMeth Full method report including method file for output
to a PC via RS interface for further processing
with the PC Windows programs "VA Back Up" and
"VA Database". The report includes an ASCII part
and finally the binary file. It has the following lay-
out:
XXXXXXXX.mth File name of method
A-Meth.spec, esize: Identification for method report
and details of file size in bytes
Report MethSpc Method report (see above)
B-File Identification for binary file
XXXXXXXX.mth Method file (binary file)

Curves
All curve plots start with a preamble containing the following details:
METROHM Name of manufacturer
746 VA TRACE ANALYZER Instrument designation
(5.746.0101) Program number
Method Method name
Mode Measurement mode
Run Run number
Curve Type of curve
(does not appear with Curve Cal)
User User name
Determ. Name of determination
Sample Sample identification 1 or S1
(appears only with Curve Cal)
Segment Segment name
Date Date of recording
Time Time of recording
V R Number of variation V and replication R
The following curves are then put out:
Curve Orig Original curve (original)
In contrast to the screen display on the "CURVES"
page (see section 5.5.3), the measured points are
connected by a line.
Curve Proc Processed curve (processed)
In contrast to the screen display on the "CURVES"
page (see section 5.5.3), the measured points are
connected by a line.
Curve Smth Smoothed curve (smoothed)
The representation corresponds to the screen
display on the "CURVES" page (see section
5.5.3).
Curve Derv Derived curve (derived)
display on the "CURVES" page (see section
5.5.3).
Curve PSA PSA curve
The smoothed substance or segment PSA curve
is plotted. The representation corresponds to the
screen display on the "CURVES" page (see sec-
tion 5.5.3).
Curve Cal Calibration curve (calibr.)
display on the "CURVES" page (see section 5.5.3)
and depends on the selected calibration tech-
nique (standard addition, calibration curve or in-
ternal standard) and the selected run mode
(determination or calibration).

5.6.5 DOCUMENTATION
The following is an overview of the possible curve plots:
I I dI/dU
Orig Smth Derv

Proc
U U U
t/U U
PSA subst PSA seg
U t
EV EV EV
std.add. cal.crv. cal.crv.

determ. calibr. determ.
eff eff eff
EVa/EVr EVa/EV r
int.std. int.std.
calibr. determ.
a/r a/r


Curve Orig, Curve Proc, Curve Smth, Curve Derv, Curve PSA
For the output of these curves, entry of the substance or segment

name and the VR number is necessary:
Sbst:<subst> Output of substance curve.
The scalings of the axes are in accordance with
the display/plot parameters for the substances
In measurements with background compensa-
tion, the background is already subtracted.
At the end of the curve output, the substances
found with name, peak/wave voltage (U) and
evaluation quantity current (I), power (P) or time (t)
are put out.
Sgmt:<segm> Output of segment curve.
The scalings of the axes are in accordance with
the display/plot parameters for the segments (see
section 5.6.2).
In measurements with background compensa-
tion, the curve 00-backgnd is also put out in addi-
tion to the 00 curve if VR = 00 or VR = ** is
selected.
VR: xx Selection of the single measurement whose curve
should be plotted by specifying the VR number (V
= variation, R = replication). On entry of *, all
variations or replications are put out.
Curve Cal
For output of the calibration curve, entry of the substance name is

necessary:
Sbst:<subst> Output of the substance calibration curve. The
scaling of the y axis (EV) is automatic, that of the x
axis () in accordance with the parameter
M.conc./cm entered on the "SUBSTANCES" page
The name of the selected substance is put out following the calibra-
tion curve.
TO destination Printer, RSIfc.1, RSIfc.2; Printer
Destination of automatic output

The automatic output of reports or curves can be sent to the following
destinations:
Printer Printer connected to parallel interface (746.0010)
or built-in thermal printer (746.0020)
RSIfc.1 RS232 interface 1
(attachment possibilities, see section 3.12)
RSIfc.2 RS232 interface 2
(attachment possibilities, see section 3.12)
If Printer has been selected as the first destination, one of the two RS
interfaces can also be selected as a second destination for simulta-
neous output.

5.6.5 DOCUMENTATION
27 Method: XXXXXXXX DOCUMENTATION

Comment
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Help Delete Insert Get Put >>

line line line line Output
26
Softkeys Meaning
Help Help message for comment page
Delete Delete line

line
Insert Insert line

line
Get Copy line to temporary storage

line
The line selected with the field cursor is copied to the temporary
storage.
Put Copy line from temporary storage and insert

line
The line stored in the temporary storage is inserted above the line
selected with the field cursor.
>> Output
Output
Switching to the subpage "Output" for the output of reports and
curves.
26


Method display only
Method name
Comment 1600 characters;
Method comment
On this page, max. 20 lines each of 80 characters can be entered as a
comment on the method.
For storage of the put in comment, this page must be quit

by pressing the softkey <Output>.
If the <ESC> key is used to quit the page, the changes
made since this page was called up will not be stored.
Pressing the <ENTER> key on this dialog page is equiva-
lent to CR/LF (jump to new line).

5.7.1 General guidelines
5.7 Program instructions

5.7.1 General guidelines
The 746 VA Trace Analyzer can be used for the free programming of the sequence
of voltammetric determinations with the aid of program instructions, the associated
parameters and a line time which can be set to any value. The two following dialog
pages are available for the entry of these instructions:
"OP.SEQUENCE" Main program with call-up of the segments

"SEGMENTS" Max. 8 segments for measured value recording
(sweeps, one sweep allowable per segment) or macros
Each program instruction is located on an instruction line with the following basic
structure:

## .. DCTMODE ..... t.step ........s t.meas ........s
Program Line Main parameters Auxiliary parameters

instruction time
Line attribute
Line number
The following rules apply to the basic elements of the instruction line (see also sec-
tion 5.6.1 and section 5.6.2):
Line number The lines are numbered consecutively on entry of the instruc-
tions. Maximum 99 instruction lines are possible on the
"OP.SEQUENCE" page, maximum 29 instruction lines per
segment on the "SEGMENTS" page.
Line attribute Each instruction line can be optionally provided with one of the
following attributes:
when the program run mode is set to Run mode =
calibration

only when the program run mode is set to Run mode =
determination.
! Inactive line; this line is not executed.

@..@ Inactive range; the range between the two lines
marked by @ is not executed.

Program An overview of the possible program instructions is given in

instruction section 5.7.2. You will find the complete, alphabetical instruction
list and the possible abbreviations in the entry in section 5.7.3.
All instructions possible on the appropriate dialog page are
displayed in alphabetical order on the softkeys and can thus be
directly adopted. When the program instruction is entered, the
associated main and auxiliary parameters are inserted auto-
matically.
Line time Most instruction lines can be optionally provided with a wait
time. During the program run, this line time will be allowed to
elapse before the next instruction is executed. With SWEEP
instructions, the line time is calculated automatically and can
not be changed.
Main The main parameters are inserted automatically on entry of the

parameters program instruction. The parameters are provided with default
values, which can be changed.
Auxiliary The auxiliary parameters are inserted automatically on entry of

parameters the program instruction. The parameters are provided with
default values, which can be changed.

5.7.2 Overview of the program instructions
The following overview tables provide a brief introduction to the program instruc-
tions separated by category. You will find more detailed information and an expla-
nation of the parameters associated with the instruction in section 5.7.3.
The overview tables for the instructions contain not only the instruction and its
meaning, but also the two columns Page (dialog page) and Stand (VA Stand).
These show where the instruction is admissible. The meaning of the letters is as
follows:
O Instruction admissible on dialog page "OP.SEQUENCE"
S Instruction admissible on dialog page "SEGMENTS"
M Instruction admissible with manual 747 VA Stand
A Instruction admissible with automatic 747 VA Stand and

695 Autosampler
Electrode
Instruction Meaning Page Stand
DME Switch on dropping mercury electrode O, S M, A
HMDE Switch on hanging mercury drop electrode O, S M, A
SMDE Switch on static mercury drop electrode O, S M, A
RDE Switch on rotating disk electrode O, S M, A
Measurement mode
AC1MODE Measurement mode for alternating current O, S M, A

st
voltammetry of the 1 harmonic
AC2MODE Measurement mode for alternating current O, S M, A

nd
voltammetry of the 2 harmonic
CYCMODE Measurement mode for cyclic voltammetry O, S M, A
DCTMODE Measurement mode for direct current voltammetry O, S M, A

(Direct Current Tast)
DPMODE Measurement mode for differential pulse O, S M, A

voltammetry
PSAMODE Measurement mode for potentiometric stripping O, S M, A

analysis
SQWMODE Measurement mode for square wave voltammetry O, S M, A

Data acquisition (sweep) and measurement
SWEEP Voltage sweep for measurement modes DCTMODE, S M, A

DPMODE, SQWMODE, AC1MODE, AC2MODE
SSWEEP Voltage sweep for measurement mode DCTMODE if S M, A

peaks appear instead of waves
FSWEEP Voltage sweep with potentiostat in the "fast" operat- S M, A

ing mode for measurement modes DPMODE and
SQWMODE
TSWEEP Current measurement at constant voltage S M, A

(coulometry)
PSWEEP Sweep for PSAMODE measurement mode S M, A
RAMP Voltage ramp for cyclic voltammetry S M, A
MEAS Apply voltage to electrodes, current measurement O, S M, A

without measured value recording
MEAS Switch off voltage, current measurement and DME O, S M, A
Replication loops
(REP Loop start for replications O, S M, A
REP)n Loop end for replications O, S M, A

n = number of repetitions
(ADD Loop start for standard addition O, S M, A
ADD)n Loop end for standard addition O, S M, A

n = number of standard additions
(CAL Loop start for calibration O, S M, A
CAL)n Loop end for calibration O, S M, A

n = number of calibration solutions
(VAR Loop start for parameter variation O, S M, A
VAR)n Loop end for parameter variation O, S M, A

n = number of repetitions
VARNI Variation of the next instruction O, S M, A

Background compensation
(BACKGND Start of block for background compensation O M, A
BACKGND) End of block for background compensation O M, A
Cyclic voltammetry
(CSWEEP Start of block for cyclic voltammetry S M, A
CSWEEP) End of block for cyclic voltammetry S M, A
Sample preparation
(PREP Start of block for parallel sample preparation on the O A

695 Autosampler
PREP) End of block for parallel sample preparation O A
>PREP Call-up of sample preparation block O A
Branching
(CASE Start of decision block with decision O, S M, A
CASE Further decision within a decision block O, S M, A
CASE) End of decision block O, S M, A
EXIT Immediate exit from loop or block when test O, S M, A

condition met
Purging
PURGE Switch on purging O, S M, A
PURGE Switch off purging O, S M, A
TPURGE Purging for a predetermined line time O, S M, A

Stirring
STIR Switch on stirrer O, S M, A
STIR Switch off stirrer O, S M, A
TSTIR Stirring for a predetermined line time O, S M, A
Addition of sample
SMPL/M Sample volume is already in measuring vessel O, S M

(MEAS)
SMPL>M Add sample volume to measuring vessel (MEAS) O, S M, A
SMPL/F Sample volume is already in sample vessel (FEED) O, S A
Dispensing of auxiliary solutions
DOS/M Auxiliary solution is already in measuring vessel O, S M

(MEAS)
DOS>M Dispense auxiliary solution into measuring vessel O, S M, A

(MEAS)
DOS>A Dispense auxiliary solution into auxiliary vessel O, S A

(AUX)
DOS>F Dispense auxiliary solution into sample vessel O, S A

(FEED)
SDOS>M Dispense auxiliary solution proportional to sample O, S M, A

size S0 into measuring vessel (MEAS)
SDOS>A Dispense auxiliary solution proportional to sample O, S A

size S0 into auxiliary vessel (AUX)
SDOS>F Dispense auxiliary solution proportional to sample O, S A

size S0 into sample vessel (FEED)
PDOS>M Dispense auxiliary solution proportional to measured O, S M, A

evaluation value into measuring vessel
FEED Dispensing and pipetting functions with the O, S M, A

700 Dosino (reserved for future applications)

Dispensing of standard addition solutions
ADD/M Standard addition solution is already in measuring O, S M

vessel (MEAS)
ADD>M Dispense standard addition solution into measuring O, S M, A

vessel (MEAS)
PADD>M Dispense standard addition solution proportional to O, S M, A

the measured evaluation value into measuring
vessel
Dispensing of calibration solutions

(calibration curve and internal standard)
CSOLN>M Dispense calibration solution into measuring vessel O, S M, A

(MEAS)
CSOLN/M Calibration solution is already in measuring vessel O, S M

(MEAS)
CSOLN/F Calibration solution is already in sample vessel O, S A

(FEED)
RADD>M Dispense reference solution with internal standard O, S M, A

into measuring vessel (MEAS)
RADD>F Dispense reference solution with internal standard O, S A

into sample vessel (FEED)
Instructions for 695 Autosampler
A>M Transfer solution from auxiliary vessel (AUX) to O, S A

measuring vessel (MEAS)
F>M Transfer solution from sample vessel (FEED) to O, S A

measuring vessel (MEAS)
F>A Transfer solution from sample vessel (FEED) to O, S A

auxiliary vessel (AUX)
RINSE Rinse measuring vessel (MEAS) and reset volume O, S M, A

bookkeeping to "0"
VMIX Mix solution in specified rack position O, S A
VWASH Additional rinsing of transfer tubing after solution O, S A

transfer to target vessel

Instructions for 717 Sample Changer
LIFT Lift position for 717 Sample Changer O, S M
SHIFT Shift position for 717 Sample Changer O, S M
Instructions for the remote interface
SCANCTRL Inquiry of input control lines 1...8 and program stop O, S M, A

until the test condition is met or the line time has
elapsed
SETCTRL Setting output control lines 1...8 O, S M, A
Instructions for RS232 interface and printer
SEND>RS1 Sending a message to RS interface 1 O, S M, A
SEND>RS2 Sending a message to RS interface 2 O, S M, A
PRINT Printout of a message O, S M, A
Miscellaneous
SEGMENT Call-up of a segment O M, A
HOLD Program hold with output of a message O, S M, A
NOP Blank line without function (No Operation) O, S M, A
REM Remarks or comments line O, S M, A
END End of main program or segment O, S M, A
DSWEEP Voltage sweep without measured value recording O, S M, A

(Dummy Sweep)
CONDC Electrochemical regeneration of carbon electrodes O, S M, A

(e.g. glassy carbon)
BEEP Audio signal O, S M, A
SIMPULSE Simulation of standard additions with the 3.496.8380 O, S M, A

Voltage Simulator
SIMRESET Resetting of the 3.496.8380 Voltage Simulator O, S M, A

5.7.3 Alphabetical instruction list
In what follows you will find detailed information regarding the program instructions
and the associated parameters. The abbreviations for Page and Stand in the title
line have the following meaning:
O Instruction admissible on dialog page "OP.SEQUENCE"
S Instruction admissible on dialog page "SEGMENTS"
M Instruction admissible with manual 747 VA Stand
A Instruction admissible with automatic 747 VA Stand and

695 Autosampler

AC1MODE Page: O, S Stand: M, A Abbreviation: A

## .. AC1MODE ..... U.ampl ........mV Modul.freq. ........Hz
t.step ........s Prep.cycles ........
Ph.angle ........ Meas.cycles ........
st
Function AC1 measurement mode for alternating current voltammetry of the 1
harmonic.
Application Alternating current voltammetry with the AC1MODE measurement mode is

primarily suitable for determinations based on reversible redox reactions
(e.g. Zn in HCl). It is virtually completely insensitive to irreversible
reactions.

U.ampl 1...35 mV; 20 mV
Effective voltage amplitude

Effective voltage amplitude (RMS voltage amplitude = maximum
voltage amplitude / 2) of the superimposed alternating voltage.
t.step 0.05...9.9 s; 0.3 s
Time interval for voltage step

Time interval after which the voltage in the sweep is increased or
decreased by the amount U.step.
The following condition applies to the definition of t.step:
Meas.cyc. + Prep.cyc.
t.step > + t.drop + 30 ms
Modul.freq.
Ph.angle -180...180; 0
Phase angle
Phase shift of the alternating voltage in regard to the measurement
interval for current addition or subtraction.
Modul.freq. 10...250 Hz; 25/30 Hz for 50/60 Hz
Modulation frequency
Modulation frequency of the superimposed alternating voltage.
Prep.cycles 0...255; 0
Number of preparation cycles

Number of alternating voltage cycles without current measurement
which are performed for every voltage step before the measurement
cycles.
Meas.cycles 1...24; 2
Number of measurement cycles

Number of alternating voltage cycles with current measurement which
are performed for every voltage step.
The following condition holds for the definition of Meas.cycles:
Meas.cycles < Modul.freq. * 0.1 s

Description In the AC1MODE measurement mode, a sinusoidal alternating voltage with

a small, constant amplitude and low frequency is superimposed on a
st
stepwise rising direct voltage ramp. The 1 harmonic wave of the alter-
nating current component I produced by the alternating voltage is
measured as a function of the voltage U. The nature of the measurement
is illustrated below using the SMDE as an example.
Area
F (Hg)
Adjustable parameters:
AC1MODE t
t.step t.drop
U.ampl
Modul.freq.
U U.step
Ph.angle
Prep.cycles
Meas.cycles U.start Prep. Meas.
cycles cycles
SWEEP
U.start t.step
U.end t
U.step
t.modul = 1/Modul.freq.
Ph.angle = 0
U.ampl 2
t.meas (In+) t.meas (In)

(current addition) (current subtraction)
Ph.angle > 0
90 180 270 360
Ph.angle
Ph.angle < 0
-180 -90 90 180 270 360
Ph.angle

The phase dependent differences in the current measurements give

peak-shaped curves which can be evaluated using the baselines of type
linear, polynom or expon. (see section 5.6.3).
(In+ In)
I I=
n
I.peak
n = Meas.cycles
U.peak U
Comments The AC1MODE measurement mode can be used with all types of
electrodes together with the instructions MEAS, SWEEP, DSWEEP,
FSWEEP or TSWEEP.
The electrode type DME, SMDE, HMDE or RDE must be entered before
the AC1MODE measurement mode.
With the AC1MODE measurement mode, the potentiostat always
operates in the operating mode "fast". SWEEP and FSWEEP are thus
identical for this mode.
The quantity t.drop important for the definition of t.step depends
on the type of electrode selected:
DME t.drop = 20 ms
HMDE and RDE t.drop = 0 ms
SMDE t.drop = Drop.size 40 ms
see also AC2MODE, SWEEP, DME, SMDE, HMDE, RDE

AC2MODE Page: O, S Stand: M, A Abbreviation: AC2

## .. AC2MODE ..... U.ampl ........mV Modul.freq. ........Hz
Ph.angle ........ Meas.cycles ........
nd
Function AC2 measurement mode for alternating current voltammetry of the 2
harmonic.
Application Alternating current voltammetry with the AC2MODE measurement mode is
primarily suitable for determinations based on reversible redox reactions
(e.g. Zn in HCl). Compared with the AC1MODE measurement mode, an in-
crease in sensitivity, resolution and separation efficiency is often
obtained.

U.ampl 1...35 mV; 20 mV
Effective voltage amplitude

Effective voltage amplitude (RMS voltage amplitude = maximum
voltage amplitude / 2) of the superimposed alternating voltage.
t.step 0.05...9.9 s; 0.3 s

Modul.freq.
Ph.angle -90...90; 45
Phase angle
Phase shift of the alternating voltage in regard to the measurement
interval for current addition or subtraction.
Modulation frequency of the superimposed alternating voltage.

Number of alternating voltage cycles without current measurement
cycles.

Number of alternating voltage cycles with current measurement which
are performed for every voltage step.
Meas.cycles < Modul.freq. * 0.1 s

Description In the AC2MODE measurement mode, a sinusoidal alternating voltage with

a small, constant amplitude and low frequency is superimposed on a
nd
stepwise rising direct voltage ramp. The 2 harmonic wave of the alter-
nating current component I produced by the alternating voltage is
measured as a function of the voltage U. The nature of the measurement
is illustrated below using the SMDE as an example.
Area
F (Hg)
AC2MODE t
t.step t.drop
U.ampl
Modul.freq.
U U.step
Ph.angle
Prep.cycles
Meas.cycles U.start Prep. Meas.
cycles cycles
SWEEP
U.start t.step
U.end t
U.step
Ph.angle = 0
U.ampl 2
(In+) t.meas t.meas t.meas t.meas (In)

(current addition) (In+) (In) (In+) (In) (current subtraction)
Ph.angle > 0
90 180 270 360
Ph.angle
Ph.angle < 0
-180 -90 90 180 270 360
Ph.angle


curves which can be evaluated using the baselines of type AC2 rel. or
AC2 abs. (see section 5.6.3).
(In+ In)
I=
n
I If n = Meas.cycles
I.abs
Ir
I.rel = If + Ir
U / 2 U
Comments The AC2MODE measurement mode can be used with all types of
FSWEEP or TSWEEP.
the AC2MODE measurement mode.
With the AC2MODE measurement mode, the potentiostat always
DME t.drop = 20 ms
see also AC1MODE, SWEEP, DME, SMDE, HMDE, RDE

(ADD Page: O, S Stand: M, A Abbreviation: (

## .. (ADD .....
Function Start of the loop for standard addition.
Description The (ADD instruction opens a loop for standard additions. This loop
must include one of the dispensing instructions ADD/M, ADD>M or PADD>M
for addition of the standard addition solution as well as a sweep or
segment call-up. Any other additional instructions can be incorporated.
The loop must be closed with the ADD)n instruction.
Comments A program can contain several ADD loops, but they must not be
nested.
REP loops are allowed within ADD loops, an ADD loop can also be
included within a REP loop.
No CAL or VAR loops are allowed within ADD loops.
In the last execution of an ADD loop, the instructions ADD>M, ADD/M or
PADD>M are no longer executed.
The EXIT instruction can be included within ADD loops for a

premature exit from this loop.
Example A standard addition is normally programmed on the "OP.SEQUENCE"

page with the following basic structure:
:
SEGMENT Call-up of the segment (measurement)
ADD>M, ADD/M or PADD>M Constant or proportional standard addition
:
see also ADD)n, ADD/M, ADD>M, PADD>M, EXIT,

Standard addition (section 5.6.3 and section 6.9.4)

ADD)n Page: O, S Stand: M, A Abbreviation: AD

## .. ADD)n .....
Function End of the loop for standard addition.

n 0...8; 0
Number of standard additions

This parameter defines the number of repetitions of the ADD loop, i.e.
the number of standard additions.
Description The ADD)n instruction ends a loop opened with (ADD for standard
additions. This loop must include one of the dispensing instructions
ADD/M, ADD>M or PADD>M for addition of the standard addition solution as
well as call-up of a sweep or segment. Any other additional instructions
can be incorporated.
Comments see (ADD
Example see (ADD
see also (ADD, ADD/M, ADD>M, PADD>M

ADD/M Page: O, S Stand: M Abbreviation: ADD/

## .. ADD/M ..... Soln.name ........ V.add ........mL
Function Standard addition solution has been added to the measuring vessel
(MEAS) (e.g. with a 665 Dosimat).

Name of the standard addition solution

The name of the standard addition solution must be identical to the
name entered on the "SUBSTANCES/Calibration" page under
Soln.name (see section 5.6.3). The mass concentration of the standard
addition solution Mass conc. must also be entered on this page.
V.add 0.010...50.000 mL; 0.100 mL
Solution volume that has been added

Volume of the standard addition solution that has been added to the
measuring vessel.
Description The ADD/M instruction is needed when a standard addition solution

should be added automatically using a dosing unit (e.g. 665 Dosimat or
725 Dosimat) which, in contrast to the 685 Dosimat or 700 Dosino, can
not be directly controlled by the 746 VA Trace Analyzer. In this case, the
addition must be initiated via the RS232 interface (using the SEND>RS#
instructions) or via the remote interface (using the SETCTRL instructions)
and then confirmed with the ADD/M instruction.
Comments The ADD/M instruction must be located within an ADD loop.

In the last execution of the ADD loop, the ADD/M instruction is no
longer executed.
The ADD/M instruction can not be used in operation with the 695
Autosampler.

Example Addition of a standard addition solution with the 665 Dosimat via the
remote interface:
746 connection: Connection "Control Lines" 23 (see section 3.13)
665 connection: Connection 8 for external dosing contact
(see 665 Instructions for Use)
Connecting cable: Cable with 25-pin connector, pin 5 (output 1) connected to red
banana plug, pin 25 (0 V) to black banana plug
Setting on 665: "DIS R" mode with fixed dispensing volume V.add
Program:
:
SETCTRL *******1 Start of dispensing at 665 Dosimat
: by setting control line 1 active
NOP xxx s Entry of a wait time until dispensing
: is at an end
SETCTRL *******0 Resetting of control line 1
ADD/M Standard addition solution has been added
:
see also (ADD, ADD)n, ADD>M, PADD>M, SETCTRL, SEND>RS#

ADD>M Page: O, S Stand: M, A Abbreviation: ADD>

## .. ADD>M ..... Soln.name ........ V.add ........mL
Function Dispense standard addition solution into measuring vessel (MEAS).


If the standard addition solution should be added automatically using a

685 Dosimat, a 700 Dosino or the 695 Autosampler, the solution name
Soln.name must be entered in the parameter of the same name on the
"SOLUTIONS" page and assigned to a position Pos. (see section
5.3.4).
Without entry of this name on the "SOLUTIONS" page or without a
position assignment, the standard addition solution must be added
manually or with the 6.5611.010 Pipetting equipment (the prompt ADD
"Soln.name" "V.add" > M appears in the program run).
V.add 0.010...50.000 mL; 0.100 mL
Solution volume that should be dispensed

Volume of the standard addition solution to be added to the measuring
vessel.
Description The ADD>M instruction is used for the automatic or manual dispensing of
standard addition solutions into the measuring vessel on the 747 VA
Stand.
The automatic addition can be performed with a 685 Dosimat, a 700
Dosino or directly with the 695 Autosampler. The appropriate position of
the standard addition solution must be specified on the "SOLUTIONS"
page (see Soln.name).

Comments The ADD>M instruction must be located within an ADD loop.

In the last execution of the ADD loop, the ADD>M instruction is no
longer executed.
On execution of the ADD>M instruction with a 685 Dosimat or 700
Dosino, a wait is made until the addition is complete before the
instruction following ADD>M is executed.
Example see (ADD
see also (ADD, ADD)n, ADD/M, PADD>M

A>M Page: O, S Stand: A Abbreviation: A>

## .. A>M ..... addition AUX -> MEAS V.add ........mL
Function Transfer solution from auxiliary vessel (AUX) on the 695 Autosampler to
the measuring vessel (MEAS) on the 747 VA Stand.

V.add 0.010...50.000 mL; 0.100 mL
Transfer volume
Solution volume that should be transferred from the auxiliary vessel on
the sample rack of the 695 Autosampler to the measuring vessel on the
747 VA Stand.
Description The A>M instruction is used to transfer the solution volume specified
under V.add from the auxiliary vessel (AUX) on the 695 Autosampler to
the measuring vessel (MEAS) on the 747 VA Stand.
Comments The A>M instruction can be used only in operation with the 695
Autosampler.
If the solution volume in the auxiliary vessel < V.add, an error
message appears.
see also F>A, F>M

(BACKGND Page: O Stand: M, A Abbreviation: (B

## .. (BACKGND .....
Function Start of the block for background compensation.
Application The background compensation is used to compensate interference of

the measured curves due to the supporting electrolyte. Such interference
includes both the presence of the analyte (blank value) and that of
foreign substances electroactive in the same range.
Description The (BACKGND instruction opens the recording of a measured curve for
the background compensation. This curve is then automatically
subtracted from all subsequent measured curves of the same segment.
The BACKGND block must include a segment call-up, in addition other
instructions whatever their nature can be incorporated. The block must
be closed with the BACKGND) instruction.
Comments The BACKGND block is admissible only on the "OP.SEQUENCE"

page.
The segment called up in the BACKGND block must be identical with
the segment used for the determination.
No replications are allowed within the BACKGND block. Replications
within the segment called up are not executed (the BACKGND curve
can thus only be recorded once).
With segments recorded following a BACKGND segment, all
substance and segment curves are compensated with the exception
of the original curves, i.e. the BACKGND curve has been subtracted.
This applies to both the display on the "CURVES" page and the curve
plot on the "DOCUMENTATION" page.
The segment recorded in the BACKGND block has the designation
00-xxxxxxxx-backgnd. It can be displayed on the "CURVES" page as
an original, processed, smoothed or derived segment curve (see
section 5.5.3), on the other hand a display as a substance curve is
not possible.
For the curve plot of background curves, which is also possible only
with segments, the segment 00 must be selected. The BACKGND
curve 00-backgnd is then plotted in addition to the normal curve 00.
On completion of the measurement with background compensation,
this can no longer be reversed. To obtain a comparison between
uncompensated and compensated measurement, the measurement
must be repeated without background compensation (e.g. by inacti-
vating the BACKGND block).

Example A measurement with background compensation and standard addition

is normally programmed on the OP.SEQUENCE page with the following
basic structure:
:
DOS>M or DOS/M Addition of supporting electrolyte
: to measuring vessel
:
(BACKGND Start of block for background compensation
SEGMENT Seg1 Call-up of the segment (BACKGND curve)
BACKGND) End of block for background compensation
:
SMPL>M or SMPL/M Sample addition to the measuring vessel
(REP Loop start for replications
SEGMENT Seg1 Call-up of the segment (measured curve)
:
see also BACKGND)

BACKGND) Page: O Stand: M, A Abbreviation: BA

## .. BACKGND) .....
Function End of the block for background compensation.
Application The background compensation is used to compensate interference of

the measured curves due to the supporting electrolyte. Such interference
includes both the presence of the analyte (blank value) and that of
foreign substances electroactive in the same range.
Description The BACKGND) instruction closes a block opened with the (BACKGND
instruction for the recording of a measured curve for the background
compensation, which is then subtracted from all subsequent measured
curves of the same segment.
The BACKGND block must include a segment call-up, in addition other
instructions whatever their nature can be incorporated.
Comments see (BACKGND
Example see (BACKGND
see also (BACKGND

BEEP Page: O, S Stand: M, A Abbreviation: B

## .. BEEP .....
Function Audio signal.
Description With the BEEP instruction, a brief audio signal is put out on the 746 VA
Trace Analyzer as an acoustic indication for the user.
Comments If several audio signals should be generated in succession, several

BEEP instructions must be entered one after the other with a line time
(e.g. 1 s).

(CAL Page: O, S Stand: M, A Abbreviation: (C

## .. (CAL .....
Function Start of the loop for the recording of a calibration curve.
Description The (CAL instruction opens a loop for recording a calibration curve with
both the calibration technique with calibration curve cal.crv. and that
with the internal standard int.std.. The CAL loop must be closed with
the CAL)n instruction.
In calibrations with a calibration curve, for the recording of this curve
the CAL loop must include one of the dosing instructions CSOLN/M,
CSOLN>M or CSOLN/F for addition of the calibration solutions as well as a
sweep or segment call-up. In addition, any other instructions can be
incorporated.
In calibrations with an internal standard, for the recording of the
calibration curve for the determination of the proportionality factor the
CAL loop must include one of the dosing instructions CSOLN/M, CSOLN>M
or CSOLN/F for addition of the calibration solutions, the instruction
RADD>M or RADD>F for addition of the internal standard as well as a
incorporated.
Comments A program can contain several CAL loops, but they must not be
nested.
REP loops are allowed within CAL loops, a CAL loop can also be
inserted within a REP loop.
No ADD or VAR loops are allowed within CAL loops.
It is advantageous to insert the MEAS instruction in the CAL loop to
switch off the electrode voltage when the solution is changed.
If the entire analysis solution is changed each time during recording
of the calibration curve, a RINSE instruction must be incorporated in
the CAL loop which resets the volume bookkeeping in the measuring
vessel to 0 (see also RINSE). If its parameter Cycles > 0 is set, the
measuring vessel is also rinsed by means of the two rinsing Dosinos
connected to the 746 VA Trace Analyzer or the 695 Autosampler. If no
rinsing Dosinos are connected, the prompt Change measuring
vessel to change the solution appears.
Without a RINSE instruction, the volume in the measuring vessel is

added continuously. This can be utilized for the recording of calibra-
tion curves in which the calibration solutions are prepared each time
by manual addition of a concentrated standard solution to the meas-
uring vessel (see CSOLN>M).
The number of calibration solutions is defined in the CAL)n instruc-
tion. A valid mass concentration Mass conc. must be entered on the
"SUBSTANCES/Calibration" page for each of these solutions.

The EXIT instruction for premature exit from the CAL loop can be
included in this loop.
For the recording of a calibration curve, the program run mode Run
mode = calibration must be set on the "MONITORING" page. The
calibration solutions are then measured in turn and the coefficients of
the calibration curve determined. To store these permanently, the
method must then be copied from the working storage to the method
memory (this occurs automatically with Auto.batch = on).
Examples Determinations using a calibration curve are normally programmed on

the "OP.SEQUENCE" page with the following basic structure:
:
C CSOLN>M or CSOLN/M Addition of calibration solution to
: measuring vessel
C (REP Loop start for replication
C SEGMENT Seg1 Call-up of the segment
: (measurement of the calibration solution)
C REP)n Loop end, n = number of replications
C MEAS Switch off voltage (solution change)
C RINSE Reset volume bookkeeping
:
D (REP Loop start for replication
D SEGMENT Seg1 Call-up of the segment
: (measurement of the sample)
D REP)n Loop end, n = number of replications
:
In this example, the instructions for the calibration (C) and determination
(D) have been clearly separated from each other. If the calibration and
determination use the same number of replications, a shorter version of
the same program can be entered as follows:
:
: measuring vessel
SEGMENT Seg1 Call-up of the segment (measurement of
: the calibration solution or sample)
:

Determinations u sing the internal standard are normally programmed

on the OP.SEQUENCE page with the following basic structure:
:
: measuring vessel
C RADD>M Addition of internal standard to
: measuring vessel
C (REP Loop start for replication
C SEGMENT Seg1 Call-up of the segment
: (measurement of the calibration solution)
C REP)n Loop end, n = number of replications
:
D SMPL>M or SMPL/M Sample addition to the measuring vessel
D RADD>M Addition of internal standard to
: measuring vessel
D (REP Loop start for replication
D SEGMENT Seg1 Call-up of the segment
: (measurement of the sample)
D REP)n Loop end, n = number of replications
:
As in the previous example, with the same number of replications for

calibration and determination in the internal standards method the
illustrative program can be shortened as follows:
:
C CSOLN>M or CSOLN/M Addition of calibration solution
RADD>M Addition of internal standard
SEGMENT Seg1 Call-up of the segment (measurement of the
: calibration solution or sample)
:
see also CAL)n, CSOLN/M, CSOLN>M, CSOLN/F, MEAS, RINSE, EXIT,

Calibration curve (section 5.6.3 and section 6.9.5),
Internal standard (section 5.6.3 and section 6.9.6)

CAL)n Page: O, S Stand: M, A Abbreviation: C

## .. CAL)n .....
Function End of the loop for recording the calibration curve.

n 0...9; 0
Number of calibration solutions 1

This parameter defines the number of times the CAL loop is executed,
i.e. how many calibration solutions are used to determine the calibra-
tion curve.
Description The CAL)n instruction ends a loop opened with (CAL for the recording
of a calibration curve with the calibration technique with calibration curve
cal.crv. or with internal standard int.std..
In calibrations with a calibration curve, for the recording of this curve

the CAL loop must include one of the dosing instructions CSOLN/M,
CSOLN>M or CSOLN/F for addition of the calibration solutions as well as a
incorporated.
In calibrations with an internal standard, for the recording of the
calibration curve to determine the proportionality factor the CAL loop
must include one of the dosing instructions CSOLN/M, CSOLN>M or
CSOLN/F for addition of the calibration solutions, the instruction RADD>M
or RADD>F for addition of the internal standard as well as a sweep or
segment call-up. In addition, any other instructions can be incorporated.
Comments see (CAL
Examples see (CAL
see also (CAL, CSOLN/M, CSOLN>M, CSOLN/F, EXIT,


(CASE Page: O, S Stand: M, A Abbreviation: (CAS

## .. (CASE ..... Calc.f.
Function Start of a decision block with decision whether or not the subsequent
instructions should be executed.

(Test) EV:<subst>,MC:<subst>,S0,S1,S2,S3,V0 <,<=,>=,> const.,C##;
STATE =,<> ctrl.line code; -
Test condition for decision

The following test conditions can be entered in the field under Main
parameters:
EV:<subst> < | <= | >= | > const. / C##

MC:<subst> < | <= | >= | > const. / C##
S0 < | <= | >= | > const. / C##
S1 < | <= | >= | > const. / C##
S2 < | <= | >= | > const. / C##
S3 < | <= | >= | > const. / C##
V0 < | <= | >= | > const. / C##
STATE = | <> ctrl.line code
The terms have the following meaning:

EV:<subst> Evaluation value (I.peak, I.wave, P.peak or
t.peak) for the specified substance (<subst>
= substance name) in A, W, or s
MC:<subst> Mass concentration s for the specified sub-

stance (<subst>=substance name) in g/L
S0 Sample size S0 in g or L
S1,S2,S3 Sample specific variables S1, S2, S3
V0 Sample volume V0.sample in measuring

vessel in L
STATE State of the input control lines 1...8 of the

remote interface
const. Constant (numeric value)
C## Common variable C01 ... C18 from the

working storage (see section 5.4.5)
ctrl.line code 8-digit numeric code for the state of the in-
put control lines 1...8. The following values
can be entered for each line:
1 on, active (0 V)
* immaterial


Calc.f. A##; A##; A## (## = 01...15); -
Alternative results
If the test condition is met, the alternative results A## (max. 3) entered
here are activated, i.e. the corresponding formulae A##=..... on the
"CALCULATION" page are set to active for the calculation and marked
with an asterisk (*).
Either a space or the ; character must be entered between the A##
values.
Description The (CASE instruction opens a decision block which can contain any
type of instructions and is closed with the CASE) instruction. On the
basis of the test condition contained in the (CASE instruction as a
parameter (see (Test)), a decision is made during the program run
whether or not the instructions which follow in the block are executed:
If the test condition is met (true), the instructions which follow in the
decision block are executed up to the next CASE, EXIT or CASE)
instruction and a jump then made to the end of the block.
If the test condition is not met (false), the instructions which follow in
the decision block are ignored up to the next CASE, EXIT or CASE)
instruction.
As an option, alternative results can also be specified which should be
activated when the test condition is met (see Calc.f.).
Comments Any number of CASE blocks (CASE ... CASE) in succession are
permitted in a program.
Maximum 2 CASE blocks can be nested, i.e. a second case block
may be located within a CASE block.
A CASE block may contain any number of additional CASE instruc-
tions. After the first CASE instruction whose test condition is met,
however, no further CASE instruction is tested and a direct jump
made to the end of the CASE block.
For test conditions with evaluation values EV:<subst> or mass
concentrations MC:<subst>, it must be borne in mind that these
values are set to 0 if no evaluation was possible. This can be used for
detection of this specific case (see examples).

Examples The first example shows a cadmium determination with proportional

standard addition as a function of the Cd content.
Method caseCd.mth OPERATION SEQUENCE

Title CASE program with proportional addition
================================================================================

2 (ADD . .
3 SEGMENT Segm.name Cd-det
4 (CASE EV:Cd <= 0 Calc.f. A01
5 CASE EV:Cd < 1e-9 Calc.f. A02
6 PADD>M Soln.name Cd-Std1 Prop.coeff. 8
Prop.subst. Cd
7 CASE EV:Cd >= 1e-9 Calc.f. A02
8 PADD>M Soln.name Cd-Std2 Prop.coeff. 0.05
Prop.subst. Cd
9 CASE) . .
10 EXIT EV:Cd <= 0
11 ADD)2 . .
12 END . .
Method caseCd SUBSTANCES

Cd - Cd-det
================================================================================

Technique std.add. Y.reg 4.371e09
Curve type linear Slope 0.002408
Nonlin.
Mean dev. 1.836e10
Additions

Soln.name Cd-Std1 Cd-Std2

Mass conc. 1 mg/L 100 mg/L g/L g/L
Range min g/L g/L g/L g/L
Range max g/L g/L g/L g/L
M.conc./cm g/L g/L g/L g/L.
Method caseCd CALCULATION

max. 15 lines
================================================================================

rho(Cd) A01 = MC:Cd no res. 2
rho(Cd) A02 = MC:Cd #g/L 5
This program runs as follows:

After the sample addition, first the segment Cd-det that provides EV:Cd
as an evaluation value is started. The remaining program run depends
on the testing of this result in the CASE block:
EV:Cd <= 0 (line 4)
If no evaluation was possible for the substance Cd, the value EV:Cd
is set to 0. In this case the alternative formula A01 is activated and
the CASE block quit, i.e. no standard addition takes place. Following
the CASE block, the EXIT instruction with identical test condition is
used to exit the ADD loop immediately.

EV:Cd < 1e-9 (line 5)

If an evaluation value EV:Cd is found for the substance Cd that is
> 0 A and < 1 nA, the evaluation formula A02 is activated and the
sample proportionally spiked with standard addition solution Cd-Std1
(1 mg/L Cd).
EV:Cd >= 1e-9 (line 7)
If an evaluation value EV:Cd is found for the substance Cd that is
1 nA, the evaluation formula A02 is activated and the sample
proportionally spiked with standard addition solution Cd-Std2
(100 mg/L Cd).
The second example shows a lead determination with consideration

of the thallium content.
Method AB231_2.mth OPERATION SEQUENCE

Title Pb/Tl - AB 231
================================================================================

2 (ADD . .
3 SEGMENT Segm.name Pb
4 ADD>M Soln.name Pb std V.add 0.100 mL
5 ADD)2 . .
6 DOS>M Soln.name EDTA V.add 0.100 mL
7 SEGMENT Segm.name Tl
8 (CASE EV:Tl > 200e-12 Calc.f. A01 A02
9 (ADD
10 SEGMENT Segm.name Tl
11 ADD>M Soln.name Tl std V.add 0.050 mL
12 ADD)2
13 CASE EV:Tl <= 200e-12 Calc.f. A03
14 CASE)
15 END . .
Method AB231_2 CALCULATION

max. 15 lines
================================================================================

rho(Pb) A01 = MC:Pb - (MC:Tl * 1.0138 * 0.5) #g/L 3
rho(Tl) A02 = MC:Tl #g/L 3
rho(Pb) A03 = MC:Pb #g/L 3
As the half-wave potentials of the two metals are virtually identical, in the
first segment Pb the sum of Pb and Tl is determined. After the masking
of Pb with EDTA, the segment Tl is then started that provides the
evaluation value EV:Tl. The remaining program run depends on the
testing of this value in the CASE block:
EV:Tl > 200e-12 (line 8)
If an evaluation value EV:Tl is found for the substance Tl that is
> 200 pA, the evaluation formulae A01 and A02 are activated and
thallium is determined with the aid of the standard addition. The mass
concentrations of lead and thallium are put out as the final results
with that of lead being corrected by the proportion due to thallium.
This proportion is calculated assuming the same sensitivity by multi-
plication of the determined Tl content by the factor 1.0138 * 0.5 (ratio
of the molar masses Pb2+/Tl+).

EV:Tl <= 200e-12 (line 13)

If an evaluation value EV:Tl is found for the substance Tl that is
200 pA (this also includes the case EV:Tl = 0 A, i.e. no evaluation
exists), the evaluation formula A03 is activated and the thallium
determination discontinued. Only the uncorrected lead concentration
is put out as the final result.
see also CASE, CASE), EXIT

CASE Page: O, S Stand: M, A Abbreviation: CASE

## .. CASE ..... Calc.f.
Function Additional CASE instruction within a decision block with decision whether
or not the subsequent instructions should be executed.
Parameter see (CASE
Description see (CASE
Comments A CASE block can contain any number of CASE instructions.

However, after the first CASE instruction whose test condition is met,
no further CASE instructions are tested and a direct jump is made to
the end of the CASE block.
values are set to 0 if no evaluation is possible. This can be used for
detection of this specific case (see examples).
Examples see (CASE
see also (CASE, CASE), EXIT

CASE) Page: O, S Stand: M, A Abbreviation: CAS

## .. CASE) .....
Function End of a decision block.
Description The CASE) instruction closes a decision block opened with (CASE.
For further details, see (CASE.
Comments see (CASE
Examples see (CASE
see also (CASE, CASE, EXIT

CONDC Page: O, S Stand: M, A Abbreviation: CO

## .. CONDC U.start ........mV Rate 1 ........mV/s
U.end ........mV Rate 2 ........mV/s
Cycles ........
Function Electrochemical regeneration of carbon electrodes.

U.start -3000...3000 mV; -1200 mV
Initial voltage of conditioning cycles

Initial voltage for every conditioning cycle.
U.end -3000...3000 mV; -100 mV
Final voltage of conditioning cycles

Final voltage for every conditioning cycle.
Cycles 1...60000; 10
Number of conditioning cycles

This parameter defines the frequency of conditioning of the electrode.
Rate 1 1...10000 mV/s; 1000 mV/s
Rate from U.start to U.end

Sweep rate for the conditioning cycles form U.start to U.end.
Rate 2 5...50000 mV/s; 10000 mV/s
Rate from U.end to U.start

Sweep rate for the conditioning cycles form U.end to U.start.
Description The CONDC instruction starts a freely selectable number of conditioning

cycles for the electrochemical regeneration of carbon electrodes (e.g.
glassy carbon).
Comments Before the call-up of CONDC, the RDE electrode must be selected. While
is possible to run CONDC with other electrode types, this is not realistic.
see also RDE

CSOLN/F Page: O, S Stand: A Abbreviation: CS

## .. CSOLN/F ..... solution added into FEED
Function Calibration solution is located in the sample vessel (FEED) on the 695
Autosampler.
Description The CSOLN/F instruction is used for the recording of calibration curves
with the techniques cal.crv. and int.std. using the 695 Auto-
sampler. Within a CAL loop, it defines that the calibration solution is
located in the sample vessel (FEED) on the sample rack of the 695
Autosampler.
In contrast to the CSOLN>M instruction, CSOLN/F is needed only when the
calibration solutions on the sample rack of the 695 Autosampler should
be pretreated before transfer to the measuring vessel (e.g. transfer to the
auxiliary vessel with the F>A instruction and subsequent dilution with the
DOS>A instruction).
Comments The CSOLN/F instruction can be used only in operation with the 695
Autosampler.
The number of calibration solutions is defined with n in the CAL)n
instruction. A valid mass concentration Mass conc. must be entered
on the "SUBSTANCES/Calibration" page for each of these solutions.
In the V0.CSoln parameter on the "SUBSTANCES/Calibration" page,
the volume valid for all calibration solutions that has been added to
the sample vessel (FEED) is entered. If no other dispensing opera-
tions are performed in this vessel, an asterisk * can also be entered
for V0.CSoln.
If work is performed with Auto.samples = on, on the "SAMPLES"
page sample data lines must be entered in immediate succession for
all n calibration solutions with the following holding for their parame-
ters:
Pos. Position number on the sample rack
(freely selectable)
S1...S3 Sample identifications (only entries of the last
calibration solution are used and stored)
Method.call Name of the method + .C
(for mode calibration)
Sample Size/S0 Entry of an asterisk *
(value not used, but field must not be blank)
For permanent storage of the coefficients of the calibration curve
determined in the recording of the calibration solutions, the method
must then be copied from the working storage to the method memory
(this occurs automatically with Auto.batch = on).

Examples Lead determination using a calibration curve with the 695 Autosampler
(basic structure only):
Method Cal695-2.mth OPERATION SEQUENCE

Title Calibration curve with 695 and CSOLN/F
================================================================================

1 D SMPL/F V.fraction mL V.total L
2 C (CAL
3 C CSOLN/F solution added into FEED
4 F>A addition FEED -> AUX V.add 8.000 mL
5 DOS>A Soln.name Sol-1 V.add 2.000 mL
6 VMIX Cycles 1 V.mix 9.000 mL
Rack pos. SA
7 A>M addition AUX -> MEAS V.add 5.000 mL
8 DOS>M Soln.name Sol-2 V.add 15.000 mL
9 (REP
11 REP)2
12 MEAS U.standby mV
13 RINSE Cycles 2 V.rinse mL
14 C CAL)3
15 END . .
Method Cal695-2 SUBSTANCES

Pb - DPASV
================================================================================

Technique cal.crv. Y.offset
Curve type 0/linear Slope 0.0006743
Temperature 20.0 C Nonlin.
Mean dev. 3.043e10
Range min 2 ug/L # CSoln.name Mass conc.

Range max 30 ug/L
M.conc./cm 5 ug/L 0 Pb-2.5 2.5 ug/L
1 Pb-5 5 ug/L
V0.CSoln. * mL 2 Pb-10 10 ug/L
3 Pb-25 25 ug/L
In the program run mode calibration, 4 calibration solutions are

measured in succession and used to determine the calibration curve.
The volume of the calibration solutions is not specified (*) as only a
defined part (8 mL) is transferred to the auxiliary vessel. Here, an
auxiliary solution is added and mixed. 5 mL of this solution are then
transferred to the measuring vessel where 15 mL of a second auxiliary
solution are added. Following the measurement, the measuring vessel is
rinsed twice. In the determination mode the instructions marked with D
are executed instead of those marked with C, otherwise the determina-
tion runs in exactly the same manner.
see also (CAL, CAL)n, CSOLN/M, CSOLN>M, F>A, F>M,


CSOLN/M Page: O, S Stand: M Abbreviation: CSOLN/M

## .. CSOLN/M ..... solution added into MEAS
Function Calibration solution is already in the measuring vessel (MEAS).
Description The CSOLN/M instruction is used for the recording of calibration curves
with the techniques cal.crv. and int.std. with the manual 747 VA
Stand. Within a CAL loop, it defines that the calibration solution is already
located in the measuring vessel (MEAS).
Comments The CSOLN/M instruction can not be used in operation with the 695
Autosampler.
In contrast to the CSOLN>M instruction, with CSOLN/M no prompt to
add the calibration solution appears during the program run. As a
new calibration solution must be used for every concentration, within
the CAL loop it is mandatory to insert a RINSE instruction which
resets the volume bookkeeping in the measuring vessel to 0 (see
also RINSE). To ensure that the prompt Change measuring vessel
to change the solution appears, its parameter Cycles > 0 must be
set.
The number of calibration solutions is defined with n in the CAL)n
In the V0.CSoln parameter on the "SUBSTANCES/Calibration" page,
the volume valid for all calibration solutions that have been added to
the measuring vessel (MEAS) must be entered.
ters:

Examples Lead determination using a calibration curve with the CSOLN/M

instruction (basic structure only):
Method Cal-2 .mth OPERATION SEQUENCE

Title Calibration curve with CSOLN/M
================================================================================

1 D SMPL/M V.fraction mL V.total L
2 C (CAL
3 C CSOLN/M solution added into MEAS
4 (REP
6 REP)2
7 MEAS U.standby mV
9 C CAL)3
10 END . .
Method Cal-2 SUBSTANCES

Pb - DPASV
================================================================================

Mean dev. 3.043e10

Range max 30 ug/L
1 Pb-5 5 ug/L
V0.CSoln. 10.000 mL 2 Pb-10 10 ug/L
3 Pb-25 25 ug/L
In the program run mode calibration, 4 calibration solutions each of

10 mL are measured in succession and used to determine the calibra-
tion curve. After each calibration solution, the prompt Change measuring
vessel to change the measuring vessel appears. Lead is then deter-
mined in the program run mode determination using the measured
calibration curve.
see also (CAL, CAL)n, CSOLN/F, CSOLN>M, RINSE,


CSOLN>M Page: O, S Stand: M, A Abbreviation: CSOLN>

## .. CSOLN>M ..... addition into MEAS
Function Dispense calibration solution into the measuring vessel (MEAS).
Description The CSOLN>M instruction is used for the recording of calibration curves
with the techniques cal.crv. and int.std. Within a CAL loop, it defines
that the calibration solution should be dispensed into the measuring
vessel.
The calibration solutions can be dispensed manually, with the
6.5611.010 Pipetting equipment, or via the 695 Autosampler, but not with
a 685 Dosimat or 700 Dosino. On manual addition with the CSOLN>M
instruction the prompt CSOLN "CSoln.name" "Mass conc." > M appears
showing the name and concentration of each calibration solution. In
additions with the 695 Autosampler, the calibration solutions are
transferred in turn to the measuring vessel from the sample rack.
Comments The number of calibration solutions is defined with n in the CAL)n

On manual addition, a name should also be entered for each solution
in the parameter CSoln.name which then appears in the message for
addition.
The addition volume valid for all calibration solutions must be entered
in the V0.CSoln parameter on the "SUBSTANCES/ Calibration" page.
ters:
Pos. Position number on the sample rack
(freely selectable, only with 695 Autosampler)
If the entire analysis solution is changed each time following the
recording of the calibration curve, a RINSE instruction must be in-
serted in the CAL loop which resets the volume bookkeeping in the
measuring vessel to 0 (see also RINSE). If its parameter Cycles > 0
is set, the measuring vessel is also rinsed by means of the two
rinsing Dosinos connected to the 746 VA Trace Analyzer or the 695
Autosampler. If no rinsing Dosinos are connected, the prompt
Change measuring vessel to change the solution appears.
Without a RINSE instruction, the volume in the measuring vessel is

added continuously. This can be utilized for the recording of calibra-
tion curves in which the calibration solutions are prepared each time
by manual addition of a concentrated standard solution to the analy-
sis solution.


Examples Lead determination using a calibration curve with the CSOLN>M

instruction (basic structure only):
Method Cal-3 .mth OPERATION SEQUENCE

Title Calibration curve with CSOLN>M
================================================================================

2 C (CAL
4 (REP
6 REP)2
7 MEAS U.standby mV
9 C CAL)3
10 END .
Method Cal-3 SUBSTANCES

Pb - DPASV
================================================================================

Mean dev. 3.043e10

Range max 30 ug/L
1 Pb-5 5 ug/L
V0.CSoln. 10.000 mL 2 Pb-10 10 ug/L
3 Pb-25 25 ug/L
In the program run mode calibration, 4 calibration solutions each of 10

mL are measured in succession and used to determine the calibration
curve. In work with the manual Stand, the prompt for addition CSOLN
"CSoln.name" "Mass conc." > M appears with every calibration solution.
Following the measurement the prompt Change measuring vessel to
change the measuring vessel appears. Lead is then determined using
the measured calibration curve.
If this program is used with the 695 Autosampler, the 4 calibration
solutions must be entered on the "SAMPLES" page. They are then
fetched in turn from the positions on the sample rack specified here and
transferred to the measuring vessel. Following every measurement, the
measuring vessel is rinsed twice. Lead is then determined in the
determination mode using the measured calibration curve.
see also (CAL, CAL)n, CSOLN/F, CSOLN/M, RINSE,


(CSWEEP Page: S Stand: M, A Abbreviation: (CS

## .. (CSWEEP
Function Start of the block for a cyclic voltage sweep.
Description The (CSWEEP instruction opens a block in a segment in which the ramps
for the cyclic voltage sweep are defined. This block can contain
maximum 5 RAMP instructions, other instructions are not allowed. The
block must be closed with the CSWEEP) instruction.
Comments Only one CSWEEP block is allowed per segment.

CSWEEP blocks may not be located within REP loops.
The electrode type (admissible are HMDE or RDE) and the measure-
ment mode CYCMODE must be entered before the CSWEEP block.
The number of measurement cycles for the CSWEEP block (max. 9)
is defined in the CYCMODE instruction by the Meas.cycles parameter.
Within a CSWEEP block a wait time between two ramps can be
programmed only by insertion of an additional, slow ramp as flat as
possible.
Example see RAMP
see also CSWEEP), CYCMODE, RAMP

CSWEEP) Page: S Stand: M, A Abbreviation: CSW

## .. CSWEEP)
Function End of the block for a cyclic voltage sweep.
Description The CSWEEP) instruction ends a block in a segment in which the ramps
for the cyclic voltage sweep are defined. This block can contain
maximum 5 RAMP instructions, other instructions are not allowed.
Comments see (CSWEEP
Example see RAMP
see also (CSWEEP, CYCMODE, RAMP

CYCMODE Page: O, S Stand: M, A Abbreviation: CY

## .. CYCMODE ..... I.range ........uA Prep.cycles ........
Meas.cycles ........
Function Measurement mode for cyclic voltammetry.
Application Cyclic voltammetry is mainly used to investigate reversible electrode

processes and for kinetic studies.

I.range 800, 450, 140, 45, 14, 4.5, 1.4, 0.45, 0.14, 0.045 uA; 14 uA
Maximum current measurement range (-I.range...+I.range)

This parameter is used to set the sensitivity of the current measurement
for the cyclic sweep. I.range must always be larger than the maximum
measured, absolute current values Icath and Ian, otherwise current values
> I.range are cut off. However, the value selected for the current
measurement range should not be too large, otherwise the sensitivity of
the current measurement is lowered unnecessarily.

This parameter specifies how often the subsequent CSWEEP block
should be executed before the actual measurement without a current
measurement being performed.

This parameter specifies how often the subsequent CSWEEP block
should be executed on completion of the preparation cycles for the
actual current measurement
Description With the CYCMODE measurement mode, direct voltage ramps can be
applied to the working electrode with a high voltage sweep rate. If the
initial and final potential are identical, this is known as cyclic voltamme-
try. The current I is measured as a function of the voltage U. The nature
of the measurement is shown below using the HMDE as an example.
Comments The CYCMODE measurement mode can be used only with the
electrode types HMDE and RDE and must be employed together with
the block for the cyclic voltage sweep (CSWEEP...CSWEEP) and the
ramps RAMP it contains.
The electrode type HMDE or RDE must be entered before the CYCMODE
measurement mode.

The current curves obtained with the CYCMODE measurement mode

can normally not be evaluated. An evaluation is possible only when
just 1 ramp is used and a peak-shaped current profile is found (the
evaluation then corresponds to the case DCTMODE with SSWEEP, i.e.
waves can not be evaluated).
F (Hg)
Area (Hg)
CYCMODE t
I.range t.HMDE
Prep.cycles
Meas.cycles U
RAMP
U.start
U.end
Prep.cycles Meas.cycles
U.step
t.step t
U.end U.start
For every measure- (ramp 1) (ramp 2)
ment cycle, maximum t.step
5 ramps are possible
U.step
U.start U.end
(ramp 1) (ramp 2)
U.red
Icath
An evaluation is I.range
possible only for
single ramps
Ian
U.ox
see also (CSWEEP, CSWEEP), RAMP, HMDE, RDE

DCTMODE Page: O, S Stand: M, A Abbreviation: D

## .. DCTMODE ..... t.step ........s t.meas ........ms
Function Measurement mode for direct current voltammetry

(DCT = Direct Current Tast).
Application Direct current voltammetry is the classic, simplest VA method with limited
sensitivity. It is mainly used for the investigation of reversible redox
systems.

t.step 0.05...9.9 s; 0.3 s

t.step > t.meas + t.drop + 30 ms
t.meas 1.0...64.0 ms; 40/50 ms for 50/60 Hz
Measurement time
Time during which the current measurement takes place. Measurement
is performed at the end of the time interval t.step.
Description With the DCTMODE measurement mode, the direct voltage applied to the
working electrode is continuously changed and the resultant current I
which flows measured as a function of the voltage U. The nature of the
measurement is shown below using the SMDE as an example.
t.meas t.meas
Area
F (Hg)
DCTMODE
t.step
t.meas
t
t.drop
SWEEP
U.start U
U.end
U.step
U.step
U.start t.step

The current measurement with the DCTMODE measurement mode

normally provides wave-shaped curves which can be evaluated using
the tangent method (baseline of type linear) (see section 5.6.3).
I.wave
U.wave U
If peak-shaped curves appear with the DCTMODE mode, these can be

evaluated only if the voltage sweep SSWEEP is used. The evaluation is
then the same as with other peaks using the baselines of type linear,
polynom or expon. (see section 5.6.3).
I
I.peak
U.peak U
Comments The DCTMODE measurement mode can be used with all types of
FSWEEP or TSWEEP.
the DCTMODE measurement mode.
With the DCTMODE measurement mode, the potentiostat always
DME t.drop = 20 ms
see also SWEEP, SSWEEP, DME, HMDE, SMDE, RDE

DME Page: O, S Stand: M, A Abbreviation: DM

## .. DME .....
Function Switch on Dropping Mercury Electrode (DME).
Description The DME instruction is used to switch on the 6.1246.020 Multi-Mode

Electrode as a dropping mercury electrode, the mercury starts to flow out
freely. In a subsequent voltage sweep, the Hg drops are knocked off by
a tapping mechanism after the time t.step set in the measurement
mode.
Area (Hg)
F (Hg)
t
t.step
The set drop time t.drop important for certain parameter settings is
20 ms for the DME.
Comments Within a program, the DME is not switched off until the MEAS
instruction or the selection of a different electrode type (HMDE, SMDE or
RDE). The DME is also switched off by END in the main program on
the "OP.SEQUENCE" page, but not by END in the segment.
The DME can be used for the following measurement modes and
sweeps: DCTMODE with SWEEP and SSWEEP,
DPMODE with SWEEP and FSWEEP,
SQWMODE with SWEEP and FSWEEP,
AC1MODE with SWEEP,
AC2MODE with SWEEP.
The following are not compatible with the DME:

CYCMODE with (CSWEEP,
PSAMODE with PSWEEP as well as
TSWEEP.
An advantage of the DME compared with the SMDE is that the MME
capillary is subjected to less mechanical stress.
A disadvantage of the DME compared with the SMDE and HMDE is
the higher mercury consumption and the lower sensitivity as the
electrode surface and hence the baseline constantly changes during
the measurement phase.
see also HMDE, SMDE, RDE

DOS>A Page: O, S Stand: A Abbreviation: DO

## .. DOS>A ..... Soln.name ........ V.add ........mL
Function Dispense auxiliary solution into auxiliary vessel (AUX) on the 695
Autosampler.

Soln.name 8 characters; -
Name of the auxiliary solution

The entry of a solution name is mandatory when the auxiliary solution
should be added automatically. In this case the solution name
"SOLUTIONS" page and assigned a position Pos. (see section 5.3.4).
Without entry of a name for Soln.name in the DOS>A instruction, without
entry of this name on the "SOLUTIONS" page or without a position
assignment, the auxiliary solution must be dispensed manually (the
prompt DOS "Soln.name" "V.add" > A then appears during the
program run).
V.add 0.010...50.000 mL; 1.000 mL

Volume of the auxiliary solution that should be dispensed into the
auxiliary vessel.
Description The DOS>A instruction is used for the manual or automatic addition of
auxiliary solutions (e.g. supporting electrolyte, reagent solution) to the
auxiliary vessel (AUX) on the 695 Autosampler.
For automatic addition with the 695 Autosampler, the appropriate
position of the auxiliary solution must be specified on the "SOLUTIONS"
Comments The DOS>A instruction can be used only in operation with the 695
Autosampler.
see also DOS/M, DOS>M, DOS>F, PDOS>M, SDOS>M, SDOS>A, SDOS>F

DOS>F Page: O, S Stand: A Abbreviation: DOS>F

## .. DOS>F ..... Soln.name ........ V.add ........mL
Function Dispense auxiliary solution into sample vessel (FEED) on the 695
Autosampler.


Without entry of a name for Soln.name in the DOS>F instruction, without
assignment, the auxiliary solution must be dispensed manually (the
prompt DOS "Soln.name" "V.add" > F then appears during the
program run).
V.add 0.010...50.000 mL; 1.000 mL

sample vessel.
Description The DOS>F instruction is used for the manual or automatic addition of
sample vessel (FEED) on the 695 Autosampler.
Comments The DOS>F instruction can be used only in operation with the 695
Autosampler.
see also DOS/M, DOS>M, DOS>A, PDOS>M, SDOS>M, SDOS>A, SDOS>F

DOS/M Page: O, S Stand: M Abbreviation: DOS/

## .. DOS/M ..... V.added ........mL
Function Auxiliary solution has been added to the measuring vessel (MEAS).

V.added 0.010...999.99 mL; 1.000 mL
Solution volume that has been added

Volume of the auxiliary solution that has been added to the measuring
vessel.
Description The DOS/M instruction is used when an auxiliary solution (e.g. supporting
electrolyte) has already been added to the measuring vessel (MEAS)
before the start of the program and defines the initial volume in the
measuring vessel.
The DOS/M instruction is also needed when an auxiliary solution should
be added automatically using a dosing unit (e.g. 665 Dosimat or 725
Dosimat) which, in contrast to the 685 Dosimat or 700 Dosino, can not
be directly controlled by the 746 VA Trace Analyzer. In this case, the
addition must be initiated via the RS232 interface (using the SEND>RS#
instructions) or via the remote interface (using the SETCTRL instruction)
and then confirmed with the DOS/M instruction.
Comments The DOS/M instruction can not be used in operation with the 695
Autosampler.
Example Addition of a auxiliary solution with the 665 Dosimat via the remote
interface:
746 connection: Connection "Control Lines" 23 (see section 3.13)
665 connection: Connection 8 for external dosing contact
(see 665 Instructions for Use)
Connecting cable: Cable with 25-pin connector, pin 5 (output 1) connected to red
banana plug, pin 25 (0 V) to black banana plug
Setting on 665: "DIS R" mode with fixed dispensing volume V.add
Program:
:
SETCTRL *******1 Start of dispensing at 665 Dosimat
: by setting control line 1 active
NOP xxx s Entry of a wait time until dispensing
: is at an end
SETCTRL *******0 Resetting of control line 1
DOS/M Auxiliary solution has been added
: to the measuring vessel
see also DOS>M, DOS>A, DOS>F, PDOS>M, SDOS>M, SDOS>A, SDOS>F

DOS>M Page: O, S Stand: M, A Abbreviation: DOS>M

## .. DOS>M ..... Soln.name ........ V.add ........mL
Function Dispense auxiliary solution into measuring vessel (MEAS).


The entry of a solution name is mandatory only when the auxiliary
solution should be added automatically using a 685 Dosimat, a 700
Dosino or the 695 Autosampler. In this case the solution name
Without entry of a name for Soln.name in the DOS>M instruction, without
assignment, the auxiliary solution must be dispensed manually or with
the 6.5611.010 Pipetting equipment (the prompt DOS "Soln.name"
"V.add" > M then appears during the program run).
V.add 0.010...50.000 mL; 1.000 mL

measuring vessel.
Description The DOS>M instruction is used for the manual or automatic addition of
measuring vessel (MEAS) on the 747 VA Stand.
the auxiliary solution must be specified on the "SOLUTIONS" page (see
Soln.name) for this.
Comments On execution of the DOS>M instruction with a 685 Dosimat, a 700 Dosino
or the 695 Autosampler, a wait is made until the addition is complete
before the instruction following DOS>M is executed.
see also DOS/M, DOS>M, DOS>A, PDOS>M, SDOS>M, SDOS>A, SDOS>F

DPMODE Page: O, S Stand: M, A Abbreviation: DP

## .. DPMODE ..... U.ampl ........mV t.meas ........ms
t.step ........s t.pulse ........ms
Function Measurement mode for differential pulse voltammetry.
Application Differential pulse voltammetry is the most universal and frequently used
voltammetric determination method. It is equally well suited for irreversi-
ble and reversible systems and offers a high sensitivity.

U.ampl -100...-1,1...100 mV; 50 mV
Pulse amplitude
Pulse amplitude of the voltage pulse superimposed on the direct
voltage.
t.step 0.05...9.9 s; 0.3 s

t.step > t.pulse + t.meas + t.drop + 30 ms
t.meas 1.0...32.0 ms; 20/16.6 ms for 50/60 Hz
Measurement time
Time during which the current is measured. Measurement is performed
at the end of the time interval t.step immediately before the pulse
start and at the end of the pulse.
t.pulse 1.0...330.0 ms; 40/33 ms for 50/60 Hz
Pulse time
Time interval during which a voltage pulse is superimposed on the
direct voltage.
The following condition applies to the definition of t.pulse:

t.pulse > t.meas + 2 ms
Description With the DPMODE measurement mode for differential pulse voltammetry,
square-wave pulses with a small, constant amplitude are superimposed
on a stepwise rising direct voltage ramp. The current I is measured as a
function of the voltage U immediately before the pulse and at the end of
the pulse. The nature of the measurement is shown below using the
SMDE as an example.
From the differences between the two current measurements, peak-
shaped curves are obtained which can be evaluated using the baselines
of type linear, polynom or expon. (see section 5.6.3).

t.meas (I1) t.meas (I2) t.meas (I1) t.meas (I2)
Area (Hg)
F (Hg)
DPMODE
t.step
t.meas
t.pulse t
t.drop
U.ampl
U
SWEEP
U.start U.step
U.ampl
U.end
U.step
U.start t.pulse t.step
t
I
I = I2 - I1
I.peak
U.peak U
Comments The DPMODE measurement mode can be used with all types of
FSWEEP or TSWEEP.
the DPMODE measurement mode.
If the DPMODE measurement mode is used with the voltage sweep
SWEEP and the electrode type HMDE, the potentiostat normally oper-
ates in the operating mode "slow". A switch is made to the operating
mode "fast" when the pulse time t.pulse < 30.05 ms.
If the DPMODE measurement mode is used with SWEEP and the
electrode type SMDE or DME, the setting of the potentiostat depends
on the measurement profile. Normally, a switch is also made from
"slow" to "fast" when the pulse time t.pulse < 30.05 ms. With very
small signals, however, the operating mode "slow" is used and with
very large signals the operating mode "fast", irrespective of the pulse
time.
SWEEP and the electrode type RDE, the potentiostat always operates in
the operating mode "fast".
FSWEEP, the potentiostat always operates in the operating mode "fast".
This mode is recommended especially for adsorptive stripping tech-
niques (e.g. Ni and Co with DMG).
DME t.drop = 20 ms
see also SWEEP, FSWEEP, DME, HMDE, SMDE, RDE

DSWEEP Page: O, S Stand: M, A Abbreviation: DS

## .. DSWEEP XXXXX U.start ........mV U.step ........mV
U.end ........mV Sweep rate XXXXXXXXmV/s
Function Voltage sweep without measured value recording (Dummy Sweep).

t/s display only
Time for voltage step

In the line time (which can not be edited), the time for the voltage
sweep is displayed and is calculated as follows:
(U.end - U.start)

Sweep time =
Sweep rate
U.start -3000...3000 mV; -
Initial voltage
Initial voltage for the voltage sweep.
U.end -3000...3000 mV; -
Final voltage
Final voltage for the voltage sweep. This voltage is retained after the
end of the sweep until a new voltage is applied or until it is switched off
by MEAS or END in the main program on the "OP.SEQUENCE" page.
U.step 2, 4, 6, 8, 10, 12 mV; 6 mV
Voltage step
Voltage step for direct current ramp.
Sweep rate display only
Ramp slope
Here, the slope of the direct current ramp is displayed in mV/s. It is
calculated as follows:
U.step
Sweep rate =
t.step
The parameter t.step originates from the measurement mode, which

must be entered before the SWEEP instruction.

Description The DSWEEP instruction (Dummy Sweep) starts the voltage sweep
defined in the parameters. While measured values are recorded during
the sweep, they are not stored.
t.step U.end
U
U.step
U.start
Comments The electrode type must be defined before the DSWEEP instruction.
Admissible are DME, SMDE, HMDE or RDE.
The measurement mode must be defined before the DSWEEP
instruction. Admissible are DCTMODE, DPMODE, AC1MODE, AC2MODE or
SQWMODE, but not PSAMODE or CYCMODE.
With the DSWEEP instruction, the potentiostat always operates in the

operating mode "fast".
If the final voltage U.end should not be switched off at the end of the
program, enter a suitable standby voltage U.standby in a MEAS
instruction.
see also SWEEP, FSWEEP, SSWEEP, DME, SMDE, HMDE, RDE, DCTMODE,
DPMODE, AC1MODE, AC2MODE, SQWMODE

END Page: O, S Stand: M, A Abbreviation: E

## END .....
Function End of the main program ("OP.SEQUENCE") or end of the segment

("SEGMENTS").
Description The END instruction closes the main program on the "OP.SEQUENCE"
page or a segment on the "SEGMENTS" page.
Comments Each program or segment must be closed with the END instruction.
The END instruction in the main program switches off all functions still
active at the 747 VA Stand (e.g. stirrer, purging, electrodes, voltage)
with exception of the standby voltage U.standby defined in a MEAS
instruction.
In contrast to END in the main program, the END instruction in the
segment simply causes a return to the location in the main program
where the segment was called up.
see also STIR, PURGE, DME, HMDE, SMDE, RDE, MEAS

EXIT Page: O, S Stand: M, A Abbreviation: EX

## .. EXIT .....
Function Immediate exit from a loop or a block if the test condition is met.

(Test) EV:<subst>,MC:<subst>,S0,S1,S2,S3,V0 <,<=,>=,> const.,C##;
STATE =,<> ctrl.line code; -
Test condition for decision

The following test conditions can be entered in the field under Main
parameters:
EV:<subst> < | <= | >= | > const. / C##

MC:<subst> < | <= | >= | > const. / C##
S0 < | <= | >= | > const. / C##
S1 < | <= | >= | > const. / C##
S2 < | <= | >= | > const. / C##
S3 < | <= | >= | > const. / C##
V0 < | <= | >= | > const. / C##
STATE = | <> ctrl.line code
The terms have the following meaning:

EV:<subst> Evaluation value (I.peak, I.wave, P.peak or
t.peak) for the specified substance (<subst>
= substance name) in A, W or s
MC:<subst> Mass concentration s for the specified sub-

stance (<subst>=substance name) in g/L
S0 Sample size S0 in g or L
S1,S2,S3 Sample specific variables S1, S2, S3
V0 Sample volume in measuring vessel

V0.sample in L
STATE State of the input control lines 1...8 of the

remote interface
const. Constant (numeric value)
C## Common variable C01 ... C18 from the

working storage (see section 5.4.5)
ctrl.line code 8-digit numeric code for the state of the in-
put control lines 1...8. The following values
can be entered for each line:
1 on, active (0 V)
* immaterial

Description The EXIT instruction can be inserted in the following loops or blocks:
(ADD ... ADD)n
(CAL ... CAL)n
(REP ... REP)n
(VAR ... VAR)n
(CASE ... CASE)
On the basis of test condition contained in the EXIT instruction as a

parameter (see (Test)), a decision is made during the program run
whether or not the loop or block should be exited:
If the test condition is met (true), a jump is made to the
end of the loop or block.
If the test condition is not met (false), the instructions
which follow in the loop or block are executed.
Comments In nested loops or blocks a jump is always made to the end of that
loop or block in which the EXIT instruction is located. If an exit from
all loops or blocks is desired, the EXIT instruction must be entered
for every loop or every block.
values are set to 0 if no evaluation was possible. This can be used for
detection of this specific case (see example).
Example see (CASE
see also (CASE, CASE), CASE, (ADD, (CAL, (REP, (VAR

F>A Page: O, S Stand: A Abbreviation: F

## .. F>A ..... addition FEED -> AUX V.add ........mL
Function Transfer solution from sample vessel (FEED) to the auxiliary vessel
(MEAS) on the 695 Autosampler.

V.add 0.010...50.000 mL; 1.000 mL
Transfer volume
Solution volume that should be transferred from the sample vessel on
the sample rack of the 695 Autosampler to the auxiliary vessel.
Description The F>A instruction transfers the solution volume specified under V.add
from the sample vessel (FEED) to the auxiliary vessel (AUX) on the 695
Autosampler.
Comments The F>A instruction can be used only in operation with the 695
Autosampler.
The auxiliary vessel (AUX) must be located on the sample rack
immediately after the sample vessel (FEED).
If the solution volume in the sample vessel < V.add, an error
message appears.
see also A>M, F>M

F>M Page: O, S Stand: A Abbreviation: F>M

## .. F>M ..... addition FEED -> MEAS V.add ........mL
Function Transfer a solution from the sample vessel (FEED) on the 695 Autosam-
pler to the measuring vessel (MEAS) on the 747 VA Stand.

V.add 0.010...50.000 mL; 1.000 mL
Transfer volume
Solution volume that should be transferred from the sample vessel on
the sample rack of the 695 Autosampler to the measuring vessel on the
747 VA Stand.
Description The F>M instruction transfers the solution volume specified under V.add
from the sample vessel (FEED) on the 695 Autosampler to the measur-
ing vessel (MEAS) on the 747 VA Stand.
Comments The F>M instruction can be used only in operation with the 695
Autosampler.
If the solution volume in the sample vessel < V.add, an error
message appears.
see also A>M, F>A

FEED Page: O, S Stand: M, A Abbreviation: F

## .. FEED ..... Dos.# ........ V.feed ........mL
Stopcock ........ Feed rate ........mL/min
Message .....................................
Function Reserved for future applications (pipetting and dispensing functions) with
the 685 Dosimat or 700 Dosino.
We advise not to use this command without having more detailed

information available from Metrohm on request.

FSWEEP Page: S Stand: M, A Abbreviation: FS

## .. FSWEEP XXXXX U.start ........mV U.step ........mV
Function Voltage sweep with potentiostat in the operating mode "fast", especially
suited for adsorptive stripping techniques.

t/s display only
Time for voltage step

(U.end - U.start)

Sweep time =
Sweep rate
U.start -3000...3000 mV; -
Initial voltage
U.end -3000...3000 mV; -
Final voltage
U.step 2, 4, 6, 8, 10, 12 mV; 6 mV
Voltage step
Ramp slope
U.step
Sweep rate =
t.step

must be entered before the FSWEEP instruction.

Description The FSWEEP instruction (Fast Sweep) starts the voltage sweep defined in
the parameters. During the sweep, the potentiostat always operates in
t.step U.end
U
U.step
U.start
Comments The electrode type must be defined before the FSWEEP instruction.
The measurement mode must be defined before the FSWEEP
The use of the FSWEEP instruction is practical only with the measure-
ment modes DPMODE and SQWMODE. With the other allowable meas-
urement modes, FSWEEP is identical to SWEEP.
The FSWEEP instruction should always be used instead of the SWEEP
instruction with adsorptive stripping techniques (e.g. Ni and Co with
DMG).
With the FSWEEP instruction maximum 1000 measured values can be
recorded.
Apart from the FSWEEP instruction, no other SWEEP instruction is
allowed in the same segment.
instruction.
see also SWEEP, DSWEEP, SSWEEP, DME, SMDE, HMDE, RDE, DPMODE,
SQWMODE

HMDE Page: O, S Stand: M, A Abbreviation: H

## .. HMDE ..... Drop size ........ Meas.cell ........
Function Switch on Hanging Mercury Drop Electrode (HMDE).
Application The HMDE is primarily used for very sensitive stripping voltammetry in
which the analyte species is not measured until it has first been
electrochemically enriched. Cyclic voltammetry and PSA are also
possible with the HMDE.

Drop size 1...9; 4
Drop size
Setting of the size of the mercury drop.
2 2
The area of the drop is ca. 0.15 mm (1) ... 0.60 mm (9).
0 ms for the HMDE by definition.
Meas.cell normal, EFTA; normal
Operation mode
Setting of the operation mode for the HMDE:
normal Normal operation for MME in measuring vessel:
4 mercury drops of defined size are formed in succes-
sion at the MME. The last drop remains suspended
EFTA Operation for EFTA cell (future application):
The valve for Hg outflow is opened until two drops have
been expelled. After a waiting time of 300 ms a new Hg
drop of the defined size Drop size is formed and re-
mains suspended.
Description The HMDE instruction is used to form mercury drops of defined size at
the 6.1246.020 Multi-Mode Electrode. The last drop remains suspended
and thus forms the hanging mercury drop electrode at which a voltage
sweep can be performed.
Area
F (Hg)
t
t.HMDE

Comments Within a program, the HMDE is not switched off until the MEAS
instruction or the selection of a different electrode type (DME, SMDE or
RDE). The HMDE is also switched off by END in the main program on
The HMDE can be used for all measurement modes and sweeps.
see also DME, SMDE, RDE

HOLD Page: O, S Stand: M, A Abbreviation: HO

## .. HOLD ..... Message ................
Function Program hold with output of a message.

Message 16 characters; -
Message
The message put in here is displayed in the screen window MEAS.TASK
MESSAGE when the HOLD instruction is reached. The program is not
continued until this message has been confirmed with the <ENTER>
key.
Description The HOLD instruction is used to interrupt the program at a specific

location. The program is not continued until the message Message
displayed on the screen associated with HOLD has been confirmed with
the <ENTER> key.

LIFT Page: O, S Stand: M Abbreviation: L

## .. LIFT ..... Height ........
Function Reserved for future applications with the 717 Sample Changer.
Detailed information is available from Metrohm on request.
see also SHIFT

MEAS Page: O, S Stand: M, A Abbreviation: M

## .. MEAS ..... U.meas ........mV
Function Application of a constant voltage to the electrodes and measurement of

the current without measured value storage.
Application The MEAS instruction is primarily used together with the HMDE or RDE
for electrochemical enrichment in stripping voltammetry.

U.meas -3000...3000 mV; -
Measurement voltage
The voltage entered here is applied to the electrodes. This voltage
remains in force even after the line time has elapsed until a SWEEP
instruction follows or until it is switched off by MEAS or END in the main
program on the "OP.SEQUENCE" page.
Description The MEAS instruction applies the voltage defined in the U.meas para-
meter to the electrode. At the same time, the current measurement is
started in accordance with the parameters defined in the measurement
mode. The duration of the measurement is defined with the line time.
During an ongoing measurement with MEAS, the current measured
values for voltage and current are displayed in the measurement window
on the "MONITORING" page (see section 5.5.1).
Comments The electrode type must be defined before the MEAS instruction.
The measurement mode must be defined before the MEAS instruc-
tion. Admissible are DCTMODE, DPMODE, AC1MODE, AC2MODE, SQWMODE,
CYCMODE or PSAMODE.
If the measured values in measurement of the current should be

plotted, the TSWEEP instruction must be used in place of the MEAS
instruction. However, this must not be in the same segment as the
measurement sweep.
If the measurement voltage U.meas should not be switched off at the
end of the program, enter a suitable standby voltage U.standby in a
MEAS instruction.

Examples Determination of cadmium by stripping voltammetry:
Method ASV-1 .mth OPERATION SEQUENCE

Title Determination of cadmium
================================================================================

2 PURGE
3 STIR 300.0 Rot speed 2000 /min
4 (REP
5 PURGE
6 STIR 20.0 Rot speed 2000 /min
7 PURGE 5.0
8 SEGMENT Segm.name CdASV
9 REP)2 . .
10 END . .
Method ASV-1.mth SEGMENT

CdASV
================================================================================

4 STIR 5.0
6 END .
In the CdASV segment, cadmium is enriched at the HMDE for 60 s at

850 mV and then determined in a sweep from 850 mV ... 450 mV.
see also MEAS, HMDE, TSWEEP, END

MEAS Page: O, S Stand: M, A Abbreviation:

## .. MEAS ..... U.standby ........mV
Function Switch off voltage, current and DME.

U.standby -3000...3000 mV; -
Standby voltage after measurement

The voltage entered here is applied to the electrodes. This voltage
remains in force even after the end of the main program on the
"OP.SEQUENCE" page. It is switched off only by a new MEAS instruc-
tion with U.standby = empty, by a MEAS instruction or by the new start
of a method.
The standby voltage U.standby is displayed on the "STAND" page.
If the voltage applied to the electrodes should be switched off,
U.standby must be empty (press <CLEAR> to empty the contents of
the field).
Description The MEAS instruction is used to switch off the current measurement and
to apply the standby voltage U.standby to the electrodes. The dropping
mercury electrode DME is also switched off, i.e. the mercury flow is
stopped.
Comment If the solution in the measuring vessel is changed during the program
run (e.g. in the recording of calibration curves), the MEAS instruction with
no standby voltage set (U.standby = empty) must be inserted before the
solution change so that no voltage flows through the electrodes.
Examples see (CAL
see also MEAS

NOP Page: O, S Stand: M, A Abbreviation: N

## .. NOP .....
Function Blank line without function (No Operation).
Description The NOP instruction can be used for the programming of wait times by
entering an appropriate line time t/s.
Comment The same function as with NOP can also be achieved with REM, but in the
latter case a line comment can also be entered.
see also REM

PADD>M Page: O, S Stand: M, A Abbreviation: P

## .. PADD>M ..... Soln.name ........ Prop.coeff. ........
Prop.subst. ........
Function Dispense standard addition solution proportional to the measured

evaluation value EV:<subst> of a substance into the measuring vessel
(MEAS).


If the standard addition solution should be added automatically using a
685 Dosimat, a 700 Dosino or 695 Autosampler, the solution name
"SOLUTIONS" page and assigned to a position Pos. (see section
5.3.4).
position assignment, the standard addition solution must be added
manually or with the 6.5611.010 Pipetting equipment (the prompt ADD
"Soln.name" "V.add" > M appears in the program run with the calcu-
lated standard addition volume being displayed for V.add in L).
Prop.subst. 8 characters; -
Name of the reference substance for proportional standard

addition
Here, the name of the substance whose evaluation value EV:<subst>
(in A, W or s) is the basis for the proportional standard addition must be
entered. This can be the analyte or one of the 7 other possible sub-
stances.
The name of the substance must be identical to one of the substance
names entered on the "SUBSTANCES/Calibration" page (see section
5.6.3).
Prop.coeff. 0.0010...99999.9; 1
Proportionality coefficient
The proportionality coefficient defines the relation between the meas-
ured mean value of the evaluation value EV:<subst> and the standard
addition volume V.add:
V.add = EV:<subst> * Prop.coeff.
Depending on the unit of the evaluation value EV:<subst> (nA, nW or

s), the proportionality coefficient has the unit L/nA, L/nW or L/s
giving a calculated standard addition volume V.add in L.

Description The PADD>M instruction is used for the automatic or manual addition of
standard addition solutions. In contrast to the ADD>M instruction, the
standard addition volume V.add can not be preallocated, but is
recalculated in every measurement from the evaluation value EV:<subst>
measured beforehand for any substance and a proportionality coefficient
Prop.coeff..

page (see Soln.name)
Comments The PADD>M instruction must be located within an ADD loop.

In the last execution of the ADD loop, the PADD>M instruction is no
longer executed.
On execution of the PADD>M instruction with a 685 Dosimat or 700
instruction following PADD>M is executed.
Example see (CASE
see also (ADD, ADD)n, ADD/M, ADD>M

PDOS>M Page: O, S Stand: M, A Abbreviation: PD

## .. PDOS>M ..... Soln.name ........ Prop.coeff. ........
Prop.subst. ........
Function Dispense auxiliary solution proportional to the measured evaluation value

EV:<subst> of a substance into the measuring vessel (MEAS).


should be added automatically using a 685 Dosimat, a 700 Dosino or
the 695 Autosampler. In this case the solution name Soln.name must
be entered in the parameter of the same name on the "SOLUTIONS"
page and assigned a position Pos. (see section 5.3.4).
Without entry of a name for Soln.name in the PDOS>M instruction,
without entry of this name on the "SOLUTIONS" page or without a
position assignment, the auxiliary solution must be dispensed manually
or with the 6.5611.010 Pipetting equipment (the prompt DOS
"Soln.name" "V.add" > M then appears during the program run with
the calculated addition volume being displayed for V.add in L).
Prop.subst. 8 characters; -
Name of the reference substance for proportional dispensing

Here, the name of the substance whose evaluation value EV:<subst>
(in A, W or s) is the basis for the proportional dispensing of an auxiliary
solution must be entered. This can be the analyte or one of the 7 other
possible substances.
The name of the substance must be identical to one of the substance
names entered on the "SUBSTANCES/Calibration" page (see section
5.6.3).
Prop.coeff. 0.0010...99999.9; 1
Proportionality coefficient
The proportionality coefficient defines the relation between the meas-
ured mean value of the evaluation value EV:<subst> and the addition
volume V.add:
Depending on the unit of the evaluation value EV:<subst> (nA, nW

or s), the proportionality coefficient has the unit L/nA, L/nW or L/s
giving a calculated standard addition volume V.add in L.
Description The PDOS>M instruction is used for the automatic or manual dispensing
of auxiliary solutions (e.g. supporting electrolyte, reagent solution) into
the measuring vessel (MEAS) on the 747 VA Stand. In contrast to the

DOS>M instruction, the addition volume V.add can not be preallocated,

but is recalculated in every measurement from the evaluation value
EV:<subst> measured beforehand for any substance and a proportion-
ality coefficient Prop.coeff..
Comments On execution of the PDOS>M instruction with a 685 Dosimat or 700

instruction following PDOS>M is executed.
see also DOS/M, DOS>M, DOS>A, DOS>F, SDOS>M, SDOS>A, SDOS>F

(PREP Page: O Stand: A Abbreviation: (P

## .. (PREP .....
Function Start of the block for sample preparation on the 695 Autosampler.
Description The (PREP instruction opens a block for sample preparation on the
sample rack of the 695 Autosampler paralleling measurement. This block
can contain any number of instructions admissible for the sample
preparation and must be closed with the PREP) instruction.
The PREP block must be called up with the >PREP instruction. As soon
as the program running for the current sample in the measuring vessel
allows, the instructions defined in the PREP block are executed with the
following sample on the sample rack of the 695 Autosampler.
Comments The (PREP instruction can be used only in operation with the 695
Autosampler and must be entered on the "OP.SEQUENCE" page.
Only one PREP block is admissible in a program.
Only the following instructions are allowed in a PREP block:
SMPL/F, CSOLN/F, DOS>F, SDOS>F, RADD>F
DOS>A, SDOS>A, F>A
VMIX, VWASH
BEEP, NOP, REM, SCANCTRL, SETCTRL
A PREP block runs only when the automatic series determination

(Auto.batch = on) on the "MONITORING" page is switched on and if
the same method is used as for the previous sample.
If the automatic transfer of sample data is switched on (Auto.samples
= on), the PREP block is executed with the next sample entered on
the "SAMPLES" page at the position on the sample rack specified
under Pos.. The sample data of this sample appear on the 2nd sam-
ple data line on the "MONITORING" page.
If the automatic transfer of sample data is switched off (Auto.samples
= off), the sample preparation block is automatically executed with
the next sample on the sample rack.
If a voltage is applied to the electrodes in the measuring vessel (by
MEAS or SWEEP instructions), no instructions from the PREP block can
be executed. As the voltage is retained on completion of the MEAS or
SWEEP instruction, the execution of instructions from the PREP block
within a program is not possible until the voltage has been switched
off with MEAS.
Instructions from the PREP block which need the functions of the 695
Autosampler can not be executed simultaneously with instructions
from the main program which also use such functions (e.g. DOS>M,
RINSE).
Instructions of the PREP block which have not yet been executed at
the end of the program are then run to completion.

Examples Determination of cadmium and lead by stripping voltammetry on the 695

Autosampler (with predilution 1:10'000):
Method ASV-2 .mth OPERATION SEQUENCE

Title Determination of cadmium and lead
================================================================================

1 (PREP
2 SMPL/F V.fraction mL V.total L
3 DOS>A Soln.name Buffer V.add 4.950 mL
4 F>A addition FEED -> AUX V.add 0.050 mL
5 VMIX Cycles 2 V.mix 4.000 mL
Rack pos. SA
6 PREP)
7 DOS>M Soln.name Buffer V.add 9.900 mL
8 A>M addition AUX -> MEAS V.add 0.100 mL
9 >PREP
10 PURGE
12 (ADD
13 (REP
14 PURGE
16 PURGE
17 SEGMENT Segm.name CdPbASV
18 REP)2
19 ADD>M Soln.name PbCD V.add 0.020 mL
20 ADD)2
21 MEAS U.standby mV
22 RINSE Cycles 1 V.rinse 40.000 mL
24 END
Method ASV-2.mth SEGMENT

CdPbASV
================================================================================

5 STIR 5.0
7 END .
In the sample preparation block (PREP ... PREP), 0.05 mL sample from
the sample vessel (FEED) are transferred to the auxiliary vessel (AUX)
where they are mixed with 4.95 mL buffer. 0.1 mL of this solution are then
transferred to the measuring vessel, mixed with 9.9 mL buffer and
purged for 10 min with stirring. During this time, the PREP block for the
next sample is started. After purging, lead and cadmium in the segment
PbCdSV are determined by stripping voltammetry with double standard
addition.
see also PREP), >PREP

PREP) Page: O Stand: A Abbreviation: PR

## .. PREP) .....
Function End of the block for sample preparation on the 695 Autosampler.
Description The PREP) instruction closes a block opened with (PREP for sample
preparation on the sample rack of the 695 Autosampler paralleling
measurement. This block can contain any number of instructions
admissible for the sample preparation.
The PREP block must be called up with the >PREP instruction. As soon
as the program running for the current sample in the measuring vessel
allows, the instructions defined in the PREP block are executed with the
following sample on the sample rack of the 695 Autosampler.
Comments see (PREP
Example see (PREP
see also (PREP, >PREP

>PREP Page: O Stand: A Abbreviation: >

## .. >PREP .....
Function Call-up of the block for sample preparation on the 695 Autosampler.
Description The >PREP instruction starts the instructions defined in the PREP block
(PREP ... PREP) for sample preparation on the sample rack of the 695
Autosampler paralleling measurement. As soon as the program running
for the current sample in the measuring vessel allows, the instructions
are executed with the following sample on the sample rack of the 695
Autosampler.
Comments The >PREP instruction can be used only in operation with the 695
Autosampler.
A PREP block runs only when the automatic series determination
(Auto.batch = on) on the "MONITORING" page is switched on and if
the same method is used as for the previous sample.
If the automatic transfer of sample data is switched on (Auto.samples
= on), the PREP block is executed with the next sample entered on
the "SAMPLES" page at the position on the sample rack specified
nd
under Pos.. The sample data of this sample appear on the 2
sample data line on the "MONITORING" page.
If the automatic transfer of sample data is switched off (Auto.samples
= off), the sample preparation block is automatically executed with
the next sample on the sample rack.
If a voltage is applied to the electrodes in the measuring vessel (by
MEAS or SWEEP instructions), no instructions from the PREP block can
be executed. As the voltage is retained on completion of the MEAS or
SWEEP instruction, this is not possible within a program until the volt-
age has been switched off with MEAS.
Instructions from the PREP block which need the functions of the 695
Autosampler can not be executed simultaneously with instructions
from the main program which also use such functions (e.g. DOS>M,
RINSE).
Instructions of the PREP block which have not yet been executed at
the end of the program are then run to completion.
Example see (PREP
see also (PREP, PREP)

PRINT Page: O, S Stand: M, A Abbreviation: PR

## .. PRINT ..... ....................................................
Function Printout of a message.

Remark 52 characters; -
Message which is printed out

The comment entered here is printed out on the printer followed by CR
and LF.
All numbers, letters and characters available on the keypad can be

printed out, in addition the entry of all ASCII characters with decimal
code 032255 is possible (see section 5.2.3). Printout of the special
characters with decimal code 000031 is not allowed as they are used
as control characters for the printer.
Description The PRINT instruction is used to put out the message entered in the
Remark parameter on the built-in thermal printer or the external printer
connected to the parallel interface.
Comments If a message should be printed out on an external printer attached to one

of the two RS232 interfaces, the SEND>RS1 or SEND>RS2 instructions
must be used.
see also SEND>RS1, SEND>RS2

PSAMODE Page: O, S Stand: M, A Abbreviation: PS

## .. PSAMODE .....
Function Measurement mode for Potentiometric Stripping Analysis.
Application Potentiometric stripping analysis is mainly used to determine substances

in an organic matrix with the aid of mercury film electrodes without prior
digestion.
Description In the PSAMODE measurement mode for potentiometric stripping analysis,

the analytes are deposited at the working electrode with the constant
voltage U.start during a predetermined time t.depos and the voltage
U then measured for 6 s as a function of time. The nature of the
measurement is shown below using the RDE (mercury film electrode) as
an example.
t.meas = 6 s
F (Hg film)
Area
t
PSWEEP
U.start U
t.depos
Resolution U.start
t
t.depos
In the PSAMODE measurement mode, the voltage measurement U vs t

(segment curves) is used to calculate the retention times t/U vs U
(substance curves). This results in peak-shaped curves which can be
evaluated automatically (see section 5.6.3). The peak voltage U.peak is
characteristic of the substance, the peak area t.peak is proportional to
its concentration.
t/U
t.peak
U.peak U

Comments The PSAMODE measurement mode can be used only with the
electrode types RDE and HMDE and must be employed together with
the PSWEEP instruction.
The electrode type RDE or HMDE must be entered before the PSAMODE
measurement mode.
The measurement time t.meas for the measurement of the voltage
drop is divided into 11 windows of different size in which 64 meas-
ured values are recorded each time (resulting in a total of 704 meas-
ured values per segment). The first measurement window has a size
of 2.944 ms, each subsequent window is twice as large as the pre-
ceding window.
With mercury film electrodes based on the RDE, it is advisable to
deposit the substances with stirring on the electrode. As in the
PSWEEP instruction, only an enrichment without stirring is possible (no
stirring is allowed during measurement), the MEAS instruction must be
inserted. The enrichment time with stirring is defined by its line time,
in general U.meas = U.start is selected for the measurement volt-
age.
Example see PSWEEP
see also PSWEEP, MEAS, RDE, HMDE

PSWEEP Page: S Stand: M, A Abbreviation: PSW

## .. PSWEEP XXXXX U.start ........mV Resolution ......../V
t.depos ........s
Function Sweep for PSAMODE measurement mode.

t/s display only
Time for sweep

The time for the entire sweep is displayed in the line time (which can
not be edited) and is calculated as follows:
Sweep time = t.depos + 6 s
U.start -3000...3000 mV; -
Initial voltage
Initial voltage for the sweep. This voltage is applied to the electrodes
during the enrichment time t.depos.
t.depos 0.1...600.0 s; 60.0 s
Deposition time
During this time, the voltage U.start is applied to the electrodes. The
preset voltage is then switched off and the free voltage drop measured
for 6 s.
Resolution 50...150 /V; 100 /V
Resolution
Number of intervals per volt for conversion of the segment curves U vs t
into substance curves t/U vs U. The lower the resolution selected, the
greater the smoothing of the substance curve.
Description The PSWEEP instruction starts the sweep defined in the parameters for
the PSAMODE measurement mode. A constant voltage U.start is
applied to the electrodes for a predetermined time t.depos, the freely
dropping voltage U is then measured for 6 s as a function of time.
U
U.start
PSWEEP
U.start
t.depos
Resolution
t.depos t.meas = 6 s
t

Comments The electrode type RDE or HMDE must be entered before the PSAMODE
measurement mode.
With mercury film electrodes on the basis of the RDE, it is advisable
to deposit the substances with stirring on the electrodes. As in the
PSWEEP instruction, only an enrichment without stirring is possible (no
stirring is allowed during measurement), the MEAS instruction must be
inserted. The enrichment time with stirring is defined by its line time,
in general U.meas = U.start is selected for the measurement volt-
age.
Examples PSA determination of lead in wine at a glassy carbon electrode:
Method PSA_wine.mth OPERATION SEQUENCE

Title Potentiometric Stripping Analysis of Pb
================================================================================

2 RDE Rot.speed 2000 /min
3 DCTMODE t.step 0.30 s t.meas 40.0 ms
4 MEAS U.meas -200 mV
5 DOS>M Soln.name HCl 30% V.add 1.000 mL
6 DOS>M Soln.name Hg 1g/L V.add 0.200 mL
7 PURGE
8 CONDC U.start -1200 mV Rate 1 1000 mV/s
U.end -100 mV Rate 2 10000 mV/s
Cycles 100
9 SEGMENT Segm.name Prp-800
Cycles 10
11 SEGMENT Segm.name Prp-800
Cycles 10
13 PURGE
14 (ADD
15 (REP
16 STIR Rot speed 2000 /min
Cycles 10
18 SEGMENT Segm.name Pb
19 REP)1
20 MEAS U.meas -200 mV
21 ADD>M Soln.name Pb-Std V.add 0.020 mL
22 ADD)2
23 END
Method PSA_wine SEGMENT

Prp-800
================================================================================

1 STIR Rot.speed 2000 /min
4 STIR
5 MEAS 6.0 U.standby mV
6 END

Method PSA_wine SEGMENT

Pb
================================================================================

3 STIR
4 PSAMODE
5 PSWEEP 11.0 U.start -800 mV Resolution 100 /V
t.depos 5.0 s
6 END
The illustrative program for the determination of lead with PSA runs as
follows:
OPERATION SEQUENCE Main program
Line 1 Addition of sample
Line 2....4 Switching on the RDE, application of a voltage
of 200 mV
Line 5....6 Addition of HCl and Hg(II) solution
Line 7...13 Preparation of the electrode, regeneration with
CONDC and formation of the Hg film in the
preparation segment Prp-800
Line 14...22 Double standard addition for lead determina-
tion
Line 15...19 Replication of the lead measurement in the
segment Pb
SEGMENT Prp-800 Preparation of the electrode
Line 1....6 Formation of the mercury film
SEGMENT Pb Determination of lead
Line 1....3 Deposition of lead at 800 mV for 60 s with

stirring
Line 4....6 Deposition of lead at 800 mV for 5 s without
stirring, then PSA measurement
see also PSAMODE, MEAS, RDE, HMDE, CONDC

PURGE Page: O, S Stand: M, A Abbreviation: PU

## .. PURGE .....
Function Switch on purging.
Description The PURGE instruction switches on the inert gas purging for the
measuring vessel on the 747 VA Stand. This is used to remove the
electrochemically active and hence interfering oxygen in aqueous
solutions. With the inert gas flow rate of ca. 20 L/h set on the 747 VA
Stand, a purging time of ca. 3...5 min usually suffices.
Purging remains active until it is switched off automatically with the
PURGE or END instruction in the main program on the "OP.SEQUENCE"
page.
Comment If the purging should be switched off automatically after a definite

time, the TPURGE instruction can also be used.
To achieve an effective purging of the analysis solution as quickly as
possible, the solution should also be stirred with the STIR or TSTIR
instruction.
see also PURGE, TPURGE, STIR, TSTIR, END

PURGE Page: O, S Stand: M, A Abbreviation: P

## .. PURGE .....
Function Switch off purging.
Description The PURGE instruction is used to switch off the inert gas purging for the
measuring vessel on the 747 VA stand switched on with PURGE. Purging
is used to remove the electrochemically active and hence interfering
oxygen in aqueous solutions. With the inert gas flow rate of ca. 20 L/h set
on the 747 VA Stand, a purging time of ca. 3...5 min usually suffices.
Comment If the purging should be switched off automatically after a definite time,
the TPURGE instruction can also be used.
see also PURGE, TPURGE, STIR, TSTIR, END

RADD>F Page: O, S Stand: A Abbreviation: R

## .. RADD>F ..... Soln.name ........ V.add ........mL
Function Dispense reference solution with internal standard into sample vessel
(FEED) on the 695 Autosampler.

Name of the reference solution

The name of the reference solution must be identical to the name
entered on the "SUBSTANCES/Calibration" page under Soln.name (see
section 5.6.3). The mass concentration of the reference solution Mass
conc. must also be entered here.
The entry of a solution name is mandatory when the reference solution

position assignment, the reference solution must be dispensed manu-
ally (the prompt ADD "Soln.name" "V.add" > F then appears during
the program run).
V.add 0.010...50.000 mL; 0.100 mL

Volume of the reference solution that should be dispensed into the
sample vessel.
Description The RADD>F instruction is used for the manual or automatic addition of a
reference solution to the sample vessel (FEED) on the 695 Autosampler.
This reference solution contains the reference substance needed for the
calibration technique with an internal standard (see section 6.9.6).
position of the reference solution must be specified on the "SOLUTIONS"
Comments The RADD>F instruction must be used in both the recording of the
calibration curve and in the determination.
For recording of the calibration curve, the RADD>F instruction must be
located within a CAL loop.
Example see (CAL
see also (CAL, CAL)n, RADD>M

RADD>M Page: O, S Stand: M, A Abbreviation: RADD>M

## .. RADD>M ..... Soln.name ........ V.add ........mL
Function Dispense reference solution with internal standard into measuring vessel
(MEAS).

Name of the reference solution

The name of the reference solution must be identical to the name
entered on the "SUBSTANCES/Calibration" page under Soln.name (see
section 5.6.3). The mass concentration of the reference solution Mass
conc. must also be entered here.
If the reference solution should be added automatically using a 685

Dosimat, a 700 Dosino or the 695 Autosampler, the solution name
position assignment, the reference solution must be dispensed manu-
ally or with the 6.5611.010 Pipetting equipment (the prompt ADD
"Soln.name" "V.add" > M then appears during the program run).
V.add 0.010...50.000 mL; 0.100 mL

Volume of the reference solution that should be dispensed into the
measuring vessel.
Description The RADD>M instruction is used for the manual or automatic addition of a
reference solution to the measuring vessel. This reference solution
contains the reference substance needed for the calibration technique
with an internal standard (see section 6.9.6).
The automatic addition of the reference solution can be performed with a
685 Dosimat, a 700 Dosino or directly with the 695 Autosampler. The
appropriate position of the reference solution must be specified on the
"SOLUTIONS" page (see Soln.name) for this.

Comments The RADD>M instruction must be used in both the recording of the
calibration curve and in the determination.
For recording of the calibration curve, the RADD>M instruction must be
located within a CAL loop.
On execution of the RADD>M instruction with a 685 Dosimat, a 700
Dosino or the 695 Autosampler, a wait is made until the addition is
complete before the instruction following RADD>M is executed.
Example see (CAL
see also (CAL, CAL)n, RADD>F

RAMP Page: S Stand: M, A Abbreviation: RAM

## .. RAMP U.start ........mV U.step ........mV
U.end ........mV t.step ........s
Sweep rate XXXXXXXXmV/s
Function Voltage ramp for cyclic voltammetry.

U.start -3000...3000 mV; -
Initial voltage
Initial voltage for the voltage ramp.
U.end -3000...3000 mV; -
Final voltage
Final voltage for the voltage ramp. This voltage is retained after the end
of the sweep until a new voltage is applied or until it is switched off by
MEAS or END in the main program on the "OP.SEQUENCE" page.
U.step 1...12 mV; 5 mV
Voltage step
The following condition holds for the definition of U.step:

U.step
< 100 V/s
t.step
t.step 0.1...9.9 ms, 0.01...9.99 s; 1.0 ms


U.step
< 100 V/s
t.step
Ramp slope
U.step
Sweep rate =
t.step

Description The RAMP instruction starts the voltage ramp defined in the parameters.
t.step U.end
U
U.step
U.start
Comments The electrode type must be defined before the RAMP instruction.
Admissible are HMDE or RDE.
The measurement mode must be defined before the RAMP instruc-
tion. Admissible is only CYCMODE.
The RAMP instruction must always be located within a CSWEEP
block. Maximum 5 RAMP instructions are allowed.
Apart from the RAMP instructions, no other SWEEP instruction is
instruction.
Within a CSWEEP block a wait time between two ramps can be
programmed only by insertion of an additional, slow ramp as flat as
possible.
Examples Cyclic voltammetry of Pb and Cd at the HMDE:
Method: cv SEGMENT
CdPb
================================================================================

2 CYCMODE I.range 1.4 uA Prep.cycles 2
Meas.cycles 5
3 (CSWEEP
4 RAMP U.start -100 mV U.step 10 mV
U.end -900 mV t.step 0.10 s
Sweep rate 100 mV/s
5 RAMP U.start -900 mV U.step 10 mV
U.end -100 mV t.step 0.10 s
Sweep rate 100 mV/s
6 CSWEEP)
7 END .
see also CYCMODE, (CSWEEP, CSWEEP), HMDE, RDE

RDE Page: O, S Stand: M, A Abbreviation: RD

## .. RDE ..... Rot.speed ......../min
Function Switch on Rotating Disk Electrode (RDE).
Application The RDE is used for direct and stripping determinations with solid
electrodes. Cyclic voltammetry and PSA are also possible with the RDE.

Rot.speed 0, 200, 400, ..., 3000 /min; 2000 /min
Rotational speed
Setting of the number of revolutions of the rotating electrode per min.
0 ms for the RDE by definition.
Description The RDE instruction is used to switch on the rotating disk electrode,
which comprises the 6.1246.000 Drive shaft and the 6.1204.XXX
Electrode tip. A voltage sweep can be carried out at the rotating
electrode.
Area
F
Comments Within a program, the RDE is not switched off until the STIR instruc-
tion or the selection of a different electrode type (DME, SMDE or HMDE).
The RDE is also switched off by END in the main program on the
"OP.SEQUENCE" page, but not by END in the segment.
The RDE can be used for all measurement modes and sweeps.
see also DME, SMDE, HMDE

REM Page: O, S Stand: M, A Abbreviation: RE

## .. REM ..... ....................................................
Function Remarks or comments line.

Remark
All numbers, letters and characters available on the keypad can be
entered, in addition the entry of all ASCII characters with decimal code
032255 is possible (see section 5.2.3). The entry of the special
characters with decimal code 000031 is not allowed as they are used
as control characters for the printer
Description The REM instruction is used for the entry of remarks and comments in
programs.
Comments If a remark should be put out on the screen as a message during the
program run, the HOLD instruction must be used for this.
If a remark should be printed out on the printer during the program
run, the PRINT instruction must be used for this.
If a remark should be printed out on an external printer attached to
one of the two RS232 interfaces, the SEND>RS1 or SEND>RS2 instruc-
tion must be used.
see also HOLD, PRINT, SEND>RS1, SEND>RS2

(REP Page: O, S Stand: M, A Abbreviation: (R

## .. (REP .....
Function Start of the loop for replications.
Description The (REP instruction opens a loop for replications. The instructions
inserted in this loop are executed repeatedly. The loop must be closed
with the REP)n instruction.
Comments A program can contain several REP loops, but they must not be
nested.
ADD, CAL and VAR loops are allowed within REP loops.
A REP loop is allowed within ADD, CAL and VAR loops.
The EXIT instruction can be inserted in REP loops for premature exit
from this loop.
Example Basic structure of a standard addition with repetitions of the measure-

ment in the segment:
:
:
see also REP)n, (ADD, ADD)n, (CAL, CAL)n, (VAR, VAR)n

REP) Page: O, S Stand: M, A Abbreviation: REP

## .. REP)n .....
Function End of the loop for replications.

n 0...8; 0
Number of replications
This parameter defines the number of times the REP loop is repeated.
Description The REP)n instruction ends a loop opened with (REP for replications.
The instructions inserted in this loop are repeated n times.
Comments see (REP
Example see (REP
see also (REP, (ADD, ADD)n, (CAL, CAL)n, (VAR, VAR)n

RINSE Page: O, S Stand: M, A Abbreviation: RI

## .. RINSE ..... Cycles ........ V.rinse ........mL
Function Rinse measuring vessel (MEAS) and/or reset volume bookkeeping to "0".

Cycles 0...5; 1
Number of rinse cycles

with rinsing Dosinos:
This parameter defines the number of times the measuring vessel
should be rinsed. A rinse cycle comprises the following:
Siphoning off of measuring vessel contents
Filling the measuring vessel with rinse solution
(Volume V.rinse)
Siphoning off of measuring vessel contents.
On entry of Cycles = 0, the measuring vessel is emptied, but not
rinsed.
without rinsing Dosinos:
With Cycles = 1...5, only the prompt Change measuring vessel to
change the measuring vessel appears.
V.rinse 0.010...100.00 mL; -
Rinse volume
Volume of the rinse solution used to rinse the measuring vessel.
Without entry of a value, rinsing is as follows:
Volume in the measuring vessel V.rinse
V.meas 6 mL 1.5 V.meas
V.meas < 6 mL 10 mL
Description The RINSE instruction is used to siphon off the contents of the measur-
ing vessel on the 747 VA Stand by means of two rinsing Dosinos, fill with
the volume of rinse solution specified in V.rinse and siphon off again.
At the same time, the automatic volume bookkeeping is reset to "0". The
entire rinse cycle can be run up to 5 times.
Comments The RINSE instruction is always needed when the analysis solutions
are changed in the recording of calibration curves (see (CAL).
If work is carried out with Auto.batch = on (automatic series
determination), the volume bookkeeping is reset at the end of the
program only if the RINSE instruction is used.
Examples see CSOLN>M
see also (CAL, CAL)n, CSOLN>M, CSOLN/M, CSOLN/F

SCANCTRL Page: O, S Stand: M, A Abbreviation: S

## .. SCANCTRL ..... Code ........ Test ....
Function Inquiry of the input control lines 1...8 and stop of the program until either
the test condition is met or the line time has elapsed.

Code 1, 0, *; *
Comparison code for test

8-digit numeric code for status of the input control lines 1...8. The
following values can be entered for each line:
1 on, active (0 V)
* immaterial
Test =, <>; =
Condition for test

This parameter can be used to select whether the program run should
be continued on correspondence or non-correspondence of compari-
son status and actual status of the input control lines:
= Program continuation if status of the control lines =
comparison code (or when line time has elapsed)
<> Program continuation if status of the control lines
comparison code (or when line time has elapsed)
Description The SCANCTRL instruction is used to stop the program run and poll the
status of the input control lines 1...8 of the remote interface "Control
Lines". The program is not continued until its status is equal (=) or not
equal (<>) to the preset comparison status Code or after elapse of the
line time.
The SCANCTRL instruction can be used to monitor functions of external
devices attached to the remote interface.
Comments The attachment of devices to the remote interface is described in section

3.13.
see also SETCTRL

SDOS>A Page: O, S Stand: A Abbreviation: SD

## .. SDOS>A ..... Soln.name ........ Prop.factor ........
Function Dispense auxiliary solution proportional to the sample size S0 into the
auxiliary vessel (AUX) on the 695 Autosampler.


Without entry of a name for Soln.name in the SDOS>A instruction,
(the prompt DOS "Soln.name" "V.add" > A then appears during the
program run).
Prop.factor 0.0010...99999.9; 1
Specification of the proportionality factor for calculation of the addition
volume V.add:
V.add (mL) = Prop.factor * S0 (mL or g)
Description The SDOS>A instruction is used to dispense an auxiliary solution (e.g.

supporting electrolyte, reagent solution) proportional to the sample size
S0 into the auxiliary vessel (AUX) on the 695 Autosampler.

Comments The SDOS>A instruction can be used only in operation with the 695
Autosampler.
see also SDOS>M, SDOS>F, DOS/M, DOS>M, DOS>F, DOS>A, PDOS>M

SDOS>F Page: O, S Stand: A Abbreviation: SDOS>F

## .. SDOS>F ..... Soln.name ........ Prop.factor ........
sample vessel (FEED) on the 695 Autosampler.


Without entry of a name for Soln.name in the SDOS>F instruction,
(the prompt DOS "Soln.name" "V.add" > F then appears during the
program run).
Prop.factor 0.0010...99999.9; 1
volume V.add:
Description The SDOS>F instruction is used to dispense an auxiliary solution (e.g.

S0 into the sample vessel (FEED) on the 695 Autosampler.

Comments The SDOS>F instruction can be used only in operation with the 695
Autosampler.
see also SDOS>A, SDOS>F, DOS/M, DOS>M, DOS>F, DOS>A, PDOS>M

SDOS>M Page: O, S Stand: M, A Abbreviation: SDOS>M

## .. SDOS>M ..... Soln.name ........ Prop.factor ........
measuring vessel (MEAS).


should be added automatically using a 685 Dosimat, a 700 Dosino or
the 695 Autosampler. In this case the solution name Soln.name must
be entered in the parameter of the same name on the "SOLUTIONS"
page and assigned a position Pos. (see section 5.3.4).
Without entry of a name for Soln.name in the SDOS>M instruction,
or with the 6.5611.010 Pipetting equipment (the prompt DOS
"Soln.name" "V.add" > M then appears during the program run).
Prop.factor 0.0010...99999.9; 1
volume V.add:
Description The SDOS>M instruction is used to dispense an auxiliary solution (e.g.

S0 into the measuring vessel (MEAS) on the 747 VA Stand.
Automatic addition can be performed with a 685 Dosimat, a 700 Dosino

or directly with the 695 Autosampler. The appropriate position of the
auxiliary solution must be specified on the "SOLUTIONS" page (see
Soln.name) for this.
Comments On execution of the SDOS>M instruction with a 685 Dosimat, a 700

Dosino or the 695 Autosampler, a wait is made until the addition is
complete before the instruction following SDOS>M is executed.
see also SDOS>A, SDOS>F, DOS/M, DOS>M, DOS>F, DOS>A, PDOS>M

SEGMENT Page: O Stand: M, A Abbreviation: SE

## .. SEGMENT Segm.name ........
Function Call-up of a segment.

Segm.name 8 characters; -
Segment name
The name entered here must be identical to the name of the segment
which should be executed.
Description The SEGMENT instruction executes the segment with the name Segm.name
and the instructions it contains.
Comments A segment can be called up several times.

The call-up of a segment from another segment is not possible.

SEND>RS1 Page: O, S Stand: M, A Abbreviation: SEN

## .. SEND>RS1 ..... ....................................................
Function Send a message to RS interface 1.

Message to be sent
The remark entered here is sent to RS232 interface 1.
All numbers, letters and characters on the keypad can be entered. The
following entry possibilities also exist:
### Characters with decimal code ### (see section
5.2.3). Characters with decimal code 000 ... 031
should not be entered as, with the exception of 010
(LF), although they can be shown on the screen, they
can not be printed out.
Character ""
092### Characters with octal code ### (092 = "\")
092x## Characters with hex code ##
092r Carriage return (CR)
092n Line feed (LF)
092f Form feed (FF)
092b Backspace (deletion of the character on the left)
092t Tab (tabulator)
092
092 Character "\"
At the end of the transmitted line, there is no

automatic CR/LF. This has to be explicitly entered
(e.g. with "........ 092r 092n").
Description The SEND>RS1 instruction is used to send the message entered in the
parameter Remark to RS232 interface 1 or output it on a device attached
to this interface. It is thus possible to send, e.g. control commands to an
external device.
Comments For the printout of a message on the built-in thermal printer or the
external printer connected to the parallel interface, the PRINT instruction
must be used.
see also SEND>RS2, PRINT

SEND>RS2 Page: O, S Stand: M, A Abbreviation: SEND>RS2

## .. SEND>RS2 ..... ....................................................
Function Send a message to RS interface 2.

Message to be sent
The remark entered here is sent to RS232 interface 2.
All numbers, letters and characters on the keypad can be entered. The
following entry possibilities also exist:
### Characters with decimal code ### (see section
5.2.3). Characters with decimal code 000 ... 031
should not be entered as, with the exception of 010
(LF), although they can be shown on the screen, they
can not be printed out.
Character ""
092### Characters with octal code ### (092 = "\")
092x## Characters with hex code ##
092r Carriage return (CR)
092n Line feed (LF)
092f Form feed (FF)
092b Backspace (deletion of the character on the left)
092t Tab (tabulator)
092
092 Character "\"
At the end of the transmitted line, there is no

automatic CR/LF. This has to be explicitly entered
(e.g. with "........ 092r 092n").
Description The SEND>RS2 instruction is used to send the message entered in the
parameter Remark to RS232 interface 2 or output it on a device attached
to this interface. It is thus possible to send, e.g. control commands to an
external device.
Comments For the printout of a message on the built-in thermal printer or the
external printer connected to the parallel interface, the PRINT instruction
must be used.
see also SEND>RS1, PRINT

SETCTRL Page: O, S Stand: M, A Abbreviation: SET

## .. SETCTRL ..... Code ........ Message ................
Function Set the output control lines 1...8.

Code 1, 0, *; *
Code for output control lines

8-digit numeric code for setting the output control lines 1...8. The
following values can be entered for each line:
0 off, inactive (open)
1 on, active (0 V)
* leave status unchanged
Message 16 characters;
Message for output control lines

Possibility for entry of a remark concerning the command.
If this field is edited, 4 preset messages for operation of the 708 Sam-
pling Unit are displayed on the softkeys. If such a message is entered
by pressing one of the softkeys, the last three digits of the code are
simultaneously changed:
FILL PUMP ON Code = *****101 Injection valve to "FILL",
pump on
FILL PUMP OFF Code = *****100 Injection valve to "FILL",
pump off
INJECT PUMP ON Code = *****011 Injection valve to "INJECT",
pump on
INJECT PUMP OFF Code = *****010 Injection valve to "INJECT",
pump off
Description The SETCTRL instruction is used to set the output control lines 1...8 of the
remote interface "Control Lines" to the status preset in Code. Functions
can thus be initiated at external devices attached to the remote interface.
Comments The attachment of devices to the remote interface is described in section

3.13.
Example see ADD/M
see also SCANCTRL

SHIFT Page: O, S Stand: M Abbreviation: SH

## .. SHIFT ..... Target ........ Height ........
Function Reserved for future applications with the 717 Sample Changer.
Detailed information is available from Metrohm on request.
see also LIFT

SIMPULSE Page: O, S Stand: M, A Abbreviation: SI

## .. SIMPULSE .....
Function Simulation of standard additions with the 3.496.8380 VA Simulator.
Description The SIMPULSE instruction is used to put out a total of 100 pulses at the
3.496.8380 VA Simulator which cause an increase in the current
measurement and hence a simulation of standard additions. The VA
Simulator can be reset to the original current level with the SIMRESET
instruction.
Comments The 3.496.8380 VA Simulator and the associated 3.496.5190

Connecting cable are available as an option. The VA Simulator gen-
erates 2 polarographic current waves with half-wave potentials of ca.
540 mV and ca. 1070 mV in a defined voltage range. You will find
further details in the 3.496.8380-SB Circuit Description supplied with
the VA Simulator.
To obtain a larger current increase, the SIMPULSE instruction can also
be entered twice in succession.
Example Test program for 3 simulated standard additions with the 3.496.8380 VA
Simulator:
Method SIMI .mth OPERATION SEQUENCE

Title Test program
================================================================================

1 SMPL/M V.fraction mL V.total L
2 SIMRESET 1.0
3 (ADD
4 SEGMENT Segm.name Seg1
5 SIMPULSE
6 ADD>M Soln.name V.add 0.100 mL
7 ADD)3
8 END
Method SIMI SEGMENT

Seg1
================================================================================

4 END
see also SIMRESET

SIMRESET Page: O, S Stand: M, A Abbreviation: SIMR

## .. SIMRESET .....
Function Resetting the 3.496.8380 VA Simulator.
Description The SIMRESET instruction is used to reset the current increases initiated
on the 3.496.8380 VA Simulator with the SIMPULSE instruction for the
simulation of standard additions.
Comments The 3.496.8380 VA Simulator and the associated 3.496.5190

Connecting cable are available as an option. The VA Simulator gen-
erates 2 polarographic current waves with half-wave potentials of ca.
540 mV and ca. 1070 mV in a defined voltage range. You will find
further details in the 3.496.8380-SB Circuit Description supplied with
the VA Simulator.
To ensure that the SIMRESET instruction functions properly, a line time
1 s must be entered.
Example see SIMPULSE
see also SIMPULSE

SMDE Page: O, S Stand: M, A Abbreviation: SM

## .. SMDE ..... Drop size ........
Function Switch on Static Mercury Drop Electrode (SMDE).
Application The SMDE is primarily used for sensitive measurements in which the
surface of the mercury drop must be renewed for every measurement.

Drop size 1...9; 4
Drop size
Setting of the size of the mercury drop. The area of the drop is
2 2
ca. 0.15 mm (1) ... 0.60 mm (9).
defined for the SMDE as follows:
t.drop = Drop.size 40 ms
Description The SMDE instruction switches on the 6.1246.020 Multi-Mode Electrode

as a static mercury drop electrode. The SMDE combines the features of
the DME and HMDE: as with the DME, the drops are constantly
renewed, but during the measurement the drop area is constant as in the
HMDE case. In a subsequent voltage sweep, the Hg drops are knocked
off by the tapping mechanism after the time t.step set in the measure-
ment mode.
F Area
(Hg)
(Hg)
t
t.drop t.step

Comments Within a program, the SMDE is not switched off until an MEAS
instruction or selection of a different electrode type (DME, HMDE or
RDE). The SMDE is also switched off by END in the main program on
The SMDE can be used for the following measurement modes and
sweeps: DCTMODE with SWEEP and SSWEEP,
DPMODE with SWEEP and FSWEEP,
SQWMODE with SWEEP and FSWEEP,
AC1MODE with SWEEP and
AC2MODE with SWEEP.
The following are not compatible with the SMDE:

CYCMODE with (CSWEEP,
PSAMODE with PSWEEP as well as
TSWEEP.
An advantage of the SMDE compared with the DME is its greater

sensitivity as the electrode surface and hence the baseline remains
constant during the measurement. Further, less mercury is needed.
On the other hand, the MME capillary is subjected to greater me-
chanical stress than in the DME case.
A disadvantage of the SMDE compared with the HMDE is the higher
mercury consumption, in addition the MME is subjected to greater
mechanical stress.
see also DME, HMDE, RDE

SMPL/F Page: O, S Stand: A Abbreviation: SMP

## .. SMPL/F ..... V.fraction ........mL V.total .........L
Function Sample volume has been added to the sample vessel (FEED) on the 695
Autosampler.

V.fraction 0.010...50.000 mL; -
Fractional volume
With diluted samples, here the volume fraction of the total volume
V.total which has been added to the sample vessel must be entered.
The following condition holds:
V.fraction V.total
V.total 0.10 mL...100000 L; -
Total volume
With diluted samples, here the total volume of sample and dilution
solution must be entered. The following condition holds:
V.total V.fraction
Description The SMPL/F instruction defines the sample volume in the sample vessel
(FEED) on the 695 Autosampler.
With undiluted samples (V.fraction and V.total blank), the sample
volume is given either by S0 (on entry of S0 as a volume) or by S0/S2
(on entry of S0 as a weight, S2 is the density in g/mL).
With diluted samples (V.fraction > 0 and V.total V.fraction), the
sample volume is given by V.fraction, irrespective of the entry of S0.
You will find further details on the sample size in the description of the
parameter Sample size/S0 in section 5.4.4.
Comments The SMPL/F instruction can be used only in operation with the 695
Autosampler.
If no other dispensing operations are performed in the sample vessel
(FEED), an asterisk * can also be entered for Sample size/S0. The
sample volume is then defined by the subsequent transfer into the
auxiliary or measuring vessel.
see also SMPL>M, SMPL/M

SMPL/M Page: O, S Stand: M Abbreviation: SMPL/M

## .. SMPL/M ..... V.fraction ........mL V.total .........L
Function Sample volume has been added to the measuring vessel (MEAS) on the
747 VA Stand.

V.fraction 0.010...50.000 mL; -
Fractional volume
V.total which has been added to the measuring vessel must be
entered. The following condition holds:
V.fraction V.total
V.total 0.10 mL...100000 L; -
Total volume
V.total V.fraction
Description The SMPL/M instruction defines the sample volume in the measuring
vessel (MEAS) on the 747 VA Stand.
Comments The SMPL/M instruction can not be used in operation with the 695
Autosampler.
see also SMPL>M, SMPL/F

SMPL>M Page: O, S Stand: M, A Abbreviation: SMPL>

## .. SMPL>M ..... V.fraction ........mL V.total .........L
Function Add sample volume to the measuring vessel (MEAS).

V.fraction 0.010...50.000 mL; -
Fractional volume
V.total which is added to the sample vessel must be entered. The
following condition holds:
V.fraction V.total
V.total 0.10 mL...100000 L; -
Total volume
V.total V.fraction
Description The SMPL>M instruction is used for the manual or automatic addition of
the sample volume to the measuring vessel (MEAS) on the 747 VA
Stand:
In manual addition or addition with the 6.5611.010 Pipet-
ting equipment, the prompt SMPL "V.sample" > M for
manual addition of the sample volume V.sample appears
in the program run.
In automatic addition with the 695 Autosampler, the sam-
ple volume is transferred from the sample vessel on the
st
sample rack defined on the 1 sample data line to the
measuring vessel.
see also SMPL/M, SMPL/F

SQWMODE Page: O, S Stand: M, A Abbreviation: SQ

## .. SQWMODE ..... U.ampl ........mV Modul.freq. ........Hz
t.meas ........ms Meas.cycles ........
Function Measurement mode for square wave voltammetry.
Application Square wave voltammetry with the SQWMODE measurement mode is

primarily suitable for reversible electrode processes. It is used particu-
larly for sensitive stripping voltammetric determinations at the HMDE or
RDE.

U.ampl 1...50 mV; 20 mV
Voltage amplitude
Voltage amplitude of the superimposed square wave voltage.
t.step 0.05...9.9 s; 0.3 s

Modul.freq.
t.meas 0.1...32.0 ms; 2.0/1.66 ms for 50/60 Hz
Measurement time
Time during which the current is measured. Measurement is performed
at the end of the time interval t.step immediately before the pulse
start and at the end of the pulse.
The following condition applies to the definition of t.meas:

0.5 32 ms
1 ms > t.meas <
Modul.freq. Meas.cycles
Modulation frequency of the superimposed square wave voltage.

Number of square wave voltage cycles without current measurement
cycles.



Number of square wave voltage cycles with current measurement
which are performed for every voltage step.
32 ms
Meas.cycles <
t.meas
Description With the SQWMODE measurement mode, a square wave alternating

voltage of small, constant amplitude and low frequency is superimposed
on a stepwise rising direct voltage ramp. Measurement of the current I as
a function of the voltage U involves several determinations of the
differences between the currents at each maximum and minimum
square wave voltage. The nature of the measurement is illustrated below
using the SMDE as an example.
Area
F (Hg)
SQWMODE t
t.step t.drop
t.meas
U.step
U.ampl
Modul.freq. U
Prep.cycles
Meas.cycles U.start
Prep. Meas.
SWEEP cycles cycles
U.start t.step
U.end
U.step t
t.meas (In1) t.meas (In2)
U.ampl


peak-shaped curves which can be evaluated using the baselines of type
linear, polynom or expon. (see section 5.6.3).
(In1 In2)
I I=
n
I.peak
n = Meas.cycles
U.peak U
Comments The SQWMODE measurement mode can be used with all types of
FSWEEP or TSWEEP.
the SQWMODE measurement mode.
If the SQWMODE measurement mode is used with the voltage sweep
SWEEP and the electrode type HMDE, the potentiostat normally oper-
ates in the operating mode "slow". A switch is made to the operating
mode "fast" when the modulation frequency Modul.freq. >120 Hz.
SWEEP and the electrode type SMDE or DME, the setting of the poten-
tiostat depends on the measurement profile. Normally, a switch is
also made from "slow" to "fast" when the modulation frequency
Modul.freq. >120 Hz. With very small signals, however, the operat-
ing mode "slow" is used and with very large signals the operating
mode "fast", irrespective of the pulse time.
SWEEP and the electrode type RDE, the potentiostat always operates in
FSWEEP, the potentiostat always operates in the operating mode "fast"
with all electrode types.
DME t.drop = 20 ms
see also SWEEP, FSWEEP, DME, SMDE, HMDE, RDE

SSWEEP Page: S Stand: M, A Abbreviation: SS

## .. SSWEEP XXXXX U.start ........mV U.step ........mV
Function Voltage sweep for the DCTMODE measurement mode if peaks and not
waves appear (particularly in stripping voltammetric measurements).

t/s display only
Time for voltage sweep

(U.end - U.start)

Sweep time =
Sweep rate
U.start -3000...3000 mV; -
Initial voltage
U.end -3000...3000 mV; -
Final voltage
U.step 2, 4, 6, 8, 10, 12 mV; 6 mV
Voltage step
Ramp slope
U.step
Sweep rate =
t.step

must be entered before the SSWEEP instruction.

Description The SSWEEP instruction starts the voltage sweep defined in the parame-
ters.
t.step U.end
U
U.step
U.start
Comments The electrode type must be defined before the SSWEEP instruction.
The measurement mode must be defined before the SSWEEP
instruction. Admissible is only DCTMODE.
Apart from the SSWEEP instruction, no other SWEEP instruction is
instruction.
With the SSWEEP instruction maximum 1000 measured values can be
recorded.
see also SWEEP, DSWEEP, FSWEEP, DME, SMDE, HMDE, RDE, DCTMODE

STIR Page: O, S Stand: M, A Abbreviation: ST

## .. STIR ..... Rot.speed ......../min
Function Switch on stirrer.

Rot.speed 0, 200, 400, ..., 3000 /min; 2000 /min
Rotational speed
Setting of the number of revolutions of the stirrer per min.
Description The STIR instruction is used to switch on the stirrer of the 747 VA Stand.
The stirrer comprises the 6.1246.010 Drive shaft and the 6.1204.090
Stirrer tip (see section 3.8).
The stirrer remains active until it is switched off by the STIR instruction
or END in the main program on the "OP.SEQUENCE" page.
Comment If the stirrer should be switched off automatically after a definite time, the
TSTIR instruction can also be used.
see also STIR, TSTIR

STIR Page: O, S Stand: M, A Abbreviation: S

## .. STIR .....
Function Switch off stirrer.
Description The STIR instruction is used to switch off the stirrer of the 747 VA Stand
switched on with STIR.
Comment If the stirrer should be switched off automatically after a definite time, the
TSTIR instruction can also be used.
see also STIR, TSTIR

SWEEP Page: S Stand: M, A Abbreviation: SW

## .. SWEEP XXXXX U.start ........mV U.step ........mV
Function Voltage sweep.

t/s display only
Time for voltage sweep

(U.end - U.start)

Sweep time =
Sweep rate
U.start -3000...3000 mV; -
Initial voltage
U.end -3000...3000 mV; -
Final voltage
U.step 2, 4, 6, 8, 10, 12 mV; 6 mV
Voltage step
Ramp slope
U.step
Sweep rate =
t.step

must be entered before the SWEEP instruction.

Description The SWEEP instruction starts the voltage sweep defined in the parame-
ters.
t.step U.end
U
U.step
U.start
Comments The electrode type must be defined before the SWEEP instruction.
The measurement mode must be defined before the SWEEP
Apart from the SWEEP instruction, no other SWEEP instruction is

instruction.
With the SWEEP instruction maximum 1000 measured values can be
recorded.
see also DSWEEP, FSWEEP, SSWEEP, DME, SMDE, HMDE, RDE

TPURGE Page: O, S Stand: M, A Abbreviation: T

## .. TPURGE .....
Function Purging for a preset line time.

t/s 0.1...999.9 s; -
Purging time
The duration of purging is entered in the line time.
Description The TPURGE instruction switches on the inert gas purging for the
measuring vessel on the 747 VA Stand for the period preset in t/s.
Purging is used to remove the electrochemically active and hence
interfering oxygen in aqueous solutions. With the inert gas flow rate of
ca. 20 L/h set on the 747 VA Stand, a purging time of ca. 3...5 min
usually suffices.
Comments If the purging should not be switched off automatically after a definite
time, the PURGE instruction can also be used.
To achieve an effective purging of the analysis solution as quickly as
possible, the solution should also be stirred with the STIR instruction.
see also PURGE, PURGE, STIR, TSTIR

TSTIR Page: O, S Stand: M, A Abbreviation: TS

## .. TSTIR ..... Rot.speed ......../min
Function Switch on stirrer or a preset line time.

t/s 0.1...999.9 s; -
Stirring time
The duration of stirring is entered in the line time.
Rot.speed 0, 200, 400, ..., 3000 /min; 2000 /min
Rotational speed
Setting of the number of revolutions of the stirrer per min.
Description The TSTIR instruction is used to switch on the stirrer of the 747 VA Stand
for the period preset in t/s.
Comment If the stirrer should not be switched off automatically after a definite time,
the STIR instruction can also be used.
see also STIR, STIR

TSWEEP Page: S Stand: M, A Abbreviation: TSW

## .. TSWEEP ..... U.meas ........mV
Function Application of a constant voltage to the electrodes and measurement of

the current with measured value storage.

t/s 0.1...999.9 s; -
Measurement duration
The duration of measurement is entered in the line time.
U.meas -3000...3000 mV; -
Measurement voltage
The voltage entered here is applied to the electrodes. This voltage is
retained even after the line time has elapsed until a SWEEP instruction
follows or until it is switched off by MEAS or END in the main program
on the "OP.SEQUENCE" page.
Description The TSWEEP instruction is used to apply the voltage defined in the
U.meas parameter to the electrode and start the current measurement in
accordance with the parameters defined in the measurement mode. The
measurement frequency is determined by the time interval t.step of the
measurement mode, the measurement duration by the line time of the
TSWEEP instruction.
In contrast to the MEAS instruction, the measured values in measurement

of the current are plotted. It is also possible to display the live curve (see
section 5.5.1), but no evaluation is performed.
U
U.meas
t
t/s

Comments The electrode type must be defined before the TSWEEP instruction.
Only HMDE or RDE are admissible.
The measurement mode must be defined before the TSWEEP
Apart from the TSWEEP instruction, no other SWEEP instruction is

If the current measurement should be performed without measured
value recording, the TSWEEP instruction must be replaced by the
MEAS instruction. In contrast to TSWEEP, this may be in the same
segment as the measurement sweep.
If the measurement voltage U.meas should not be switched off at the
end of the program, enter a suitable standby voltage U.standby in a
MEAS instruction.
Maximum 1000 measured values can be recorded in a segment. The

number of measured values is calculated as follows:
Measurement duration t/s
Number of measured values =
Time interval t.step
see also HMDE, RDE, MEAS

(VAR Page: O, S Stand: M, A Abbreviation: (V

## .. (VAR .....
Function Start of the loop for parameter variation.
Description The (VAR instruction opens a loop for the variation of a parameter
defined by the VARNI instruction. The instructions incorporated in the
VAR loop are executed repeatedly. The loop must be closed by the
VAR)n instruction.
Comments A program can contain several VAR loops, but they must not be
nested.
REP loops are allowed within VAR loops and a VAR loop can be
inserted in a REP loop.
No ADD or CAL loops are allowed within VAR loops.
Within VAR loops, the EXIT instruction for a premature exit from this
loop can be inserted.
Example see VARNI
see also VAR)n, VARNI, (REP, REP)n

VAR)n Page: O, S Stand: M, A Abbreviation: V

## .. VAR)n .....
Function End of the loop for parameter variation.

n 0...8; 0
Number of repetitions
This parameter defines the number of times the VAR loop is repeated.
Description The VAR)n instruction ends a loop opened with (VAR for the variation of
a parameter defined by the VARNI instruction. The instructions inserted
in this loop are repeated n times.
Comments see (VAR
Example see VARNI
see also (VAR, VARNI, (REP, REP)n

VARNI Page: O, S Stand: M, A Abbreviation: VARN

## .. VARNI ..... Param.name ............ Delta ........
Function Variation of the next instruction (Variation of Next Instruction).

Param.name Meas.cycles, Modul.freq., Ph.angle, Prep.cycles, Rot.speed,
t.line, t.meas, t.pulse, t.step, U.ampl, U.end, U.meas,
U.start, U.step; t.line
Name of the parameter to be varied

The name entered here must be identical to the name of the parameter
which should be varied in the following instruction. The following
parameters can be varied:
Meas.cycles Number of measurement cycles with measurement

modes SQWMODE, AC1MODE, AC2MODE.
Modul.freq. Modulation frequency with measurement modes

SQWMODE, AC1MODE, AC2MODE.
Ph.angle Phase angle with measurement modes AC1MODE,

AC2MODE.
Prep.cycles Number of preparation cycles with measurement

modes SQWMODE, AC1MODE, AC2MODE.
Rot.speed Rotational speed with STIR, TSTIR, RDE.
t.line Line time for all instructions with line time.
t.meas Measurement time with measurement modes

DCTMODE, DPMODE, SQWMODE.
t.pulse Pulse time with measurement mode DPMODE.
t.step Time interval for voltage step with measurement

modes DCTMODE, DPMODE, SQWMODE, AC1MODE,
AC2MODE.
U.ampl Pulse amplitude with measurement modes DPMODE,

SQWMODE, AC1MODE, AC2MODE (with DPMODE a varia-
tion is possible only in either the negative or the
positive region).
U.end Final voltage for SWEEP instructions.
U.meas Measurement voltage for MEAS instructions.
U.start Initial voltage for SWEEP instructions.
U.step Voltage step for SWEEP instructions.


Delta -1e30...1e30; 0
Step size for the variation

This parameter defines the amount by which the selected parameter
with the name Param.name is varied. With a positive value of Delta, the
parameter is increased, with a negative value it is decreased.
The step size must be entered for all parameters

in the base units s, V, Hz or .
The following conditions apply to entry of the step size:
Parameter Unit Deltamin

Meas.cycles Number 1
Modul.freq. Hz 1
Ph.angle 1
Prep.cycles Number 1
Rot.speed Number/min 200
t.line s 0.1
t.meas s 0.0001
t.pulse s 0.0001
t.step s 0.00005
U.ampl V 0.001
U.end V 0.001
U.meas V 0.001
U.start V 0.001
U.step V 0.002
Description The VARNI instruction defines the variation of a parameter within a VAR
loop. The parameter of the following instruction specified in Param.name
is increased or decreased after the first execution of the VAR loop by the
amount Delta.
Comments The instruction with the parameter to be varied must be entered after
the VARNI instruction.
The parameter to be varied is not increased or decreased by the
amount Delta until the second execution of the VAR loop, in the first
execution the value entered in the parameter of the instruction is
used.
Several VARNI instructions for different instructions are possible
within a VAR loop. However, it is not advisable to take advantage of
this possibility to change different parameters simultaneously.
REP loops are allowed within VAR loops, a VAR loop can also be
inserted in a REP loop.
No ADD or CAL loops are allowed within a VAR loop.
Within VAR loops, the EXIT instruction can be inserted for a
premature exit from this loop.

Example Variation of the pulse amplitude with the SQWMODE measurement mode:
Method: VAR SEGMENT

Seg1
================================================================================

1 (VAR
3 VARNI Param.name U.ampl Delta 0.005
4 SQWMODE U.ampl 10 mV Modul.freq. 50 Hz
t.step 0.30 s Prep.cycles 0
t.meas 2.0 ms Meas.cycles 4
6 VAR)8
7 END .
In this segment, the pulse amplitude in increased by 5 mV in every

measurement from 10 mV to 50 mV. A total of 9 measurements are
performed and are designated in the results as VR = 00...80.
see also (VAR, VARNI, (REP, REP)n

VMIX Page: O, S Stand: A Abbreviation: VM

## .. VMIX ..... Cycles ........ V.mix ........mL
Rack pos. ........
Function Mix solution at the specified rack position on the 695 Autosampler.

Cycles 1...5; 1
Number of mixing cycles

This parameter defines the number of times the solution located in the
position on the 695 Autosampler specified in the parameter Rack.pos.
should be mixed. A mixing cycle comprises the following:
Siphoning off the volume V.mix from the vessel.
Delivery of the volume V.mix into the same vessel.
Rack pos. SF, SA, A01...A44, B01...B44; SF
Rack position at which the solution should be mixed

This parameter defines the rack position at which the solution should
be mixed. The following positions can be entered:
SF Current sample vessel (FEED) on the sample rack
SA Current auxiliary vessel (AUX) on the sample rack
A01...A44 Position 1...44 on standard rack A
B01...B44 Position 1...44 on standard rack B
V.mix 0.010...10.000 mL; 1.000 mL
Mixing volume
Solution volume that is siphoned off per mixing cycle and then deliv-
ered.
Description The VMIX instruction is used to mix the solution of a vessel on the 695
Autosampler by siphoning off and subsequent delivery of a defined
mixing volume. The entire mixing cycle can run up to 5 times.
Comment Thorough mixing of a solution is achieved by multiple siphoning off and

delivery of only part of the solution.
Example see CSOLN/F

VWASH Page: O, S Stand: A Abbreviation: VW

## .. VWASH ..... V.add ........mL
Function Additional wash volume for subsequent dispensing or transfer instruction

on the 695 Autosampler.

V.add 0.010...10.000 mL; 1.000 mL
Addition volume
Additional solution volume that is delivered following the dispensing or
transfer instruction.
Description The VWASH instruction delivers an additional wash volume V.add of

hydraulic solution following a dispensing or transfer instruction on the
695 Autosampler. This ensures that the preceding solution transfer was
actually complete.
Comment The VWASH instruction refers only to the immediately following

dispensing or transfer instruction.
The VWASH instruction can be used with the following dispensing or
transfer instructions for the 695 Autosampler:
SMPL>M
DOS>M, DOS>A, DOS>F, SDOS>M, SDOS>A, SDOS>F, PDOS>M
ADD>M, PADD>M, CSOLN>M, RADD>M, RADD>F
A>M, F>A, F>M
For solution transfers on the 695 Autosampler, the following generally

holds:
Transfer volume VWASH Siphoning off Delivery
< 200 L V.add = 0 100% 100%
V.add > 0 100% 100% + V.add
200 L V.add = 0 105% 100% (+ 5% in waste)
V.add > 0 100% 100% + V.add
see also DOS>A, DOS/M, DOS>M, DOS>F, PDOS>M, SDOS>M, SDOS>A,

SDOS>F, ADD/M, ADD>M, PADD>M, RADD>F, RADD>M


6.1 Operational chart for determinations
6 Data processing
and evaluation
This section first provides you with an overview of the processes
running automatically on the 746 VA Trace Analyzer in the recording of
a determination. Finally the various phases of the data acquisition,
data processing and evaluation are described in detail.
6.1 Operational chart for determinations
Preparations Method definition section 6.2

Definition of the sample size
Method-independent settings
<START>
Data acquisition Original curves (original) section 6.3
Spike elimination Processed curves (processed) section 6.4

(background comp.)
Smoothing/derivation Smoothed curves (smoothed) section 6.5

Derived curves (derived)
Recognition Peak/wave results section 6.6

Assignment to substance
Baseline calculation Baseline section 6.7

Subtracted curve (subtrac. )
Height/area calculation Evaluation value EV:<subst> section 6.8
Content calculation Mass concentration section 6.9

(Calculation using the selected calibration
with volume correction and error calculation)
Formula calculation Final results section 6.10

6 Data processing and evaluation
6.2 Preparations before start of a determination
The following three points constitute the preparations before the start of a determi-
nation:
Method definition
Definition of all functions and parameters applicable to the determi-
nation by loading an existing method or developing a new method.
Definition of the sample size
Entry of the sample size on the dialog page MONITORING or
SAMPLES.
Method-independent settings
Additional, method-independent settings for the sequence of the
determination.
6.2.1 Method definition
The sequence of a determination is defined in the method loaded in the working

storage, which involves the following 5 dialog pages summarized under the title
Method specifications:
OP. SEQUENCE Main program (see section 5.6.1)

SEGMENTS Segment program (see section 5.6.2)
SUBSTANCES Substance parameters (see section 5.6.3)
CALCULATION Calculation formulae (see section 5.6.4)
DOCUMENTATION Report and curve output (see section 5.6.5)
Before the start of a determination, you must load the desired method from the
method memory or the data card into the working storage. If desired, you can mod-
ify this method to suit your needs or even redevelop it completely.
The functions and parameters of the 5 method dialog pages relevant for the deter-
mination are described in detail in section 5.6. In what follows, the most important
functions and settings of these pages will be summarized again in brief:
OPERATION SEQUENCE
On this dialog page program instructions and their parameters (see section
5.7.3) are used to define the sequence of a determination. The most impor-
tant instructions include:

SMPL Addition of the sample volume

DOS Addition of auxiliary solutions
PURGE Purging of the analysis solution
STIR Stirring
SEGMENT Call-up of segments
REP)n
(REP Replications (repetitions)
ADD
(ADD ADD)n Definition of standard additions
CSOLN
(CAL CAL)n Definition of calibration curves

SEGMENTS
This dialog page is used to define the measured value recording using pro-
gram instructions and their parameters (see section 5.7.3). The most impor-
tant instructions concern selection of the electrode, the measurement mode
and the sweep:
Electrode DME, SMDE, HMDE, RDE
Measurement DCTMODE, DPMODE, SQWMODE, AC1MODE,

mode AC2MODE, PSAMODE, CYCMODE
Sweep SWEEP, SSWEEP, FSWEEP, TSWEEP, PSWEEP,

(CSWEEP...RAMP...CSWEEP)
A total of 8 different segments can be programmed to which the desired sub-

stances can be assigned. The segments are distinguished by their name.
SUBSTANCES
On this dialog page maximum 8 different substances with their specific pa-
rameters can be defined. Each desired substance requires the following en-
tries:
Substance name
Assignment to a segment
(without assignment, there is no substance evaluation)
Parameters for substance recognition (Recognition)
Parameters for baseline calculation (Baseline)
Definition of the evaluation quantity (Evaluation)
Parameters for curve display and plot (Display/Plot)
Parameters for calibration
(standard addition, calibration curve or internal standard)
CALCULATION
On this dialog page freely selectable calculation formulae for further calcula-
tion of the standard results obtained in the evaluation to produce the desired
final results can be entered.
DOCUMENTATION
This dialog page is used for definition of the automatic output of reports and
curves on the built-in printer or the printer connected at the parallel or RS232
interface. Further, there is a possibility to enter a detailed comment on the
method.

6.2.2 Definition of the sample size
Before the start of a determination, it is mandatory to enter the sample size as a

volume or weight in the parameter Sample size/S0, either on the dialog page
"MONITORING" or (with automatic sample data transfer) on the "SAMPLES" page.
You will find a detailed description of the parameter Sample size/S0 in section
5.4.4. The most important points which must be considered in the entry of the sam-
ple size are listed again below:
With undiluted samples and entry of S0 as a volume, S0 is used as
addition volume for the SMPL instruction. The substance content of the
sample in g/L is identical to the calculated mass concentration MC:<subst>.
With undiluted samples and entry of S0 as a weight, the quantity S0/S2 is

used as addition volume for the SMPL instruction with mandatory entry of the
density in g/mL for S2. To obtain the substance content of the sample in g/g,
the calculated mass concentration MC:<subst> must be divided by S2*1000.
With diluted samples, S0 designates the original sample size before the
dilution. The dilution must be defined by the two parameters V.fraction and
V.total of the SMPL instruction. V.fraction is then used as the addition
volume for the SMPL instruction. The calculation mass concentration
MC:<subst> refers to this volume. To obtain the substance content of the
original sample in g/L or g/g, this value must be multiplied by the factor
V.total/S0.
The terms "undiluted samples" and "diluted samples" refer only to dilutions during
the sample preparation. Dilutions which are initiated during the program run by dis-
pensing or transfer instructions are automatically taken into consideration in the
volume bookkeeping.
The following is an overview of the various possibilities to enter S0 and their con-
sequences for the definition of the addition volume and the calculation of the final
results:
Sample S0 S2 SMPL instr. SMPL instr. Formula for Result

Parameter Add. volume final result unit
undiluted L S0 MC:<subst> g/L
undiluted g d S0/S2 MC:<subst>/ g/g

(S2*1000)
diluted L V.fraction > 0 V.fraction MC:<subst>* g/L

V.total V.fraction (V.total/S0)
diluted g V.fraction > 0 V.fraction MC:<subst>* g/g

V.total V.fraction (V.total/S0)

6.2.3 Method-independent settings
Depending on the method selected and before the start of a definition, in addition
to the parameters defined on the method dialog pages other method-independent
parameter settings are needed on other dialog pages:
MONITORING (see section 5.5.1)

Run mode Run mode (determination, calibration or test)
User name Optional entry of the user name
Stand address Entry of the stand address (1, 2 or 3)
Auto.samples Automatic transfer of sample data from the
"SAMPLES" page
Auto.batch Automatic series determination of the specified
number of samples
Det.storage Automatic storage of determinations
Sample data Pos., Ident.1/S1, Ident.2/S2, Ident.3/S3,
Method.call, Sample size/S0 (see also section
6.2.2)
SAMPLES (see section 5.4.4)

Entry of sample data if these should be transferred automatically to the
"MONITORING" page (with Auto.samples = on).
DOSIMATS (see section 5.3.3)

Setting of parameters for 685 Dosimats and 700 Dosinos used for the auto-
matic addition of standard addition or auxiliary solutions.
SOLUTIONS (see section 5.3.4)

Definition of standard addition and auxiliary solutions which should be added
automatically with the 685 Dosimats and 700 Dosinos or with the 695 Auto-
sampler.
Before the start of a determination, ensure that all solutions defined in the
method for automatic dispensing are entered on this page and that these
solutions are located in the correct positions on the Dosimats or the Auto-
sampler.
COMMON VARIABLES (see section 5.4.5)

Definition of variables common to all methods.

6.3 Data acquisition

After the start of a determination the first step involves the acquisition and storage
of the experimental data. The 746 VA Trace Analyzer operates according the poten-
tiostatic, 3-electrode principle in which the voltage of the working electrode is con-
trolled with the aid of a virtually currentless reference electrode to the preset desired
value and the current flows across a separate auxiliary electrode. The voltage drop
in the analysis solution is automatically compensated. Measurement of the current
with digitalization involves automatic matching of the amplifier sensitivity to the lat-
est measured value so that measurements are always performed with optimum ac-
curacy.
The type of measured value recording, the measurement range and the measure-
ment frequency are defined by the selection of electrode, measurement mode and
sweep. The following combinations are possible here:
Electrode Measurement mode Sweep Measured variables
DME SMDE HMDE RDE DCT DP SQW AC1 AC2 PSA CYC y axis x axis
l l l l l l l l l SWEEP current voltage
l l l l l l FSWEEP current voltage
l l l l l SSWEEP current voltage
l l l l l l l TSWEEP current time
l l n PSWEEP voltage time
l l n CYCSWEEP current voltage
l adjustable n no other choice possible adjustable, but without function
You will find details regarding the different measurement modes and sweeps in the
description of the corresponding program instructions in section 5.7.3.
The measured value pairs (current/voltage, current/time or voltage/time) recorded
per single measurement with the SWEEP instruction are stored in data blocks which
are unambiguously characterized by the segment name and the VR number
(variation and replication). This identification can be used to select the single
sweeps for the display and the output of results, reports and curves.
In connection with the measured value recording, the following rules apply to seg-
ments and sweeps:
Per method maximum 8 segments are allowed.
Per segment only 1 sweep instruction is allowed.
Per single sweep maximum 1000 measured values are allowed
(with PSWEEP 704 measured values, with RAMP 6000 measured values).
The maximum number of variations (V) and replications (R)
is limited to 8 each (that is a total of 9 single sweeps).
Per determination maximum 60 single sweeps are allowed.
The measured values recorded in the data acquisition are stored in the determina-
tion as original measured values (original) and can not be changed later. All other
steps in the data processing are based on these original data and are recalculated
each time the determination is loaded.

6.4 Spike elimination and background compensation
6.4 Spike elimination and background

compensation
The first step in the data processing involves calculation of the processed meas-
ured values processed from the original measured values original. This also in-
cludes an automatic search of all recorded data records for spikes including over-
flow values throughout all sweeps with the exception of the cyclic sweep with
several ramps. Each measured value I2 is compared with the mean value I13 of its
immediate neighboring values I1 and I3 and marked as a spike "k" or overflow "" in
the original curve original if the following conditions are met:
I2
DCTMODE with SWEEP: I
I > 100 pA + 0.06 I13 I = (I2 I13)
all other measurement modes: I3
I > 300 pA + 0.18 I13 I13 = (I3 I1)/2

I1
n
Recognized spikes and overflow measured values I2 are replaced in the processed
curve processed by the mean value I13 and shown as valid measured values " ".
The automatic spike elimination always involves only the elimination of single
spikes and not several spikes in succession. As a result, spikes "k" can still exist in
the processed curve. If desired, such measured values can be changed manually
on completion of the evaluation (see softkey <Spike elimin.> in section 5.5.3).
However, the following should be noted in such a case:
On confirmation with <ENTER>, the manual spike elimination auto-
matically initiates a recalculation with both the changed and unchanged
measured values (spikes still present can thus disappear without man-
ual change of the measured value). To be able to return to the original
measurement data, the softkey <Recalc. from orig.> on the
"MONITORING" page must be pressed.
In the storage of a determination in the determination memory or on the
data card, only the original measurement data original are retained
and not the measured values processed changed with the spike elimi-
nation.
In determinations with background compensation with the aid of the instructions
(BACKGND...BACKGND) (see section 5.7.3), the calculation of the processed curve
processed involves not only spike elimination, but also subtraction of the values
measured in the recording of the background from the original values.

6.5 Smoothing and differentiation

Following the spike elimination and the background compensation, the measured
values of the processed curve processed are smoothed. This is done in a sliding
window with a fixed number of measured points, which depends on the SWEEP in-
struction as follows:
Sweep U.step Smoothing window Number of points
SWEEP 2 48 mV 25
4 56 mV 15
FSWEEP
6 60 mV 11
SSWEEP 8 64 mV 9
10 60 mV 7
12 72 mV 7
CYCSWEEP 1 24 mV 25
with 1 ramp 2 48 mV 25
3 72 mV 25
4 56 mV 15
5 60 mV 15
6 60 mV 11
7 70 mV 11
8 64 mV 9
9 72 mV 9
10 60 mV 7
11 66 mV 7
12 72 mV 7
TSWEEP 7
PSWEEP 7
For the measured points in the smoothing window, a digital filter is applied and its
mid-point Is stored in the window as "smoothed". The window is now continuously
shifted by 1 measured point and the procedure repeated until all measured points
have been smoothed.
I Smoothing window
Is
For every single sweep, the total of all smoothed measured points results in the
smoothed curve smoothed. In smoothing, the curve is also automatically differenti-
ated to give the derived curve derived (1st derivative).
The smoothing reduces the influence of the signal noise due to the scatter of the
measured values at a very low signal level. In the development of a new method,
particularly with low analyte content, the original curve and the smoothed curve
should be compared with each other to assess the effect of smoothing.

6.6 Recognition of peaks and waves
6.6 Recognition of peaks and waves

The smoothed segment curves are searched for peaks and waves. The curves
used for their detection depend on the measurement mode as follows:
DP, SQW, AC1, PSA 1st derivation of smoothed curve, derived
DCT with SWEEP (waves) 2nd derivation of smoothed curve
DCT with SSWEEP (peaks) 1st derivation of smoothed curve, derived
CYC with 1 ramp (peaks) 1st derivation of smoothed curve, derived
AC2 Smoothed curve, smoothed
With these curves a search is made for successive minima and maxima. A maxi-
mum followed by a minimum indicates a positive peak, a minimum followed by a
maximum a negative peak. With the aid of these measured maxima and minima
values, the following coarse approximate values for the recognition tests are deter-
mined:
aU.peak = (aU.max + aU.min)/2 estimated peak voltage
aU.width = aU.min - aU.max estimated peak width
approx.peak = minmax fMM estimated peak height (for PSA, estimated
peak area) calculated with the assumption of
an ideal gaussian-shaped peak with the
empirical factor fMM dependent on the meas-
urement mode
The peaks found are assigned to predetermined substances with the aid of these
approximate values and the recognition parameters specified for the individual
substances. The following three recognition tests are performed:
1. Peak voltage test: aU.peak = U.verify U.tol
2. Peak width test: U.width min < aU.width < U.width max
3. Peak height test: approx.peak > I.threshold or

Peak area test: approx.peak > t.threshold (for PSA)
U.width max
I
aU.width
estimated U.width min
gaussian approx.peak = minmax fMM
peak
I.threshold
U
U.verify U.tol
dI/dU
minmax
aU.max aU.min U
aU.peak

In the recognition of peaks or waves using these tests, the following three cases
must be distinguished:
Defined substances with inputted verification voltage
For every peak found in the segment, the three recognition tests are per-
formed for the substances assigned to this segment:
1. aU.peak = U.verify U.tol
2. U.width min < aU.width < U.width max
3. approx.peak > I.threshold or
approx.peak > t.threshold (for PSA)
If all three test conditions are met, this peak is assigned to the corresponding
substance and thus recognized as a substance peak.
Defined substances without inputted verification voltage
For every peak found in the segment, the two recognition tests for the peak
width and the peak height or peak area are performed in turn for the sub-
stances assigned to this segment:
1. U.width min < aU.width < U.width max
2. approx.peak > I.threshold or
approx.peak > t.threshold (for PSA)
If the two test conditions are met, this peak is assigned to the corresponding
substance and thus recognized as a substance peak.
No defined substances
For every peak found in the segment the two recognition tests for the peak
width and the peak height or peak area are performed with the following
comparison parameters:
1. 25 mV < aU.width < 150 mV
2. approx.peak > 200 pA or
approx.peak > 4 ms (for PSA)
If the two test conditions are met, this peak is incorporated in the list of peaks
recognized in a segment but not assigned to a substance. In the representa-
tion of this segment on the dialog page "CURVES", the corresponding peak or
wave voltages can be shown in the system window by pressing the softkey
<Unlinked peaks> (see section 5.5.3).
Maximum 12 peaks or waves independent of any assignment to a substance can

be detected per segment. With recognized substance peaks, the exact position of
the minimum U.min and the maximum U.max as well as the peak voltage U.peak
(or half-wave potential U/2) are then determined exactly by interpolation. After the
recognition, the following results are thus available:
U.peak or U/2 Peak voltage or half-wave potential
U.width = U.min - U.max Peak width or wave width
With detected peaks which differ drastically from the gaussian form,
the values aU.peak, aU.width and approx.peak estimated from the
differentiation can deviate greatly from the actual values U.peak,
U.width and I.peak or t.peak not available until later. The ranges
selected for the substance parameters important for the recognition
test U.tol, U.width min, U.width max and I.threshold or
t.threshold should thus not be too narrow.

6.7 Baseline calculation
6.7.1 General
Recognized peaks or waves are evaluated by the 746 VA Trace Analyzer using ap-
proximated baselines. This section first explains the most important concepts for
the determination of these baselines.
Baseline parameters
The calculation of baselines from the smoothed measured curves is deter-
mined by the baseline parameters on the dialog page "SUBSTANCES" (see
section 5.6.3) where the following 6 parameters can be defined individually
for every substance:
Type Baseline type (linear, polynom, expon., AC2 rel., AC2 abs.)
Scope Baseline range (whole, f.half, r.half, f.double, r.double)
dU.front Difference to front base point
S.front Slope at front base point
dU.rear Difference to rear base point
S.rear Slope at rear base point
The setting possibilities of these parameters depend on the selected meas-
urement mode and are described in detail in section 6.7.2 through section
6.7.5. The following table provides an overview of the different selection and
combination possibilities for these parameters:
Type Scope
Measurement lin. pol. exp. AC2 AC2 whole f.half f.double dU.front S.front
mode rel. abs. r.half r.double dU.rear S.rear
DCT (waves) l n l l
l l l l
DCT (peaks),
DP, SQW, AC1, l l l l
CYC (1 ramp)
l l l l l l
AC2 l l n
l n l
PSA n n n n
l adjustable n no other choice possible adjustable, but without function

Base points
Selection of the base points is decisive for the determination of all baselines.
In the automatic determination of the base points (dU.front = auto and
dU.rear = auto), these are determined from the results U.max, U.min, and
U.peak (see section 6.6) obtained in the recognition of peaks or waves. For
this, the two differences Uw.front and Uw.rear (which are identical only for
symmetrical peaks) are multiplied by the empirical factor fG defined using
ideal gaussian-shaped curves such that the height at the base point is 5% of
the maximum peak height. In the case of baselines with Type = linear or
Type = AC2..., this factor is multiplied by 0.8, i.e. the base points are nearer
the peak maximum than baselines with Type = polynom or Type = expon..
U.max U.min
I
Uw.front Uw.rear Uw.front = U.peak - U.max
U.width
Uw.rear = U.peak - U.min
U.width = Uw.front + Uw.rear
dU.front = Uw.front fG
dU.front dU.rear dU.rear = Uw.rear fG
U.peak U
Slopes
Equally important as the selection of
S=
base points is that of the associated
slopes. In the automatic determination S = -1 S=1
of the slopes (S.front = auto and
S.rear = auto), these are calculated
from the smoothed curves at the loca- S=0 S=0
tion of the base points. The slopes are
standardized so that the following al-
ways holds:
S = 0 horizontal slope
S = 1 diagonal slope
S = vertical slope
Overlapping
Two peaks which overlap can mutually U.peak
influence each other to an extent which,
depending on the degree of overlap-
ping, can impair or even completely
prevent their evaluation. With the 746 VA U.width1
U.width2
Trace Analyzer, the peaks are automati-
Uf1
cally investigated for any overlapping Uf2 Ur1 Ur2
with neighboring peaks. The position of

the base points Ur1 and Uf2 is used
as a criterion for determination of the
overlapping:
Ur1 > Uf2 Overlapping at the rear of the 1st peak

Uf2 < Ur1 Overlapping at the front of the 2nd peak

If overlapping exists, the following 4 cases are distinguished:

Negligible overlapping: approx.peak1/approx.peak2 > 10
If the ratio of the estimated peak heights of the two neighbouring peaks
is larger that 10, the influence of the overlapping can be completely ig-
nored.
Admissible overlapping: approx.peak1/approx.peak2 10

U.peak > 0.9 * (U.width1 + U.width2)
If the difference between the two peak voltages U.peak is greater
than 90% of the sum of the two peak widths (overlapping <10%), this is
shown in the results with the comments front overlapping or rear
overlapping. The overlapping leads to no noticeable falsification of the
results, an evaluation with Scope = whole is still possible.
Critical overlapping: approx.peak1/approx.peak2 10

U.peak 0.9 * (U.width1 + U.width2)
U.peak > 0.6 * (U.width1 + U.width2)
If the difference between the two peak voltages U.peak is 60 ... 90%
of the sum of the two peak widths (overlapping 10...40%), this is shown
in the results with the comments crit. front ovlp. or crit. rear
ovlp.. The overlapping is so large that an evaluation with Scope =
whole leads to relatively large errors. However, an evaluation with
Scope = f.double/r.double or possibly Scope = f.half/r.half is
possible.
Inadmissible overlapping: approx.peak1/approx.peak2 10

U.peak 0.6 * (U.width1 + U.width2)
If the difference between the two peak voltages U.peak is less than
60% of the sum of the two peak widths (overlapping >40%), this is
shown in the results with the comments illeg. front ovlp. or
illeg. rear ovlp.. The overlapping is so large that an evaluation is no
longer possible. In this case, an attempt must be made to separate the
two peaks by chemical or measurement technique measures (see sec-
tion 7.5.8).
6.7.2 Baselines for waves
With wave-shaped curves which have been recorded with the DCTMODE meas-
urement mode, the two tangents before and after the wave are determined as
baselines. These tangents are then used to calculate the wave current I.wave.
The selection possibility for the base- dU.front dU.rear Base point
line parameters is restricted here to (rear)
Type = linear and Scope = whole. The
S.rear
base points dU.front and dU.rear
and the associated slopes S.front Base point
(front)
and S.rear can be determined I.wave
automatically or entered manually.

With wave-shaped curves, no display S.front
of the subtracted curve subtracted is U.wave
possible.

6.7.3 Baselines for peaks
With peak-shaped curves which have been recorded with the DPMODE,
SQWMODE, AC1MODE, DCTMODE (with SSWEEP) and CYMODE (with 1 ramp)
measurement mode, the following possibilities exist for calculation of the baseline:
Type = linear, Scope = whole
The baseline of type linear is determined using the tangent method. With
the peak base points dU.front and dU.rear determined beforehand as a
basis, an iterative search is made within a fixed range for identical slopes. The
range for the tangent search is ca. 20 mV outward and inward up to 1 point
before the peak maximum.
If two points with an identical slope are found, the two points of tangency are
connected to give the linear baseline. If no common slope is found, the linear
baseline is drawn directly through the two base points.
Instead of being deter- linear, whole
mined automatically, the dU.front dU.rear
two base points dU.front
and dU.rear can also be (front) (rear)
entered manually either by Point of tangency
numeric entry or by shift- (front)
ing using the cursor keys

(see "CURVES", section Point of tangency
5.5.3). In contrast, the two (rear)
slopes S.front and Range for Range for

S.rear are always calcu- tangent search tangent search
lated automatically, a nu-

meric entry here is ig- Subtracted
curve
nored.
Type = linear, Scope = f.half/r.half

The baseline of type linear, f.half is determined only by starting from the
peak front half, that of type linear, r.half only by starting from the peak
rear half. In the first case, the baseline is given by the tangent with the slope
S.front at the base point dU.front, in the second case by the tangent with
the slope S.rear at the base point dU.rear.
The two base points dU.front and linear, f.half linear, r.half
dU.rear as well as the two slopes
S.front and S.rear can also be
entered manually instead of being
determined automatically.
Type = linear, Scope = f.double/r.double

This type of baseline is used for the evaluation of overlapping peaks; for the
1st peak the type linear, f.double must be used and for the 2nd peak the
type linear, r.double. The baseline is calculated in exactly the same man-
ner as for linear, whole using the tangent method. With the previously de-
termined peak base points dU.front for the 1st peak and dU.rear for the 2nd
peak as a basis, an iterative search is made within a fixed range for identical
slopes. The range for the tangent search is ca. 20 mV outward and inward up
to 1 point before the corresponding peak maximum.

If two points with identical slope are found, the two points of tangency are
connected with each other to give the linear baseline. If no common slope is
found, the linear baseline is drawn directly through the two base points.
Instead of being determined linear, f.double linear, r.double
automatically, the two base
points dU.front and dU.rear
can also be entered manually by
numeric entry. In contrast, the
two slopes S.front and S.rear
are always calculated automati-
cally, a numeric entry here is ig-
nored.
Type = polynom, Scope = whole

In the baseline of type polynom, the curvature of the peak baseline is appro-
ximated by a polynomial curve. With the previously determined peak base
points dU.front and dU.rear as a basis, the two associated slopes
S.front and S.rear are used to calculate the curved baseline.
The two base points polynom, whole

dU.front and dU.rear as dU.front dU.rear
well as the two slopes
S.front and S.rear can Base point Base point
(front) (rear)
also be entered manually
instead of being deter-
mined automatically.
Subtracted
curve
Type = polynom, Scope = f.double/r.double

1st peak the type polynom, f.double must be used and for the 2nd peak the
type polynom, r.double. The baseline is calculated in exactly the same man-
ner as for polynom, whole. With the previously determined peak base points
st nd
dU.front for the 1 peak and dU.rear for the 2 peak as a basis, the two
associated slopes S.front and S.rear are used to calculate the curved
baseline.
The two base points dU.front polynom, f.double polynom, r.double
and dU.rear as well as the two
slopes S.front and S.rear
can also be entered manually
instead of being determined
automatically.
Type = expon., Scope = whole

With the baseline of type expon., the curvature of the peak baseline is ap-
proximated by an exponential curve. With the previously determined peak
base points dU.front and dU.rear as a basis, the two associated slopes
S.front and S.rear are used to calculate the exponential baseline.

The two base points dU.front and expon., whole

dU.rear as well as the two slopes dU.front dU.rear
S.front and S.rear can also be
entered manually instead of being Base point
Base point
determined automatically. (front) (rear)
S.rear
S.front
Subtracted
curve
Type = expon., Scope = f.double/r.double

1st peak the type expon., f.double must be used and for the 2nd peak the
type expon., r.double. The baseline is calculated in exactly the same man-
ner as for expon., whole. With the previously determined peak base points
st nd
dU.front for the 1 peak and dU.rear for the 2 peak as a basis, the two
associated slopes S.front and S.rear are used to calculate the exponen-
tial baseline.
The two base points expon., f.double
dU.front and dU.rear as
well as the two slopes
S.front and S.rear can
expon., r.double
also be entered manually in-
stead of being determined
automatically.
With all peak-shaped curves not only the smoothed curve, but also the subtracted
curve subtracted in which the calculated baseline is subtracted from the
smoothed measured values (see the examples with Scope = whole) can be shown.
This curve or its knee region can be used to assess the evaluation, but the following
cases must be distinguished:
Curve knee nicely Curve knee too steep, Undershooting, base

curved, base point base point too near the point too far removed
correctly selected peak maximum from the peak maxi-
mum

6.7.4 Baselines for AC2 curves
With curves recorded with the measurement mode AC2MODE, only the following two
possibilities are available for calculation of the baseline:
Type = AC2 rel., Scope = whole

In the evaluation of AC2 curves with the baseline type AC2 rel., the previ-
ously determined peak base points dU.front and dU.rear are connected
with each other to give the linear baseline. The two peak heights If and Ir are
then determined relative to the linear baseline and added to the result I.rel.
Instead of being determined
automatically, the two base AC2 rel. dU.front dU.rear
points dU.front and dU.rear
can also be entered manually
I.rel = If + Ir
either by numeric entry or by If
shifting using the cursor keys
(see "CURVES", section 5.5.3).
Ir
In contrast, the two slopes
S.front and S.rear have no
meaning here, a numeric entry U/2
is ignored.
Type = AC2 abs./linear, Scope = whole

In the evaluation of AC2 curves with the baseline type AC2 abs. or linear,
while the previously determined peak base points dU.front and dU.rear
are shown and connected to give a linear baseline, this baseline is not
needed for the evaluation. The entire peak height I.abs is determined and
put out as the result.
The two base points dU.front and AC2 abs. dU.front dU.rear
dU.rear and the two slopes
S.front and S.rear have no
meaning here, a numeric entry is
ignored with these parameters.
I.abs
U/2

6.7.5 Baselines for PSA curves
With curves recorded with the measurement mode PSAMODE, there is no possibility
to select a method to calculate the baseline, the corresponding baseline parame-
ters are missing on the dialog page "SUBSTANCES".
The baseline is calculated automatically with the predetermined parameters Type =
linear and Scope = whole. The baseline is determined by the tangent method
where, starting from the automatically determined peak base points dU.front and
dU.rear, an iterative search is made within a fixed range for identical slopes. The
range of the tangent search is ca. 20 mV outward and inward up to 1 point before
the peak maximum.
If two points with identical slopes are found, the two points of tangency are con-
nected with each other to give the linear baseline. If no common slope is found, the
linear baseline is drawn directly between the two base points.
The two base points dU.front PSA

and dU.rear are only displayed dU.front dU.rear
and can not be changed. On the
other hand, it is possible to dis- (front) (rear)
play the subtracted curve Point of tangency
subtracted to check the (front)
evaluation (see section 6.7.4).

Point of tangency
(rear)
Range for Range for

tangent search tangent search
Subtracted
curve

6.8 Height/area calculation
6.8 Height/area calculation
With the aid of the calculated baselines, the evaluation quantity EV:<subst> is de-
termined for each substance and displayed as a result. Depending on the meas-
urement mode, the following quantities are possible as evaluation quantities:
Measurement I.wave I.peak P.peak I.abs I.rel t.peak

mode
DCT (waves) n
DCT (peaks),
DP, SQW, AC1, l l
CYC (1 ramp)
AC2 l l
PSA n
l adjustable n no other choice possible
These evaluation quantities are calculated as follows:

I.wave
The wave current I.wave is calculated
from the tangents before and after the I.wave
wave (details, see section 6.7.2).
I.peak
The peak height I.peak is determined
from the previously calculated baseline I.peak
(details, see section 6.7.3) and the ex-
actly interpolated current height at the
peak maximum.
P.peak
The peak area P.peak is determined
from the previously calculated baseline P.peak
(details, see section 6.7.3) by integra-
tion.
Scope = whole
With a linear baseline with Scope =
f.half and Scope = r.half, only the
area up to the peak maximum is taken
as an evaluation quantity.
Scope = f.half Scope = r.half
I.abs / I.rel
With AC2 curves, either the absolute or the relative peak height can be cal-
culated. Details are given in section 6.7.4.
t.peak
With PSA curves, the peak area
t.peak
t.peak is determined by integration
of the previously calculated base-
line (details, see section 6.7.5).

6.9 Content calculation
6.9.1 General
With polarographic and voltammetric methods, the measured evaluation quantities

EV:<subst> (wave height, peak height or peak area, see section 6.8) for a sub-
stance are proportional to its mass concentration subst:
EV:<subst> = ( subst )
The relation between evaluation quantity and mass concentration must be deter-
mined by a calibration with reference solutions. The 746 VA Trace Analyzer offers
the following three techniques for this:
Standard addition (see section 6.9.4)
Content determination using single or multiple addition of a standard
solution
Calibration curve (see section 6.9.5)
Content determination using a calibration curve previously determined
with reference solutions
Internal standard (see section 6.9.6)
Content determination by addition of a reference substance using the
proportionality factor determined previously with reference solutions
The goal of all three calibration methods is to calculate the mass concentration s of
the sample referred to the added sample volume V.sample, which is then put out
on the dialog page "RESULTS/Evaluations" and in Report Full as Mass conc. =
MC:<subst>:
m.sample m0.sample
s = =
V.sample V0.sample
s Mass concentration of the sample

(= Mass conc. on the "RESULTS/Evaluations" page)
m.sample Substance mass in the sample
V.sample Sample volume (addition volume for SMPL instruction), dependent on
the entry of the sample size (see section 5.4.4):
V.sample = S0 (undiluted, S0 in L)
V.sample = S0/S2 (undiluted, S0 in g)
V.sample = V.fraction (diluted, S0 in L or g)
m0.sample Substance mass in the measuring vessel
(= Mass on the "RESULTS/Evaluations" page):
m0.sample = m.sample * fAS
V0.sample Sample volume in the measuring vessel
(displayed on the "RESULTS/Evaluations" page):
V0.sample = V.sample * fAS
The automatically calculated dilution factor fAS takes into account all
dilutions of the sample volume on the 695 Autosampler before addi-
tion to the measuring vessel:
fAS = 1 no dilution on the Autosampler
fAS < 1 dilution on the Autosampler

6.9.2 Dilution calculation
In all cases in which only part of the sample volume V.sample is added to the
measuring vessel or in which the sample is additionally diluted before or after addi-
tion to the measuring vessel (e.g. by addition of auxiliary solutions), instead of the
sought mass concentration s the effective mass concentration eff,s is measured in
the measuring vessel. The relation between these two quantities is given by the di-
lution factor fV:
eff,s = fV * s
eff,s Effective mass concentration of the sample in the measuring vessel at

the time of measurement (shown only in the calibration curve)
s Mass concentration of the sample
(= Mass conc. on the "RESULTS/Evaluations" page)
fV Dilution factor
With the aid of the automatic volume bookkeeping of the 746 VA Trace Analyzer,
the dilution factor fV is recalculated continuously for every dilution step. In connec-
tion with the volume bookkeeping, the following points should be noted:
At the start of a determination with the <START> key, the volume
bookkeeping is automatically reset to 0.
If work is carried out with Auto.batch = on (automatic series de-
termination), the volume bookkeeping at the end of the program is
reset to 0 only if the RINSE instruction is used.
The RINSE instruction resets the volume bookkeeping to 0.
The simple addition of an auxiliary solution to a sample solution in a measuring

vessel will serve to illustrate the dilution calculation:
Sample Measuring vessel Auxiliary solution
DOS>M
SMPL>M
V.sample V0.sample = V.sample V.add

m.sample m0.sample = m.sample
V.eff = V.sample + V.add
m.sample m.sample
s = eff,s = = fV * s
V.sample V.eff
V.sample
fV =
V.eff
V.eff
s = * eff,s
m.sample

6.9.3 Result calculation from calibration curves and error

calculation
With all three possible calibration methods, the mass concentration eff in the
measuring vessel must be determined with the aid of a calibration curve. This cali-
bration curve itself must be determined by the measurement of solutions of known
mass concentration. The measured value pairs EV:<subst> / eff are then used to
calculate the parameters for a given linear or nonlinear curve function. As the cal-
culation of the calibration curves, the results based on them and the associated
error calculation are basically the same in all calibration techniques, in what follows
the calculation procedure used by the 746 VA Trace Analyzer will be described in
general terms.
A search is made for the relation between the variables x and y using the measured
values xi, yi with the following assumptions:
The variable x is error free.

Function y = y ( x )
The variable y depends on x and y
can be described by the function
y = y ( x ).
yi
The error in the measurement of y ^
yi Measured value
has a normal distribution and is Estimated value
sufficiently small to allow use of a
xi
linear error calculation. x
For the calculation of the calibration curve y = y ( x ), the 746 has the following 4
model functions available, depending on the calibration technique selected:
y = a + bx Straight line
y = bx Straight line through zero
y = a + bx + cx4 Nonlinear curve of 4th degree
y = bx + cx4 Nonlinear curve of 4th degree through zero
To calculate the parameters a, b and c, the method of least squares is used in

which the sum of the squared deviations of the measured values yi from the esti-
mated values ^y i is minimized. As the scatters y,i of the measured values depend
on the measured value y, these deviations are weighted with the factor gi:
n
1 1

i=1
yi )2 = minimum
gi ( yi ^ with gi =
( y,i )2
=
( p 0,i )2
The dependence of the scatters y of the y ( y ) = p 0 ( y )

measured value y has been determined by
the 746 VA Trace Analyzer experimentally. y < 15 nA: 0 = 15 nA
0 y 15 nA: 0 = y
Here, it was apparent that the scatter
remained constant up to a measured value
of 15 nA, but above this value then in-
creased in direct proportion to the measured
value. The factor p takes into account the 15 nA y
influence of the changing disturbance
variables (capillary, temp., etc.).

As a consequence of the weighting of the least squares, the contribution of the

measured points xi, yi for the determination of the curve parameters differs in ac-
cordance with the position of yi. With yi > 15 nA, the influence on the calibration
curve becomes smaller, the greater yi.
The calculated calibration curve is used in subsequent measurements to determine
the associated result xM from the mean value yM of the m measured quantities yM.
Mean value yM and scatter y,M of the individual values are defined as follows:
1
m (y M,i yM )2
^
y
i=1
yM = M,i y,M =
m m1
i=1
The estimation of the total error x of the result xM is performed by the 746 VA Trace
Analyzer with a linear error calculation which takes into account both the error
contribution from the measurement and that from the calibration. As the two contri-
butions are statistically independent, their variances 2 and not the individual errors
are added:
(x )2 = (x,M )2 + (x,C )2
The error contribution from the actual measurement is calculated from the x, y de-
rivative of the calibration function, the measured scatter y,M and the Student factor
tM as follows:
x 2
(x,M )2 = (tM )2
y
(y,M )2 ( )
For the calculation of the error contribution from the calibration, the errors of the in-
dividual parameters of the calibration function used are determining. As these pa-
rameters zr (a, b, c) are statistically dependent on one another, here all covariances
cov (zr, zs) must be taken into account (tC is again the Student factor):
x x
(x,C)2 = (tC )2 z
r,s r zs
cov (zr, zs)
In measurements with the 746 VA Trace Analyzer, from the statistical point of view
only small samples (<10) are determined from a population with gaussian distribu-
tion. These samples have a Student distribution. Both the error contribution from
the measurement and that from the calibration are thus multiplied by the Student
factor t2. This factor depends on the number of measurements n and the number of
degrees of freedom f and is defined for a probability of 68.3% as follows:
nf t nf t nf t f
1 1.837 6 1.091 15 1.035 tM 1
2 1.321 7 1.077 20 1.026 tC for y = bx 1
3 1.197 8 1.067 30 1.017 tC for y = a + bx 2
4
4 1.142 9 1.059 50 1.010 tC for y = bx + cx 2
4
5 1.111 10 1.053 100 1.005 tC for y = a + bx + cx 3
The total error x of the result xM consequently gives the range xM x in which the
result xM may be expected with a probability of 68.3%.

6.9.4 Standard addition
In the standard addition method, a known amount of the analyte is added once or
several times to the sample. The addition may be performed manually or automati-
cally and is programmed with the following instructions and parameters on the dia-
log page "OP.SEQUENCE" (see section 5.7.3):
(ADD...ADD)n Loop for standard addition
n Number of standard additions
ADD... Constant standard addition
Soln.name Name of the standard addition solution
V.add Addition volume
PADD... Proportional standard addition
Soln.name Name of the standard addition solution
Prop.subst. Name of the reference substance for
proportional standard addition
Prop.coeff. Proportionality coefficient
The remaining parameters needed for the standard addition are entered on the
dialog page "SUBSTANCES/Calibration" (see section 5.6.3). The most important of
these are:
Technique Selection of the calibration technique
std.add Standard addition
Curve type Curve type for calculation of the standard addition
nonlin Curve of type y = a + bx + cx4
Soln.name Name of the standard addition solution (must be identical
to the name specified in the ADD instruction)
Mass conc. Mass concentration of the standard addition solution
In the standard addition, the following procedure is used to calculate the sought
mass concentration eff,s of the sample (see also example in section 4.2):

The sample solution with the unknown mass concentration eff,s of the sam-
ple is measured one or more times. This gives:
EVs Evaluation quantity for sample
EVs.mean Mean value of the evaluation quantity for sample
Std.dev. Standard deviation of the individual value EVs
2 Measurement of the spiked sample solutions

The sample solution is spiked one or more times with a standard solution of
known mass concentration std. Each of these spiked solutions is measured
one or more times. This gives:
EVn Evaluation quantity for nth spiked sample
EVn.mean Mean value of the evaluation quantities for
nth spiked sample
Std.dev. Standard deviation of the nth individual value EVn

eff,n eff,s Difference in the mass concentrations between

the nth spiked sample and the original sample
solution (calculated from the known volumes
V.sample and V.addn as well as std)
3 Determination of the calibration curve for the standard

addition
The parameters for the two possible model functions
are determined by the procedure described in section 6.9.3 with y = EV and
x = eff eff,s by weighted least squares minimization. These parameters are
displayed on the "RESULTS/Calibrations" page and have the following
meaning:
a Y.reg/offset Intercept of calibration curve
b Slope Slope of calibration curve in the linear region
c Nonlin. Non-linearity factor
4 Calculation of the mass concentration eff,s

A requirement for the use of the standard addition is that when eff = 0 the
evaluation quantity EV = 0. If 0 is substituted for these two quantities in the
calibration function, the sought mass concentration eff,s can be calculated
from the following two equations:
b eff,s a = 0 for y = a + bx
c eff,s4 + b eff,s a = 0 for y =a + bx + cx4
In the graphical representation of the standard addition curve, the sought
mass concentration on the x-axis is given by the distance between the zero
point and the intersection point with the calibration function.
std.add.
EV linear
nonlin
Sample
Standard solution
a
0
eff eff,s
eff,s
5 Display of the standard addition curve

The curve shown above EV vs eff eff,s is not displayed and plotted by the
VA Trace Analyzer. Instead, it displays and plots EV vs eff in which the
coordinate origin is shifted to the left by the amount eff,s. The parameter a in
this representation denotes the value estimated from the curve for the sam-
ple and is thus designated by Y.reg.

std.add.
EV linear
nonlin
Sample
Standard solution
a
0
eff
The non-linear curve shown in the new coordinate grid is not de-
scribed completely by the parameters a, b and c determined for the
original curve.
6 Calculation of the mass concentration s

The found, effective mass concentration eff,s is converted into the sought
mass concentration s by taking the dilution into account (see section 6.9.2):
Mass conc. = s = eff,s / fV
7 Calculation of the total scatter x

As measurement of the sample is part of the calibration in standard addition,
for the determination of the total scatter x only the error contribution from
the calibration must be taken into account (see section 6.9.3):
x = x,C
As the total scatter x refers to the effective mass concentration eff,s, it must
also be converted by taking the dilution into account:
MC.dev. = x / fV
To be able to calculate the total scatter MC.dev., with the linear curve type at
least 3, with the nonlinear curve at least 4 measured value pairs must be
available, otherwise MC.dev. = 0 will be set and the message no
meas.deviation put out on the "RESULTS/Evaluations" page.
Standard addition is the usual calibration method for the majority of the applications
possible with the 746 VA Trace Analyzer. Its advantage lies in its high dependability
as the calibration in the sample takes place under real matrix conditions and all
measurement parameters remain unchanged. With regard to optimum accuracy
and scatter, several rules must be observed in standard addition:
In development of the method, the linearity range should be checked for each
substance. This involves performing several standard additions over a wide
concentration range. Using the calibration curve shown on the "CURVES"
page, you can then determine the region in which the standard addition is
linear and that in which it is nonlinear.
If the substance content lies in the linear range, multiple standard addition is
meaningful only if you wish to check the linearity in every determination. To
reduce the scatter, it is better to spike the solution once only and to choose
as many replications as possible.

Working in the nonlinear range

If the substance content is in the nonlinear range, several standard additions
have to be performed to determine the nonlinear curve shape exactly.
Standard addition ratio 1:2 to 1:5
The optimum standard addition ratio for the entire standard addition is from
1:2 to 1:5, i.e. the sum of all standard addition amounts should be 2 to 5
times the amount of sample in the measuring vessel. This can be easily
checked later with the parameters Mass and Add.mass put out on the dialog
page "RESULTS/Evaluations".
Any blank values must be determined separately and subtracted in the for-
mula calculation on the dialog page "CALCULATIONS".
6.9.5 Calibration curve
The content determination using a calibration curve is performed in two steps:

First the relation between the mass concentration eff of a sub-
stance and the evaluation quantity EV is determined by measur-
ing different reference solutions.
Finally, the sample is measured and its mass concentration eff,s
determined using the recorded calibration curve.
The recording of a calibration curve is programmed with the following instructions
and parameters on the "OP.SEQUENCE" page (see section 5.7.3):
(CAL...CAL)n Loop for recording the calibration curve
n Number of calibration solutions 1
CSOLN... Addition of the calibration solutions
The remaining parameters needed for the calibration curve are entered on the dia-
log page "SUBSTANCES/Calibration" (see section 5.6.3). The most important of
these are:
cal.crv. Calibration curve
Curve type Curve type
0/linear Straight line of type y = bx
nonlin Curve of type y = a + bx + cx4
0/nonlin Curve of type y = bx + cx4
V0.CSoln. Addition volume of the calibration solutions
In the content determination using a calibration curve, the following procedure is

used to calculate the sought mass concentration eff,s of the sample (see also ex-
ample in section 4.3):

1 Measurement of the calibration solutions

The calibration solutions of known mass concentration n are each meas-
ured several times. This gives:
EVn Evaluation quantity for nth calibration solution
EVn.mean Mean value of the evaluation quantities for nth calibra-
tion solution
eff,s Effective mass concentrations of the calibration solu-
tions (calculated from n taking the dilution into ac-
count)
2 Determination of the calibration curve

The parameters of the four possible model functions
y = bx Straight line through zero point
y = bx + cx4 Nonlinear curve of 4th degree through zero point
are determined by the procedure described in section 6.9.3 with y = EV and
x = eff by weighted least squares minimization. These parameters are
displayed on the "RESULTS/Calibrations" page and have the following
meaning:
a Y.reg/offset Intercept of calibration curve
b Slope Slope of calibration curve in the linear region
c Nonlin. Non-linearity factor
3 Display of the calibration curve

The calibration curve EV vs eff is displayed and plotted by the 746 VA Trace
Analyzer:
linear
EV cal.crv.
nonlin
Slope
0/linear
0/nonlin
Y.offset 0
0 eff

The sample solution with the unknown mass concentration eff,s of the sam-
ple is measured one or more times. This gives:
EVs Evaluation quantity for sample
EVs.mean Mean value of the evaluation quantity for sample

5 Calculation of the mass concentration eff,s

The sought mass concentration eff,s of the sample is calculated by inserting
EVs.mean in the calibration function determined earlier:
c eff,s4 + b eff,s a = EVs.mean

In the graphical representation of the calibration curve, EVs.mean and the
calculated mass concentration eff,s are marked:
EV
cal.crv.
EVs.mean
eff,s eff

The found, effective mass concentration eff,s is converted into the sought
Mass conc. = s = eff,s / fV
7 Calculation of the total scatter MC.dev

The total scatter x is calculated from the two error contributions of the
calibration and the measurement as described in section 6.9.3:
(x )2 = (x,M )2 + (x,C )2
As these scatters refer to the effective mass concentration eff,s, they must
MC.dev. = x / fV
Meas.dev. = x,M / fV
Cal.dev. = x,C / fV
To be able to calculate Cal.dev., the following conditions for the number of

measured value pairs n in the calibration must be met:
n2 for y = bx
n3 for y = a + bx
n3 for y = bx + cx4
n4 for y = a + bx + cx4
If this is not the case, Cal.dev.= 0 is set and the message no cal.devia-
tion put out on the "RESULTS/Evaluations" page.
The calculation of Meas.dev. uses the number of measured value pairs m in

the measurement of the sample solution. The following cases must be
distinguished:

m4 Meas.dev. is calculated from x,M (see section 6.9.3).

m2 If sufficient calibration points are available (see above),
Meas.dev. is estimated from Cal.dev. and the message
dev.estimated put out on the "RESULTS/Evaluations" page.
If this is not the case, Meas.dev. is calculated from x,M (see
section 6.9.3).
m=1 If sufficient calibration points are available (see above),
If this is not the case, Meas.dev. = 0 is set and the message
no meas.deviation put out.
The result determination with the aid of a calibration curve saves time compared
with standard additions, but is reliable only
if the matrix of all samples and calibration solutions is identical or has
no influence on the measurement
if all measurement parameters (capillary, temperature, etc.) remain un-
changed during measurements
if the accuracy of the results obtained is checked regularly with the
standard addition method.
With regard to optimum accuracy and scatter, a number of rules must be observed
with calibration curves:
In development of the method, the linearity range of the calibration curve
should be checked for each substance by recording the curve over a wide
concentration range. Using the calibration curve shown on the "CURVES"
page, you can then determine the region in which the curve is linear and that
in which it is nonlinear.
If you wish to perform determinations only in the linear range, to keep the
scatter as low as possible it is advisable to calibrate above all in the lower
and upper part of this range and select as many replications as possible.
Working in the nonlinear range
If you wish to perform determinations in the nonlinear range, as many calibra-
tion solutions as possible with concentrations uniformly distributed over the
entire range should be recorded so that the nonlinear curve shape can be
determined exactly. To keep the scatter as low as possible, select as many
replications as possible.
Checking the offset
Before you deliberately force the calibration curve through the zero point, you
should first check curves with linear or nonlin to see whether the offset
Y.offset may be neglected. The size of the offset indicates a possible sys-
tematic error or blank value. To convert this error into the effective mass con-
centration in g/L, Y.offset must be divided by Slope.
Determining the working range
The calibration curve is defined only for the range between the calibration
solutions with the lowest and highest mass concentrations. Extrapolations
outside this range are not allowed. Hence, enter the maximum possible

working range on the dialog page "SUBSTANCES" with the two parameters
Range min and Range max. If a mass concentration Mass conc. outside the
defined working range is found for the substance, an error message is put
out and conc. out of range displayed on the results page.
( 2%/C), it is advisable to work with the 6.1418.220 thermostatted measur-
ing vessel.
6.9.6 Internal standard
In the method of internal standards a known quantity of a reference substance (r =

reference) is added to the analysis solution. The mass concentration eff,a of the
analyte (a = analyte) is calculated as follows from the ratio of the two evaluation
quantities EVa/EVr and the proportionality factor Prop.fact. determined before-
hand by measurement of different reference solutions:
a = r EVa/EVr 1/ Prop.fact.
As in the case of the calibration curve, the content is determined with an internal
standard in two steps:
First the relation between the ratio of the mass concentrations eff,a /eff,r of
analyte and reference substance and the ratio of the evaluation quantities
EVa/EVr is determined by measurement of different reference solutions.
Finally, the ratio of the mass concentrations eff,a /eff,r in the sample is meas-
ured and the mass concentration eff,a determined using the recorded cali-
bration curve.
The method of internal standards is programmed on the dialog page "OP.SE-

QUENCE" with the following instructions and parameters (see section 5.7.3):
(CAL...CAL)n Loop for recording the calibration curve
n Number of calibration solutions 1
CSOLN... Addition of the calibration solutions
RADD... Addition of the internal standard
Soln.name Name of the solution with the internal standard
V.add Addition volume of the solution with the internal standard
The remaining parameters needed for the internal standards method are entered
on the dialog page "SUBSTANCES/Calibration" (see section 5.6.3). The most im-
portant of these are:
int.std. Internal standard
Mode Mode for parameter display
analyte Measured substance (analyte)
referen. Reference substance (internal standard)

Ref.subst Name of reference substance

V0.CSoln. Addition volume of the calibration solutions
Mass conc. Mass concentration a of the calibration solutions
Soln.name Name of the solution with the internal standard
(for Mode = referen., must be identical with the name
specified in the RADD instruction)
Mass conc. Mass concentration r of the solution with the internal stan-
dard (for Mode = referen.)
In the content determination using an internal standard, the following procedure is

used to calculate the sought mass concentration eff,s of the sample (see also ex-
ample in section 4.4):
1 Measurement of the calibration solutions

The calibration solutions of known mass concentration a,n and r,n are each
measured several times. This gives:
EVn Evaluation quantity for nth calibration solution
(for analyte and reference substance)
EVn.mean Mean value of the evaluation quantities for nth calibra-
tion solution (for analyte and reference substance)
(for measurement and reference substance)
EVa,n/EVr,n Ratio of the evaluation quantities for nth calibration
solution
eff,a,n Effective mass concentrations of the analyte for the
calibration solutions (calculated from a,n taking the
dilution into account)
eff,r,n Effective mass concentration of the reference sub-
stance for the calibration solutions (calculated from
r,n taking the dilution into account)
eff,a,n /eff,r,n Ratio of the effective mass concentrations of analyte
and reference substance for nth calibration solution
2 Determination of the calibration curve

The calibration curve is determined using a linear function of type 0/linear:
y = bx Straight line through zero point
The parameter b is determined by the procedure described in section 6.9.3

with y = EVa/EVr and x = eff,a /eff,r by weighted least squares minimization.
This parameter is displayed on the "RESULTS/Calibrations" page and has
the following meaning:
b Prop.factor Proportionality factor (slope of the calibration curve)

3 Display of the calibration curve

The 746 VA Trace Analyzer displays and plots the calibration curve EVa/EVr vs
eff,a /eff,r:
EVa int.std.
0/linear
EVr
Slope = Prop.fact.
0
0 eff,a /eff,r

The internal standard is added to the sample solution with the unknown
mass concentration eff,a,s of the sample. Finally, analyte and reference
substance are measured one or more times. This gives:
EVa,s Evaluation quantity for analyte of the sample
EVr,s Evaluation quantity for reference substance of the
sample
EVs.mean Mean value of the evaluation quantities for sample
EVa,s/EVr,s Ratio of the evaluation quantities for sample
eff,r,s Effective mass concentrations of the reference sub-
stance for the sample solutions (calculated from r
taking the dilution into account)
5 Calculation of the mass concentration eff,a,s

The sought mass concentration eff,a,s of the sample is calculated using the
following formula:
eff,a,s EVa,s
eff,a,s =
b EVr,s
In the graphical representation of the calibration curve, EVa,s.mean/

EVr,s.mean and the calculated ratio of the mass concentrations eff,a,s /eff,r,s
are marked:
EVa
int.std.
EVr
EVa,s.mean/EVr,s.mean
eff,a,s /eff,r,s eff,a /eff,r


The found, effective mass concentration eff,a,s is converted into the sought
Mass conc. = s = eff,a,s / fV
7 Calculation of the total scatter MC.dev

The total scatter x is calculated from the two error contributions of the
calibration and the measurement as described in section 6.9.3:
(x )2 = (x,M )2 + (x,C )2
As these scatters refer to the effective mass concentration eff,a,s, they must
MC.dev. = x / fV
Meas.dev. = x,M / fV
Cal.dev. = x,C / fV
To be able to calculate Cal.dev., the following conditions for the number of

measured value pairs n in the calibration must be met:
n2 for y = bx
n3 for y = a + bx
n3 for y = bx + cx4
n4 for y = a + bx + cx4
If this is not the case, Cal.dev.= 0 is set and the message no cal.devia-
tion put out on the "RESULTS/Evaluations" page.
The calculation of Meas.dev. uses the number of measured value pairs m in

the measurement of the sample solution. The following cases must be
distinguished:
m4 Meas.dev. is calculated from x,M (see section 6.9.3).
m2 If sufficient calibration points are available (see above),
If this is not the case, Meas.dev. is calculated from x,M (see
section 6.9.3).
m=1 If sufficient calibration points are available (see above),
If this is not the case, Meas.dev. = 0 is set and the message
no meas.deviation put out.

The result determination with the aid of an internal standard saves time compared
with standard additions (particularly when several substances are determined with
the aid of the same internal standard), but is reliable only
if analyte and reference substance can be measured in the same segment
if the requirement of a linear relation between analyte and reference sub-
stance is met
if the matrix of all samples and calibration solutions is identical or has no
influence on the measurement
if all measurement parameters (capillary, temperature, etc.) remain un-
changed during measurements
if the accuracy of the results obtained is checked regularly with the stan-
dard addition method.
With regard to optimum accuracy and scatter, a number of rules must be observed
with the internal standard method:
In development of the method, the linearity range of the calibration curve for
the internal standard should be checked for each substance by recording the
curve over a wide concentration range. Using the calibration curve shown on
the "CURVES" page, you can then determine the region in which the curve
EVa/EVr vs eff,a,s /eff,r,s is linear and hence where the method of internal
standards may be used.

To keep the scatter as low as possible, calibrate above all in the lower and
upper part of the linear range and select as many replications as possible.
Determining the working range

The calibration curve is defined only for the range between the calibration
solutions with the lowest and highest mass concentrations. Extrapolations
outside this range are not allowed. Hence, enter the maximum possible
working range on the dialog page "SUBSTANCES" with the two parameters
Range min and Range max. If a mass concentration Mass conc. outside the
defined working range is found for the substance, an error message is put
out and conc. out of range displayed on the results page.

( 2%/C), it is advisable to work with the 6.1418.220 thermostatted measur-
ing vessel.


6.10 Formula calculation
The last step in the evaluation is the calculation of the calculation formulae entered
on the dialog page "CALCULATIONS" for the output of the final results Final
results. In addition to the actual calculation formulae with value assignments, vari-
ables, constants and operators, text designations for the result quantities and result
units as well as the number of significant figures can be entered (for details, see
section 5.6.4).
The most frequent application of the formula calculation concerns the conversion of
the mass concentrations of the substances Mass conc. = MC:<subst> obtained in
the content calculation (section 6.9), which refer to the added sample volume
V.sample, into the desired final result which should generally refer to the original
sample size S0. By pressing the softkey <Upd.from method> on the dialog page
"CALCULATIONS", standard formulae can be read in from the method automati-
cally to provide the mass concentration referred to S0 in g/L and g/g.
The type of standard formula entered depends on whether the sample size has
been entered as a volume or weight or whether diluted or undiluted samples have
been used (see also section 5.4.4 and section 6.2.2). The dependence of the in-
putted sample size S0 and the parameters of the SMPL instructions has the fol-
lowing appearance:
S0 S2 V.fraction V.total Standard formula for final result Result unit

L MC:<subst> g/L
g d MC:<subst>/(S2*1000) g/g
L V.fraction V.total MC:<subst>*(V.total/S0) g/L
g V.fraction V.total MC:<subst>*(V.total/S0) g/g
The standard formulae shown above refer to the basic quantities g and L, but the
results are automatically provided with the appropriate prefix by simultaneous entry
of #g/L or #g/g in the field Res.unit (see section 5.6.4). Standard formulae can
also be modified later in any way to specify the result in another unit (e.g. ppm) or
for further calculation.
If quantities associated with errors are calculated in result formulae, in addition to
the results the corresponding result scatters Res.dev. are also calculated from the
scatters of these quantities. Of the instrument variables usable for formulae, the
following two quantities are affected by this:
Mass concentration MC:<subst>: Scatter = MC.dev.
Evaluation quantity EV:<subst>: Scatter = Std.dev.
For calculation of the result scatter c for the addition, subtraction, multiplication or
division of two quantities a and b associated with errors with the corresponding
scatters a and b, the following error propagation rules are used:
Result c Scatter c
a + b a + b
a b a + b
a b a b + b a
2
a/b a / b + (a b) / b

7.1 Electrical safety
7 Safety, Errors,
Troubleshooting,
Diagnosis, GLP
7.1 Electrical safety
While electrical safety in the handling of the 746 VA Trace Analyzer and 747 VA
Stand is assured in the context of the specifications IEC 1010-1 (protection class I,
degree of protection IP20), the following points should be noted:
Mains connection
Setting the mains voltage, checking the mains fuse and the mains
connection must be effected in accordance with the instructions in
section 3.2.
Opening the instruments
When the 746 VA Trace Analyzer and 747 VA Stand are connected to
the power supply, neither the 746 VA Trace Analyzer not the 747 VA
Stand or the 695 Autosampler may be opened nor parts of them be
removed, otherwise there is a danger of coming into contact with
components which are live. Always disconnect the instruments from
all voltage sources before you open it and ensure that the mains
cable is disconnected from mains connection plug 13 !
Protection against static charges
Electronic components are sensitive to static charging and can be

destroyed by discharges. Before you touch any of the components
inside the 746 VA Trace Analyzer or 747 VA Stand, you should earth
yourself and any tools you are using by touching an earthed object
(e.g. green housing of the instrument or a radiator) to eliminate any
static charges which exist.

7 Safety, Errors, Troubleshooting, Diagnosis, GLP
7.2 Safety considerations concerning mercury
7.2.1 Properties of mercury
The most important properties of mercury (Hg) are listed in the Table below. This
compilation allows the following summary:
Mercury is a heavy metal with a very high density and is liquid at room tem-
perature.
Mercury is mobile at room temperature and tends to form drops because of
its high surface tension. The surface tension is around 6 times greater than
that of water, Hg is thus not wetted by water.
Mercury has a relatively high electrical conductivity (at room temperature
it is only some 60 times lower than that of silver).
Mercury has a relatively high vapor pressure compared with other metals.
Mercury vapor is some seven times heavier than air (so that it sinks rapidly
and specifically to the floor).
The odor threshold is very high relative to the threshold limit value (TLV).
Air saturated with Hg vapor (which naturally does not occur in practice) con-
tains approximately 250 times the amount of Hg specified by the TLV at room
temperature.
Properties of mercury
Property Value Ref.

Density (liquid mercury) 13.5451 g/cm 3
(at = 0 C) [1]
Density (mercury vapor) 8.959 g/dm 3
(at = 0 C) [2]
Melting point F 38.86 C (at pair = 1.01325 bar) [3]
Melting enthalpy HF 2.295 kJ/mol (at pair = 1.01325 bar) [3]
Boiling point V 356.73 C (at pair = 1.01325 bar) [3]
Boiling enthalpy HF 59.1 kJ/mol (at pair = 1.01325 bar) [3]
Vapor pressure p 0.0253 Pa (at = 0 C) [2, 4]
0.17 Pa (at = 20 C)
0.391 Pa (at = 30 C)
0.81 Pa (at = 40 C)
1.69 Pa (at = 50 C)
Mass concentration in air 2.0 mg/m3 (at = 0 C) [2, 4]
(after reaching equilibrium) 13.6 mg/m3 (at = 20 C)
29.6 mg/m3 (at = 30 C)
62.7 mg/m3 (at = 40 C)
126 mg/m3 (at = 50 C)
Evaporation rate 85 g/hcm2 (at = 25 C) [2]
Surface tension 4.6710 3
N/cm (at = 20 C) [5]
Electrical conductivity 1.04410 4
S/cm (at = 20 C) [6]
3
Odor threshold 13 mg/m [2]
Threshold limit value (TLV) for air
for mercury 0.1 mg/m3 [4, 7]
for organic mercury com- 0.01 mg/m3 [2, 4, 7]
pounds (calculated as Hg)

7.2.2 Toxicity of mercury and its compounds
Mercury and its compounds are toxic since they react with enzymes containing
sulfur and decompose them with the formation of HgS. The toxicity depends on the
chemical and physical state of the mercury [4, 8 10]:
Metallic liquid mercury is readily resorbed by the skin and finds its way
through glandular passages into lower skin regions where it is oxidized and
carried on as a salt.
The low-solubility mercury (I) compounds and metallic mercury in the form
of a coherent liquid have low toxicity when taken up orally (but not through
the skin!).
Mercury (II) compounds are more readily soluble and therefore much more
toxic: LD100 (the 100% lethal dose) for oral take-up is approx. 0.21 g.
Mercury vapor is highly toxic: vapor with an Hg concentration exceeding the
TLV of 0.1 mg/m3 air causes chronic poisoning after prolonged breathing for 5
to 8 hours per day.
Despite the large number of laboratories involved in polarographic/voltammetric
work, sensible and proper handling (see section 7.2.3) has ensured that not one
single case of mercury poisoning has been reported to date. The real Hg concen-
trations measured in the laboratory atmosphere are consistently far below the TLV
(threshold limit value).
7.2.3 Handling of mercury
Several safety rules, described in detail in what follows, must be observed in the
handling of mercury owing to its toxicity (see section 7.2.2):
Working in a fume cupboard

The handling of mercury should, if possible, always be carried out in a fume
cupboard (hood). It must be ensured that no metal drops or spilling drop on
the floor or the lab bench and that no evaporation of the metal occurs.
Working over plastic trays

Movements with vessels containing mercury must be carried out in, or at least
above, rigid seamless trays made from plastic or enamelled metal. The sup-
plied 6.2711.030 Drip pan made of polystyrene is eminently suitable for this.
Collecting mercury from the measuring vessel

If work is performed with the MME, at the end of the determination the analy-
sis solution contains mercury which must be collected for later disposal. This
can be done by collecting the analysis solutions in a large vessel and then
decanting, by filtering the analysis solutions or by siphoning off the mercury
using vacuum.

Trapping of mercury drops

Single mercury drops in this drip pan or any other spilt mercury can be bound
in a simple manner by amalgamation:
with silver (Ag):
Metrohm drop catcher Type 6.2406.000 which is included
in the standard outfit of the 747 VA Stand
with tin (Sn):
e.g. the thin tin foil supplied by Merck, Darmstadt/FRG
with special laboratory aids:
e.g. Mercurisorb-Roth from Roth, Karlsruhe/FRG; e.g. Mercury
Sponge and Resisorb from Baker, Phillipsburg, N.J./USA
Empty reservoir of mercury trap regularly

The storage container of the 6.2406.000 mercury trap should be emptied
regularly and rinsed thoroughly several times. If the mercury trap is needed
outside the fume cupboard, a minimum safety distance of 50 cm between the
head and the mercury trap must be observed.
Never leave mercury in open vessels

Mercury must never be left exposed to the air. The upper layer of water or
supporting electrolyte in no way suppresses nor reduces Hg evaporation [11,
12].
Store mercury container in fume cupboard

The tightly closed mercury container as well as all parts which come into
contact with mercury must be stored in a fume cupboard which is always
switched on.
Use gas wash bottles when siphoning off mercury under vacuum
If mercury is siphoned off under vacuum using a water jet pump, one or two
gas wash bottles must always be connected between the vacuum pump and
the suction tube to ensure trapping of the siphoned-off mercury.
Ventilate laboratory areas well

Rooms where work with mercury is being carried out should be thoroughly
aired from time to time.
Dispose of mercury properly

Mercury can be cleaned by distillation [13 16], but the apparatus is exten-
sive and the time needed considerable. For this reason, waste mercury is
normally collected in a closed container and then sent for disposal to the re-
sponsible authorities in accordance with the national legal requirements.

7.2.4 References dealing with mercury

[1] Documenta Geigy
Wissenschaftliche Tabellen, 7. Ausgabe, Seite 210
(Masseinheiten, Dichte), Georg Thieme Verlag, Stuttgart (BRD), 1975
[2] Berufsgenossenschaft der chemischen Industrie (Herausgeber)
Quecksilber und seine Verbindungen
Merkblatt, Seite 3...4, Verlag Chemie, Weinheim (BRD), 1980
[3] Synowietz, C.; Schfer, K. (Herausgeber)
Chemiker-Kalender, 3. Aufl., 560/561, 590
Springer-Verlag, Berlin+Heidelberg (BRD), 1984
[4] Falbe, J.; Regitz, M.
Rmpps-Chemie-Lexicon, 9. Aufl., Seite 3737
Georg Thieme Verlag, Stuttgart, New York, 1992
[5] D'Ans/Lax
Taschenbuch fr Chemiker und Physiker, 3. Aufl., Band I, Seite 1...135
Springer-Verlag, Berlin+Heidelberg (BRD), 1967
[6] Weast, R.C. (Editor)
Handbook of Chemistry and Physics, 57th edition, page E-84, B-32
The Chemical Rubber Publishing Co., Cleveland, Ohio (USA), 1976
[7] Roth, L.
Sicherheitsdaten MAK-Werte, 3. Aufl.
Ecomed Verlagsgesellschaft mbH, Mnchen, 1984
[8] Mutschler, E.
Arzneimittelwirkungen, Seite 379
Wissenschaftliche Verlagsgesellschaft, Stuttgart (BRD), 1970
[9] Auterhoff, H.
Lehrbuch der pharmazeutischen Chemie, Seite 75
Wissenschaftliche Verlagsgesellschaft, Stuttgart (BRD), 1968
[10] Strong, L.E.
Mercury Poisoning
J. Chem. Educ. 49 (1972), 28
[11] Sanders, M.L.; Becket, R.R.
The Mercury-Water System
J. Chem. Educ. 52 (1975), 117
[12] Lo, J.M.; Wal, C.M.
Mercury Loss from Water during Storage
Mechanisms and Prevention
Anal. Chem. 47 (1975), 1869
[13] Monaghan, C.P.; O'Brien, E.J. (Jr.); Good, M.L.
Cleaning Mercury
J. Chem Educ. 55 (1978), Fasc 11., 734
[14] Bergmeyer, H.U.
Vollautomatische Quecksilber-Waschapparatur fr
den Laboratoriumsgebrauch
Chem. Ing. Techn. 22 (1950), 330
[15] Hamilton, P.B.
Continuous Mercury Still
Anal. Chem. 23 (1951), 1526
[16] Quecksilberreinigung
GIT 6 (1962), 351

7.3 Error messages
7.3.1 General information on error messages
The occurrence of errors of all types during operation of the 746 VA Trace Analyzer
is indicated by error messages, which normally appear in a separate window and
have the following structure:
Window title
ERROR MESSAGE

MEASURE - ERROR 34: <Start> from this page impossible

<ENTER>: continue

Error class and Directions for exiting Error description

error number the error message message
The error message first provides information for error identification (error class
and error number), this is followed by a short error description. You will find fur-
ther details on the error messages, their possible causes and the procedure for
their rectification in the alphabetical list of error messages in section 7.3.2.
Error messages arising from errors in the method test (<Check method> on the
MONITORING page) or in the syntax test (<Syntax check> on the CALCU-
LATION page) appear in the ERROR WINDOW in which the last 18 error messages
are always stored. In addition to the normal error messages, the error messages
displayed in the ERROR WINDOW contain the date and time of occurrence of the er-
ror. The 4-line window can be enlarged by pressing the softkey <Zoom> so that all
stored error messages can be read.
In the Exit column of the list of error messages, you will find abbreviations de-
scribing how you should acknowledge the error message and how an ongoing
program behaves after it has been exited. In automatic series determinations with
Auto.batch = on, the errors are automatically acknowledged after a wait time of
10 s if at all possible.
Should you require the support of your Metrohm agency in the case of malfunc-
tions or faults which can not be rectified or explained, proceed as follows:
Copy the questionable determination to a data card or with the aid of the PC
program VA Back Up or "VA Database" to a diskette and send the card or
diskette together with a description of the fault to the Metrohm agency, or
Load the questionable determination into the working storage. Print out the
full report Report Full, the method report Report MethSpc, the desired
substance or segment curves and possibly the list of measured points and
send these together with a description of the fault to the Metrohm agency.

7.3 Error messages
7.3.2 List of error messages
The following list contains all error messages in alphabetical order. You will find ex-
planations regarding how to proceed should the instrument need to be initialized
(reset or overall initialization) in section 7.3.3. The abbreviations in the Exit column
have the following meaning:
Exit Meaning with Auto.batch = off Meaning with Auto.batch = on
E Exit with <ENTER> or any other key;

no program has been started.
E/C Exit with <ENTER> or any other key; The error message is displayed for
a program already started continues. 10 s and is then acknowledged
automatically with <ENTER>; the
started program continues to run.
E/S Exit with <ENTER> or any other key; The error message is displayed for
a program already started is stopped. 10 s and is then acknowledged
started program is stopped.
E/N Exit with <ENTER> or any other key; The error message is displayed for
a program already started is stopped. 10 s and is then acknowledged
started program is stopped. The next
determination is then started.
S The instrument is blocked, exit is no The instrument is blocked, exit is no

longer possible; the instrument must longer possible; the instrument must
be reinitialized (see section 7.3.3). be reinitialized (see section 7.3.3).
r/a Exit with <r> (r = retry) or The error message is displayed for
<a> (a = abort). 10 s and is then acknowledged
automatically with <r>.
Esc Exit with <ESC> (Escape);

for the acknowledgment of error
messages in the error window.

Error message Meaning/Causes Rectification Exit

CALCUL - ERROR 1: Number of different variables Reduce number of variables on the Esc
Variables list overflow > 25 CALCULATION page
CALCUL - ERROR 2: Variable name too long Shorten variable name to max. Esc
Illegal identifier (> 8 characters) 8 characters
Inadmissible assignment Check formulae on the
(e.g. 5 = 7) CALCULATION page and change
Inadmissible constant Check formulae on the
(e.g. A = 5.4+) CALCULATION page and change
CALCUL - ERROR 3: Unlawful overwriting of a Check formulae on the Esc
Illegal write to system system variable CALCULATION page and change
variable (e.g. S0, S1, S2, S3)
CALCUL - ERROR 4: Missing equals sign Check formulae on the Esc
Expects token (=) CALCULATION page and change
CALCUL - ERROR 5: Variable used without previous Check formulae on the Esc
Illegal use before set assignment CALCULATION page and change
CALCUL - ERROR 6: Too many nested brackets Check formulae on the Esc
Bracket nesting level CALCULATION page and change
too deep
CALCUL - ERROR 7: Number of opening and closing Check brackets in formulae on the Esc
Illegal nesting of brackets not identical CALCULATION page and change
brackets
CALCUL - ERROR 8: System variable used in the Enter system variable on the Esc
System variable not formula has not been defined SAMPLES pages or modify formulae
found (e.g. S1 without entry)
CALCUL - ERROR 9: Unlawful multiple assignment to Check formulae on the Esc
Illegal multiple assign same variable CALCULATION page and change
(R) (e.g. R1 = aaa; R1 = bbb)
CALCUL - ERROR 10: End of formula not defined Check formulae on the Esc
Unexpected end of (e.g. R2 = ) CALCULATION page and change
formula
CALCUL - ERROR 11: Constant in the formula lies Check formulae on the Esc
Value out of range outside the admissible numeric CALCULATION page and change
range (3.7.1033... 1.7.1033 / 0
/ 1.7.1033 ... 3.7.1033)
CALCUL - ERROR 12: Undefined error Check formulae on the Esc
Undefined error CALCULATION page and change
CALIBR - ERROR 1: Unsuitable procedure in non- Select linear standard addition E/C
Calibration procedure linear standard addition, no Increase amount/concentration of
inadequate evaluation possible standard addition solution
Increase number of standard addi-
tions
CALIBR - ERROR 2: Inadmissible dilution (dilution SMPL instruction missing E/C
Illegal dilution factor >1 or <10-6) or faulty Check dilution of sample (dispensing
program flow in conjunction instructions)
with calibration (no evaluation Check SUBSTANCES/Calibration
possible) page
CALIBR - ERROR 3: Invalid result, mass concentra- Check program or calibration E/C
Invalid result tion >10 kg/L (no evaluation
possible)
CALIBR - ERROR 4: Current or concentration Check standard addition or calibration E/C
Difference of calibr. change in standard additions or solutions
solutions too low in plotting of calibration curves
<1%
CALIBR - ERROR 5: No coefficients for calibration Rerecord calibration curve or enter E/C
Missing calibration curve available coefficients on the
coefficients SUBSTANCES/Calibration page

7.3 Error messages

CALIBR - ERROR 6: No reference to reference E/C
Missing reference substance in the calibration
with internal standard (no
evaluation possible)
No reference substance Enter reference substance on the
entered SUBSTANCES/Calibration page
No result for reference Check peak recognition for reference
substance found substance
CALIBR - ERROR 7: Sample mass in measuring Check sample size S0 on the E/C
Sample mass too low vessel <0.1 pg (no evaluation SAMPLES page
possible) Check program, above all the
SMPL/M and SMPL>M instructions
CALIBR - ERROR 8: Solution volume <1 mL or Check sample size S0 on the E/C
Measuring volume out of > V.meas max SAMPLES page
range Check program, above all the
SMPL/M and SMPL>M instructions
Change V.meas max
CALIBR - ERROR 9: Too few measured points Increase number of measured points E/C
Missing evaluation (calibration solutions) for the (calibration solutions) or change
values selected calibration mode calibration mode
No calibration curve available Plot new calibration curve or if no
calibration desired set Technique
to none
No results for calibration Check peak recognition for calibration
curve found
Quantity = P.peak Set Quantity to I.peak
inadmissible for AC2MODE
Quantity = P.peak Set Quantity to I.peak or use
inadmissible for DCTMODE DCTMODE with SSWEEP
with SWEEP
CONFIG - ERROR 1: Stand address and configu- Change stand address to 3 or E/S
Bad Autosampler ration entry on the VA restart VA Trace Analyzer
configuration TRACE ANALYZER page do
not agree
Wrong configuration of 695 Install Autosampler according to
Autosampler section 3.9
CONFIG - ERROR 2: Wrong Dosimat number Set Dosimat number to 1...4 E/S
Illegal Dosimat number
CONFIG - ERROR 3: Wrong stand number Set stand number to 1 or 2 E/S
Illegal stand number
CONFIG - ERROR 4: Stand address and configura- Change stand address or restart VA E/C
Bad VA Stand tion entry on the VA TRACE Trace Analyzer
configuration ANALYZER page do not agree
CONFIG - ERROR 5: Dosimat address and configu- Change Dosimat address or restart VA E/S
Bad Dosimat ration entry on the VA TRACE Trace Analyzer
configuration ANALYZER page do not agree
CONFIG - ERROR 6: Address of the 717 Sample Change address at 717 Sample E/S
Bad Sample Changer Changer and configuration Changer or restart VA Trace Analyzer
configuration entry on the VA TRACE
ANALYZER page do not agree
CURVES - ERROR 1: No result data for selected Perform recalculation E
No data assigned to substance available If error reappears, perform initializa-
substance tion (see section 7.3.3)
If error reappears, start new meas-
urement
CURVES - ERROR 2: Modify baseline is possible Switch to smoothed or subtracted curve E
Modify baseline with only with smoothed or sub- using <Select curve>
smoothed curve only tracted curves


CURVES - ERROR 3: No segment data whatsoever Start new measurement E
No segment available available
CURVES - ERROR 4: The selected segment (VR) was Switch to available segment E
Selected segment not not found
found
CURVES - ERROR 5: Action can not be executed Start new measurement E
Can not execute, owing to missing result data
missing data
CURVES - ERROR 6: No calibration curve available If really desired, start new measurement E
Can not display with calibration
calibration curve
CURVES - ERROR 7: The current method has been Reload determination with original E
Can not handle so changed that the experi- method or start new measurement
meas.data with actual mental data curves can no
method longer be displayed
CURVES - ERROR 8: The requested operation can Read remarks on selected peak on the E
Unqualified peak not be performed with the RESULTS/Evaluation page
attribute for this selected peak (e.g. <Modify
operation baseline> with peak without
baseline)
CURVES - ERROR 9: The segment curve can not be Reset segment name (the name may E
Can not find plot displayed as no plot parame- not be changed after the determination
parameters of segment ters are available (e.g. as the has been recorded)
segment name has been
changed)
DATA CARD - ERROR 1: Hardware fault on data card or Check data card, reinsert and attempt E/C
Hardware error unexpected write/read error write/read operation again
If error reappears, repeat write/read
test with a different data card (if suc-
cessful, reformat old card)
If error reappears, inform Metrohm
service
DATA CARD - ERROR 2: No data card inserted Insert data card E/C
Card invalid or not Data card not inserted Take out data card then reinsert and
available properly push right in
Battery of data card fully Change battery of data card
discharged
DATA CARD - ERROR 3: Test pattern in RAM of data Change battery of data card E/C
Battery word bad card destroyed, i.e. data card
battery discharged
DATA CARD - ERROR 4: Charge of data card battery low Copy all data on data card to instru- E/C
Low battery charge ment memory
detected Change battery
Recopy data to data card
DATA CARD - ERROR 6: Data interchange with data Press Reset key E/C
Invalid file descriptor card not possible
DATA CARD - ERROR 7: Data interchange with data Press Reset key E/C
Can not open more files card not possible
simultaneously
DATA CARD - ERROR 8: Error in changing file name: Use a different file name or delete old E/C
File name already Inputted new name is inadmis- file
exists sible as a file with the same
name exists (overwrite protec-
tion)

7.3 Error messages

DATA CARD - ERROR 9: Error in copying from or to data Attempt copying again E/C
File name not found card If error reappears, delete file in
question
If error reappears with this data card,
save all files and reformat data card
File already closed card If error reappears, delete file in
question
File already opened card If error reappears, delete file in
question
DATA CARD - ERROR 12: No more free storage space on Use new data card or clear data E/C
Card is already full data card
Invalid mode card If error reappears, delete file in
question
DATA CARD - ERROR 14: The selected file can not be Disable overwrite protection with E/C
File is protected copied to the data card as a <Secure/Unsecure> or change file
protected file with the same name
name is already present
(overwrite protection)
Unexpected end of file card If error reappears, delete file in
question
DATA CARD - ERROR 16: The data card is write protected Disable overwrite protection or use a E/C
Card is write protected different data card
DATA CARD - ERROR 17: Unspecified error in data traffic Press Reset key E/C
Undefined error with the data card
DATA CARD - ERROR 18: Charge of data card battery Copy all data on data card to instru- E/C
Bad battery charge bad ment memory
detected Change battery
Recopy data to data card
DATA PROC - ERROR 1: Too few measured points Extend measurement range or reduce E/C
Not enough measuring available for the smoothing U.step
points
DATA PROC - ERROR 2: More than 2 overflow measured Start new measurement or remove E/C
Current overload, data values have appeared in overflow measured values manually
not evaluable succession, the curve can thus using the spike elimination
not be evaluated
DATA PROC - ERROR 3: No background sweep avail- Rerecord measurement with back- E/C
No background sweep able ground compensation
found
DIAGNOSIS - ERROR 1: Diagnostic fault; connection to Check connection to 747 VA Stand: E/C
No VA Stand found 747 VA Stand broken:
connecting cable not plug in connecting cable
plugged in
wrong address set address correctly and restart 746
VA Trace Analyzer


DIAGNOSIS - ERROR 2: Diagnostic fault; not all keys Repeat keypad test E/C
Left some keys pressed in keypad test
unpressed
DIAGNOSIS - ERROR 3: Diagnostic fault; error in RS232 Inform Metrohm service r/a
RS232 receive timeout test
DIAGNOSIS - ERROR 4: Diagnostic fault; error in RS232 Inform Metrohm service E/C
RS232 sendtext test
receivetext diff.
RS232 config. register test
1 read failed
RS232 config. register test
2 read failed
DIAGNOSIS - ERROR 7: Diagnostic fault; no 6.496.8480 Attach 6.496.8480 Test Plug to RS 232 E/C
Loopback, on-chip test Test Plug attached to RS 232 Interface # output and repeat test
failed with code .... Interface # output
DIAGNOSIS - ERROR 8: Diagnostic fault; no 3.496.8550 Attach 3.496.8550 Remote Test Plug to E/C
Control lines, line Remote Test Plug attached to Control Lines output and repeat test
read failed Control Lines output
DIAGNOSIS - ERROR 9: Diagnostic fault; no EBUS test Attach EBSU test plug to External Bus E/C
EBUS loopback connector plug attached to External Bus output and repeat test
can not be accessed output
DIAGNOSIS - ERROR 10: Diagnostic fault; error in EBUS Inform Metrohm service E/C
EBUS I/O lines read test
failed
EBUS, detected request test
not confirmed
EBUS, unexpected test
request detected
EBUS, expected request test
not received
DIAGNOSIS - ERROR 14: Diagnostic fault; no data card Insert data card E/C
Data card not found found
DIAGNOSIS - ERROR 15: Diagnostic fault; battery run Change battery of data card E/C
Data card battery stage down (low) or discharged (bad)
warning level ...
DIAGNOSIS - ERROR 16: Diagnostic fault; test pattern in Change battery of data card E/C
Data card battery word RAM of data card destroyed,
bad i.e. the battery of the data card
is probably discharged
DIAGNOSIS - ERROR 17: Diagnostic fault; non-formatted Format data card E/C
Data card not data card
initialized (formatted)
DIAGNOSIS - ERROR 18: Diagnostic fault; error in testing Inform Metrohm service E/C
Data card slot number the data card
system corrupt
DIAGNOSIS - ERROR 19: Diagnostic fault; error in Data Copy all files from data card to method E/C
Data card unchained card confidence test and/or determination memory, reformat
block(s) marked as in data card
use
DIAGNOSIS - ERROR 20: Diagnostic fault; data card is Disable write protection of data card or E/C
Cant test, while data write protected use a different data card
card is write protected

7.3 Error messages

DIAGNOSIS - ERROR 21: Diagnostic fault; no Dosi- Attach Dosimat/Dosino to 746 VA Trace E/C
No dosimats available mats/Dosinos attached Analyzer
DIAGNOSIS - ERROR 22: Diagnostic fault; error in Wait a short time then press <r> r/a
Dosimats timeout, Dosimat test (retry)
awaiting busyline .... If the error reappears, press <a>
(abort> and inform Metrohm service
DIAGNOSIS - ERROR 23: Diagnostic fault; error in Inform Metrohm service E/C
Dosi. wayregister Dosimat test
read/write failed
DIAGNOSIS - ERROR 24: Diagnostic fault; no data card Insert data card or disable write protec- E/C
Data card not available inserted or write protection tion
enabled
DIAGNOSIS - ERROR 25: Diagnostic fault; error in testing Inform Metrohm service E/C
Data card memory test the data card
failed
DIAGNOSIS - ERROR 26: Diagnostic fault; error in RS test Press <a> (abort) r/a
Receive text Ifc.2 <> Quit diagnostic routine with
send text Ifc.1 <CLEAR>
Reset RS interfaces (press <Reset
Ifc. 1/2> on VA TRACE ANA-
LYZER page)
Restart RS test in diagnostic routine
DIAGNOSIS - ERROR 27: Diagnostic fault; error in RS test Press <a> (abort) r/a
Receive text Ifc.1 <> Quit diagnostic routine with
send text Ifc.2 <CLEAR>
Reset RS interfaces (press <Reset
Ifc. 1/2> on VA TRACE ANA-
LYZER page)
Restart RS test in diagnostic routine
DIALOGUE - ERROR 1: Display of the time needed for Press <r> (retry) to continue the r/a
This operation takes filling Dosimats/Dosinos (if a filling
... minutes low filling rate has been Press <a> (abort) if the filling time is
selected) too long. Increase filling rate and
restart filling process
DIALOGUE - ERROR 2: Insufficient free lines for Delete solutions not needed on the E/C
Not enough free lines transfer of solutions with SOLUTIONS page
on page <Upd.from method> on the
SOLUTIONS page
Insufficient free lines for Delete formulae not needed on the
transfer of standard formulae CALCULATION page
solutions with <Upd.from
method> on the
CALCULATION page
DIALOGUE - ERROR 3: The RS232 configuration can Wait a short time then press <r> r/a
RS232 configuration not be changed at present (retry) and try again
timed out If the error reappears, press <a>
(abort) and reset RS interface with the
softkey <Reset Ifc.#> on the VA
TRACE ANALYZER page
DIALOGUE - ERROR 4: The RS232 interface is still Wait a short time then press <r> r/a
RS232 interface still active (retry) and try again
busy If the error reappears, press <a>
TRACE ANALYZER page
DIALOGUE - ERROR 5: No VA Stand found when Switch off 746 VA Trace Analyzer E
No measuring stand instrument switched on Attach 747 VA Stand properly
found
Switch on 746 VA Trace Analyzer


DIALOGUE - ERROR 6: Warning that pressing the <a> press <a> to initiate the automatic r/a
Abort <a> resets VA (abort) key initiates an auto- reset
Trace Analyzer matic reset at the 746 VA Trace press <r> to prevent the automatic
Analyzer reset
DOSIMAT - ERROR 1: Dosimat/Dosino cylinder is Fill Dosimat/Dosino cylinder by pressing E/S
Cylinder empty empty, no dispensing is the softkey <Fill Dosimat>
possible in manual operation
DOSIMAT - ERROR 2: Wrong Dosimat number Set Dosimat number to 1...4 E/S
Illegal Dosimat number
DOSIMAT - ERROR 3: Dispensing is not possible as Check dispensing instructions on the E/S
V.meas max too low for the inputted maximum meas- OP.SEQUENCE and SEGMENTS
dosing uring vessel volume V.meas pages or, if possible, increase V.meas
max would be exceeded max
DOSIMAT - ERROR 4: Dosimat/Dosino can not Press <Exchange position> key on E/C
Dosimat overload dispense (drive jammed) the DOSIMATS page
DOSIMAT - ERROR 5: Wrong stopcock position of Press <Exchange position> key on E/S
Unlawful stopcock Dosimat/Dosino the DOSIMATS page
position
DOSIMAT - ERROR 6: Volume to be dispensed too Use larger Exchange or Dosing Unit or E/S
Dispensing volume too large for mounted Exchange or reduce volume to be dispensed
large Dosing Unit
DOSIMAT - ERROR 7: Dispensing not possible as Increase safety volume or use larger E/S
Safety volume reached safety volume of Dosimat/ Exchange or Dosing Unit
Dosino would be exceeded
DOSIMAT - ERROR 8: Dosimat/Dosino not attached Attach Dosimat/Dosino, check con- E/S
Missing device or connecting cable faulty necting cable
DOSIMAT - ERROR 9: No exchange Unit mounted on Mount Exchange Unit E/S
No Exchange Unit the Dosimat
DOSIMAT - ERROR 10: Inadmissible dispensing units Mount different Dispensing Units E/S
Illegal dosing units are mounted on the Dosinos
DOSIMAT - ERROR 11: Inadmissible dilution settings Change parameters for Dil.settings E/S
Illegal Dilution on the "DOSIMATS" page (e.g. on the "DOSIMATS" page
settings V.tube out too low for
pipetting volume, cylinder
volume too low, pipetting
volume < 10 L)
EVAL - ERROR 1: The evaluation routine can not Wait and retry E/C
Evaluation occupied be used at present
EVAL - ERROR 2: No evaluation is possible with Change measurement mode E/C
Evaluation not possible the selected measurement
mode CYCMODE
EVAL - ERROR 3: No peak at rear in the double If there is no 2nd peak at rear, set E/C
Double peak: missing peak evaluation Scope to whole, f.half or r.half
rear peak The peak at the rear has not Check peak recognition for peak at
been evaluated rear
EVAL - ERROR 4: In the double peak evaluation, Set baseline type Type the same for E/C
Double peak: wrong both peaks must be evaluated both peaks
baseline type with the same baseline type
EVAL - ERROR 5: No peak at front in the If there is no 2nd peak at front, set E/C
Double peak: missing double peak evaluation Scope to whole, f.half or r.half
front peak The peak at the front has not Check peak recognition for peak at
been evaluated front
EVAL - ERROR 6: With selected baseline type, If half-peak evaluation desired, set E/C
Half peak: illegal selection of f.half or baseline type to linear, otherwise set
baseline scope r.half is not admissible Scope to whole or f.double or
r.double

7.3 Error messages

EVAL - ERROR 7: With measurement mode Set Scope to whole E/C
AC2: illegal baseline AC2MODE, only whole is
scope allowed for Scope
EVAL - ERROR 8: With measurement mode Set baseline type to AC2 rel., AC2 E/C
AC2: illegal baseline AC2MODE, selection of polynom abs. or linear (identical to AC2
type or expon. for the baseline abs.)
type is not admissible
EVAL - ERROR 9: In the measurement mode Set Scope to whole E/W
Wave: illegal baseline DCTMODE, only whole is
scope admissible for Scope
GRAPHICS - ERROR 1: The selected display range is Expand display range (change dis- E/C
Display sector too too small play/plot parameters)
small
KEYBOARD - ERROR 1: Keypad hardware faulty Press Reset key S

Keyboard hardware If error reappears, inform Metrohm
defect service
KEYBOARD - ERROR 2: Handshake error in the RS232 Press Reset key S
HSA is ON, RS module module If error reappears, inform Metrohm
has not set HSA off service
HSB is ON before data module If error reappears, inform Metrohm
is set service
HSA and HSB are ON module If error reappears, inform Metrohm
before data is set service
CNT is ON in spite of module If error reappears, inform Metrohm
write cycle service
CNT is not ON in spite module If error reappears, inform Metrohm
of read cycle service
HSB is not set to ON at module If error reappears, inform Metrohm
read cycle service
HSA is not set to OFF module If error reappears, inform Metrohm
at read cycle service
HSB is not set to OFF module If error reappears, inform Metrohm
at read cycle service
HSA + HSB are not set module If error reappears, inform Metrohm
to OFF at read cycle service
KEYBOARD - ERROR 11: Initializing error Press Reset key S
Keyboard interface, If error reappears, inform Metrohm
data not equal service
KEYBOARD - ERROR 12: Initializing error Press Reset key S
EOS is not set to ON If error reappears, inform Metrohm
after configuration service
HSA is not set to OFF module If error reappears, inform Metrohm
after write cycle service
KEYBOARD - ERROR 14: Non-specified keypad error Press Reset key S
Unknown keyboard error If error reappears, inform Metrohm
service


MALLOC - ERROR 1: Insufficient system storage This error message is acknowledged r/a
System heap, not enough space available (typical case: automatically after 10 s waiting time.
memory sending large or many files)
MALLOC - ERROR 2: Insufficient storage space Press <a> (abort) r/a
Determination heap, not available for determinations Create storage space by deleting old
enough memory determinations
Restart copying
Method heap, not enough available for methods Create storage space by deleting old
memory methods
Restart copying
Storage heap, not available for methods or Create storage space by deleting old
enough memory determinations methods or determinations
Restart copying
Can not realloc, not available Create storage space by deleting old
enough memory methods or determinations
Restart copying
MALLOC - ERROR 6: Inadmissible power failure Press <r> (retry) r/a
Last powerdown failed, during data storage (this error Store data from method and determi-
malloc data incon- message appears when the nation memory on data card
sistent instrument is switched on) Reinitialize method and data memory
MALLOC - ERROR 7: Insufficient system storage Wait a short time, then press <r> r/a
System heap out of space available (retry)
memory If error reappears, press <a> (abort);
an instrument reset is initiated auto-
matically
Note:
If this error message appears, the
<PRINT SCREEN> key must not be
pressed (danger of crash)
MEASURE - ERROR 1: The method called with Load method in method memory or E/S
Missing method Method.call is missing in the correct method name
method memory
MEASURE - ERROR 2: Programming error on Check programs on the two pages E/S
Faulty method OP.SEQUENCE or and correct
SEGMENTS page If the programming error is not found,
press the softkey <Check method>
(method test) on the MONITORING
page and note error messages in
error window
Correct programs in accordance with
the error messages
MEASURE - ERROR 3: With automatic program call Enter new sample data or set E/S
Missing sample Auto.samples = on, no Auto.samples to off
sample available in sample
memory
With manual sample call Enter Sample size/S0 on the
Auto.samples = off, no MONITORING page
value for S0 available
MEASURE - ERROR 4: The maximum of 60 sweep Reduce number of sweeps E/S
Too many sweeps blocks has been exceeded

7.3 Error messages

MEASURE - ERROR 5: The program contains inadmis- Check programs on both pages and E/N
Illegal instruction for sible instructions for operation correct
VA Stand with the VA Stand (autosampler
instructions) on the
OP.SEQUENCE or
SEGMENTS page
MEASURE - ERROR 6: The called-up alternative Enter alternative formula A## on the E/C
Missing A-formula formula A## is not available on CALCULATION page
the CALCULATION page
MEASURE - ERROR 7: The parameter specified in the Check program on the OP.SE- E/S
Variation parameter not VARNI instruction was not QUENCE or SEGMENTS page and
found found correct
MEASURE - ERROR 8: No background compensation Delete BACKGND instructions or E/C
Backgnd subtraction possible with the measurement change measurement mode
impossible modes CYCMODE and
PSAMODE
MEASURE - ERROR 9: The substance name specified Define substance or change substance E/C
Missing substance in the PDOS, PADD and CASE name
instructions was not found
MEASURE - ERROR 10: No sweep block associated E/C
Missing sweep block with the substance specified in
the PDOS, PADD and CASE
instructions was found
Call of a substance which is Link substance to segment (<Link
not linked with a segment to segm.>)
The segment is not called up Insert SEGMENT instruction with
on the OP.SEQUENCE segment name on the
page OP.SEQUENCE page
MEASURE - ERROR 11: No result (EV/MC) associated Check peak recognition or peak E/C
Missing result with the substance specified in evaluation for the substance in question
the PDOS, PADD and CASE
instructions was found
MEASURE - ERROR 12: The CSOLN instruction has Link substance to segment (<Link E/S
Missing substance for found no associated sub- to segm.>)
calibration stance
The calibration mode of the Set calibration mode for substance to
substance is not set to cal.crv. or int.std.
cal.crv. or int.std.
MEASURE - ERROR 13: No solution for ADD instruc- Enter solution name Soln.name in E/S
Missing standard tion specified ADD instruction
addition solution The standard addition Enter name of standard addition
solution specified in the ADD solution on the SUBSTANCES/Cali-
instructions was not found on bration page
the SUBSTANCES/Calibra-
tion page
MEASURE - ERROR 14: The mass concentration of a Change mass concentration Mass E/C
Mass conc. out of calibration solution CSoln. conc. of the calibration solution or
working range lies outside the working range working range (Range min/Range max)
defined by Range min/Range on the SUBSTANCES/Calibration
max page
MEASURE - ERROR 15: Entry of the asterisk in Sample Enter volume or mass in Sample E/N
Illegal * in sample size/S0 is not admissible size/S0
size/S0 when metered volumes or
concentrations have to be
calculated
MEASURE - ERROR 16: The CSOLN instruction has not Link substance to segment (<Link to E/S
Missing segment for found an associated segment segm.>)
calibration


MEASURE - ERROR 17: Different volume for calibration Set V0.CSoln. on the SUBSTANCES/ E/S
Different V0.CSoln. solutions V0.CSoln. with Calibration page equal for all sub-
several substances with stances
calibration mode cal.crv.
/int.std. in same segment
MEASURE - ERROR 18: Mass concentrations on the Set mass concentrations equal on both E/S
Different mass conc. SUBSTANCES/Calibration pages
and SOLUTIONS pages do
not agree
MEASURE - ERROR 19: The mass concentration Enter Mass conc. on the E/S
Missing mass Mass conc. is missing for SUBSTANCES/Calibration page
concentration ADD and CSOLN instructions
(SUBSTANCES) No solution for ADD instruc- Enter solution name Soln.name in
tion specified ADD instruction
MEASURE - ERROR 20: The SMPL/M and CSOLN/M Correct SMPL or CSOLN instructions on E/C
Illegal instruction for instructions are not allowed the OP.SEQUENCE or SEGMENTS
Autosampler with the 695 Autosampler page
MEASURE - ERROR 21: The maximum volume Lower volume V.add for dispensing or E/S
V.sample max too small V.sample max of the sample transfer instruction
for dosing vessels on the sample rack is
too small for the volume to be
dispensed
MEASURE - ERROR 22: The entry of the asterisk in Enter volume or mass in Sample E/S
Unknown volume in FEED Sample size/S0 is here not size/S0
for dosing admissible in conjunction
with the SMPL/F instruction
The entry of the asterisk in Enter volume in V0.Csoln.
V0.CSoln. is here not ad-
missible in conjunction with
the CSOLN/F instruction
MEASURE - ERROR 23: The entry of the asterisk in Enter volume in V0.CSoln. E/S
Illegal * in V0.CSoln. is not admissible in
calibration volume operation without the 695
V0.CSoln. Autosampler
MEASURE - ERROR 24: No numeric value in S2. If S0 Enter density in g/mL in S2 on the E/N
Illegal variable S2 has been entered as the mass, SAMPLES page
the density must be entered in
S2 in g/mL
MEASURE - ERROR 25: Undefined electrode type Enter instruction for the electrode type E/S
Undefined electrode (electrode type must be before that for the measurement mode
entered before the measure- on the OP.SEQUENCE or
ment mode) SEGMENTS page
MEASURE - ERROR 26: Undefined measurement Enter instruction for the measurement E/S
Undefined measurement mode (measurement mode mode before that for the sweep on
mode must be entered before the the OP.SEQUENCE or
sweep) SEGMENTS page
Wrong measurement mode Enter correct measurement mode on
(e.g. CYCMODE with SWEEP) the OP.SEQUENCE or
SEGMENTS page
MEASURE - ERROR 27: The maximum number of 1000 Reduce number of measured points by E/S
Too many measuring measured points for a sweep shortening the sweep (U.start/U.end)
points was exceeded or increase the voltage step U.step
MEASURE - ERROR 28: Command for start of the cyclic Enter instruction (CSWEEP on the E/S
Missing (CSWEEP loop missing OP.SEQUENCE or SEGMENTS
page
MEASURE - ERROR 29: Program instruction necessary Check program instructions on the E/S
Missing instruction for the procedure missing OP.SEQUENCE or SEGMENTS
page

7.3 Error messages

MEASURE - ERROR 30: Voltage value in sweep is not Enter voltage values in the SWEEP E/S
Missing voltage value defined (U.end, U.start or instruction
U.meas)
MEASURE - ERROR 31: Inadmissible replication in Clear replication (REP...REP)n E/C
Illegal replication conjunction with measurement
mode CYCMODE
MEASURE - ERROR 32: The mass concentration Mass Enter mass concentration Mass conc. E/S
Missing mass concentra- conc. is missing on the on the SOLUTIONS page
tion (SOLUTIONS) SOLUTIONS page
MEASURE - ERROR 33: In the standard addition, Check programming of the CASE E/C
Standard addition with spiking was not performed with instructions
different solutions the same standard addition
solution (different sequence in
conjunction with CASE instruc-
tions)
MEASURE - ERROR 34: Program start from the Switch to the MONITORING page and E/C
<Start> from this page STAND and CURVES press <START>
impossible pages not possible
MEASURE - ERROR 35: The range limits of the varied Change Delta parameter in the E/S
Variation parameter out parameter were exceeded VARNI instruction or number of variation
of range cycles
MEASURE - ERROR 36: An entry is not available for Enter solution for every substance on E/S
Missing solution every substance on the the SOLUTIONS page (also with
SOLUTIONS page mixed solutions)
Missing or wrong substance Check substance name on the
name SOLUTIONS, SUBSTANCES and
OP.SEQUENCE or SEGMENTS
pages
MEASURE - ERROR 37: The experimental data are Restart measurement E/C
Measurement data incomplete, e.g. owing to
inconsistent instrument being switched off
during an ongoing measure-
ment
MEASURE - ERROR 38: Insufficient solution for the Lower volume V.add for transfer E/S
Too small volume in desired transfer instruction in instruction
FEED or AUX the sample vessel FEED or in
the auxiliary vessel AUX on the
695 Autosampler
MEASURE - ERROR 39: The calibration has not been Restart calibration E/S
Incomplete calibration run to completion
MEASURE - ERROR 40: PREP loops are admissible only Set Auto.batch = on on the E/C
PREP demands Auto.batch when Auto.batch = on is set MONITORING page
= on
MEASURE - ERROR 41: On entry of several SMPL Set V.total the same for all SMPL E/C
Different V.total in instructions, V.total must be instructions on the OP.SEQUENCE or
SMPL identical in all cases SEGMENTS page
MONITORING - ERROR 1: The called-up function can not Wait until measurement ended E/C
Can not start as busy be executed as a measurement
measuring is running
MONITORING - ERROR 2: Display of the live curve not Start measurement E
Live display only when possible as no measurement is
BUSY running
OP.SEQ. - ERROR 1: Missing END instruction Append END instruction to end of Esc
Missing END instruction program on the OP.SEQUENCE page
OP.SEQ. - ERROR 2: Error in the nesting of instruc- Check program on the OP.SE- Esc
Nesting violation: line tions with brackets QUENCE page for correct use of
## instructions with brackets and correct if
necessary


OP.SEQ. - ERROR 3: Wrong use of instructions with Check program on the Esc
Incorrect bracket brackets (e.g. (ADD ..... OP.SEQUENCE page for correct use
matching: line ## REP)) of instructions with brackets and correct
if necessary
OP.SEQ. - ERROR 4: .... = (PREP Delete unnecessary (PREP or PREP) Esc
Multiple use of .... The (PREP or PREP) in- instructions
struction is admissible once
only
.... = SWEEP Delete unnecessary SWEEP instruc-
Only one SWEEP instruction is tions
admissible in a segment
OP.SEQ. - ERROR 5: There is an inadmissible Delete inadmissible instruction on the Esc
Instruction not allowed instruction in the specified OP.SEQUENCE page
in block: line ## program line
OP.SEQ. - ERROR 6: One of the three instructions for In program on the OP.SEQUENCE Esc
Missing part of prep. a PREP block missing page, check that all three instructions
(PREP, PREP), >PREP (PREP, PREP) and >PREP are present
OP.SEQ. - ERROR 7: Inadmissible instruction in the Delete inadmissible instruction on the Esc
Not allowed in PREP PREP block OP.SEQUENCE page
block: line ##
OP.SEQ. - ERROR 8: Inadmissible parameter for Check parameter name for Esc
Invalid with VARNI: parameter variation Param.name on the OP.SEQUENCE
line ## page and correct
OP.SEQ. - ERROR 9: Inadmissible instruction in the Delete inadmissible instruction in the Esc
Invalid with (CSWEEP: CSWEEP block (only RAMP is CSWEEP block on the
line ## allowed) OP.SEQUENCE page
OP.SEQ. - ERROR 10: Inadmissible value for the Change parameter value on the Esc
Inconsist. value in specified parameter OP.SEQUENCE page
.....: line ##
OP.SEQ. - ERROR 11: t.step value for specified Increase t.step or reduce t.modul Esc
Value inconsist. with electrode too low Change electrode type
electrode: t.step in
line ##
OP.SEQ. - ERROR 12: Missing parameter value in the Enter parameter value on the Esc
Missing value in line specified program line OP.SEQUENCE page
##
OP.SEQ. - ERROR 13: Inadmissible data-generating Delete inadmissible instruction on the Esc
Not allowed data- instruction in the specified OP.SEQUENCE page
generating: line ## program line
OP.SEQ. - ERROR 14: Inadmissible instruction in the Delete inadmissible instruction Esc
Not allowed in segment: segment
line ##
OP.SEQ. - ERROR 15: The segment with the specified Check name of segment Segm.name to Esc
Segment ........ not name is not available be called in the SEGMENT instruction
found and correct
OP.SEQ. - ERROR 16: If several CAL loops are used in Enter RINSE instructions on the Esc
Incorrect use of (CAL a program, every loop must OP.SEQUENCE page
... RINSE sequence have a RINSE instruction
OP.SEQ. - ERROR 17: Sweep range too small Increase sweep range or decrease Esc
Sweep range too small (< 8 measured values) U.step or t.step
OP.SEQ. - ERROR 18: Sweep range too large Decrease sweep range or increase Esc
Sweep range too large (> 1000 measured values) U.step or t.step
OP.SEQ. - ERROR 19: t.step value missing or is Enter variation loop for t.step in the Esc
Missing "t.step" <1 ms (possible only in segment <segm> so that t.step
variation loops) remains >1 ms
OP.SEQ. - ERROR 20: Initial voltage U.start and Change U.start and/or U.end in the Esc
Conditioning cycle final voltage U.end of the COND instruction
range too small COND instruction are identical

7.3 Error messages

PRINTER - ERROR 1: Printer hardware faulty Press <r> (retry) r/a
Printer hardware faulty If error reappears, press Reset key
If error reappears, start diagnostic
routine and test printer
PRINTER - ERROR 2: Printer does not read data Press <r> (retry) r/a
Printer not reading (interface fault) If error reappears, press Reset key
data
PRINTER - ERROR 3: Printer is still busy Wait and press <r> (retry) r/a
Printer is not ready If error reappears, press Reset key
PRINTER - ERROR 4: Hardware fault at printer Press <r> (retry) r/a
Printer interface, data interface (diagnostic fault) If error reappears, inform Metrohm
valid not set service
PRINTER - ERROR 5: Hardware fault at printer Press <r> (retry) r/a
Printer interface, data interface (diagnostic fault) If error reappears, inform Metrohm
not equal service
PRINTER - ERROR 6: Printer has run out of paper Load paper r/a
No paper! Load paper, Press <r> (retry)
please!
PRINTER - ERROR 7: Non-specified printer fault Press <r> (retry) r/a
Unknown printer error If error reappears, press Reset key
If error reappears, inform Metrohm
service
RACKDEF - ERROR 1: Too many positions entered for Delete redundant positions E
Too many definitions the selected rack type
for this rack type
(max. ...)
RACKDEF - ERROR 2: The specified position is not Check position and re-enter E
Line .., defined admissible (restricted zone)
location mismatches
with area
RESULTS - ERROR 1: No results available for loaded Start new measurement E/C
No evaluation results method
available
RESULTS - ERROR 2: Different measurement meth- Check program (only one measurement E/C
Ambiguous sweep ods for the same substance mode per substance is admissible)
identification per
sweep
RESULTS - ERROR 4: No substance evaluation Start new measurement E/C
No substance evaluation available
available
RS IFC.# - ERROR 1: RS232 hardware faulty Press Reset key r/a

RS232 hardware faulty (# = 1 or 2) If error reappears, start diagnostic
routine and run RS test
RS IFC.# - ERROR 2: Handshake error in the RS232 Press Reset key r/a
HSA is ON, RS module module If error reappears, start diagnostic
has not set HSA off (# = 1 or 2) routine and run RS test
HSB is ON before data module If error reappears, start diagnostic
is set (# = 1 or 2) routine and run RS test
HSA and HSB are ON module If error reappears, start diagnostic
before data is set (# = 1 or 2) routine and run RS test


CNT is ON in spite of module If error reappears, start diagnostic
write cycle (# = 1 or 2) routine and run RS test
CNT is not ON in spite module If error reappears, start diagnostic
of read cycle (# = 1 or 2) routine and run RS test
HSB is not set to ON at module If error reappears, start diagnostic
read cycle (# = 1 or 2) routine and run RS test
HSA is not set to OFF module If error reappears, start diagnostic
at read cycle (# = 1 or 2) routine and run RS test
HSB is not set to OFF module If error reappears, start diagnostic
at read cycle (# = 1 or 2) routine and run RS test
HSA + HSB are not set module If error reappears, start diagnostic
to OFF at read cycle (# = 1 or 2) routine and run RS test
RS IFC.# - ERROR 11: Error in transmission in RS232 Press <r> (retry) r/a
Send timeout: XOFF=& module (# = 1 or 2; & = 0 or If error reappears, check receiver
CTS=& DCD=& DSR=& 1). Possible causes: Press <a> (abort)
XOFF=1: Stop by receiver Reset RS interface (press softkey
CTS=1: Receiver not <Reset Ifc.#> on the VA TRACE
ready ANALYZER page)
DCD=1: Receiver
transmitting
DSR=1: Receiver not in
operation
alle=0: Character without
delimiter in receive
buffer prevents
transmission
RS IFC.# - ERROR 12: Error in RS232 module interface Press <r> (retry) r/a
EOS timeout at CTRL If error reappears, press Reset key
reg. read cycle
RS IFC.# - ERROR 13: Error in receiving in RS232 Press <r> (retry) r/a
Parity=& Stopbit=& module (# = 1 or 2; & = 0 or If error reappears, press <a> (abort)
Overrun=& Recbuff=& 1). Possible causes: Check RS parameters on the VA
Parity=1: Parity error TRACE ANALYZER page
Stopbit=1: Stop bit error
Overrun=1: Data bit error
or baud rate
error
Recbuff=1: Buffer full, no
termination
available
RS IFC.# - ERROR 14: Error in RS232 module interface Press <r> (retry) r/a
Busy timeout, remote If error reappears, press <a> (abort)
keyb. mode not possible
Reset RS interface (press softkey
<Reset Ifc.#> on the VA TRACE
ANALYZER page), start diagnostic
RS IFC.# - ERROR 15: Non-specified RS232 error Press Reset key r/a
Unknown RS232 error If error reappears, inform Metrohm
service

7.3 Error messages

SAMPLER - ERROR 1: Connection to 747 VA Stand or Check connection to 747 VA Stand or E/S
Missing device 695 Autosampler broken: 695 Autosampler:
connecting cable not plug in connecting cable
plugged in
wrong address restart 746 VA Trace Analyzer
hardware fault in VA Stand run diagnostic routine for VA Stand
SAMPLER - ERROR 2: EBUS interface faulty Inform Metrohm service E/C
Hardware defect U1 or
U5 EBUS
SAMPLER - ERROR 3: Transfer needle of 695 Clean transfer needle E/S
Transfer needle blocked Autosampler blocked
695 Autosampler switched Switch on 695 Autosampler
off
Wrong response of RS232 Inform Metrohm service
interface of 695 Autosampler
SAMPLER - ERROR 4: No response of RS232 inter- Inform Metrohm service E/S
No reply from RS232 face of 695 Autosampler
SAMPLER - ERROR 5: Faulty RS232 transfer Inform Metrohm service E/S
RS232 command too long
Command to RS232 not
sent
RS232 communication
error
SAMPLER - ERROR 8: Hardware fault in 695 Auto- Inform Metrohm service E/C
Hardware defect U4 VART sampler
SAMPLER - ERROR 9: No electrical connection to Inform Metrohm service E/C
No small syringe small syringe of 695 Autosam-
detected pler
SAMPLER - ERROR 10: No electrical connection to Inform Metrohm service E/C
No large syringe large syringe of 695 Autosam-
detected pler
SAMPLER - ERROR 11: No rack mounted on 695 Mount rack E/C
No rack detected Autosampler
No rack type defined for Define rack type on the STAND/
mounted rack Rack definition page and store data
in 695 Autosampler
SAMPLER - ERROR 12: Hardware fault Inform Metrohm service E/C
Hardware defect U3
EEPROM
SAMPLER - ERROR 13: Hardware fault Inform Metrohm service E/C
Hardware defect U9
D-Latch
SAMPLER - ERROR 14: Inadmissible position number Change position number Pos. on the E/S
Illegal position number for the mounted rack SAMPLES and MONITORING pages
SAMPLER - ERROR 15: The specified rack type number Define rack type on the STAND/Rack E/S
Illegal rack number is not admissible definition page and store data in 695
Autosampler


SAMPLER - ERROR 16: There is too little solution for Check vessel or reduce transfer E/N
Siphoning volume XXX the desired transfer com- volume V.add
too low mand at the vessel XXX on
the sample rack (SXX), on
the standard racks (AXX,
BXX) or in the vessel with
cleaning solution (C01; soft-
key <Cond.tube>) of the 695
Autosampler
Liquid sensor dirty Clean liquid sensor
SAMPLER - ERROR 17: Liquid sensor dirty Clean liquid sensor E/S
Incorrect air pump Air pump for liquid sensor Inform Metrohm service
signal faulty
SAMPLER - ERROR 18: 695 Autosampler incorrectly Inform Metrohm service E/S
Illegal X/Y position adjusted
SAMPLER - ERROR 19: 695 Autosampler incorrectly Inform Metrohm service E/S
Illegal X or Y position adjusted
SAMPLER - ERROR 20: Connection to 717 Sample Check connection to 717 Sample E/S
Missing 717 Sample Changer broken: Changer:
Changer connecting cable not plug in connecting cable
plugged in
wrong address restart 746 VA Trace Analyzer
SAMPLER - ERROR 21: No rack mounted on 717 Mount rack E/S
717 no rack detected Sample Changer
SAMPLER - ERROR 22: Motor at 717 Sample Changer Check 717 Sample Changer and restart E/S
717 overload blocked
SAMPLER - ERROR 23: No beaker on the sample rack Load sample beakers on sample rack E/S
717 no beaker detected of the 717 Sample Changer
SAMPLES - ERROR 1: No value for Sample size/S0 Enter numeric value or * for Sample E/C
Missing sample size/S0 available size/S0 on the SAMPLES page
SAMPLES - ERROR 2: Inadmissible blank line on the Delete or fill in blank line E/C
Blank sample line found SAMPLES page
SAMPLES - ERROR 3: The method called up with Load method into method memory or E/C
Method in Meth.call not Method.call is missing in the change method name Method.call
found method memory
SAMPLES - ERROR 4: No density information (if Enter density in g/mL under S2 E/C
Inconsistent S2.Var sample quantity entered as
weight, S2 must be entered as
density in g/mL)
SAMPLES - ERROR 5: The sample table contains two Check sample data on the SAMPLES E/C
Equal entry already lines with identical entries page and change
exists
SAMPLES - ERROR 6: The data receipt from a Wait a short time then press <r> r/a
Can not reconfig. while balance can not be switched (retry) and try again
RS232 busy on if the RS interface is still If the error reappears, press <a>
active (abort) and reset RS interface with the
TRACE ANALYZER page
SEGM.<segm> - ERROR 1: Missing END instruction Append END instruction to end of Esc
Missing END instruction program in the segment <segm>
SEGM.<segm> - ERROR 2: Error in the nesting of instruc- Check program in the segment <segm> Esc
Nesting violation: line tions with brackets for correct use of instructions with
## brackets and correct if necessary
SEGM.<segm> - ERROR 3: Wrong use of instructions with Check program in the segment <segm> Esc
Incorrect bracket brackets (e.g. (ADD ..... REP)) for correct use of instructions with
matching: line ## brackets and correct if necessary

7.3 Error messages

SEGM.<segm> - ERROR 5: There is an inadmissible Delete inadmissible instruction in the Esc
Instruction not allowed instruction in the specified segment <segm>
in block: line ## program line
SEGM.<segm> - ERROR 6: One of the three instructions for In program in the segment <segm>, Esc
Missing part of prep. a PREP block missing check that all three instructions (PREP,
(PREP, PREP), >PREP PREP) and >PREP are present
SEGM.<segm> - ERROR 8: Inadmissible parameter for Check parameter name for Esc
Invalid with VARNI: parameter variation Param.name in the segment <segm>
line ## and correct
SEGM.<segm> - ERROR 9: Inadmissible instruction in the Delete inadmissible instruction in the Esc
Invalid with (CSWEEP: CSWEEP block (only RAMP is CSWEEP block in the segment <segm>
line ## allowed)
SEGM.<segm> - ERROR 10: Inadmissible value for the Change parameter value in the segment Esc
Inconsist. value in specified parameter <segm>
.....: line ##
SEGM.<segm> - ERROR 11: t.step value for specified Increase t.step or reduce t.modul Esc
Value inconsist. with electrode too low Change electrode type
electrode: t.step in
line ##
SEGM.<segm> - ERROR 12: Missing parameter value in the Entry parameter value in the segment Esc
Missing value in line specified program line <segm>
##
SEGM.<segm> - ERROR 13: Inadmissible data-generating Delete inadmissible instruction in the Esc
Not allowed data- instruction in the specified segment <segm>
generating: line ## program line
SEGM.<segm> - ERROR 14: Inadmissible instruction in the Delete inadmissible instruction in the Esc
Not allowed in segment: segment segment <segm>
line ##
SEGM.<segm> - ERROR 16: If several CAL loops are used in Enter RINSE instructions in the seg- Esc
Incorrect use of (CAL a program, every loop must ment <segm>
... RINSE sequence have a RINSE instruction
SEGM.<segm> - ERROR 17: Sweep range too small Increase sweep range or decrease Esc
Sweep range too small (< 8 measured values) U.step or t.step
SEGM.<segm> - ERROR 18: Sweep range too large Decrease sweep range or increase Esc
Sweep range too large (> 1000 measured values) U.step or t.step
SEGM.<segm> - ERROR 19: t.step value missing or is Enter variation loop for t.step in the Esc
Missing t.step <1 ms (possible only in segment <segm> so that t.step
variation loops) remains >1 ms
SEGM.<segm> - ERROR 20: Initial voltage U.start and Change U.start and/or U.end in the Esc
Conditioning cycle final voltage U.end of the CONDC instruction
range too small CONDC instruction are identical
SOLUTIONS - ERROR 1: The mass concentrations of Check mass concentrations Mass Esc
Mass conc. conflict on solutions with the same name conc. of the solutions on the
line ## do not match SOLUTIONS, OP.SEQUENCE,
SEGMENTS and SUBSTANCES/
Calibration page and change
STORAGE - ERROR 1: Secured file can not be deleted Unsecure file before deleting or over- E/C
Destination file or overwritten writing with <Secure/Unsecure>
secured
STORAGE - ERROR 2: The file to be copied is not Check source (working storage or E/C
Can not find source available at the source speci- RS232 interfaces) to see whether the file
fied to be copied exists
STORAGE - ERROR 3: Maximum number of files (256) Delete old files E/C
Entry table full reached


STORAGE - ERROR 4: Copying the file with the Change file name E/C
Files are identical specified name is not possible
as a file with the same name
already exists
STORAGE - ERROR 5: Inadmissible destination for the Copy one file only E/C
Invalid destination for copying of several files
multiple files
STORAGE - ERROR 6: Inadmissible destination for the Change destination for copying E/C
Invalid destinations copying of methods
for methods
Invalid destinations copying of determinations
for determinations
Invalid determination copying of files
STORAGE - ERROR 9: Copying from RS232 interface Enable receive mode on the VA TRACE E/C
RS232 Receive mode off not possible as receive mode ANALYZER page (Receive mode =
disabled on) and restart copying
STORAGE - ERROR 10: Copying to or from RS interface Set Remote keyboard = off on the E/C
RS232 Keyboard send not possible as Remote VA TRACE ANALYZER page and
mode still active keyboard = on is set restart copying
STORAGE - ERROR 11: Copying from RS interface not Wait a short time then press <r> r/a
RS232 RS232 interface possible as it is still active (retry) and try again
still active If the error reappears, press <a>
TRACE ANALYZER page
STORAGE - ERROR 12: The inputted file name contains Correct file name E/C
Invalid file name inadmissible characters or a
wrong extension
STORAGE - ERROR 13: Invalid internal parameters on Wait a short time then press <r> E/C
RS232 interface, copying to or from RS interface (retry) and try again
invalid internal If the error reappears, press <a>
parameters (abort) and reset RS interface with the
TRACE ANALYZER page
STORAGE - ERROR 14: Copying ended with error Check which files have not been E/C
Copy terminated with copied, try again
error
STORAGE - ERROR 15: Unexpected block size in Wait a short time then press <r> r/a
Unexpected file copying from RS interface (retry)
blocksize If the error reappears, press <a>
(abort) and try copying again
STORAGE - ERROR 16: Error in the data expansion in Wait a short time then press <r> r/a
Memory blocksize copying from RS interface (retry)
violation If the error reappears, press <a>
(abort) and try copying again
STORAGE - ERROR 17: Non-specified storage error Press Reset key E/C
Undefined error
SUBSTANCES - ERROR 1: The lower limit of the working Enter Range min and Range max Esc
Range min greater than range is greater than the upper parameters on the SUBSTANCES
Range max limit page properly
SUBSTANCES - ERROR 2: The specified entry for the Change Curve type parameter on the Esc
Param. Curve type Curve type parameter is not SUBSTANCES page
inconsistent with admissible for the selected
Technique calibration technique

7.3 Error messages

SUBSTANCES - ERROR 3: Missing value for the Mass Enter Mass conc. parameter on the Esc
Param. Mass conc. conc. parameter SUBSTANCES page
missing
SUBSTANCES - ERROR 4: The f.half/r.half pa- Change Scope or Type parameter on Esc
Param. Scope f./r.half rameter is admissible only with the SUBSTANCES page
only with linear a linear baseline
SUBSTANCES - ERROR 5: Missing counterpart for the Check Scope parameter for both Esc
Param. Scope evaluation with f.double or substances and change
f./r.double missing r.double; in double peak
counterpart evaluation the first peak must
be evaluated with f.double
and the second peak with
r.double
SUBSTANCES - ERROR 6: Wrong assignment of the two Check Scope parameter for both Esc
Param. Scope peaks in the double peak substances and change
f./r.double direction evaluation; the first peak (in
conflict sweep direction) must be
evaluated with f.double, the
second with r.double
SUBSTANCES - ERROR 7: Non-specified error on the Check the SUBSTANCES page Esc
Undefined error SUBSTANCES page
VA STAND - ERROR 1: Connection to 747 VA Stand Check connection to 747 VA Stand: E/S
Missing device broken:
Connecting cable not Plug in connecting cable
plugged in
Wrong address Correct address and restart 746 VA
Trace Analyzer
Hardware fault at VA Stand Run diagnostic routine for VA Stand
VA STAND - ERROR 2: Fault at MME working electr.: Check MME: r/a
Working electrode No connection Connect reference electrode with WE
faulty cable
Too less mercury Fill MME with mercury (see section
3.4.2 and 3.4.7)
Bad mercury quality Clean MME (see section 3.4.9) and
use ultrapure mercury (w 0.99999)
or filtered mercury
Dirty or clogged capillary Change capillary (see section 3.4.8)
Dirty or damaged sealing Clean MME (see section 3.4.9) and
needle replace sealing needle if need be
No inert gas pressure Check inert gas connection (see
section 3.3.3)
Dirty electrode body Rub the MME body dry, clean with
distilled water of dilute acid and dry
with a lint-free cloth
Fault at reference electrode see VA STAND - ERROR 4
No solution in measuring Add measuring solution
vessel
No electrolyte in measuring Add a few drops of KCl 3 mol/L to the
vessel measuring solution
Tapping strength in DME Turn slotted screw 71 on the 747 VA
operation too weak Stand during operation in an anti-
clockwise direction until a drop falls
each time the tapper is triggered
Fault at RDE working electrode: Check RDE:
No connection Connect reference electrode with WE
cable
Electrode tip not firmly Install RDE properly (see section 3.5)
screwed on to the drive shaft
Contaminated electrode Regenerate RDE (see section 3.5.2)
surface


VA STAND - ERROR 3: Fault at reference electrode: Check reference electrode: r/a
Auxiliary electrode No connection Connect reference electrode with AE
faulty cable
VA STAND - ERROR 4: Fault at reference electrode: Check reference electrode: r/a
Reference electrode No connection Connect reference electrode with RE
faulty cable
Air bubbles in electrolyte Shake the electrode like a clinical
thermometer
Too less electrolyte Refill reference electrode (see section
3.6.2)
VA STAND - ERROR 5: Empty measuring vessel Add analyte solution r/a
Empty vessel or Several electrodes faulty Check electrodes
electrodes faulty
VA STAND - ERROR 6: Current overload Change t.pulse or Modul.freq. E/S
IR current overlod
VA STAND - ERROR 7: Stirrer/RDE does not rotate Remove stirrer/RDE, clean and reinsert r/a
Stirrer/RDE overload
VA STAND - ERROR 8: Break on EBUS connection Check connections to the devices E/S
EBUS timeout occured during the program flow attached via EBUS (VA Stand, Dosi-
mats, etc.)
VA STAND - ERROR 9: Current compensator or Run diagnostic routine for VA Stand E/S
I compensator or gain measuring amplifier faulty If error reappears, inform Metrohm
amplifier faulty service
VA STAND - ERROR 10: Modulation frequency faulty Inform Metrohm service E/S
faulty
VA STAND - ERROR 11: AD converter faulty Inform Metrohm service E/S
AD converter faulty
VA STAND - ERROR 12: Modulator RAM faulty Inform Metrohm service E/S
Modulator RAM faulty
VA STAND - ERROR 13: Voltage polarization faulty Inform Metrohm service E/S
U polarisation faulty
VA STAND - ERROR 14: Measured value acquisition Inform Metrohm service E/S
Adder faulty faulty
VA STAND - ERROR 15: Current limit value detectors Inform Metrohm service E/S
Current limits faulty
detectors faulty
VA STAND - ERROR 16: Measurement cycles counter Inform Metrohm service E/S
Meas.cycles counter faulty
faulty
VA STAND - ERROR 17: Preparation cycles counter Inform Metrohm service E/S
Prep.cycles counter faulty
faulty

7.3 Error messages
7.3.3 Instrument initialization
Certain errors can appear in the 746 VA Trace Analyzer which can be rectified only
by initializing the instrument (see Rectification column of the error list in section
7.3.2). Three types of initialization are possible; these are called Normal Reset,
Reset with deletion of working storage and Overall initialization in what fol-
lows.
If an error appears which requires initialization of the instrument, your first step
should always be an attempt to restart the instrument with a Normal Reset.
If the instrument cannot be started properly and an error message appears during
the startup procedure or if errors occur with the method or determination loaded in
the working storage, a Reset with deletion of working storage should be per-
formed.
Perform an Overall initialization only if the instrument still refuses to function

properly. However, it is essential to note the following in this case:
With an Overall initialization, all stored methods and determinations
are irrevocably cleared. Hence, always try to start the instrument with
one of the two other reset possibilities before an overall initialization
and save the contents of the method memory and the determination
memory on a data card.
To avoid unnecessary data losses should an overall initialization be-
come necessary, you should save all important methods and data at
regular intervals by storing them on a data card or, via the RS232 in-
terface, on a PC.
Normal Reset
Hardware reset and internal software reset.
The instrument is reinitialized, but all instrument parameters, the data loaded in the
method and determination storage as well as the method and determination loaded
in the working storage are retained.
This type of instrument initialization runs automatically each time the 746 VA Trace
Analyzer is switched on.
There are three possibilities to initiate a reset:
Switching the instrument off and on
Pressing the Reset button 15 at the rear of the
746 VA Trace Analyzer
Pressing the <BREAK> key when the instrument is on
standby (* READY *), followed by the <ENTER> key.
The instrument is then powered up and the MONITORING page appears.

Reset with deletion of working storage

Hardware reset and internal software reset with deletion of the working storage.
The instrument is reinitialized. All instrument parameters and the data loaded in the
method and determination storage are retained. The method and determination
loaded in the working storage are cleared and all method parameters are reset to
their default values.
This reset is performed as follows:
1 Start reset
Initiate a reset using one of the 3 methods listed under Normal Reset, then
press the space key several times when the instrument is powering up until
the following screen display appears:
RAM initialization 746

-> contrast = ###
hit any key to confirm contrast
2 Adjust screen contrast

The screen contrast is now continuously varied from completely dark to
extremely light. Press any key as soon as the contrast has reached the
desired value. (If you are not satisfied with the result, you can improve the
contrast setting later on the VA TRACE ANALYZER page.)
3 Run RAM test

Next you are asked whether or not you wish to perform a RAM test. If an
error has been found, it is advisable to press <y> here. If the RAM test is
successful, the following screen display appears:
-> contrast = 108

-> non destructive RAM test: y/n ? y
- running non destructive RAM test
RAM test passed ok
4 Start reset with deletion of working storage

After the RAM test, answer the following three questions with <n> and the
fourth question reset working memory: y/n ? with <y>.
-> reset all memory and hardware setup to default: y/n ? n

-> reset filling and dosing rate of Dosimats: y/n ? n
-> reset storage memory: y/n ? n
-> reset working memory: y/n ? y
5 Testing the beep

The functioning of the beep can be tested by pressing <y>. Press <n> to
continue.

7.3 Error messages
-> test beep: y/n ? n
The instrument is now powered up and the MONITORING page appears.
6 Load method or determination

Select the "METHODS", "DETERMINATIONS" or "DATA CARD" page and
copy desired method or determination to the working storage.
Overall initialization
Reinitialization of the entire hardware and software.
The instrument is reinitialized completely, the data loaded in the method and de-
termination storage as well as the method and determination loaded in the working
storage are cleared and all instrument parameters are reset to their default values.
The overall initialization is performed as follows:
1 Start reset
Initiate a reset using one of the 3 methods listed under Normal Reset, then
press the space key several times when the instrument is powering up until
the following screen display appears:
RAM initialization 746

-> contrast = ###
hit any key to confirm contrast
2 Adjust screen contrast

The screen contrast is now continuously varied from completely dark to
extremely light. Press any key as soon as the contrast has reached the
desired value. (If you are not satisfied with the result, you can improve the
contrast setting later on the VA TRACE ANALYZER page.)
3 Run RAM test

Next you are asked whether or not you wish to perform a RAM test. If an
error has been found, it is advisable to press <y> here. If the RAM test is
successful, the following screen display appears:
-> contrast = 108

-> non destructive RAM test: y/n ? y
- running non destructive RAM test
RAM test passed ok

4 Start overall initialization

After the RAM test, you are asked whether or not you wish to perform a
global, overall initialization:
-> reset all memory and hardware setup to default: y/n ?
<y> All data memories are cleared, all instrument parameters

are reset to their default value.
<n> Possibility to switch to the Reset with deletion of the work-
ing storage (see above) or to abort the overall initialization
(answer all subsequent inquiries also with <n>).
5 Testing the beep

The functioning of the beep can be tested by pressing <y>. Press <n> to
continue.
-> test beep: y/n ? n
The instrument is now powered up and the MONITORING page appears.

7.4 Troubleshooting
7.4 Troubleshooting
7.4.1 General rules for VA trace analysis
In order to get correct results in VA trace analysis, a number of general rules must
always be observed:
Chemicals and equipment

The purity of the reagents plays an important role in determining the re-
sults. Extremely pure chemicals should be used for determining lower
concentrations (see VA Application Note V-49).
Measuring vessel, electrodes and all other equipment in contact with the
sample solution must be clean and free of contamination substances.
Electrolytes
The pH during a determination plays an important role (e.g. for Zn, Cd, Pb,
Cu it should be approx. 4.5). Acetate, Ammonium acetate or PIPES buffer
are often used. For more information see the Application Bulletins.
The electrolyte must be sufficiently conductive and concentrated.
The purity of the electrolytes and the cleanliness of the reagent bottles is
very important.
The working life of the electrolytes is limited, particularly for organic addi-
tives (buffer substances, complex formers). It may be necessary to make
up fresh solutions every day.
Standard solutions
The standard solutions should be made acidic (approx. pH = 12) and
stored in plastic bottles.
Diluted standard solutions (ppb range) are very unstable and must be
freshly made. They must also be made sufficiently acidic.
The concentration of the standard solutions must be arranged so that a
volume between 20 and 500 L has to be added.
Standard additions are recommended. The peak height after the last addi-
tion should be 25 times higher than the sample peak.
1000 ppm solutions (self-made or commercially available) are often used
as stock solutions. They are stable over long periods of time. Dilutions
have to be made with dilute acids.
Samples
The amount of sample depends on the concentration of the element to be
determined.
If the sample matrix is known, a better assessment of the analysis can be
made (organic components?).
A digestion must be carried out on contaminated samples and on sam-
ples where contamination is suspected (see Metrohm Monograph
Sample preparation for techniques in voltammetric trace analysis).
A lot of errors are made during sampling and when storing the sample.
Caution and a critical approach are required.
The sample should have a good solubility in the electrolyte and be mixable
with it.

Blank values, contamination

The following points should be checked if the results are too high:
Have the dilutions been made correctly?
Have contamination risks been excluded?
Contamination risks are very high at low concentrations:
measuring vessels should be conditioned with dilute HNO3 solution.
Are the chemicals pure enough?
"Suprapure" grade reagents should be used at low concentrations.
Very high concentrations were measured in the previous analysis:
electrodes and measuring vessels must be carefully cleaned and condi-
tioned (memory effects).
Has the standard addition been carried out properly?
Was the volume set correctly on the pipetting unit?
The following points should be checked if the results are too low:
Concentration too high?
HMDE overloaded, use DME/SMDE instead?
Buffer not correct?
Make up new one if necessary.
Addition ratio too low?
Addition ratio too high?
Measurement modes
The following points should be considered by selecting the measurement mode:
DPMODE (Differential Pulse) should be always the first choice. It is the
most universal and frequently used voltammetric determination method
and is equally well suited for reversible and irreversible systems. It offers a
high sensitivity down to 108 mol/L and a separation ability of 1:50'000.
DCTMODE (Direct Current) is the classic, simplest VA method with limited
sensitivity (down to 105 mol/L) and a separation ability of only 1:10. It is
mainly used for the investigation of reversible redox systems.
AC1MODE (Alternating Current, 1st derivative) is primarily suitable for de-
terminations based on reversible redox reactions and is virtually com-
pletely insensitive to irreversible reactions.
AC2MODE (Alternating Current, 2nd derivative) is also primarily suitable for
determinations based on reversible redox reactions. Compared with the
AC1MODE measurements, an increase in sensitivity, resolution and
separation efficiency is often obtained.
SQWMODE (Square Wave) is primarily suitable for investigations of re-
versible electrode processes and kinetic studies. It is used particularly for
sensitive stripping voltammetric determinations at the HMDE or RDE.
PSAMODE (Potentiometric Stripping Voltammetry) is mainly used to de-
termine substances in an organic matrix by means of mercury film elec-
trodes without prior digestion and deaeration. Only analytes which form an
amalgam can be analyzed.

7.4 Troubleshooting
7.4.2 Problems with DME/SMDE
Low background current or unstable baseline

The electrode drops irregularly: check MME.
Adjust sealing needle (see section 3.4.4/3.4.5). If necessary, change capillary
(see section 3.4.8) or replace sealing needle (see section 3.4.9).
Check electrolyte concentration and pH of the solution.
Check initial potential and final potential of the analysis.
If the ion concentration in the solution is too high: dilute the electrolyte.
If the concentration to be determined is considerably lower than anticipated:
increase sample volume or change mode (e.g. HMDE).
Has the sample been degassed? Degassing with nitrogen for at least 5 min is
recommended, for alkaline solutions approx. 10 min is recommended.
Check tapping mechanism on VA Stand. If tapping strength is too weak, turn
slotted screw 71 on the valve block during operation in an anticclockwise di-
rection until a drop falls each time the tapper is triggered.
Is the gas pressure correctly set (1 bar)?
Is the reference electrode sufficiently full (inside and outside, see section
3.6)?
Curves look like a "starry night"

The electrode drops irregularly: check MME.
Adjust sealing needle (see section 3.4.4/3.4.5). If necessary, change capillary
(see section 3.4.8) or replace sealing needle (see section 3.4.9).
Check contact between needle and capillary. If necessary, clean the MME
Have stirring or degassing been switched off during the measurement?
If the electrode drops much too quickly: reduce t.step in program.
Check tapping mechanism on stand. If tapping strength is too weak, turn
Standard addition curves are not reproducible

Check program in the instrument (stirring time, etc.).
Check MME, change capillary if necessary (see section 3.4.8).
The pipetting process was not correct: was the pipetting unit used properly?
Repeat the analysis again or try out automatic standard addition with Dosi-
mat, Dosino or 6.5611.010 Pipetting equipment.
Pipetting the standard solutions must be carried out by one and the same
person or with the same instrument or the same pipette.
Check and test pipetting process. When were the pipettes last calibrated
(GLP)?
Organic components interfere with the analysis: carry out a UV digestion or
other suitable sample preparation.
Are the calibration solutions too old?
Would a calibration curve or the internal standard method be more suitable?

Peak displacement
Check and adjust the pH of the solution.
Check electrolyte composition and correct if necessary. Use a buffer solution
instead of an acid.
Carry out a standard addition to check whether the correct peak has been
evaluated.
Enter a new half-wave potential in the instrument and recalculate the results.
Check reference electrode (see section 3.6).
No peak found
The peak is only displaced: adjust the half-wave potential and recalculate the
results.
The sample concentration is too low: increase the sample volume or the
amount of sample.
The concentration of the ion to be determined is too low: use HMDE (inverse
voltammetry) instead of DME or SMDE.
Are the initial and final potentials correct?
Peak is in the highest A range

The concentration of the ion to be determined is too high: reduce the sample
volume and carry out the analysis again.
The preconcentration time under MEAS is too high, reduce it and try the
analysis again.
Double peak
Check MME. If necessary, change capillary (see section 3.4.8) or replace
sealing needle (see section 3.4.9).
If a second element is present at the same potential: add this element to the
sample and carry out the analysis again. If the second peak has become
higher then the second element is present.
Has any substance been precipitated out in the measuring vessel (e.g. lead
perchlorate standard with KCl as electrolyte)?
Try out eluents with different compositions (addition of complex formers).
Check analysis parameters.
Try another measurement mode like AC1. If one substance is reversible and
the second one irreversible, only the reversible substance is detected by
AC1.
Standard addition peaks displaced

Standard solutions have been made too acidic.
Buffering capacity of the electrolyte is not sufficient: increase electrolyte vol-
ume.

7.4 Troubleshooting
No addition
Has the correct standard solution been used or is the concentration of the
solution too low: increase the volume of the standard addition or use a higher
concentration or reduce the sample amount accordingly.
If organic components are present: carry out a UV digestion or similar.
Could it be possible that the peak is not the peak which is being looked for?
Concentration of the analyte is too high: dilute.
7.4.3 Problems with HMDE
Low background current or unstable baseline

The electrode drops or the drops do not remain hanging: check MME.
Change capillary if necessary (see section 3.4.8) or replace sealing needle
Has the sample been properly degassed?
Check the concentration of the electrolyte and the pH of the solution.
Check the initial potential and final potential of the analysis.
If the concentration to be determined is considerably higher than expected:
reduce sample volume or change the mode (e.g. from HMDE to SMDE or
DME).
Electrolyte solution too old: make up a new one. Its working life with organic
additives may be as short as 1 day or less.
Curves look like a "starry night"

Check MME. Check for break in contact between needle and capillary. If nec-
essary, clean the MME (see section 3.4.9).
If the electrode surface is overcharged: check deposition potential and time.
No drops at the capillary: change the capillary (see section 3.4.8) or replace
Have stirring and degassing been switched off during the measurement?
Check tapping mechanism on stand. If tapping strength is too weak, turn

Standard addition curves are not reproducible or non-linear

Check MME, change capillary if necessary (see section 3.4.8) or replace
(GLP)?
Would a calibration curve be more suitable?
The linearity at the HMDE is naturally not as good as with the DME. The linear
range is in general no larger than 1 - 2 decades.
Peak displacement
Check and adjust the pH of the solution.
Check electrolyte composition and correct if necessary.
Carry out a standard addition to check if the correct peak is present.
No peak found
The peak is only displaced: adjust the half-wave potential and recalculate.
The sample concentration is too small: increase the sample volume.
Has the complex former been forgotten? (adsorptive voltammetry).
The deposition time under Meas in "OP.SEQUENCE" in the inverse voltam-
metry is too short: increase the time.
No Hg drops at the capillary: check MME. Adjust sealing needle (see section
3.4.4/3.4.5). If necessary, change capillary (see section 3.4.8) or replace
Are organic components present? Carry out a UV digestion or other suitable
sample preparation.

7.4 Troubleshooting

The sample volume is too large: reduce the volume. Carry out the analysis
again.
The enrichment period (for HMDE) is too long: Reduce the time.
If necessary use a SMDE or DME electrode instead of HMDE.
Double peak
Check MME. If necessary, change capillary (see section 3.4.8) or replace
Organic components interfere with the analysis? Carry out a UV digestion or
If a second element is present at the same potential: add this element to the
sample and carry out the analysis again. If the second peak has become
higher then the second element is present.
Might it be possible to selectively mask this second element with a complex
former?
For Cu: work without chlorides in the electrolyte or increase the chloride con-
centration massively.
AC1.

If HMDE is used potential displacements of more than 2030 mV are often
normal and have to be accepted; particularly in adsorption voltammetry.
ume.
No addition
If organic components are present: carry out a UV digestion or other suitable
sample preparation.
Concentration of the analyte is too high: dilute.
Addition solution with metal complexing solution (time reaction).

7.4.4 Problems with RDE
There are various different types of RDE:

GC: Glassy carbon electrode, can be polished with aluminium oxide, glossy
surface.
Au: Gold electrode, can be polished with aluminium oxide, mat surface.
UT: Ultra-trace graphite electrode, can be scraped and polished with alumin-
ium oxide, mat surface.
Ag: Silver electrode, can be polished with aluminium oxide, mat surface.
Pt: Platinum electrode, looks very similar to Ag, mat surface.
Low background current or unstable base line

The electrode surface must be repolished.
Has the correct RDE been used?
Exchange RDE.
Check concentration of electrolyte and pH of the solution.
Has the electrode been conditioned (e.g. with CONDC) ?
Check initial and final potential of the analysis.
If the concentration to be determined is considerably higher than expected:
reduce sample volume.
The background current is normally higher if RDE is used in place of MME.
A background current of several 100 nA is entirely possible.
Standard addition curves are not reproducible

Check RDE (see section 3.5).
(GLP)?
Would a calibration curve be more suitable?
Peak displacement
Check and adjust pH of the solution.
Check electrolyte composition and correct if necessary.

7.4 Troubleshooting
No peak found
The peak is only displaced: adjust the half-wave potential and recalculate.
The background current is too high: repolish the electrode.
The sample concentration is too low: increase sample volume.
The deposition time under MEAS in "OP.SEQUENCE" in the inverse voltam-
metry is too short: increase the time.

The sample volume is too large: reduce the volume. Carry out the analysis
again.
The background current is too high: repolish the electrode.
The deposition time is too long: reduce the time.
Is the deposition potential correct?
Double peak
Check RDE and polish if necessary (see section 3.5).
sample preparation.
AC1.

ume.
Electrode surface overcharged: reduce sample volume.
No addition
sample preparation.
Concentration of the analyte too high: dilute.

7.5 Hardware/software faults in the instruments

or simply the vagaries of the chemistry
7.5.1 General
The hardware and software of the 746 and 747 VA instruments are constructed of
tested, reliable and checked components. While this does not exclude faults, it en-
sures they appear only rarely. What you should do in such cases is described in
sections 7.3 and 7.4.
Much more likely than genuine hardware/software faults however, are peculiarities
and vagaries of the chemistry which simulate instrument faults and thus give
grounds for inquiries. Such faults manifest themselves primarily in the fact that the
automatic peak evaluation no longer functions properly and results on the dialog
page RESULTS (see section 5.5.2) are either missing completely or are marked
by appropriate comments as having errors or difficulties associated with the peak
evaluation.
In both cases, the first move is to check whether the faults are caused by undesired
chemical processes occurring at the electrode or in the analysis solution. Here,
such faults due to the chemistry can usually only be rectified in whole or at least in
part by chemical countermeasures (e.g. different supporting electrolyte concentra-
tion, different supporting electrolyte, different pH, longer enrichment time, modifica-
tion or change of the measurement technique). In what follows, such vagaries of
chemistry are explained in more detail with the aid of a few interesting and oft-
occurring examples.
7.5.2 Oxygen in the analysis solution
Oxygen can be electrochemically reduced and produces two waves in the voltam-
mogram, one of which is characterized by the appearance of a pronounced maxi-
mum. The oxygen reduction can interfere for two reasons:
The signals of the analytes are masked by the oxygen waves.

This becomes noticeable primarily in trace analysis as the oxygen
is present in a relatively high concentration in solutions saturated
with air (ca. 8 mg/L at room temperature).
The hydrogen peroxide formed in the 1st step of the oxygen re-
duction can react further with certain substances.
For these reasons, oxygen must be removed from the analysis solution before the
polarographic analysis by saturation with inert gas (usually nitrogen). With the inert
gas flow rate of ca. 20 L/h set on the 747 VA Stand in the factory, a purging time of
3...5 min usually suffices.

7.5 Vagaries of the chemistry
7.5.3 Unsuitable bridging electrolyte solution in the reference

electrode
When choosing the bridging electrolyte in the reference electrode, possible compli-
cations with the substances present in the analysis solution must be taken into ac-
count.
With regard to the bridging electrolyte solution KCl 3 mol/L used in many cases,
the following are examples of disturbances which can appear:
Precipitation of KClO4 in the ceramic diaphragm

with supporting electrolytes containing HClO4
With partial blockage, inexplicable side peaks can appear, with complete
blockage one of the following error messages appears:
VA STAND - ERROR 2: Working electrode faulty
VA STAND - ERROR 4: Reference electrode faulty
To avoid such precipitations, with analysis solutions containing HClO4 a

bridging electrolyte solution free from alkalis or alkaline earths (e.g. acetate
buffer) must be used.
Introduction of Cl through KCl outflow from

the reference electrode
The outflow of bridging electrolyte from the ceramic diaphragm of the
6.1245.010 Electrolyte vessel (part of the reference electrode) is 2...5 L/h.
The Cl flowing into the analysis solution can interfere with the determination
of vitamin C or the determination of Cu (see also section 7.5.6).
The use of Cl free bridging electrolyte solutions (e.g. KNO3 sat.) is rec-
ommended as a countermeasure.
7.5.4 Overcharging of the working electrode
Under unfavorable conditions (high concentrations and/or long enrichment times),

the enrichment of species at polarized electrodes leads to overcharging phenom-
ena such as non-linear standard addition curves or splitting into multiple peaks
which are caused by saturation and different deposition forms.
A shorter enrichment time usually solves the problem. The following rule of
thumb holds: In general, enrichment should not be carried out except in solutions
with a mass concentration < 0.5 mg/L (= 0.5 ppm). In several cases work can be
carried out without enrichment even with concentrations > 100 g/L (e.g. DP
voltammetry at the HMDE or also at the DME).
The effects of an enrichment time which is too long are shown by the following two
examples:
Nickel and cobalt determination in the trace region by cathodic
adsorption stripping voltammetry (with dimethylglyoxime com-
plexes)
Prolongation of the enrichment time from 30 s to 120 s (keeping all other
measurement parameters constant) leads to non-linear standard additions
and in the case of nickel also to shifts in the peak maximum:

Enrichment time: 30 s Enrichment time: 120 s
Ni
Co
Ni
Co
Analysis solution: 20 g/L Ni; 20 g/L Co

Supporting electrolyte: 0.1 mol/L NH4Cl/NH3; pH = 9.3
-4
510 mol/L dimethylglyoxime (DMG)
Standard addition: with 200 ng Ni / 200 ng Co
Electrode: HMDE
Mercury determination at the gold electrode

On prolongation of the enrichment time from 30 s to 240 s, side peaks ap-
pear during standard addition:
Enrichment time: 30 s Enrichment time: 240 s
Hg
Hg
Analysis solution: 100 g/L Hg

Supporting electrolyte: HClO4/HCl
Standard addition: with 1 g Hg
Electrode: Au-RDE

7.5.5 Disturbances at the HMDE through gas formation
Gas formation at the HMDE during the deposition phase can lead to drop fall or to
a contact break in the Hg capillary. The following example illustrates such a case:
Determination of zinc in deionised water

If the zinc sample is acidified to pH 2 with HClO4, hydrogen is also formed
at the voltage selected for enrichment. In the present example this leads to
premature release of an Hg drop in the 2nd standard addition thus making
an evaluation impossible.
If acetate buffer (pH = 4.64) is used, no such difficulties arise. However, a
requirement for this is that chemicals of the highest purity are used to keep
the zinc blank value as low as possible (it is advisable to prepare the ace-
tate buffer using ultrapure ammonia and ultrapure acetic acid).
Supporting electrolyte: Supporting electrolyte:

0.01 mol/L HClO4; pH = 2 acetate buffer pH = 4.64
Zn Zn
Analysis solution: deionised water

Standard addition: with 50 ng Zn
Electrode: HMDE (enrichment 60 s at 1.2 V)

7.5.6 Complex formation
Substances determined polarographically can occur in various complexed forms,

depending on the composition of the analysis solution. As complexing is always
associated with a shift in the half-wave potential and the limiting current, difficulties
can arise in the peak evaluation. Such difficulties must be eliminated by appropriate
changes in the composition of the supporting electrolyte.
If it is not possible to remove the interfering complexing agents from the analysis
solutions or to mask them by suitable substances, it is often helpful to change the
pH of the supporting electrolyte. Another measure which is often used involves the
addition of a ligand of high complexing power (e.g. EDTA) to bring about 100%
change of the analyte to a definitive form. The latter possibility is also used in the
following example:
Copper determination in chloride-containing solutions

Copper can occur in chloride-containing solutions as both a CuCl42 and a
CuCl2 complex. The two associated current peaks are near each other. In
unfavourable cases, the determination of copper is not possible. The diffi-
culties disappear after addition of the complexing agent EDTA as now all
copper is completely in the form of a Cu-EDTA complex. (Increasing the
chloride concentration [e.g. by addition of 1 mL of a 1.5 mol/L KCl solution
of the greatest possible purity per 10 mL analysis solution] would also give
a clearly defined current peak for CuCl2.)

without EDTA with EDTA (0.001 mol/L)
2
CuCl4

CuCl2 CuEDTA
Analysis solution: 25 g/L Cu; 10 L HCl 30%

Standard addition: with 250 ng Cu
Electrode: HMDE (enrichment 90 s at 600 mV)

7.5.7 Peak on highly curved baseline
If peaks lie on a highly curved baseline, the first attempts at rectification should in-
volve chemical or measurement technique countermeasures to eliminate the ad-
verse effect on the peak evaluation due to the highly curved baseline. Such meas-
ures include longer purging times (if oxygen interferes, see section 7.5.2), changing
the pH value, changing the supporting electrolyte concentration, modifying or
changing the supporting electrolyte, use of complexing agents (see example in
section 7.5.6), longer enrichment times and changing the measurement technique.
If the curvature of the baseline can not or only partially be eliminated by the above
measures, the 746 VA Trace Analyzer offers the two following possibilities to ap-
proximate a curved baseline (see section 5.6.3):
Type = polynom for baselines with normal curvature
Type = expon. for baselines with exponential curvature
A further possibility to evaluate peaks on curved baselines involves the background

subtraction, in particular when the curved baseline can be clearly attributed to the
supporting electrolytes (see instruction BACKGDN, section 5.7.3).
7.5.8 Peak overlapping
The 746 VA Trace Analyzer offers the possibility to evaluate overlapping peaks (see
section 6.7.1). If an overlapping is found at the front or rear of the peak, this is
displayed on the dialog page RESULTS/Evaluation by appropriate comments in
the Comments column (see section 5.5.2). Depending on the extent of the overlap-
ping, the following three cases are distinguished:
Overlapping < 10%

Comment front overlapping or rear overlapping. This overlapping is
admissible and leads to no noticeable result falsifications.
Overlapping 10 40%
Comment crit. front ovlp. or crit. rear ovlp.. Although the peak is
evaluated, the overlapping has reached a critical level at which the calcu-
lated peak height or peak area is falsified by the neighbouring peak. In this
case it is advisable to take the overlapping into account by a change in the
baseline calculation. For this, the parameter Scope of whole (calculation
for the entire curve) must be set to either f.double or r.double
(calculation for double peak) or to f.half or r.half (calculation only for
front or rear, see sections 5.6.3 and 6.7).
Overlapping > 40%

Comment illeg. front ovlp. or illeg. rear ovlp.. The overlapping
is too large, the peak can no longer be evaluated. In this case chemical or
measurement technique countermeasures must be used to attempt to
separate these peaks better. Possible measures include changing the pH
value (see example below), changing the supporting electrolyte concen-
tration, changing the supporting electrolyte, use of complexing agents
(see example in section 7.5.6), longer enrichment times and modifying or
changing the measurement technique.

Determination of lead and thallium

With a supporting electrolyte of pH = 1, Pb and Tl peaks overlap greatly.
Changing the pH to 13 separates the two peaks. (The separation of lead
and thallium can also be achieved by subsequent electrolysis or in acetate
buffer with EDTA).

pH = 1 pH = 13
Pb
Tl
Analysis solution: 0.5 mg/L Pb; 1 mg/L Tl

Standard addition: with 10 g Pb and 10 g Tl
Electrode: SMDE
7.5.9 Calibration with chemically non-isoformal standards
With all three possible calibration techniques, it must be ensured that the standards
used for calibration are chemically isoformal with the analytes. The standard sub-
stances must therefore have the same valency (e.g. with Fe, Al) or complex forma-
tion form (e.g. with As, Cr, Se) as the substances already present in the analysis
solution. If this is not the case the calibration can produce completely wrong results
owing to the different peak voltages and sensitivities.

7.6 Diagnosis
7.6 Diagnosis
7.6.1 General
The 746 VA Trace Analyzer and 747 VA Stand are very precise and dependable in-
struments. Thanks to their rugged construction, it is highly unlikely that external me-
chanical or electrical influences will have an adverse affect on their functions.
Although the appearance of a fault in the instrument can not be excluded with cer-
tainty, it is far more likely that malfunctions will be caused by faulty operation or
handling or through improper connections and operation with third-party devices.
It is always advisable to isolate the fault with the diagnostic program as this is sim-
ple and easy to run. The customer need call Metrohm service only when the instru-
ment really has a fault. Moreover, he can then provide the service engineer with
much more detailed information using the numbering in the diagnostic program.
When making inquiries, always quote the serial number 7 (see section 2.1) and
program number (see section 5.3.1) and any error displays which may have ap-
peared.
Procedure
If a malfunction occurs, the directions of the appropriate diagnostic step
(see following test list) must be followed. The ensuing reactions of the VA
Trace Analyzer must be compared with the descriptions in the diagnostic
step.
If the instrument does not show the expected reaction (no case), the ap-
propriate diagnostic step must be repeated to exclude an operating error.
It is highly probable, however, that multiple wrong reactions indicate a
malfunction.
Test list
1. Prepare instrument for diagnostic test section 7.6.2
2. Check thermal printer section 7.6.3
3. Check RS232 interfaces section 7.6.4
4. Check control lines section 7.6.5
5. Check keypad section 7.6.6
6. Check VA Stand (perform measurement section 7.6.7
routine with polarogram simulator)
Instruments needed
Necessary only if RS232 and control lines are also checked:
3.496.8550 Test plug (to connection 'Control lines')
3.496.8480 Test plug (to connection 'RS232')

7.6.2 Prepare instrument for diagnostic test
1 Power off.
2 Disconnect all cables at rear panel, except mains cable and connecting cable
to VA Stand.
3 Power on.
7.6.3 Checking thermal printer
1 Prepare instrument for diagnostic test (see section 7.6.2).
2 <VA TRACE ANALYZER>
3 <Diagn.>
4 <Thermoprinter>
5 <Test print>
A test printout is outputted (see following page).
Check printout for completeness and neatness.
The character set (the first five lines) must match the specimen.
The very top and very bottom points of a line must be printed clearly;
check K and p especially.
The printout must have a total length of 260 mm (tolerance: 10 mm)
6 Press <ESC> several times until the MONITORING page appears.

7.6 Diagnosis

7.6.4 Checking RS232 interfaces

For this test a 3.496.8480 Test plug is needed, This plug can be purchased by customers quoting the
above number or they can make it themselves by following the diagram below:
PIN PIN PIN PIN

2 3 20 6
2 8 4 5
Connections in 3.496.8480 Plug
3 <Diagn.>
4 <RS232 interf.>
5 Plug 3.496.8480 Test plug into 'RS232 Interface 1' connection.
6 <Loopback test>
7 The test runs automatically.

(If a fault appears, an error message is outputted.)
8 <Change Ifc.>
9 Plug 3.496.8480 Test plug into 'RS232 Interface 2' connection.
10 <Loopback test>

(If a fault appears, an error message is put out.)
13 Remove test plug.
7.6.5 Checking control lines

For this test a 3.496.8550 Test plug is needed, This plug can be purchased by customers quoting the
above number or they can make it themselves by following the diagram below:
PIN PIN PIN PIN

1 24 5 21
2 12 9 18
3 23 10 17
4 22 11 16
Connections in 3.496.8550 Plug

7.6 Diagnosis
3 <Diagn.>
4 Plug 3.496.8550 Test plug into 'Control Lines' connection.
5 <Control Lines>

(If a fault appears, an error message is outputted.)
8 Remove test plug.
7.6.6 Checking the keypad
3 <Diagn.>
4 <Keyboard tests>
5 <All keys>
6 With the exception of the special keys <CAPS>, <SHIFT> and <SPACE>,
all keys must be pressed once. The special keys must be pressed as follows:
<CAPS> + <Z>
<SHIFT> (on the left of the space bar) + <!>
<SHIFT> (on the right of the space bar) + <@>
The space bar consists of a combination of three individual keys. It
must be pressed on the left, in the middle and on the right.
The keypad is shown symbolically on the screen. If the test is successful, the
gray background behind each key disappears.

7.6.7 Checking the VA Stand

(performing measurement routine with program simulator)
2 <STAND>
3 <Pressure> press several times and check the on/off switching of the valve
4 <Purging> press several times and check the on/off switching of the valve
5 <Stirrer> press several times and check the on/switching of the motor
The VA Stand includes a dummy cell and a polarogram simulator. In polarography,

this polarogram simulator replaces the electrochemical system (sample, electrode)
and thus performs extremely valuable service if a malfunction occurs to allow the
user to decide whether the malfunction is traceable to the instrument or the electro-
chemical system. This simulator can naturally also be used to practice operating
the instrument.
In the factory a special test method is stored in the VA Stand. This test method
TEST747.mth is written for the polarogram simulator and allows virtually 100% con-
trol of the entire measurement system.
Should the test method be deleted by accident, a new one can be generated with
the aid of the enclosed program sequences.
6 Copy test method TEST747.mth to working storage.

<METHODS>
Position cursor on TEST747.mth.
<Copy to>, <Working storage>
7 Define sample size.

<MONITORING>
Position cursor on Sample size/S0.
<CLEAR>
<*>, <ENTER>
8 Start TEST747.mth method.

<START>
The message AE->AE / RE->RE appears on the screen.
Attach electrode cable AE to clamping screw AE.
Attach electrode cable RE to clamping screw RE.
<ENTER>
The message WE -> WE-L appears on the screen.
Attach electrode cable WE to clamping screw WE-L.
<ENTER>
The message WE -> WE-D appears on the screen.

7.6 Diagnosis
Attach electrode cable WE to clamping screw WE-D.

<ENTER>
2 diagrams are printed out and must be assessed as follows:
Segment WE-L (DCTMODE):

In principle, the plotted diagonal must be straight. Small deviations
are partly due to the resolution of the printer.
Current at voltage 200 mV: 1.6 A ... 2.4 A*
Current at voltage +200 mV: +1.6 A ... +2.4 A*
* These tolerance values refer to illustrative scatters, that is to the differences
between individual instruments. The value determined for a specific instrument
shows less scatter. The deviation depends mainly on the temperature and should
be around 10%.
Segment WE-D (AC1MODE):

A symmetrical, gaussian-shaped peak should be plotted. The
evaluation must provide a result for the peak voltage U and the peak
current I, which are printed out at the end of the curve.
Peak voltage U : 450 mV ... 550 mV

Method: TEST747 .mth OPERATION SEQUENCE

Title : Test of 747 VA Stand with internal dummy cell

1 RDE Rot.speed 0 /min
2 HOLD Message AE->AE / RE->RE
3 NOP
4 HOLD Message WE -> WE-L
5 SEGMENT Segm.name WE-L
6 NOP
7 HOLD Message WE -> WE-D
8 SEGMENT Segm.name WE-D
9 END
Method: TEST747 SEGMENT

WE-L

U.end 200 mV Sweep rate 60 mV/s
3 END


I.scale fixed
I.begin -2 uA
I.end 2 uA
U.div 50.00 mV/cm
<Esc>
/ <Enter>

Method: TEST747 SEGMENT

WE-D

1 AC1MODE U.ampl 25 mV Modul.freq. 25 Hz
t.step 0.20 s Prep.cycles 0
Ph.angle 0 Meas.cycles 2
3 END


I.scale fixed
I.begin 0 A
I.end 600 nA
U.div 50.00 mV/cm
<Esc>
/ <Enter>


7.6 Diagnosis
Method: TEST747 SUBSTANCES

Subst1 - WE-D

U.verify -500 mV I.scale auto
U.tol (+/-) 50 mV U.div 50.00 mV/cm
U.width min 10 mV U.begin mV
U.width max 200 mV U.end mV
I.threshold 200 pA
Baseline Evaluation

Type linear Mode VA
Scope whole Quantity I.peak
dU.front 250 mV Sign. digits 4
S.front auto
dU.rear 250 mV
S.rear auto
Method: TEST747 DOCUMENTATION

Output
Auto form feed no Auto error printing no

Curve Orig Sgmt:WE-L VR:00 Printer
Curve Orig Sgmt:WE-D VR:00 Printer

7.7 Standard operating procedure in the context

of GLP/ISO 9001 guidelines
The requirements of GLP (Good Laboratory Practice) include the

periodic testing of analytical instruments with regard to reproducibility
and accuracy using standard operating procedures. Metrohm
suggests the procedure described below as the standard operating
procedure for testing the 746 VA Trace Analyzer and 747 VA Stand.
The standard operating procedure comprises two parts:
In the first step the correct functioning of the 746 VA Trace
Analyzer and 747 VA Stand is tested using the built-in polaro-
gram simulator and the method TEST747.mth. The procedure
is identical to that part of the instrument diagnostic test de-
scribed in section 7.6.7.
Finally, the TESTPb.mth method stored in the method memory
is used to perform a lead determination with standard ad-
dition to allow assessment of the accuracy and reproducibility
of this polarographic analysis. As the TESTPb.mth method has
already been described in detail in section 4.2, no explanation
will be given here of the individual dialog pages and only the
procedure to perform the method will be described. Before the
method is started, the 746 VA Trace Analyzer and 747 VA Stand
must first be prepared for the measurement as described in
section 4.1.
7.7.1 Checking 747 VA Stand with polarogram simulator
The procedure for checking the 747 VA Stand with the polarogram simulator built
into the stand is described in detail in section 7.6.7. Only the most important points
will be repeated here in brief:
1 Preparation
Prepare instrument for diagnostic test (see section 7.6.2).
2 Switch to dialog page "STAND"

Press the yellow <STAND> key.
3 Testing the inert gas pressure

Press the softkey <Pressure> several times and check the on/off
switching of the valve.
4 Testing the purging

Press the softkey <Purging> several times and test the on/off switching
of the valve.

7.7 Standard operating procedure in the context of GLP/ISO 9001 guidelines
5 Testing the stirrer

Press the softkey <Stirrer> several times and check the on/off switch-
ing of the stirrer motor.
6 Copying the TEST747.mth method to the working storage

Press the yellow <METHODS> key.
Use the cursor keys to select the TEST747.mth method.
Press the softkey <Copy to> and then <Working storage>.

Press the yellow <MONITORING> key.
Use the cursor keys to select the parameter Sample size/S0.
Press the <CLEAR> key.
Enter <*> and press <ENTER>.
8 Start program
Press the <START> key.
Attach the electrode cable as described in the instructions on the screen
to the clamping screws of the dummy cell.
9 Assessment of the linearity

The first of the printed curves should satisfy the following conditions:
In principle, the plotted diagonal must be straight. Small deviations
are partly due to the resolution of the printer.
Current at voltage 200 mV: 1.6 A ... 2.4 A*
Current at voltage +200 mV: +1.6 A ... +2.4 A*
* These tolerance values refer to illustrative scatters, that is to the differences
between individual instruments. The value determined for a specific instrument
shows less scatter. The deviation depends mainly on the temperature and should
be around 10%.
10 Assessment of peak measurement

The second curve plot should satisfy the following conditions:
A symmetrical, gaussian-shaped peak should be plotted. The
evaluation must provide a result for the peak voltage U and the peak
current I, which are printed out at the end of the curve.
Peak voltage U : 450 mV ... 550 mV

7.7.2 Loading the TESTPb.mth method
To load the TESTPb.mth method from the method memory to the working storage,
the instrument.

Press the yellow <METHODS> key. The dialog page METHODS
3 Selection of the TESTPb.mth method

Use the cursor keys to select the TESTPb.mth method, which then be-
comes black-backed.
4 Copying the TESTPb.mth method to the working storage

Press the softkey <Copy to>. The softkey boar changes and presents the
Press the softkey <Working storage>. The TESTPb.mth method is copied
to the working storage.
7.7.3 Preparing the sample solution
The sample solution for the lead determination is prepared as follows:
1 Addition of 20 mL dist. water

Add 20 mL dist. or deion. water to the measuring vessel.
2 Addition of 0.5 mL KCl 3 mol/L (6.2308.020)

Add 0.5 mL potassium chloride c(KCl) = 3 mol/L to the measuring ves-
sel.
3 Addition of 100 L Pb ion standard solution (6.2301.100)

Add 100 L Pb ion standard solution (Pb) = 1 g/L to the measuring
vessel (this results in 100 g Pb in the measuring vessel).

7.7 Standard operating procedure in the context of GLP/ISO 9001 guidelines
To perform the lead determination in the prepared sample solution, the following
steps are necessary:
1 Switch to dialog page MONITORING

Press the yellow <MONITORING> key.
2 Switching the program run mode to determination

If the parameter Run mode is set to calibration, proceed as follows
key.

Use the cursor keys to select the first field below the title Sample size/S0.
Enter 0.1 mL and confirm this entry with the <ENTER> key.

The sample solution is measured three times. On completion of the third
measurement, the program is interrupted. The screen shows the prompt
to add 50 L of the standard addition solution PbStd to the measuring
vessel ADD PbStd 50.000 uL > M.
5 First standard addition

Remove stopper 25 and add 50 L of the lead ion standard solution to
the measuring vessel through the pipetting opening using a pipette. Then
key.
The spiked sample solution is measured three times. On completion of
the third measurement, the program is interrupted. The screen again
shows the prompt to add 50 L of standard addition solution PbStd to
the measuring vessel ADD PbStd 50.000 uL > M.
6 Second standard addition

Remove stopper 25 and add 50 L of the lead ion standard solution to
the measuring vessel through the pipetting opening using a pipette. Then
key.
The sample solution spiked a second time is measured three times. On
completion of the third measurement, the results are calculated and the
reports and curves printed out (see section 4.2).

7.7.5 Assessment of the determination
To assess the recorded lead determination, the results printed out in the full report
for the mass concentration of lead Mass conc. and its total scatter MC.dev. are
used (example, see section 4.2). The limit values of these two results depend
greatly on the care taken in the preparation of the analysis solution and in the dis-
pensing of the standard addition solutions.
When the procedure is carried out properly and carefully, the following results
should be expected:
Accuracy = 95 105 % : Mass conc. = 0.95 1.05 g/L
Scatter 3% : MC.dev. 0.03 g/L (

3 %)
The reproducibility can be determined by performing the Testpb method several

times and comparing the results obtained for the mass concentration Mass conc..

8.1 746 VA Trace Analyzer
8 Technical data
Subject to changes !
The listed technical data apply to an ambient temperature of 25C.
Brief characterization
Compact control and data acquisition instrument for max. three 747 VA Stands,
a 695 Autosampler and up to four 685 Dosimats or 700 Dosinos with screen,
printer (optional), keypad and 2 bi-directional RS232C interfaces.
Circuitry based on SMD technology, 32-bit microprocessor, 16 MHz clock fre-
quency, 2 MBytes battery-backed SRAM.
Real-time multitasking operating system with dynamic memory management.
Current measurement techniques

DC Direct Current
DP Differential Pulse
SQW Square Wave (10 ... 250 Hz)
AC1 Phase-sensitive Alternating Current 1st harmonic
(10 ... 250 Hz)
AC2 Phase-sensitive Alternating Current 2nd harmonic
(10 ... 250 Hz)
PSA Potentiometric Stripping Analysis (chronopotentiometry)
CV Cyclic Voltammetry (digital ramp, 0.1 mV/s ... 100 V/s)
Data acquisition
SWEEP Current I as a function of the voltage U: I = f(U)
Voltage sweep for DC, DP, SQW, AC1, AC2
SSWEEP Current I as a function of the voltage U: I = f(U)
Voltage sweep for DC (if peaks must be evaluated instead
of waves)
FSWEEP Current I as a function of the voltage U: I = f(U)
Voltage sweep for DC, DP, SQW, AC1, AC2
(measurement always in operation mode fast)
PSWEEP Voltage U as a function of the time t: U = f(t)
Voltage sweep for PSA
TSWEEP Current I as a function of the time t: I = f(t)
Current measurement at constant voltage for DC, DP,
SQW, AC1, AC2
RAMP Current I as a function of the voltage U: I = f(U)
Voltage sweep for CV

8 Technical data
Measured value processing

Spike elimination Automatic spike elimination with floating spike test, can
be supplemented by manual spike elimination if need be
Curve smoothing Automatic digital filtering
U.step Smoothing Number of
window points
2 48 mV 25
4 56 mV 15
6 60 mV 11
8 64 mV 9
10 60 mV 7
12 72 mV 7
Recognition Automatic peak/wave recognition for specific sub-

stances with the aid of preset criteria for characteristic
voltage, peak/wave width and peak/wave height
Baseline calculation Automatic calculation of the baseline with selectable
parameters (dependent on measurement mode)
Type linear (tangent), polynomial,
exponential, AC2 abs., AC2 rel.
Range entire peak, peak half, double peak
Evaluation Automatic calculation of the analysis results (peak
current, peak area or wave current) with the aid of the
determined baseline
Content calculation Automatic content calculation from the analysis results
by 3 different procedures:
standard addition (constant or prop.)
calibration curve
internal standard
Formula calculation Further calculation of analysis results and mass
concentrations using predefined formulae
Keypad
Type Piezoelectric, splashwater-proof
Keys Alphanumeric keypad with upper- and lowercase letters,
punctuation and special characters; numeric block;
dialog keys, main function keys, softkeys
Screen
Type LCD, backlit
Screen diagonal 257 mm (10)
Resolution 640 400 points, 16 gray levels
28 lines, each of 80 characters
Refresh rate 72 Hz
Contrast adjustable

Printer connection
(only for 746.0010 version without built-in printer)
Type Parallel port for standard printers
Connector D-Sub 9-pin
Printer (only for 746.0020 version with built-in printer)

Type Thermal printer
Paper 6.2237.040 Continuous thermal paper, perforated
Single page size 209 300 mm ( format A4)
Pen travel 171 mm
Resolution 84 dpi in alphanumeric mode
160 dpi in graphics mode
Memory
Working memory EPROM
Data memory 2 MBytes SRAM, battery-backed, for all data in the
instrument (methods, determinations, configuration,
etc.)
Method memory max. 256 user methods
Determination memory max. 256 determinations (incl. method)
Data card
Type memory card following standard JEIDA ICMC 4.0 /
PCMCIA (68 pins)
Memory capacity depending on model, max. 256 methods and/or
determinations
Metrohm data card 6.2245.030 Data card storage capacity 2 MB
RS232 interfaces
Standard EIA RS232C, CCITT V.24, ISO 2110, DIN 66020
Balance connection Automatic data receipt (weight, unit, sample identifi-
cation) from balances with serial data interface
(Mettler, Mettler AT, Sartorius, Precisa, AND)
Printer connection Output of all reports and curves on an external 80-
character printer, selectable printer type (IBM, Epson,
HP), adjustable printing width
PC connection Possibility of file transfer (methods, determinations,
reports) between 746 VA Trace Analyzer and PC
Detailed description see section 8.3

8 Technical data
Remote interface
Control lines 8 input lines, 8 output lines
Detailed description see section 3.13
Connection of Dosimats/Dosinos
Type 685 Dosimat or 700 Dosino
Number 1...4
Manual operation Dispensing, filling, adjustment of feed and filling rate
Mains connection
Voltage 115 V: 100...120 V 10 %
230 V: 220...240 V 10 %
Switching with mains voltage selector
(see section 3.2.1)
Frequency 50...60 Hz
Power consumption max. 160 VA
Fuse 2 ATH, slow-blow, high breaking capacity
5 mm, length 20 mm
Safety specifications
Construction/testing According to IEC 1010 / EN 61010 / UL 3101-1,
protection class I, degree of protection IP20
Safety directions The Instructions for Use include information and
warnings which must be heeded by the user to
assure safe operation of the instrument.
Electromagnetic compatibility (EMC)

Emitted interference Standards met:
EN 55011 (class B), EN 55022 (class B),
EN 50081-1
Immunity to interference Standards met:
EN 50082-2, EN50093, IEC801-2, IEC801-3,
IEC801-4, IEC801-5, IEC801-6
Ambient temperature
Nominal operating range 0+45 C
at 2080 % atmospheric humidity
Storage, transport 25+60 C
at T 40C: max. 95% atmospheric humidity
at T = 45C: max. 70% atmospheric humidity

Diagnostic tests
Self-diagnostic test Automatic self-diagnosis when instrument switched
on
User diagnostic test Built-in diagnostic program (see section 5.4)
Housing
Material of cover Polyurethane rigid foam (PUR) with fire protection for
fire class UL94VO, FCH-free
Material of base Steel, enamelled
Dimensions
Width 400 mm
Height 175 mm (without printer); 205 mm (with printer)
Depth 508 mm
Weight 15.6 kg (incl. accessories)

8 Technical data
8.2 747 VA Stand
Brief characterisation
Measuring stand for the 746 VA Trace Analyzer with potentiostat and measuring
amplifier.
With multi-mode electrode, rotating disk electrode (RDE) as option.
Tilt-back measuring arm, integrated drip pan.
Potentiostat
Output voltage (AE) 12 V
Output current (AE) mode fast: 12 mA
mode slow: 1.5 mA
Input impedance (RE) R 51011
Input Offset Voltage (RE) 1 mV
Input Bias Current (RE) 2 pA
Noise mode fast: typ. 500 pA
mode slow: typ. 200 pA
Circuit for measurement of the noise:
82 nF 82
AE RE WE
Sweep voltage range 3V
Voltage steps 2, 4, 6, 8, 10, 12 mV
(cyclic voltammetry: 1 ... 12 mV)
Sweep rate cyclic voltammetry: 0.1 mV/s ... 100 V/s
other meas. modes: 0.2 ... 240 mV/s
Pulse amplitudes AC1, AC2: 1 ... 35 mV
DP: 100 ... 100 mV
SQW: 1 ... 50 mV
Current measurement
Minimum current Imin 2.4 pA
Maximum current Imax DC, CV: 1.5 mA
DP: 1.2 mA
SQW: 1.4 mA
AC1, AC2: 0.6 mA
Current drift Idrift 0.03 %/K
Integration times DC: 1 ... 64 ms
DP, SQW: 1 ... 32 ms
Measurement interval 0.05 ... 9.9 s

8.2 747 VA Stand
Measuring amplifier
Max. phase error 1 at 250 Hz
Resolution 24 pA
Multi-mode electrode MME (working electrode WE)

Designation 6.1246.020
Electrode types DME (dropping mercury electrode)
HMDE (hanging mercury drop electrode)
SMDE (static mercury drop electrode)
Drop surface 0.15 ... 0.60 mm2 (DME and SMDE)
Glass capillary 6.1226.030 (set of 10)
internal diameter = 0.05 mm
Mercury reservoir 6 mL 81.2 g
sufficient for ca. 200'000 Hg drops
Auxiliary power inert gas (generally nitrogen N2)
p = 1 0.2 bar
Rotating disk electrode RDE (working electrode WE, option)

Construction 6.1246.000 Drive shaft + screw-on
6.1204.XXX Electrode tip
Electrode tips 6.1204.100 Ultra trace graphite
6.1204.110 glassy carbon (GC)
6.1204.120 platinum (Pt)
6.1204.130 silver (Ag)
6.1204.140 gold (Au)
Disk diameter 2.0 +0 / 0.05 mm
Radial eccentricity 0.2 mm
Regeneration with 6.2802.000 Polishing kit
Rotational speed 200, 400, 600, ... , 3000 min1
Speed constancy 2%
Reference electrode (RE)

Construction double-junction;
6.0728.0X0 Ag/AgCl Reference system +
6.1245.010 Electrolyte vessel to be filled by user
Reference system Ag/AgCl/c(KCl) = 3 mol/L
Diaphragm ceramic diaphragm
diameter = 3 mm
Auxiliary electrode (AE)

Pt auxiliary electrode 6.0343.000 Platinum electrode
GC auxiliary electrode 6.1241.020 Electrode holder + 6.1247.000 Glassy
(option) carbon tip

8 Technical data
Stirrer
Construction 6.1246.010 Drive shaft + screw-on
6.1204.090 Stirrer tip
Material PTFE
Rotational speed 200, 400, 600, ... , 3000 min1
Speed constancy 2%
Measuring vessels
6.1415.210 standard measuring vessel made of lead-free
borosilicate glass 3.3
working volume = 10 ... 90 mL
6.1415.150 measuring vessel made of lead-free borosilicate
glass 3.3 (option)
6.1418.220 measuring vessel made of lead-free borosilicate
glass 3.3 with thermostat jacket (option)
6.1450.210 measuring vessel made of PFA (option)
Dummy Cell
Use checking the 747 VA Stand
determination of the signal/noise ratio
Connections AE auxiliary electrode
RE reference electrode
WE-L working electrode linear mode
(RC element)
WE-D working electrode differential mode
(peak/wave)
Inert gas (in general nitrogen N2)

Use operation of MME deaeration of sample solution
Required pressure p = 1 0.2 bar (this gas pressure results in a gas
flow rate of ca. 20 L/h)
Safety specifications
Construction/testing According to IEC 1010 / EN 61010 / UL 3101-1
Safety directions The Instructions for Use include information and
warnings which must be heeded by the user to
assure safe operation of the instrument.

8.2 747 VA Stand
Electromagnetic compatibility (EMC)

Immunity to interference Standards met:
IEC801-2, IEC801-3
Ambient temperature
Nominal operating range 0+45 C
at 2080 % atmospheric humidity
Storage, transport 40+70 C
at T 40C: max. 95% atmospheric humidity
Housing
Material of cover Polyurethane rigid foam (PUR) with fire protection for
fire class UL94VO, FCH-free
Material of base Steel, enamelled
Dimensions
Width 220 mm
Height 280 mm (520 mm with cover raised)
Depth 382 mm
Weight 12.1 kg (incl. accessories)

8 Technical data
8.3 RS232 interfaces
This section describes the technical data and features of the RS232
interfaces 16 and 17 of the 746 VA Trace Analyzer. You will find details
regarding attachment of instruments to these interfaces in section
3.12.
8.3.1 Features of the RS232 interfaces
The two RS232 interfaces of the 746 VA Trace Analyzer are configured as DTE
(Data Terminal Equipment) with the following technical specifications:
Standard Data interface in accordance with EIA standard RS 232C

(DIN 66020, page 1), transmission parameters can be
set on dialog page "VA TRACE ANALYZER", see section
5.3.1).
Code 8 Bit World Trade Character Set 437 (USA)
Baud rate 300, 600, 1200, 2400, 4800, 9600 (adjustable)
Handshake HWshort, HWfull, SWchar, SWline, none (details, see
section 8.3.5)
Parity even, odd, none
Stop bits 1 or 2
Data bits 7 or 8
Max. line length 80 characters + CR LF
Control characters CR Carriage Return DEC 13 HEX 0D
LF Line Feed DEC 10 HEX 0A
XON Data transmission start DEC 17 HEX 11
XOFF Data transmission stop DEC 19 HEX 13
SOH Start of Heading DEC 01 HEX 01
ETX End of text DEC 03 HEX 03
EOT End of transmission DEC 04 HEX 04
CAN Cancel DEC 24 HEX 18
Mode Full duplex (simultaneous transmission and receiving)
Restriction:
If data are first received by the interface, transmission is
not started until the receipt is at an end.
Cable For interconnection of the 746 VA Trace Analyzer with
third-party devices, only a shielded data cable may be
used (e.g. Metrohm D.104.0201). The cable shield must
be perfectly earthed at both devices (pay attention to
current loops: always use star earthing). Use only
connectors with sufficient shielding (e.g. Metrohm
K.210.0001 with K.210.9004).
Cable length max. ca. 15 m

8.3.2 Data transmission protocols
In the 746 VA Trace Analyzer, methods and determinations are stored as a file in
binary compressed form. Such binary files can be transferred via the RS232 in-
terfaces and also be read back in. The binary data are transferred with a block-
oriented protocol. The blocks, comprising 128 data bytes and 5 control characters,
have the following structure:
Block head Block number Useful data CRC CRC

1 Byte 1 Byte 128 Byte 1st Byte 2nd Byte
CRC = Cyclical Redundancy Check following CCITT V.41
The control characters SOH (any block), EOT (last block) and CAN (premature
abort) can be used a block head. For the transfer of binary files between the 746 VA
Trace Analyzer and a PC, the two Windows PC programs 6.6017.000 Metrodata
VA Back Up and 6.6016.103 Metrodata VA Database are available.
In the output of ASCII reports (e.g. Full report) to the RS232 interfaces, strings
of up to 82 ASCII characters incl. data delimiters (CR or LF) are transferred. If no
printer is attached (Printer = none), an ETX with CR/LF is sent at the end of each
such text block and an EOT with CR/LF at the end of a transfer.
In addition to the output of normal ASCII reports, the 746 VA Trace Analyzer also
offers the possibility of transferring the two special reports ActDetm and ActMeth
comprising a binary file (determination or method) and an ASCII report. The two
Windows PC programs 6.6017.000 Metrodata VA Back Up and 6.6016.103 Met-
rodata VA Database are available for the receipt and further processing of these
reports.
8.3.3 Settings and modes
The two RS232 interfaces are set as follows when first initialized:
Baud rate 9600
Data bits 8
Stop bit(s) 1
Parity none
Handshake HWshort
Receive mode off
If characters are nonetheless received in this default setting with the receive mode
switched off, these are read individually and discarded. This prevents the external
device blocking the transmission process of the 746 VA Trace Analyzer by sending
characters.
The internal mode of the RS232 interfaces is switched automatically, depending on
the type of transfer (see section 8.3.2). This concerns both the receive abort criteria
and the partition of the buffer. The following modes are possible:
Receive balance data
The buffer of the RS232 interface is divided into 82 characters for receive and
82 characters for send. The receive buffer is emptied following the delimiter
character LF. Otherwise, the RS232 parameters set on the dialog page VA
TRACE ANALYZER apply.

8 Technical data
Receive binary files

The buffer of the RS232 interface is set to 133 characters receive. The receive
buffer is emptied after the receipt of 133 characters. In this mode, a software
handshake (SWchar or SWline) is not allowed.
Send binary files

The buffer of the RS232 interface is set to 133 characters send. The receive
buffer is emptied after the receipt of every character. In this mode, a software
handshake (SWchar or SWline) is not allowed.
Send ASCII reports

The RS232C parameters set on the dialog page VA TRACE ANALYZER ap-
ply. The key remote control mode must be switched off (Remote keyboard =
off).
Send special reports ActDetm and ActMeth

The special reports comprise an ASCII report and a binary file together. The
settings and criteria described above apply to both parts.
Send contents of current field

If the <?> key is pressed in the navigation mode (see section 5.2.2), the
contents of the selected field (position of the field cursor) are put out as an
ASCII string to RS232C interface 1.
Send contents of the current screen page

If the <@> key is pressed in the navigation mode (see section 5.2.2), the
contents of the entire screen page on which the field cursor is positioned are
put out to the RS232C interface 1. Text is put out as an ASCII string, graphics
as printer code depending on the printer type selected for the RS interface
on the "VA TRACE ANALYZER" page.
8.3.4 Key remote control mode
The key code of the 746 VA Trace Analyzer can be sent to RS232 interface 1 or re-
ceived from there. This allows, e.g. remote control of the VA Trace Analyzer by a PC
by sending keystrokes or stored key entries to the VA Trace Analyzer.
The key remote control mode is switched on and off with the parameter Remote
keyboard on the dialog page VA TRACE ANALYZER as follows:
off off
send send key code
receive receive key code
(Receive mode must be set to on for this)

In the send mode Remote keyboard = send, each time a key is pressed on the 746
VA Trace Analyzer the corresponding key code is put out via RS232 interface 1 as
an ASCII character. These key codes can be stored using a suitable PC program.
In the receive mode Remote keyboard = receive, every ASCII character received
via RS232 interface 1 is interpreted as a key code and initiates the same functions
as if the appropriate key on the keypad were to be pressed. The key codes for the
special keys on the 746 VA Trace Analyzer are listed below. It is thus possible to
control all functions of the 746 VA Trace Analyzer from an external device. Even in-
dividual parameters (e.g. sample data on the dialog page SAMPLES) can be en-
tered in this manner. It is also possible to send the key code for <?> or <@> to ini-
tiate the output of the contents of a field or screen (see section 8.3.3).
Key code for special keys on the 746 VA Trace Analyzer
Alt + Key Alt + Key Alt + Key
008 <BACK SPACE> 183 <F6> 203 <INSERT>
012 <PG DN> 184 <F7> 204 <DELETE>
013 <ENTER> 185 <F8> 206 <>
032 <Space> 188 <CLEAR> 207 <HOME>
063 ? Field output 190 <START> 208 <PG UP>
064 @ Screen output 191 <PRINT SCREEN> 218 <FORM FEED>
176 <ESC> 194 <> 235 <SHIFT> <>
177 <BREAK> 195 <> 236 <SHIFT> <>
178 <F1> 196 <> 237 <SHIFT> <>
179 <F2> 197 <LINE FEED> 238 <SHIFT> <>
180 <F3> 198 <DELAY STOP> 239 <PRINT STOP>
181 <F4> 199 <ABBREV>
182 <F5> 200 <HOLD>

8 Technical data
8.3.5 Handshake
The 746 VA Trace Analyzer offers the following possibilities to set the handshake
(see section 5.3.1):
No handshake (none)
The 746 VA Trace Analyzer neither checks handshake inputs (CTS, DSR, DCD) nor
sets handshake outputs (DTR, RTS).
Reduced hardware handshake (HWshort)

746 VA Trace Analyzer as receiver:
746 External device

RTS RTS
DTR DTR
LF
RxD RxD
Time
746 VA Trace Analyzer as sender:
746 External device

Gert
DTR DTR
RTS RTS
CTS CTS
LF
TxD TxD
Time
The data flow can be interrupted by deactivating the CTS line.
Full hardware handshake (HWfull)

All handshake inputs are checked, all handshake outputs are set.
746 External device

RTS RTS
DTR DTR
LF
RxD RxD
Time

746 External device
DTR DTR
RTS RTS
DSR DSR
DCD DCD
CTS CTS
LF
TxD TxD
Time
The data flow can be interrupted by deactivation of the CTS line.
Software handshake with character stop (SWchar)

Handshake inputs are (CTS, DSR, DCD) are not checked at the 746 VA Trace Ana-
lyzer, handshake outputs (DTR, RTS) are set.
As soon as an LF is recognised, the 746 VA Trace Analyzer sends XOFF. After this
time, it can still receive 6 characters and store them temporarily.
However, the 746 VA Trace Analyzer also sends XOFF when its input buffer con-
tains 80 characters. After this time, it can still receive maximum 2 more characters
(incl. LF).
If the transmission is interrupted for 35 ms after the 746 VA Trace Analyzer has sent
XOFF, the string previously received will be processed even if no LF has been sent.
746 External device

max. 2 Gert
80 characters char. LF
RxD Data
output
35 ms
XOFF XON XOFF
Data
TxD
input
Process 400 s
string
Time

8 Technical data

746 External device
XOFF XON
Data
RxD output
LF
Data
TxD input
max. 4 Data output Data output free
characters blocked
Time
Software handshake with line stop (SWline)

Handshake inputs are (CTS, DSR, DCD) are not checked at the 746 VA Trace Ana-
lyzer, handshake outputs (DTR, RTS) are set.
The 746 VA Trace Analyzer has an input buffer which can accept a string of up to 80
characters + CR LF. As soon as an LF is recognized, the 746 VA Trace Analyzer
sends XOFF. After this time, it can still receive max. 6 characters and store them
temporarily. The string sent previously is now processed by the 746 VA Trace Ana-
lyzer. It then sends XON and is again ready to receive.

746 746 input External device
blocked Gert
LF LF
Data
RxD output
XOFF XON
Data
TxD input
400 s Process string
Time
746 External device
XOFF Inquiry LF XON
Data
RxD output
1st line LF Response LF

Data
TxD input
Data output of 746 Data output of
blocked 746 free
Time
The transmission of the 746 VA Trace Analyzer can be stopped by the external de-
vice with XOFF. After the receipt of XOFF, the VA Trace Analyzer finishes transmis-
sion of the line already started. If the data output is blocked for more than 10 s by
XOFF, the error message RS IFC.# - ERROR 11 appears in the display.

8.3.6 Pin assignment
RS232C interface external
Transmitted Data (TxD) Fehler! Keine gltige Verknpfung.

If no data transmission takes place, the line is maintained in
the ON condition. Data are sent only when CTS and DSR are
in the ON condition and DCD is in the OFF condition.
Received Data (RxD)

Data are received only when DCD is ON.
Request to Send (RTS)

ON condition: 746 VA Trace Analyzer is ready to send data.
Clear to Send (CTS)

ON condition: Remote station is ready to receive data.
Data Set Ready (DSR)

ON condition: The transmission line is connected.
Signal Ground (GND)
Data Carrier Detect (DCD)

ON condition: The received signal level is within the tolerance
range (remote station is ready to send data).
Data Terminal Ready (DTR)

ON condition: 746 VA Trace Analyzer is ready to receive data.
Protective earth Contact arrangement at the sockets

Direct connection from cable connector to protective earth of "RS 232 Interface 1" and "RS Interface 2"
the device. (male)
Polarity assignment of the signals 1 13
Data lines (TxD, RxD)
Voltage negative (<3 V): signal status ONE
Voltage positive (>+3 V): signal status ZERO
Control or message lines (CTS, DSR, DCD, RTS, DTR)
Voltage negative (<3 V): OFF status 14 25
Voltage positive (>+3 V): ON status
Connection cables to external devices must
In the transition region from +3 V to 3 V, the signal status is have an appropriate 25-pin connector (female).
undefined. Metrohm offers connector sockets (K.210.9004)
Driver 14C88 acc. to EIA RS 232C specification and the associated housing (K.210.0001) as an
option for the preparation of such cables.
Receiver 14C89 acc. to EIA RS 232C specification
No liability whatsoever will be accepted for damage arising from the improper connection of devices.

8 Technical data

9 Scope of delivery,
Options, Warranty
Subject to changes !
All dimensions are given in mm.
The 2.746.0010 VA Trace Analyzer without internal printer includes the following ac-
cessories:
Quant. Order No. Description
1 6.2122.0X0 Mains cable

to customer's specifications:
Cable socket Cable plug
Type IEC 320/C 13 Type SEV 12 (CH) ............................ 6.2122.020
Type IEC 320/C 13 Type CEE (7), VII (D) ........................ 6.2122.040
Type CEE (22), V Type NEMA 5-15 (USA) ................... 6.2122.070
1 6.2135.000 EBUS cable 200
Connecting cable 746 VA Trace

Analyzer 747 VA Stand
1 6.2245.030 Data card

Memory card with 2 MB capacity, in
accordance with standard JEIDA- 54
ICMC-V4.0
Supplied with separate battery;
Battery lifetime ca. 5 years
86
1 6.2723.280 Dust cover

for 746 VA Trace Analyzer
1 6.6017.000 Metrodata VA Back Up

PC program (Windows 3.1) for storage and backup of methods
and determinations, incl. 8.693.8007 Instructions for use in
English and German.
1 8.746.1053 Instructions for Use (English)

for 746 VA Trace Analyzer and 747 VA Stand

9 Scope of delivery, Options, Warranty
The 2.746.0020 VA Trace Analyzer with internal printer includes the following ac-
cessories:
1 6.2122.0X0 Mains cable

to customer's specifications:
Cable socket Cable plug
Type IEC 320/C 13 Type SEV 12 (CH)............................ 6.2122.020
Type IEC 320/C 13 Type CEE (7), VII (D)........................ 6.2122.040
Type CEE (22), V Type NEMA 5-15 (USA) ................... 6.2122.070
1 6.2135.000 EBUS cable 200
Connecting cable 746 VA Trace

Analyzer 747 VA Stand
1 6.2237.040 Thermal paper 60
Roll of app. 40 m (ca. 130 A4 12
pages)
210
1 6.2241.020 Paper spindle

Axis for 6.2237.040
thermal paper
215.5
1 6.2245.030 Data card

Memory card with 2 MB capacity, in
accordance with standard JEIDA- 54
ICMC-V4.0
Supplied with separate battery;
Battery lifetime ca. 5 years
86
1 6.2723.280 Dust cover

for 746 VA Trace Analyzer
1 6.6017.000 Metrodata VA Back Up

PC program (Windows 3.1) for storage and backup of methods
and determinations, incl. 8.693.8007 Instructions for use in
English and German.
1 8.746.1053 Instructions for Use (English)

for 746 VA Trace Analyzer and 747 VA Stand

9.3 747.0010 VA Stand
9.3 747.0010 VA Stand
The 2.747.0010 VA Stand is suited for manual operation as well as for operation
with the 695 Autosampler and includes the following accessories:
1 6.0343.000 Pt Auxiliary electrode
116
11
1 6.0728.020 Ag/AgCl reference system 11
with ceramic diaphragm

Ag/AgCl/c(KCl) = 3 mol/L
Together with the 6.1245.010 Electrolyte
vessel forms a complete reference
electrode (double-junction construction,
assembly, see section 3.6.2). 116
The Ag/AgCl reference system is

supplied with a screwed-on holder filled
with c(KCl) = 3 mol/L.
1 6.1204.090 Stirrer tip (PTFE)

7 M3
Together with the 6.1246.010
Drive shaft forms the stirrer.
58
1 6.1226.030 Glass capillaries 116

for 6.1246.020 Multi-mode
electrode
Set of 10 incl. two 4.420.2800
sealing rings
1 6.1244.020 Drive belt

made of EPDM (ethylene
propylene rubber), set of 3
Connection motor drive shaft
(6.1246.010 or 6.1246.000)


15
1 6.1245.010 Electrolyte vessel
B-NS
Together with the 6.0728.020 14/15
Ag/AgCl reference system forms a
complete reference electrode
(double-junction construction, 82
assembly, see section 3.6.2).
1 6.1246.010 Drive shaft

for stirrer incl. 2 O-rings FPM
(Viton)
Together with the 6.1204.090 stirrer 46
tip forms a complete stirrer.
14
1 6.1246.020 Multi-mode electrode

incl. 2 O-rings NBR (nitril rubber)
Together with the 6.1226.030 glass 78
capillary forms a complete working
electrode.
70
1 6.1247.020 Sealing needle

for 6.1246.020 Multi-mode
electrode
Set of 3 44
78
1 6.1415.210 Measuring vessel
clear glass
Volume: 10 ... 90 mL
80
23
7 6.1446.040 Dummy stopper

made of PVDF, with M6 thread 4.9
For closing the unused open-

ings in the measuring vessel
upper half
21.5

9.3 747.0010 VA Stand
1 6.1801.080 PVC tubing

for supply of the inert gas 4 7
Length L = 4 m
4 6.1808.000 Tubing coupling

made of ETFE, with 2 M6 threads M6 10
For the connection of 2 lengths of

tubing with thread M6 (e.g. 25
6.1805.XXX)
1 6.1817.000 Filling tubing, made of PVC

incl. 4.420.2860 Filling cone and
6.1809.000 Tubing coupling
520
For filling the MME with mercury.
1 6.1824.000 4-way microtip

made of PTFE
With 4 lengths of PTFE tubing with 700
connection nipples with thread M6
for the attachment of 4 685 Dosi-
mats/700 Dosinos.
100
1 6.2301.100 Lead standard solution

2+
(Pb ) = 1.000 0.003 g/L
plastic bottle, volume V = 50 mL
To perform the test methods.
1 6.2308.020 KCl electrolyte solution

c(KCl) = 3 mol/L plastic bottle,
volume V = 250 mL
For 6.0728.020/6.1245.010
Ag/AgCl reference electrode
1 6.2406.000 Mercury drop catcher

silver wire in plastic bottle
For the destruction of mercury 100
32
drops by amalgamation
1 6.2615.030 Electrode holder

52
For filling and storing the
6.1246.020 Multi-mode electrode
80

1 6.2703.000 Stand ring made of PVC

To hold the 6.1415.210 meas- 63
uring vessel outside the 747 VA
Stand
50 53.2
1 6.2709.050 Stopper
made of PCTFE, incl. E.301.0004
O-ring of NBR (nitril rubber)
For closing the stirrer aperture of
the 747 VA Stand
36
18
1 6.2709.080 Stopper
For closing the pipetting
aperture of the 747 VA Stand
76
1 6.2711.030 Drip pan 60

made of PS (polystyrol)
For filling the Multi-mode
electrode with mercury
210
290
1 6.2711.050 Drip pan 40

made of PS (polystyrol)
To be inserted in the 747 VA
Stand
150
200
1 6.2723.230 Dust cover

for 747 VA Stand

9.3 747.0010 VA Stand
1 6.2730.030 Stopper
with nipple and O-ring
For closing the opening of the
747 VA Stand when the
38
6.1824.000 4-way microtip is
not used
1 6.2739.000 Spanner
for screwing down plastic
nipples
8 10
68
1 6.2816.020 Syringe
made of PP, with Luer connection
Volume V = 10 mL
For filling the MME
102
0.8
1 6.2816.030 Needle
for 6.2816.020 syringe
80

9.4 Options for 747 VA Stand
Order No. Description
6.0728.010 Ag/AgCl reference system 11

Together with the 6.1245.010 Electrolyte
vessel forms a complete reference
electrode (double-junction construction,
assembly, see section 3.6.2).
The Ag/AgCl reference system is 116
supplied with an empty holder screwed

on; the holder can be filled with the
desired reference electrolyte.
6.1204.XXX Electrode tip

Together with the 6.1246.000 Drive shaft forms the M3
rotating disk electrode (RDE). The following electrode

tips are available:
Order No. Disk material Shaft material
6.1204.100 Ultra Trace Graphite PVC
6.1204.110 Glassy Carbon (GC) PEEK
52.5
6.1204.120 Pt PEEK
6.1204.130 Ag PEEK
6.1204.140 Au PEEK
Disk diameter: 2.0 +0 / 0.05 mm
Concentricity error: 0.2 mm
7
6.1241.020 Electrode holder

to take the 6.1247.000 glassy carbon rod
Together with the 6.1247.000 glassy carbon rod
forms the GC auxiliary electrode.
65
2.1
6.1246.000 Drive shaft for rotating disk electrode
incl. 2 O-rings FPM (Viton)
Together with the 6.1204.XXX electrode
tips forms the rotating disk electrode
(RDE). 46
14

9.4 Options for 747 VA Stand
6.1247.000 Glassy carbon tip 65

2
Together with the 6.1241.020
electrode holder forms the GC
auxiliary electrode.
6.1415.150 Measuring vessel 78
clear glass
Volume: 5 ... 70 mL
80
23
78
6.1418.220 Measuring vessel
clear glass, with thermostatic jacket;
incl. 6.2036.000 holding ring
82
30
78
Made of PFA (polyfluoralkyloxy-
copolymer), incl. 2036.000 holding
ring
80
23
78
clear glass
For operation with the 695 Autosam- 80
pler or with Rinsing Dosinos
35
78
clear glass, with thermostatic jacket
80
For operation with the 695 Autosam-
pler or with Rinsing Dosinos
35

6.1807.000 Y-Connection 19
for 6.1801.080 PVC tubing

5.7
For inert gas supply of two 747 VA
Stands.
16
6.2709.040 Stopper
made of PVC, incl. 2 E.301.0004 O-rings of
NBR (nitril rubber)
For closing the MME opening when the RDE
is used; with two dummy holes (thread M6)
for holding the two MME gas lines not used
68
in operation with the RDE.
6.2802.000 Polishing kit

for mechanical regeneration of the active surface of 6.1204.XXX
electrode tips
comprising: 1 2 g -Al2O3 (0.3 m)
1 polishing cloth
53
6.2827.000 Trimming tool
for regeneration of the 6.1204.100 Ultra Trace
Graphite electrode
49
6.5323.000 Rinsing equipment

For automatic rinsing of the measuring vessel at the 747 VA Stand by
means of two 700 Dosinos with 50 mL Dosing units.
incl. the following accessories:
1 6.1456.210 Measuring vessel
2 6.1567.250 50 mL Dosing Unit
2 6.1618.050 Thread adapter 40 mm/GL45
2 6.1621.000 PE Container, V = 10 L
1 6.1805.100 FEP Tubing, L = 40 cm
4 6.1805.120 FEP Tubing, L = 100 cm
1 6.1805.180 FEP Tubing, L = 16 cm
3 6.1808.000 Tubing coupling, with 2 M6 threads
2 6.1819.010 PTFE Tube, L = 86 mm
2 6.1829.020 Aspiration tube, L = 50 cm
The two 700 Dosinos needed for rinsing must be ordered separately
(see section 9.5).
6.5611.010 Pipetting equipment

For easy pipetting functions with the 685 Dosimat or 700 Dosino.
incl. the following accessories:
1 6.1562.040 Pipetting handle; incl. 6.1562.050 pipetting tubing
1 6.1829.020 Aspiration tube, L = 50 cm
1 6.2052.010 Pipetting handle holder
1 6.2754.000 Rinsing quiver
The 685 Dosimat or 700 Dosino needed for pipetting must be ordered separately
(see section 9.5).

9.5 Optional peripherals, cables and software
2.685.0010 685 Dosimat

Dispenser for 746 VA Trace Analyzer and 747 VA Stand
The 6.2134.000 Connecting cable for attachment to 746 VA Trace Analyzer must
be ordered separately.
6.3014.XXX Exchange unit

with standard reagent bottle of brown glass, rectangular, volume V = 1 L, with
GL 45 ISO/DIN glass thread; burette cylinder of clear glass with light protector;
PCTFE/PTFE flat stopcock
2.700.0010 700 Dosino

Dispenser for 746 VA Trace Analyzer and 747 VA Stand
with integral connecting cable for attachment to 746 VA Trace Analyzer
6.3030.XXX Dosing unit

incl. accessories, with GL 45 ISO/DIN glass thread; with ETFE burette cylinder
2.695.0010 695 Autosampler

X,Y,Z Autosampler for fully automatic routine polarographic analysis with the VA
Trace Analyzer and 747 VA Stand. Processing of up to 80 samples. Automatic
addition of standard solutions, electrolytes and auxiliary solutions by 2 built-in
dosing systems. Minimal risk of contamination thanks to surface sensor. With an
extensive range of accessories.
To empty and rinse the measuring vessel, two 2.700.0010 Dosinos and two
6.1567.250 Dosing Units must also be ordered.
6.2125.010 Cable
for the attachment of an IBM PC or
compatible computer with 9-pin RS232
connector to the RS232 interface of the 9 p neg.
746 VA Trace Analyzer (the 6.2125.060 25 p pos.
Cable is also needed) 300
6.2125.020 Cable
for the attachment of Mettler balances
(Option 011, 012) or AND balances to
the RS232 interface of the 746 VA Trace
Analyzer 25 p pos. 25 p neg.
3m

6.2125.030 Socket-outlet adapter

for the simultaneous attachment of a
printer and a balance to the RS232 57
interface of the 746 VA Trace Analyzer
42
6.2125.040 Cable
for the attachment of printers with 6-pin
circular connector (e.g. EPSON EX-800,
EPSON LQ) to the RS232 interface of the
746 VA Trace Analyzer 25 p neg.
2m
6.2125.050 Cable
for the attachment of printers with 25-pin
RS232 connector (e.g. IBM Proprinter,
EPSON LX/FX, HP printers) to the RS232
interface of the 746 VA Trace Analyzer 25 p neg. 25 p pos.
2m
6.2125.060 Cable
Cable for the attachment of an IBM PC
or compatible computer with 25-pin
RS232 connector to the RS232 interface
of the 746 VA Trace Analyzer 25 p neg. 25 p neg.
3m
6.2125.070 Cable
for the attachment of Sartorius MP8/MC1
balances to the RS232 interface of the
25 p pos. 25 p neg.
2m
6.2125.080 Cable
for the attachment of Precisa balances
to the RS232 interface of the 746 VA
Trace Analyzer
25 p pos. 25 p neg.
2m
6.2134.000 Cable
for the attachment of 685 Dosimats to
the 746 VA Trace Analyzer
9 p pos. 9 p neg.
2m
6.2143.100 Cable 3m
for the attachment of a 708 Sampling
Unit to the 746 VA Trace Analyzer
25 p pos.

3m
6.2143.110 Cable
for the attachment of two 708 Sampling
Units to the 746 VA Trace Analyzer
25 p pos.
3m
6.2143.120 Cable
for the attachment of a 708 Sampling
Unit and up to four 683 Pump Units to
the 746 VA Trace Analyzer
25 p pos.
6.6016.113 Metrodata VA Database 2.1

PC program (Windows) for the storage and backup of methods, determina-
tions and sample data of the 746 VA Trace Analyzer. Special report generator
with filter functions.
Curves and results can be viewed on the screen. Preparation for the export of
data to LIMS (PE, VG). Dialog and instructions for use in English

9.6 Warranty
The warranty on our products is limited to defects that are traceable to material,
construction or manufacturing error which occur within 12 months from the day of
delivery. In this case, the defects will be rectified in our workshops free of charge.
Transport costs are to be paid by the customer.
For day and night operation, the warranty is limited to 6 months.
Glass breakage in the case of electrodes or other parts is not covered by the war-
ranty. Checks which are not a result of material or manufacturing faults are also
charged during the warranty period. For parts of outside manufacture insofar as
these constitute an appreciable part of our instrument, the warranty stipulations of
the manufacturer in question apply.
With the regard to the guarantee of accuracy, the technical specifications in the in-
struction manual are authoritative.
Concerning defects in material, construction or design as well as the absence of
guaranteed features, the orderer has no rights or claims except those mentioned
above.
If damage of the packaging is evident on receipt of a consignment or if the goods
show signs of transport damage after unpacking, the carrier must be informed im-
mediately and a written damage report demanded. lack of an official damage report
releases Metrohm from any liability to pay compensation.
If any instruments and parts have to be returned, the original packaging should be
used if at all possible. This applies above all to instruments, electrodes, burette
cylinders and PTFE pistons. Before embedment in wood shavings or similar mate-
rial, the parts must be packed in a dustproof package (for instruments, use of a
plastic bag is imperative). If open assemblies are enclosed in the scope of delivery
that are sensitive to electromagnetic voltages (e.g. data interfaces etc.) these must
be returned in the associated original protective packaging (e.g. conductive protec-
tive bag). (Exception: assemblies with built-in voltage source belong in a non-
conductive protective packaging). For damage which arises as a result of non-
compliance with these instructions, no warranty responsibility whatsoever will be
accepted by Metrohm.

9.7 EU Declaration of conformity
9.7 EU Declaration of conformity
EU Declaration of Conformity
The METROHM AG company, Herisau, Switzerland hereby certifies, that the in-
strument:

meets the requirements of EC Directives 89/336/EWG and 73/23/EWG.
Source of the specifications:

EN 50081-1 Electromagnetic compatibility, basic specification
Emitted Interference
Interference Immunity
EN 61010 Safety requirements for electrical equipment for measure-
ment, control and laboratory use
Description of the instrument:

Measuring instrument for polarographic and voltammetric trace analysis of
organic and inorganic substances.
Herisau, January 20, 1997
Dr. J. Frank Ch. Buchmann
Development Manager Production and

Quality Assurance Manager

EU Declaration of Conformity
The METROHM AG company, Herisau, Switzerland hereby certifies, that the in-
strument:
747 VA Stand
meets the requirements of EC Directives 89/336/EWG and 73/23/EWG.
Source of the specifications:

Interference Immunity
EN 61010 Safety requirements for electrical equipment for measure-
ment, control and laboratory use
Description of the instrument:

Wet-chemical working station with electrode system for voltammetric
analysis with the 746 VA Trace Analyzer.


9.8 Certificate of conformity and system validation
9.8 Certificate of conformity and

system validation
Certificate of Conformity and System Validation

This is to certify the conformity to the standard specifications for electrical appli-
ances and accessories, as well as to the standard specifications for security and
to system validation issued by the manufacturing company.
Name of commodity: 746 VA Trace Analyzer

System software: Stored in ROMs
Name of manufacturer: Metrohm Ltd., Herisau, Switzerland
Principal technical information: Voltages: 100120, 220240 V
Frequency: 5060 Hz
This Metrohm instrument has been built and has undergone final type testing
according to the standards:
IEC801-2/IEC1000-4-2 (level 3), IEC801-3 (level 2), IEC801-4/IEC1000-4-4

(level 4), IEC 801-5/IEC1000-4-5 (level 2/3), IEC801-6/IEC1000-4-6 (level 3),
EN55011 (class B), EN55022 (class B), EN50081-1, EN50082-2 03.95,
EN50093/IEC1000-4-11 Electromagnetic compatibility
IEC1010/EN61010/UL3101-1 Security specifications
It has also been certified by the Swiss Electrotechnical Association (SEV), which
is member of the International Certification Body (CB/IEC).
The technical specifications are documented in the instruction manual.
The system software, stored in Read Only Memories (ROMs) has been validated
in connection with standard operating procedures in respect to functionality and
performance. The features of the system software are documented in the instruc-
tion manual.
Metrohm Ltd. is holder of the SQS-certificate of the quality system ISO 9001 for
quality assurance in design/development, production, installation and servicing.


Certificate of Conformity and System Validation

This is to certify the conformity to the standard specifications for electrical appli-
ances and accessories, as well as to the standard specifications for security and
to system validation issued by the manufacturing company.
Name of commodity: 747 VA Stand

Name of manufacturer: Metrohm Ltd., Herisau, Switzerland
Principal technical information: Voltages: 5 V DC, 24 V DC
This Metrohm instrument has been built and has undergone final type testing
according to the standards:
IEC801-2/IEC1000-4-2 (level 3), IEC801-3/IEC1000-4-3 (level 2),

EN50082-1 Electromagnetic compatibility
IEC1010/EN61010/UL3101-1 Security specifications
The technical specifications are documented in the instruction manual.
Metrohm Ltd. is holder of the SQS-certificate of the quality system ISO 9001 for
quality assurance in design/development, production, installation and servicing.


10 Index
10 Index
! ................................................................ 5-123,5-126,5-175 Address numbers ............................................................. 5-18
(ADD......................................................................5-178,5-190 Adopt measured value.................................................... 5-116
(BACKGND.............................................................5-179,5-197 Adopt position................................................................... 5-35
(CAL......................................................................5-178,5-201 Adsorptive stripping voltammetry .....5-231,5-240,5-242,5-292
(CASE ...................................................................5-179,5-205 A-Fullreport ................................................... 5-169,5-169
(CSWEEP...............................................................5-179,5-219 Ag electrode tip (6.1204.130) ..................................... 3-27,9-8
(PREP ...................................................................5-179,5-254 Ag/AgCl filling 126
(REP......................................................................5-178,5-273 Figure............................................................................ 3-29
(VAR......................................................................5-178,5-305 Ag/AgCl reference system .................... see Reference system
@..@........................................................... 5-123,5-126,5-175 Alphabetical instruction list ............................................. 5-183
>PREP ...................................................................5-179,5-257 Alphabetical list of error messages .................................... 7-7
0/linear.......................................................................5-149 Alphanumeric keys ............................................................. 5-3
0/nonlin.......................................................................5-149 Alternating current voltammetry .................... 5-184,5-187,7-34
MEAS ...................................................................5-178,5-248 Alternative results.................................................. 5-161,5-206
PURGE .................................................................5-179,5-265 Ambient temperature .................................................... 8-4,8-9
STIR ...................................................................5-180,5-298 A-Meth.spec ..................................................... 5-169,5-169
4-way microtip .......................................................see Microtip Analyte .............................................................................. 6-31
665 Dosimat .................................................. see Dosimat 665 analyte .............................................................. 5-155,5-158
685 Dosimat .................................................. see Dosimat 685 Application Bulletins ........................................................... 1-4
695 Autosampler .................................... see Autosampler 695 Application Notes................................................................ 1-6
<695 Autosampler>.....................................................5-23 Application of a voltage .................................................. 5-303
700 Dosino ...................................................... see Dosino 700 approx.peak ......................................................... 5-132,6-9
708 Sampling Unit................................see Sampling Unit 708 approx.peak<thresh.................................................. 5-89
717 Sample Changer ...................... see Sample Changer 717 Approximated peak height................................................ 5-89
<717 Smpl Changer> ..................................................5-23 Arrangement of the instruments ......................................... 3-1
725 Dosimat .................................................. see Dosimat 725 ASCII characters ............................................................... 5-13
746 VA Trace Analyzer ................... see VA Trace Analyzer 746 ASCII reports............................................................. 8-11,8-12
747 VA Stand................................................ see VA Stand 747 A-Sweeps (smooth) ........................................ 5-169,5-169
Atmospheric humidity ................................................... 8-4,8-9
Au electrode tip (6.1204.140) ..................................... 3-27,9-8
A aU.max............................................................................... 6-9
aU.min............................................................................... 6-9
A>M........................................................................5-181,5-196 aU.peak .................................................................. 5-132,6-9
A-Baselines ......................................................5-169,5-169 aU.width ................................................................ 5-132,6-9
<ABBREV> ........................................................................5-8 aU/2 ............................................................................... 5-131
Abbreviate current instruction..............................................5-8 Audio signal ............................................................ 5-17,5-200
Absolute error ....................................................................5-83 Auto error printing.............................................. 5-167
AC1MODE...................................................... 5-177,5-184,7-34 Auto form feed......................................................... 5-167
AC2 abs................................................................5-138,6-17 Auto.batch............................................................ 5-75,5-78
AC2 curves ......................................................................5-100 Auto.samples ....................................................... 5-75,5-78
AC2 rel................................................................5-137,6-17 Autoincrement ............................................................. 5-61
AC2MODE.............................................. 5-177,5-187,6-17,7-34 Automatic Address 3................................................ 5-22
A-Calibrations ...............................................5-169,5-169 Automatic call-up of a method.................................. 5-63,5-80
Accessories for rinsing and siphoning off .........................3-10 Automatic determination start........................................... 5-77
ActDetm...........................................................................8-11 Automatic error printing .................................................. 5-167
Activate base point shift ..................................................5-107 Automatic page advance................................................ 5-167
Activate single measurements ..........................................5-84 Automatic scaling ................................................. 5-134,5-135
ActMeth...........................................................................8-11 Automatic series determination ........................................ 5-75
ADD)n ...................................................................5-178,5-191 Automatic spike elimination ................................................ 6-7
Add.mass.........................................................................5-86 Automatic storage of determinations................................ 5-77
ADD/M ...................................................................5-181,5-192 Automatic transfer of sample data.................................... 5-75
ADD>M ...................................................................5-181,5-194 Autosampler 695
Addition ...........................................................................5-164 Manual operation .......................................................... 5-27
Addition of sample ..........................................................5-180 Ordering designation .................................................... 9-11
Addition volume...............................................................5-311 Auxiliary electrode 60
Addition volume of calibration solutions................5-151,5-157 Construction.................................................................. 3-31
Electrical connection..................................................... 3-31
Additions ....................................................................5-145 Figure.............................................................. 2-9,3-28,3-32
Address...........................................................................5-18 Insertion in measuring head ................................... 3-8,3-31

10 Index
Installation......................................................................3-31
Startup procedure .........................................................3-31
Technical data .................................................................8-7
C
C ................................................................5-123,5-126,5-175
Auxiliary function keys .................................................. 5-2,5-9
C.end dilution........................................................... 5-42
Auxiliary parameters ....................... 5-123,5-126,5-175
C.init std.................................................................... 5-42
Auxiliary solutions .............................. 5-43,5-226,5-227,5-228,
...................................................... 5-252,5-277,5-278,5-279 Cable (3.496.5190) ............................................... 5-285,5-286
Auxiliary vessel (AUX) ....................... 5-196,5-226,5-237,5-277 Cable (6.2125.010) ........................................................... 9-11
Available...................................................... 5-49,5-54,5-58 Cable (6.2125.020) ........................................................... 9-11
Axis scaling........................................ 5-98,5-103,5-111,5-112, Cable (6.2125.040) ........................................................... 9-12
................................................................ 5-118,5-120,5-125 Cable (6.2125.050) ........................................................... 9-12
Axis scaling for plot of calibration curve............... 5-151,5-156 Cable (6.2125.060) ........................................................... 9-12
Axis scaling for plot of standard addition curve ..............5-146 Cable (6.2125.070) ........................................................... 9-12
Cable (6.2125.080) ........................................................... 9-12
Cable (6.2134.000)
B Connection of Dosimats ............................................... 3-33

Ordering designation .................................................... 9-12
<BACK SPACE> ..............................................................5-10 Cable (6.2143.100) ........................................................... 9-12
BACKGDN ...........................................................................7-47 Cable (6.2143.110) ........................................................... 9-13
BACKGND)............................................................ 5-179,5-199 Cable (6.2143.120) ........................................................... 9-13
backgnd .............................................................. 5-112,5-112 Cables............................................................................... 9-11
Background compensation ..........5-179,5-197,5-199,6-7,7-47 CAL)n................................................................... 5-178,5-204
bad U.peak interp....................................................5-90 cal.crv. .............................................................. 5-92,5-147
Balance Cal.dev. ........................................................5-86,6-29,6-34
Connection to RS232 interface......................................3-55 Calc.f. ........................................................................ 5-206
Data receipt display.......................................................5-61 <Calcul.> .............................................................. 5-84,5-91
Receive balance data ....................................................8-11
Selection of balance type ..............................................5-19 Calculation formulae ............................................. 5-160,5-161
Switch data input on/off.................................................5-60 Calculation of mass concentration ...........6-25,6-26,6-29,6-33
Balance input..............................................................5-61 Calculation of result scatter .............................................. 6-36
<Balance on/off> .......................................................5-60 Calculation of total scatter ................................6-26,6-29,6-34
Balance type................................................................5-19 "CALCULATION" ....................................................... 5-160,6-3
Base point .................................................... 5-101,5-139,6-12 <CALCULATION> ......................................................... 5-160
Base point shift................................................................5-107 Calculations ............................................................... 5-82
basel.type error .......................................................5-90 <Calibr.> ......................................................5-82,5-84,5-97
Baseline.......................................................................5-136 calibr............................................................................. 5-99
Baseline calculation.................................................... 6-11,8-2 Calibration
Baseline parameters............................. 5-98,5-106,5-136,6-11 Calibration technique .................................................. 5-141
Content calculation ....................................................... 6-20
Baseline range........................................................ 5-138,6-11 Display of calibration curve........................................... 5-97
Baseline type .......................................................... 5-136,6-11 Result calculation.......................................................... 6-22
Baselines for AC2 curves ..................................................6-17 Run mode ..................................................................... 5-74
Baselines for peaks ...........................................................6-14 calibration......................... 5-74,5-142,5-147,5-153,5-158
Baselines for PSA curves ..................................................6-18 Calibration curve
Baselines for waves...........................................................6-13 Calibration technique .................................................. 5-147
Curve type................................................................... 5-149
Basic method for DP polarography...................................4-56
Display .......................................................................... 5-97
Basic method for DPASV...................................................4-61 Illustrative method ......................................................... 4-29
Baud rate.............................................................. 5-18,8-11 Model functions ............................................................ 6-22
BEEP..................................................................... 5-182,5-200 Procedure ..................................................................... 6-27
Program instructions.......... 5-201,5-204,5-213,5-215,5-217
Beeper .............................................................................5-17
Programming .................................................... 5-148,5-148
Begin of x axis for plot of calibration curve........... 5-151,5-156 Result display................................................................ 5-92
B-File ................................................................ 5-169,5-169 Calibration technique ............... 5-92,5-141,5-142,5-147,5-153
Binary file .............................................. 5-169,5-169,8-11,8-12 Calibrations ............................................................... 5-91
Blank values ..........................5-143,5-143,5-149,5-149,5-155, Call-up of a segment ...................................................... 5-280
..........................................5-155,5-197,6-27,6-31,6-35,7-34
Cancel selection ...............................................5-48,5-52,5-57
Brackets...........................................................................5-164
Capacity ........................................................................ 5-58
Branching ........................................................................5-179
Capillary ......................................................see Glass capillary
<BREAK>...........................................................................5-7
Caps lock key ..................................................................... 5-3
Bridging electrolyte................................................... 3-30,7-43
Carbon electrodes .......................................................... 5-212
Buffer .................................................................................7-33
CASE ..................................................................... 5-179,5-210
Burette volume...................................................................5-40
CASE)................................................................... 5-179,5-211
BUSY........................................................... 5-7,5-11,5-37,5-72
Caution................................................................................ 1-3
BUSY (BREAK)................................................. 5-7,5-11,5-73
Certificate of conformity and system validation ................ 9-17
BUSY (DSTOP)................................................. 5-7,5-11,5-73
<Change Autoinc.> .................................................... 5-60
BUSY (HOLD) ................................................... 5-8,5-11,5-73
<Change display> ......................................5-48,5-52,5-57
<Change full cd.> .................................................... 5-53

10 Index
Changing capillary ............................................................3-24 Connection of 700 Dosinos .............................................. 3-41

Changing Dosing unit........................................................3-45 Connection of a balance................................................... 3-55
Changing Exchange unit ...................................................3-37 Connection of a PC........................................................... 3-53
Character fields .................................................................5-13 Connection of a printer ..................................................... 3-54
Character keys ..............................................................5-2,5-3 Connection of siphoning Dosino ...................................... 3-47
Character set.....................................................................5-13 const.................................................................. 5-205,5-235
Characteristic voltage......................................................5-131 Constants..........................................5-163,5-163,5-205,5-235
<Check method> ...........................................................5-71 <(CONT)> ......................................................................... 5-7
Check of instruments ..........................................................3-1 Contact pin 102
<Check samples> .........................................................5-60 Figure............................................................................ 3-15
<Check soln.s> ...........................................................5-43 Contamination........................................................... 7-33,7-34
Check solutions.................................................................5-43 Content .......................................................... 5-49,5-54,5-58
Checking 747 VA Stand ....................................................7-58 Content calculation ..................................................... 6-20,8-2
Checking control lines .......................................................7-52 Content information for determination .............................. 5-54
Checking RS232 interfaces ...............................................7-52 Content information for file................................................ 5-58
Checking the keypad.........................................................7-53 Contrast ........................................................................ 5-18
Checking the VA Stand .....................................................7-54 <Contrast down>......................................................... 5-17
Checking thermal printer ...................................................7-50 <Contrast up> ............................................................. 5-16
Chemicals .........................................................................7-33 Control Lines 23
Check............................................................................ 7-52
Clean transfer tubing .........................................................5-28
Connection of devices .................................................. 3-56
Cleaning the MME.............................................................3-25 Figure........................................................................ 2-3,2-5
<CLEAR>.................................................................5-10,5-12 Manual settings............................................................. 5-19
Clear field contents....................................................5-10,5-12 Pin assignement ........................................................... 3-57
Code......................................................................5-276,5-283 Status............................................................................ 3-57
Technical data ................................................................ 8-4
Code for output control lines ...........................................5-283
Conversions of standard formulae ................................. 5-165
Coefficients......................................... 5-145,5-151,5-157
COPY ............................................................................... 5-167
Collecting mercury ..............................................................7-3
Copy determinations......................................................... 5-52
Commands for 708 Sampling Unit....................................5-16
Copy files .......................................................................... 5-56
Comment.............................................................................1-3
<Copy from RS Ifc.1> ............................................. 5-60
Comment...............................................................5-173,5-174
<Copy from> ................................................. 5-48,5-52,5-56
<Comment> ....................................................................5-166
<Copy line> ................................................................. 5-60
Comment on common variable.........................................5-67
Copy methods .................................................................. 5-48
Comment on method ......................................................5-173
<Copy prev.> ............................................................... 5-32
Comment report ....................................................5-169,5-169
Copy previous line .................................................... 5-32,5-60
Comments line ................................................................5-272
Copy rack data to data card............................................. 5-33
Comments........................................................ 5-83,5-87,5-89
Copy sample data ............................................................ 5-60
Common variable ..................... 5-66,5-161,5-162,5-205,5-235
<Copy to Data Cd.>.......................................... 5-33,5-60
"COMMON VARIABLES"..............................................5-66,6-5
<Copy to RS Ifc.1>.................................................. 5-60
<COMMON VARIABLES> ...............................................5-66
<Copy to>...................................................... 5-48,5-52,5-56
Common variables in working memory.............................5-66
Covariances ...................................................................... 6-23
Comparison code for test................................................5-276
Cover 24 of measuring head arm
Complex formation ............................................................7-46 Figure.............................................................................. 2-6
conc. out of range ..................................................5-87 crit. front ovlp. .................................... 5-90,6-13,7-47
<Cond. tube>................................................................5-28 crit. rear ovlp. ...................................... 5-90,6-13,7-47
CONDC ...................................................................5-182,5-212 crit.basept.interp................................................. 5-90
Condition for test .............................................................5-276 CSoln.name........................................................ 5-152,5-157
Conditioning cycles .........................................................5-212 CSOLN/F .............................................................. 5-181,5-213
Configuration..............................................................5-18 CSOLN/M .............................................................. 5-181,5-215
Conformity .................................................................9-15,9-17 CSOLN>M .............................................................. 5-181,5-217
Connection 30 for inert gas lead-off CSWEEP) .............................................................. 5-179,5-220
Figure ..............................................................................2-7
Inert gas lead-off ...........................................................3-12 ctrl.line code............................................... 5-205,5-235
Connection 31 for waste solution lead-off Current measurement ......................................................... 8-6
Figure ..............................................................................2-7 Current rack position ........................................................ 5-36
Connection 32 for inert gas supply Current x position.............................................................. 5-36
Figure ..............................................................................2-7 Current y position.............................................................. 5-36
Inert gas supply.............................................................3-12 Current z position.............................................................. 5-36
Connection 93 for inert gas supply Cursor keys................................................................. 5-2,5-10
Attachment of FEP tubing 51 ........................................3-10
Curve.................................................5-99,5-112,5-112,5-170
Figure ............................................................................3-15
Inert gas connection scheme ........................................3-13 Curve Cal.......................................................... 5-170,5-172
Connection 94 for inert gas supply Curve Derv.................................................................. 5-170
Attachment of FEP tubing 5 9 ........................................3-10 Curve identification ................................................. 5-99,5-111
Figure ............................................................................3-15 Curve Orig.................................................................. 5-170
Inert gas connection scheme ........................................3-13
Curve Proc.................................................................. 5-170
Connection of 685 Dosimats.............................................3-33

10 Index
Curve PSA.....................................................................5-170 <Delete Resid.CV> .................................................... 5-67

Curve Smth ..................................................................5-170 <Delete segment> .................................................... 5-125
Curve type for calibration curve.......................................5-149 <Delete subst.>....................................................... 5-130
Curve type for standard addition.....................................5-144 Delete substance ............................................................ 5-130
Curve type ....................................................... 5-144,5-149 <Delete Workg.CV> .................................................... 5-67
Curved baseline.................................................................7-47 Deletion of working storage .............................................. 7-30
Curves .................................................................... 5-93,5-170 Delta............................................................................. 5-308
"CURVES" ..........................................................................5-93 Density ........................................................5-62,5-63,5-80,6-4
<CURVES> ......................................................................5-93 Deposition time ............................................................... 5-261
Cycles ...................................................... 5-212,5-275,5-310 Depth ............................................................................ 8-5,8-9
Cyclic curves ...................................................................5-117 <Derived> ............................................................ 5-96,5-110
Cyclic voltage sweep............................................ 5-219,5-220 derived ................................................5-99,5-112,5-112,6-8
Cyclic voltammetry ..................................... 5-179,5-221,5-269 Derived curve ..........................................5-96,5-110,5-170,6-8
CYCMODE .............................................................. 5-177,5-221 Destination of automatic output...................................... 5-172
Det.storage.................................................................. 5-77
Determ. ..................................... 5-83,5-85,5-91,5-167,5-170
D <Determ. storage> ............................................ 5-52,5-56
Determination name......................... 5-11,5-54,5-83,5-85,5-91
D ................................................................ 5-123,5-126,5-175
Determination of calibration curve ............................ 6-28,6-32
Data acquisition.................................................. 5-178,6-6,8-1
determination ..................................................... 5-74,5-77
Data bits.............................................................. 5-18,8-11
Determinations
Data card Automatic storage......................................................... 5-77
Changing the battery .......................................................3-5 Dialog page .................................................................. 5-51
Dialog page ...................................................................5-55 Run mode ..................................................................... 5-74
Formatting .....................................................................5-57
"DETERMINATIONS" ......................................................... 5-51
Handling ..........................................................................3-4
Inserting...........................................................................3-5 <DETERMINATIONS>..................................................... 5-51
Inserting the battery.........................................................3-4 dev.estimated .....................................5-87,6-30,6-30,6-34
Ordering designation................................................ 9-1,9-2 Deviation due to calibration .............................................. 5-86
Preparation ......................................................................3-4 Deviation due to measurement ......................................... 5-86
Removing ........................................................................3-5
Storage capacity ...........................................................5-58 Deviation of the mass concentration ................................ 5-85
Technical data .................................................................8-3 <Diagn.> ........................................................................ 5-17
"DATA CARD".....................................................................5-55 Diagnosis .......................................................................... 7-49
<DATA CARD> ................................................................5-55 Diagnostic routine ............................................................. 5-17
<Data card> ................................................. 5-48,5-52,5-56 Dialog keys ................................................................... 5-2,5-4
Data input from balance....................................................5-60 Dialog page
Data processing ..................................................................6-1 Description.................................................................... 5-15
Layout ........................................................................... 5-11
Data receipt from balance.................................................5-61 Notation........................................................................... 1-3
Data transmission protocols..............................................8-11 Diaphragm 129
Date............................................................. 5-17,5-167,5-170 Figure............................................................................ 3-29
Date of calibration ............................ 5-142,5-147,5-153,5-158 Diaphragm 132
Date of recording.................................................. 5-167,5-170 Figure............................................................................ 3-29
Date transfer rate...............................................................5-18 Diaphragm support 128
DCTMODE ...................................................... 5-177,5-223,7-34 Figure............................................................................ 3-29
Deaeration of analyte solution ...........................................3-12 Difference in evaluation quantities .................................... 5-89
Decimal code ............................................... 5-13,5-281,5-282 Difference of mean values of evaluation quantities ........ 5-162
Decision...........................................................................5-236 Difference to base point.......................................... 5-139,6-11
Decision block............................................ 5-205,5-210,5-211 Differential pulse voltammetry................. see DP polarography
Declaration of conformity ..................................................9-15 Differentiation ...................................................................... 6-8
Decrease screen contrast .................................................5-17 Digestion........................................................................... 7-33
<Default values> .............................................. 5-24,5-38 Digital filter .................................................................... 6-8,8-2
Definition of sample size .....................................................6-4 Dil.settings ............................................................... 5-42
Degree of protection..................................................... 7-1,8-4 Diluted samples .......................................................... 5-64,6-4
Degrees of freedom...........................................................6-23 Dilution calculation............................................................ 6-21
<DELETE> .............................................................. 5-10,5-32 Dilution factor ............................................................ 6-20,6-21
Delete character key..........................................................5-10 Dilution operation.............................................................. 5-39
Delete common variables..................................................5-67 Dilution settings for Dosimats/Dosinos............................. 5-42
Delete determinations........................................................5-52 Dimensions ................................................................... 8-5,8-9
<Delete file(s)> ...................................... 5-48,5-52,5-56 Direct current voltammetry.............................................. 5-223
Delete files .........................................................................5-56 Dispense initial volume ..................................................... 5-38
<Delete instr.> ............................................ 5-122,5-124 Dispensed volume ............................................................ 5-40
Delete line...........................5-32,5-59,5-67,5-160,5-166,5-173 Dispensing of auxiliary solutions..................................... 5-180
<Delete line>...............5-43,5-59,5-67,5-160,5-166,5-173 Dispensing of calibration solutions................................. 5-181
Delete methods .................................................................5-48 Dispensing of standard addition solutions ........... 5-181,5-194
Delete program instruction ................................... 5-122,5-124 Dispensing position .......................................................... 5-40

10 Index
Display...........................................................................5-17 Choice of dosing unit.................................................... 3-41

Display next curve ........................................ 5-98,5-110,5-118 Ordering designation .................................................... 9-11
Display of calibration curve .......................................6-28,6-33 Dosino 700
Addition of auxiliary solutions ....................................... 3-43
Display of curves ...............................................................5-93
Addition of standard solutions ...................................... 3-42
Display of live curve...........................................................5-71 Connection of pipetting equipment .............................. 3-48
Display previous curve ................................. 5-98,5-111,5-118 Dosing units .................................................................. 3-41
<Display segment>.....................................................5-95 Electrical connection..................................................... 3-41
<Display subst.>.....................................................5-109 Filling............................................................................. 5-38
Initializing ...................................................................... 5-38
Display/Plot....................................................5-134,5-135 Installation or rinsing equipment................................... 3-46
Display/plot parameters ............................ 5-103,5-112,5-120, Manual operation .......................................................... 5-37
................................................................ 5-127,5-134,5-135 Ordering designation .................................................... 9-11
Dispose of mercury .............................................................7-4 Rinsing the measuring vessel ....................................... 3-46
div. by zero................................................................5-83 Tubing connections .............................................. 3-42,3-43
Division ............................................................................5-164 Double peaks......................... 5-138,6-12,7-36,7-39,7-41,7-47
Division of time axis.........................................................5-128 <Down>............................................................................. 5-35
Division of voltage axis ............................... 5-128,5-134,5-135 DP polarography............................................. 4-56,5-230,7-34
DME DPASV .............................................................................. 4-61
Operating characteristics ..............................................3-14 DPMODE......................................................... 5-177,5-230,7-34
Program instruction .....................................................5-225 Drip pan 29 (6.2711.050)
Switching off ................................................................5-248 Figure.............................................................................. 2-6
Switching on/off.............................................................5-22 Ordering designation ...................................................... 9-6
Test..................................................................................4-7 Setting up........................................................................ 3-1
Troubleshooting.............................................................7-35 Drip pan 113 (6.2711.030)
<DME> .............................................................. 5-22,5-24,5-29 Figure.................................................................... 3-16,3-20
DME............................................................... 5-25,5-177,5-225 Ordering designation ...................................................... 9-6
"DOCUMENTATION" .................................................5-166,6-3 Drive belt 49 (6.1244.020)
<DOCUMENTATION> ...................................................5-166 Figure...................................................................... 2-9,3-28
Installation....................................................................... 3-8
<Dos V.init>................................................................5-38
Ordering designation ...................................................... 9-3
DOS/M ...................................................................5-180,5-228
Drive shaft 45 (6.1246.010)
DOS>A ...................................................................5-180,5-226 Figure.............................................................................. 2-9
DOS>F ...................................................................5-180,5-227 Insertion in measuring head ........................................... 3-8
DOS>M ...................................................................5-180,5-229 Installing the drive belt .................................................... 3-8
Dosimat 665 ..........................................................5-192,5-228 Ordering designation ...................................................... 9-4
Dosimat 685 Drive shaft 121 (6.1246.000)
Addition of auxiliary solutions ........................................3-35 Construction of RDE ..................................................... 3-27
Addition of standard solutions.......................................3-34 Figure............................................................................ 3-28
Connection of pipetting equipment ...............................3-38 Insertion in measuring head ........................................... 3-8
Electrical connection .....................................................3-33 Ordering designation ...................................................... 9-8
Exchange units ..............................................................3-33 Drive wheel 52
Filling .............................................................................5-38 Figure...................................................................... 2-9,3-28
Initializing.......................................................................5-38 Installing the drive belt 49...............................................
49 3-8
Manual operation...........................................................5-37 Drop size..........................................5-25,5-30,5-242,5-287
Ordering designation.....................................................9-11 Dropping Mercury Electrode...................................... see DME
Tubing connections...............................................3-34,3-35
DSWEEP................................................................. 5-182,5-232
Dosimat 725 ..........................................................5-192,5-228
dU.front .................................................... 5-101,5-139,6-11
Dosimat connection 18
dU.rear ...................................................... 5-102,5-139,6-11
Connection of Dosimat 685...........................................3-33
Connection of Dosino 700.............................................3-41 Dummy cell ................................................................. 7-54,8-8
Figure ........................................................................2-3,2-5 Dummy cell connection 67 WE-D
Dosimat connection 19 Figure............................................................................ 2-10
Connection of Dosimat 685...........................................3-33 Dummy cell connection 68 WE-L
Connection of Dosino 700.............................................3-41 Figure............................................................................ 2-10
Figure ........................................................................2-3,2-5 Dummy cell connection 69 RE
Dosimat connection 20 Figure............................................................................ 2-10
Connection of Dosimat 685...........................................3-33 Dummy cell connection 70 AE
Connection of Dosino 700.............................................3-41 Figure............................................................................ 2-10
Figure ........................................................................2-3,2-5 Dummy stopper 42 (6.1446.040)
Dosimat connection 21 Figure.............................................................................. 2-9
Connection of Dosimat 685...........................................3-33 Insertion in measuring head ........................................... 3-7
Connection of Dosino 700.............................................3-41 Ordering designation ...................................................... 9-4
Figure ........................................................................2-3,2-5 Dummy stopper 60 (6.1446.040)
Dosimat type .....................................................................5-40 Insertion in measuring head ........................................... 3-7
"DOSIMATS" ................................................................5-37,6-5 Ordering designation ...................................................... 9-4
<DOSIMATS> ..................................................................5-37 Dummy stopper 61 (6.1446.040)
dosing .............................................................................5-40 Figure.............................................................................. 2-9
Insertion in measuring head ........................................... 3-7
Dosing rate ..................................................................5-41
Dosing tube.......................................................................5-41
Dummy stopper 62 (6.1446.040)
Dosing unit (6.3030.XXX) Figure.............................................................................. 2-9
Changing dosing unit ....................................................3-45
Dummy Sweep ............................................................... 5-232

10 Index
Dust cover (6.2723.230) ......................................................9-6 Empirical factor ........................................................... 6-9,6-12

Dust cover (6.2723.280) ............................................... 9-1,9-2 Empty 700 Dosino ............................................................ 5-37
<Empty Dosimat>......................................................... 5-37
Empty Dosinos.................................................................. 5-28
E <Empty Dosinos>......................................................... 5-28
Empty rinsing Dosinos...................................................... 5-23
Earth socket 8
END ....................................................................... 5-182,5-234
Earthing ...........................................................................3-3
Figure ....................................................................... 2-3,2-5 End concentration............................................................. 5-42
Earth socket 36 End of main program...................................................... 5-234
Figure ..............................................................................2-7 End of segment............................................................... 5-234
EBUS ...........................................see External Bus connection End volume ....................................................................... 5-42
EBUS cable (6.2135.000)....................................... 3-6,9-1,9-2 Enrichment...................................................................... 5-246
ED:<subst>:<V> ................................................ 5-89,5-162 Enrichment time ................................................................ 7-43
Edit field.............................................................................5-12 <ENTER> .......................................................................... 5-8
Edit mode ................................................................. 5-12,5-14 Entry in character fields .................................................... 5-13
EDTA .................................................................................7-46 Entry in numeric fields....................................................... 5-13
Effective mass concentration .............. 5-64,5-97,5-144,5-149, Entry in selection fields ..................................................... 5-13
......................................................6-21,6-26,6-28,6-32,6-34 EPSON printers.........................................3-51,3-54,5-19,5-20
Effective voltage amplitude .................................. 5-184,5-187 Equipping the measuring head .......................................... 3-7
EFTA................................................................................5-242 Error calculation ................................................................ 6-22
Eject button 2 for data card Error class........................................................................... 7-6
Ejection of data card .......................................................3-5 Error description ................................................................. 7-6
Figure ....................................................................... 2-2,2-4
Error identification ............................................................... 7-6
<Electr. test> .................................................. 5-24,5-29
ERROR MESSAGE ............................................................... 7-6
Electrical connection 124
Figure ............................................................................3-29 Error messages........................................................... 5-71,7-6
Electrical connection 133 Error number....................................................................... 7-6
Figure ............................................................................3-32 Error printing ................................................................... 5-167
Electrical safety ...................................................................7-1 Error propagation rules ..................................................... 6-36
Electrochemical enrichment ............................................5-246 <Error window>........................................................... 5-71
Electrochemical regeneration of carbon electrodes........5-212 ERROR WINDOW ................................................................. 7-6
Electrode ............................................................ 5-177,6-3,6-6 ES:<subst>:<V>................................................. 5-89,5-162
Electrode cable 37 (WE) <ESC>............................................................................... 5-9
Connection to MME.......................................................3-10 Escape key ......................................................................... 5-9
Connection to RDE ..........................................................3-8 esize................................................................... 5-169,5-169
Figure ..................................................................... 2-9,3-28
Estimated peak area ........................................................... 6-9
Electrode cable 48 (RE)
Estimated peak height ........................................................ 6-9
Attachment to reference electrode ................................3-30
Connection to reference electrode ..................................3-8 Estimated peak voltage ...................................................... 6-9
Figure ..............................................................................2-9 Estimated peak width.......................................................... 6-9
Electrode cable 58 (AE) EU Declaration of conformity ............................................ 9-15
Attachment to auxiliary electrode ..................................3-31 EU:<subst>:<V>................................................. 5-88,5-162
Connection to auxiliary electrode ....................................3-8 EV:<subst>:<V>.........................................5-89,5-89,5-162
Figure ..................................................................... 2-9,3-28
EV:<subst>.............................................5-205,5-235,5-250,
Electrode holder 114 (6.2615.030) ............................................................5-252,6-19,6-20,6-36
Figure ................................................................... 3-16,3-20
Ordering designation.......................................................9-5 <Eval.> .................................................................. 5-82,5-91
Electrode holder 136 (6.1241.020) eval. impossible ...................................................... 5-90
Figure ............................................................................3-32 Evaluation ..................................................................... 6-1,8-2
Ordering designation.......................................................9-8 Evaluation.................................................................. 5-140
Electrode test............................................................ 5-24,5-29 Evaluation mode ............................................................. 5-140
Electrode tip 120 (6.1204.XXX) Evaluation parameters .................................................... 5-140
Construction of RDE......................................................3-27 Evaluation quantity.................................5-88,5-140,6-19,6-20,
Figure ............................................................................3-28 ..............................................................6-24,6-28,6-32,6-36
Insertion in measuring head ............................................3-8
Installation........................................................................3-8 Evaluation quantity for AC2 curves ................................. 5-100
Ordering designation.......................................................9-8 Evaluation quantity for PSA curves ................................. 5-101
Regeneration .................................................................3-27 Evaluation report............................................................. 5-168
Electrolyte compartement 127 Evaluation value ....................... 5-97,5-144,5-149,5-205,5-235
Figure ............................................................................3-29 Evaluations.................................................................. 5-84
Electrolyte compartement 131 Examples ............................................................................ 4-1
Figure ............................................................................3-29
exchange ........................................................................ 5-40
Electrolyte vessel 123 (6.1245.010)
<Exchange all>........................................................... 5-39
Figure ............................................................................3-29
Ordering designation.......................................................9-4 Exchange position ........................... 5-23,5-26,5-29,5-31,5-40
Electrolytes ........................................................................7-33 <Exchange position>................................5-23,5-29,5-38
Electromagnetic compatibility ...................................... 8-4,8-9 Exchange unit (6.3014.XXX)
Changing the exchange unit ......................................... 3-37
EMC.............................................................................. 8-4,8-9
Choice of exchange unit ............................................... 3-33
Emitted interference ............................................................8-4 Ordering designation .................................................... 9-11

10 Index
<Exec. all> ................................................................5-166 Filling tubing 115 (6.1817.000)

<Exec. line>..............................................................5-166 Figure............................................................................ 3-20
Execute all lines...............................................................5-166
Final results............................................................. 5-83,5-161
Execute selected line.......................................................5-166
Final results ..................................................... 5-83,6-36
EXIT......................................................................5-179,5-235
Final value for current axis .............................................. 5-128
Exit from loop or block ....................................................5-235
Final value for scaling of current axis.............................. 5-134
expon. .................................................. 5-137,6-15,6-16,7-47
Final value for scaling of the y axis of PSA curves.......... 5-135
Exponential baseline ...................................... 5-137,6-15,6-16
Final value for scaling of voltage axis ................... 5-134,5-135
Exponential format ............................................................5-13
Final value for the voltage axis of PSA segments ........... 5-128
Ext. start ....................................................................5-20
Final voltage........................... 5-232,5-240,5-269,5-295,5-299
External Bus connection 22
Connection of EBUS cable..............................................3-6 Final voltage of conditioning cycles................................ 5-212
Figure ........................................................................2-3,2-5 Fixed scaling......................................................... 5-134,5-135
External Bus connection 34 <FORM FEED> ................................................................. 5-9
Connection of EBUS cable..............................................3-6 <Format card> ............................................................. 5-57
Figure ..............................................................................2-7
Formula ........................................................................ 5-161
External start/stop function........................................3-56,5-20
Formula calculation .................................................... 6-36,8-2
Fractional volume .................. 5-163,5-163,5-289,5-290,5-291
Free storage space........................................... 5-49,5-54,5-58
F Freely definable variables ............................................... 5-161
f.double...................................... 5-138,6-14,6-15,6-16,7-47 Front base point.............................................................. 5-101
f.half .......................................................... 5-138,6-14,7-47 front overlapping .................................... 5-90,6-13,7-47
F>A........................................................................5-181,5-237 FSWEEP........................................................... 5-178,5-240,8-1
F>M........................................................................5-181,5-238 Full condition........................................................... 5-54
Fast sweep ......................................................................5-240 Full hardware handshake.................................................. 8-14
FEED......................................................................5-180,5-239 Full method report ................................................ 5-169,5-169
FEP tubing 39 (6.1805.180) Full report.............................................................. 5-168,5-169
Figure ..............................................................................2-9 Full report ................................................................. 8-11
FEP tubing 51 (6.1805.180) Fuses ................................................................see Mains fuse
Connection to MME.......................................................3-10
Connection to stopper 119 ...........................................3-10
Figure ......................................................................2-9,3-28
FEP tubing 53 (6.1805.040) G
Figure ..............................................................................2-9 Gas formation at HMDE.................................................... 7-45
FEP tubing 55 (6.1805.100) Gas wash bottle 27 (6.2405.030)
Figure ......................................................................2-9,3-11 Figure........................................................................ 2-6,2-9
FEP tubing 56 (6.1805.090) Filling with water............................................................ 3-12
Figure ......................................................................2-9,3-28 Inert gas connection scheme ....................................... 3-13
FEP tubing 57 (6.1805.180) Gas wash bottle 65 (6.2405.030)
Figure ......................................................................2-9,3-28 Figure.................................................................... 2-10,3-11
FEP tubing 59 (6.1805.180) Gas wash bottle 117
Connection to MME.......................................................3-10 Figure............................................................................ 3-20
Connection to stopper 119 ...........................................3-10 Gaussian distribution ........................................................ 6-23
Figure ......................................................................2-9,3-28
GC electrode tip (6.1204.110) .................................... 3-27,9-8
FEP tubing 89 (6.1805.180)
Figure ............................................................................3-11 Gen.settings ............................................................... 5-40
Insertion in measuring head ..........................................3-10 General information on error messages ............................. 7-6
FEP tubing 90 (6.1805.100) General rules for VA trace analysis ................................... 7-33
Figure ............................................................................3-11 <Get line>.................................................................. 5-173
Insertion in measuring head ..........................................3-10 Glass breakage................................................................. 9-14
File................................................................. 5-49,5-54,5-58 Glass capillary 109 (6.1226.030)
File extensions...................................................................5-56 Figure.................................................................... 3-15,3-20
File name...........................................................................5-58 Filling with vacuum ....................................................... 3-19
Files .............................................................. 5-49,5-54,5-58 Filling without vacuum .................................................. 3-18
Mounting the capillary................................................... 3-17
<Fill all> ....................................................................5-40 Ordering designation ...................................................... 9-3
Fill all Dosimats/Dosinos ...................................................5-40 Replacement................................................................. 3-24
<Fill Dosimat> ...........................................................5-38 Glassy carbon tip 138 (6.1247.000)
Fill Dosimat/Dosino ...........................................................5-38 Figure............................................................................ 3-32
Fill transfer tubing..............................................................5-28 Ordering designation ...................................................... 9-9
Fill volume for measuring vessel .......................................5-26 GLP/ISO 9001 guidelines ................................................. 7-58
Filling capillary using vacuum ...........................................3-19 Graphite electrode tip (6.1204.100)............................ 3-27,9-8
Filling capillary without vacuum.........................................3-18 grouped VR.................................................................... 5-99
Filling cone 116 (4.420.2860)
Figure ............................................................................3-20
Filling MME with mercury ..................................................3-16
Filling rate................................................................5-41
H
Half-wave voltage ............................................. 5-88,5-99,6-10
Filling station .....................................................................3-20

10 Index
Handling of data cards........................................................3-4 Basic method for DPASV .............................................. 4-61

Handling of mercury ............................................................7-3 Lead determination with calibration curve .................... 4-29
Lead determination with internal standard.................... 4-42
Handshake ............................................................... 5-18,8-14
Lead determination with standard addition .................... 4-9
Handshake.............................................................. 5-18,8-11 Preparations.................................................................... 4-2
Hanging Mercury Drop Electrode............................ see HMDE Immunity to interference................................................ 8-4,8-9
Hardware reset ......................................................... 7-29,7-30 Inactive line .................................................5-123,5-126,5-175
Hazard .................................................................................1-3 Inactive range .............................................5-123,5-126,5-175
Headers .............................................................................5-11 Increase screen contrast .................................................. 5-16
Height ........................................................................... 8-5,8-9 Increment for automatic numbering.......................... 5-60,5-61
Height/area calculation......................................................6-19 Inert gas .............................................................................. 8-8
<Help> .............................................................................5-12 Inert gas connection ......................................................... 3-12
Help message ........................................................ 5-12,5-173 Inert gas lead-off............................................................... 3-12
Hex code .............................................................. 5-281,5-282 Inert gas pressure ..................................................... 3-12,5-21
HMDE Inert gas supply ................................................................ 3-12
Drop size .............................................................. 5-25,5-30
Information about the Instructions for Use.......................... 1-2
Gas formation................................................................7-45
Operating characteristics ..............................................3-14 Initial standard concentration............................................ 5-42
Program instruction .....................................................5-242 Initial value for current axis.............................................. 5-128
Switching on/off .............................................................5-22 Initial value for scaling of current axis ............................. 5-134
Test..................................................................................4-7
Initial value for scaling of the y axis of PSA curves ......... 5-135
Troubleshooting.............................................................7-37
Initial value for scaling of voltage axis................... 5-134,5-135
<HMDE> ............................................................ 5-22,5-24,5-29
Initial voltage ..............................................5-232,5-240,5-261,
HMDE............................................................. 5-25,5-177,5-242
................................................................5-269,5-295,5-299
<HOLD> ............................................................................5-8
Initial voltage of conditioning cycles ............................... 5-212
HOLD..................................................................... 5-182,5-244
Initial volume ............................................................. 5-38,5-41
Holder 26 for measuring vessel
Initialization ....................................................................... 7-29
Figure ..............................................................................2-6
Installing measuring vessel ...........................................3-10 Initialize all Dosimats/Dosinos .......................................... 5-39
<HOME>..........................................................................5-10 Initialize Dosimat/Dosino................................................... 5-38
<Home position> .........................................................5-27 Initialize rinsing Dosinos ........................................... 5-23,5-28
HP printers................................................ 3-51,3-54,5-19,5-20 Input bias current ................................................................ 8-6
HWfull .............................................................................8-14 Input control lines....................... 3-56,5-20,5-205,5-235,5-276
HWshort ...........................................................................8-14 Input impedance................................................................. 8-6
Hydraulic solution ..............................................................5-45 Input offset voltage ............................................................. 8-6
Inquiry of input control lines ............................................ 5-276
<Insert instr.>............................................. 5-122,5-124
I Insert line.................................... 5-32,5-59,5-160,5-166,5-173

<Insert line> ...............................5-59,5-160,5-166,5-173
I .......................................................................................5-88 Insert mode....................................................................... 5-10
I.abs ............................................................ 5-100,6-17,6-19 Insert program instruction..................................... 5-122,5-124
I.begin .............................................................. 5-128,5-134 Insert ring 105 (4.420.3011)
I.delta ...........................................................................5-89 Figure............................................................................ 3-15
I.end .................................................................. 5-128,5-134 <INSERT> ............................................................... 5-10,5-32
I.mean .............................................................................5-88 Inserting the data card........................................................ 3-5
I.peak ................................................ 5-88,5-100,5-140,6-19 Installation ........................................................................... 3-1
I.range .........................................................................5-221 Installing paper ................................................................... 3-3
I.rel ............................................................ 5-100,6-17,6-19 Instructions...................................................................... 5-175
I.scale .............................................................. 5-127,5-134 Instructions .........................................5-123,5-126,5-175
I.threshold ................................................. 5-89,5-132,6-9 Instructions for 695 Autosampler .................................... 5-181
I.wave .................................................. 5-88,5-100,6-13,6-19 Instructions for 717 Sample Changer ............................. 5-182
IBM character set 437 .......................................................5-13 Instructions for remote interface ..................................... 5-182
IBM printers .............................................. 3-51,3-54,5-19,5-20 Instructions for RS232 interface and printer ................... 5-182
Ident.1/S1 ................................................. 5-62,5-80,5-167 Instructions for Use.................................................1-2,9-1,9-2
Ident.2/S2 ................................................. 5-62,5-80,5-167 Instrument configuration ................................................... 5-18
Ident.3/S3 ................................................. 5-62,5-80,5-167 Instrument description ........................................................ 1-1
Identification for binary file.................................... 5-169,5-169 Instrument designation ......................................... 5-167,5-170
Identification for curve .......................................................5-99 Instrument initialization...................................................... 7-29
Identification for method report ............................ 5-169,5-169 Instrument variables........................................................ 5-162
Identification for report.......................................... 5-169,5-169 Instrument-resident common variables .................... 5-66,5-67
illeg. basel.scope...................................................5-90 int.std. .............................................................. 5-92,5-153
illeg. front ovlp................................... 5-90,6-13,7-47 Integration ......................................................................... 6-19
illeg. rear ovlp..................................... 5-90,6-13,7-47 Intercept ............................................................................ 5-92
illegal basel.type...................................................5-90 Intercept of calibration curve ..........................5-151,6-25,6-28
illegal U.width .........................................................5-90 Intermediate result .......................................................... 5-161
Illustrative methods Internal electrolyte ............................................................. 3-30
Basic method for DP polarography ...............................4-56 Internal standard

10 Index
Addition of reference solution............................5-266,5-267 Link substance to segment............................................. 5-130

Calibration technique ..................................................5-153 <Link to segment> .................................................. 5-130
Display of calibration curve ...........................................5-97
List of baseline points ........................................... 5-169,5-169
Illustrative method .........................................................4-42
Procedure......................................................................6-31 List of calibration points........................................ 5-169,5-169
Program instructions ................... 5-201,5-204,5-213,5-215, List of error messages ........................................................ 7-7
................................................................ 5-217,5-266,5-267 List of measured points .................................................. 5-168
Programming...............................................................5-154 List of smoothed measured points ....................... 5-169,5-169
Result display ................................................................5-92
Live curve.......................................................................... 5-71
Introduction .........................................................................1-1
<Live display>........................................................... 5-71
Introduction to the operation ...............................................4-1
<Load all>.................................................................... 5-67
Load common variables ................................................... 5-67
Load from 695 .................................................................. 5-33
J Load rack data.................................................................. 5-33
Javelle water ......................................................................5-28 Location of instruments ...................................................... 3-1
Locking ring 95 (4.420.2920)
Figure............................................................................ 3-15
K Locking ring 107 (4.420.2870)

Figure............................................................................ 3-15
KCl electrolyte solution (6.2308.020)...................................9-5 Locking ring 137
KD:<subst> ............................................... 5-92,5-152,5-162 Figure............................................................................ 3-32
Key categories.....................................................................5-2 Loop for calibration curve ..................................... 5-201,5-204
Key code ...........................................................................8-12 Loop for parameter variation ................................ 5-305,5-306
Key code for special keys .................................................8-13 Loop for replications ............................................. 5-273,5-274
Key remote control mode..................................................8-12 Loop for standard addition ................................... 5-190,5-191
Keying aid..........................................................................5-12 Low background current................................... 7-35,7-37,7-40
Keypad 5 Lower limit of working range ....................... 5-146,5-150,5-156
Check ............................................................................7-53 <Lwr/rght corner> ............................. 5-104,5-107,5-113,
Figure ........................................................................2-2,2-4 ................................................................ 5-115,5-117,5-120
Key categories.................................................................5-2
Technical data .................................................................8-2
Keys
Alphanumeric keys ..........................................................5-3 M
Auxiliary function keys .....................................................5-9 M.conc./cm.............................................. 5-146,5-151,5-156
Categories .......................................................................5-2
M.conc.begin ................................................... 5-151,5-156
Cursor keys ...................................................................5-10
Dialog keys......................................................................5-4 m.sample ................................................................ 6-20,6-21
Main function keys...........................................................5-7 m0.sample.............................................................. 6-20,6-21
Notation ...........................................................................1-3 MA:<subst>.......................................................... 5-86,5-162
Softkeys ...........................................................................5-9 Main function keys ........................................................ 5-2,5-7
Kinetic studies .................................................................5-221 Main parameters................................... 5-123,5-126,5-175
KN:<subst> ..................................... 5-92,5-145,5-151,5-162 Main program ................................................................. 5-122
KS:<subst> ........................... 5-92,5-145,5-157,5-163,5-163 Mains cable ............................................................ 3-3,9-1,9-2
KY:<subst> ........................... 5-92,5-145,5-151,5-163,5-163 Mains connection.................................................... 3-3,7-1,8-4
Mains connection plug 13
Figure........................................................................ 2-3,2-5
L Mains connection............................................................ 3-3
Mains frequency ................................................................. 8-4
Label ...............................................................................5-58
Mains fuse 10
Layout of dialog pages......................................................5-11 Figure........................................................................ 2-3,2-5
Lead determination with calibration curve.........................4-29 Replacement................................................................... 3-2
Lead determination with internal standard ........................4-42 Technical data ................................................................ 8-4
Lead determination with standard addition.........................4-9 Mains fuse 12
Lead standard solution (6.2301.100) ..................................9-5 Replacement................................................................... 3-2
Technical data ................................................................ 8-4
Learning position.....................................................5-36
Mains pilot lamp 4
Least squares....................................................................6-23 Figure........................................................................ 2-2,2-4
Letter keys .....................................................................5-2,5-3 Function .......................................................................... 3-3
LIFT......................................................................5-182,5-245 Mains switch 11
Limiting current value ......................................................5-132 Figure........................................................................ 2-3,2-5
Line..................................................................................5-61 Switch instrument on/off ................................................. 3-3
Line attribute............................................... 5-123,5-126,5-175 Mains voltage
Setting............................................................................. 3-2
<LINE FEED> ....................................................................5-9 Technical data ................................................................ 8-4
Line number ....................................... 5-61,5-123,5-126,5-175 Mains voltage selector 9
Line time ..................................................... 5-123,5-126,5-176 Figure........................................................................ 2-3,2-5
linear ..............................5-136,5-144,5-149,6-14,6-17,6-18 Setting mains voltage ..................................................... 3-2
Linear baseline ................................................................5-136 Manual Address 1 ...................................................... 5-22
Linearity range................................. 5-143,5-143,5-148,5-148, Manual Address 2 ...................................................... 5-22
.................................................. 5-155,5-155,6-26,6-30,6-35 Manual spike elimination .......................................... 5-115,6-7

10 Index
Marking of files ................................................. 5-47,5-51,5-55 Measuring vessels .............................................................. 8-8

Marking of instruction lines................................... 5-123,5-126 Memory ............................................................................... 8-3
Mass......................................................................... 5-64,5-86 Memory size......................................................5-49,5-54,5-58
Mass conc. ........................................ 5-45,5-64,5-85,5-146, Mercury
........................................................ 5-152,5-157,5-159,6-20 Filling capillary with vacuum ......................................... 3-19
Mass concentration .....................5-45,5-63,5-85,5-162,5-205, Filling capillary without vacuum .................................... 3-18
............................................5-235,6-20,6-21,6-27,6-32,6-36 Filling with mercury ....................................................... 3-16
Handling.......................................................................... 7-3
Mass concentration
Properties........................................................................ 7-2
of calibration solutions...................................... 5-152,5-157
References ...................................................................... 7-5
Mass concentration of solution Replenishing ................................................................. 3-23
with internal standard ..................................................5-159 Safety considerations...................................................... 7-2
Mass concentration of Threshold limit value (TLV).............................................. 7-2
standard addition solution...........................................5-146 Toxicity ............................................................................ 7-3
Material of base............................................................ 8-5,8-9 Mercury drop catcher (6.2406.000) .................................... 9-5
Material of cover ........................................................... 8-5,8-9 Mercury electrodes ........................................................... 3-14
Maximum current measurement range ...........................5-221 Mercury reservoir 103
Maximum fill volume................................................. 5-26,5-30 Figure............................................................................ 3-15
Maximum peak width ......................................................5-132 Filling with mercury ....................................................... 3-16
Replenishing the mercury ............................................. 3-23
Maximum sample volume ........................................ 5-34,5-36
Message ...........................................5-258,5-281,5-282,5-283
MC.dev. ..........................................5-85,6-26,6-29,6-34,6-36
Message .............................................................. 5-244,5-283
MC:<subst> .....................5-85,5-162,5-205,5-235,6-20,6-36
Method............................... 5-73,5-83,5-85,5-91,5-123,5-125,
MD:<subst> ......................................................... 5-85,5-162 ................................. 5-131,5-161,5-167,5-168,5-170,5-174
Mean dev................................................. 5-145,5-152,5-157 Method ASV.mth ............................................................... 4-61
Mean deviat.................................................................5-92 Method CALCRV.mth........................................................ 4-30
Mean deviation of calibration curve........................ 5-92,5-152 Method call-up ................................................5-63,5-80,5-167
Mean deviation of calibration curve Method comment.................................................. 5-173,5-174
for internal standard ....................................................5-157
Method definition ................................................................ 6-2
Mean deviation of standard addition curve ............ 5-92,5-145
Method INTSTD.mth ......................................................... 4-43
Mean value of evaluation quantities ....................... 5-88,5-162
<Method labels>....................................................... 5-122
Mean value of peak voltages...........................................5-162
Method name................ 5-11,5-49,5-73,5-83,5-85,5-91,5-123,
Meas.cell.....................................................................5-242 ....................... 5-125,5-131,5-161,5-167,5-168,5-170,5-174
Meas.cycles .......................5-184,5-187,5-221,5-293,5-307 Method of least squares ................................................... 6-22
Meas.dev............................................................... 6-29,6-34 Method POL.mth............................................................... 4-56
MEAS..................................................................... 5-178,5-246 Method report ................................................................. 5-168
<Measure position>...................................................5-27 Method specifications..................................................... 5-121
Measured point report .....................................................5-168 <Method storage> .............................................. 5-48,5-56
Measured value processing ................................................8-2 Method test ....................................................................... 5-71
Measurement...................................................................5-178 Method TEST747.mth ............................................... 7-54,7-59
Measurement cycles ........................ 5-184,5-187,5-221,5-293 Method TESTPb.mth................................................... 4-9,7-60
Measurement duration ....................................................5-303 Method title ...........................................5-49,5-73,5-123,5-168
Measurement mode .........................5-170,5-177,6-3,6-6,7-34 Method.call................................................5-63,5-80,5-167
Measurement of calibration solutions....................... 6-28,6-32 Method-independent settings ............................................. 6-5
Measurement techniques ....................................................8-1 Methods
Measurement temperature ......................... 5-150,5-156,5-159 Dialog page .................................................................. 5-47
Measurement time...................................... 5-223,5-230,5-292 Examples ........................................................................ 4-1
Measurement voltage........................................... 5-246,5-303 Standard methods ........................................................ 5-50
Measurement window .......................................................5-72 "METHODS" ...................................................................... 5-47
Measuring amplifier .............................................................8-7 <METHODS> .................................................................. 5-47
Measuring head 41 Metrodata VA Back Up (6.6017.000) ....................8-11,9-1,9-2
Equipping ........................................................................3-7 Metrodata VA Database (6.6016.113) ...................... 8-11,9-13
Figure ............................................................. 2-9,3-11,3-28 Microtip 47 (6.1824.000)
Measuring head arm 40 Connection to 685 Dosimat .......................................... 3-34
Figure ............................................................. 2-9,3-11,3-28 Connection to 700 Dosino ............................................ 3-42
Measuring vessel 28 (6.1415.210) Figure.............................................................................. 2-9
Figure ..............................................................................2-6 Insertion in measuring head............................................ 3-7
Installation at 747 VA Stand...........................................3-10 Ordering designation ...................................................... 9-5
Maximum fill volume ............................................. 5-26,5-30 Minimum peak width....................................................... 5-131
Ordering designation.......................................................9-4 missing front peak .................................................. 5-90
Measuring vessel (6.1415.150) ...........................................9-9 missing rear peak .................................................... 5-90
Measuring vessel (6.1418.220) ...........................................9-9 Mix solutions ................................................................... 5-310
Measuring vessel (6.1450.210) ...........................................9-9 Mixed solution ................................................................... 5-44
Measuring vessel (6.1456.210) ...........................................9-9 Mixing cycles .................................................................. 5-310
Measuring vessel (6.1457.210) ...........................................9-9 Mixing volume ................................................................. 5-310
Measuring vessel (MEAS) ............... 5-192,5-194,5-196,5-215, ML:<subst>.......................................................... 5-86,5-162
...........................................5-217,5-228,5-229,5-238,5-250, MME.................................................see Multi-mode electrode
............................................5-252,5-267,5-279,5-290,5-291
Mode .................................................5-140,5-155,5-158,5-170

10 Index
Mode for parameter display ..................................5-155,5-158 Figure.............................................................................. 2-9

Mode for program execution.............................................5-74 Insertion in measuring head ........................................... 3-7
Mode when memory full ....................................................5-54 Nitrogen ............................................................................ 3-12
Modification flag ..............................................................5-167 No addition ....................................................... 7-37,7-39,7-41
Modified...............................................................5-77,5-167 no cal.deviation ...................................... 5-87,6-29,6-34
<Modify baseline>.....................................................5-98 no meas.deviation ................... 5-87,6-26,6-30,6-30,6-34
<Modify column> .........................................................5-12 No peak found .................................................. 7-36,7-38,7-41
<Modify dU.front>...................................................5-107 Noise................................................................................... 8-6
<Modify dU.rear>.....................................................5-107 Non-assigned peaks....................................................... 5-111
<Modify line>..............................................................5-12 Non-isoformal standards .................................................. 7-48
Modify rack parameters ....................................................5-33 nonlin................................................................. 5-144,5-149
<Modify recogn.>.......................................................5-98 Nonlin. ...........................................5-92,5-144,5-145,5-149,
.................................................................... 5-151,6-25,6-28
Modul.freq. ................................. 5-184,5-187,5-292,5-307
Nonlinear curve................................................................. 6-22
Modulation frequency................................. 5-184,5-187,5-292
Non-linearity factor............. 5-92,5-145,5-151,5-162,6-25,6-28
"MONITORING"............................................................5-69,6-5
NOP ....................................................................... 5-182,5-249
<MONITORING> .............................................................5-69
Normal Reset .................................................................... 7-29
Monographs ........................................................................1-8
Notation .............................................................................. 1-3
Mounted racks...................................................................5-31
Number of calibration solutions...................................... 5-204
<Move needle>..............................................................5-27
Number of conditioning cycles ....................................... 5-212
Move position in x direction...............................................5-35
Number of files.................................................. 5-49,5-54,5-58
Move position in y direction...............................................5-35
Number of measurement cycles.......5-184,5-187,5-221,5-293
Move position in z direction...............................................5-35
Number of mixing cycles ................................................ 5-310
Move transfer needle.........................................................5-27
Number of preparation cycles ..........5-184,5-187,5-221,5-292
MS:<subst> ..........................................................5-86,5-162
Number of rack positions ......................................... 5-34,5-36
Multi-mode electrode 38
Changing capillary ........................................................3-24 Number of repetitions ..................................................... 5-306
Cleaning ........................................................................3-25 Number of replications ................................................... 5-274
Construction ..................................................................3-14 Number of rinse cycles ................................................... 5-275
Electrical connection .....................................................3-21
Number of samples for series determination.................... 5-76
Figure ............................................................. 2-9,3-16,3-20
Filling capillary with vacuum..........................................3-19 Number of standard additions........................................ 5-191
Filling capillary without vacuum.....................................3-18 Numbering of instruction lines .............................. 5-123,5-126
Filling with mercury........................................................3-16 Numeric fields................................................................... 5-13
Insertion in measuring head ..................................3-10,3-21 Numeric keys ................................................................ 5-2,5-3
Mounting capillary .........................................................3-17
Operating characteristics ......................................3-14,3-15
Ordering designation.......................................................9-4
Replenishing mercury....................................................3-23
Storage..........................................................................3-22 O
Technical data .................................................................8-7 Octal code ............................................................ 5-281,5-282
Multiplication ...................................................................5-164 Offset ............................................................ 5-148,5-148,6-30
Opening 72
Figure.............................................................................. 3-9
N Insertion of auxiliary electrode ................................ 3-8,3-31

Opening 73
Name..................................................................................5-61 Inserting PTFE tube 92 ................................................. 3-10
Name of auxiliary solution ............... 5-226,5-227,5-229,5-252, Insertion of stopper 61 ................................................... 3-7
................................................................ 5-277,5-278,5-279 Opening 74
Name of calibration solutions................................5-152,5-157 Inserting PTFE tube 91 ................................................. 3-10
Insertion of stopper 60 ................................................... 3-7
Name of determination..........................................5-167,5-170
Opening 76
Name of manufacturer ..........................................5-167,5-170 Figure.............................................................................. 3-9
Name of parameter to be varied .....................................5-307 Inserting stopper 119 ................................................... 3-10
Name of reference solution ...................................5-266,5-267 Inserting the MME......................................................... 3-10
Name of reference substance .................... 5-156,5-250,5-252 Opening 78
Name of sample data table............................ 5-61,5-78,5-167 Insertion of stopper 42 ................................................... 3-7
Name of solution with internal standard ..........................5-159 Opening 79
Figure.............................................................................. 3-9
Name of standard addition solution .....................5-146,5-192,
Insertion of reference electrode .............................. 3-8,3-30
...........................................................................5-194,5-250
Opening 81
Name of standard substance............................................5-45
Figure.............................................................................. 3-9
Navigation mode .......................................................5-12,5-14 Insertion of RDE .............................................................. 3-8
Needle 112 (6.2816.030) Insertion of stirrer ............................................................ 3-8
Figure ............................................................................3-16 Opening 86
Ordering designation.......................................................9-7 Figure.............................................................................. 3-9
Needle position .........................................................5-33,5-36 Insertion of PTFE tubing.................................................. 3-7
<New calcul.>....................................................5-84,5-160 Opening the instruments .................................................... 7-1
<New display>................... 5-104,5-105,5-107,5-113,5-120 Operation .................................................................... 5-1,5-68
<Next VR> ................................................. 5-98,5-110,5-118 Operation mode for HMDE ............................................. 5-242
Nipple 44 (6.2730.030) "OPERATION SEQUENCE"....................................... 5-122,6-2

10 Index
<OPERATION SEQUENCE> .........................................5-122 <PG DN>......................................................................... 5-10

Operational chart for determinations...................................6-1 <PG UP> ......................................................................... 5-10
Operators ........................................................................5-164 pH ..................................................................................... 7-33
Optional peripherals, cables and software........................9-11 Ph.angle ..................................................5-184,5-187,5-307
Options ................................................................................9-8 Phase angle .......................................................... 5-184,5-187
original.............................................. 5-99,5-112,5-112,6-7 Pictograms.......................................................................... 1-3
<Original> ......................................................... 5-95,5-109 Pin assignment of RS232 interfaces ................................. 8-17
Original curve ............................................... 5-95,5-109,5-170 Pipetting equipment (6.5611.010)
<Output>.......................................................................5-173 Installation ............................................................. 3-38,3-48
Ordering designation .................................................... 9-10
Output control lines ........................................ 3-56,5-20,5-283
Start dilution operation .................................................. 5-39
Output current .....................................................................8-6 Use........................................................................ 3-38,3-48
Output of a message.......................................................5-244 Pipetting handle (6.1562.040)................................... 3-38,3-56
Output of calibration curve ..............................................5-172 Pipetting opening 75
Output of reports and curves ..........................................5-166 Figure.............................................................................. 3-9
Output of segment curve.................................................5-172 Pipetting tubing (6.1562.050).................................... 3-38,3-48
Output of substance curve ..............................................5-172 <Plot param.> ........................................................... 5-125
Output voltage.....................................................................8-6 Points of tangency ............................................6-14,6-15,6-18
Overall initialization ............................................................7-31 Polarogram simulator................................................ 7-54,7-58
Overcharging of working electrode ...................................7-43 Polarography....................................................................... 1-1
Overflow............................................................ 5-96,5-110,6-7 Polishing kit (6.2802.000).................................................. 9-10
Overlapping.......................................................................6-12 polynom ........................................................5-137,6-15,7-47
Overview of program instructions....................................5-177 Polynomial baseline ........................................................ 5-137
Overwrite mode .................................................................5-10 Pos. .......................................................5-45,5-61,5-79,5-167
Oxygen ............................................................................5-264 Position ........................................................................ 5-40
Oxygen in the analysis solution .........................................7-42 Position number ..............................................5-61,5-79,5-167
Position of Dosimat/Dosino .............................................. 5-40
Position of rinsing Dosinos ....................................... 5-26,5-31
P Position of solution............................................................ 5-45
Potentiometric Stripping Analysis ........................... 5-259,7-34
P .......................................................................................5-88
Potentiostat ......................................................................... 8-6
P.delta ...........................................................................5-89
Power consumption ............................................................ 8-4
P.mean .............................................................................5-88
Prefix ................................................................................. 6-36
P.peak ................................................ 5-88,5-100,5-140,6-19
PREP)................................................................... 5-179,5-256
Packaging............................................................................3-1
Prep.cycles....................... 5-184,5-187,5-221,5-292,5-307
PADD>M ................................................................ 5-181,5-250
Preparation cycles ............................5-184,5-187,5-221,5-292
Page advance .................................................................5-167
Preparation of diluted solutions ................................ 3-39,3-49
Page Down ........................................................................5-10
Pressure............................................................................ 5-25
Page parameters ...............................................................5-11
<Pressure>.................................................................... 5-21
Page title............................................................................5-11
<Prev. VR>................................................5-98,5-111,5-118
Page Up ............................................................................5-10
<Prime all>.................................................................. 5-39
Paper spindle (6.2241.020)
Installing paper ................................................................3-3 <Prime Dosimat>......................................................... 5-38
Ordering designation.......................................................9-2 <Prime Dosinos>................................................. 5-23,5-28
Parallel interface ..............................see Printer connection 14 <Prime tube> ............................................................... 5-28
Param.name ..................................................................5-307 PRINT................................................................... 5-182,5-258
Parameter <Print all>................................. 5-44,5-48,5-53,5-57,5-60
Notation ...........................................................................1-3 Print list of all determinations ............................................ 5-53
Parameter variation............................................... 5-305,5-306 Print list of all files.............................................................. 5-57
Parity .................................................................... 5-18,8-11 Print list of all methods...................................................... 5-48
Parts and controls ...............................................................2-1 Print list of all samples ...................................................... 5-60
PC Print list of all solutions...................................................... 5-44
Connection to RS232 interface......................................3-53 <PRINT SCREEN> ............................................................ 5-9
PDOS>M ................................................................ 5-180,5-252 Print screen contents .......................................................... 5-9
Peak area.............................................. 5-88,5-100,5-140,6-19 <PRINT STOP> ................................................................. 5-9
Peak area test......................................................................6-9 Printer ................................................................ 5-20,5-172
Peak current ......................................................................5-88 Printer 6
Peak displacement ........................................... 7-36,7-38,7-40 Check............................................................................ 7-50
Peak height................................................... 5-100,5-140,6-19 Figure.............................................................................. 2-4
Peak height test ...................................................................6-9 Installing paper ............................................................... 3-3
Technical data................................................................. 8-3
Peak overlapping...............................................................7-47
Printer (external)
Peak voltage ..................................................... 5-88,5-99,6-10 Connection to parallel interface .................................... 3-51
Peak voltage test .................................................................6-9 Connection to RS232 interface ..................................... 3-52
Peak width .......................................................................5-101 Printer driver ..........................................3-51,3-54,5-19,5-20
Peak width test ....................................................................6-9 Printer connection 14
Peripherals.........................................................................9-11 Connection of printers................................................... 3-51

10 Index
Figure ..............................................................................2-3 PVC tubing (6.1801.080)............................................. 3-12,9-5

Selection of printer type.................................................5-20
Printer type................................................................5-19
Printout of a message .....................................................5-258
Problems with DME/SMDE................................................7-35
Q
Problems with HMDE ........................................................7-37 Quantity ............................................................ 5-140,5-161
Problems with RDE............................................................7-40
<Processed> ........................................................5-96,5-110
processed ........................................... 5-99,5-112,5-112,6-7
Processed curve........................................... 5-96,5-110,5-170
R
R ............................................................................ 5-88,5-170
Program...........................................................................5-17
r.double ..................................... 5-138,6-14,6-15,6-16,7-47
Program execution mode ..................................................5-74
r.half........................................................... 5-138,6-14,7-47
Program hold...................................................................5-244
<Rack def>.................................................................... 5-29
Program instructions .................................. 5-123,5-126,5-175
Rack definition......................................................... 5-32
Program interruption............................................................5-8
Rack name.............................................................. 5-33,5-36
Program number ...................................................5-167,5-170
<Rack param.> ............................................................. 5-33
Program start.......................................................................5-7
Rack pos............................................................. 5-34,5-310
Program stop.......................................................................5-7
Rack position .................................................................... 5-34
Program test..........................................................5-122,5-125
Rack position for mixing ................................................. 5-310
Program test run................................................................5-74
Rack type.............................................................. 5-33,5-36
Program version number...................................................5-17
Racks of 695 Autosampler................................................ 5-31
Prop.coeff. ......................................................5-250,5-252
Racks............................................................................... 5-31
Prop.fact. ............................................... 5-154,5-157,6-31
RADD>F................................................................. 5-181,5-266
Prop.factor ................................... 5-277,5-278,5-279,6-32
RADD>M................................................................. 5-181,5-266
Prop.subst. ......................................................5-250,5-252
RAM test ................................................................... 7-30,7-31
Properties of mercury ..........................................................7-2
Ramp slope ........................... 5-232,5-240,5-269,5-295,5-299
Proportional dispensing ................... 5-252,5-277,5-278,5-279
RAMP ............................................................... 5-178,5-269,8-1
Proportional standard addition........................................5-250
Range max................................................ 5-146,5-150,5-156
Proportionality coefficient ......................................5-250,5-252
Range min................................................ 5-146,5-150,5-156
Proportionality factor ......................... 5-92,5-154,5-157,5-163,
range violat. ............................................................. 5-83
......................................5-163,5-277,5-278,5-279,6-31,6-32
Rate 1........................................................................... 5-212
Protection against static charges ........................................7-1
Rate 2........................................................................... 5-212
Protection class .............................................................7-1,8-4
Ratio of effective mass concentrations........... 5-97,5-154,6-32
PSA curves ........................................... 5-101,5-170,6-18,6-19
Ratio of evaluation values ............................... 5-97,5-154,6-32
PSA segments.................................................................5-128
RDE
PSAMODE.............................................. 5-177,5-259,6-18,7-34
Construction.................................................................. 3-27
PSWEEP .......................................................... 5-178,5-261,8-1 Figure............................................................................ 3-28
Pt Auxiliary electrode 134 (6.0343.000) Insertion in measuring head ........................................... 3-8
Figure ............................................................................3-32 Program instruction..................................................... 5-271
Ordering designation.......................................................9-3 Regeneration................................................................. 3-27
Pt electrode tip (6.1204.120) .......................................3-27,9-8 Rotational speed ................................................... 5-25,5-30
Pt tip 135 Startup procedure......................................................... 3-27
Figure ............................................................................3-32 Switching on/off ............................................................ 5-22
Technical data ................................................................ 8-7
PTFE tube 46 (6.1819.000) Troubleshooting ............................................................ 7-40
Figure ..............................................................................2-9
<RDE>............................................................... 5-22,5-24,5-29
PTFE tube 50 (4.647.1350)
Figure ..............................................................................2-9 RDE ............................................................... 5-25,5-177,5-271
PTFE tube 64 (6.1819.010) READY................................................................. 5-7,5-11,5-72
Figure ....................................................................2-10,3-11 Reagents........................................................................... 7-33
PTFE tube 66 (6.1819.010) Rear base point .............................................................. 5-102
Figure ....................................................................2-10,3-11 rear overlapping ...................................... 5-90,6-13,7-47
PTFE tube 91 (6.1819.010) <Recalc. file(s)> ............................................ 5-53,5-57
Figure ............................................................................3-11 <Recalc. from orig.> ............................................... 6-7
Insertion in measuring head ..........................................3-10
<Recalc.>...................................................................... 5-69
PTFE tube 92 (6.1819.010)
Recalculation ................................. 5-53,5-57,5-69,5-84,5-160
Figure ............................................................................3-11
Insertion in measuring head ..........................................3-10 Receive mode ....................................................... 5-19,8-11
Pulse amplitude.........................................................5-230,8-6 Recognition......................................................................... 8-2
Pulse time........................................................................5-230 Recognition ............................................................... 5-131
PURGE ...................................................................5-179,5-264 Recognition of peaks .......................................................... 6-9
Purging .............................5-21,5-179,5-264,5-265,5-301,7-42 Recognition of waves.......................................................... 6-9
<Purging> ......................................................................5-21 Recognition parameters ....................................... 5-105,5-131
Purging...........................................................................5-25 Recognition tests ................................................................ 6-9
Purging time ....................................................................5-301 red. fitting prec........................................... 5-88,5-88
Purity of reagents ..............................................................7-33 Reduced hardware handshake......................................... 8-14
<Put line> ..................................................................5-173 Ref.subst................................................................... 5-156

10 Index
referen............................................................. 5-155,5-158 Resolution.................................................................. 5-261

Reference electrode 43 Resolution for PSA measurement ................................... 5-261
Add bridging electrolyte ................................................3-30 Result calculation.............................................................. 6-22
Add internal electrolyte ..................................................3-30
Result deviation................................................................. 5-83
Construction ..................................................................3-29
Electrical connection .....................................................3-30 Result quantity ................................................................ 5-161
Figure ..................................................................... 2-9,3-29 Result unit ....................................................................... 5-165
Insertion in measuring head ................................... 3-8,3-30 "RESULTS" ........................................................................ 5-82
Installation......................................................................3-30 <RESULTS> .................................................................... 5-82
Startup procedure .........................................................3-30
Technical data .................................................................8-7 Retaining nut 108 (4.420.2850)
Figure............................................................................ 3-15
Reference solution................................................ 5-266,5-267 Mounting the capillary................................................... 3-17
Reference substance.................................... 5-155,5-158,6-31 Return to start position...................................................... 5-10
Reference substance for Reversible electrode processes............................ 5-221,5-292
proportional dispensing...............................................5-252
Reversible redox reactions.................................... 5-184,5-187
Reference substance for
proportional standard addition ....................................5-250 Reversible redox systems ............................................... 5-223
Reference system 122 (6.0728.0X0) RINSE...........................................................5-181,5-275,6-21
Figure ............................................................................3-29 Rinse cycles .................................................................... 5-275
Ordering designation................................................ 9-3,9-8 <Rinse meas.v.>................................................. 5-23,5-28
References dealing with mercury ........................................7-5 Rinse measuring vessel ..................................5-23,5-28,5-275
Reformat data card ...........................................................5-57 <Rinse needle>........................................................... 5-27
Regeneration of carbon electrodes .................................5-212 Rinse position ...........................................5-23,5-26,5-29,5-31
Regeneration of RDE.........................................................3-27 Rinse transfer needle ........................................................ 5-27
Regression value ...............................................................5-92 Rinse unit pos.................................................. 5-26,5-31
Regression value calculated for sample .........................5-145 Rinse volume ..................................................5-26,5-30,5-275
REM....................................................................... 5-182,5-272 Rinsing Dosinos ...................................................... 5-44,5-275
Remark ............................................................................5-272 <Rinsing Dosinos> ............................................ 5-23,5-28
Remark ............................5-45,5-67,5-258,5-272,5-281,5-282 Rinsing equipment (6.5323.000)
Remark 1.............................................................. 5-74,5-168 Installation ..................................................................... 3-46
Remark 2.............................................................. 5-74,5-168 Ordering designation .................................................... 9-10
Remarks regarding solution ..............................................5-45 Rinsing quiver (6.2754.000) ...................................... 3-39,3-48
Remote interface .....................................see Control Lines 23 Rinsing solution................................................................. 5-45
Remote keyboard ................................................ 5-19,8-12 RMS voltage amplitude......................................... 5-184,5-187
Remote keypad mode .......................................................5-19 Rot.speed ..................... 5-25,5-30,5-271,5-297,5-302,5-307
Removing the data card ......................................................3-5 Rotating Disk Electrode ..............................................see RDE
<Rename table> ...........................................................5-60 Rotational speed of RDE.................................5-25,5-30,5-271
REP)................................................................................5-274 Rotational speed of stirrer.....................5-25,5-30,5-297,5-302
REP)n .............................................................................5-178 <RS232 Ifc.1> .....................................5-48,5-52,5-56,5-57
Replenishing mercury........................................................3-23 <RS232 Ifc.2> .....................................5-48,5-52,5-56,5-57
Replication........................................... 5-88,5-99,5-168,5-170, RS232 Interface 16
.......................................................... 5-172,5-273,5-274,6-6 Connection of devices .................................................. 3-52
Figure........................................................................ 2-3,2-5
Replication loops.............................................................5-178
RS232 Interface 17
Report ActDetm .............................................. 5-169,5-169 Connection of devices .................................................. 3-52
Report ActMeth .............................................. 5-169,5-169 Figure........................................................................ 2-3,2-5
Report Comment .............................................. 5-169,5-169 RS232 interfaces
Report Eval ................................................................5-168 Check............................................................................ 7-52
Report Full ..................................................... 5-168,5-169 Connection of devices .................................................. 3-52
Features ........................................................................ 8-10
Report MethSpc .............................................. 5-168,5-169
Handshake.................................................................... 8-14
Report Mpts ..................................................... 5-168,5-169 Pin assignment ............................................................. 8-17
Report Short..............................................................5-168 Settings ......................................................................... 8-11
Reports ............................................................................5-167 Technical data......................................................... 8-3,8-10
Reprints ...............................................................................1-8 RS232 settings........................................................... 5-18
Res.dev..........................................................................5-83 RSIfc.1 ........................................................................ 5-172
Res.unit.............................................................. 5-165,6-36 RSIfc.2 ........................................................................ 5-172
Reset ...................................................................................5-7 Run ....................................................................... 5-167,5-170
Reset button 15 Run mode ........................................................................ 5-74
Figure ....................................................................... 2-3,2-5 Run number ..................................................5-75,5-167,5-170
Initiating a reset .............................................................7-29
<Reset Ifc.1>..............................................................5-17
<Reset Ifc.2>..............................................................5-17
<Reset param.> ................5-104,5-105,5-107,5-113,5-121
S
Reset RS232 interfaces .....................................................5-17 S.front ..............................................5-102,5-139,6-11,6-12
Reset with deletion of working storage..............................7-30 S.rear.................................................5-102,5-139,6-11,6-12
<Reset zoom>..............................................................5-118 S0.................................. 5-63,5-163,5-163,5-205,5-235,5-277,
................................................... 5-278,5-279,6-4,6-20,6-36
Resetting the VA Simulator ..............................................5-286
S1..................................... 5-62,5-80,5-163,5-163,5-205,5-235
Resid.com.var..............................................................5-67

10 Index
S2 ...................... 5-62,5-80,5-163,5-163,5-205,5-235,6-4,6-20 Screw thread 104

S3 .....................................5-62,5-80,5-163,5-163,5-205,5-235 Figure............................................................................ 3-15
Safety...................................................................................7-1 SDOS>A................................................................. 5-180,5-277
Safety considerations concerning mercury.........................7-2 SDOS>F................................................................. 5-180,5-278
Safety directions............................................................8-4,8-8 SDOS>M................................................................. 5-180,5-279
Safety specifications .....................................................8-4,8-8 Sealing needle 97 (6.1247.020)
Adjusting ............................................................... 3-18,3-22
Sample Changer 717 ............................................5-245,5-284
Figure............................................................................ 3-15
Manual operation...........................................................5-23
Operating characteristics.............................................. 3-14
Sample data ................................................................5-78,6-5 Ordering designation ...................................................... 9-4
Sample data files...............................................................5-56 Replacement................................................................. 3-26
Sample data line........................................................5-78,5-79 Sealing ring 106 (4.420.2800)
Sample data table .....................................................5-59,5-78 Figure............................................................................ 3-15
Sample digestion ..............................................................7-33 Replacement................................................................. 3-26
Sample holder ...................................................................5-33 <Secure/Unsecure> .................................... 5-49,5-53,5-57
Sample identification 1 ......................... 5-62,5-80,5-167,5-170 see Evaluations......................................................... 5-83
Sample identification 2 ................................... 5-62,5-80,5-167 Segm.name.................................................................... 5-280
Sample identification 3 ................................... 5-62,5-80,5-167 Segment ............................... 5-111,5-125,5-170,5-182,5-279
Sample preparation.......................... 5-179,5-254,5-256,5-257 Segment call-up.............................................................. 5-280
Sample rack ..............................................................5-31,5-33 Segment curves .............................................................. 5-108
Sample size ......................................... 5-63,5-81,5-163,5-163, Segment name .................................5-125,5-131,5-170,5-280
.................................................. 5-167,5-205,5-235,6-4,6-36 <Segment name>......................................................... 5-125
Sample size/S0 .................................. 5-63,5-81,5-167,6-4 Segment programs......................................................... 5-124
Sample table......................................................5-78,5-167 "SEGMENTS" ............................................................ 5-124,6-3
Sample vessel (FEED)............................... 5-213,5-227,5-237, <SEGMENTS> .............................................................. 5-124
...................................................... 5-238,5-266,5-278,5-289 <Select all> ............................................... 5-48,5-53,5-57
Sample volume................................... 5-289,5-290,5-291,6-20 <Select curve>................................................. 5-95,5-109
Sample volume Select determinations ....................................................... 5-53
in measuring vessel......5-87,5-163,5-163,5-205,5-235,6-20 Select files......................................................................... 5-57
Sample ...........................................................................5-170 Select measured value ................................................... 5-115
Samples ............................................................................7-33 Select methods ................................................................. 5-48
"SAMPLES" ..................................................................5-59,6-5 Select segment curves ................................................... 5-117
<SAMPLES> ....................................................................5-59 <Select segment> ................................ 5-109,5-117,5-125
Sample-specific variable S1............. 5-163,5-163,5-205,5-235 <Select subst.>....................................... 5-84,5-95,5-130
Sample-specific variable S2............. 5-163,5-163,5-205,5-235 Select substance .................................................... 5-84,5-130
Sample-specific variable S3............. 5-163,5-163,5-205,5-235 Select substance curves................................................... 5-95
Sampling ...........................................................................7-33 Select zoom range....... 5-103,5-106,5-113,5-114,5-117,5-120
Sampling Unit 708...........................................................5-283 Selection fields.................................................................. 5-13
Commands....................................................................5-16
Selection of objects for automatic output ....................... 5-167
<Save all> ....................................................................5-67
Send contents of current field........................................... 8-12
Save common variables ....................................................5-67
Send contents of current screen page ............................. 8-12
<Save Ifc.par.> .........................................................5-17
SEND>RS1 ............................................................ 5-182,5-281
<Save param.>.........5-105,5-105,5-107,5-107,5-113,5-121
SEND>RS2 ............................................................ 5-182,5-282
Sbst:<subst>....................................................5-168,5-172
Sending ASCII reports ...................................................... 8-12
<Scale>...................................................... 5-98,5-111,5-118
Sending binary files .......................................................... 8-12
Scaling of current axis ...........................................5-127,5-134
Sending messages ............................................... 5-281,5-282
Scaling of voltage axis for PSA segments.......................5-128
Serial interface .........................................see RS 232 interface
Scaling of y axis of PSA curves .......................................5-135
Serial number 7
Scan..................................................................................5-20 Figure........................................................................ 2-3,2-5
SCANCTRL.............................................................5-182,5-276 Serial number 33
Scheme of inert gas connections......................................3-13 Figure.............................................................................. 2-7
Scheme of the tubing connections Series determination ......................................................... 5-75
for Rinsing and Siphoning Dosino.................................3-47 <Set Ctrl lines> ...................................................... 5-16
Scope .....................................................................5-138,6-11 Set ................................................................................... 5-20
Scope of delivery.................................................................9-1 Set Up ............................................................................... 5-15
Screen 1 SETCTRL .............................................................. 5-182,5-283
Figure ........................................................................2-2,2-4
Setting instrument supply voltage....................................... 3-2
Technical data .................................................................8-2
Setting output control lines ............................................. 5-283
Screen contrast .................................................. 4-5,5-16,5-18
Setting up filling station..................................................... 3-20
Screen dialog ....................................................................5-11
Setting up instruments ........................................................ 3-1
Screw connection 110
Connection of electrode cable 37 .................................3-10 <Settings>.................................................................... 5-22
Figure ............................................................................3-15 Sgmt:<segm> ..................................................... 5-168,5-172
Screw thread 98 SHIFT................................................................... 5-182,5-284
Figure ............................................................................3-15 Shift key .............................................................................. 5-3
Screw thread 100 Shift measured values .................................................... 5-116
Figure ............................................................................3-15

10 Index
Short report......................................................................5-168 Sort methods .................................................................... 5-49

Sign.dig......................................................................5-165 Sort solutions .................................................................... 5-44
Sign.digits ................................................................5-140 Space bar ................................................................... 5-3,5-12
Signal noise .........................................................................6-8 Spanner (6.2739.000) ......................................................... 9-7
Significant digits ................................................... 5-140,5-165 Special needle position............................................. 5-33,5-36
SIMPULSE............................................................ 5-182,5-285 Special reports.......................................................... 8-11,8-12
SIMRESET............................................................ 5-182,5-286 Speed............................................................................... 5-34
Simulation of standard additions.....................................5-285 <Spike elimin.>....................................................... 5-111
Size................................................................. 5-49,5-54,5-58 Spike elimination.......................................5-111,5-115,6-7,8-2
Skip to next instruction ........................................................5-8 Spikes .....................................................5-96,5-110,5-115,6-7
Slope .................................................... 5-92,5-163,5-163,6-12 Square wave voltammetry....................................... 5-292,7-34
Slope ..................... 5-92,5-144,5-145,5-149,5-151,6-25,6-28 SQWMODE ......................................................5-177,5-292,7-34
Slope at base point ................................................ 5-139,6-11 SSWEEP...........................................................5-178,5-295,8-1
Slope of baseline.............................................................5-102 Stand address .................................................................. 5-75
Slope of calibration curve............................... 5-151,6-25,6-28 Stand address ............................................................. 5-75
Slope of standard addition curve ....................................5-145 Stand address 35
Slot 3 for data card Figure.............................................................................. 2-7
Figure ....................................................................... 2-2,2-4 Setting ............................................................................. 3-6
Inserting the data card ....................................................3-5 Stand ring (6.2703.000) ...................................................... 9-6
Slotted screw 54 <STAND> ........................................................................ 5-21
Figure ..............................................................................2-9 Standard addition
Inert gas connection scheme ........................................3-13 Calibration technique .................................................. 5-142
Slotted screw 71 Curve type................................................................... 5-144
Adjusting tapping mechanism.......................................7-35 Display of calibration curve........................................... 5-97
Figure ............................................................................2-10 Illustrative method ........................................................... 4-9
Inert gas connection scheme ........................................3-13 Procedure ..................................................................... 6-24
Slotted screw 96 (3.420.3920) Program instructions.....................5-190,5-191,5-192,5-250
Adjusting the mercury flow ................................... 3-18,3-22 Programming .................................................... 5-143,5-143
Figure ............................................................................3-15 Result display................................................................ 5-92
Slotted screw 101 (4.420.2960) Standard addition curve.................................................... 6-25
Figure ............................................................................3-15 Standard addition mass.......................................... 5-86,5-162
SMDE Standard addition ratio ..................................................... 6-27
Drop size .............................................................. 5-25,5-30 Standard addition solutions .........................5-43,5-145,5-181,
Operating characteristics ..............................................3-14 ................................................................5-192,5-194,5-250
Program instruction .....................................................5-287
Standard deviation............................................6-24,6-28,6-32
Switching on/off .............................................................5-22
Troubleshooting.............................................................7-35 Standard deviation of evaluation quantities ............ 5-89,5-162
<SMDE> ............................................................ 5-22,5-24,5-29 Standard formulae .................................................. 5-164,6-36
SMDE............................................................. 5-25,5-177,5-287 Standard operating procedure ......................................... 7-58
<Smoothed> ......................................................... 5-96,5-110 Standard rack ...........................................5-31,5-34,5-34,5-45
smoothed.............................................. 5-99,5-112,5-112,6-8 Standard solutions ............................................................ 7-33
Smoothed curve ..................................... 5-96,5-110,5-170,6-8 Standard substance.......................................................... 5-45
Smoothing .................................................................... 6-8,8-2 Standby voltage ..............................................5-26,5-31,5-248
Smoothing window ....................................................... 6-8,8-2 Standby volume ........................................................ 5-26,5-30
SMPL/F ................................................................ 5-180,5-289 <START>........................................................................... 5-7
SMPL/M ................................................................ 5-180,5-290 Start dilution operation...................................................... 5-39
SMPL>M ................................................................ 5-180,5-291 <Start dilution> ...................................................... 5-39
Socket-outlet adapter (6.2125.030).......................... 3-54,9-12 Start interval........................................................... 5-77
Softkey Start recalculation ............................................................. 5-69
Notation ...........................................................................1-3 Start zoom............................................................. 5-114,5-120
Softkey bar ........................................................................5-12 <Start zoom> ...............................5-103,5-106,5-113,5-117
Softkeys ........................................................................ 5-2,5-9 STATE................................................................... 5-205,5-235
Software.............................................................................9-11 Static charges ..................................................................... 7-1
Software handshake with character stop ..........................8-15 Static Mercury Drop Electrode.................................see SMDE
Software handshake with line stop ....................................8-16 Status messages .............................................................. 5-11
Software reset........................................................... 7-29,7-30 std.add. .............................................................. 5-92,5-142
Soln.name.............................5-44,5-146,5-159,5-192,5-194, Std.dev. ................................................................ 5-89,6-36
...........................................5-226,5-227,5-229,5-250,5-252, Std.subst..................................................................... 5-45
............................................5-266,5-267,5-277,5-278,5-279 Step size for variation...................................................... 5-308
Solution name....................................................................5-44 <(STEP)>........................................................................... 5-8
"SOLUTIONS" ............................................................. 5-43,6-5 STIR ..................................................................... 5-180,5-297
<SOLUTIONS> ................................................................5-43 Stirrer
<Sort> ............................................................ 5-49,5-53,5-57 Construction.................................................................. 3-32
<Sort by name> ...........................................................5-44 Insertion in measuring head.......................................... 3-32
<Sort by position>...................................................5-44 Program instructions...............................5-297,5-298,5-302
Rotational speed ................................................... 5-25,5-30
Sort determinations ...........................................................5-53
Startup procedure......................................................... 3-32
Sort files.............................................................................5-57 Switching on/off ............................................................ 5-22

10 Index
Technical data .................................................................8-8 Switch off instrument .......................................................... 3-3

Test..................................................................................4-7 Switch off pressure ........................................................... 5-21
Stirrer tip 63 (6.1204.090) Switch off purging................................................... 5-21,5-265
Figure ............................................................................2-10
Switch off stirrer ...................................................... 5-22,5-298
Insertion in measuring head ............................................3-8
Ordering designation.......................................................9-3 Switch on instrument .......................................................... 3-3
<Stirrer> ......................................................................5-22 Switch on pressure ........................................................... 5-21
Stirrer...........................................................................5-25 Switch on purging................................................... 5-21,5-264
Stirring .............................................................................5-180 Switch on stirrer ............................................ 5-22,5-297,5-302
Stirring time .....................................................................5-302 Switch to Rinsing Dosinos ................................................ 5-28
Stock solutions ..................................................................7-33 <Switches>............................................................ 5-24,5-29
Stop bit(s) ..........................................................5-18,8-11 Switch-off time......................................................... 5-17
Stop of printing....................................................................5-9 SWline............................................................................. 8-16
Stopper 25 (6.2709.080) <Syntax check>......................................................... 5-160
Figure ............................................................... 2-6,2-9,3-28 Syringe 111 (6.2816.020)
Ordering designation.......................................................9-6 Figure............................................................................ 3-16
Stopper 119 (6.2709.040) Filling with mercury ....................................................... 3-17
Connection of FEP tubing 51 ........................................3-10 Ordering designation ...................................................... 9-7
Connection of FEP tubing 59 ........................................3-10 System messages ............................................................ 5-71
Figure ............................................................................3-28 System validation.............................................................. 9-17
Insertion in measuring head ..........................................3-10 <System window>......................................................... 5-71
Ordering designation.....................................................9-10
Stopper (6.2709.050) ..........................................................9-6
Stopper (6.2730.030) ..........................................................3-7
Storage capacity of data card...........................................5-58 T
Storage of RS232 parameters...........................................5-17 t ...................................................................................... 5-88
Storage space .................................................. 5-49,5-54,5-58 t.delta .......................................................................... 5-89
Storage temperature .....................................................8-4,8-9 t.depos ........................................................................ 5-261
Storages ............................................................................5-46 t.div............................................................................. 5-128
<Store param.> .........................................................5-104 t.drop................................. 5-186,5-189,5-224,5-225,5-231,
Store rack data ..................................................................5-33 ......................................................5-242,5-271,5-287,5-294
<Store to 695> ...........................................................5-33 t.line........................................................................... 5-307
Storing the MME................................................................3-22 t.mean............................................................................. 5-88
Straight line........................................................................6-22 t.meas.............................................5-223,5-230,5-292,5-307
Stripping voltammetry ....see Adsorptive stripping voltammetry t.peak........................................................... 5-88,5-101,6-19
Student factor ....................................................................6-23 t.pulse ........................................................................ 5-307
Subpage............................................................................5-12 t.step............................................5-184,5-187,5-223,5-230,
Subsequent modification ..................................................5-77 ................................................................ 5-269,5-292,5-307
<Subst. name>............................................................5-130 t.threshold ................................................. 5-89,5-133,6-9
Substance ..................................................... 5-85,5-91,5-99 t/s ............................. 5-123,5-126,5-175,5-232,5-240,5-261,
........................................... 5-295,5-299,5-301,5-302,5-303
Substance curves..............................................................5-95
t/U.begin.................................................................... 5-135
Substance mass..............................................................5-162
t/U.end ........................................................................ 5-135
Substance mass in measuring vessel...............................5-86
t/U.scale.................................................................... 5-135
Substance mass in the sample .........................................6-20
Takeover solutions from method ...................................... 5-44
Substance name .................................. 5-85,5-91,5-130,5-131
Tangent method.............................................. 5-136,6-14,6-18
Substance parameter test ...............................................5-130
Tapping mechanism ......................................................... 7-35
Substance parameters ....................................................5-129
<Teach mode> ............................................................... 5-32
Substance recognition ................................. 5-98,5-105,5-131
Techn.............................................................................. 5-92
"SUBSTANCES".........................................................5-129,6-3
Technical data .................................................................... 8-1
<SUBSTANCES>...........................................................5-129
Technique ............................................................. 5-141,5-147
<Subtrac.> ....................................................................5-96
Technique.......................................................... 5-142,5-153
subtracted ............................................................5-99,6-16
Temperature ................................................................... 5-150
Subtracted curve ...............................................................5-96
Temperature ..................................................... 5-156,5-159
Subtraction ......................................................................5-164
Temperature dependence ...............5-149,5-149,5-150,5-155,
Supply voltage............................................. see Mains voltage ............................................... 5-155,5-156,5-159,6-31,6-35
Support documentation.......................................................1-4 test ....................................................................... 5-74,5-276
Suspend single measurements.........................................5-84 Test condition ................................................................. 5-276
<Suspend/activate> ..................................................5-84 Test condition for decision.................................... 5-205,5-235
SWchar .............................................................................8-15 Test method...................................................................... 7-54
Sweep....................................................... 5-178,5-299,6-3,6-6 Test plug (3.496.8480).............................................. 7-49,7-52
SWEEP ............................................................ 5-178,5-299,8-1 Test plug (3.496.8550)...................................................... 7-49
Sweep rate ................................................................5-299,8-6 Testing beep ............................................................. 7-30,7-32
Sweep rate ................................... 5-232,5-240,5-269,5-295 Testing purging................................................................... 4-6
Sweep rate for conditioning cycles .................................5-212 Testing stirrer ...................................................................... 4-7
Sweep voltage range...........................................................8-6 Tests to check the 747 VA Stand........................................ 4-6
Switch between insert/overwrite mode..............................5-10

10 Index
Thermal paper (6.2237.040)

Installing paper ................................................................3-3
Ordering designation.......................................................9-2
U
U ...................................................................................... 5-88
Thermal printer ........................................................ see Printer
U.ampl.................................. 5-184,5-187,5-230,5-292,5-307
Threaded opening 73
Connection of FEP tubing 89 ........................................3-10 U.begin .............................................................. 5-134,5-135
Figure ..............................................................................3-9 U.div.........................................................5-128,5-134,5-135
Threaded opening 74 U.end................................... 5-128,5-134,5-135,5-212,5-232,
Connection of FEP tubing 90 ........................................3-10 ........................................... 5-240,5-269,5-295,5-299,5-307
Figure ..............................................................................3-9 U.max............................................................................... 6-10
Threaded opening 77 U.meas.......................................................5-246,5-303,5-307
Figure ..............................................................................3-9 U.min............................................................................... 6-10
Threaded opening 80 U.peak.............................................................5-88,5-99,6-10
Figure ..............................................................................3-9
U.scale ........................................................................ 5-128
Threaded opening 82
U.standby ....................................................5-26,5-31,5-248
Figure ..............................................................................3-9
U.start .........................................5-212,5-232,5-240,5-261,
Threaded opening 83
......................................................5-269,5-295,5-299,5-307
Figure ..............................................................................3-9
U.step........................ 5-232,5-240,5-269,5-295,5-299,5-307
Threaded opening 84
Figure ..............................................................................3-9 U.tol....................................................................... 5-131,6-9
Threaded opening 85 U.verify ................................................................ 5-131,6-9
Figure ..............................................................................3-9 U.width max.......................................................... 5-132,6-9
Threaded opening 87 U.width min.......................................................... 5-131,6-9
Connection of FEP tubing 89 ........................................3-10 U.width ................................................................ 5-101,6-10
Figure ..............................................................................3-9
U/2 ...................................................................5-88,5-99,6-10
Threaded opening 88
Uf2 ................................................................................... 6-12
Figure ..............................................................................3-9
Ultra Trace Graphite electrode tip (6.1204.100) ......... 3-27,9-8
Time............................................................. 5-17,5-167,5-170
Undiluted samples ...................................................... 5-63,6-4
Time for sweep ................................................................5-261
<Unlinked peaks> ............................................ 5-111,6-10
Time for voltage step ............................................ 5-232,5-240
Unselect file(s) .................................................................. 5-52
Time for voltage sweep ........................................ 5-295,5-299
<Unselect file(s)> .......................................... 5-48,5-57
Time interval for automatic determination start .................5-77
Unstable baseline .............................................7-35,7-37,7-40
Time interval for voltage step..................... 5-184,5-187,5-223,
................................................................ 5-230,5-269,5-292 Unsuitable bridging electrolyte ......................................... 7-43
Time limit value................................................................5-133 <Up> ................................................................................. 5-35
Time of recording ................................................. 5-167,5-170 <Upd.from method> ................................5-44,5-160,5-164
Title .......................................................... 5-73,5-123,5-168 Upper limit of working range.......................5-146,5-150,5-156
Title of data card................................................................5-58 <Uppr/lft corner> .............................5-103,5-107,5-113,
................................................................5-115,5-117,5-120
TO destination .........................................................5-172
Ur1 ................................................................................... 6-12
Tolerance for characteristic voltage ................................5-131
User name ....................................................5-74,5-167,5-170
Total deviation for mass concentration .............................5-85
User name ...................................................................... 5-74
Total error ..........................................................................6-23
User ..................................................................... 5-167,5-170
Total scatter ...................................................... 6-26,6-29,6-34
UV sample rack (6.2041.100) ................................... 5-62,5-62
Total volume ...........................5-163,5-163,5-289,5-290,5-291
UV sample rack (6.2041.110) ................................... 5-62,5-62
Toxicity of mercury...............................................................7-3
Uw.front ........................................................................ 6-12
TPURGE ................................................................ 5-179,5-301
Uw.rear .......................................................................... 6-12
Trace analysis rules ...........................................................7-33
Transfer needle..................................................................5-27
Transfer of standard formulae .........................................5-160
Transfer speed ..................................................................5-34 V
Transfer tubing ..................................................................5-28 V ............................................................................ 5-88,5-170
Transfer volume.......................................... 5-196,5-237,5-238 V.add......................... 5-192,5-194,5-196,5-226,5-227,5-229,
Transport damage...................................................... 3-1,9-14 ................................ 5-237,5-238,5-250,5-252,5-266,5-267,
Transport temperature.................................................. 8-4,8-9 ............................................. 5-277,5-278,5-279,5-311,6-21
Trapping of mercury drops..................................................7-4 V.added ........................................................................ 5-228
Trimming tool (6.2827.000) ...............................................9-10 V.burette ...................................................................... 5-40
Troubleshooting.................................................................7-33 V.display ...................................................................... 5-40
TSTIR .................................................................. 5-180,5-302 V.eff............................................................................... 6-21
TSWEEP .......................................................... 5-178,5-303,8-1 V.end dilution........................................................... 5-42
Tubing coupling 118 (6.1809.000) V.fraction............... 5-64,5-289,5-290,5-291,6-4,6-20,6-36
Figure ............................................................................3-20 V.init............................................................................. 5-41
Tubing coupling (6.1808.000) .............................................9-5 V.meas max............................................................ 5-26,5-30
Type............................................................... 5-40,5-136,6-11 V.meas........................................................................... 5-275
Type of curve ...................................................................5-170 V.mix............................................................................. 5-310
V.rinse ........................................................5-26,5-30,5-275
V.sample max ....................................................... 5-34,5-36
V.sample ................................................................ 6-20,6-21

10 Index
V.standby ..............................................................5-26,5-30 Variable V0........................................................................ 5-87

V.total..............................5-64,5-289,5-290,5-291,6-4,6-36 Variances .......................................................................... 6-23
V.tube in ......................................................................5-41 Variation ..................... 5-88,5-99,5-168,5-170,5-172,5-307,6-6
V.tube out ....................................................................5-41 VARNI................................................................... 5-178,5-307
V0 ............................................. 5-87,5-163,5-163,5-205,5-235 Vent opening 125
V0.CSoln. ..........................................................5-151,5-157 Figure............................................................................ 3-29
V0.sample ............................................. 5-64,5-87,6-20,6-21 Vent opening 130
Figure............................................................................ 3-29
VA Back Up ................................... see Metrodata VA Back Up
Verification voltage.................................................. 5-131,6-10
VA Database.................................see Metrodata VA Database
Vfrac................................................................... 5-163,5-163
VA Simulator (3.496.8380).....................................5-285,5-286
Vmeas................................................................... 5-163,5-163
<VA Stand 1>................................................................5-22
VMIX ..................................................................... 5-181,5-310
<VA Stand 2>................................................................5-22
Voltage amplitude....................................... 5-184,5-187,5-292
VA Stand 747
Accessories for rinsing and siphoning off .....................3-10 Voltage difference to front base point............................. 5-101
Certificate of conformity and system validation.............9-18 Voltage difference to rear base point.............................. 5-102
Check ....................................................................7-54,7-58 Voltage ramp for cyclic voltammetry .............................. 5-269
Connection at 746 VA Trace Analyzer .............................3-6
Voltage source.................................................................... 8-6
EU declaration of conformity .........................................9-16
Front ................................................................................2-6 Voltage step .......................... 5-184,5-187,5-223,5-230,5-232,
Inert gas connection......................................................3-12 ..................................... 5-240,5-269,5-292,5-295,5-299,8-6
Installation .......................................................................3-6 Voltage sweep ................................................................ 5-299
Installation of rinsing equipment....................................3-46 Voltammetry........................................................................ 1-1
Instrument description.....................................................1-1 Volume bookkeeping .............................................. 5-275,6-21
Left side view ...................................................................2-8
Manual operation...........................................................5-21 Volume of auxiliary solution ..............5-226,5-227,5-228,5-229
Options............................................................................9-8 Volume of dosing tube...................................................... 5-41
Parts and controls ...........................................................2-6 Volume of measuring solution ........................................ 5-163
Rear .................................................................................2-7 Volume of reference solution ................................ 5-266,5-267
Right side view ................................................................2-8
Volume of rinse solution.................................................. 5-275
Scope of delivery.............................................................9-3
Technical data .................................................................8-6 Volume of standard addition solution ................... 5-192,5-194
"VA STAND" .......................................................................5-21 VR ................................................................... 5-88,5-99,5-111
VA trace analysis ...............................................................7-33 VR: xx................................................................. 5-168,5-172
VA Trace Analyzer 746 Vtot ..................................................................... 5-163,5-163
Certificate of conformity and system validation.............9-17 VWASH................................................................... 5-181,5-311
EU declaration of conformity .........................................9-15
Figure ..............................................................................2-5
Front ..........................................................................2-2,2-4
Installation .......................................................................3-2
Instrument description.....................................................1-1
W
Parts and controls .....................................................2-2,2-4 Wait time for instruction line........................ 5-123,5-126,5-176
Rear .................................................................................2-3 Warning............................................................................... 1-3
Scope of delivery.............................................................9-1 Warranty............................................................................ 9-14
Technical data .................................................................8-1 <Wash position>......................................................... 5-27
"VA TRACE ANALYZER".....................................................5-16 Wash volume .................................................................. 5-311
<VA TRACE ANALYZER> ................................................5-16 <Waste position> ...................................................... 5-27
Vacuum pump...................................................................3-19 Wave current..................................................................... 6-19
Vagaries of chemistry........................................................7-42 Wave height .................................................................... 5-100
Valid entries......................................................5-34,5-36 Wave width...................................................................... 5-101
Value assignments ..........................................................5-161 Weight........................................................................... 8-5,8-9
Valves ................................................................................3-13 Weighting of least squares ............................................... 6-23
VAR)n ...................................................................5-178,5-306 whole.....................................................5-138,6-15,6-17,6-18
var. not found ...........................................................5-83 Width............................................................................. 8-5,8-9
Variable ED:<subst>:<V> .............................................5-89 <Wipe position>......................................................... 5-27
Variable ES:<subst>:<V> .............................................5-89 Workg.com.var ............................................................. 5-67
Variable EU:<subst>:<V> .............................................5-88 <Working determ.> .................................................... 5-57
Variable EV:<subst>:<V> .............................................5-88 <Working method> ...................................................... 5-56
Variable KD:<subst> ......................................................5-92 Working range ...................... 5-146,5-149,5-149,5-150,5-155,
Variable KN:<subst> ......................................................5-92 ..........................................................5-155,5-156,6-30,6-35
Variable KS:<subst> ......................................................5-92 <Working storage> .................................... 5-48,5-52,5-56
Variable KY:<subst> .....................................................5-92
Variable MA:<subst> ......................................................5-86
Variable MC:<subst> ......................................................5-85
Variable MD:<subst> ......................................................5-85
X
X position .......................................................................... 5-34
Variable ML:<subst> ......................................................5-86
X= ..................................................................................... 5-36
Variable MS:<subst> ......................................................5-86
X-pos./mm...................................................................... 5-34
Variable S1 ................................................................5-62,5-80
Variable S2 ................................................................5-62,5-80
Variable S3 ................................................................5-62,5-80

10 Index
Y
Y position...........................................................................5-34
Y.offset.............................................. 5-92,5-151,6-25,6-28
Y.reg .................................................. 5-92,5-144,5-145,6-25
Y= ......................................................................................5-36
Y-Connection (6.1807.000)....................................... 3-12,9-10
Y-pos./mm.......................................................................5-34
Z
Z position...........................................................................5-34
Z= ......................................................................................5-36
Zoom range ..................5-103,5-106,5-113,5-114,5-117,5-120
<Zoom> .............................................................................5-71

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Section 1

746 VA Trace Analyzer Section 3

1 Introduction ...................................................................................... 1-1

1.2 Information about the Instructions for Use ...................... 1-2

1.3 Support documentation.............................................................. 1-4

2 Parts and controls .................................................................... 2-1

2.2 746.0020 VA Trace Analyzer .................................................... 2-4

2.3 747.0010 VA Stand ........................................................................ 2-6

3 Installation ........................................................................................ 3-1

3.2 Installation of 746 VA Trace Analyzer ................................. 3-2

3.3 Installation of 747 VA Stand ..................................................... 3-6

746 VA Trace Analyzer / 747 VA Stand I

3.4 Multi-mode electrode (MME) .................................................. 3-14

3.5 Rotating disk electrode (RDE) .............................................. 3-27

3.6 Reference electrode ................................................................... 3-29

3.7 Auxiliary electrode ...................................................................... 3-31

3.8 Stirrer ................................................................................................. 3-32

3.9 Connection of 685 Dosimats ................................................. 3-33

3.10 Connection of 700 Dosinos .................................................... 3-41

3.11 Connection of printers via parallel interface................. 3-51

3.12 Connection of devices via RS232 interfaces ................ 3-52

3.13 Connection of devices via remote interface.................. 3-56

II 746 VA Trace Analyzer / 747 VA Stand

4 Introduction to the operation ..................................... 4-1

4.2 Lead determination with standard addition ..................... 4-9

4.3 Lead determination with calibration curve ..................... 4-29

4.4 Lead determination with internal standard .................... 4-42

4.5 Basic method for DP polarography .................................... 4-56

4.6 Basic method for DPASV ......................................................... 4-61

746 VA Trace Analyzer / 747 VA Stand III

5 Operation ............................................................................................ 5-1

5.2 Screen dialog ................................................................................. 5-11

5.3 Set Up ................................................................................................ 5-15

5.4 Storages ........................................................................................... 5-46

5.5 Operation ......................................................................................... 5-68

5.6 Method Specifications ............................................................5-121

5.7 Program instructions...............................................................5-175

IV 746 VA Trace Analyzer / 747 VA Stand

6 Data processing and evaluation ............................. 6-1

6.2 Preparations before start of a determination .................. 6-2

6.3 Data acquisition .............................................................................. 6-6

6.4 Spike elimination and background compensation....... 6-7

6.5 Smoothing and differentiation ................................................ 6-8

6.6 Recognition of peaks and waves .......................................... 6-9

6.7 Baseline calculation ................................................................... 6-11

6.8 Height/area calculation ............................................................. 6-19

6.9 Content calculation..................................................................... 6-20

6.10 Formula calculation .................................................................... 6-36

746 VA Trace Analyzer / 747 VA Stand V

7 Safety, Errors, Troubleshooting,

7.2 Safety considerations concerning mercury ..................... 7-2

7.3 Error messages ............................................................................... 7-6

7.4 Troubleshooting ........................................................................... 7-33

7.5 Hardware/software faults in the instruments

7.6 Diagnosis ......................................................................................... 7-49

7.7 Standard operating procedure in the context of

VI 746 VA Trace Analyzer / 747 VA Stand

8 Technical data .............................................................................. 8-1

8.2 747 VA Stand .................................................................................... 8-6

8.3 RS232 interfaces .......................................................................... 8-10

9 Scope of delivery, Options, Warranty ................ 9-1

9.2 746.0020 VA Trace Analyzer .................................................... 9-2

9.3 747.0010 VA Stand ........................................................................ 9-3