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Sensor Performance
Titrant Performance &
Standardization
Content
Content
1
Introduction
Instrument Installation
Sensor Performance
Titrants Performance
Sample Size
Titrant Standarization
More Information
11
12
15
Disclaimer
The information contained in this guide is based on the current knowledge and experience of the authors. The
guide represents selected, possible application examples. The experiments were conducted and the resulting
data evaluated in our lab with the utmost care using the instruments specified in the description of each
application. The experiments were conducted and the resulting data evaluated based on our current state of
knowledge.However, this guide does not absolve you from personally testing its suitability for your intended
methods, instruments and purposes. As the use and transfer of an application example are beyond our control,
we cannot accept responsibility therefore.
When chemicals, solvents and gases are used, the general safety rules and the instructions given by the
manufacturer or supplier must be observed.
METTLERTOLEDO
Introduction
1. Introduction
Analytical instruments need regular maintenance to ensure proper working conditions and finally correct results.
One part of maintenance is concerned with instrument adjustment, certification and the like. Here manufacturer's
service engineers are due to take actions.
Another part are checks which are carried out by the users or an instrument responsible person. They are
performed frequently, on a daily or weekly base. The purpose of these checks is mainly to show whether the
instrument still performs according to expectation. If deviations occur, the check outcomes indicate correction
measures to the users.
For titrators, such maintenance tasks include its installation arrangement, the influence of temperature, the
sensor functionality, the titrant status and considerations regarding the sample size.
METTLERTOLEDO
Instrument Installation
2. Instrument Installation
Professional installation is fundamental to every analytical system. Depending on the requirements, the right
level of measures needs to be applied. The measures encompass the following 4 topics.
GLP
International bodies have elaborated a set of rules concerning the analytical work in labs in order to achieve
a standard regulation recognized and accepted in all countries of the world. These rules are commonly known
as GLP rules (Good Laboratory Practice). GLP is a formal framework for testing chemicals and consists of
10 specific rules.
Certification of an automatic titrator
The certification is a check of the instrument in order to verify that the technical specifications are fulfilled,
or to verify if the actual specifications meet the required level.
Certification is only part of a list of measures to guarantee correct results.
Validation of Titration Methods
While the goal of the analysis is to get correct results, very often the correct result is not necessarily the true
result. As a result, our goal is in fact to get the best possible result. This means a result as accurate, precise and
true as possible. To do this its important to critically investigate the factors affecting each of these things and
minimize the negative influences.
Qualification
Quality management requires the documentation of the performance over the lifetime of the instrument, i.e., from
the project phase through manufacturing, installation and operation through disposal of the instrument. All these
steps are resumed in the comprehensive concept of qualification:
Specification Qualification (SQ): Requirements, Functions, Design, HW/SW
Construction Qualification (CQ): Production control for each product
Design Qualification (DQ): Selection of correct instrument for intended use
Installation Qualification (IQ): Evidence of correct installation at customers facility
Operational Qualification (OQ): Evidence and compliance to specifications, SOPs, initial calibration,
user training
Performance Qualification (PQ): Periodic performance tests
Maintenance Qualification (MQ): Definition of preventive maintenance and calibration/certification intervals
Specially trained METTLER TOLEDO service engineers are able to perform the calibration and certification of the
titrator hardware with specific calibrated and certified tools (CertiCase, Excellence Test Unit).
Recommendations
Have the titration system installed by the instrument manufacturers specialist.
Perform a General System Suitability Test, proving that the titrator is performing according to the specifications.
Apply the concept of qualifications.
METTLERTOLEDO
Instrument Installation
Figure 1: Lab titrator family
METTLERTOLEDO
0.1 M NaOH
0.027
1 M NaOH
0.036
0.1 M HCl
0.026
1 M HCl
0.029
0.092
Recommendations
The best solution is to maintain constant temperature in the laboratory e.g. by air condition. Air condition
prevents temperature shifts.
Keep samples in the same place as titrants to ensure the same termperature. If the titrant concentration
(i.e. titer determination) and samples are measured at the same temperature then there is no error.
Do not expose the instrument to direct sunlight. Place it in a protected area.
Measure the temperature when performing pH measurements or end point titrations.
- METTLER TOLEDO offers pH sensors with integrated temperature probes for this purpose.
Use certified pH buffers for sensor calibration and apply their temperature table.
- METTLER TOLEDO titrators and pH meters automatically offer this possibility.
Perform titrant standardization when the temperature changes significantly. Re-standardizing reduces errors
due to temperature changes considerably.
Apply a temperature correction factor: Measure the temperature of the titrant and correct for the temperataure
change.
Example: Karl Fischer reagent, 10C temperature difference in the lab
f = 1 + (Ttiter Tsample) x CONC-ERR
CON C-ERR = 0.092 / 100 = 0.00092
TT TS = -10
f = 1 10 x 0.00092 = 0.9908
Multiplying raw results by this factor will account for the error.
METTLERTOLEDO
Sensor Performance
4. Sensor Performance
In pH endpoint titrations, critical factors affecting result accuracy are the slope and zero point of the sensor.
Both of these parameters are used to convert the raw mV signal from the sensor into the pH of the sample
solution using the Nernst equation:
pH = pHo E
S
E
S
pH0
, where
Since sensors are the actual measurement devices, they have a very large influence on the result of any
titration. Several factors contribute to their behaviour:
Response: If a sensor is sluggish because of old age or bad maintenance, the mV reading detected by the
sensor will lag behind the true value.
Calibration: Sensor calibration is particularly important for endpoint titrations (mainly pH endpoints). The
accuracy of the measured value is directly related to the determined amount of the analyte content in the sample.
Every maintenance procedure performed on a sensor (cleaning, regeneration, etc.), requires that the sensor
be calibrated again.
For pH, we recommend to apply a two or three point calibration. If samples are usually around 7, three
calibration points at pH 4, 7 and 9 (or 10) are good practice. This ensures that pH values below and above
7 are measured correctly. If the samples are acidic, a two point calibration between 4 and 7 is usually
acceptable and yields reliable results.
mV
real
pH
ideal
Reference electrode: A reference electrode has to provide a stable reference signal against which the
measurement signal is determined.
Conditioning: The measuring membrane of any pH or ion selective electrode needs to be conditioned before
the sensor can be used.
METTLERTOLEDO
Sensor Performance
When a pH sensor is used in non-aqueous media, the sensor needs to be conditioned before its next use to
restore the hydration layer.
Recommendations
Define a sensor calibration frequency to make sure that the sensor is measuring correctly, e.g. at least once
per day.
Instead of frequent calibrations, a sensor check can be performed. Such a check shows that the sensor is
still functioning correctly but it does not change calibration data. The sensor check should include the signal
drift over one minute, which is an important indication of the response time and signal stability. Use pH buffer
4 or 9 as a sample for this check.
Take the appropriate measures to automatically remind users to calibrate.
- METTLER TOLEDO Excellence titrators offer the functionality of monitoring sensors life span as well as usable
life. When a calibration needs to be performed or the sensor needs replacing, the user is automatically
reminded. A sensor can even be blocked from use if the setting is chosen accordingly.
Define acceptance limits for the calibration results.
- All METTLER TOLEDO titrators allow these limits to be set in the method. If the limit is exceeded, the user is
prompted and the calibration data is not saved.
When not in use, sensors should be stored in electrolyte.
METTLERTOLEDO
Titrants Performance
5. Titrants Performance
The concentration of a titrant needs to be known accurately to be able to determine the content of analyte in the
sample solution. If the titrant concentration is unknown or inaccurate, there will inevitably be a degree of error.
Titer
From the determined titrant concentration and the nominal titrant concentration, a titer value t is calculated. The
titer is the ratio of determined concentration / nominal concentration and is generally close to 1.
t = current titrant concentration / nominal titrant concentration
Example:
Current titrant concentration, by determination: 0.1036 mol/L
Nominal titrant concentration, by declaration: 0.1 mol/L
Titer t = 0.1036 / 0.1 = 1.036
For titer determinations, a primary standard is preferable. A primary standard is a substance that reacts with the
titrant in a known ratio ("stoichimetrically"). Its purity is high and well defined. It is very stable and has a high
molecular weight.
Examples of primary standards:
METTLERTOLEDO
Titrants Performance
In the case of alkaline titrants such as sodium and potassium hydroxide, its important that they are prepared
with water or solvent free of carbon dioxide, and that they are protected from atmospheric exposure to carbon
dioxide. Attach a drying tube containing an absorbent (e.g. NaOH on a granular carrier) to the titrant bottle.
Titrants such as iodine, permanganate and dichromate are light sensitive and need to be protected by storing
them in brown glass bottles. Karl Fischer reagents need to be protected from light as well as from the ingress
of atmospheric humidity. This is done by attaching a drying tube containing silica gel or molecular sieve to
the titrant bottle.
METTLERTOLEDO
10
Sample Size
6. Sample Size
By far, the biggest source of random errors resulting in precision problems is sample handling. These errors
include inhomogeneity of the sample, sample storage problems, incorrect sample size, weighing errors, and
careless handling. Critical in most cases is the sample size.
The sample should be large enough to ensure that it is representative, but it shouldnt be so large that repeated
burette fillings are necessary during the titration. The ideal sample size should give a titrant consumption of 30
to 80% of a single burette volume.
On the other extreme, the sample should be large enough so that weighing or sample measuring errors are kept
to a minimum. Here, a suitable balance must be used to ensure that the sample size exceeds the minimum
weight of the balance. This minimum weight is defined as the weight which when measured tenfold, results in a
repeatability of less than a certain pre-defined value; for example, United States Pharmacopoeia (USP) states
a value of less than 0.1%.
The sample volume including deionized water and/or other solvents that is used for any titration should be
sufficient to cover the sensors active parts (junction and sensing membrane or metal ring). Normally, this
volume should be around 50 mL to be able to fit the stirrer, titration tubes and dosing tubes in with the probe.
For smaller sample sizes, special micro-titration beakers can be used.
Recommendations
Make sure that you're using the needed balance resolution for your sample size. The accuracy and precision
of the sample size must be smaller than the expected accuracy and precision of the titration result.
For solid samples, use a calibrated analytical balance with 0.1 mg or 0.01 mg readability.
For liquid samples use a calibrated high quality Rainin pipette.
Choose a sample size that consumes 30 to 80% of the burettes volume. The sample size, titrant concentration
or burette size can be changed to reach this goal
Dilute the sample with an appropriate solvent volume to make sure the active parts of the equipment are
covered (approximately 50 mL). If necessary, use micro-titration equipment.
METTLERTOLEDO
11
Frequence of
Standarization
Protection of Titrant /
General Remarks
DG111SC
Deion. H2O
weekly
M002
DG111SC
Deion. H2O
weekly
Benzoic acid
C7H6O2; M =
122.12
M010
DG115SC
LiCl 1M
in EtOH
Isopropanol
weekly
M026
DG115SC
LiCl 1M
in EtOH
Methanol
daily
Potassium
hydroxide
c(KOH) = 0.1
mol/L
Benzoic acid
C7H6O2; M =
122.12
M027
DG115SC
LiCl 1M
in EtOH
Ethanol
weekly
Sulfuric acid
c(1/2 H2SO4) =
0.1 mol/L
Tris(hydroxymethyl)aminomethane [THAM]
C4H11NO3; M = 121.14
g/mol
M011
DG111SC
Deion. H2O
every 2
weeks
Hydrochloric
acid
c(HCl) = 0.1
mol/L
Tris(hydroxymethyl)aminomethane
[THAM] C4H11NO3; M
= 121.14 g/mol
M003
DG111SC
Deion. H2O
every 2
weeks
Perchloric acid
c(HClO4) = 0.1
mol/L
Tris(hydroxymethyl)aminomethane [THAM]
C4H11NO3; M = 121.14
g/mol
M005
DG115SC
LiCl 1M
in EtOH
Acetic acid
weekly
Titrant
Standard Substance
Method
Indication
M025
Alkalimetry
Acidimetry
METTLERTOLEDO
12
Titrant
Frequence of
Standarization
Protection of Titrant /
General Remarks
every 2
weeks
Keep bottle in
dark
M028
every 2
weeks
M024
DP550
Deion. H2O
Buffer pH 4
Thorin
weekly
Standard Substance
Method
Indication
Silver nitrate
c(AgNO3) = 0.1
mol/L
Sodium chloride
NaCl; M =
58.44
M006
Sodium chloride
c(NaCl) = 0.1
mol/L
Silver nitrate
AgNO3;
M=169.89
Barium chloride
c(BaCl2) = 0.1
mol/L
Sodium sulfate
Na2SO4; M =
142.05
Solvent and
Auxiliary reagents
Precipitation
Complexometry
Complexone III
c(EDTA) = 0.1
mol/L
Zink sulfate
ZnSO4; M =
161.44
M007
DP660
Deion. H2O
Buffer pH 10,5
Indicator Erio T
every 2
weeks
Use PE bottles
Complexone III
c(EDTA) = 0.1
mol/L
Calcium
carbonate
CaCO3; M =
100.09
M022
DP660
Deion. H2O
Indicator buffer
tablet MERCK
every 2
weeks
Use PE bottles
Complexone VI
c(EGTA) = 0.1
mol/L
Calcium
carbonate
CaCO3; M =
100.09
M014
DP660
Deion. H2O
Indicator buffer
tablet MERCK
every 2
weeks
Use PE bottles
Zink sulfate
c(ZnSO4) = 0.1
mol/L
EDTA . 2H2O
EDTA ;
M=372.24
M029
DP660
Deion. H2O
Buffer pH 10,5
Indicator Erio T
every 2
weeks
Use PE bottles
Barium perchlorate
c(Ba(ClO4)2) = 0.005
mol/L
EDTA . 2H2O
EDTA ; M=372.24
M023
DP550
Deion. H2O /
methanol NH3
solution 5%
Indicator
Phthaleinpurpur
weekly
Use PE bottles
METTLERTOLEDO
13
Titrant
Standard Substance
Method
Indication
Solvent and
Auxiliary reagents
Frequence of
Standarization
Protection of Titrant /
General Remarks
Potassium iodate
KIO3;
M = 214.00 g/mol
M009
DM140-SC
Hydrochloric
acid 0.1 M
every 2 weeks
Hydroquinone
c(C6H6O2)= 0.1 mol/L
Potassium
dichromate
K2Cr2O7;
M = 294.19 g/mol
M017
DM140-SC
Sulfuric acid 5%
weekly
Potassium
dichromate
K2Cr2O7;
M = 294.19 g/mol
M008
DM140-SC
Sulfuric acid 5%
daily
Ascorbic acid
C6H8O6;
M = 176.13 g/mol
M030
DM140-SC
Deion. H2O
every 2 weeks
Potassium dichromate
c(1/6 K2Cr2O7) =
0.1 mol/L
(CH2NH3)2SO4
FeSO4 4H2O
M = 382.15
M031
DM140-SC
Sulfuric acid 5%
every 2 weeks
Iodine
c(1/2 I2) = 0.1 mol/L
di-Arsenic trioxide
As2O3;
M = 197.84 g/mol
M016
DM140-SC
DG111-SC
Deion. H2O
NaHCO3
daily
Cerium sulfate
c(Ce(SO4)2) =
0.1 mol/L
di-Sodium oxalate
C2Na2O4;
M=134.00 g/mol
M015
DG140-SC
Deion. H2O
Sulfuric acid 5%
every 2 weeks
Potassium
permanganate
c(1/5 KMnO4) =
0.1 mol/L
di-Sodium oxalate
C2Na2O4;
M=134.00 g/mol
M013
DG140-SC
Sulfuric acid 5%
70 C
every 2 weeks
Sodium nitrite
c(NaNO2) =
0.1 mol/L
Sulfanilic acid
C6H7NO3S;
M = 173.19 g/mol
M032
DM140-SC
weekly
Fehling solution
Glucose 1% in
water C6H12O6;
M = 180.16 g/mol
M033
Combi
Pt-ring
(Ingold)
Deion. H2O
weekly
Prepare Glucose
solution daily.
Ascorbic acid
C6H8O6;
M = 176.13 g/mol
M021
DM142 mit
DK102
Deion. H2O
daily
Titrant
Standard Substance
Method
Indication
Solvent and
Auxiliary reagents
Frequence of
Standarization
Protection of Titrant /
General Remarks
Turbidimetric Titrations
Sodium dodecylsulfate
c(SDS) = 0.01 mol/L
N-Cetylpyridinium
chloride [CPC]
M = 358.01 g/mol
M035
DP550
Deion. H2O
every 2 weeks
Hyamine c(Hyamine)
= 0.01 mol/L
Sodium
dodecylsulfate
[SDS];
M = 288.4 g/mol
M036
DP550
Deion. H2O
every 2 weeks
N-Cetylpyridinium
chloride c(CPC) =
0.01 mol/L
Sodium
dodecylsulfate
[SDS];
M = 288.4 g/mol
M012
DP660
Deion. H2O
every 2 weeks
14
More Information
8. More Information
7.1 Brochures
GTP Risk Checker, Mettler-Toledo Analytical, 10/2010
Validation of Titration Methods, Application Brochure 16, Mettler-Toledo Analytical, 03/2015, 51724912A
7.2 Webinars
We provide web-based seminars (webinars) on different topics. You can participate in on-demand webinars
at any convenient time and place.
Live webinars offer the added benefit of allowing you to ask questions and discuss points of interest with
METTLER TOLEDO specialists and other participants.
www.mt.com/webinars
7.3 Applications and UserComs
We offer comprehensive titration application support
Titration applications
www.mt.com/titration_applications
Titration UserCom
www.mt.com/anachem-usercom
METTLERTOLEDO
15
5
Routine
Operation
Calibration /
Qualication
1
Evaluation
Good
Measuring
Practices
2
Selection
3
Installation /
Training
www.mt.com
For more information