Impact of Film-Forming Amines On The Reliability of Online Analytical Instruments Marco Lendi

SPECIAL PRINT
PowerPlant Chemistry
Impact of Film-Forming Amines on the Reliability

of Online Analytical Instruments
Marco Lendi
Dr. Peter Wuhrmann
SWAN Analytische Instrumente AG, 8340 Hinwil/Switzerland
AMI INSPECTOR
Conductivity with Case
SPECIAL PRINT (2014)
AMI Sodium P
PowerPlant Chemistry 2012, 14(9)
ANALYTICAL INSTRUMENTS
AMI Soditrace

On-line analyzer for the continuous measurement of sodium ions in

trace amounts in steam and high purity water.
n Fully Automated Sodium Analyzer

Automatic 3-point known addition
calibration in ppb-range
Automatic regeneration of sodium
electrode
Automatic control loop for sample
pH conditioning
n Lowest detection limit for sodium
ion concentration: 0.001 ppb
n Factory tested and ready for
installation and operation.
Ask for technical documentation or
check our homepage
Made in Switzerland
www.swan.ch
SWAN Analytische Instrumente AG 8340 Hinwil/Switzerland
Sonderdruck_Lendi March2014:Innenseiten 12.03.14 09:38 Seite 1
PPChem
Impact of Film-Forming Amines on the Reliability of Online Analytical Instruments
Impact of Film-Forming Amines on the Reliability of

Online Analytical Instruments
Marco Lendi and Peter Wuhrmann
ABSTRACT
There are very few reports describing the effects of the dosing of film-forming amines (FFAs) on the online monitoring
equipment. This paper describes controlled, laboratory-like tests performed to ascertain the impact of three different
brands of film-forming amines on system parameters. Specific conductivity, pH drift, cation resin retention, pH stability, sodium step response, sodium calibration, oxygen sensor response and ORP probe response were considered.
While with some measurements no negative influence could be observed, with other equipment there was a loss of
sensitivity and speed of response time due to coating effects. There were also differences in some results depending
on the FFA used.
INTRODUCTION
Organic additives like oxygen scavengers or film-forming
amines (FFA) are widely used in small industrial watersteam cycles, and their use in larger installations is suggested more and more frequently. Hardly any reports
describe their influence on the online monitoring system,
and their impact on specific parameters has never been
reviewed properly [1].
A field test in a waste incineration plant [2] showed significant coating effects on conductivity and oxygen probes.
With the test methods available in the field, no negative
effects on pH and sodium probes could be measured. But
to draw a final conclusion, the recorded data showed too
many pattern noises coming from the operation mode of
the plant. Furthermore, in this field test only one FFA product was involved.
This situation was the main motivation to repeat the test in
a controlled laboratory-like installation with as few disturbing effects as possible. Additionally, the tests were performed with three different brands of film-forming amines
to give more relevant results.
NaCl/NH3
addition
Input
UPW
FFA
addition
Oxygen
removal
Exposed
instruments
Reference
instruments
Figure 1:
Flow scheme of the test system.
Parameter
Sodium
Silica
Conductivity
Oxygen
Range
0.010.02 g L1
0.1 g L1
0.0550.057 S cm1
Oxygen saturated (89 g L1)
Table 1:
ONLINE TEST SYSTEM

The flow scheme is shown in Figure 1. The raw water was
purified by reverse osmosis, mixed-bed ion exchange and
UV disinfection to obtain ultrapure water (UPW). Table 1
lists the average specifications of the UPW.
Average specifications of the input ultrapure water.
Oxygen Removal
The oxygen level could be reduced from saturation
(8 mg L1) to below 10 g L1 with three Liqui-Cel
Membrane Contactors connected in series. For a reduction to 10 g L1 O2 the contactors were evacuated with
2012 by Waesseri GmbH. All rights reserved.
PPChem
high vacuum and purged with nitrogen. In this way it was

possible to keep a stable oxygen level below 10 g L1 for
hours. The oxygen was only reduced for a short period to
test the oxidation-reduction potential (ORP) and the oxygen probe's response while the other data was recorded
with saturated oxygen levels.
Dosing Points
Dosing was designed for a flow-dependent addition such
that a constant concentration of a given substance could
be maintained over several days. The first dosing point
was used to dose sodium chloride solution and/or ammonia. With the second dosing point, the film-forming amines
(FFA) were dosed. The reference instruments were
mounted upstream of the second dosing point, so that
these instruments were never exposed to film-forming
amines.
Online Instruments
The complete list of the tested instruments is given in
Table 2.
Phase 2: Dosing of a small amount of FFA

A target concentration of 0.5 mg L1 as FFA
was dosed. The goal of this phase was to
observe possible effects with low FFA concentration.
Phase 3: Verification stage
The dosing of FFA was interrupted, performance tests were continued. This phase gave
an impression of the irreversibility of the coating
effects.
Phase 4: High concentration FFA dosing
Target concentrations up to 3 mg L1 as FFA
were dosed. Depending on brand and application, these are the recommended concentrations of the manufacturers.
Three commonly used film-forming amine brands were
tested. In the following report, the names as well as the
manufacturers have been made anonymous. The shown
FFA concentrations were calculated based on the flowdependent addition and were frequently measured with
the available test methods of the used products.
Test Procedures and Materials
TEST RESULTS
Phase 1: Recording of the base line
During this phase, no FFA was dosed. Tests like
sodium step responses or oxygen reduction
were performed to see the instruments reaction
under laboratory conditions.
Conductivity Probe
The installed conductivity probes on the AMI Deltacon DG
are titanium 2-electrode types with a cell constant of
0.04 cm1 and an integrated PT1000 temperature sensor.
Instruments
Parameter
AMI Deltacon DG
Specific conductivity
Acid conductivity
Degassed acid conductivity
Calculated pH
AMI Sodium P
Sodium
AMI Deltacon DG
Specific conductivity
Acid conductivity
Degassed acid conductivity
Calculated pH
AMI pH
Ion selective pH
AMI ORP
Oxidation-reduction potential
AMI Soditrace
Trace sodium
AMI Oxytrace QED
Trace oxygen with online verification
AMI Sodium A
Sodium
Sample
Reference instruments
Exposed instruments
Table 2:
Online instruments and parameters.
PPChem
FFA no. 1
FFA no. 2
FFA no. 3
Coating on SC probe
No
Yes
Yes
pH drift
No
No
Yes
Poor
Poor
Poor
Retention capacity
Table 3:
Summary of results on specific conductivity, pH drift, and resin retention.
Points of interest were:

(1) Coating effects on specific conductivity (SC) probe
(2) Drift between pH calculation and ion selective measurement
(3) Retention capacity of the cation exchange resin
A summary of the impact of the FFAs tested on specific
conductivity, pH drift, and cation resin retention is given in
Table 3.
Coating Effects on Specific Conductivity Probe

This sensor is in direct contact with the FFA. The acid conductivity and the degassed acid conductivity sensors are
protected by the cation exchange resin. Of the three
tested brands, only one substance did not decrease the
specific conductivity compared with acid and degassed
acid conductivity.
Two criteria were established to detect a coating effect:
Decrease in specific conductivity
(SC) compared with degassed acid
conductivity (DC) during FFA dosing;
Figure 2 shows the behavior of the SC

with FFA no. 3. The FFA concentration
of substance no. 3 was 1 mg L1
during the whole measuring period. At
the beginning, the SC reading was
17.38 S cm1, then it dropped to
14.58 S cm1. The decrease of
2.06 S cm1 within three days is
clearly an indication of coating on the
conductivity probe. This is supported
by the observation that during the
same period the degassed acid conductivity (DC) is more or less constant
between 0.143 and 0.164 S cm1.
At the beginning, the reading of the exposed sensor is

0.489 S cm1, which is considerably lower than the SC
of the reference instrument (0.513 S cm1). Figure 3 also
shows that the coating effect disappeared about half an
hour after the FFA dosing was stopped.
Difference between pH Calculation and Ion Selective

Measurement
According to VGB-450L [3], the pH of
a sample can be calculated with the specific and acid
conductivity. As shown previously, the specific conductivity sensors are coated by two of the three film-forming
amines. As a result, the calculated pH should also
decrease compared to the ion selective measurement with
a glass electrode.
50
40
Specific conductivity (SC)
30
Degassed acid conductivity (DC)
20
Conductivity [S cm1]
Lower specific conductivity values

of the exposed instrument compared with the reference after a
longer period of FFA dosing.
Figure 3 shows the coating effect of FFA no. 2. After a

three-day exposure time at 1 mg L1 FFA, a step
response with a target concentration of 100 g L1
sodium was performed. The readings of the non-exposed
reference conductivity probe and the exposed sensor
were compared.
10
0.5
0.4
0.3
0.2
0.1
0
Time [day]
Figure 2:
Coating of specific conductivity (SC) probe during an exposure to 1 mg L1 of FFA
no. 3.
SC exposed instrument
0.7
Dosing of NaCl
0.6
2.5
0.4
2.0
0.5
0.3
0.4
0.2
0.3
0.2
0.1
Retention Capacity of the Cation

Exchange Resin
The quality of the cation exchange
resin is a key factor in measuring a
reliable and stable acid and degassed
acid conductivity. The resin utilized
was a strongly acidic cation
exchanger in H+ form. Under normal
operation, the tested resin will hold
back ammonia-treated water for
approximately 1 month before the
resin is exhausted.
0.5
Dosing of FFA
00:00
00:30
01:00
1.5
1.0
0.1
0.5
FFA Dosing [mg kg1]
A coating-like behavior of FFA no. 2

could be demonstrated with a step
response, but the measured deviation
was much lower than the one from
FFA no. 3. The influence on pH calculation was too small to demonstrate a
significant drift.
SC reference instrument
Na Dosing [mg kg1]
In Figure 4 the deviation between the

calculated and measured pH during
FFA no. 3 dosing is shown as pH.
Over a three-day exposure time, the
deviation was 0.10 pH. Another
piece of evidence for the 'coating theory' is the fact that in the shown time
the ion selective measured pH (separated measuring and reference electrode) is not drifting.
PPChem
01:30
Time [hh:min min]
Figure 3:
Step response with a sodium chloride solution after a FFA dosing period (substance
no. 2) to compare the specific conductivity (SC) reading of the exposed and reference
instrument.
DpH
0.8
Control line
11
Calculated pH
pH
DpH
Ion selective measured pH

The dosed FFA substances contain
0.6
not only the film-forming amines.
10
According to the Material Safety Data
0.4
Sheets of the tested substances, the
mixtures contain a high load of other
9
0.2
cationic molecules. Figure 5 shows
the beginning of a dosing (phase 2)
0
with a low concentration of FFA no. 1.
8
After three days, it seems that the
0.2
cation exchange resin cannot hold
back all cationic substances because
7
0.4
the degassed acid conductivity (DC)
0
0.5
1.0
1.5
2.0
2.5
3.0
of the exposed instrument is beginTime [day]
ning to rise. Figure 6 shows the continued test with FFA no. 1 after 44
Figure 4:
days of exposure. After the dosing of
Drift between the calculated and ion selective measured pH (1 mg L1 FFA no. 3).
FFA no. 1 was stopped, the DC of the
exposed instrument remained on a
high level. It seems that the cation
FFAs no. 2 and no. 3 gave the same picture. The only difexchange resin is continuing to release ionic substances.
ference between the substances was the time until ionic
The DC reading went back to normal after a new bottle of
substances broke through.
resin was installed. This is the proof that the source of the
ionic substances responsible for the higher DC readings
was the cation exchange resin.
PPChem
pH/Sodium (Ion Selective Glass

Electrode)
FFA dosing
0.5
1.0
0.5
0.05
0
0
4
Time [day]
(2) Sodium: reaction time during step

response
FFA Dosing [mg kg1]
1.5
0.1
The installed pH electrode used a separated reference electrode system

based on Ag/AgCl with a KCl liquid
junction.
(1) pH: stability during long-term

exposure
2.0
DC of exposed instrument
The installed sodium reference instrument was an AMI Sodium P and the
exposed sodium probes were on an
AMI Soditrace. On both instruments,
the same types of measuring and reference electrodes were used. The reference electrode was a calomel
(Hg/HgCl) electrode with a KCl liquid
junction.
DC of reference instrument
1.0
Figure 5:
Retention capacity of cation exchange resin with respect to the degassed acid
conductivity (DC) during a dosing period of FFA no. 1.
(3) Sodium: calibration data

DC of reference instrument
1.0
Table 4 shows a summary of the test

results.
5.0
DC of exposed instrument
FFA dosing
Sodium Step Response

The normal sodium level during the test was
between 0.02 g L1 and 0.10 g L1
sodium. The sensors were regenerated weekly with a sodium-free etching solution. With flow-dependent
injection of a sodium chloride solution,
a 'contamination' of 200 g L1 Na
pH Stability
Figure 7 shows a 10day exposure period with FFA no. 1.
The stability during that test was
good, and the response to changes in
FFA concentrations was fast and
reversible. Therefore, no negative
influence could be noticed.
3.0
New cation
exchange resin
2.0
0.1
1.0
0.05
44
FFA Dosing [mg kg1]
4.0
0.5
46
48
50
52
54
Time [day]
Figure 6:
Retention capacity of cation exchange resin with respect to the degassed acid
conductivity (DC) after a dosing period of FFA no. 1.
FFA no. 1
FFA no. 2
FFA no. 3
pH stability
No influence
No influence
No influence
Sodium step response
No influence
No influence
No influence
Sodium calibration
No influence
Table 4:
Summary of results on pH stability, sodium step response, and sodium calibration.
12
10
pH
FFA dosing
11
10
6
9
4
8
FFA Dosing [mg kg1]
was simulated. The most important

parameter to evaluate the performance of an ion selective sodium sensor is the response time to concentration changes. Figure 8 summarizes
five step responses during long-term
exposure to different concentrations
of FFA no. 1. No significant loss of the
sodium probe's response time can be
observed.
pH
PPChem
Oxygen and ORP Sensor

For direct oxygen measurement a
Clark oxygen sensor with a gold cathode and silver anode was used.
Additionally, a Faraday electrode for
online verification was built in.
The ORP was measured with a separated platinum (Pt) measuring electrode and reference electrodes with a
KCl liquid junction were used.
0
0
6
Time [day]
10
12
Figure 7:
Long-term stability of ion selective pH probe during dosing of FFA no. 1.
300

3 days (0.5 mg kg1 FFA)
(1) Clark probe: response time during

oxygen concentration reduction
250
20 days (0 mg kg1 FFA)
(2) ORP probe: response time during

oxygen concentration reduction
200
Na [g kg1]
Response Time of Oxygen and ORP

Probes to Oxygen Concentration
Changes
The long-term
stability tests were performed with
oxygen saturated ultrapure water
(8 mg L1O2). To test the oxygen and
ORP probes' performance, oxygen
was removed (see Figure 1) from the
sample water. The oxygen concentration of the water during removal was
the same. Table 5 shows a summary of
the test results.

150
100
50
0
0.00
0.01
0.02
0.03
0.04
Time [h]
Figure 8:
Recorded step responses from an AMI Soditrace during long-term exposure to FFA
no. 1.
Oxygen response time

ORP response time
FFA no. 1
FFA no. 2
FFA no. 3
Good
Good
Good
Bad
Bad
Bad
Table 5:
Summary of results on oxygen sensor response and ORP response.
PPChem
20
8 000
0 mg kg1 FFA
0.5 mg kg1 FFA

20
1 mg kg1 FFA
40
No alteration of the Clark sensor characteristics was observed under any of

the conditions tested in these experiments (Figure 10).
6 000
Oxygen level
60
80
4 000
100
O2 [g kg1]
ORP [mV]
Figure 9 shows three examples of ORP

responses during different FFA dosing
phases. The ORP readings in Figure 9
are standardized because the FFA
concentration itself also influences the
ORP value. The red line (0.5 mg L1)
shows an ORP response after a 5-day
period of FFA dosing while the green
line (1 mg L1) was recorded after a
13-day dosing period.
120
2 000
140
160
180
00:00
00:20
00:40
01:00
0
01:40
01:20
Time [day]
Reaction of an ORP probe during oxygen removal with different FFA concentrations of
FFA no. 1.
200
1.2
FFA concentration
O2 level
1.0
150
0.8
0.6
100
0.4
FFA Dosing [mg kg1]
The impact of three different conditioning reagents containing film-forming

amines on online instrumentation was
tested in a laboratory-like installation.
On pH, ion selective sodium measurement as well as on a Clark-type oxygen probe, no negative influence could
be observed. On oxygen reduction
potential (ORP) measurement, all
tested FFA substances result in a loss
of sensitivity and speed of response
time due to coating effects. The impact
on conductivity measurement differed
between the tested substances. With
two tested substances, coating effects
on the conductivity probe could be
observed which resulted in a drift of
the specific conductivity reading as
well as in a drift of the calculated pH.
With one film-forming amine product,
such effects could not be observed.
Figure 9:
O2 [g kg1]
CONCLUSION
50
0.2
0
0
8
Time [day]
10
12
14
16
Figure 10:
Response of a Clark oxygen probe during FFA dosing (FFA no. 1).
PPChem
REFERENCES
[1] Verheyden, K. S., Ertryckx, R. A. M., De Wispelaere,
M., Poelemans, N., PowerPlant Chemistry 2003, 5(9),
516.
[2] Lendi, M., Wuhrmann, P., EPRI Major Component
Reliability Meeting, 2011 (Barcelona, Spain). Paper
#16.
[3] VGB Guideline for Boiler Feedwater, Boiler Water and
Steam of Steam Generators with a Permissible
Operating Pressure of > 68 bar, 1988. VGB Power
Tech e.V., Essen, Germany, VGB-R 450-Le.
Degassed Cation Conductivity

Analyzer AMI Deltacon DG
THE AUTHORS
Marco Lendi (B.S., Chemistry, University of Applied
Science, Zurich, Switzerland) joined Swan Analytical
Instruments in 2009, working first as a quality manager
and from 2010 in SWAN's customer support group. In
2012 he was promoted to the R&D group.
Peter Wuhrmann (Ph.D., Analytical Chemistry, Swiss
Federal Institute of Technology (ETHZ), Zurich, Switzerland) conducted several years of research work with ion
sensitive microelectrodes for intracellular ion measurements at the Institute of Cell Biology at the Swiss Federal
Institute of Technology (ETHZ). He was a member of the
founding group of Swan Analytical Instruments, where he
has been responsible for R&D since 1991.
Automatic and continuous
CONTACT
Marco Lendi
Swan Analytical Instruments AG
P.O. Box 398
8340 Hinwill
Switzerland
E-mail: marco.lendi@swan.ch
measurement of total, cation and

degassed cation conductivity.
Re-boiler according to LarsonLane (ASTM D4519-94).

Tightly controlled degassing
temperature.
Calculation of sample pH and
ammonia concentration.
Dr. Peter Wuhrmann
pedro.wuhrmann@swan.ch
Ask for technical documentation

or check our homepage.
www.swan.ch
SWAN ANALYTISCHE INSTRUMENTE AG CH -8340 HINWIL
www.swan.ch swan@swan.ch Phone +41 44 943 63 00
Your notes:
AMI Oxytrace QED -
.....................................
Dissolved oxygen in high purity water

with integrated autoverification.
.....................................
.....................................
.....................................
.....................................
.....................................
.....................................
.....................................
.....................................
.....................................
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n Faraday electrode and control

unit for the automatic verification
by electrochemically generated
oxygen in the ppb range
n Extension of the maintenance
intervals: no calibration as long
as the verification is valid
n Sample flow monitoring with
alarm Flow out of range
n Easy maintenance due to
sensor cap concept.
.....................................
.....................................
Made in Switzerland
SWAN Analytische Instrumente AG

www.swan.ch Hinwil/Switzerland

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SPECIAL PRINT

Impact of Film-Forming Amines on the Reliability

SPECIAL PRINT (2014)

PowerPlant Chemistry 2012, 14(9)

On-line analyzer for the continuous measurement of sodium ions in

n Fully Automated Sodium Analyzer

Sonderdruck_Lendi March2014:Innenseiten 12.03.14 09:38 Seite 1

Impact of Film-Forming Amines on the Reliability of Online Analytical Instruments

Impact of Film-Forming Amines on the Reliability of

ONLINE TEST SYSTEM

Average specifications of the input ultrapure water.

2012 by Waesseri GmbH. All rights reserved.

PowerPlant Chemistry 2012, 14(8)

Sonderdruck_Lendi March2014:Innenseiten 12.03.14 09:38 Seite 2

Impact of Film-Forming Amines on the Reliability of Online Analytical Instruments

high vacuum and purged with nitrogen. In this way it was

Phase 2: Dosing of a small amount of FFA

Test Procedures and Materials

AMI Oxytrace QED

Trace oxygen with online verification

PowerPlant Chemistry 2012, 14(9)

Sonderdruck_Lendi March2014:Innenseiten 12.03.14 09:38 Seite 3

Impact of Film-Forming Amines on the Reliability of Online Analytical Instruments

Summary of results on specific conductivity, pH drift, and resin retention.

Points of interest were:

Coating Effects on Specific Conductivity Probe

Figure 2 shows the behavior of the SC

PowerPlant Chemistry 2012, 14(9)

At the beginning, the reading of the exposed sensor is

Difference between pH Calculation and Ion Selective

Specific conductivity (SC)

Degassed acid conductivity (DC)

Lower specific conductivity values

Figure 3 shows the coating effect of FFA no. 2. After a

Sonderdruck_Lendi March2014:Innenseiten 12.03.14 09:38 Seite 4

Retention Capacity of the Cation

FFA Dosing [mg kg1]

A coating-like behavior of FFA no. 2

Na Dosing [mg kg1]

In Figure 4 the deviation between the

Impact of Film-Forming Amines on the Reliability of Online Analytical Instruments

Time [hh:min min]

Ion selective measured pH

PowerPlant Chemistry 2012, 14(9)

Sonderdruck_Lendi March2014:Innenseiten 12.03.14 09:38 Seite 5

Impact of Film-Forming Amines on the Reliability of Online Analytical Instruments

pH/Sodium (Ion Selective Glass

Points of interest were:

(2) Sodium: reaction time during step

FFA Dosing [mg kg1]

The installed pH electrode used a separated reference electrode system

(1) pH: stability during long-term

(3) Sodium: calibration data

Table 4 shows a summary of the test

Sodium Step Response

FFA Dosing [mg kg1]

Sodium step response

PowerPlant Chemistry 2012, 14(9)

Sonderdruck_Lendi March2014:Innenseiten 12.03.14 09:38 Seite 6

FFA Dosing [mg kg1]

was simulated. The most important

Impact of Film-Forming Amines on the Reliability of Online Analytical Instruments

Oxygen and ORP Sensor