Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

Evaluation of Degassed After-Cation-Exchange

Conductivity Techniques

In feed and boiler waters, the effect of the anions on con-

Nigel J. Drew
ductivity is masked by the presence of the alkali. For many
decades, the use of after-cation-exchange conductivity
(ACC) has been the solution to this problem. A typical sys-
tem is shown in Figure 1 and a brief example of the im-
ABSTRACT
provement in sensitivity available by replacement of
After-cation-exchange conductivity (ACC) systems are sodium as a counter ion with hydrogen ion is shown be-
the universally used method for rapid detection of an- low. Measurements are corrected to a sample tempera-
ionic impurity ingress into the steam/water circuit of ture of 25 C.
power plant. In some utilities, ACC is measured after

Pure water has a conductivity of 0.055 S cm1.
degassing the sample. It is generally considered that
carbon dioxide is the least aggressive contaminant of
10 mg kg1 of sodium chloride in pure water raises
1
feedwater that is normally present and causes eleva- conductivity to 0.077 S cm .
tion of the measured ACC. The elevation of ACC by

1 mg kg1 of ammonia in a sample would have a con-
carbon dioxide can be particularly noticeable when the 1
ductivity of 6.721 S cm but with the addition of
oxygen scavenger is carbohydrazide, or the water con- 1
10 g kg of sodium chloride this rises to
tains dosed amines or neutral organic compounds in 1
6.743 S cm .
the make-up water. Ingress of carbon dioxide could be
considerable in the case of tube leakage in some parts
The cation exchange column (with R = resin + sulpho-
of the boilers of gas-cooled nuclear stations. The ele- nate group) replaces cations, thus:
vated ACC then delays unit start-up. There are two
+ +
widely used techniques for degassed ACC systems: Na + R-H
Na-R + H (1)
gas stripping with nitrogen and heating to near boil-
and
ing. Membrane gas-exchange systems are now also
beginning to appear on the market. British Nuclear NH4+ + R-H
NH4-R + H+ (2)
Fuels Plc. and British Energy arranged for an evalua-
tion of these three types of system to determine if they
The resulting solution containing HCl from 10 g kg1
would be sufficiently effective for use in their power of sodium chloride and 1 mg kg1 of ammonia has an
1
stations. The results of the evaluation are summarised ACC of 0.098 S cm .
here and measured values are compared with theoret-
ical calculations for ACC and degassed ACC.

INTRODUCTION
Feedwater, boiler water and steam in generating plant
should contain as little as possible of any ionic species
known to initiate or enhance corrosion, such as chloride,
sulphate, acetate and formate. To ameliorate the effects
of any traces of these ions alkalising agents are added to
ensure that the resulting water (or salts deposited) remains
alkaline, typically in the range of pH 9 to pH 9.8 at 25 C
in the feedwater. The alkali added may be ammonia, amine
(such as morpholine) or, in drum boilers, sodium phos-
phate or sodium hydroxide. The presence of ionic impuri-
ties in water is readily detectable by measuring the elec-
trolytic conductivity of the water, a technique that is ro-
bust and responds rapidly. Identification of the individual
ions requires more complex techniques, such as ion chro-
matography, with each analysis taking some time to be
completed.

Figure 1: A typical after-cation-exchange conductivity

2004 by PowerPlantChemistry GmbH. All rights reserved. system.

PowerPlant Chemistry 2004, 6(6) 343

Evaluation of Degassed After-Cation-Exchange Conductivity Techniques
Using the cation exchange column has nearly doubled the
conductivity from the presence of sodium chloride and
eliminated the background contribution from ammonia ad-
dition. When measuring direct conductivity, variations in
large background conductivity will make the small contri-
bution from sodium chloride undetectable. The after-col-
umn technique is particularly sensitive in the detection of
condenser tube leaks when measuring condensate.
Another contaminant of boiler water and condensate is
carbon dioxide. There are several sources of this, such as
absorption from air in the condenser at start-up, decom-
position of any organic compounds in the feed such as
those deliberately introduced, e.g., amines, carbohy-
drazide (for oxygen removal), and from polysaccharides
and humic acids in make-up. Dissolved carbon dioxide
alone will promote corrosion of mild steel. However, when
carbon dioxide and excess alkali (e.g., ammonia) are both
present, the high temperature pH remains protectively al-
kaline [1]. [2] calculates the effect of anions with ammonia
on pH (at 100 C) and puts them in the following order:
Chloride > sulphate, formate >> acetate >> carbon dioxide
This order of the effect on pH and thus potential for corro-
sion is the reason why many operators would prefer ACC
not to include the contribution from carbon dioxide.
Currently, there are three techniques available to measure
degassed conductivity directly:

Heating the sample to boiling or near boiling point

Gas stripping with a "bubbler" system

Diffusion of dissolved gases out of the sample through
a membrane.
Systems based upon these three methods were evaluated
by British Nuclear Fuels Plc. (BNFL) Nuclear Sciences and
Technology Services and the results are reported here.
This paper attempts to look at the generic merits of each
method, without reference to the particular manufacturer
of the systems. Systems that extract and measure the car-
bon dioxide concentration and then calculate its effect on
conductivity were not examined.
SYSTEMS TESTED
Heating
A widely used "reboiler" system was loaned by the manu-
facturer. It consisted of a single cation exchange column
with downward flow, a vented reboiler operating near
100 C and three conductivity cells connected to a single
transmitter. The conductivity of the incoming sample was
measured at sample temperature, as was the ACC value,
with the degassed conductivity (DGCC) measured near
100 C. The optimum sample flow rate was found to be in
3 1
the range of 170 to 200 cm min and the system was
operated near the mid-point of this range during all tests
344
except when investigating the effect of sample flow rate
variations.
Gas Stripper
Another manufacturer loaned a gas stripping system. This
comprised a cation exchange column with downward flow,
followed by a ~ 0.6 x 0.05 m gas stripper that used a
counter-current flow of nitrogen applied through a stain-
less steel sinter. Sample from the DGCC measuring cell
had to be returned to the system for liquid height control
of the gas stripper. Water and sample flows were 160 and
3 1
700 cm min respectively, except when investigating the
effect of sample flow rate variations.
Membrane Gas Stripper
A prototype system was supplied on a single panel with a
cation exchange column and a polysulphone-membrane
2
gas exchanger of an approximate active area of 1.38 m .
Two conductivity cells measured ACC and DGCC, being
connected to a dual channel conductivity analyser with
"acid" temperature compensation selected. Being a pro-
totype, optimum operating conditions were not well es-
tablished until the effect of sample flow rate variations had
been investigated. Optimal sample water and gas flow
3 1
rates were then found to be 150 and 250 cm min re-
spectively. The manufacturer is subsequently considering
fitting a second membrane to operate with lower gas flow
rates and some results from an early 2-membrane system
are included here.
TEST PROCEDURES
The three measurement systems were supplied with sam-
ple water from a recirculating de-ionising system as shown
schematically in Figure 2. Solutions of known concentra-
tion of sodium chloride and sodium carbonate were ap-
plied using a flow dilution technique, in which concen-
trated solutions prepared volumetrically were continuously
added from a motorised syringe into known flows of sam-
ple water. Flow rates were calibrated by gravimetric meth-
ods. Solutions of organic acids were prepared and applied
in the same fashion. However, when adding acids, ammo-
nia solution was simultaneously applied by a second mo-
torised syringe, such that the concentration of ammonia in
1
the sample would be 2 mg kg .
After-cation-exchange conductivity (ACC) and degassed
conductivity (DGCC) were measured on the systems' in-
ternal instrumentation (where fitted) and on a reference in-
strument. All values quoted here have been "normalised"
as if taken by the reference instrument; see Figure 2.
Test solutions were devised and applied as in Table 1 to
ascertain the following:
PowerPlant Chemistry 2004, 6(6)
 Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

i. Did ACC values match theo-

retically calculated values for
the concentrations applied?
ii. Did degassing affect the val-
ues for mineral and light or-
ganic acids?
iii. Did degassing remove carbon
dioxide from water?
iv. What was the combined ef-
fect of degassing on solutions
containing both acids and
carbon dioxide?
v. Did variations in sample tem-
perature affect the degassing
system?

Figure 2:
Test apparatus.

Solution Nominal ACC Chloride Carbon dioxide Formate Acetate

1 1 1 1
[S cm ] [g kg ] [g kg ] [g kg ] [g kg1]
1 0.14 10
2 0.31 25
3 1.2 100
4 0.14 25
5 0.32 100
6 0.54 250
7 0.11 10
8 0.45 50
9 0.15 20
10 0.32 50
11 0.62 10 250
12 1.5 100 250
13 0.83 250 50
1
14 0.055 2 000 g kg NH3

Table 1: Test solutions and their nominal conductivity.

PowerPlant Chemistry 2004, 6(6) 345

Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

THEORETICAL VALUES
ACC is an important measurement in power plant, hence
the opportunity was taken to compare the theoretically
calculated conductivity to the measured value for each so-
lution applied. During the experimental programme, theo-
retical values were calculated using a computer pro-
gramme written by the Central Electricity Generating
Board (CEGB) in the UK. The programme had not been
verified against more recent data for ionisation, equilib-
rium and mobility constants but used the values accepted
in the 1980s. Table 2 compares the values calculated from
the CEGB programme and those from the EPRI code
CCHEM v. 0.91 (2002) quoted in [2].
It can be seen that for calculation of the ACC values pre-
sented here, the two methods differed only in the last sig-
nificant figure. (The two calculation methods exhibited
more significant disagreements for mixtures of ammonia
and salts, but this was not relevant to the work reported
here.)
RESULTS
Comparison of ACC with Theoretical Values
All three systems gave excellent agreement between the
calculated and measured ACC values as shown in Table 3.
All indications were that the uppermost values (above
1
1 S cm ) were consistently lower than the calculated
value by some 3 to 4 %. Background conductivity values
1
when pure water was applied were near 0.070 S cm
and any excess in background from 0.055 S cm1 has
been deducted from the measured values in Table 3.
Effect of Degassing on Acids
All three systems exhibited negligible differences between
measurements of ACC and DGCC with acids (in the ab-
sence of carbon dioxide). Results are shown in Table 4,
where a positive difference between the ACC and DGCC
value would indicate that some of the anion species had
been removed, and a negative value that some contami-
nation had been added. Notice that when adding formic
1
or acetic acids to the sample, 2 mg kg of ammonia had
also been added prior to the ion exchange column.
Effect of Degassing on Carbon Dioxide
Table 5 shows the results when the sample contained
sodium carbonate, and hence carbon dioxide after the col-
umn. Concentrations are given for the resulting carbon
dioxide after the cation exchange. Each system removed
some carbon dioxide and hence DGCC was lower than
ACC. These reductions are given as percentages of the
reduction in conductivity that would be achieved if all car-
bon dioxide were removed. The equation used was:
Reduction in ACCmeasured DGCCmeasured
= 1003 (3)
conductivity ACCtheory DGCCtheory
The results indicated the difficulty of removing all the car-
bon dioxide from pure water in the absence of any other
acids, a situation that would represent an unlikely extreme
on power plant.

Concentration 20 g kg1 50 g kg1 60 g kg1

Species EPRI CEGB NNC EPRI CEGB NNC EPRI CEGB NNC
HCl 0.249 0.250 0.250 0.603 0.604 0.604 n/a 0.724 0.724
H2SO4 0.191 0.192 0.192 0.451 0.453 0.453 0.539 0.542 0.542
Formate 0.190 0.191 0.191 0.450 0.452 0.452 0.537 0.539 0.540

Concentration 20 g kg1 50 g kg1 250 g kg1

Species EPRI CEGB NNC EPRI CEGB NNC EPRI CEGB NNC
Acetate 0.145 0.145 0.145 0.321 0.323 0.323 1.371 1.380 1.380

Concentration 20 g kg1 200 g kg1 1 000 g kg1

Species EPRI CEGB NNC EPRI CEGB NNC EPRI CEGB NNC
CO2 0.123 0.124 0.123 0.474 0.476 0.472 1.149 1.153 1.140

Table 2: A comparison of methods of calculating after-cation conductivity.

All data are stated in S cm1.
EPRI values calculated by EPRI CCHEM v. 0.91
CEGB values calculated by CEGB programme MIXT2
NNC values calculated using a programme recently derived by B. Handy of NNC Limited, courtesy of
NNC Limited

346 PowerPlant Chemistry 2004, 6(6)

 Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

Species Concentration Calculated ACC Measured ACC

1 1 1
[g kg ] [S cm ] [S cm ]
Pure water 0.055 0.061 to 0.079
10.3 0.141 0.146
Chloride 25.7 0.316 0.309
102.7 1.234 1.169
25.7 0.143 0.146
Carbon dioxide 102.7 0.324 0.320
256.7 0.549 0.548
10.3 0.113 0.136
Formate
51.3 0.463 0.443
20.4 0.148 0.159
Acetate
51.0 0.329 0.333
10.3 / 256.7 0.625 0.610
Chloride / CO2
102.7 / 256.7 1.484 1.420
Formate and CO2 51.3 / 256.7 0.847 0.856

Table 3: Comparison of calculated and measured after-cation-exchange conductivity (ACC) values.

Species Concentration Difference ACC DGCC (measured)

1
[g kg ] [S cm1]
Reboiler Gas stripper Membrane
10.3 0.003 0.007 0.014
Chloride 25.7 +0.003 0.002 0.003
102.7 +0.019 +0.005 +0.014

NH3 2 000 0.001 +0.001 0.001

10.3 0.009 +0.019 +0.003

Formate *
51.3 0.085 +0.013 +0.010
20.4 0.011 +0.009 0.005
Acetate *
51.0 0.004 +0.008 +0.004
Table 4: The effect of degassing on acids in the absence of carbon dioxide.
* 2 mg kg1 of ammonia had been added prior to the ion exchange column.

Solution applied Efficiency of reduction in degassed conductivity value

[%]
Reboiler Sparger Membrane
1
25.7 g kg CO2 58 70 40; with 2 membranes: 48
1
102.7 g kg CO2 46 70 59
1
256.7 g kg CO2 28 70 63

Table 5: The efficiency of degassing solutions containing carbon dioxide.

PowerPlant Chemistry 2004, 6(6) 347

Evaluation of Degassed After-Cation-Exchange Conductivity Techniques
Solution applied Efficiency of reduction in degassed conductivity value
Reboiler
1
256.7 g kg CO2 and
28
10.3 g kg1 chloride
256.7 g kg1 CO2 and
1 44
102.7 g kg chloride
256.7 g kg1 CO2 and
11
51.3 g kg1 formate
Table 6: The efficiency of degassing when other anions are present.
Effect of Degassing on Other Species
Table 6 shows the results when both "strong" acids and
carbon dioxide are present in the degassing system. Not
surprisingly, the efficiencies have increased because wa-
ter has poor buffering capacity and carbon dioxide solu-
bility reduces with reduced pH. Calculated pH values with
chloride present were 6.5, 5.8 and 5.55 for concentrations
1 membrane system had significant potential for further de-
of 10, 50 and 100 g kg respectively.
Influence Quantities
The test programmes used by BNFL are derived from a
Company Standard for Chemical Analysis Equipment [3].
This standard incorporates developments in instrument
evaluation techniques since the 1960s, but in the 1990s
was aligned with procedures and nomenclature in modern
IEC standards [47]. In accord with the Company Stan-
dard, each system was subjected to the appropriate tests
for the effects of influence quantities. These were: varia-
tion of sample flow rate, variation of gas flow rate (where
appropriate), variation of sample temperature and electri-
cal supply variations. Each system required some degree
of optimisation, for example for sample flow rate. The re-
sults, in as much as they pertain to the method of de-
gassing, are summarised below.
The reboiler system could be affected if the electrical sup-
ply was reduced or sample flow increased to a point where
the reboiler temperature was not maintained. Very low
sample temperatures also reduced the efficiency of the re-
boiler system.
The gas stripping system showed no marked effect with
variations in sample temperature. However, degassing ef-
ficiency was significantly increased by decreasing sample
flow rate and/or increasing gas flow rate. The values
quoted in Tables 5 and 6 are therefore only indicative of
efficiencies obtainable within the manufacturer's rated flow
ranges. The sample used during flow variation tests con-
1 1
tained 257 g kg of carbon dioxide with 10.3 g kg
of chloride. Efficiency rose from 61 % to 80 % as the
gas/water flow ratio was increased from 2.7 to 6.7; the re-
sults in Tables 5 and 6 were taken with a ratio of 4.7.
348
[%]
Sparger Membrane
70 58; with 2 membranes: 64
89 83
84 82
The membrane diffusion system showed slight evidence
of small increases in degassing efficiency with increasing
sample temperature. However, like the gas stripping sys-
tem, the largest effect was related to the gas/water flow
ratio. The membrane system was tested with only some
35 % of the flow used for the gas stripper, i.e., over a range
of 1.0 to 1.7 for the gas/water flow ratio. The prototype
velopment to improve degassing efficiency.
SUMMARY
The measured effect for ions on the ACC was in excellent
agreement with values calculated by two independent
methods. The effect of dissolved carbon dioxide was also
as predicted by calculation. This confirms that indicative
impurity concentrations calculated from ACC values are
correct.
The three systems tested all significantly reduced the con-
tribution to ACC from dissolved carbon dioxide (i.e., DGCC
was lower than ACC). None of them achieved 100 % re-
moval of carbon dioxide, although the presence of other
acid species aided degassing.
For on-line operation on power plant each system has its
advantages and disadvantages. The advantage for the re-
boiler was that it required no supply of nitrogen. However
the solubility of carbon dioxide is not zero even at 100 C,
so the efficiency may not be 100 % even at boiling point.
A significant disadvantage was that the displaced carbon
dioxide could be entrained in the sample and re-dissolve
if the sample was cooled. Hence, measurement of the de-
gassed conductivity at elevated temperature was essen-
tial, thus requiring highly accurate sample temperature
compensation over a 75 C range.
The gas stripping system had the advantage of simplicity
and within the conditions used for this evaluation showed
the highest degassing efficiency. However, for this high
degassing efficiency the nitrogen usage would amount to
typically one cylinder per week.
PowerPlant Chemistry 2004, 6(6)
 Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

Both the above systems were vented and, hence, provided THE AUTHOR
a final sample having little pressure to operate a column
Nigel J. Drew (B.S., Ph.D., University of Nottingham,
rinsing down, which would be useful because these sys-
England) started his career in the power industry in 1978,
tems only had one column.
with the South Western Scientific Services of the Central
Electricity Generating Board. He worked with suppliers to
The membrane system tested showed a similar efficiency
assist with development of chemical instrumentation for
to the gas stripper, but with much lower gas consumption
gas analysis, oil in water, moisture in gases and water oil.
and outlet sample was at pressure. The membrane itself
During the last 25 years, the emphasis of Nigel Drew's
took some time to rinse to low conductivity and initially in-
work has changed to mainly chemical instrument evalua-
dicated a slightly elevated conductivity with pure water.
tion (of water and gas instrumentation), and monitoring
The system was a prototype and showed potential for fur-
applications for decommissioned nuclear plants. His em-
ther development.
ployers since 1990 have been nuclear power generation
companies in the United Kingdom. He was a member of
IEC SC65D during the drafting of the international stan-
dards for chemical analyzers for gas and water. He is a
REFERENCES
member of the Royal Society of Chemistry and a
[1] Bursik, A., PowerPlant Chemistry 2003, 5(4), 225. Chartered Chemist.
[2] Bursik A., PowerPlant Chemistry 2002, 4(10), 597.
[3] Magnox Company Standard M/CS/TCED/100, 1997.
Magnox Electric plc., Berkeley, United Kingdom.
[4] IEC Standard 770, 1984. International Electro- CONTACT
chemical Commission, Geneva, Switzerland.
Nigel Drew
[5] IEC Standard 60359, 2001. International Electro- BNFL
chemical Commission, Geneva, Switzerland. Nuclear Sciences & Technology Services
Berkeley Centre
[6] IEC Standard 60746, 2002. International Electro-
Berkeley, GL13 9PB
chemical Commission, Geneva, Switzerland.
United Kingdom
[7] IEC Standard 61207, 1994. International Electro-
chemical Commission, Geneva, Switzerland. E-mail: nigel.j.drew@magnox.co.uk

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