An American National Standard

Designation: D 6504 – 00

Standard Practice for

On-Line Determination of Cation Conductivity in High Purity
Water1
This standard is issued under the fixed designation D 6504; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 5391 Test Method for Electrical Conductivity and Resis-

1.1 This practice describes continuous sample conditioning tivity of a Flowing High Purity Water Sample2
by hydrogen ion exchange and measurement by electrolytic D 5540 Practice for Flow Control and Temperature Control
conductivity. It is commonly known as cation conductivity for On-Line Water Sampling and Analysis2
measurement in the power industry although it is actually an 3. Terminology
indication of anion contamination in high purity water samples.
Measurements are typically in a range less than 1 µS/cm. 3.1 Definitions— For definitions of terms used in this
1.2 The actual conductivity measurements are made using practice, refer to Test Methods D 1125, Terminology D 1129,
Test Method D 5391. and Practice D 3864.
1.3 This practice does not provide for separate determina- 3.2 Definitions of Terms Specific to This Standard:
tion of dissolved carbon dioxide. Refer to Test Methods 3.2.1 cation conductivity, n—the parameter obtained by
D 2186 and D 4519. conditioning a sample by passing it through a hydrogen form
1.4 This standard does not purport to address all of the cation ion exchange resin column and then measuring its
safety concerns, if any, associated with its use. It is the electrolytic conductivity, on-line.
responsibility of the user of this standard to establish appro- 3.2.2 specific conductivity, n—direct electrolytic conductiv-
priate safety and health practices and determine the applica- ity measurement of a power plant sample, usually dominated
bility of regulatory limitations prior to use. by treatment chemicals, such as ammonia or amines.

2. Referenced Documents 4. Summary of Practice

2.1 ASTM Standards: 4.1 The sample is passed continuously through a small
D 1066 Practice for Sampling Steam2 cation exchange column in the hydrogen form, which ex-
D 1125 Test Methods for Electrical Conductivity and Re- changes all cations for H+. In this process, pH adjusting
sistivity of Water2 treatment chemicals, such as ammonia and amines are re-
D 1129 Terminology Relating to Water2 moved.
D 1193 Specification for Reagent Water2 4.2 Measurement is made continuously on the conditioned
D 2186 Test Methods for Deposit-Forming Impurities in sample with a process high purity conductivity analyzer/
Steam3 transmitter.
D 3370 Practices for Sampling Water from Closed Con- 4.3 Temperature conditioning of the sample and specialized
duits2 compensation of the measurement are used to minimize
D 3864 Guide for Continual On-Line Monitoring Systems temperature effects on the performance of the ion exchange
for Water Analysis2 resin and the measurement.
D 4519 Test Method for On-Line Determination of Anions 4.4 Few studies have been published on the performance of
and Carbon Dioxide in High Purity Water by Cation cation conductivity measurement but one collaborative effort
Exchange and Degassed Cation Conductivity2 provides some background (1).4

1
This practice is under the jurisdiction of ASTM Committee D-19 on Water and
is the direct responsibility of Subcommittee D19.03 on Sampling Water and
Water-Formed Deposits, Analysis of Water for Power Generation and Process Use,
On-Line Water Analysis, and Surveillance of Water.
Current edition approved June 10, 2000. Published September 2000.
2 4
Annual Book of ASTM Standards, Vol 11.01. The boldface numbers given in parentheses refer to a list of references at the
3
Annual Book of ASTM Standards, Vol 11.02. end of this standard.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 6504 – 00
5. Significance and Use The use of fresh resin completely in the hydrogen form and
5.1 Cation conductivity provides one of the most sensitive thoroughly rinsed is recommended. An exhausted resin column
and dependable on-line means of detecting anionic contamina- will have the same effect but with more rapidly increasing
tion in the boiler/steam cycle, such as chlorides, sulfates, errors.
nitrates, bicarbonates, and organic acids, such as formic and 6.7 Fouled resin can leach conductive components even
acetic. with an absolutely pure influent sample. Fresh resin is recom-
5.2 High sensitivity is provided by intentionally eliminating mended.
the pH adjusting treatment chemical(s), for example, ammonia 6.8 Some cation resins contain leachables which can raise
and amines, from the sample and converting remaining salt background conductivity and reduce sensitivity to sample
contaminants into their acid forms which are approximately impurities. Extensive rinsing usually is required. A continuous
three times as conductive. rinsing scheme is given in Appendix X1.2. Some success also
5.3 Guidelines on cation conductivity limits for various has been achieved with a hydrochloric acid (1+4) pre-rinse.
cycle chemistry and boiler types have been established by 6.9 For interferences with basic high purity conductivity
EPRI (2-4) and by ASME (5,6). measurements, refer to Test Method D 5391.
5.4 The sample effluent from the cation exchange column 7. Apparatus
also may be used, and in some cases is preferred, for ion
7.1 Cation Exchange Column:
chromatography or other anion measurements.
7.1.1 The cation exchange column shall have an inside
diameter of less than 60 mm (2.4 in.) and produce a flow
6. Interferences
velocity greater than 300 mm/min (1 ft/min) at the sample flow
6.1 Some weakly ionized cations may not be completely rate (see Appendix X1). The column shall have end screens to
exchanged by the resin. This will produce positive or negative distribute flow across the cross-section of the column and to
errors in the measurement depending on the sample composi- prevent resin beads and fines from escaping. The column may
tion. These errors can reduce sensitivity to corrosive contami- be piped for upward or downward flow. Upward flow provides
nants. automatic purging of air at startup which is helpful in cycling
6.2 Temperature effects on the cation resin may alter its plants. However, the resin must be packed full to prevent
equilibrium properties. Control sample temperature within the fluidizing and channeling. Downward flow eliminates the
resin manufacturers’ temperature limits to obtain consistent possibility of fluidizing but requires the means to vent air from
results. the column at startup. Care must be exercised to eliminate all
6.3 The large temperature effects of high purity conductivity air pockets which could cause channeling. The column should
measurement must be minimized by sample conditioning and be constructed of nonleaching material, such as polycarbonate
temperature compensation. Although sample temperature may or polypropylene. Materials, such as polyvinylchloride, may
be controlled closely, it may be significantly influenced by the leach chlorides and are not recommended. Flexible tubing used
ambient temperature as it passes through the column, tubing to make connections to the column should have minimal length
and flow chamber. The temperature coefficient of pure water is and diameter to minimize the amount of leaching and air
near 5 % of measurement per °C at 25°C, which can contribute (carbon dioxide) permeation.
substantial errors if not compensated properly. Temperature 7.1.2 The resin shall be a sulfonated styrene-divinylbenzene
compensation must be appropriate for the unique acidic com- with at least 8 % cross-linkage, strong acid gel cation exchange
position of cation conductivity samples. Conventional high resin in the hydrogen form, filling the column. An indicating
purity temperature compensation for neutral mineral contami- resin which changes color as its hydrogen ions are displaced is
nants is not suitable for this application (7,8). The user is strongly preferred for convenient monitoring of the progress of
cautioned that the accuracy of algorithms for cation conduc- resin exhaustion through the column.
tivity compensation may vary widely. The user should deter- 7.1.3 The resin must be rinsed to remove leachables before
mine the applicability and accuracy of the instrument’s tem- full sensitivity can be reached. A convenient arrangement of
perature compensation in the anticipated temperature range. multiple resin columns to provide the rinse and for easy
6.4 Carbon dioxide may be in a sample and will be change-out is described in X1.2.
converted to carbonic acid and raise cation conductivity. This 7.2 Process Sensor— The conductivity cell shall be suitable
is not strictly an interference; however, carbon dioxide gener- for measurement of high purity water and shall include an
ally is not as corrosive as mineral salts and enters the cycle by integral temperature sensor for simultaneous temperature mea-
different means. Where it is commonly present it may be surement within the cell volume. The temperature measure-
desirable to obtain a cation conductivity measurement with ment shall be used for compensation in the instrument as
carbon dioxide removed (see Test Methods D 2186 and described in 6.3 and in Test Method D 5391. The cell shall be
D 4519. housed in a small volume flow chamber to provide fast
6.5 Carbon dioxide may also be aspirated as a component of response.
air, into the sample line through loose fittings in the exchange 7.3 Process Instrument—The instrument shall provide mea-
column, flowmeter, valves, etc. This is not representative of the surement, indication and temperature compensation as de-
actual sampling point and produces positive errors. scribed in 6.3 and Test Method D 5391. It also may include
6.6 Incompletely regenerated or inadequately rinsed resin alarm relays and analog or digital output signals as required by
will release trace ionic impurities that produce positive errors. the application.

2
 D 6504 – 00
8. Reagents 11. Procedure
8.1 Purity of Reagents—Reagent grade chemicals shall be 11.1 Connect the apparatus as shown in Fig. 1 or X1.2, for
used in all tests. Unless otherwise indicated, it is intended that continuous sampling and measurement. Follow the column
all reagents conform to the specifications of the Committee on manufacturer’s instructions for purging air from the cation
Analytical Reagents of the American Chemical Society where exchange column.
such specifications are available.5 Other grades may be used, 11.2 Set sample and bypass flowrates as needed to provide
provided it is first ascertained that the reagent is of sufficiently sufficient sample velocity in the main sample line and the
high purity to permit its use without lessening the accuracy of recommended sample flow through the column. See 7.1.1,
the determination. X1.1 and manufacturer’s instructions.
11.3 Measure conductivity continuously, referring to Test
8.2 Purity of Water— Unless otherwise indicated, refer-
Method D 5391.
ences to water shall be understood to mean reagent water as
11.4 Monitor for resin exhaustion. With indicating resin,
defined by Type II of Specification D 1193.
note color change and replace the column when 75 % of the
8.3 Hydrochloric Acid (1 + 4)—Mix one volume of con- column length has been exhausted. With conventional resin,
centrated HCl (sp gr 1.19) with 4 volumes of water. keep a record of the total time, flow, and specific conductivity
values of the sample during the exchange life of the resin. Use
9. Sampling this for scheduling future resin replacement well before ex-
9.1 For sampling refer to Practices D 1066, D 3370, and haustion.
D 5540, as well as Test Method D 5391. Cation conductivity is 12. Keywords
one of the highest purity, lowest conductivity measurements in
12.1 boiler cycle chemistry; cation conductivity; on-line;
a power plant, and therefore, is vulnerable to trace contamina-
process measurement
tion. Care should be exercised in closely following proper
sampling techniques.

10. Calibration
10.1 For calibration refer to Test Methods D 1125 and
D 5391.

5
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd, Poole, Dorset, U.K., and the United States Pharmacopeia and FIG. 1 Cation Conductivity Apparatus (Flow direction through the
National Formulary, U.S. Pharmaceutical Convention Inc. (USPC), Rockville, MD. column may also be downward. See 7.1.1.)

APPENDIX

(Nonmandatory Information)

X1. CATION EXCHANGE COLUMN

X1.1 Column Diameter

X1.1.1 The flowrate and column inside diameter should
provide a flow velocity of at least 300 mm/min to minimize
leaching from the resin. Fig. X1.1 illustrates this relationship.
X1.2 Continuous Resin Rinse Scheme
X1.2.1 Lead and trail cation resin columns allow continuous
rinsing of the trailing column while the lead column is
“working.” When the lead column is exhausted the trailing
column is rinsed fully, air has been purged and it can be valved
easily into the lead position with minimal interruption. The
exhausted column is replaced and valved in for rinsing. Figs.
X1.2-X1.4 illustrate the three modes of operation with heavy
lines and shaded valve ports indicating the sample flow
direction (9). FIG. X1.1 Sample Flowrate Versus Column Inside Diameter

3
 D 6504 – 00

FIG. X1.2 Column 1 is exchanging cations and Column 2 is

rinsing

FIG. X1.3 Column 1 is exhausted and Column 2 has been valved

in to exchange cations, allowing replacement of Column 1

4
 D 6504 – 00

FIG. X1.4 Column 2 continues to exchange cations and a new

Column 1 is rinsing

REFERENCES

(1) Scheerer, C. C., Cluzel, J., and Lane, R. W., “Monitoring Condensate SR) Electric Power Research Institute, Palo Alto, CA, 1982.
Polisher Operation Using Conductivity (Specific, Cation, and De- (5) “Consensus on Operating Practices for the Control of Feedwater and
gassed Cation) and Sodium Analysis,” International Water Conference Boiler Water Chemistry in Modern Industrial Boilers,” American
Proceedings, Engineers Society of Western Pennsylvania, Pittsburgh, Society of Mechanical Engineers, New York, 1994.
1989, pp. 321–334. (6) Tvedt, T. J., Holloway, R. T., “Control of Industrial Boiler Water
(2) “Interim Consensus Guidelines on Fossil Plant Cycle Chemistry,” Chemistry: A New ASME Consensus,” Industrial Water Treatment,
Report CS4629, Electric Power Research Institute, Palo Alto, CA, May/June 1996, 28: 3, 40–43.
1986. (7) Gray, D., and Tenney, A., “Improved Conductivity/Resistivity Tem-
(3) “Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treat- perature Compensation for High Purity Water,” Ultrapure Water, Vol
ment,” (Report TR-105041); “Cycle Chemistry Guidelines for Fossil 3, No. 2, July/August 1986, pp. 27–30.
Plants: Oxygenated Treatment,” (Report TR-102285); “Cycle Chem- (8) Bursik, A., “Monitoring of Temperature-Compensated Conductivity in
istry Guidelines for Fossil Plants: Phosphate Treatment for Drum Fossil Power Plants,” Fourth International Conference on Cycle
Units,” (Report TR-103665), “Guideline Manual on Instruments & Chemistry in Fossil Plants, Atlanta, September, 1994.
Control for Fossil plant Cycle Chemistry,” (Report CS-5164), Electric (9) Maughan, E., Memo relating Eskom Power Company, South Africa,
Power Research Institute, Palo Alto, CA. lead-and-trail method of cation conductivity measurement, September
(4) “PWR Secondary Water Chemistry Guidelines,” (Report NP-2704- 1998.

BIBLIOGRAPHY

(1) Bevilacqua, A. and Gray, D.,“ Evaluating Cation Conductivity 1999, pp. 60–63.
Temperature Compensation,” Ultrapure Water, Vol 16, No. 4, April

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