An American National Standard

Designation: D 4519 – 94 (Reapproved 1999)e1

Standard Test Method for

On-Line Determination of Anions and Carbon Dioxide in
High Purity Water by Cation Exchange and Degassed Cation
Conductivity1
This standard is issued under the fixed designation D 4519; 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.

e1 NOTE—Footnotes were editorially removed in June 1999.

1. Scope TABLE 1 Increase in Conductivity of Pure Water Expressed as

Chloride Ion or Sulfate Ion
1.1 This on-line test method includes hydrogen exchange
Conductivity due to Concentration Conductivity due to Concentration
and degassing by boiling and provides means for determining Chlorides Chlorides (PPB) Sulfates Sulfates (PPB)
anions (such as Cl −, SO 4−−, NO 3 −, and F −) at levels as low
0.0548 0.0 0.0548 0.0
as 2 µg/L (2 ppb) and carbon dioxide at the level of 0.01 to 10 0.0595 1 0.0608 1
mg/L (ppm) at 25°C in high purity water and steam condensate 0.0651 2 0.0669 2
0.0717 3 0.0732 3
by measuring electrical conductivity. 0.0791 4 0.0797 4
1.2 The conductivity of all anions (except OH −) is deter- 0.0872 5 0.0862 5
mined and not the conductivity of an individual anion if more 0.0958 6 0.0929 6
0.1049 7 0.0997 7
than one is present. If only one anion is present (such as Cl − 0.1145 8 0.1066 8
or SO4 −−), reference to Table 1 and Table 2 or Figs. 1-3 0.1243 9 0.1137 9
provides the chloride or sulfate and CO2 concentration. 0.1344 10 0.1208 10
0.2427 20 0.1969 20
1.3 This test method has been improved in accuracy by 0.3560 30 0.2780 30
using a modern microprocessor instrument for conductivity 0.4709 40 0.3616 40
and temperature measurement and appropriate temperature 0.5865 50 0.4455 50
0.7023 60 0.5320 60
compensation algorithms for compensation to 25°C. 0.8183 70 0.6181 70
1.4 This standard does not purport to address all of the 0.9345 80 0.7044 80
safety concerns, if any, associated with its use. It is the 1.0507 90 0.7909 90
1.1669 100 0.8775 100
responsibility of the user of this standard to establish appro- 2.2209 200 1.7470 200
priate safety and health practices and determine the applica- 5.8252 500 4.362 500
bility of regulatory limitations prior to use.
2. Referenced Documents D 2186 Test Methods for Deposit-Forming Impurities in
2.1 ASTM Standards: Steam3
D 1066 Practice for Sampling Steam2 D 2777 Practice for Determination of Precision and Bias of
D 1125 Test Methods for Electrical Conductivity and Re- Applicable Methods of Committee D-19 on Water2
sistivity of Water2 D 3370 Practices for Sampling Water from Closed Con-
D 1129 Terminology Relating to Water2 duits2
D 1192 Specifications for Equipment for Sampling Water D 3864 Guide for Continual On-Line Monitoring Systems
and Steam in Closed Conduits2 for Water Analysis2
D 1193 Specification for Reagent Water2
3. Terminology
3.1 Definitions—For definitions of terms used in this test
1
This test method is under the jurisdiction of ASTM Committee D-19 on Water method, refer to Test Methods D 1125 and Terminology
and is the direct responsibility of Subcommittee D19.03 on Sampling of Water and
Water-Formed Deposits, Surveillance of Water, and Flow Measurement of Water.
D 1129.
Current edition approved July 15, 1994. Published September 1994. Originally
published as D 4519 – 85. Last previous edition D 4519 – 93.
2 3
Annual Book of ASTM Standards, Vol 11.01. Annual Book of ASTM Standards, Vol 11.02.

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

1
 D 4519 – 94 (1999)e1
TABLE 2 25°C Conductivity of the Sample Immediately After the
Cation Column, Relating to the CO2 Concentration with the Anion
Component Subtracted Out (See 11.7)
Conductivity Carbon Dioxide
µs/cm
ppm ppb
0.0548 0 0
0.09 0.01 10
0.12 0.02 20
0.16 0.03 30
0.19 0.04 40
0.21 0.05 50
0.24 0.06 60
0.26 0.07 70
0.28 0.08 80
0.3 0.09 90
0.32 0.1 100
0.48 0.2 200
0.61 0.3 300
0.71 0.4 400
0.81 0.5 500
0.89 0.6 600
0.97 0.7 700
1.04 0.8 800
1.11 0.9 900
1.17 1.0 ...
1.69 2.0 ...
2.09 3.0 ...
2.42 4.0 ...
2.72 5.0 ...
2.98 6.0 ...
3.23 7.0 ...
3.46 8.0 ...
3.67 9.0 ...
3.88 10 ...
5.46 20 ...

4. Summary of Test Method FIG. 1 Chloride Ion vs. Conductivity

4.1 This test method measures the anion concentration (such
as Cl − and SO4 −−) by measuring the electrical conductivity of 5.2 The measurement of such impurities is most important
the anions after passing cooled condensate or high purity water to these industries since plant outages or product contamination
through a cation exchanger in the hydrogen form, then through can result from events such as condenser leakage. Also, water
an electric reboiler. Passage through the cation resin replaces quality deviations can occur from condensate polishing and
cations (including ammonia and amines) in the water with makeup water equipment malfunctions.
hydrogen ions. This eliminates interference in the measure- 5.3 The continuous measurement and trends provided by
ment of anions. Three conductivity cells located in the instru- this test method are of particular interest and can indicate the
ment provide measurements of the influent conductivity, cation need for corrections in water treating or operating procedures
conductivity at the incoming sample temperature, and the and equipment. The equipment for this test method can be
effluent conductivity at atmospheric boiling water temperature considered more rugged and adaptable to installation under
after acidic (volatile) gas removal. Conductivity values are plant operating conditions than the more accurate laboratory
then corrected to 25°C. While the influent conductivity mea- methods, such as ion chromatography and atomic absorption.
surement is not necessary in determining the total anion
conductivity, its determination provides a more complete 6. Interferences
evaluation of the sample, which can also include an estimation 6.1 It is important to devote particular attention to accurate
of the amine content. Measurement of the cation and reboil flow and temperature control as variations can cause inaccu-
effluent conductivities are necessary in determining the com- racies. See Annex A1, Annex A2, and Annex A3 for additional
position of the influent (total anions and acidic gas content). information on this subject.
Reference to Table 1 and Table 2 or Figs. 1-3, or both, are then
necessary to complete the determinations. 7. Apparatus
7.1 Mechanical Ion Exchanger-Degasser Instrument.
5. Significance and Use 7.2 Constant Head Device, for providing approximately 1.5
5.1 This test method can be a useful diagnostic tool in m (5 ft) head pressure for water entering the instrument.
measuring the impurities and detecting their sources in high 7.3 Constant Temperature Equipment, for adjusting the
purity water, the steam condensate of high pressure power influent temperature to 25°C 6 0.5°C.
plants, and in the process water of certain industries requiring 7.4 Conductivity Instruments and Sensors, for measuring
water of the highest purity attainable. the conductivity of the sample to determine the concentration

2
 D 4519 – 94 (1999)e1

FIG. 2 Sulfate Ion vs. Conductivity FIG. 3 Carbon Dioxide vs. Conductivity

Chemical Society, where such specifications are available.4

of anions and carbon dioxide. Use of instruments that have a Other grades may be used, provided it is first ascertained that
specialized temperature compensation for high purity water (to the reagent is of sufficiently high purity to permit its use
25°C) based on an acid such as HCl or H2SO4 is required for without lessening the accuracy of the determination.
this test method. 8.2 Purity of Water—Unless otherwise indicated, references
7.5 Hydrogen Exchange Cartridge, 15⁄8 in. inside diameter, to water shall be understood to mean reagent water conforming
12 in. height, containing 1 lb of 8 % cross-linked styrene- to Specification D 1193, Type II.
divinylbenzene, strong acid gel cation exchange resin in the 8.3 Chloride Solution, Stock (1 mL = 0.1 mg Cl −)— Dis-
H + form; U.S. standard mesh 16 by 50 (1190 by 297 µm) may solve in water 0.1649 g of sodium chloride (NaCl) dried to
be used. Regenerate with 1500 mL of hydrochloric acid (1 + 6) constant weight at 105°C, and dilute to 1 L in a thoroughly
at a flow rate of 40 to 50 mL/min, followed by rinsing with 300 cleaned polyethylene flask.
mL of Type II water at the same flow rate. Then rinse with 3500 8.4 Chloride Solution, Standard (1.00 mL = 0.001 mg)—
mL of Type II water at a flow rate of 100 to 150 mL/min. Rinse Dilute 10.00 mL of chloride stock solution (8.3) to 1 L with
down when placing in service. water.
8.4.1 This standard chloride solution is to be used in the
NOTE 1—The column inside diameter, resin bed height, inlet sample
calibration of the instrument if desired, or reference can be
temperature (11.3), and service flowrate (11.4) have been standardized to
provide comparable results. They may not be the optimum values. The made to the instruction booklet furnished with the instrument.
user should realize that those parameters affect the measurement. 8.5 Hydrochloric Acid (1 + 6)—Add 100 mL concentrated
HCl (sp. gr. 1.19) to 600 mL water.
7.6 Software to automate the determination of anions and
carbon dioxide is available.
4
Reagent Chemicals, American Chemical Society Specifications, American
8. Reagents Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
8.1 Purity of Reagents—Reagent grade chemicals shall be
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
used in all tests. Unless otherwise indicated, it is intended that and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
all reagents shall conform to the specifications of the American MD.

3
 D 4519 – 94 (1999)e1
9. Sampling order to maintain a stable flow rate, otherwise changes in
9.1 Collect the sample in accordance with the applicable cation resin exchange efficiency may occur with changes in the
ASTM standards: Practice D 1066, Specification D 1192, and flow rate.
Practices D 3370. 11.5 Clean up the system by maintaining the recommended
flow rate through the instrument for 24 h or longer to approach
10. Calibration a minimum value of 0.055 µS/cm reading for pure water at the
10.1 The instrument may be calibrated by pumping solu- final effluent conductivity. On restart, several hours of opera-
tions of known concentrations of Cl −(in NaCl form) or tion may be required before this minimum conductivity value
SO4 −−(in Na2SO 4 form) through the instrument and observing is obtained.
the conductivity increases. It may be preferred to use the 11.6 Refer to Table 1, or Fig. 1 and Fig. 2, or both, to
calibration charts shown in the instruction book accompanying determine the equivalent concentration of chloride ion or
the instrument or in referenced articles. 5 , 6, 7 , 8 sulfate ion based on the conductivity reading of the final
10.2 If it is desired to calibrate the instrument using known conductivity cell.
chloride solutions, the range of 0.001 to 0.010 mg/L (1 to 10 11.7 In order to obtain the volatiles expressed as carbon
ppb) of chloride may be covered by application of 0.2 to 2.0 dioxide in Table 2, subtract the conductivity of pure water
mL/min of the standard chloride solution (8.4.1) to the 200 (0.055 µS/cm) from the conductivity of the final effluent cell.
mL/min flow by injecting the flow from a small peristaltic Then deduct this value from the cation conductivity obtained
pump to a hypodermic needle inserted in a plastic tubing from the cell immediately after the cation exchange resin. Use
connection. this adjusted conductivity value to look up the concentration of
volatiles expressed as a concentration of carbon dioxide in
11. Procedure Table 2, or Fig. 3, or both.
11.1 Flush out the piping thoroughly by flow of high purity 11.7.1 Example: Based on a final cell conductivity reading
water through the instrument before starting the flow of water of 0.087µ S/cm (equivalent to 5 ppb of Cl − in a system
to be tested. predominant in chloride ion), 0.055 µS/cm is deducted for the
11.2 Refer to the manufacturer’s instruction booklet before conductivity of pure water to obtain a value of
starting the instrument. Because of the nature of this measuring 0.087 − 0.055 = 0.032 µS/cm. Then deduct this number (0.032)
technique, it is very important to follow the manufacturer’s from the cation conductivity (0.242 − 0.032) = 0.21 µS/cm due
instructions very carefully in order to achieve accurate results. to volatiles, which corresponds to 50 µg/L (ppb) of carbon
See Annex A1-Annex A4 for a discussion on the effects caused dioxide, as read from Table 2. This deduction is necessary to
by variations in operating conditions and interfering sub- account for the anion conductivity (other than carbon dioxide)
stances. obtained in the cation conductivity measurement.
11.3 Connect the high purity water or condensate to be 11.8 The service life of the cation cartridge may vary from
tested to the instrument influent connection. This water should one month to several months depending on the amine concen-
preferably be at a temperature of 25 6 0.5°C. The flow shall tration in the influent.
first pass through the constant head device, then into the 12. Report
instrument through the hydrogen ion exchanger and electric
12.1 Report the results as µg/L Cl −, or SO4 −−, or both, and
reboiler and out the reboil chamber effluent (Fig. 4 and Fig. 5).
CO2 as obtained from Table 1 and Table 2, or Figs. 1-3, or both.
11.4 Adjust the flow through the instrument to the proper
flow rate (200 mL/min), or as specified by the instrument 13. Precision and Bias
manufacturer. It is important to use a constant head device in 13.1 Since this test method involves continuous sampling
and measurement, Practice D 2777 is not applicable. Footnotes
5
7 through 10 do show that there is excellent agreement between
Lane, R. W., Sollo, F. W., Neff, C. H., “Continuous Monitoring of Anions in
Feedwater by Electrical Conductivity,” Illinois State Water Survey Reprint 473,
the theoretical and measured conductivity values of Cl − and
Reprinted from “Water and Steam, Their Properties and Current Industrial Appli- SO4 −− ions in the 0 to 50 µg/L (ppb) range.
cations,” Pergammon Press, Oxford and New York, 1980.
6
Electric Power Research Institute, “Monitoring Cycle Water Chemistry in 14. Keywords
Fossil Plants,” EPRI GS-7556, Vol 1: Monitoring Results.
7
Continuous Conductivity Monitoring of Anions in High-Purity Water, ASTM
14.1 anion electrical conductivity; carbon dioxide; cation
STP 742, ASTM, 1981, p. 195. conductivity; degassed cation conductivity; electrical conduc-
8
Internal report from Carl C. Scheerer, C.I.P.S., Springfield, IL, April 18, 1989. tivity; high purity water; reboiled conductivity

4
 D 4519 – 94 (1999)e1

FIG. 4 Flow Diagram for Mechanical-Ion Exchanger-Degasser Instrument

5
 D 4519 – 94 (1999)e1

FIG. 5 Mechanical-Ion Exchanger-Degasser Instrument (Larson-Lane Condensate Reboiler)

6
 D 4519 – 94 (1999)e1
ANNEXES

(Mandatory Information)

A1. EFFECTS OF THE INFLUENT WATER TEMPERATURE

A1.1 The cation resin loses its ability to maintain its

holding power with increases in temperature. Therefore, it is
important to maintain a constant temperature so as to avoid any
changes in the baseline of the measurement. Fig. A1.1 shows
the effects of temperature of the influent water versus the
conductivity (at 25°C) of the effluent water of a cation column
when supplied with 0.055 µS/cm water.

FIG. A1.1 Cation Resin Performance, Amount of Ionic Leaching

Versus the Flow Rate for IWC Type TCD1 Resin in a 2-in.
Diameter Tube

7
 D 4519 – 94 (1999)e1

A2. EFFECTS OF SAMPLE VELOCITY

A2.1 The cation resin has an optimum dynamic efficiency

at a given sample flow rate. Fig. A2.1 depicts the change in
conductivity of the effluent of a 2 in. insider diameter column
with 1 lb of cation resin versus flow rate. As indicated by this
chart, it is important to provide a flow of 200 mL/min through
the resin in order to maximize the efficiency of the resin and to
minimize resin bleed-off. While this is a larger-sized diameter
cartridge than that described in the present test method (15⁄8 in.
(41 mm) inside diameter), the same conclusions and need for
accurate flow control are to be expected. Any deviations in the
flow rate will cause variations in the baseline of the measure-
ment and therefore should be held to a minimum in order to
reduce any errors in measurement. More accurate cation
conductivity results have been reported with this lesser diam- FIG. A2.1 Cation Resin Performance, Amount of Ionic Leaching
eter column. 10 Versus the Temperature for IWC Type TCD1 Resin in a 2-in.
Diameter Tube

8
 D 4519 – 94 (1999)e1

A3. TEMPERATURE COMPENSATION OF THE INSTRUMENT

A3.1 In the past, conductivity instruments without tempera- counted for. With a modern microprocessor instrument that
ture compensation were used for this test method. This led to measures the temperature very accurately and by using appro-
large errors due to fluctuations in temperature at the reboil priate temperature compensation algorithms to correct the
chamber effluent and difficulty in accounting accurately for conductivity to the equivalent conductivity at 25°C, one can
conductivity changes resulting from changes in atmospheric minimize the errors associated with the effluent temperature
boiling water temperature. Due to the steep slope of pure water and the atmospheric pressure over the previous test method
samples (5 %/°C) and the large temperature variations (often described in Test Method D 4519 – 85.
more than 5°C), large errors were introduced and not ac-

A4. ORGANIC ACIDS

A4.1 It has been theorized that the final effluent results presence of 100 µg/L TOC (as acetic acid) did not appreciably
(degassed cation conductivity) for Cl − and SO4 −− may be change the carbon dioxide and the degassed cation conductiv-
inaccurate if there are appreciable organic acids present (as ity results. There is no other known data available on organic
acetic and formic). 9 However, footnote 9 revealed that the acid removal by this instrumental reboil procedure.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or [email protected] (e-mail); or through the ASTM website
(www.astm.org).