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On-Line Determination of Anions and Carbon Dioxide in High Purity Water by Cation Exchange and Degassed Cation Conductivity
On-Line Determination of Anions and Carbon Dioxide in High Purity Water by Cation Exchange and Degassed Cation Conductivity
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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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 ...
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D 4519 – 94 (1999)e1
FIG. 2 Sulfate Ion vs. Conductivity FIG. 3 Carbon Dioxide vs. Conductivity
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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
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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
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D 4519 – 94 (1999)e1
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D 4519 – 94 (1999)e1
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D 4519 – 94 (1999)e1
ANNEXES
(Mandatory Information)
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D 4519 – 94 (1999)e1
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D 4519 – 94 (1999)e1
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-
A4.1 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.
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