ASTM D4519-94(1999)e1

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An American National Standard
e1
Designation:D4519–94(Reapproved1999)
Standard Test Method for
On-Line Determination of Anions and Carbon Dioxide in
High Purity Water by Cation Exchange and Degassed Cation
Conductivity
This standard is issued under the fixed designation D4519; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
e NOTE—Footnotes were editorially removed in June 1999.
TABLE 1 Increase in Conductivity of Pure Water Expressed as
1. Scope
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)
− 4−− − −
anions (such as Cl ,SO ,NO , 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)at25°Cinhighpuritywaterandsteamcondensate 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
0.0958 6 0.0929 6
mined and not the conductivity of an individual anion if more
− 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 SO ), reference to Table 1 and Table 2 or Figs. 1-3
0.1243 9 0.1137 9
0.1344 10 0.1208 10
provides the chloride or sulfate and CO concentration.
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
0.5865 50 0.4455 50
and temperature measurement and appropriate temperature
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
1.0507 90 0.7909 90
safety concerns, if any, associated with its use. It is the
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
D2186 Test Methods for Deposit-Forming Impurities in
2.1 ASTM Standards:
Steam
D1066 Practice for Sampling Steam
D2777 Practice for Determination of Precision and Bias of
D1125 Test Methods for Electrical Conductivity and Re-
Applicable Methods of Committee D-19 on Water
sistivity of Water
D3370 Practices for Sampling Water from Closed Con-
2 2
D1129 Terminology Relating to Water
duits
D1192 Specifications for Equipment for Sampling Water D3864 Guide for Continual On-Line Monitoring Systems
and Steam in Closed Conduits
for Water Analysis
D1193 Specification for Reagent Water
3. Terminology
3.1 Definitions—For definitions of terms used in this test
This test method is under the jurisdiction ofASTM Committee D-19 on Water
method, refer to Test Methods D1125 and Terminology
and is the direct responsibility of Subcommittee D19.03 on Sampling of Water and
D1129.
Water-Formed Deposits, Surveillance of Water, and Flow Measurement of Water.
Current edition approved July 15, 1994. Published September 1994. Originally
published as D4519–85. Last previous edition D4519–93.
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.
e1
D4519–94 (1999)
TABLE 2 25°C Conductivity of the Sample Immediately After the
Cation Column, Relating to the CO 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 Thistestmethodmeasurestheanionconcentration(such
− −−
as Cl and SO ) by measuring the electrical conductivity of
5.2 The measurement of such impurities is most important
theanionsafterpassingcooledcondensateorhighpuritywater
totheseindustriessinceplantoutagesorproductcontamination
throughacationexchangerinthehydrogenform,thenthrough
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
mentprovidemeasurementsoftheinfluentconductivity,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
6. Interferences
conductivity, its determination provides a more complete
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. SeeAnnexA1,AnnexA2, andAnnexA3 for additional
position of the influent (total anions and acidic gas content). information on this subject.
Reference toTable 1 andTable 2 or Figs. 1-3, or both, are then
7. Apparatus
necessary to complete the determinations.
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
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D4519–94 (1999)
FIG. 3 Carbon Dioxide vs. Conductivity
FIG. 2 Sulfate Ion vs. Conductivity
Chemical Society, where such specifications are available.
of anions and carbon dioxide. Use of instruments that have a
Other grades may be used, provided it is first ascertained that
specializedtemperaturecompensationforhighpuritywater(to
the reagent is of sufficiently high purity to permit its use
25°C) based on an acid such as HCl or H SO is required for
2 4
without lessening the accuracy of the determination.
this test method.
8.2 Purity of Water—Unlessotherwiseindicated,references
7.5 Hydrogen Exchange Cartridge,1 ⁄8 in. inside diameter,
towatershallbeunderstoodtomeanreagentwaterconforming
12 in. height, containing 1 lb of 8% cross-linked styrene-
to Specification D1193, 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
beused.Regeneratewith1500mLofhydrochloricacid(1+6)
constant weight at 105°C, and dilute to 1 L in a thoroughly
ataflowrateof40to50mL/min,followedbyrinsingwith300
cleaned polyethylene flask.
mLofTypeIIwateratthesameflowrate.Thenrinsewith3500
8.4 Chloride Solution, Standard (1.00 mL=0.001 mg)—
mLofTypeIIwaterataflowrateof100to150mL/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
made to the instruction booklet furnished with the instrument.
provide comparable results. They may not be the optimum values. The
8.5 Hydrochloric Acid (1+6)—Add 100 mL concentrated
user should realize that those parameters affect the measurement.
HCl (sp. gr. 1.19) to 600 mL water.
7.6 Software to automate the determination of anions and
carbon dioxide is available.
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
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