ASTM D4519-16

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it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D4519 − 10 D4519 − 16
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. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This on-line test method includes hydrogen exchange and degassing by boiling heating or gas stripping and provides means
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for determining anions (such as Cl Cl , SO , NO , and F F ) at levels as low as 2 μg/L (2 ppb) and carbon dioxide at the
4 3
level of 0.01 to 10 mg/L (ppm) at 25°C in high purity water and steam condensate in steam and water samples in power plants
by measuring electrical conductivity.
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1.2 The conductivity of all anions (except OH OH ) is determined and not the conductivity of an individual anion if more than
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one is present. If only one anion is present (such as Cl Cl or SO ), reference to Section 4, Table 1 and Table 2 or Figs. 1-3
provides the chloride or sulfate and CO concentration.
1.3 This test method has been improved in accuracy by using a modern microprocessor instrument for conductivity and
temperature measurement and appropriate temperature compensation algorithms for compensation to 25°C.compensation, by using
final sample cooling to 25°C, or both.
1.4 The values stated in either SI units or inch-pound units are to be regarded separately as standard. The values stated in each
system may not be exact equivalents; therefore, each system shall be used independently of the other. Combining values from the
two systems may result in non-conformance with the standard.
This test method is under the jurisdiction of ASTM Committee D19 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 Dec. 1, 2010June 1, 2016. Published March 2011June 2016. Originally approved in 1985. Last previous edition approved in 20052010 as
D4519 – 94 (2005).D4519 – 10. DOI: 10.1520/D4519-10.10.1520/D4519-16.
TABLE 1 Increase in Conductivity of Pure Water Expressed as
Chloride Ion or Sulfate Ion
Conductivity due to Concentration Conductivity due to Concentration
Chlorides Chlorides (PPB) Sulfates Sulfates (PPB)
0.0548 0.0 0.0548 0.0
0.0595 1 0.0608 1
0.0651 2 0.0669 2
0.0717 3 0.0732 3
0.0791 4 0.0797 4
0.0872 5 0.0862 5
0.0958 6 0.0929 6
0.1049 7 0.0997 7
0.1145 8 0.1066 8
0.1243 9 0.1137 9
0.1344 10 0.1208 10
0.2427 20 0.1969 20
0.3560 30 0.2780 30
0.4709 40 0.3616 40
0.5865 50 0.4455 50
0.7023 60 0.5320 60
0.8183 70 0.6181 70
0.9345 80 0.7044 80
1.0507 90 0.7909 90
1.1669 100 0.8775 100
2.2209 200 1.7470 200
5.8252 500 4.362 500
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D4519 − 16
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 .
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D1066 Practice for Sampling Steam
D1125 Test Methods for Electrical Conductivity and Resistivity of Water
D1129 Terminology Relating to Water
D1192 Guide for Equipment for Sampling Water and Steam in Closed Conduits (Withdrawn 2003)
D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits
3. Terminology
3.1 Definitions—For definitions of terms used in this test method, refer to Test Methods D1125 and Terminology D1129.
3.1 Definitions:
3.1.1 For definitions of terms used in this standard, refer to Test Methods D1125 and Terminology D1129.
4. Summary of Test Method
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4.1 This test method measures the anion concentration (such as Cl Cl and SO ) by measuring the electrical conductivity
of the anions after passing cooled condensate or high purity water the sample through a cation exchanger in the hydrogen form,
then through an electric reboiler. a degasifier. Passage through the cation resin replaces cations (including ammonia and other
amines) in the water with hydrogen ions. This eliminates interference in the measurement of anions. Three conductivity cells
located in the instrument provide measurements of the influent conductivity, cation conductivity at the incoming sample
temperature, and the effluent conductivity at atmospheric boiling water temperature after acidic (volatile) gas removal.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
D4519 − 16
FIG. 1 Chloride Ion vs. Conductivity
Conductivity values are then corrected The sample is then either cooled to 25°C or conductivity values are compensated to 25°C.
While the influent conductivity measurement is not necessary in determining the total anion conductivity, its determination
provides a more complete evaluation of the sample, which can also include an estimation of the amine content. Measurement of
the cation and reboil effluentdegassed sample conductivities are necessary in determining the composition of the influent (total
anions and acidic gas content). Reference to Table 1 and Table 2 or Figs. 1-3, or both, are then necessary to complete the
determinations.
4.2 In-depth studies provide additional background and updated experience with the degassed cation conductivity techni-
que.technique (1).
5. Significance and Use
5.1 This test method can be a useful diagnostic tool in measuring the impurities and detecting their sources in high purity water,
the boiler feed water and steam condensate of high pressure power plants, and in the process water of certain industries requiring
water of the highest purity attainable.high purity water.
5.2 The measurement of such impurities is most important to these industries since plant outages or product contamination can
result from events such as condenser leakage. Also, water quality deviations can occur from condensate polishing and makeup
water equipment malfunctions.
5.3 The continuous measurement and trends provided by this test method are of particular interest and can indicate the need for
corrections in water treating or operating procedures and equipment. The equipment for this test method can be considered more
rugged and adaptable to installation under plant operating conditions than the more accurate laboratory methods, such as ion
chromatography and atomic absorption.
The last approved version of this historical standard is referenced on www.astm.org.boldface numbers in parentheses refer to a list of references at the end of this standard.
D4519 − 16
FIG. 2 Sulfate Ion vs. Conductivity
6. Interferences
6.1 It is important to devote particular attention to accurate flow and temperature control as variations can cause inaccuracies.
See Annex A1, Annex A2, and Annex A3 for additional information on this subject.information.
7. Apparatus
7.1 Mechanical Ion Exchanger-Degasser Instrument.
7.2 Constant Head Device, for providing approximately 1.5 m (5 ft) head pressure for water entering the instrument.
7.3 Constant Temperature Equipment, for adjusting the influent temperature to 25°C 6 0.5°C.
7.4 Conductivity Instruments and Sensors, for measuring the conductivity of the sample to determine the concentration of
anions and carbon dioxide. Use of instruments that have a specialized temperature compensation for high purity water (to 25°C)
based on an acid such as HCl or H SO is required for this test method.
2 4
7.1 Hydrogen Exchange Cartridge ,Degassed Cation Conductivity System, 1 ⁄8 in. inside diameter, 12 in. height, containing 1
+
lb of 8 % cross-linked styrene-divinylbenzene, strong acid gel cation exchange resin in the H form; U.S. standard mesh 16 by
50 (1190 by 297 μm) may be used. Regenerate with 1500 mL of hydrochloric acid (1 + 6) at a flow rate of 40 to 50 mL/min,
followed by rinsing with 300 mL of Type II water at the same flow rate. Then rinse with 3500 mL of Type II water at a flow rate
of 100 to 150 mL/min. Rinse down when placing in service.may be provided as a complete panel or may be assembled from
components.
NOTE 1—The column inside diameter, resin bed height, inlet sample temperature (11.3), and service flowrate (11.4) have been standardized to provide
comparable results. They may not be the optimum values. The user should realize that those parameters affect the measurement.
7.1.1 Constant Head Device or Other Means, for providing constant sample flow through the apparatus.
7.1.2 Constant Temperature Equipment, for adjusting the influent temperature to 25 6 0.5°C.
7.1.3 Flow or Temperature Safety Shutoff, as needed to protect the degasifier heater.
D4519 − 16
FIG. 3 Carbon Dioxide vs. Conductivity
7.1.4 Conductivity Instrument(s) and Sensors, for measuring the conductivity of the sample to determine the concentration of
anions and carbon dioxide. Use of instruments that have a specialized temperature compensation for high purity water (to 25°C)
based on a trace acid contaminant such as HCl or H SO is required for this test method. Instrumentation may also include software
2 4
to automate the determination of anions and carbon dioxide based on Table 1 and Table 2.
7.1.5 Hydrogen Ion Exchange Cartridge, 1 ⁄8 in. inside diameter, 12 in. height, containing 1 lb of 8 % cross-linked
+
styrene-divinylbenzene, strong acid gel cation exchange resin in the H form; U.S. standard mesh 16 by 50 (1190 by 297 μm) may
be used. Regenerate with 1500 mL of hydrochloric acid (1 + 6) at a flow rate of 40 to 50 mL/min, followed by rinsing with 300
mL of Type II water at the same flow rate. Then rinse with 3500 mL of Type II water at a flow rate of 100 to 150 mL/min. Rinse
down when placing in service.
NOTE 1—The column inside diameter, resin bed height, inlet sample temperature (11.3), and service flowrate (11.4) have been standardized to provide
comparable results. They may not be the optimum values. The user should realize that those parameters affect the measurement.
7.1.6 Degasifier, for removing carbon dioxide from the sample. The degasifier may operate by heating the sample to near boiling
temperature with a reboiler or by sparging with a CO -free gas such as nitrogen. Following a reboiler, a cooler may be used to
reduce the sample temperature and potential errors in temperature compensation. (Membrane gas stripping has been used
experimentally for degassing but this technique has not been standardized.) (2)
7.6 Software to automate the determination of anions and carbon dioxide is available.
8. Reagents
8.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the American Chemical Society, where such specifications are available. Other
grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening
the accuracy of the determination.
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 National
Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.
D4519 − 16
FIG. 4 Flow Diagram for Mechanical-Ion Exchanger-Degasser InstrumentBlock Diagram of Measurement Apparatus
8.2 Purity of Water—Unless otherwise indicated, references to water that is used for reagent preparation, rinsing or dilution shall
be understood to mean water that conforms to the quantitative specifications of Type II reagent water of Specification D1193.
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8.3 Chloride Solution, Stock (1 mL = 0.1 mg Cl Cl )—Dissolve in water 0.1649 g of sodium chloride (NaCl) dried to constant
weight at 105°C, and dilute to 1 L in a thoroughly cleaned polyethylene flask.
8.4 Chloride Solution, Standard (1.00 mL = 0.001 mg)—Dilute 10.00 mL of chloride stock solution (8.3) to 1 L with water.
8.4.1 This standard chloride solution is to be used in the calibration of the instrument if desired, or reference can be made to
the instruction booklet furnished with the instrument.
8.5 Hydrochloric Acid (1 + 6)—Add 100 mL concentrated HCl (sp. gr. 1.19) to 600 mL water.
9. Sampling
9.1 Collect the sampleEstablish sampling conditions in accordance with the applicable ASTM standards: Practice D1066,
Specification D1192, and Practices D3370.
10. Calibration
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10.
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