ASTM 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

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, boiler feed water and steam condensate of high pressure power plants, and in the process water of certain industries requiring 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.
SCOPE
1.1 This on-line test method includes hydrogen exchange and degassing by heating or gas stripping and provides means for determining anions (such as Cl−, SO4—, NO3−, and F−) at levels as low as 2 μg/L (2 ppb) and carbon dioxide at the level of 0.01 to 10 mg/L (ppm) at 25°C in high purity water and in steam and water samples in power plants by measuring electrical conductivity.  
1.2 The conductivity of all anions (except OH−) is determined and not the conductivity of an individual anion if more than one is present. If only one anion is present (such as Cl− or SO4—−), reference to Section 4, Table 1 and Table 2 or Figs. 1-3 provides the chloride or sulfate and CO2 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, 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.  
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.

General Information

• Status: Published
• Publication Date: 31-May-2016
• ICS: 17.220.20 - Measurement of electrical and magnetic quantities
• Technical Committee: D19 - Water
• Drafting Committee: D19.03 - Sampling Water and Water-Formed Deposits, Analysis of Water for Power Generation and Process Use, On-Line Water Analysis, and Surveillance of Water

Relations

• Refers: ASTM D1066-18 - Standard Practice for Sampling Steam
• Effective Date: 01-Aug-2018
• Refers: ASTM D1066-18e1 - Standard Practice for Sampling Steam
• Effective Date: 01-Aug-2018
• Referred By: ASTM D6317-15 - Standard Test Method for Low Level Determination of Total Carbon, Inorganic Carbon and Organic Carbon in Water by Ultraviolet, Persulfate Oxidation, and Membrane Conductivity Detection
• Effective Date: 01-Jun-2016
• Referred By: ASTM D6504-11(2016)e1 - Standard Practice for On-Line Determination of Cation Conductivity in High Purity Water
• Effective Date: 01-Jun-2016
• Referred By: ASTM D1125-23 - Standard Test Methods for Electrical Conductivity and Resistivity of Water
• Effective Date: 01-Jun-2016
• Referred By: ASTM D5997-15 - Standard Test Method for On-Line Monitoring of Total Carbon, Inorganic Carbon in Water by Ultraviolet, Persulfate Oxidation, and Membrane Conductivity Detection
• Effective Date: 01-Jun-2016
• Referred By: ASTM D5391-23 - Standard Test Method for Electrical Conductivity and Resistivity of a Flowing High Purity Water Sample
• Effective Date: 01-Jun-2016

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D4519 − 16
Standard Test Method for
On-Line Determination of Anions and Carbon Dioxide in
High Purity Water by Cation Exchange and Degassed Cation
1
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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
1.1 This on-line test method includes hydrogen exchange
Barriers to Trade (TBT) Committee.
and degassing by heating or gas stripping and provides means
− − − −
for determining anions (such as Cl,SO ,NO , and F)at
4 3
2. Referenced Documents
levels as low as 2 µg/L(2 ppb) and carbon dioxide at the level
2
2.1 ASTM Standards:
of 0.01 to 10 mg/L (ppm) at 25°C in high purity water and in
D1066Practice for Sampling Steam
steam and water samples in power plants by measuring
D1125Test Methods for Electrical Conductivity and Resis-
electrical conductivity.
tivity of Water
−
1.2 The conductivity of all anions (except OH ) is deter-
D1129Terminology Relating to Water
mined and not the conductivity of an individual anion if more
D1193Specification for Reagent Water
−
thanoneispresent.Ifonlyoneanionispresent(suchasCl or
D2777Practice for Determination of Precision and Bias of
−
SO ), reference to Section 4, Table 1 and Table 2 or Figs. 1-3
4
Applicable Test Methods of Committee D19 on Water
provides the chloride or sulfate and CO concentration.
2
D3370Practices for Sampling Water from Closed Conduits
1.3 This test method has been improved in accuracy by
3. Terminology
using a modern microprocessor instrument for conductivity
and temperature measurement and appropriate temperature
3.1 Definitions:
compensation algorithms for compensation, by using final
3.1.1 For definitions of terms used in this standard, refer to
sample cooling to 25°C, or both.
Test Methods D1125 and Terminology D1129.
1.4 The values stated in either SI units or inch-pound units
4. Summary of Test Method
are to be regarded separately as standard. The values stated in
each system may not be exact equivalents; therefore, each
4.1 Thistestmethodmeasurestheanionconcentration(such
− −
system shall be used independently of the other. Combining
as Cl and SO ) by measuring the electrical conductivity of
4
values from the two systems may result in non-conformance
the anions after passing the sample through a cation exchanger
with the standard.
in the hydrogen form, then through a degasifier. Passage
through the cation resin replaces cations (including ammonia
1.5 This standard does not purport to address all of the
and other amines) in the water with hydrogen ions. This
safety concerns, if any, associated with its use. It is the
eliminates interference in the measurement of anions. Three
responsibility of the user of this standard to establish appro-
conductivity cells located in the instrument provide measure-
priate safety, health, and environmental practices and deter-
ments of the influent conductivity, cation conductivity at the
mine the applicability of regulatory limitations prior to use.
incoming sample temperature, and the effluent conductivity
1.6 This international standard was developed in accor-
after acidic (volatile) gas removal. The sample is then either
dance with internationally recognized principles on standard-
cooled to 25°C or conductivity values are compensated to
ization established in the Decision on Principles for the
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
1
This test method is under the jurisdiction ofASTM 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,
2
On-Line Water Analysis, and Surveillance of Water. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved June 1, 2016. Published June 2016. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 1985. Last previous edition approved in 2010 as D4519–10. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D4519-16. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
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
1
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
− −− — − −
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.
−
1.2 The conductivity of all anions (except OH OH ) is determined and not the conductivity of an individual anion if more than
− −−—−
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
4
provides the chloride or sulfate and CO concentration.
2
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.
1
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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1

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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
2
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
2.1 ASTM Standards:
D1066 Practice for Sampling Steam
D1125 Test Methods for Electrical Conductivity and Resistivity of Water
D1129 Terminology Relating to Water
3
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 Samplin
...