ASTM D4519-94(2005)
(Test Method)Standard Test Method for On-Line Determination of Anions and Carbon Dioxide in High Purity Water by Cation Exchange and Degassed Cation Conductivity
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
This test method can be a useful diagnostic tool in measuring the impurities and detecting their sources in high purity water, the steam condensate of high pressure power plants, and in the process water of certain industries requiring water of the highest purity attainable.
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.
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 boiling and provides means for determining anions (such as Cl , SO 4, NO 3 , and F ) at levels as low as 2 g/L (2 ppb) and carbon dioxide at the level of 0.01 to 10 mg/L (ppm) at 25C in high purity water and steam condensate 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 and or 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 to 25C.
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
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:D4519–94(Reapproved2005)
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 (´) indicates an editorial change since the last revision or reapproval.
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
4 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
D1193 Specification for Reagent Water
2.1 ASTM Standards:
D2777 Practice for Determination of Precision and Bias of
D1066 Practice for Sampling Steam
Applicable Test Methods of Committee D19 on Water
D1125 Test Methods for Electrical Conductivity and Resis-
D3370 Practices for Sampling Water from Closed Conduits
tivity of Water
3. Terminology
D1129 Terminology Relating to Water
D1192 GuideforEquipmentforSamplingWaterandSteam
3.1 Definitions—For definitions of terms used in this test
in Closed Conduits
method,refertoTestMethodsD1125andTerminologyD1129.
4. Summary of Test Method
This test method is under the jurisdiction ofASTM Committee D19 on Water
4.1 Thistestmethodmeasurestheanionconcentration(such
and is the direct responsibility of Subcommittee D19.03 on Sampling of Water and
− −−
as Cl and SO ) by measuring the electrical conductivity of
Water-Formed Deposits,Analysis of Water for Power Generation and Process Use,
On-Line Water Analysis, and Surveillance of Water.
theanionsafterpassingcooledcondensateorhighpuritywater
Current edition approved Jan. 1, 2005. Published January 2005. Originally
throughacationexchangerinthehydrogenform,thenthrough
´1
approved in 1985. Last previous edition approved in 1999 as D4519–94(1999) .
an electric reboiler. Passage through the cation resin replaces
DOI: 10.1520/D4519-94R05.
cations (including ammonia and amines) in the water with
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
hydrogen ions. This eliminates interference in the measure-
Standards volume information, refer to the standard’s Document Summary page on
ment of anions. Three conductivity cells located in the instru-
the ASTM website.
mentprovidemeasurementsoftheinfluentconductivity,cation
Withdrawn. The last approved version of this historical standard is referenced
on www.astm.org. conductivity at the incoming sample temperature, and the
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D4519–94 (2005)
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 .
FIG. 1 Chloride Ion vs. Conductivity
effluent conductivity at atmospheric boiling water temperature
after acidic (volatile) gas removal. Conductivity values are
then corrected to 25°C. While the influent conductivity mea-
plant operating conditions than the more accurate laboratory
surement is not necessary in determining the total anion methods, such as ion chromatography and atomic absorption.
conductivity, its determination provides a more complete
6. Interferences
evaluation of the sample, which can also include an estimation
of the amine content. Measurement of the cation and reboil
6.1 It is important to devote particular attention to accurate
effluent conductivities are necessary in determining the com-
flow and temperature control as variations can cause inaccu-
position of the influent (total anions and acidic gas content).
racies. SeeAnnexA1,AnnexA2, andAnnexA3 for additional
ReferencetoTable1andTable2orFigs.1-3,orboth,arethen
information on this subject.
necessary to complete the determinations.
7. Apparatus
5. Significance and Use
7.1 Mechanical Ion Exchanger-Degasser Instrument.
5.1 This test method can be a useful diagnostic tool in 7.2 Constant Head Device, for providing approximately 1.5
measuring the impurities and detecting their sources in high m (5 ft) head pressure for water entering the instrument.
purity water, the steam condensate of high pressure power 7.3 Constant Temperature Equipment, for adjusting the
plants, and in the process water of certain industries requiring influent temperature to 25°C 6 0.5°C.
water of the highest purity attainable. 7.4 Conductivity Instruments and Sensors, for measuring
5.2 The measurement of such impurities is most important the conductivity of the sample to determine the concentration
totheseindustriessinceplantoutagesorproductcontamination of anions and carbon dioxide. Use of instruments that have a
can result from events such as condenser leakage.Also, water specializedtemperaturecompensationforhighpuritywater(to
quality deviations can occur from condensate polishing and 25°C) based on an acid such as HCl or H SO is required for
2 4
makeup water equipment malfunctions. this test method.
5.3 The continuous measurement and trends provided by 7.5 Hydrogen Exchange Cartridge,1 ⁄8 in. inside diameter,
this test method are of particular interest and can indicate the 12 in. height, containing 1 lb of 8% cross-linked styrene-
need for corrections in water treating or operating procedures divinylbenzene, strong acid gel cation exchange resin in the
+
and equipment. The equipment for this test method can be H form; U.S. standard mesh 16 by 50 (1190 by 297 µm) may
considered more rugged and adaptable to installation under beused.Regeneratewith1500mLofhydrochloricacid(1+6)
D4519–94 (2005)
FIG. 3 Carbon Dioxide vs. Conductivity
FIG. 2 Sulfate Ion vs. Conductivity
ataflowrateof40to50mL/min,followedbyrinsingwith300 8.2 Purity of Water—Unlessotherwiseindicated,references
towatershallbeunderstoodtomeanreagentwaterconforming
mLofTypeIIwateratthesameflowrate.Thenrinsewith3500
mLofTypeIIwaterataflowrateof100to150mL/min.Rinse to Specification D1193, Type II.
−
8.3 Chloride Solution, Stock (1 mL = 0.1 mg Cl )— Dis-
down when placing in service.
solve in water 0.1649 g of sodium chloride (NaCl) dried to
NOTE 1—The column inside diameter, resin bed height, inlet sample
constant weight at 105°C, and dilute to 1 L in a thoroughly
temperature (11.3), and service flowrate (11.4) have been standardized to
cleaned polyethylene flask.
provide comparable results. They may not be the optimum values. The
8.4 Chloride Solution, Standard (1.00 mL = 0.001 mg)—
user should realize that those parameters affect the measurement.
Dilute 10.00 mL of chloride stock solution (8.3) to 1 L with
7.6 Software to automate the determination of anions and
water.
carbon dioxide is available.
8.4.1 This standard chloride solution is to be used in the
calibration of the instrument if desired, or reference can be
8. Reagents
made to the instruction booklet furnished with the instrument.
8.1 Purity of Reagents—Reagent grade chemicals shall be
8.5 Hydrochloric Acid (1 + 6)—Add 100 mL concentrated
used in all tests. Unless otherwise indicated, it is intended that
HCl (sp. gr. 1.19) to 600 mL water.
allreagentsshallconformtothespecificationsoftheAmerican
Chemical Society, where such specifications are available.
9. Sampling
Other grades may be used, provided it is first ascertained that
9.1 Collect the sample in accordance with the applicable
the reagent is of sufficiently high purity to permit its use
ASTM standards: Practice D1066, Specification D1192, and
without lessening the accuracy of the deter
...
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