ASTM D4519-2010 Standard Test Method for On-Line Determination of Anions and Carbon Dioxide in High Purity Water by Cation Exchange and Degassed Cation Conductivity《为测量高纯度水中阴离子和二氧化.pdf

1、Designation:D451994(Reapproved2005) Designation: D4519 10Standard Test Method forOn-Line Determination of Anions and Carbon Dioxide inHigh Purity Water by Cation Exchange and Degassed CationConductivity1This standard is issued under the fixed designation D4519; the number immediately following the d

2、esignation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This on-line test method in

3、cludes hydrogen exchange and degassing by boiling and provides means for determining anions(such as Cl,SO4,SO4,NO3, 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

4、.2 The conductivity of all anions (except OH) is determined and not the conductivity of an individual anion if more thanone is present. If only one anion is present (such as Clor SO4), reference to Table 1 and Table 2 or Figs. 1-3 provides thechloride or sulfate and CO2concentration.1.3 This test me

5、thod has been improved in accuracy by using a modern microprocessor instrument for conductivity andtemperature measurement and appropriate temperature compensation algorithms for compensation to 25C.1.41.4 The values stated in either SI units or inch-pound units are to be regarded separately as stan

6、dard. The values stated in eachsystem may not be exact equivalents; therefore, each system shall be used independently of the other. Combining values from thetwo 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,

7、associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1066 Practice for Sampling SteamD1125 Test Methods for

8、Electrical Conductivity and Resistivity of WaterD1129 Terminology Relating to WaterD1192 Guide for Equipment for Sampling Water and Steam in Closed ConduitsD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water

9、D3370 Practices for Sampling Water from Closed Conduits3. Terminology3.1 DefinitionsFor definitions of terms used in this test method, refer to Test Methods D1125 and Terminology D1129.4. Summary of Test Method4.1 This test method measures the anion concentration (such as Cland SO4) by measuring the

10、 electrical conductivity ofthe anions after passing cooled condensate or high purity water through a cation exchanger in the hydrogen form, then throughan electric reboiler. Passage through the cation resin replaces cations (including ammonia and amines) in the water with hydrogenions. This eliminat

11、es interference in the measurement of anions. Three conductivity cells located in the instrument providemeasurements of the influent conductivity, cation conductivity at the incoming sample temperature, and the effluent conductivityat atmospheric boiling water temperature after acidic (volatile) gas

12、 removal. Conductivity values are then corrected to 25C. While1This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.03 on Sampling of Water andWater-Formed Deposits, Analysis of Water for Power Generation and Process Use, On-L

13、ine Water Analysis, and Surveillance of WaterWater.Current edition approved Jan.Dec. 1, 2005.2010. Published January 2005.March 2011. Originally approved in 1985. Last previous edition approved in 19992005 asD451994(1999)1.D4519 94 (2005). DOI: 10.1520/D4519-94R05.10.1520/D4519-10.2For referencedAST

14、M standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.1This document is not an ASTM standard and is intended only to provide the user

15、of an ASTM standard an indication of what changes have been made to the previous version. Becauseit 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 versionof the standard as p

16、ublished by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.the influent conductivity measurement is not necessary in determining the total anion conductivity, its determination provides

17、amore complete evaluation of the sample, which can also include an estimation of the amine content. Measurement of the cationand reboil effluent 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.

18、 1-3, or both, are then necessary to complete the determinations.TABLE 1 Increase in Conductivity of Pure Water Expressed asChloride Ion or Sulfate IonConductivity due toChloridesConcentrationChlorides (PPB)Conductivity due toSulfatesConcentrationSulfates (PPB)0.0548 0.0 0.0548 0.00.0595 1 0.0608 10

19、.0651 2 0.0669 20.0717 3 0.0732 30.0791 4 0.0797 40.0872 5 0.0862 50.0958 6 0.0929 60.1049 7 0.0997 70.1145 8 0.1066 80.1243 9 0.1137 90.1344 10 0.1208 100.2427 20 0.1969 200.3560 30 0.2780 300.4709 40 0.3616 400.5865 50 0.4455 500.7023 60 0.5320 600.8183 70 0.6181 700.9345 80 0.7044 801.0507 90 0.7

20、909 901.1669 100 0.8775 1002.2209 200 1.7470 2005.8252 500 4.362 500TABLE 2 25C Conductivity of the Sample Immediately After theCation Column, Relating to the CO2Concentration with the AnionComponent Subtracted Out (See 11.7)Conductivitys/cmCarbon Dioxideppm ppb0.0548 0 00.09 0.01 100.12 0.02 200.16

21、 0.03 300.19 0.04 400.21 0.05 500.24 0.06 600.26 0.07 700.28 0.08 800.3 0.09 900.32 0.1 1000.48 0.2 2000.61 0.3 3000.71 0.4 4000.81 0.5 5000.89 0.6 6000.97 0.7 7001.04 0.8 8001.11 0.9 9001.17 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 .D4519

22、 1024.2 In-depth studies provide additional background and updated experience with the degassed cation conductivity technique.35. Significance and Use5.1 This test method can be a useful diagnostic tool in measuring the impurities and detecting their sources in high purity water,the steam condensate

23、 of high pressure power plants, and in the process water of certain industries requiring water of the highestpurity attainable.5.2 The measurement of such impurities is most important to these industries since plant outages or product contamination canresult from events such as condenser leakage. Al

24、so, water quality deviations can occur from condensate polishing and makeupwater equipment malfunctions.5.3 The continuous measurement and trends provided by this test method are of particular interest and can indicate the need forcorrections in water treating or operating procedures and equipment.

25、The equipment for this test method can be considered morerugged and adaptable to installation under plant operating conditions than the more accurate laboratory methods, such as ionchromatography and atomic absorption.6. Interferences6.1 It is important to devote particular attention to accurate flo

26、w and temperature control as variations can cause inaccuracies.See Annex A1, Annex A2, and Annex A3 for additional information on this subject.7. Apparatus7.1 Mechanical Ion Exchanger-Degasser Instrument.7.2 Constant Head Device, for providing approximately 1.5 m (5 ft) head pressure for water enter

27、ing the instrument.3Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed bythe American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the Uni

28、ted States Pharmacopeia and NationalFormulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.3Gruszkiewicz, M. and Bursik, A., “Degassed Conductivity Comments on an Interesting and Reasonable Plant Cycle Chemistry Monitoring Technique,” Parts 1, 2, 3,PowerPlant Chemistry, Vol 6, No. 3,

29、March 2004, pp. 177-184; Vol 6, No. 5, May 2004, pp. 279-289; Vol 7, No. 5, May 2005, pp 289-296.FIG. 1 Chloride Ion vs. ConductivityD4519 1037.3 Constant Temperature Equipment, for adjusting the influent temperature to 25C 6 0.5C.7.4 Conductivity Instruments and Sensors, for measuring the conductiv

30、ity of the sample to determine the concentration ofanions and carbon dioxide. Use of instruments that have a specialized temperature compensation for high purity water (to 25C)based on an acid such as HCl or H2SO4is required for this test method.7.5 Hydrogen Exchange Cartridge ,158 in. inside diamet

31、er, 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 m) 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

32、 300 mL of TypeII 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 whenplacing in service.NOTE 1The column inside diameter, resin bed height, inlet sample temperature (11.3), and service flowrate (11.4) have been standardized to pr

33、ovidecomparable results. They may not be the optimum values. The user should realize that those parameters affect the measurement.7.6 Software to automate the determination of anions and carbon dioxide is available.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall be used in all tests.

34、Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the American Chemical Society, where such specifications are available.4Othergrades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use witho

35、ut lesseningthe accuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, references to water shall be understood to mean reagent water conforming toSpecification Unless otherwise indicated, references to water that is used for reagent preparation, rinsing or dilution shall beunde

36、rstood to mean water that conforms to the quantitative specifications of Type II reagent water of Specification D1193, TypeII. .4Lane, R. W., Sollo, F. W., Neff, C. H., “Continuous Monitoring of Anions in Feedwater by Electrical Conductivity,” Illinois State Water Survey Reprint 473, Reprintedfrom “

37、Water and Steam, Their Properties and Current Industrial Applications,” Pergammon Press, Oxford and New York, 1980.4Reagent Chemicals, American Chemical Society Specifications , American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed bythe American Chemical S

38、ociety, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.FIG. 2 Sulfate Ion vs. ConductivityD4519 1048.3 Chloride Solution, Stock (1 mL = 0.1 mg Cl) Disso

39、lve in water 0.1649 g of sodium chloride (NaCl) dried to constantweight at 105C, 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 i

40、s to be used in the calibration of the instrument if desired, or reference can be made tothe 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. Sampling9.1 Collect the sample in accordance with the applicable

41、ASTM standards: Practice D1066, Specification D1192, and PracticesD3370.10. Calibration10.1 The instrument may be calibrated by pumping solutions of known concentrations of Cl(in NaCl form) or SO4(inNa2SO4form) through the instrument and observing the conductivity increases. It may be preferred to u

42、se the calibration chartsshown in the instruction book accompanying the instrument or in referenced articles.,articles.5,6 , 7,810.2 If it is desired to calibrate the instrument using known chloride solutions, the range of 0.001 to 0.010 mg/L (1 to 10 ppb)of chloride may be covered by application of

43、 0.2 to 2.0 mL/min of the standard chloride solution (8.4.1) to the 200 mL/min flowby injecting the flow from a small peristaltic pump to a hypodermic needle inserted in a plastic tubing connection.5Electric Power Research Institute, “Monitoring Cycle Water Chemistry in Fossil Plants,” EPRI GS-7556,

44、 Vol 1: Monitoring Results.5Lane, R. W., Sollo, F. W., Neff, C. H., “Continuous Monitoring of Anions in Feedwater by Electrical Conductivity,” Illinois State Water Survey Reprint 473, Reprintedfrom “Water and Steam, Their Properties and Current Industrial Applications,” Pergammon Press, Oxford and N

45、ew York, 1980.6Continuous Conductivity Monitoring of Anions in High-Purity Water, ASTM STP 742, ASTM, 1981, p. 195.6Electric Power Research Institute, “Monitoring Cycle Water Chemistry in Fossil Plants,” EPRI GS-7556, Vol 1: Monitoring Results.7Internal report from Carl C. Scheerer, C.I.P.S., Spring

46、field, IL, April 18, 1989.7Continuous Conductivity Monitoring of Anions in High-Purity Water, ASTM STP 742, ASTM, 1981, p. 195.8Internal report from Carl C. Scheerer, C.I.P.S., Springfield, IL, April 18, 1989.FIG. 3 Carbon Dioxide vs. ConductivityD4519 10511. Procedure11.1 Flush out the piping thoro

47、ughly by flow of high purity water through the instrument before starting the flow of water tobe tested.11.2 Refer to the manufacturers instruction booklet before starting the instrument. Because of the nature of this measuringtechnique, it is very important to follow the manufacturers instructions

48、very carefully in order to achieve accurate results. SeeAnnex A1-Annex A4 for a discussion on the effects caused by variations in operating conditions and interfering substances.11.3 Connect the high purity water or condensate to be tested to the instrument influent connection.This water should pref

49、erablybe at a temperature of 25 6 0.5C. The flow shall first pass through the constant head device, then into the instrument throughthe hydrogen ion exchanger and electric reboiler and out the reboil chamber effluent (Fig. 4 and Fig. 5).11.4 Adjust the flow through the instrument to the proper flow rate (200 mL/min), or as specified by the instrumentmanufacturer. It is important to use a constant head device in order to maintain a stable flow rate, otherwise changes in cation resinexchange efficiency may occur with changes in the f