ASTM D5391-1999(2009) Standard Test Method for Electrical Conductivity and Resistivity of a Flowing High Purity Water Sample《高纯度流动水样品电导性和电阻率的标准试验方法》.pdf

1、Designation: D 5391 99 (Reapproved 2009)Standard Test Method forElectrical Conductivity and Resistivity of a Flowing HighPurity Water Sample1This standard is issued under the fixed designation D 5391; the number immediately following the designation indicates the year oforiginal adoption or, in the

2、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 test method covers the determination of electricalconductivity and resistivity of h

3、igh purity water samples below10 S/cm (above 0.1 Mohm-cm). It is applicable to bothcontinuous and periodic measurements but in all cases, thewater must be flowing in order to provide representativesampling. Static grab sampling cannot be used for such highpurity water. Continuous measurements are ma

4、de directly inpure water process lines, or in side stream sample lines toenable measurements on high temperature or high pressuresamples, or both.1.2 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.3 This standard does not pur

5、port to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D

6、1066 Practice for Sampling SteamD 1125 Test Methods for Electrical Conductivity and Re-sistivity of WaterD 1129 Terminology Relating to WaterD 1192 Guide for Equipment for Sampling Water andSteam in Closed Conduits3D 1193 Specification for Reagent WaterD 2186 Test Methods for Deposit-Forming Impurit

7、ies inSteamD 2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD 3370 Practices for Sampling Water from Closed ConduitsD 3864 Guide for Continual On-Line Monitoring Systemsfor Water AnalysisD 4519 Test Method for On-Line Determination of Anionsa

8、nd Carbon Dioxide in High Purity Water by CationExchange and Degassed Cation Conductivity3. Terminology3.1 Definitions:3.1.1 electrical conductivityrefer toTest Methods D 1125.3.1.2 electrical resistivityrefer to Test Methods D 1125.3.1.3 For definitions of other terms used in these testmethods, ref

9、er to Terminology D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 cell constantthe ratio of the length of the path, L(cm) and the cross-sectional area of the solution, A (cm2),between the electrodes of a conductivity/resistivity cell, withunits of cm1. In high purity water measuremen

10、ts, the cellconstant is normally between 0.001 and 0.1 cm1to preventelectrical interference. This is lower than the 1 cm1of thestandard centimetre cube and is taken into account by directreading instrument ranges that are matched with specific cellconstants.4. Summary of Test Method4.1 Conductivity

11、or resistivity is measured with a cell andtemperature sensor or compensator in a flowing, closed systemto prevent trace contamination from wetted surfaces and fromthe atmosphere. Specialized temperature compensation cor-rects the measurement to 25C, taking into account thetemperature effects on the

12、ionization of water, the contami-nants, and interactions between the two. In the absence ofspecialized temperature compensation, the sample temperatureis controlled to 25 6 0.2C.4.2 To determine the cell constant of a high purity conduc-tivity cell with an instrument capable of accurate measuremento

13、ver the range of pure water to 150 S/cm with a single cell1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.03 on Sampling Water andWater-Formed Deposits, Analysis of Water for Power Generation and Process Use,On-Line Water

14、 Analysis, and Surveillance of Water.Current edition approved May 1, 2009. Published June 2009. Originallyapproved in 1993. Last previous edition approved in 2005 as D 5391 99 (2005).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.

15、org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocke

16、n, PA 19428-2959, United States.constant, Test Methods D 1125 are used directly. Manufactur-ers certification of cell constant traceability by this means is anacceptable alternative.4.3 To determine the cell constant of a high purity conduc-tivity cell with an instrument which does not accurately co

17、verthe range from pure water to 150 S/cm with a single cellconstant, a secondary standard cell is used that has an inter-mediate cell constant with precise value determined by TestMethods D 1125. That secondary standard cell is then used inlow conductivity water (not a standard) and readings arecomp

18、ared with those of the low constant cell under test. In thismanner, the cell constant of the latter is determined. Manufac-turers certification of cell constant traceability by this means isan acceptable alternative.5. Significance and Use5.1 Conductivity measurements are typically made onsamples of

19、 moderate to high ionic strength where contamina-tion of open samples in routine laboratory handling is negli-gible. Under those conditions, standard temperature compen-sation using coefficients of 1 to 3 % of reading per degreeCelsius over wide concentration ranges is appropriate. Incontrast, this

20、test method requires special considerations toreduce trace contamination and accommodates the high andvariable temperature coefficients of pure water samples thatcan range as high as 7 % of reading per degree Celsius. Inaddition, measuring instrument design performance must beproven under high purit

21、y conditions.5.2 This test method is applicable for detecting traceamounts of ionic contaminants in water. It is the primary meansof monitoring the performance of demineralization and otherhigh purity water treatment operations. It is also used to detectionic contamination in boiler waters, microele

22、ctronics rinsewaters, pharmaceutical process waters, etc., as well as tomonitor and control the level of boiler and power plant cyclechemistry treatment chemicals. This test method supplementsthe basic measurement requirements for Test Methods D 1125,D 2186, and D 4519.5.3 At very low levels of alka

23、line contamination, for ex-ample, 01 g/L NaOH, conductivity is suppressed, and canactually be slightly below the theoretical value for pure water.(13,14)4Alkaline materials suppress the highly conductivehydrogen ion concentration while replacing it with less con-ductive sodium and hydroxide ions. Th

24、is phenomenon is not aninterference with conductivity or resistivity measurement itselfbut could give misleading indications of inferred water purityin this range if it is not recognized.6. Interferences6.1 Exposure of the sample to the atmosphere may causechanges in conductivity/resistivity due to

25、loss or gain ofdissolved ionizable gases. Carbon dioxide, normally present inthe air, can reach an equilibrium concentration in water ofabout 1 mg/L and add approximately 1 S/cm to the conduc-tivity due to formation of carbonic acid. Closed flow-throughor sealed in-line cell installation is required

26、 for this reason.6.2 Power plant installations utilizing long sample lines canexperience significant sampling problems. New sample linesnormally require longterm conditioning. Iron oxides and otherdeposits accumulate in slow flowing horizontal sample linesand can develop chromatograph-like retention

27、 of ionic species,resulting in very long delay times. Precautions are described inSection 9.6.3 Cell and flow chamber surfaces will slowly leach traceionic contaminants, evidenced by increasing conductivity read-ings with very low or zero flowrate. There must be sufficientflow to keep these contamin

28、ants from accumulating to the pointthat they affect the measurement. The high and convolutedsurface area of platinized cells precludes their use for highpurity measurements for this reason.6.4 Capacitance of the cell and extension leadwire, espe-cially in high purity ranges can add significant posit

29、ive error toconductance readings (negative error to resistance readings).The measuring instrument must be designed to accommodatecell and leadwire characteristics in high purity water asdescribed in 7.1.1 and Annex A1. In addition, the instrumentmanufacturers recommendations on cell leadwire must be

30、carefully followed.6.5 Conductivity and resistivity measurements are refer-enced to 25C. Either samples must be controlled to 25.0 60.2C or specialized temperature compensation must be em-ployed that accounts for the characteristics of high purity waterwith specific contaminants, as described in 7.1

31、.2.6.6 Samples containing dissolved gases must have sufficientflow through the cell that bubbles cannot accumulate andoccupy sample volume within the cell, causing low conductiv-ity (high resistivity) readings. This problem is typical inmakeup water treatment systems where water warms up, dropsin pr

32、essure, and is acidified by cation exchange operations.This releases dissolved air and converts carbonates to carbondioxide gas.6.7 High purity conductivity measurement must not bemade on a sample downstream of pH sensors since theyinvariably contaminate the sample with traces of referenceelectrolyt

33、e salts. Use a dedicated sample line or place theconductivity cell upstream from the pH sensors.6.8 Conductivity cells mounted downstream from ion ex-changers are vulnerable to catching resin particles between thecell electrodes. Resin particles are sufficiently conductive toshort the cell and cause

34、 high off-scale conductivity or ex-tremely low resistivity readings. Resin retainers must beeffective and cells must be accessible for cleaning. Cell designswith electrode spacing greater than 0.06 in. (1.5 mm) havebeen found to be less likely to trap such particles.6.9 Conductivity cells, if subjec

35、ted to demineralizer regen-eration reagents, would require excessive rinse time to obtainsatisfactory results. Therefore, locate cells where they will beisolated during regeneration cycles.7. Apparatus7.1 Measuring Instrument:4The boldface numbers in parentheses refer to a list of references at the

36、end ofthis standard.D 5391 99 (2009)27.1.1 The instrument shall be continuously reading in eitherconductivity or resistivity units. It shall be specifically de-signed to measure in high purity ranges, measuring with ac ofappropriate voltage, frequency, wave shape, phase correction,and wave sampling

37、technique to minimize errors due to paralleland series capacitance of cell and leadwire as well as minimiz-ing electrode polarization errors and effects of small directcurrent (dc) potentials.Acell simulation technique to verify theperformance of an unproven measuring circuit design underhigh purity

38、 conditions is provided in Annex A1.7.1.2 The measurement shall include algorithms to tempera-ture compensate conductivity or resistivity values to 25.0C.The algorithm shall compensate for changes in water ionizationas well as for solute ion mobility for neutral salt contaminants.The conductivity of

39、 pure water has been documented with highaccuracy (15,1).7.1.3 In the case of samples containing acidic or basicsolutes (such as power plant treatment using ammonia, mor-pholine, etc., or acidic cation conductivity samples or micro-electronics acid etch rinse monitoring), special algorithms shallbe

40、employed that account for the interaction of acids and baseswith the ionization of water (2, 3, 4). The user is cautioned thataccuracy of temperature compensation algorithms for thesesolutes may vary significantly. The user must determine theapplicability and accuracy for a particular sample in thea

41、nticipated temperature range. Fig. 1 illustrates the variation intemperature effects on conductivity representative of neutralsalts, ammonia, morpholine, and acids. Where specialized highpurity temperature compensation algorithms are not providedto accurately compensate for these effects, sample tem

42、peratureshall be controlled to 25.06 0.2C. (Note that conductivitytemperature coefficients exceed 7 % of reading per degreeCelsius in the temperature range of 0 to 10C.)7.1.4 Output signal(s) from the instrument, if provided,shall be electrically isolated from the cell and from the earthground to pr

43、event ground loop problems when the instrumentis connected to grounded external devices.7.2 Cell:7.2.1 Flow-through or in-line conductivity/resistivity cellsshall be used to prevent contamination from the atmosphereand wetted surfaces as described in 6.1 and 6.3. Flowrates shallbe maintained within

44、the manufacturers recommendations.The cell shall retain its constant calibration under the condi-tions of flowrate, temperature, and pressure of the installation.The cell shall incorporate an integral precision temperaturesensor to ensure that it accurately senses the sample tempera-ture where the c

45、onductivity/resistivity is being detected toensure accurate temperature compensation.7.2.2 The cell for high purity water measurements shall notbe used for measuring higher ionic content samples (greaterthan 20 S/cm, less than 0.05 Mohm-cm) since it would retainionic contaminants and require excessi

46、ve rinse-down time forvalid measurements in high purity ranges. A high purity cell ina demineralizer system shall not be located where it can beexposed to regeneration reagents.7.2.3 Electrodes of the cell shall not be platinized for purewater measurements since the microscopically rough, poroussurf

47、ace would retain ionic contaminants and produce excessivedownscale response times. Only a trace or flash of platinumblack is permissible on electrode surfaces. Electrodes oftitanium, nickel, monel, stainless steel, or platinum are suitablefor high purity measurement. However, extra care must betaken

48、 using platinum cells not to exceed manufacturersrecommended flowrate and not to permit rough handling thatcould bend the electrodes and change the cell constant.7.2.4 If the cell constant as checked does not fall withinacceptable limits of its nominal value, it is necessary to cleanNOTECurves repre

49、sent concentrations of impurities given in Table 1.FIG. 1 Temperature Effects on the Conductivity of High PurityWaterTABLE 1 Concentrations of Trace Contaminants Plotted in Fig. 1ConductivityS/cm at 25CConcentration (g/L)NaCl HCl NH3Morpholine5.00 2295 430 638 13 7552.00 903 172 177 26321.00 439 86 76 8370.500 207 42.6 34.4 2980.250 91 20.7 16.1 1170.100 21.0 6.5 5.4 34.60.055 0.0 0.0 0.0 0.0D 5391 99 (2009)3or replace the cell. Even in pure water samples, coatings suchas iron oxide crud in power plant installations, resin fines, andother solids and fi