1、Designation: D2022 89 (Reapproved 2016)Standard Test Methods ofSampling and Chemical Analysis of Chlorine-ContainingBleaches1This standard is issued under the fixed designation D2022; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision,
2、 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.This standard has been approved for use by agencies of the U.S. Department of Defense.1. Scope1.1 These test methods
3、cover the sampling and chemicalanalysis of chlorine-containing bleaches. The methods appearin the following order:SectionsSodium Hypochlorite (Soda Bleach) Solutions:Sampling 5Available Chlorine 69Sodium Chlorate 1014Total Chlorine 1518Sodium Chloride 19 and 20Total Alkalinity as Sodium Oxide (Na2O)
4、 2124Free Alkali as Sodium Hydroxide (NaOH) 2528Calcium Hypochlorite:Sampling 30Available Chlorine 3134Water 3540Chloroisocyanuric Acids and Their Derived Salts:Sampling 42Available Chlorine (IodometricThiosulfate Method) 4346Available Chlorine (ArseniteIodometric Method) 4750Moisture 51541.2 This s
5、tandard does not purport 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. Material SafetyData Shee
6、ts are available for reagents and materials. Reviewthem for hazards prior to usage.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent Water3. Terminology3.1 Definitions:3.1.1 available chlorinethe measure of the oxidizing pow-der of the chlorine present as hypochlorite. It is
7、 expressed interms of chlorine with a gram-equivalent weight of 35.46.4. Reagents4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the Am
8、erican Chemical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.4.2 Unless otherwise indicated, references to water shall beu
9、nderstood to mean reagent water conforming to SpecificationD1193.SODIUM HYPOCHLORITE (SODA BLEACH) SOLUTIONS5. Sampling5.1 The stability of soda bleach is influenced to a consider-able degree by the purity of the alkali used in its preparation,by the excess of alkali remaining, and by the kind and a
10、mountof metal contamination from equipment. Owing to the rela-tively unstable nature of bleach solutions, special attentionshall be given to the collection and preservation of the sample.1These test methods are under the jurisdiction of ASTM Committee D12 onSoaps and Other Detergents and are the dir
11、ect responsibility of SubcommitteeD12.12 on Analysis and Specifications of Soaps, Synthetics, Detergents and theirComponents.Current edition approved July 1, 2016. Published August 2016. Originallyapproved in 1962. Last previous edition approved in 2008 as D2022 89(2008).DOI: 10.1520/D2022-89R16.2Fo
12、r referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Reagent Chemicals, American Chemical Society Specifications , A
13、mericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (
14、USPC), Rockville,MD.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1Exposure to heat and sunlight promotes decomposition, andshall be avoided. Samples shall be kept cool in a dark place (orin dark-colored bottles) until analyzed, whic
15、h shall be donewithout unnecessary delay.5.2 Strong solutions of bleach shall be accurately dilutedand aliquots taken for determination of available chlorine,chlorate, and total chlorine. The size of aliquots shall be suchthat approximately 40 mL of the 0.1 N reagent is required. Thealkali determina
16、tions shall be made directly on the samplereceived and sample sizes to require about 10 mL of 0.1 Nreagent are recommended.5.3 Precision results will require sampling at a standardtemperature such as 20C. Results expressed in terms of weightpercent will require determination of the density or specif
17、icgravity. This may be determined with a hydrometer or byweighing the sample, after pipetting the amount to be dilutedfor analysis into a tared weighing bottle. The weighed samplemay be transferred to a volumetric flask and used for subse-quent analysis.AVAILABLE CHLORINE6. Summary of Test Method6.1
18、 The sample is added to an acidified solution of potas-sium iodide and the released iodine is titrated with standardsodium thiosulfate solution to the usual starch end point.7. Reagents7.1 Acetic Acid, glacial.7.2 Potassium Iodide (KI), crystals, iodate-free.7.3 Sodium Thiosulfate Solution Standard,
19、 (0.1 N)Dissolve 25 g of sodium thiosulfate (Na2S2O35H2O) crystalsin freshly boiled and cooled water and dilute to 1 L. Thesolution is more stable if the glassware is cleaned withsulfuric-chromic acid and thoroughly rinsed with water. Stan-dardize against potassium iodate as follows: Weigh out accu-
20、rately 3.567 g of dry potassium iodate (KIO3) and transfer to a1-L volumetric flask. Dissolve with water, make up to themark, and mix thoroughly. This solution will be exactly 0.1000N. To standardize the Na2S2O3solution, carefully pipet a 50-mL aliquot of the KIO3solution into a 250-mL Erlenmeyerfla
21、sk and dilute to 100 mL with water. Add1gofKIcrystals.When it is dissolved, add 15 mL of 1.0 N hydrochloric acid andtitrate immediately with the Na2S2O3solution. When the solu-tion becomes light yellow, add 1 mL of starch indicatorsolution and complete the titration to the disappearance of theblue c
22、olor. Standardize at least monthly. Calculate the normal-ity of the Na2S2O3solution as follows:Normality 5 50 30.1!/A (1)where:A =Na2S2O3solution required for titration of theKIO3solution, mL.7.4 Starch Indicator Solution (0.5 %)Mix 0.5 g of solublestarch with 5 mL of cold water and add to 95 mL of
23、boilingwater. Mix, cool, and store in a sterilized bottle. Replacefrequently or add 0.1 % salicylic acid to minimize deteriora-tion.8. Procedure8.1 Dissolve 2 to3gofKIcrystals in 50 mL of water in a250-mL Erlenmeyer flask.Add 10 mL of acetic acid, then pipetthe aliquot of sample into the solution, k
24、eeping the tip of thepipet beneath the surface of the solution until drained. Titrate atonce with 0.1 N Na2S2O3solution until the iodine color isnearly gone, then add 1 mL of starch indicator solution andcomplete the titration to the disappearance of the blue color.Record the titration as A (see Sec
25、tion 14).9. Calculation9.1 Calculate the available chlorine as follows:Available chlorine as Cl, g/L 5 AN 335.46!/V (2)Available chlorine as Cl, weight % 5 AN 30.03546!/VS# 31009.2 Calculate the sodium hypochlorite content as follows:Sodium hypochlorite NaOCl!, g/L 5 AN 337.22!/V (3)Sodium hypochlor
26、ite NaOCl!, weight %5AN 30.03722!/VS# 3100where:A =Na2S2O3solution required for titration of the sample,mLN = normality of the Na2S2O3solution,V = original sample in aliquot used, mL, andS = specific gravity of the sample.SODIUM CHLORATE10. Summary of Test Method10.1 Sodium chlorate is reduced with
27、sodium bromide in 8N hydrochloric acid.4,5After dilution and addition of potassiumiodide, the released iodine (equivalent to the hypochlorite pluschlorate) is titrated with standard sodium thiosulfate solutionand starch indicator.11. Apparatus11.1 The apparatus (Fig. 1) consists of 1-L wide-mouthrea
28、ction vessel, A (a 1-qt fruit jar will serve), fitted with a 2-hole rubber stopper carrying a separatory funnel, B, conve-niently graduated or marked at the 10, 20, and 100-mL levels,and a delivery tube leading to a 50-mL test-tube gas trap, C,which is fitted with rubber tubing and a glass mouthpiec
29、e, D.12. Reagents12.1 Hydrochloric Acid (sp gr 1.42)Concentrated hydro-chloric acid (HCl). For highest accuracy, it should be checkedfor the presence of oxidizing or reducing matter. When used foran analysis of pure potassium chlorate (KClO3) by this method,there should be no fading or return of the
30、 end point, and theassay error should not exceed 60.5 %.4Ditz, Hugo, “Determination of Chlorates in Electrolytic Bleaching Lyes and inLyes Obtained from Absorption Vessels During the Production of PotassiumChlorate,” Chemiker Zeitung, Vol 25, 1901 p. 727.5White, J. F., “Determination of Available Ch
31、lorine in Solutions ContainingTextone (NaClO2),” American Dye-stuff Reporter, Vol 31, 1942 pp. 4847.D2022 89 (2016)212.2 Sodium Bromide Solution (10 %)Prepare a 10 %solution of sodium bromide (NaBr).12.3 Potassium Iodide Solution (10 %)Prepare a 10 %solution of potassium iodide (KI). Decolorize with
32、Na2S2O3when necessary.12.4 Sodium Thiosulfate Solution Standard, (0.1 N)See7.3.12.5 Starch Indicator Solution (0.5 %)See 7.4.13. Procedure13.1 Pipet an aliquot of the sample (same amount as usedfor available chlorine determination, Sections 69) into thereaction vessel. Assemble the apparatus and put
33、 25 mL of KIsolution in the gas trap. Close the funnel stopcock, pour 20 mLof NaBr solution into the funnel, open the stopcock, and withgentle suction on the mouthpiece, draw the NaBr solution intothe sample. Close the stopcock and pour 100 mL of HCl intothe funnel. Open the stopcock and allow the a
34、cid to drain intothe sample. Draw in the last drops with suction, close thestopcock, swirl the vessel to mix the acid, and let stand exactly5 min (use time clock). There will be a tendency for a vacuumto form and draw KI solution from the trap back into thesample. This must be avoided by filling the
35、 funnel with waterand relieving the vacuum by opening the stopcock and addinga small amount of water.13.2 After 5 min, open the stopcock and allow the water todrain into the sample, swirling to dilute the acid. Add waterthrough the funnel sufficient to dilute the sample to about 700mL. Close the sto
36、pcock, and add 10 mL of KI solution to thefunnel. Apply pressure at the mouthpiece to blow the contentsof the trap back into the vessel, opening the stopcock to allowthe necessary amount of gas to escape through the funnel.Rinse the trap twice with water, each time blowing the contentsinto the vesse
37、l as above. Finally, allow the contents of thefunnel to drain into the vessel, rinse down the funnel andstopper, and thoroughly mix the contents of the vessel. Titrateat once with 0.1 N Na2S2O3solution. When the iodine color isnearly gone, add 5 mL of starch indicator solution andcomplete the titrat
38、ion to the disappearance of the blue color.Record the titration as B.14. Calculation14.1 Calculate the sodium chlorate content as follows:Sodium chlorate NaClO3!, g/L 5 B 2 A!N 317.74#/V (4)Sodium chlorate NaClO3!, weight %B 2 A!N 30.01774VS3100where:A =Na2S2O3solution required for titration for ava
39、ilablechlorine (Section 8), mLB =Na2S2O3solution required for titration for sodiumchlorate (Section 13), mLN = normality of the Na2S2O3solution,V = original sample in aliquot used, mL, andS = specific gravity of the sample.TOTAL CHLORINE15. Summary of Test Method15.1 All hypochlorite and chlorate pr
40、esent is reduced tochloride by sodium metabisulfite in the presence of nitric acid.The total chloride is then determined by a standard Volhardtitration.16. Reagents16.1 Iron Indicator SolutionDissolve 6.25 g of ferricammonium sulfate (Fe2(SO4)3 (NH4)2SO424H2O) in 50mL of water and add 45 mL of HNO3.
41、16.2 Nitric Acid, (sp gr 1.42)Concentrated nitric acid(HNO3).16.3 Potassium Thiocyanate Solution Standard, (0.05 N)Prepare a 0.05 N solution of potassium thiocyanate (KCNS)and standardize against 0.05 N AgNO3solution.16.4 Silver Nitrate Solution Standard (0.05 N)Prepare a0.05 N solution of silver ni
42、trate (AgNO3) and standardizeagainst sodium chloride (NaCl) by Mohrs Method (K2CrO4indicator). 2.923 g of NaCl dissolved and diluted to exactly1000 mL yields a solution exactly 0.0500 N.16.5 Sodium Metabisulfite(Na2S2O5), powder.17. Procedure17.1 To a 250-mL beaker add 50 mL of water and about 0.5go
43、fNa2S2O5powder. Then pipet into the mixture a samplealiquot of the same size as used for available chlorine andchlorate. Add about 10 drops of HNO3to acidify the solutionand boil until all the SO2has been expelled. Cool to roomtemperature and add 5 mL of iron indicator solution. From aburet add 0.5
44、mL of 0.05 N KCNS solution (Note 1). Thentitrate to complete decolorization with 0.05 N AgNO3solution.Filter off the precipitate by suction and wash three times withwater. Finally, back-titrate the filtrate and washings with 0.05 NKCNS solution until a faint reddish color persists. For lessFIG. 1 Ap
45、paratus for Determination of Sodium Chlorate in So-dium Hypochlorite (Soda Bleach) SolutionsD2022 89 (2016)3accurate work the filtration may be avoided by adding 1 mL ofnitrobenzene to coagulate the suspension before back-titratingthe excess AgNO3.NOTE 1This small amount of KCNS solution serves as a
46、n indicator toshow when an excess of AgNO3solution has been added. The backtitration is continued from the same buret and the total volume of KCNSsolution used is noted and used in the calculation.18. Calculation18.1 Calculate the total chlorine content as follows:Total Chlorine as Cl, g/L 5 CN1! 2
47、DN2! 335.46#/V (5)Total chlorine as Cl, weight %5CN1! 2 DN2! 30.03546#VS3100where:C = AgNO3solution required for titration of the sample,mL,D = KCNS solution required for back-titration, total mLN1= normality of the AgNO3solution,N2= normality of the KCNS solution,V = original sample in aliquot used
48、, mL, andS = specific gravity of the sample.SODIUM CHLORIDE19. Summary of Test Method19.1 Any chlorine present as a sodium chloride is deter-mined by calculation as the difference between the totalchlorine and the sum of the chlorine present as hypochloriteand as chlorate.20. Calculation20.1 Calcula
49、te the sodium chloride content as follows:Sodium chloride NaCl!, g/L 5 E 2 F/2! 2 G/3!# 31.649 (6)Sodium chloride NaCl!, weight % 5 J 2 K/2! 2 L/3!# 31.649where:E = total chlorine, g/L (Section 18),F = available chlorine, g/L (Section 9),G = sodium chlorate, g/L (Section 14),J = total chlorine, in weight percent (Section 18),K = available chlorine, in weight percent (Section 9), andL = sodium chlorate, in weight percent (Section 14).TOTAL ALKALINITY AS SODIUM OXIDE (Na2O)21. Summary of Test Method21.1 A sample is added
