ASTM D2036-2009(2015) Standard Test Methods for Cyanides in Water《水中氰化物的标准试验方法》.pdf

1、Designation: D2036 09 (Reapproved 2015)Standard Test Methods forCyanides in Water1This standard is issued under the fixed designation D2036; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in par

2、entheses 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 cover the determination of cyanidesin water

3、. The following test methods are included:SectionsTest Method ATotal Cyanides after Distillation1218Test Method BCyanides Amenable to Chlorination2by Difference1925Test Method CWeak Acid Dissociable Cyanides2632Test Method DCyanides Amenable to Chlorination withoutDistillation (Short-Cut Method)3339

4、1.2 Cyanogen halides may be determined separately.NOTE 1Cyanogen chloride is the most common of the cyanogenhalide complexes as it is a reaction product and is usually present whenchlorinating cyanide-containing industrial waste water. For the presenceor absence of CNCl, the spot test method given i

5、n Annex A1 can be used.1.3 These test methods do not distinguish between cyanideions and metallocyanide compounds and complexes.Furthermore, they do not detect the cyanates. Cyanates can bedetermined using ion chromatography without digestion.NOTE 2The cyanate complexes are decomposed when the sampl

6、e isacidified in the distillation procedure.1.4 The cyanide in cyanocomplexes of gold, platinum,cobalt and some other transition metals is not completelyrecovered by these test methods. Refer to Test Method D6994for the determination of cyanometal complexes.1.5 Cyanide from only a few organic cyanid

7、es arerecovered, and those only to a minor extent.1.6 Part or all of these test methods have been usedsuccessfully with reagent water and various waste waters. It isthe users responsibility to assure the validity of the testmethod for the water matrix being tested.1.7 The values stated in SI units a

8、re to be regarded asstandard. No other units of measurement are included in thisstandard.1.8 This standard 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 practice

9、s and determine the applica-bility of regulatory limitations prior to use. Specific hazardstatements are given in 5.1, 8.8, 8.18, Section 9, 11.3, and16.1.9.2. Referenced Documents2.1 ASTM Standards:3D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determina

10、tion of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD5788 Guide for Spiking Organics into Aqueous SamplesD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water AnalysisD6696 Guide for Understanding Cyanide SpeciesD6888 Test Method for A

11、vailable Cyanide with LigandDisplacement and Flow InjectionAnalysis (FIA) UtilizingGas Diffusion Separation and Amperometric DetectionD6994 Test Method for Determination of Metal CyanideComplexes in Wastewater, Surface Water, Groundwaterand Drinking Water Using Anion Exchange Chromatog-raphy with UV

12、 DetectionD7284 Test Method for Total Cyanide in Water by MicroDistillation followed by Flow Injection Analysis with GasDiffusion Separation and Amperometric DetectionD7365 Practice for Sampling, Preservation and MitigatingInterferences in Water Samples for Analysis of CyanideE60 Practice for Analys

13、is of Metals, Ores, and RelatedMaterials by Spectrophotometry1These test methods are under the jurisdiction of ASTM Committee D19 onWater and are the direct responsibility of Subcommittee D19.06 on Methods forAnalysis for Organic Substances in Water.Current edition approved July 15, 2015. Published

14、July 2015. Originallyapproved in 1964. Last previous edition approved in 2009 as D2036 09. DOI:10.1520/D2036-09R15.2For an explanation of the term cyanides amenable to alkaline chlorination, seeLancy, L. E. and Zabban, W., “Analytical Methods and Instrumentation forDetermining Cyanogen Compounds,” P

15、apers on Industrial Water and IndustrialWaste Water, ASTM STP 337, 1962, pp. 3245.3For 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 pag

16、e onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1E275 Practice for Describing and Measuring Performance ofUltraviolet and Visible Spectrophotometers3. Terminology3.1 Definitions:3.1.1 For definitions of terms used

17、in this standard, refer toTerminology D1129 and Guide D6696.3.2 Acronyms:3.2.1 FIA, nflow injection analysis3.2.2 HPLC, nhigh performance liquid chromatography3.2.3 IC, nion chromatography3.2.4 PAD, npulsed amperometric detection4. Summary of Test Method4.1 The cyanide as hydrocyanic acid (HCN) is r

18、eleasedfrom compounds by means of reflux distillation and absorbedin sodium hydroxide solution. The conditions used for thedistillation distinguish the type of cyanide.The sodium cyanidein the absorbing solution can be determined colorimetrically,by ion chromatography, titration, by selective ion el

19、ectrode, oras described in Test Method D6888 using flow injection withamperometric detection.4.2 Test Method A, Total Cyanides, is based on the decom-position of nearly all cyanides in the presence of strong acid,magnesium chloride catalyst, and heat during a 1-h refluxdistillation.4.3 Test Method B

20、, Cyanide Amenable to Chlorination, isbased on chlorinating a portion of the sample under controlledconditions followed by the determination of total cyanide inboth the original and chlorinated samples. Cyanides amenableto chlorination are calculated by difference.4.3.1 This test method can be affec

21、ted by compounds thatare converted during chlorination to color-producing com-pounds or react with the reagents used, and cause interferencein the procedure employed to determine cyanide in the absorp-tion solution.4.4 Test Method C, Weak Acid Dissociable Cyanides, isbased on the decomposition of cy

22、anides in the presence ofweak acid, zinc acetate and heat during a 1-h reflux distillation.4.5 Test Method D, Cyanide Amenable to Chlorinationwithout Distillation, is a direct colorimetric procedure.4.6 In the absence of interference, the minimum concentra-tion of cyanide in the absorption solution

23、that can be accuratelydetermined colorimetrically is 0.005 mg/L, ion chromatogra-phy and Test Method D6888 are 0.002 mg/L, titration is 0.4mg/L and by selective ion electrode is 0.05 mg/L. Pretreatmentincluding distillation tends to increase these concentrations toa degree determined by the amount o

24、f manipulation requiredand the type of sample.4.7 Round-robin data indicate the following minimum con-centrations: colorimetric 0.03 mg/L; titration 1.0 mg/L; andselective ion electrode 0.03 mg/L. Ion chromatography andTest Method D6888 have a minimum levels equal to approxi-mately 0.002 mg/L.5. Sig

25、nificance and Use5.1 Cyanide is highly toxic. Regulations have been estab-lished to require the monitoring of cyanide in industrial anddomestic wastes and in surface waters (Appendix X1).5.2 Test Method D is applicable for natural water and cleanmetal finishing or heat treatment effluents. It may be

26、 used forprocess control in wastewater treatment facilities providing itsapplicability has been validated by Test Method B or C.5.3 The spot test outlined in AnnexA1 can be used to detectcyanide and thiocyanate in water or wastewater, and toapproximate its concentration.6. Interferences6.1 Common in

27、terferences in the analysis for cyanide in-clude oxidizing agents, sulfides, aldehydes, glucose and othersugars, high concentration of carbonate, fatty acids,thiocyanate, and other sulfur containing compounds.6.2 It is beyond the scope of these test methods to describeprocedures for overcoming all o

28、f the possible interferences thatmay be encountered. Refer to Practice D7365 for potentialinterferences for the analysis of cyanide in water.7. Apparatus7.1 Distillation ApparatusThe reaction vessel shall be a1-L round bottom flask, with provision for an inlet tube and acondenser. The inlet tube sha

29、ll be a funnel with an 8-mmdiameter stem that extends to within 6 mm of the bottom of theflask. The condenser, which is recommended, shall be areflux-type, cold finger, or Allihn. The condenser shall beconnected to a vacuum-type absorber which shall be in turnconnected to a vacuum line which has pro

30、vision for finecontrol. The flask shall be heated with an electric heater.FIG. 1 Cyanide Distillation ApparatusD2036 09 (2015)2Examples of the apparatus are shown in Fig. 1. Equivalentapparatus is acceptable provided cyanide recoveries of 100 64 % are documented.7.1.1 Smaller distillation tubes such

31、 as 50-mL MIDI tubesor 6-mL MicroDist (trademarked) tubes described in TestMethod D7284 can be used if the quality control requirementsin Section 40 are satisfied. The reagents should be addedproportionately to those specified in this test method forsmaller sample sizes. While the use of smaller dis

32、tillation tubesis generally accepted, the interlaboratory study was conductedwith 500-mL samples; therefore, the user is responsible todetermine the actual precision and bias when using a differenttype of distillation apparatus.7.2 Spectrophotometer or Filter Photometer, suitable formeasurement in t

33、he region of 578 nm, using 1.0-, 2.0-, 5.0-,and 10.0-cm absorption cells. Filter photometers and photo-metric practices used in these test methods shall conform toPractice E60. Spectrophotometers shall conform to PracticeE275.7.3 Selective Ion Meter, or a pH meter with expandedmillivolt scale equipp

34、ed with a cyanide activity electrode anda reference electrode.7.4 Mixer, magnetic, with a TFE-fluorocarbon-coated stir-ring bar.7.5 Buret, Koch, micro, 2- or 5-mL, calibrated in 0.01 mL.7.6 Ion Chromatograph, high performance ion chromato-graph equipped with a 10-L sample injection device andpulsed-

35、amperometric detector.7.7 Chromatography Column, Dionex IonPac AS7 anion-exchange, 4 250 mm and matching guard column or equiva-lent.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall con

36、form to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.4Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of th

37、e determination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water that meetsthe purity specifications of Type I or Type II water, presentedin Specification D1193.8.3 Acetic Acid (1+9)Mix 1 volume of glacial aceticacid with 9 volumes of water.

38、8.4 Acetate BufferDissolve 410 g of sodium acetate trihy-drate (NaC2H3O23H2O) in 500 mLof water.Add glacial aceticacid to yield a solution pH of 4.5, approximately 500 mL.8.5 Barbituric Acid.8.6 Calcium Hypochlorite Solution (50 g/L)Dissolve 5 gof calcium hypochlorite (Ca(OCl)2) in 100 mL of water.

39、Storethe solution in an amber glass bottle in the dark. Prepare freshmonthly.8.7 Chloramine-T Solution (10 g/L)Dissolve 1.0 g of thewhite-colored, water-soluble grade powder chloramine-T in100 mL of water. Prepare fresh weekly.8.8 Cyanide Solution, Stock (1 mL = 250 g CN)Dissolve 0.6258 g of potassi

40、um cyanide (KCN) in 40 mL ofsodium hydroxide solution (40 g/L). Dilute to 1 L with water.Mix thoroughly. Standardize with standard silver nitrate solu-tion following the titration procedure (see 16.2). (WarningBecause KCN is highly toxic, avoid contact or inhalation (seeSection 9).) Commercial solut

41、ions may also be used if certifiedby the manufacturer and used within the recommended storagedate.8.8.1 Cyanide I Solution, Standard (1mL=25gCN)Dilute a calculated volume (approximately 100 mL) of KCNstock solution to 1 L with NaOH solution (1.6 g/L).8.8.2 Cyanide II Solution, Standard (1 mL = 2.5 g

42、 CN)Dilute exactly 100 mL of KCN standard solution I to 1 L withNaOH solution (1.6 g/L).8.8.3 Cyanide III Solution, Standard (1 mL = 0.25 gCN)Dilute exactly 100 mL of KCN standard solution II to1 L with NaOH solution (1.6 g/L). Prepare fresh solution dailyand protect from light.8.8.4 Cyanide IV Solu

43、tion, Standard (1 mL = 0.025 gCN)Dilute exactly 100 mL of KCN standard solution III to1 L with NaOH solution (1.6 g/L). Prepare fresh solution dailyand protect from light.8.9 Hydrogen Peroxide Solution,3%Dilute 10 mL of30 % hydrogen peroxide (H2O2) to 100 mL. Prepare freshweekly.8.10 Isooctane, Hexa

44、ne, Chloroform (solvent preference inthe order named).8.11 Lead Carbonate (PbCO3), Lead Acetate(Pb(C2H3O2)23H2O), or Lead Nitrate (Pb(NO3)2)Lead ac-etate and lead nitrate can be put in solution with water, ifdesired, at a suggested concentration of 50 g/L.8.12 Lime, hydrate (Ca(OH)2), powder.8.13 Ma

45、gnesium Chloride SolutionDissolve 510 g ofmagnesium chloride (MgCl26H2O) in water and dilute to 1 L.8.14 Potassium Iodide-Starch Test Paper.8.15 Pyridine-Barbituric Acid ReagentPlace 15 g of bar-bituric acid in a 250-mL volumetric flask and add just enoughwater to wash the sides of the flask and wet

46、 the barbituric acid.Add 75 mL of pyridine and mix. Add 15 mL of hydrochloricacid (sp gr 1.19), mix, and cool to room temperature. Dilute tovolume with water and mix until all of the barbituric acid isdissolved. This solution is usable for about 6 months if stored4Reagent Chemicals, American Chemica

47、l Society Specifications, AmericanChemical 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. Pharm

48、acopeial Convention, Inc. (USPC), Rockville,MD.D2036 09 (2015)3in a cold dark place. Commercially prepared solutions may beavailable; follow the manufacturers expiration date.8.16 Rhodanine Indicator Solution (0.2 g/L)Dissolve 0.02g of (p-dimethylaminobenzylidene) in 100 mL of acetone.8.17 Silver Ni

49、trate Solution, Standard (0.01 N)Dissolve1.6987 g of silver nitrate (AgNO3) in water and dilute to 1 L.Mix thoroughly. Commerical solutions that are certified at thedesignated normality are suitable if used within the manufac-turers recommended storage date. Store in a dark container.8.18 Sodium Arsenite Solution (20 g/L)Dissolve2gofNaAsO2in 100 mL of water. (WarningThis material hasappeared on lists of suspected and known carcinogens. Avoidcontact with skin.)8.19 Sodium Hydroxide Solution (40 g/L)Dissolve 40 g ofsodium hydroxide