1、Designation: D4165 06 (Reapproved 2012)Standard Test Method forCyanogen Chloride in Water1This standard is issued under the fixed designation D4165; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A numbe
2、r 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 cyanogenchloride in water. Cyanogen chloride is normally present onlyat very low concentrations
3、; it is a very labile and sparselysoluble gaseous compound. Water samples may contain cya-nogen chloride after the chlorination of waste waters contain-ing cyanide or thiocyanate compounds.1.2 Cyanogen chloride is unstable. A quick test using a spotplate or comparator as soon as the sample is collec
4、ted may bethe best test, reducing the loss of cyanogen chloride during thetime lapse between sampling and analysis. (See Fig. 1 for atypical decay curve for cyanogen chloride in a solution.)1.3 This test method has been used successfully withreagent water. The analyst is responsible for determiningw
5、hether the test method is applicable to the water matrix beingtested. Reference is made to Test Method D of Test MethodsD2036 which is based on similar chemical reactions and hasbeen evaluated by collaborative testing in this matrix.1.4 The lower limit of detectability is 0.005 mg CN/L.1.5 This stan
6、dard 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. Specific hazardstatements a
7、re given in Note 1 and Note 2 and Section 9.2. Referenced Documents2.1 ASTM Standards:2D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2036 Test Methods for Cyanides in WaterD3370 Practices for Sampling Water from Closed ConduitsD3856 Guide for Management Systems in Laborato
8、riesEngaged in Analysis of WaterD4210 Practice for Intralaboratory Quality Control Proce-dures and a Discussion on Reporting Low-Level Data3D5789 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Organic Constituents3D5847 Practice for Writing Quality Control Specifica
9、tionsfor Standard Test Methods for Water AnalysisE60 Practice for Analysis of Metals, Ores, and RelatedMaterials by SpectrophotometryE275 Practice for Describing and Measuring Performanceof Ultraviolet and Visible Spectrophotometers3. Terminology3.1 DefinitionsFor definitions of terms used in this t
10、estmethod, refer to Terminology D1129.1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved June 15, 2012. Published August 2012. Originallyappro
11、ved in 1982. Last previous edition approved in 2006 as D4165 06 DOI:10.1520/D4165-06R12.2For 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 Summa
12、ry page onthe ASTM website.3Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.FIG. 1 Cyanogen Chloride Stability1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4. Summary of Test Method4.1
13、The water sample is mixed with a pyridine-barbituricacid solution and the color produced is measured with aspectrophotometer.5. Significance and Use5.1 The presence of cyanogen chloride in chlorinated sani-tary and industrial effluents and therefore receiving waters is ofconcern because of its toxic
14、ity to aquatic life.5.2 This test method provides an analytical procedure formeasuring cyanogen chloride in water.5.3 This test method is applicable for clean metal finishingand chlorinated sanitary and industrial effluents, and also canbe used to establish process control of cyanide destruction byc
15、hlorination in waste water treatment facilities.6. Interferences6.1 Color and turbidity can interfere.7. Apparatus7.1 Spectrophotometer or Filter Photometer, suitable formeasurement in the region of 578 nm, using 1.0-cm absorptioncells. Filter photometers and photometric practices used in thistest m
16、ethod shall conform to Practice E60. Spectrophotometersshall conform to Practice E275.8. Reagents8.1 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 onAnalytical Rea
17、gents of theAmerican Chem-ical 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 the determination.8.2 Purity of Water Unless otherwise indicated
18、, refer-ences to water shall be understood to mean reagent water thatmeets the purity specifications of Type I or Type II waterpresented in Specification D1193.8.3 Barbituric Acid.8.4 Chloramine-T Solution (10 g/L)Dissolve 1.0 g of thewhite colored, water-soluble grade powder chloramine-T in100 mL o
19、f water. Store in an amber bottle under refrigeration.Prepare fresh weekly.8.5 Cyanide Solution, Stock (1 mL = 250 g CN)Dissolve 0.6258 g of potassium 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-t
20、ion (see Section 8 of Test Methods D2036).NOTE 1Warning: Because KCN is highly toxic, avoid contact orinhalation. Do not pipet by mouth (see Section 9).8.5.1 Cyanide Solution I, Standard (1 mL = 25 g CN)Dilute a calculated volume (approximately 100 mL) of KCNstock solution to 1 L with NaOH solution
21、(1.6 g/L).8.5.2 Cyanide Solution II, Standard (1 mL = 2.5 g CN)Dilute exactly 100 mL of cyanide Solution I to 1 L with NaOHsolution (1.6 g/L).8.5.3 Cyanide Solution III, Standard (1 mL = 0.25 gCN)Dilute exactly 100 mL of cyanide Solution II to 1 Lwith NaOH solution (1.6 g/L). Prepare fresh solution
22、daily andprotect from light.8.6 Phosphate Buffer Dissolve 138 g of sodium dihydro-gen phosphate (NaH2PO4H2O) in water and dilute to 1 L.Refrigerate this solution.8.7 Pyridine.NOTE 2Warning: Pyridine may cause irritation to the skin andrespiratory tract. Do not pipet by mouth (see Section 9).8.8 Pyri
23、dine-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 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 wi
24、th water and mix until all of the barbituric acid isdissolved. This solution is usable for about 6 months if storedin a cold, dark place.8.9 Sodium Hydroxide Solution (40 g/L)Dissolve 40 g ofsodium hydroxide in water and dilute to 1 L with water.8.10 Sodium Hydroxide Solution (1.6 g/L)Dilute 40 mLof
25、NaOH (40 g/L) solution to 1 L with water.9. Hazards9.1 Warning: Because of the toxicity of cyanogen chlorideand cyanide, great care must be exercised in its handling.Acidification of cyanide solutions produces toxic hydrocyanicacid (HCN). All manipulations should be done in a well-ventilated hood so
26、 that any HCN gas that might escape is safelyvented.9.2 Warning: Many of the reagents used in this test methodare highly toxic. These reagents and their solutions must bedisposed of properly (such as potassium cyanide and pyridine).10. Sampling and Sample Preservation10.1 Collect the sample in accor
27、dance with PracticesD3370.10.2 Collect a separate sample in a closed container. DONOTADD NaOH, as cyanogen chloride will be hydrolyzed tocyanate at pH 12 or more. As soon as possible after collection,analyze in accordance with Section 12. If the sample should bepreserved and the pH is high, reduce t
28、he pH to the 8.0 to 8.5range with careful additions of phosphate buffer when thesample is collected, and immediately cool to 4C.11. Standardization11.1 Prepare a series of cyanide standard solutions bypipetting aliquots of cyanide Solution III into 50-mL volumet-ric flasks (see Note 1). Dilute to ap
29、proximately 20 mL withNaOH solution (1.6 g/L).NOTE 3Aliquots should cover the concentration range expected in thesamples.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemic
30、al Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D4165 06 (2012)211.2 Place 20 mL of NaOH solution (1.6 g/L) in a flask fora blank. (The procedu
31、re described in 11.3 through 11.6 shouldbe performed on the blank also.)11.3 Add 2 mL of chloramine-T solution and 4 mL ofphosphate buffer, stopper, and mix by inversion two or threetimes.11.4 Add 5 mL of pyridine-barbituric acid reagent, dilute tovolume with water, mix thoroughly, and allow to stan
32、d exactly8 min for color development.11.5 Measure the absorbance at 578 nm in a 1.0-cm cellusing water as a reference.11.6 Calculate the slope and intercept of the calibrationcurve (see 13.1.1).12. Procedure12.1 Conduct the analysis immediately after sampling be-cause cyanogen chloride is a volatile
33、 and labile compound. Ifspectrophotometric facilities are not available at the samplingsite, the spot test described in Annex of Test Methods D2036,omitting the chloramine-T addition, should be used to establishthe presence of cyanogen chloride.12.2 Check the pH of the sample. If the pH is high and
34、hasnot been adjusted at the time of sampling, measure outapproximately a 50 to 100-mL volume and with carefuladditions of phosphate buffer, reduce the pH into the 8.0 to 8.5range.12.3 Pipet 20.0 mL of the sample into a 50-mL volumetricflask. If more than 0.25 mg CN/L is known to be present, usea sma
35、ller aliquot, diluted to 20 mL with water. The accuracy ofthis test method is improved in the lower concentration; it isbest not to exceed the concentration limit of 0.25 mg CN/L.12.4 Add 1 mL of phosphate buffer, stopper, and mix byinversion one time. Allow to stand 2 min.12.5 Add 5 mL of pyridine-
36、barbituric acid reagent, stopperand mix by inversion one time, allow the color to develop for3 min, dilute to volume with water, mix thoroughly, and allowto stand an additional 5 min.12.6 Measure the absorbance at 578 nm in a 1.0-cm cell inaccordance with 11.5.13. Calculation13.1 Calculate the conce
37、ntration of cyanogen chloride(CNCl) in milligrams per litre as follows:13.1.1 Slope and Intercept of Standard Curve:m 5n ( ca 2 ( c ( an ( a22 ( a!2(1)b 5( a2( c 2 ( a ( acn ( a22 ( a!2(2)where:a = absorbance of standard solution,c = concentration of CN in standard, mg/L,n = number of standard solut
38、ions,m = slope of standard curve, andb = intercept on c axis.13.1.1.1 In Eq 1 and Eq 2, the blank concentration, 0.0mg/L, and the absorbance of the blank must be included.13.1.2 Concentration:Cyanogen Chloride, as CN2, mg/L5 ma11 b! 350sample, mL(3)where:a1= absorbance of sample solution.14. Precisi
39、on and Bias514.1 The instability of cyanogen chloride precludes round-robin testing procedures (see Fig. 1), so only single operatorprecision is provided.14.2 Six operators have conducted duplicate analyses ondifferent samples of various concentrations within the appli-cable range of the test method
40、. From this study, the overallsingle operator precision of this test method within its desig-nated range may be expressed as follows:log So5 0.5308 log c 2 1.9842log R 5 0.5292 log c# 2 1.8436where:So= single-operator precision in the range of this testmethod (mg/L). The precision is dependent on co
41、n-centration (c, mg/L), andR = range (mg/L) between duplicate determinations.14.2.1 Fig. 2 provides a plot of the precision of this testmethod.14.3 These collaborative test data were obtained on reagentgrade water. For other matrices, these data may not apply.15. Quality Assurance/Quality Control15.
42、1 Before this test method is applied to the analysis ofsamples of unknown cyanogen chloride concentration, the5Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR:D19-1100.FIG. 2 PrecisionD4165 06 (2012)3analyst must establish qualit
43、y control by procedures recom-mended in Practice D4210 and Guide D3856.15.2 A known standard must be run each day that theanalysis is performed.15.3 All analyses must be performed in duplicate since theinstability of cyanogen chloride precludes spiking. The resultsmust meet the limits established in
44、 Section 14 of this testmethod before the data are acceptable.15.4 Analysts performing this test method will be requiredto measure their performance against the performance levelachieved by interlaboratory (single-operator precision) study ofthe test method.15.5 Verification of Colorimetric Procedur
45、e:15.5.1 Prepare a series of cyanide standards including zero(blank), based on the expected concentration range of thesamples, and follow the standardization (Section 11) each timenew reagents are prepared or every six months.15.5.2 The slope (m) of the standard curve should check thetheoretical val
46、ue. (1.0cm cell, 0.220.24 mg CN/L/a; 5.0cmcell, 0.0440.048 mg CN/L/a; 10.0cm cell, 0.0220.024 mgCN/L/a).15.5.3 At least one standard solution and one blank shouldbe checked each time the procedure is used.16. Keywords16.1 cynanide; cyanogen chloride; pyridine-barbituric acid;spectrophotometerASTM In
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