1、Designation: D 4165 06Standard Test Method forCyanogen Chloride in Water1This standard is issued under the fixed designation D 4165; 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 parentheses
2、 indicates the year of last reapproval. Asuperscript epsilon (e) 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; it is a very
3、labile and sparselysoluble gaseous compound. Water samples may contain cyano-gen chloride after the chlorination of waste waters containingcyanide or thiocyanate compounds.1.2 Cyanogen chloride is unstable. A quick test using a spotplate or comparator as soon as the sample is collected may bethe bes
4、t 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 determiningwhether the test m
5、ethod is applicable to the water matrix beingtested. Reference is made to Test Method D of Test MethodsD 2036 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 standard does not pu
6、rport 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 are given in Note
7、 1 and Note 2 and Section 9.2. Referenced Documents2.1 ASTM Standards:2D 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterD 2036 Test Methods for Cyanides in WaterD 3370 Practices for Sampling Water from Closed ConduitsD 3856 Guide for Good Laboratory Practices in Laborato-rie
8、s Engaged in Sampling and Analysis of WaterD 4210 Practice for Intralaboratory Quality Control Proce-dures and a Discussion on Reporting Low-Level Data3D 5789 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Organic Constituents3D 5847 Practice for Writing Quality Con
9、trol Specificationsfor Standard Test Methods for Water AnalysisE60 Practice for Analysis of Metals, Ores, and RelatedMaterials by Molecular Absorption SpectrometryE 275 Practice for Describing and Measuring Performanceof Ultraviolet, Visible, and Near-Infrared Spectrophotom-eters3. Terminology3.1 De
10、finitionsFor definitions of terms used in this testmethod, refer to Terminology D 1129.1This 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 July
11、 1, 2006. Published July 2006. Originally approvedin 1982. Last previous edition approved in 2000 as D 4165 00.2For 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 s
12、tandards Document Summary page onthe ASTM website.3Withdrawn.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 The water sample is mixed with a pyridine-barbituricacid solu
13、tion 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 toxicity to aquatic life.5.2 This test method provides an analytic
14、al 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 bychlorination in waste water treatment facilities.6. Interferen
15、ces6.1 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 method shall conform to Practice E60. Spectrophotom-eters shal
16、l conform to Practice E 275.8. 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 Reagents of theAmerican Chem-ical Society,where such specific
17、ations 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, refer-ences to water shall be understood to mean reagent
18、 water thatmeets the purity specifications of Type I or Type II waterpresented in Specification D 1193.8.3 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 of water. Store in an amber bottle under refrigeration.Pre
19、pare 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-tion (see Section 8 of Test Methods D 2036).NOTE 1Warning:
20、 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 (1.6 g/L).8.5.2 Cyanide Solution II, Standard (1 mL = 2.
21、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 daily andprotect from light.8.6 Phosphate Buffer Dissolv
22、e 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 Pyridine-Barbituric Acid ReagentPlace 15 g of bar-bituric ac
23、id 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 with water and mix until all of the barbituric acid isdiss
24、olved. 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 mLofNaOH (40 g/L) solution to 1 L with water.9. Hazards9.1 W
25、arning: 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 that any HCN gas that might escape is safelyvented.9.2
26、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 accordance with PracticesD 3370.10.2 Collect a separate sampl
27、e 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 the pH to the 8.0 to 8.5range with careful additions of
28、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 approximately 20 mL withNaOH solution (1.6 g/L).NOTE 3Ali
29、quots 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 Chemical Society, see Analar Standards for LaboratoryChemical
30、s, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D 4165 06211.2 Place 20 mL of NaOH solution (1.6 g/L) in a flask fora blank. (The procedure described in 11.3 through 11.6 shouldbe performed on the b
31、lank 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 stand exactly8 min for color development.11.5 Measure the absorba
32、nce 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 and labile compound. Ifspectrophotometric facilities are not
33、 available at the samplingsite, the spot test described in Annex of Test Methods D 2036,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 hasnot been adjusted at the time of sampling, measure outapp
34、roximately 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 smaller aliquot, diluted to 20 mL with water. The accuracy ofth
35、is 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-barbituric acid reagent, stopperand mix by inversion one tim
36、e, 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 concentration of cyanogen chloride(CNCl) in milligrams per litre
37、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 solutions,m = slope of standard curve, andb = intercept on c axis
38、.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. Precision and Bias514.1 The instability of cyanogen chloride preclu
39、des 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. From this study, the overallsingle operator precision of t
40、his 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 con-centration (c, mg/L), andR = range (mg/L) between duplicat
41、e 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.5Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting
42、 Research Report RR: D191100.FIG. 2 PrecisionD 4165 06315. Quality Assurance/Quality Control15.1 Before this test method is applied to the analysis ofsamples of unknown cyanogen chloride concentration, theanalyst must establish quality control by procedures recom-mended in Practice D 4210 and Guide
43、D 3856.15.2 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 Section 14 of this testmethod before the data are acceptable.15
44、.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 Procedure:15.5.1 Prepare a series of cyanide standards including zero(bl
45、ank), 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 value. (1.0cm cell, 0.220.24 mg CN/L/a; 5.0cmcell, 0.0440.048 mg CN
46、/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 International takes no position respecting the validity of any pat
47、ent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision
48、 at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comm
49、ents will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585
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