ASTM E806-17a Standard Test Method for Carbon Tetrachloride and Chloroform in Liquid Chlorine by Direct Injection (Gas Chromatographic Procedure).pdf

1、Designation: E806 17aStandard Test Method forCarbon Tetrachloride and Chloroform in Liquid Chlorine byDirect Injection (Gas Chromatographic Procedure)1This standard is issued under the fixed designation E806; the number immediately following the designation indicates the year oforiginal adoption or,

2、 in the 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. Scope*1.1 This test method is designed for the determination ofcarbon tetrachloride (CCl4

3、) and chloroform (CHCl3) in liquidchlorine. The lower limit of detection is dependent on thesample size and the instrument used; five ppm (w/w) isachievable.1.2 Review the current Safety Data Sheet (SDS) for detailedinformation concerning toxicity, first aid procedures, and safetyprecautions.1.3 The

4、 values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 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-priat

5、e safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific hazardsstatements are given in Section 7 and in 9.2.3.1.5 This international standard was developed in accor-dance with internationally recognized principles on standard-ization establishe

6、d in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D6809 Guide for Quality Control and Quality AssuranceProcedures for

7、Aromatic Hydrocarbons and Related Ma-terialsE180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals (Withdrawn 2009)32.2 Federal Standard:449 CFR 173 Code of Federal Regulations Title 49 Transpor-tation; ShippersGeneral Requirements

8、for Shipments andPackagings, including Sections:173.304 Charging of Cylinders with Liquefied CompressedGas173.314 Requirements for Compressed Gases in Tank Cars173.315 Compressed Gases in Cargo Tanks and PortableTank Containers2.3 Other Document:Chlorine Institute Pamphlet No. 1 Chlorine Basics53. S

9、ummary of Test Method3.1 A sample of liquid chlorine is injected into a gaschromatograph (GC), equipped with a column capable ofseparating CCl4and CHCl3from Cl2and other impurities,using a suitable syringe. The amounts of CCl4and CHCl3inthe sample are determined by comparison of the areas of thepeak

10、s, obtained with the samples, to areas of peaks obtainedwith suitable calibration standards, under the same conditions.4. Significance and Use4.1 CCl4and CHCl3may be present in trace amounts inliquid chlorine. The use of chlorine to purify water would thentransfer these compounds to the water. There

11、fore, when theconcentrations of the CCl4and CHCl3in the liquid chlorine areknown, the maximum amounts contributed to the water by thechlorine can be estimated.5. Apparatus5.1 Gas Chromatograph, equipped with:5.1.1 Injection Port, must be lined with glass, Monel,6ornickel; or column must be installed

12、 for on-column injection.1This test method is under the jurisdiction of ASTM Committee D16 onAromatic, Industrial, Specialty and Related Chemicals and is the direct responsi-bility of Subcommittee D16.16 on Industrial and Specialty Product Standards.Current edition approved July 1, 2017. Published J

13、uly 2017. Originally approvedin 1981. Last previous edition approved in 2017 as E806 17. DOI: 10.1520/E0806-17a.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

14、standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.4Available from U.S. Government Printing Office, Superintendent ofDocuments, 732 N. Capitol St., NW, Washington, DC 20401-0001, http:/www.access.gpo.gov.5Available f

15、rom The Chlorine Institute Inc., 1300 Wilson Blvd., Suite 525,Arlington, VA 22209, https:/www.chlorineinstitute.org.6Monel is a registered trademark of Special Metals Corporation.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO

16、Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by

17、 the World Trade Organization Technical Barriers to Trade (TBT) Committee.15.1.2 Septa, from Viton.7Silicone septa may produce arti-facts that may interfere with the analysis.5.1.3 Column, Column Materials, and Packing, must becompatible with chlorine. Silanized supports and silanizedglass wool must

18、 be avoided. Column must be able to separateCl2, CCl4, and CHCl3. Columns that have been found to besuitable are:5.1.3.1 Nickel Tubing, 3.05 m by 3.175 mm outsidediameter, packed with 10 % sodium chloride solution onPorasil C8(see Appendix X1 for packing preparation). This isthe preferred packing.5.

19、1.3.2 Polytetrafluoroethylene Tubing, 3.05mby2mminside diameter, packed with 20 % Kel-F9No. 10 oil on 60/80mesh Chromosorb10WAW.5.1.3.3 Glass Tubing, 3.05 m by 2 mm inside diameter,packed with 20 % Halocarbon111025 on 60/80 mesh Chromo-sorb W AW.5.1.4 Flame Ionization Detector.5.1.5 Recorder, compat

20、ible with the GC detector output.5.1.6 Electronic Integrator (optional), compatible with theGC detector output.5.2 Balance, capacity 5000 g, reading to 6 1g.126. Reagents and Materials6.1 Purity of ReagentsUnless otherwise indicated, it isintended that all reagents shall conform to the specification

21、s ofthe Committee onAnalytical Reagents of theAmerican Chemi-cal Society, where such specifications are available.13Othergrades may be used, provided it is first ascertained that thereagent is of sufficiently high purity to permit its use withoutlessening the accuracy of the determination.6.2 Chlori

22、ne, liquid, with less than 10 g/g each of CCl4andCHCl3. This may be prepared by condensing the gaseous phaseabove regular production chlorine.146.3 Carbon Tetrachloride, reagent grade.146.4 Chloroform, reagent grade.146.5 Sample Cylinder Assembly (Fig. 1), consisting of:6.5.1 Sample Cylinders;15nick

23、el, Monel, or tantalum (Note1), 400-mL capacity, double-ended, specially cleaned (Note 2).6.5.2 Valves, having a packing resistant to liquid chlorine.166.5.3 Holder for a Septum, that can be easily assembled.17NOTE 1Carbon or stainless steel cylinders and fittings are not suitableas CHCl3is unstable

24、 in the presence of FeCl3and Cl2.NOTE 2A procedure for cleaning cylinders and valves, for use withliquid chlorine, is given in Appendix X2.6.6 Fittings, for transferring chlorine from one cylinder toanother.6.7 Syringe, 10 to 100-L, capable of holding liquid chlo-rine under pressure, with 26-gage di

25、sposable needle.NOTE 3Disposable needles are recommended because corrosion withpermanent needles may cause problems.7. Hazards7.1 Chlorine is a corrosive and toxic material. A well-ventilated fume hood should be used to house all testequipment, except the gas chromatograph, when this product isanaly

26、zed in the laboratory.7Viton is a registered trademark of The Chemours Company.8Porasil is a trademark of Waters Associates, Inc.9Kel-F is a registered trademark of 3M Company.10Chromosorb is a registered trademark of Imerys Minerals California, Inc.11Halocarbon is a registered trademark of Halocarb

27、on Products Corporation.12A 400-mL nickel cylinder filled with liquid chlorine weighs about 4000 g.13Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Anala

28、r Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.14This reagent is used for calibration purposes only.15If samples are to be shipped outside any plant, cylinders appr

29、oved by the U.S.Department of Transportation must be used.16Packing made from Teflon, registered trademark of The Chemours Company,Viton, Kel-F, or equivalent have been found suitable for this purpose.17Swagelok, registered trademark of Swagelok Company, or equivalent fittingshave been found suitabl

30、e for this purpose.FIG. 1 Sample Cylinder AssemblyE806 17a27.2 The analysis should be attempted only by persons whoare thoroughly familiar with the handling of chlorine, and evenan experienced person should not work alone. The operatormust be provided with adequate eye protection and a respirator.Sp

31、lashes of liquid chlorine destroy clothing and, if suchclothing is next to the skin, will produce irritations and burns.7.3 When sampling and working with chlorine out of doors,people downwind from such operation should be warned of thepossible release of chlorine vapors.7.4 It is recommended that m

32、eans be available for disposalof excess chlorine in an environmentally safe and acceptablemanner. If chlorine cannot be disposed of in a chlorineconsuming process, a chlorine absorption system should beprovided. When the analysis and sampling regimen requires aninitial purging of chlorine from a con

33、tainer, the purged chlorineshould be similarly handled. Purging to the atmosphere shouldbe avoided.7.5 In the event chlorine is inhaled, first aid should besummoned immediately and oxygen administered withoutdelay.8. Sampling8.1 Sampling from tank cars, barges, storage tanks, andlarge cylinders pres

34、ents unique problems. Each facility,however, must be capable of delivering a liquid sample (notgas) for test. See Chlorine Institute Pamphlet No. 1.8.2 Since the location of these larger facilities may not be atthe immediate site of analysis, sample collection in a suitablesecondary container is rec

35、ommended to facilitate its safetransport to the laboratory for tests (DOT regulations may beapplicable).8.3 It is recommended that samples be collected from thesefacilities in small-size cylinders, with cylinders and valvesfabricated of tantalum, Monel, or nickel (carbon or stainlesssteel are unsuit

36、able), and capable of being negotiated in thelaboratory fume hood. Proper and safe sampling techniquesmust be followed. Do not allow the sample cylinder to becomeliquid full. A good rule is that the weight of the chlorine in thecylinder should not be more than 125 % of the weight of thewater that th

37、e cylinder could contain. This rule is stated inaccordance with 49 CFR 173.9. Preparation of Standards for Calibration9.1 Prepare standards in liquid chlorine, so that matrixeffects of the chlorine on the gas chromatographic column anddetector are compensated.9.2 Method of AdditionsAdd CCl4and CHCl3

38、to cylindercontaining liquid chlorine as follows:9.2.1 Obtain a supply cylinder of liquid chlorine that hasless than 10 ppm each of CCl4and CHCl3, and that contains atleast 5000 g of chlorine. Label this cylinder No. 1.9.2.2 Obtain a clean, evacuated, sample cylinder equippedwith a septum on one of

39、the valves. Label this cylinder No. 2and weigh it to 6 1g.9.2.3 Connect cylinder No. 1 to cylinder No. 2 by means offittings (6.6) such that the liquid phase of chlorine can flowfrom 1 to 2. Open the valves between the cylinders and coolcylinder No. 2 with ice. Liquid chlorine will be transferredfro

40、m cylinder No. 1 to cylinder No. 2. Close the valves whensufficient chlorine has been transferred. Disconnect the cylin-ders and weigh cylinder No. 2 to 6 1 g to determine the weightof chlorine transferred. (WarningDo not allow cylinder No.2 to become liquid full. A good rule is that the weight ofch

41、lorine in the cylinder should not be more than 125 % of theweight of water that the cylinder could contain.)9.2.4 Retain cylinder No. 1 to prepare further standards.9.2.5 Prepare an approximately 50/50 mix of CCl4andCHCl3and record amounts of each added. Calculate thevolume of this mixture needed to

42、 prepare one level of standardfor calibration, using a calculation similar to that given in 9.3.9.2.6 Fill the high-pressure syringe (6.7) with approxi-mately the volume of the CCl4/CHCl3mixture as calculated in9.3.3. Weigh the syringe plus liquid to 6 0.1 mg. Transfer theliquid mixture through the

43、septum into the vapor space ofcylinder No. 2. Keep a finger tightly over the plunger toprevent blow out. Immediately remove and reweigh the syringeto 6 0.1 mg. The difference between the two weights is thetotal weight of CCl4and CHCl3added.9.2.7 Shake cylinder No. 2 to assure complete solution ofthe

44、 CCl4and CHCl3in the chlorine.9.2.8 Calculate the added concentration of CCl4and CHCl3in the spiked standard as indicated in 9.4.9.2.9 Prepare at least three standards containing three dif-ferent levels of CCl4and CHCl3, bracketing the expected level.Also, transfer some of the original chlorine into

45、 a samplecylinder without adding CCl4or CHCl3.9.2.10 The long term stability of the calibration standardshas not been evaluated.9.3 Example of amounts of CCl4and CHCl3to be added toliquid chlorine to produce desired standard:9.3.1 Proposed mixture of CCl4and CHCl3(average densityabout 1.5 g/mL, or 1

46、.5 mg/L)CCl447.55 gCHCl344.40 gTotal 91.95 g9.3.2 To prepare 500 g of chlorine with spiked levels of 20ppm each of CCl4and CHCl3(total of 40 g/g), the necessarygrams (W) of the CCl4/CHCl3mixture is as follows:W500540106(1)orW 5 0.020 g 5 20 mg (2)9.3.3 The necessary volume in L (V) is then:V 5Wdensi

47、ty5201.55 13 L (3)9.4 Example of calculation of spiked amounts of CCl4andCHCl3added:9.4.1 The weight of mixture added is:Initial syringe weight with 13 L 17.6715gWeight of syringe after transfer 17.6529gCCl4/CHCl3added 0.0186g9.4.2 The weight of cylinder No. 2:E806 17a3Weight with chlorine 3575gWeig

48、ht empty 3088gWeight of chlorine 487g9.4.3 Weight of CCl4added:0.0186!47.5591.955 0.0096 g (4)9.4.4 Concentration of CCl4in the spiked chlorine:0.0096487106! 5 19.7 g/g w/w! (5)9.4.5 Weight of CHCl3added:0.0186!44.4091.955 0.0090 g (6)9.4.6 Concentration of CHCl3in the spiked chlorine:0.0090487106!

49、5 18.5 g/g w/w! (7)10. Chromatographic Conditions10.1 ColumnNaCl on Porasil or equivalent:10.1.1 DetectorFlame ionization.10.1.2 Detector Temperature150C.10.1.3 Carrier GasNitrogen at 30 mL/min.10.1.4 Column TemperatureProgrammed, 60 to 200C at15C/min.10.1.5 Injector Temperature90C.10.2 ColumnKel F on Chromosorb or equivalent:10.2.1 DetectorFlame ionization.10.2.2 Detector Temperature150C.10.2.3 Carrier GasNitrogen at 30 mL/min.10.2.4 Column Temperature60C.10.2.5 Injector Temperature75C.10.3 ColumnHalocarbon on Chromosorb