1、Designation: E806 17E806 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 adopt
2、ion or, 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 of carbon tetrachlori
3、de (CCl4) and chloroform (CHCl3) in liquid chlorine.The lower limit of detection is dependent on the sample size and the instrument used; five ppm (w/w) is achievable.1.2 Review the current Safety Data Sheet (SDS) for detailed information concerning toxicity, first aid procedures, and safetyprecauti
4、ons.1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establi
5、sh appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. Specific hazards statements are given in Section 7 and in 9.2.3.1.5 This international standard was developed in accordance with internationally recognized principles on standardizatione
6、stablished in the Decision on Principles for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D6809 Guide for Quality Control and Quality Assurance Proce
7、dures for Aromatic Hydrocarbons and Related MaterialsE180 Practice for Determining the Precision of ASTM Methods for Analysis and Testing of Industrial and Specialty Chemicals(Withdrawn 2009)32.2 Federal Standard:449 CFR 173 Code of Federal Regulations Title 49 Transportation; Shippers General Requi
8、rements for Shipments andPackagings, including Sections:173.304 Charging of Cylinders with Liquefied Compressed Gas173.314 Requirements for Compressed Gases in Tank Cars173.315 Compressed Gases in Cargo Tanks and Portable Tank Containers2.3 Other Document:Chlorine Institute Pamphlet No. 1 Chlorine B
9、asics53. Summary of Test Method3.1 A sample of liquid chlorine is injected into a gas chromatograph (GC), equipped with a column capable of separating CCl4and CHCl3 from Cl2 and other impurities, using a suitable syringe. The amounts of CCl4 and CHCl3 in the sample are determinedby comparison of the
10、 areas of the peaks, obtained with the samples, to areas of peaks obtained with suitable calibration standards,under the same conditions.1 This test method is under the jurisdiction of ASTM Committee D16 on Aromatic Hydrocarbons Aromatic, Industrial, Specialty and Related Chemicals and is the direct
11、responsibility of Subcommittee D16.16 on Industrial and Specialty Product Standards.Current edition approved March 1, 2017July 1, 2017. Published March 2017July 2017. Originally approved in 1981. Last previous edition approved in 20082017 asE806 08.E806 17. DOI: 10.1520/E0806-17.10.1520/E0806-17a.2
12、For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 The last approved version of this historical standard is refe
13、renced on www.astm.org.4 Available from U.S. Government Printing Office, Superintendent of Documents, 732 N. Capitol St., NW, Washington, DC 20401-0001, http:/www.access.gpo.gov.5 Available from The Chlorine Institute Inc., 1300 Wilson Blvd., Suite 525, Arlington, VA 22209, https:/www.chlorineinstit
14、ute.org.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult p
15、rior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 1
16、9428-2959. United States14. Significance and Use4.1 CCl4 and CHCl3 may be present in trace amounts in liquid chlorine. The use of chlorine to purify water would then transferthese compounds to the water. Therefore, when the concentrations of the CCl4 and CHCl3 in the liquid chlorine are known, thema
17、ximum amounts contributed to the water by the chlorine can be estimated.5. Apparatus5.1 Gas Chromatograph, equipped with:5.1.1 Injection Port, must be lined with glass, Monel,6 or nickel; or column must be installed for on-column injection.5.1.2 Septa, from Viton.7 Silicone septa may produce artifac
18、ts that may interfere with the analysis.5.1.3 Column, Column Materials, and Packing, must be compatible with chlorine. Silanized supports and silanized glass woolmust be avoided. Column must be able to separate Cl2, CCl4, and CHCl3. Columns that have been found to be suitable are:5.1.3.1 Nickel Tubi
19、ng, 3.05 m by 3.175 mm outside diameter, packed with 10 % sodium chloride solution on Porasil C8 (seeAppendix X1 for packing preparation). This is the preferred packing.5.1.3.2 Polytetrafluoroethylene Tubing, 3.05 m by 2 mm inside diameter, packed with 20 % Kel-F9 No. 10 oil on 60/80 meshChromosorb1
20、0 W AW.5.1.3.3 Glass Tubing, 3.05 m by 2 mm inside diameter, packed with 20 % Halocarbon11 1025 on 60/80 mesh Chromosorb WAW.5.1.4 Flame Ionization Detector.5.1.5 Recorder, compatible with the GC detector output.5.1.6 Electronic Integrator (optional), compatible with the GC detector output.5.2 Balan
21、ce, capacity 5000 g, reading to 6 1 g.126. Reagents and Materials6.1 Purity of ReagentsUnless otherwise indicated, it is intended that all reagents shall conform to the specifications of theCommittee onAnalytical Reagents of theAmerican Chemical Society, where such specifications are available.13 Ot
22、her grades maybe used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracyof the determination.6.2 Chlorine, liquid, with less than 10 g/g each of CCl4 and CHCl3. This may be prepared by condensing the gaseous phaseabove r
23、egular 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;15nickel, Monel, or tantalum (Note 1), 400-mL capacity, double-ended, specially cleaned (Note 2).6.5.2 Valves, having a p
24、acking 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 suitable as CHCl3 is unstable in the presence of FeCl3 and Cl2.NOTE 2A procedure for cleaning cylinders and valves, for use with liquid chlor
25、ine, is given in Appendix X2.6.6 Fittings, for transferring chlorine from one cylinder to another.6.7 Syringe, 10 to 100-L, capable of holding liquid chlorine under pressure, with 26-gage disposable needle.NOTE 3Disposable needles are recommended because corrosion with permanent needles may cause pr
26、oblems.6 Monel is a registered trademark of Special Metals Corporation.7 Viton is a registered trademark of The Chemours Company.8 Porasil is a trademark of Waters Associates, Inc.9 Kel-F is a registered trademark of 3M Company.10 Chromosorb is a registered trademark of Imerys Minerals California, I
27、nc.11 Halocarbon is a registered trademark of Halocarbon Products Corporation.12 A 400-mL nickel cylinder filled with liquid chlorine weighs about 4000 g.13 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reage
28、nts not listed bythe American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.14 This reagent is used for calibration purposes only.15 I
29、f samples are to be shipped outside any plant, cylinders approved by the U.S. Department of Transportation must be used.16 Packing made from Teflon, registered trademark of The Chemours Company, Viton, Kel-F, or equivalent have been found suitable for this purpose.17 Swagelok, registered trademark o
30、f Swagelok Company, or equivalent fittings have been found suitable for this purpose.E806 17a27. Hazards7.1 Chlorine is a corrosive and toxic material. A well-ventilated fume hood should be used to house all test equipment, exceptthe gas chromatograph, when this product is analyzed in the laboratory
31、.7.2 The analysis should be attempted only by persons who are thoroughly familiar with the handling of chlorine, and even anexperienced person should not work alone. The operator must be provided with adequate eye protection and a respirator. Splashesof liquid chlorine destroy clothing and, if such
32、clothing 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 means be available for disposal of excess chlorine in a
33、n environmentally safe and acceptable manner.If chlorine cannot be disposed of in a chlorine consuming process, a chlorine absorption system should be provided. When theanalysis and sampling regimen requires an initial purging of chlorine from a container, the purged chlorine should be similarlyhand
34、led. Purging to the atmosphere should be avoided.7.5 In the event chlorine is inhaled, first aid should be summoned immediately and oxygen administered without delay.8. Sampling8.1 Sampling from tank cars, barges, storage tanks, and large cylinders presents unique problems. Each facility, however, m
35、ustbe capable of delivering a liquid sample (not gas) for test. See Chlorine Institute Pamphlet No. 1.FIG. 1 Sample Cylinder AssemblyE806 17a38.2 Since the location of these larger facilities may not be at the immediate site of analysis, sample collection in a suitablesecondary container is recommen
36、ded to facilitate its safe transport to the laboratory for tests (DOT regulations may be applicable).8.3 It is recommended that samples be collected from these facilities in small-size cylinders, with cylinders and valvesfabricated of tantalum, Monel, or nickel (carbon or stainless steel are unsuita
37、ble), and capable of being negotiated in the laboratoryfume hood. Proper and safe sampling techniques must be followed. Do not allow the sample cylinder to become liquid full.Agoodrule is that the weight of the chlorine in the cylinder should not be more than 125 % of the weight of the water that th
38、e cylindercould contain. This rule is stated in accordance with 49 CFR 173.9. Preparation of Standards for Calibration9.1 Prepare standards in liquid chlorine, so that matrix effects of the chlorine on the gas chromatographic column and detectorare compensated.9.2 Method of AdditionsAdd CCl4 and CHC
39、l3 to cylinder containing liquid chlorine as follows:9.2.1 Obtain a supply cylinder of liquid chlorine that has less than 10 ppm each of CCl4 and CHCl3, and that contains at least5000 g of chlorine. Label this cylinder No. 1.9.2.2 Obtain a clean, evacuated, sample cylinder equipped with a septum on
40、one of the valves. Label this cylinder No. 2 andweigh it to 6 1 g.9.2.3 Connect cylinder No. 1 to cylinder No. 2 by means of fittings (6.6) such that the liquid phase of chlorine can flow from1 to 2. Open the valves between the cylinders and cool cylinder No. 2 with ice. Liquid chlorine will be tran
41、sferred from cylinderNo. 1 to cylinder No. 2. Close the valves when sufficient chlorine has been transferred. Disconnect the cylinders and weigh cylinderNo. 2 to 6 1 g to determine the weight of chlorine transferred. (WarningDo not allow cylinder No. 2 to become liquid full.A good rule is that the w
42、eight of chlorine in the cylinder should not be more than 125 % of the weight of water that the cylindercould contain.)9.2.4 Retain cylinder No. 1 to prepare further standards.9.2.5 Prepare an approximately 50/50 mix of CCl4 and CHCl3 and record amounts of each added. Calculate the volume of thismix
43、ture needed to prepare one level of standard for calibration, using a calculation similar to that given in 9.3.9.2.6 Fill the high-pressure syringe (6.7) with approximately the volume of the CCl4/CHCl3 mixture as calculated in 9.3.3.Weigh the syringe plus liquid to 6 0.1 mg. Transfer the liquid mixt
44、ure through the septum into the vapor space of cylinder No.2. Keep a finger tightly over the plunger to prevent blow out. Immediately remove and reweigh the syringe to 6 0.1 mg. Thedifference between the two weights is the total weight of CCl4 and CHCl3 added.9.2.7 Shake cylinder No. 2 to assure com
45、plete solution of the CCl4 and CHCl3 in the chlorine.9.2.8 Calculate the added concentration of CCl4 and CHCl3 in the spiked standard as indicated in 9.4.9.2.9 Prepare at least three standards containing three different levels of CCl4 and CHCl3, bracketing the expected level. Also,transfer some of t
46、he original chlorine into a sample cylinder without adding CCl4 or CHCl3.9.2.10 The long term stability of the calibration standards has not been evaluated.9.3 Example of amounts of CCl4 and CHCl3 to be added to liquid chlorine to produce desired standard:9.3.1 Proposed mixture of CCl4 and CHCl3 (av
47、erage density about 1.5 g/mL, or 1.5 mg/L)CCl4 47.55 gCHCl3 44.40 gTotal 91.95 g9.3.2 To prepare 500 g of chlorine with spiked levels of 20 ppm each of CCl4 and CHCl3 (total of 40 g/g), the necessary grams(W) of the CCl4/CHCl3 mixture is as follows:W500 54010 6 (1)orW 50.020 g520 mg (2)9.3.3 The nec
48、essary volume in L (V) is then:V 5 Wdensity 5 201.5 513 L (3)9.4 Example of calculation of spiked amounts of CCl4 and CHCl3 added:9.4.1 The weight of mixture added is:Initial syringe weight with 13 L 17.6715gWeight of syringe after transfer 17.6529gCCl4/CHCl3 added 0.0186g9.4.2 The weight of cylinde
49、r No. 2:E806 17a4Weight with chlorine 3575gWeight empty 3088gWeight of chlorine 487g9.4.3 Weight of CCl4 added:0.0186! 47.5591.95 50.0096 g (4)9.4.4 Concentration of CCl4 in the spiked chlorine:0.0096487 106!519.7 g/gw/w! (5)9.4.5 Weight of CHCl3 added:0.0186! 44.4091.95 50.0090 g (6)9.4.6 Concentration of CHCl3 in the spiked chlorine:0.0090487 106!518.5 g/gw/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 Co
