1、Designation: E 806 99 (Reapproved 2003)Standard Test Method forCarbon Tetrachloride and Chloroform in Liquid Chlorine byDirect Injection (Gas Chromatographic Procedure)1This standard is issued under the fixed designation E 806; the number immediately following the designation indicates the year ofor
2、iginal adoption or, in the case of revision, the year of last revision. A number in parentheses 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 is designed for the determination ofcarbon
3、tetrachloride (CCl4) 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 material safety data sheet (MSDS)for detailed information concerning toxicity, first aid proce-dures,
4、 and safety precautions.1.3 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 practices and determine the applica-bility of regulatory limitations prio
5、r to use. Specific hazardsstatements are given in Section 7 and in 9.2.3.2. Referenced Documents2.1 ASTM Standards:2E 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals2.2 Federal Standard:349 CFR 173 Code of Federal Regulations
6、Title 49 Trans-portation; Shippers General Requirements for Shipmentsand Packagings, including Sections:173.304 Charging of Cylinders with Liquified CompressedGas173.314 Requirements for Compressed Gases in Tank Cars173.315 Compressed Gases in Cargo Tanks and PortableTank Containers2.3 Other Documen
7、t:Chlorine Institute Pamphlet No. 77 Sampling Liquid Chlo-rine43. Summary 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 CHC
8、l3inthe sample are determined by comparison of the areas of thepeaks, 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
9、purify water would thentransfer these compounds to the water. Therefore, 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, mus
10、t be lined with glass, Monel,t5ornickel; or column must be installed for on-column injection.5.1.2 Septa, from Viton.t6Silicone septa may produceartifacts that may interfere with the analysis.1This test method is under the jurisdiction of ASTM Committee E15 onIndustrial and Specialty Chemicals and i
11、s the direct responsibility of SubcommitteeE15.02 on Product Standards.Current edition approved Sept. 10, 1999. Published December 1999. Originallypublished as E 806 81. Last previous edition E 806 93.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Servi
12、ce at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Available from the U.S. Government Printing Office, Superintendent ofDocuments, Washington, DC 20402.4Available from The Chlorine Institute Inc., 70 W. 40th St
13、., New York, NY10018.5Available from the International Nickel Company, Park 80 West, Plaza 2,Saddlebrook, NJ 07662.6Vitont septa can be prepared from Pierce No. 13235 Vitont hypo vial seals,available from the Pierce Chemical Co., Rockford, IL 61105. The septum isprepared by using a sharp blade to cu
14、t off the tip of the seal and then punching outa septum from the remaining flat disc. A cork borer or leather punch can be used topunch out the septum. Vitont septa are also available from Canton Bio-MedicalProducts, P.O. Box 2017, Boulder, CO 80302, Catalog No. V-101.1Copyright ASTM International,
15、100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.1.3 Column, Column Materials, and Packing, must becompatible with chlorine. Silanized supports and silanizedglass wool must be avoided. Column must be able to separateCl2, CCl4, and CHCl3. Columns that have been fo
16、und to besuitable are:5.1.3.1 Nickel Tubing,10ftby18 in. outside diameter,packed with 10 % sodium chloride solution on Porasil C (seeAppendix X1 for packing preparation). This is the preferredpacking.5.1.3.2 Polytetrafluoroethylene Tubing,10ftby2mminside diameter, packed with 20 % Kel-Ft No. 10 oil
17、on 60/80mesh Chromosorbt WAW.5.1.3.3 Glass Tubing, 10 ft by 2 mm inside diameter, packedwith 20 % Halocarbont 1025 on 60/80 mesh Chromosorbt 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 theGC detect
18、or output.5.2 Balance, capacity 5000 g, reading to 6 1g.76. Reagents and Materials6.1 Purity of ReagentsUnless otherwise indicated, it isintended that all reagents shall conform to the specifications ofthe Committee on Analytical Reagents of the American Chemi-cal Society, where such specifications
19、are available.8Othergrades 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 Chlorine, liquid, with less than 10 ppm each of CCl4andCHCl3. This may be prepared by condensing the gaseou
20、s phaseabove regular production chlorine.96.3 Carbon Tetrachloride, reagent grade.96.4 Chloroform, reagent grade.96.5 Sample Cylinder Assembly (Fig. 1), consisting of:6.5.1 Sample Cylinders10; nickel, Monelt, or tantalum(Note 1), 400-mL capacity, double-ended, specially cleaned(Note 2).6.5.2 Valves,
21、 having a packing resistant to liquid chlorine.116.5.3 Holder for a Septum, that can be easily assembled.12NOTE 1Carbon or stainless steel cylinders and fittings are not suitableas CHCl3is unstable in the presence of FeCl3and Cl2.NOTE 2A procedure for cleaning cylinders and valves, for use withliqui
22、d 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 disposable needle.13NOTE 3Disposable needles are recommended because corrosion withpermanent needles may
23、cause problems.7. Hazards7.1 Chlorine is a corrosive and toxic material. A well-ventilated fume hood should be used to house all test equip-ment, except the gas chromatograph, when this product isanalyzed in the laboratory.7.2 The analysis should be attempted only by persons whoare thoroughly famili
24、ar with the handling of chlorine, and evenan experienced person should not work alone. The operator7A 400-mL nickel cylinder filled with liquid chlorine weighs about 4000 g.8Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the
25、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. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.9This reagent is used for calibration purpos
26、es only.10If samples are to be shipped outside any plant, cylinders approved by the U.S.Department of Transportation must be used. DoT-approved (1979) nickel cylindersare available from Crown Controls, Inc., 388 Getty Ave., Clifton, NJ 07011, Hokequotation SP78-12-26.11Packing made from Teflont, Vit
27、ont, or Kel-Ft have been found suitable forthis purpose.12Swagelokt fittings have been found suitable for this purpose.13Two sources have been found to be suitable: Glenco Scientific Inc., 2802 OakDrive, Houston, TX 77007, model 925-MV-2 micro valve and model KFLL Luerlock adapter; and Precision Sam
28、pling Co., P.O. Box 15119, Baton Rouge, LA 70815,Pressure-Lok, series A.FIG. 1 Sample Cylinder AssemblyE 806 99 (2003)2must be provided with adequate eye protection and a respirator.Splashes of liquid chlorine destroy clothing and, if suchclothing is next to the skin, will produce irritations and bu
29、rns.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 disposalof excess chlorine in an environmentally safe and acceptablemanner. If chlorine cannot
30、 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 container, the purged chlorineshould be similarly handled. Purging to the atmosphere shouldbe avoided.7.5 In the event
31、chlorine is inhaled, first aid should besummoned immediately and oxygen administered withoutdelay.8. Sampling8.1 Sampling from tank cars, barges, storage tanks, andlarge cylinders presents unique problems. Each facility, how-ever, must be capable of delivering a liquid sample (not gas)for test. Acce
32、ptable samples can be obtained by sampling inaccordance with the Chlorine Institute Pamphlet No. 77.8.2 Since the location of these larger facilities may not be atthe immediate site of analysis, sample collection in a suitablesecondary container is recommended to facilitate its safetransport to the
33、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 unsuitable), and capable of being negotiated in thelab
34、oratory 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 the cylinder could contain. This rule is stated in
35、accordance 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 CHCl3to cylindercontaining liquid chlorine as follows
36、: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 the valves. Label this cylinder No. 2and weigh i
37、t 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 transferredfrom cylinder No. 1 to cylinder No. 2. Close the va
38、lves 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 ofchlorine in the cylinder should not be more than 1
39、25 % 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 prepare one level of standardfor calibration, u
40、sing 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 septum into the vapor space ofcylinder No. 2. Ke
41、ep 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 CCl4and CHCl3in the chlorine.9.2.8 Calculate th
42、e 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 a samplecylinder without adding CCl4or CHCl3.9.
43、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 1.5 mg/L)CCl447.55 gCHCl344.40 gTotal 91.95 g9.3.
44、2 To prepare 500 g of chlorine with spiked levels of 20ppm each of CCl4and CHCl3(total of 40 ppm), 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 5Wdensity5201.55 13 L (3)9.4 Example of calculation of
45、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:Weight with chlorine 3575gWeight empty 3088gWeight of chlorine 487g9.4.3 Weight of CCl4
46、added:E 806 99 (2003)30.0186!47.5591.955 0.0096 g (4)9.4.4 Concentration of CCl4in the spiked chlorine:0.0096487106! 5 19.7 ppm 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! 5 18.5 ppm w/w! (7)10. Chromatographic Co
47、nditions10.1 ColumnNaCl on Porasil: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:10.2.1 DetectorFlame ionization.10.2.2 De
48、tector 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:10.3.1 DetectorFlame ionization.10.3.2 Detector Temperature150C.10.3.3 Carrier GasNitrogen at 30 mL/min.10.3.4 Column Temperature55C.10.3.5 I
49、njector Temperature90C.NOTE 4The conditions listed have produced acceptable results. Theseparameters serve only as a guide in optimizing conditions for the columnused.11. Preparation of Calibration Curve11.1 Obtaining Sample from Cylinders Containing Calibra-tion Standards:11.1.1 Invert the cylinder and open the sampling valve sothat there will be liquid chlorine at the septum.11.1.2 With the plunger in place, close the syringe valve andinsert the needle of the syringe through the septum into thesample cylinder.11.1.3 Open the syrin
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