1、Designation: E 2037 07Standard Test Method forBromine Chloride in Liquid Chlorine by High PerformanceLiquid Chromatography (HPLC)1This standard is issued under the fixed designation E 2037; the number immediately following the designation indicates the year oforiginal adoption or, in the case of rev
2、ision, 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. Scope*1.1 This test method uses high performance liquid chroma-tography (HPLC) to determine bromine chlorid
3、e levels inliquid chlorine at the 10 to 1400 g/g (ppm) range.1.2 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for informationonly.1.3 Review the current material safety data sheet (MSDS)for detailed information concerning toxicity, first aid proce-
4、dures, and safety precautions.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-priate safety and health practices and determine the applica-bility of regulatory limitation
5、s prior to use. Specific hazardstatements are given in Section 8.2. Referenced Documents2.1 ASTM Standards:2E 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty ChemicalsE 806 Test Method for Carbon Tetrachloride and Chloro-form in Liquid
6、Chlorine by Direct Injection (Gas Chro-matographic Procedure)2.2 Federal Standards3CFR 173 Title 49 Transportation; Shippers General Re-quirements for Shipments and Packaging, including Sec-tions:173.304 Charging of Cylinders with Liquified Com-pressed Gas173.314 Requirements for Compressed Gases in
7、 TankCars173.315 Compressed Gases in Cargo Tanks and PortableTank Containers2.3 Other DocumentChlorine Institute Pamphlet No. 77 Sampling Liquid Chlo-rine43. Summary of Test Method3.1 Weighed samples of chlorine delivered into a cooledgraduated centrifuge tube. One mL of cooled HPLC eluent isadded b
8、efore the chlorine is allowed to evaporate. After thechlorine has evaporated the remaining eluent is analyzeddirectly on the HPLC for bromine chloride concentration.4. Significance and Use4.1 This test method was developed for the determination ofbromine chloride in liquid chlorine. Bromide is a com
9、moncontaminant in all salt sources that are used in the productionof chlorine. This bromide content of the salt is converted intobromine chloride in the liquid chlorine product. This testmethod is sensitive enough to measure the levels of brominechloride observed in normal production chlorine.5. Int
10、erferences5.1 This test method is selective for bromine chloride. Atthis time there are no known interference in the materials usedin this test method.5.2 Contact with any metal surfaces should be avoided dueto the corrosive nature of the sample.6. Apparatus6.1 Ahigh performance liquid chromatograph
11、 (HPLC) com-posed of the following:6.1.1 HPLC Pump, capable of 1 mL/min flow,6.1.2 HPLC UV Detector, capable of operating at 221 nmwith a 1-cm cell,6.1.3 HPLC Injection Valve, 20 l loop, all nonmetal, and6.1.4 HPLC Column, C18 reverse phase, 25 cm by 4.6 mm.1This test method is under the jurisdictio
12、n of ASTM Committee E15 onIndustrial and Specialty Chemicals and is the direct responsibility of SubcommitteeE15.02 on Product Standards.Current edition approved April 1, 2007. Published May 2007. Originallyapproved in 1999. Last previous edition approved in 2001 as E 2037-01.2For referenced ASTM st
13、andards, 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 Summary page onthe ASTM website.3Available from the U.S. Government Printing Office, Superintendent ofDocuments, Was
14、hington, DC 20402.4Available from The Chlorine Institute Inc., 70 W. 40thSt., New York, NY10018.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6.2 Plastic Syringes, 1
15、, 2.5, 5, 10, 20, and 60 mL.6.3 Nonmetallic Syringe Needles.6.4 Top Loader Balance, capable of 0.01 g resolution with a1-kg capacity.6.5 TFE-Fluorocarbon Tubing, 1.59 mm outside diameter.6.6 Stainless Steel Sample Cylinder, with a needle valve onone end.6.7 Graduated Centrifuge Tube,15mL.7. Reagents
16、7.1 Purity of ReagentsUnless otherwise indicated, it isintended that all reagents shall conform to the specifications ofthe Committee onAnalytical Reagents of theAmerican Chemi-cal Society, where such specifications are available.5Othergrades may be used, provided it is first ascertained that therea
17、gent is of sufficiently high purity to permit its use withoutlessening the accuracy of the determination.7.2 Water, HPLC grade.7.3 Methanol, HPLC grade.7.4 Sodium Acetate, reagent grade.7.5 Glacial Acetic Acid, reagent grade.7.6 Dry Ice.7.7 Potassium Bromide, reagent grade.7.8 Chlorine, reagent grad
18、e.8. Hazards8.1 Chlorine is a corrosive and toxic material. A well-ventilated fume hood should be used to house all samplehandling and to vent the test equipment when this product isanalyzed in the laboratory.8.2 The analysis should be attempted only by persons whoare thoroughly familiar with the ha
19、ndling of chlorine, and evenan experienced person should not work alone. The operatormust be provided with adequate eye protection and a respirator.Splashes of liquid chlorine destroy clothing and if suchclothing is next to the skin, it will produce irritations and burns.8.3 If liquid samples are to
20、 be taken in cylinders, do notallow the sample cylinder to become liquid full. Test Method806, 49 CFR 173.314, 173.315, and 173.304 advise that theweight of the chlorine in the cylinder should not be more than125 % of the weight of the water that the cylinder couldcontain. See the Chlorine Institute
21、 Pamphlet No. 77 for specificinstructions on the sampling of liquid chlorine.8.4 When sampling and working with chlorine out-of-doors,people downwind from such an operation should be warned ofthe possible release of chlorine vapors.8.5 In the event chlorine is inhaled, first aid should besummoned im
22、mediately and oxygen administered withoutdelay.8.6 Store pressurized samples where involuntary releasewould not cause excessive risk to people or property.8.7 It is recommended that means be available for disposalof excess chlorine in an environmentally safe and acceptablemanner. If chlorine cannot
23、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.8.8 Safety and Hea
24、lth PrecautionsExposure to all sol-vents used in this test method should be avoided.9. Typical Instrument Parameters9.1 Adjust the chromatograph in accordance with the fol-lowing parameters and allow the instrument to equilibrate untila steady baseline is obtained:9.1.1 ColumnC18 reverse phase ODS (
25、C18) 25 cm by 4.6mm, 10 m,9.1.2 Eluent60 % by volume methanol, 40 % by volume0.1 mol/L (M) acetate buffer, pH 4.5, helium sparged,9.1.3 Flow Rate1 mL/min,9.1.4 Injection Volume20-l sample loop, and9.1.5 Detector WavelengthUV at 221 nm.10. Preparation of Buffer Solution10.1 Sodium Acetate Buffer Stoc
26、k Solution (1 mol/L (M)Dissolve 136 g of sodium acetate (NaOOCCH33H2O) and 60g of glacial acetic acid (HOOCCH3) in water and dilute to 1 L.10.2 Sodium Acetate Buffer (0.1 mol/L (M)Transfer 100mL of the stock buffer solution into a 1-L volumetric flask anddilute to volume with water.11. Preparation o
27、f Eluent11.1 Add 600 mL of methanol to 400 mL of 0.1 mol/L (M)sodium acetate buffer solution and mix well. Before use, purgethe solution with helium for 20 min to remove dissolvedoxygen.12. Preparation of the Sample Cylinder12.1 Clamp the sample cylinder in a vertical position withthe needle valve i
28、n the downward position. Insert the 6.35 mmend of the reducing tube fitting into the needle valve and set the6.35 mm nut and ferrule of the fitting. Insert the 1.59 mmfluoropolymer tubing in the reducing tube fitting and tightenthe 1.59 mm nut and ferrule. See Fig. 1. It may be helpful to cuta 6.35
29、mm circle of fluoropolymer frit material and place it intothe reducing fitting prior to assembly to prevent plugging of the1.59 mm tubing. Cut the length of the 1.59 mm tubing so thatonly 38.10 mm protrudes out of the fitting.5Reagent Chemicals, American Chemical Society Specifications , AmericanChe
30、mical Society, Washington, DC. For suggestions on the 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), Roc
31、kville,MD. FIG. 1 Sample CylinderE203707213. Standardization of the HPLC13.1 Prepare a 1000 g/g (ppm) stock solution of potassiumbromide in water. Make a series of standards of potassiumbromide by serial dilution covering the range between 1 and650 g/g (ppm) potassium bromide. Calculate the brominec
32、hloride concentration of each standard from the potassiumbromide concentration by multiplying by the ratio of themolecular weights:BrCl/KBr!5115.4/119!50.97 (1)13.2 Withdraw 0.5 mLof a potassium bromide standard intoa 1-mL plastic syringe and then pull the plunger back to the 1mL mark to fill the re
33、mainder of the syringe with air.13.3 Clamp a sample cylinder containing reagent chlorinevertically in a ring stand and attach a 152.40 mm piece of 1.59mm outside diameter TFE-fluorocarbon tubing to the top valve.Take a second 1-mL plastic syringe and pull the plunger backto the 1 mL mark. Insert the
34、 1.59 mm TFE-fluorocarbon tubinginto the syringe and gently purge chlorine through the syringefilling this second syringe with reagent chlorine gas. Removethe TFE-fluorocarbon tubing from the syringe and attach anonmetal needle to the luer tip.13.4 Holding the first syringe pointed upward, use these
35、cond syringe equipped with the nonmetal needle to bubblethe reagent chlorine gas through the potassium bromide stan-dard solution, converting the bromide ions to bromine chloride.One mL of reagent chlorine gas is required for the conversionof each 500 g/g (ppm) of bromide ion in the standard.Althoug
36、h the amount of chlorine used to chlorinate thestandards is extremely small when compared to that of thesample, it is always a good idea to prepare the first standard inany calibration curve without the addition of the potassiumbromide to serve as a reagent blank.13.5 Using the entire 0.5 mL of stan
37、dard flush the injectionvalve and fill the sample loop in the injection valve. Immedi-ately inject this standard into the HPLC for analysis. Thebromine chloride peak will elute between 4 and 4.25 min in thechromatogram. The bromide chloride peak elutes between thewater dip and the peak caused by the
38、 excess chlorine. See Fig.2.13.6 Measure and record the peak height of the brominechloride peak in the analysis of each of the standard solutions.Plot the peak heights of each standard versus the concentra-tions of the bromine chloride in each standard analyzed. Theslope and intercept of this line a
39、re used in the calculation of thesample analysis values. See Fig. 3.NOTE 1Bromine chloride is formed by simply mixing bromine andchlorine. This is a reversible equilibrium reaction that can rapidlyexchange back to bromine and chlorine depending on the amounts ofbromine and chlorine present. The resp
40、onse to a particular brominechloride standard can be influenced by the amount of bromide alreadypresent in the HPLC column from previous injections. In Fig. 4, the lowerline on the calibration graph is the response to bromine chloride standardswith one or more blank runs between the analysis of each
41、 standard toensure that the column was background-free. The upper response line inthe calibration curve was obtained by injecting a 94 g/g (ppm) standardbetween the analysis of each standard. These two curves very rapidlymerge above 200 g/g (ppm) in the injected solution. Keep in mind thatthe concen
42、trations listed on the calibration curve are the concentrations ofthe injected solution and must be divided by the number of grams ofchlorine that was evaporated (typically 10 g), to obtain the concentrationin the original chlorine. The bromine chloride concentration in mostchlorine samples is high
43、enough that the lower level calibration will neverbe used.14. Procedure14.1 Tare a metal sample cylinder equipped with a closedneedle valve on one end and cool the cylinder in dry ice.Sample the liquid chlorine source using metal tubing or pipeconnections.14.2 Reweigh the sample cylinder to determin
44、e the weightof chlorine collected in the cylinder before the cylinder isallowed to warm. If the cylinder is more than 60 % full, drainthe liquid chlorine out of the bottom of the cylinder andreweigh until the weight of the chlorine is within acceptablelimits for that cylinder.NOTE 2For example, a 15
45、0-mL cylinder should not contain more than90 mL of chlorine at a density of 1.467 g/mL (that is, 132 g of chlorine).14.3 Attach a 38.10 mm piece of 1.59 mm TFE-fluorocarbon tubing and reducing fitting to the needle valve onthe chlorine cylinder, weigh, and record the sample cylinderweight to the nea
46、rest 0.1 g.14.4 Clamp the cylinder in a ring stand with the needlevalve and fluoropolymer tubing pointed down.14.5 Fill a 1-mL plastic syringe with 1 mL of HPLC eluentand cool by placing it in crushed dry ice.14.6 Cool a 15-mL centrifuge tube in crushed dry ice forseveral minutes. Remove the tube fr
47、om the dry ice and hold iton the 1.59 mm TFE-fluorocarbon tubing with the tubingextending down to the bottom of the centrifuge tube. Slowlyopen the needle valve on the cylinder and deliver 5 mL ofliquid chlorine into the centrifuge tube. Reweigh the samplecylinder, record the sample weight to the ne
48、arest 0.1 g.14.7 Before the chlorine starts to evaporate slowly add the 1mL of cooled eluent and mix. Some spattering can be expectedwhen the eluent first contacts the chlorine. Be sure that the tubeis pointed away from the analyst.14.8 Place the centrifuge tube with chlorine in a smallbeaker contai
49、ning about 6.35 mm of water at room tempera-ture. This will start the evaporation of the chlorine at amoderate rate. The total amount of chlorine will evaporate inabout 3 to 5 min.FIG. 2 Typical ChromatogramsE203707314.9 Allow the chlorine to evaporate and the tube to warmslightly to decrease the amount of chlorine dissolved in theeluent. This sample must not be allowed to warm to roomtemperature and must be analyzed as soon as it can be drawninto the syringe.14.10 Withdraw 0.5 mL of the eluent from the centrifugetube and use the entire quantity to flush the i
