1、Designation: E2037 15Standard Test Method forBromine Chloride in Liquid Chlorine by High PerformanceLiquid Chromatography (HPLC)1This standard is issued under the fixed designation E2037; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revis
2、ion, 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. Scope1.1 This test method uses high performance liquid chroma-tography (HPLC) to determine bromine chloride le
3、vels inliquid chlorine at the 10 to 1400 g/g (ppm) range.1.2 Review the current safety data sheet (SDS) for detailedinformation concerning toxicity, first aid procedures, and safetyprecautions.1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included
4、 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-priate safety and health practices and determine the applica-bility of regulatory limitations prior to us
5、e. Specific hazardstatements are given in Section 8.2. Referenced Documents2.1 ASTM Standards:2E180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals (Withdrawn 2009)3E806 Test Method for Carbon Tetrachloride and Chloroformin Liquid
6、 Chlorine by Direct Injection (Gas Chromato-graphic Procedure)2.2 Federal Standards:4CFR 173 Title 49 Transportation; Shippers General Re-quirements for Shipments and Packaging, including Sec-tions:173.304 Charging of Cylinders with Liquefied Com-pressed Gas173.314 Requirements for Compressed Gases
7、in TankCars173.315 Compressed Gases in Cargo Tanks and PortableTank Containers2.3 Other Document:5Chlorine Institute Pamphlet No. 1 Chlorine Basics3. Summary of Test Method3.1 Weighed samples of chlorine delivered into a cooledgraduated centrifuge tube. One mL of cooled HPLC eluent isadded before th
8、e 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 commonconta
9、minant 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. Interferenc
10、es5.1 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 (HPLC)
11、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, and1This test method is under the jurisdiction of ASTM Committee E15 onIndustrial and Specialty Chemicals a
12、nd is the direct responsibility of SubcommitteeE15.02 on Product Standards.Current edition approved June 1, 2015. Published June 2015. Originallyapproved in 1999. Last previous edition approved in 2007 as E2037-07. DOI:10.1520/E2037-15.2For referenced ASTM standards, visit the ASTM website, www.astm
13、.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.3The last approved version of this historical standard is referenced onwww.astm.org.4Available from U.S. Government Publishin
14、g Office, 732 N. Capitol St., NW,Washington, DC 20401-0001, http:/www.gpo.gov.5Available from The Chlorine Institute, 1300 Wilson Blvd., Ste. 525, Arlington,VA 22209, http:/www.chlorineinstitute.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. U
15、nited States16.1.4 HPLC Column, C18 reverse phase, 25 cm by 4.6 mm.6.2 Plastic Syringes, 1, 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 Sam
16、ple Cylinder, with a needle valve onone end.6.7 Graduated Centrifuge Tube, 15 mL.7. Reagents7.1 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 specifi
17、cations are available.6Othergrades 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.7.2 Water, HPLC grade.7.3 Methanol, HPLC grade.7.4 Sodium Acetate, reagent grade.7.5 Glacial Acetic Aci
18、d, reagent grade.7.6 Dry Ice.7.7 Potassium Bromide, reagent grade.7.8 Chlorine, reagent grade.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
19、.8.2 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.Splashes of liquid chlorine destroy clothing and if suchclot
20、hing is next to the skin, it will produce irritations and burns.8.3 If liquid samples are to be taken in cylinders, do notallow the sample cylinder to become liquid full. Test MethodE806, 49 CFR 173.314, 173.315, and 173.304 advise that theweight of the chlorine in the cylinder should not be more th
21、an125 % of the weight of the water that the cylinder couldcontain. See the Chlorine Institute Pamphlet No. 1 for addi-tional technical information regarding liquid chlorine.8.4 When sampling and working with chlorine out-of-doors,people downwind from such an operation should be warned ofthe possible
22、 release of chlorine vapors.8.5 In the event chlorine is inhaled, first aid should besummoned immediately 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
23、 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 container, the purged ch
24、lorineshould be similarly handled. Purging to the atmosphere shouldbe avoided.8.8 Safety and Health PrecautionsExposure to all solventsused 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 in
25、strument to equilibrate untila steady baseline is obtained:9.1.1 ColumnC18 reverse phase ODS (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 Det
26、ector WavelengthUV at 221 nm.10. Preparation of Buffer Solution10.1 Sodium Acetate Buffer Stock 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 stoc
27、k buffer solution into a 1-L volumetric flask anddilute to volume with water.11. Preparation of 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 t
28、he Sample Cylinder12.1 Clamp the sample cylinder in a vertical position withthe needle valve in 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 tu
29、be fitting and tightenthe 1.59 mm nut and ferrule. See Fig. 1. It may be helpful to cuta 6.35 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
30、 out of the fitting.13. Standardization of the HPLC13.1 Prepare a 1000 g/g (ppm) stock solution of potassiumbromide in water. Make a series of standards of potassium6Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing
31、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.E2037 152bromide by serial dilution covering the ran
32、ge between 1 and650 g/g (ppm) potassium bromide. Calculate the brominechloride concentration of each standard from the potassiumbromide concentration by multiplying by the ratio of themolecular weights:BrCl/KBr! 5 115.4/119! 5 0.97 (1)13.2 Withdraw 0.5 mL of a potassium bromide standard intoa 1-mL p
33、lastic syringe and then pull the plunger back to the 1mL mark to fill the remainder 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 secon
34、d 1-mL plastic syringe and pull the plunger backto the 1 mL mark. Insert the 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 nee
35、dle to the luer tip.13.4 Holding the first syringe pointed upward, use thesecond 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 fo
36、r the conversionof each 500 g/g (ppm) of bromide ion in the standard.Although 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 potas
37、siumbromide to serve as a reagent blank.13.5 Using the entire 0.5 mL of standard 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
38、bromide chloride peak elutes between thewater dip and the peak caused by the 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 bromi
39、ne chloride in each standard analyzed. Theslope and intercept of this line are 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 an
40、d chlorine depending on the amounts ofbromine and chlorine present. The response 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 bromin
41、e chloride standardswith one or more blank runs between the analysis of each 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 rapidlymer
42、ge above 200 g/g (ppm) in the injected solution. Keep in mind thatthe concentrations 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 c
43、hlorine. The bromine chloride concentration in mostchlorine samples is high 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
44、metal tubing or pipeconnections.14.2 Reweigh the sample cylinder to determine 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 c
45、hlorine is within acceptablelimits for that cylinder.NOTE 2For example, a 150-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 ont
46、he chlorine cylinder, weigh, and record the sample cylinderweight to the nearest 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-
47、mL centrifuge tube in crushed dry ice forseveral minutes. Remove the tube from 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 cen
48、trifuge tube. Reweigh the samplecylinder, record the sample weight to the nearest 0.1 g.FIG. 1 Sample CylinderFIG. 2 Typical ChromatogramsE2037 15314.7 Before the chlorine starts to evaporate slowly add the 1mL of cooled eluent and mix. Some spattering can be expectedwhen the eluent first contacts t
49、he chlorine. Be sure that the tubeis pointed away from the analyst.14.8 Place the centrifuge tube with chlorine in a smallbeaker containing 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.14.9 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 syring
