1、Designation: E 506 08Standard Test Method forMercury in Liquid Chlorine1This standard is issued under the fixed designation E 506; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses i
2、ndicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method2covers the determination of mercuryin liquid chlorine with a lower limit of detection of 0.1 g/L.1.2 The values stated in SI units are to be
3、 regarded asstandard. No other units of measurement are included in thisstandard.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 de
4、termine the applica-bility of regulatory limitations prior to use. Specific precau-tionary statements are given in Sections 7, 6.3, 6.4, 6.5, andNote 2.1.4 Review the current material safety data sheet (MSDS)for detailed information concerning toxicity, first-aid proce-dures, and safety precautions.
5、2. Referenced Documents2.1 ASTM Standards:3D 1193 Specification for Reagent WaterE 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty ChemicalsE 200 Practice for Preparation, Standardization, and Stor-age of Standard and Reagent Solutions
6、for ChemicalAnalysis3. Summary of Test Method3.1 Liquid chlorine samples are taken in chilled glass flasks,then allowed to evaporate slowly to dryness. The mercury isleft in the residue. The residue is dissolved in dilute nitric acidand diluted to volume. The addition of nitric acid prevents anyloss
7、 of mercury from the aqueous solution on standing. Foranalysis, an aliquot of the acidic aqueous solution is boiledwith excess permanganate to remove interfering materials. Themercuric ions are then reduced to metallic mercury withstannous chloride. The solution is aerated and the mercury,now in the
8、 air stream, is determined using an atomic absorptionspectrophotometer.4. Significance and Use4.1 This test method was developed primarily for thedetermination of traces of mercury in chlorine produced by themercury-cell process.5. Apparatus5.1 Atomic Absorption Spectrophotometer, equipped withmount
9、ing to hold absorption cell and a fast response (0.5 s)recorder.45.2 Mercury Hollow Cathode Lamp, primary line 253.7 nm.5.3 Absorption Cell, 10-cm path length with quartz win-dows.4,55.4 Gas Washing Bottle, 125 mL, with extra-coarse frittedbubbler.4,6The bottle has a calibration line drawn at the 60
10、-mLmark.5.5 Stopcock, 3-way, with plug of TFE-fluorocarbon.4,71This test method is under the jurisdiction of ASTM Committee E15 onIndustrial and Specialty Chemicals and is the direct responsibility of SubcommitteeE15.02 on Product Standards.Current edition approved Dec. 15, 2008. Published January 2
11、009. Originallyapproved in 1973. Last previous edition approved in 2003 as E 506 98(2003).2Analytical Methods for Atomic Absorption Spectrophotometry , Perkin-ElmerLtd., September 1968.“Determination of Mercury in Effluents and Process Streams from a Mercury-Cell Chlorine Plant (Atomic Absorption Fl
12、ameless Method)” CAS-AM-70.13, June23, 1970, Analytical Laboratory, Dow Chemical of Canada, Ltd., Sarnia, Ontario,Canada.“Determination of Mercury in Liquid Chlorine,” CSAL-M72.4, Feb. 25, 1972,Anaytical Laboratory, Dow Chemical of Canada, Ltd., Sarnia, Ontario, Canada.Chlorine Institute Reference N
13、o. MIR-104.3For 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 standards Document Summary page onthe ASTM website.4The sole source of supply of the Beckman 10in. re
14、corder Model No. 100502known to the committee at this time is Beckman Instruments Inc., 2500 HarborBlvd., Fullerton, CA92634. If you are aware of alternative suppliers, please providethis information to ASTM International Headquarters. Your comments will receivecareful consideration at a meeting of
15、the responsible technical committee1, whichyou may attend.5The sole source of supply of the Beckman 75144 known to the committee atthis time is Beckman Instruments Inc., 2500 Harbor Blvd., Fullerton, CA 92634. I6The sole source of supply of the Corning 31770 (125 EC) known to thecommittee at this ti
16、me is Fisher Scientific, 711 Forbes Ave., Pittsburgh, PA15219-4785. I7The sole source of supply of the Corning 7382 known to the committee at thistime is Fisher Scientific, 711 Forbes Ave., Pittsburgh, PA 15219-4785.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM In
17、ternational, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.6 Gas Washing Bottle, 125-mL without frit.85.7 Drying Tube.95.8 Flow Meter, capable of measuring and maintaining aflow of 42.5 L/h.105.9 Large Dewar Flasks, two, with sufficient capacity tohold a 500-m
18、L flask and a large volume of dry ice coolingmixture.5.10 Flexible Connection.4,115.11 Stainless Steel Compression Nut.5.12 Two-Hole Rubber Stopper.5.13 Fluorocarbon Tubing.NOTE 1The procedure, as described in this test method, was devel-oped using a Perkin-Elmer Model 303 atomic absorption spectrop
19、hotom-eter equipped with a 10-cm absorption cell. Any other equivalent atomicabsorption spectrophotometer may be used as well as one of the manycommercial instruments specifically designed for measurement of mer-cury by flameless atomic absorption. However, variation in instrumentgeometry, cell leng
20、th, sensitivity, and mode of response measurement mayrequire appropriate modifications of the operating parameters.6. Reagents6.1 Purity of ReagentsUnless otherwise indicated, it isintended that all reagents should conform to the specificationsof the Committee on Analytical Reagents of the AmericanC
21、hemical Society, where such specifications are available.12Blanks should be run on all reagents to assure a negligiblemercury content.6.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean Type II or Type IIIreagent water conforming to Specification D 1193.6.3
22、Aqua RegiaCarefully add 10 mL of concentratedHNO3(sp gr 1.42) to 30 mL of concentrated HCl (sp gr 1.19)in a 100-mL beaker. Let the mixture stand for 5 min before use.This mixture is unstable and should not be stored. (WarningUse goggles when preparing or using this solution.)6.4 Nitric Acid (1 + 9)P
23、ipet 25 mL of concentratedHNO3(sp gr 1.42) into a 250-mL volumetric flask containingabout 150 mL of water. Dilute to volume with water and mixwell. (WarningUse goggles when preparing this solution.)6.5 Sulfuric Acid (1 + 4)Add slowly with stirring 200 mLof concentrated H2SO4(sp gr 1.84) to 800 mL of
24、 water.(WarningUse goggles when preparing this solution.)6.6 Cooling Mixture for Dewar FlasksFill two thirds ofthe Dewar flask with dichloromethane. Add dry ice slowly,allowing time for the solution to cool, until there is nosublimation of dry ice on further addition. Replenish the dryice when neces
25、sary. See the MSDS sheet for dichloromethanebefore using this material.6.7 Hydroxylamine Hydrochloride Solution (100 g/L)SeePractice E 200. This reagent is dispensed with a droppingbottle.6.8 Mercury Standard Solution (50 g Hg/mL)As pre-pared in Practice E 200.6.9 Mercury Standard Solution (10 g Hg/
26、mL)Pipet 10mL of the standard mercury solution containing 50 g Hg/mLinto a 50-mL volumetric flask, acidify with 5 mL of 1 + 4H2SO4and dilute to volume with water. Mix well. Prepare freshdaily.6.10 Mercury Standard Solution (1 g Hg/mL)Pipet 10mL of the standard mercury solution containing 10 g Hg/mLi
27、nto a 100-mL volumetric flask, acidify with 5 mL 1 + 4 H2SO4and dilute to volume with water. Mix well. Prepare fresh daily.6.11 Potassium Permanganate Solution (40 g/L) (4 %)Weigh 40 g of KMnO4into a 1000-mL beaker. Add about 800mL of water and stir with a mechanical stirrer until completelydissolve
28、d. Allow the solution to stand overnight and filter.Transfer to a 1000-mL volumetric flask, dilute to volume, andstore in a brown bottle.6.12 Stannous Chloride (10 %)Dissolve 20 g of stannouschloride (SnCl22H2O) in 40 mL of warm concentrated HCl(sp gr 1.19). Add 160 mL of water when all the stannous
29、chloride has dissolved. Allow the solution to stand overnightand filter. Mix and store in a 250-mL reagent bottle. Preparefresh once a week. A piece of metallic tin in the bottle allowslonger term storage if the bottle is well sealed.7. Safety Precautions7.1 Sulfuric acid will cause severe burns if
30、allowed to comein contact with any part of the skin or eyes. All spillages mustbe immediately flushed from the skin or eyes with cold water.This acid must always be added slowly to water with adequatestirring since heat is developed and spattering occurs if the acidis added too quickly.7.2 Aqua regi
31、a contains both HNO3and HCl, which willcause severe burns if allowed to come in contact with any partof the skin or eyes. All spillages must be immediately flushedfrom the skin or eyes with cold water. Vapors produced by aquaregia can cause burns if inhaled. It should be used only in ahood or with s
32、imilar ventilation. This solution is unstable andmust not be placed in a stoppered flask or bottle.7.3 Nitric acid will cause severe burns if allowed to come incontact with any part of the skin or eyes. All spillages must beimmediately flushed from the skin or eyes with cold water.7.4 Chlorine is a
33、corrosive and toxic material. A well-ventilated fume hood should be used to house all test equip-ment when this product is analyzed in the laboratory.7.5 Liquid chlorine sampling should be performed only bythose persons thoroughly familiar with the handling of thismaterial and the operation of the s
34、ampling system. Personnelshould be equipped with monogoggles, gloves (if desired), anda respirator. Sampling should be done in a well-ventilated areaor in a hood.7.6 The analysis should be attempted only by persons whoare thoroughly familar with the handling of chlorine, and even8Corning 1760, avail
35、able from Fisher Scientific, 711 ForbesAve., Pittsburgh, PA15219-4785, or equivalent has been found suitable.9The sole source of supply of the Corning 7775 known to the committee at thistime is Fisher Scientific, 711 Forbes Ave., Pittsburgh, PA 15219-4785.10Brooks Tube P-2-15A with saphire float, av
36、ailable from Brooks InstrumentDiv., Emerson Electric Co., 407 West Vine St., Hatfield, PA19440, or equivalent hasbeen found suitable.11The sole source of supply of Tygon known to the committee at this time isFisher Scientific, 711 Forbes Ave., Pittsburgh, PA 15219-4785.12Reagent Chemicals, American
37、Chemical Society Specifications , AmericanChemical 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.
38、S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.E506082an 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, will produce irritations and bu
39、rns.7.7 When sampling and working with chlorine out of doors,people downwind from such operation should be warned of thepossible release of chlorine vapors.7.8 It is recommended that means be available for disposalof excess chlorine in an environmentally safe and acceptablemanner. If chlorine cannot
40、 be disposed of in a chlorineconsuming process, the chlorine should be discharged into acaustic scrubber containing an appropriate amount of 20 %caustic solution to neutralize all the chlorine. This reaction isexothermic, and care should be taken to avoid excess heatingby choosing a sufficiently lar
41、ge volume of caustic solution toserve as a heat sink. When the analysis and sampling regimenrequires an initial purging of chlorine from a container, thepurged chlorine should be similarly handled. Purging to theatmosphere should be avoided.7.9 In the event chlorine is inhaled, first aid should besu
42、mmoned immediately and oxygen administered withoutdelay.7.10 Handle all other reagents as recommended by thesupplier.8. Sampling8.1 Soak all 500-mL receiver flasks carefully in 50C aquaregia and rinse with water before use.8.2 Cool two receiver flasks in the dichloromethane-dry icemixture.8.3 Assemb
43、le the sampling apparatus as shown in Fig. 1.8.4 With a respirator ready for immediate use, locate your-self upwind of the receiver flask.8.5 Keeping the receiver flask in the dry ice solution, purgethe sampling system allowing 100 to 200 mL of liquid chlorineto flow through the sampling system into
44、 the flask. This purgesany residual mercury deposits from the lines and sample point.8.6 Stop the flow of liquid chlorine.8.7 Cap the waste liquid chlorine flask with an open,one-hole stopper and store in a dry ice bath for disposal in anenvironmentally safe and acceptable manner.8.8 Attach the deli
45、very system to a cooled 500-mL receiverflask and fill with liquid chlorine to the 200-mL mark. Othervolumes may be used if desired.8.9 Stop the flow of liquid chlorine.8.10 Cap the flask with an open, one-hole stopper and storein a dichloromethane-dry ice mixture.NOTE 2Except for properly designed c
46、ylinders, never completelystopper a vessel containing liquid chlorine. A vent must always be presentto relieve the pressure from evaporating liquid chlorine.8.11 Remove the sample of liquid chlorine and waste liquidchlorine from the dichloromethane-dry ice mixture and allowthem to evaporate to dryne
47、ss into a chlorine absorption systemor some other type of enviornmentally safe and acceptablemanner of chloride disposal. Discard the residue from thewaste chlorine.8.12 Add 10 mL of HNO3(1 + 9) to the flask containing theresidue from the liquid chlorine sample. Swirl to assurecomplete solution of t
48、he residue. Add 25 mL of water andtransfer to a 50-mL volumetric flask. Dilute to volume with thewater used to rinse the flask and mix well.8.13 Prepare a blank consisting of 10 mL of HNO3(1+9)ina 50-mL volumetric flask, dilute to volume with water, and mixwell.9. Calibration9.1 Care must be taken t
49、o avoid contamination of theapparatus with mercury. Soak all glass apparatus (pipets,beakers, and gas washing bottle) in aqua regia prior to use andrinse thoroughly with water before use.9.2 Connect the apparatus shown in Fig. 2 to the atomicabsorption spectrophotometer and adjust the air flow rate to42.5 L/h.9.3 Adjust the operating conditions in accordance with themanufacturers recommendations for doing mercury analysisand allow the spectrophotometer to warm up for at least 15 min(see Note 1). Listed below are typical conditions for oneinstrument.Waveleng
