1、Designation: D 5799 95 (Reapproved 2004)An American National StandardStandard Test Method forDetermination of Peroxides in Butadiene1This standard is issued under the fixed designation D 5799; the number immediately following the designation indicates the year oforiginal adoption or, in the case of
2、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 covers the determination of peroxidesin butadiene.1.2 This test method covers
3、the concentrations range of 1 to10 ppm by mass (ppmw) as available oxygen.1.3 The values stated in SI units are to be regarded as thestandard.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
4、 to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 1265 Practice for Sampling Liquefied Petroleum (LP)GasesManual MethodD 3700 Practice for Containing Hydrocarbons FluidSamples Us
5、ing a Floating Piston Cylinder3. Summary of Test Method3.1 A known mass of the butadiene sample is placed in aflask and evaporated. The residue is then refluxed with aceticacid and sodium iodide reagents. The peroxides react toliberate iodine which is titrated with standard sodium thiosul-fate solut
6、ion using visual end-point detection. Interfering tracesof iron are complexed with sodium fluoride.4. Significance and Use4.1 Due to the inherent danger of peroxides in butadiene,specification limits are usually set for their presence. This testmethod will provide values that can be used to determin
7、e theperoxide content of a sample of commercial butadiene.4.2 Butadiene polyperoxide is a very dangerous product ofthe reaction between butadiene and oxygen that can occur. Theperoxide has been reported to be the cause of some violentexplosions in vessels that are used to store butadiene.5. Apparatu
8、s5.1 Condensers, Liebig, with 24/40 standard-taperedground-glass joint connections.5.2 Cylinders, graduated, 100-mL capacity.5.3 Flask, Erlenmeyer, 250-mL capacity, with 24/40standard-tapered ground-glass connections with marking at100 mL.5.4 Heating Mantle, electric, for 250-mL Erlenmeyer flasks.5.
9、5 Microburette, 10-mL capacity, graduated in 0.02-mLdivisions.5.6 Water Bath, a thermostatically controlled liquid bathcapable of maintaining a water temperature of 60 6 1C (1406 2F).6. Reagents6.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is
10、 intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use
11、 without lessening theaccuracy of the determination.6.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean deionized or distilledwater.6.3 Acetic Acid, 94 % by volume. Mix 60 mL of water with940 mL of glacial acetic acid (CH3COOH). (WarningPoisonous and corrosi
12、ve. Combustible. May be fatal if swal-lowed. Causes severe burns. Harmful if inhaled.)1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.D0 on Hydrocarbons for Chemical and Special Uses.Current edi
13、tion approved Nov. 1, 2004. Published November 2004. Originallyapproved in 1995. Last previous edition approved in 2000 as D 5799 95 (2000)e1.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards vol
14、ume information, refer to the standards Document Summary page onthe ASTM website.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for Lab
15、oratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6.4 Carbon Dioxide, s
16、olid (dry ice). (WarningUse glovesto avoid frostbite when handling.)6.5 Potassium Dichromate Solution, Standard (0.1 N)Dissolve 2.452 g of potassium dichromate (K2Cr2O7) in waterand dilute to 500 mL in a volumetric flask.(WarningAvoidcontact with eyes and skin and avoid breathing of dust.)6.6 Sodium
17、 Fluoride.6.7 Sodium Iodide.6.8 Sodium Thiosulfate Solution, Standard (0.1 N)Dissolve 12.5 g of sodium thiosulfate (Na2S2O33 5H2O) plus0.1 g of sodium carbonate (Na2CO3) in 500 mL of water (theNa2CO3is added to stabilize the Na2S2O3solution). Let thissolution stand a week or more before using. Stand
18、ardizeagainst 0.1 N K2Cr2O7solution. Restandardize at frequenciesto detect changes of 0.0005 in normality.7. Sampling7.1 Butadiene should be sampled in a metal container of atype which ensures maximum safety and which is resistant tobutadiene corrosion. The size of the container is dependentupon the
19、 number of times the test is to be performed accordingto this test method. Refer to Practice D 1265 or PracticeD 3700 for instructions on sampling.8. Procedure8.1 Remove the oxygen from a 250-mL Erlenmeyer flask byadding several pellets (approximately 1 cm in size) of dry iceand allowing the CO2to d
20、isplace the air. This will takeapproximately 5 min.8.2 Record the weight to one decimal place of the samplecylinder, and then transfer approximately 100 mLs of butadi-ene sample from the cylinder to the 250 mL Erlenmeyer flaskcontaining several pellets of dry ice. Reweigh the samplecylinder and reco
21、rd the weight of the sample as the differenceof the two weights. (WarningButadiene is a flammable gasunder pressure.)8.3 Place the flask in a water bath at 60C in a wellventilated hood. Allow the butadiene to evaporate whilekeeping an inert atmosphere above the liquid butadiene bycontinuing to add p
22、ellets of dry ice at intervals until all thebutadiene has evaporated. (WarningPeroxides are unstableand react violently when taken to dryness. Peroxides at thelevels experienced during the test method evaluation have notcaused a problem, but caution needs to be exhibited in handlingby the use of per
23、sonal protective equipment.)8.4 Remove the flask from the water bath and allow to coolto ambient temperature. Add 50 mL of 94 % acetic acid and0.20 6 0.02 g of sodium fluoride. Add several more pellets ofdry ice to the flask and allow to stand for 5 min.8.5 Add 6.0 6 0.2 g of sodium iodide to the fl
24、ask andimmediately connect to the Liebig condenser. Turn on theheating mantle and reflux the solution for 25 6 5 min. Keep theequipment away from strong light during refluxing.8.6 At the end of the reaction period, turn off the heatingmantle and remove the flask with condenser from the mantle.Immedi
25、ately add 100 mL of water through the top of thecondenser followed by several pellets of dry ice.8.7 Maintaining an inert atmosphere with CO2pellets,remove the flask from the condenser and allow to cool toambient temperature. Cold water may be used to assist in thisstep. Titrate the liberated iodine
26、 with 0.1 N sodium thiosulfateuntil a clear endpoint is reached.8.8 Repeat 8.4 through 8.7 for the reagent blank.9. Calculation9.1 Calculate the peroxide content as follows:peroxide, as O2, ppmw 5A 2 B! 3 N 3 16 000W(1)where:A =Na2S2O3solution required for titration of thesample, mL,B =Na2S2O3soluti
27、on required for titration of theblank, mL,N = normality of the Na2S2O3solution,W = sample weight, g, and16 000 = milliequivalents of oxygen.10. Precision and Bias410.1 PrecisionThe precision of this test method as deter-mined by statistical examination of interlaboratory results is asfollows:10.1.1
28、RepeatabilityThe difference between two test re-sults obtained by the same operator with the same apparatusunder constant operating conditions on identical test materialswould, in the long run, in the normal and correct operation ofthe test method, exceed the following values only in one caseof twen
29、ty:R 5 1.4 ppmw (2)10.1.2 ReproducibilityThe difference between two singleand independent results, obtained by different operators work-ing in different laboratories on identical test material, would, inthe long run and in the normal and correct operation of the testmethod, exceed the following valu
30、es only in one case intwenty.R 5 3.4 ppmw (3)10.2 BiasAs no reliable source of butadiene polyperoxideis available, the actual bias of the test method is unknown; butpublished data reports that this test method determines 90 % ofthe polyperoxide.511. Keywords11.1 butadiene; butadiene polyperoxide; pe
31、roxide4Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR: D02:1372.5For a discussion of the background for this test method, see Mayo, Hendry,Jones, and Scheatzle, Industrial and Engineering Chemical, Product Research, Vol7, 1968,
32、p. 145.D 5799 95 (2004)2ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringe
33、ment of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard o
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35、nown to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).D 5799 95 (2004)3
