1、Designation: D1159 07 (Reapproved 2017)Designation: 130/98Standard Test Method forBromine Numbers of Petroleum Distillates and CommercialAliphatic Olefins by Electrometric Titration1This standard is issued under the fixed designation D1159; the number immediately following the designation indicates
2、the year oforiginal adoption or, in the case of revision, 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.This standard has been approved for use by agencies of the U
3、.S. Department of Defense.1. Scope1.1 This test method2covers the determination of thebromine number of the following materials:1.1.1 Petroleum distillates that are substantially free ofmaterial lighter than isobutane and that have 90 % distillationpoints (by Test Method D86) under 327 C (626 F). Th
4、is testmethod is generally applicable to gasoline (including leaded,unleaded, and oxygenated fuels), kerosine, and distillates in thegas oil range that fall in the following limits:90 % Distillation Point, C (F) Bromine Number, max2Under 205 (400) 175205 to 327 (400 to 626) 101.1.2 Commercial olefin
5、s that are essentially mixtures ofaliphatic mono-olefins and that fall within the range of 95 to165 bromine number (see Note 1). This test method has beenfound suitable for such materials as commercial propylenetrimer and tetramer, butene dimer, and mixed nonenes, octenes,and heptenes. This test met
6、hod is not satisfactory for normalalpha-olefins.NOTE 1These limits are imposed since the precision of this testmethod has been determined only up to or within the range of thesebromine numbers.1.2 The magnitude of the bromine number is an indicationof the quantity of bromine-reactive constituents, n
7、ot an iden-tification of constituents; therefore, its application as a measureof olefinic unsaturation should not be undertaken without thestudy given in Annex A1.1.3 For petroleum hydrocarbon mixtures of bromine num-ber less than 1.0, a more precise measure for bromine-reactiveconstituents can be o
8、btained by using Test Method D2710.Ifthe bromine number is less than 0.5, then Test Method D2710or the comparable bromine index methods for industrialaromatic hydrocarbons, Test Methods D1492 or D5776 mustbe used in accordance with their respective scopes. Thepractice of using a factor of 1000 to co
9、nvert bromine numberto bromine index is not applicable for these lower values ofbromine number.1.4 The values stated in SI units are to be regarded as thestandard.1.4.1 ExceptionThe values given in parentheses are forinformation only.1.5 This standard does not purport to address all of thesafety con
10、cerns, 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 use. For specificwarning statements, see Sections 7, 8, and 9.1.6 This international
11、standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.
12、2. Referenced Documents2.1 ASTM Standards:3D86 Test Method for Distillation of Petroleum Products andLiquid Fuels at Atmospheric PressureD1193 Specification for Reagent WaterD1492 Test Method for Bromine Index of Aromatic Hydro-carbons by Coulometric TitrationD2710 Test Method for Bromine Index of P
13、etroleum Hydro-carbons by Electrometric Titration1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.06 on Analysis of Liquid Fuels and Lubricants.In the IP, this test method is under
14、 the jurisdiction of the StandardizationCommittee.Current edition approved May 1, 2017. Published July 2017. Originally approvedin 1951. Last previous edition approved in 2012 as D1159 07 (2012). DOI:10.1520/D1159-07R17.2Dubois, H. D., and Skoog, D. A., “Determination of Bromine AdditionNumbers,” An
15、alytical Chemistry, Vol 20, 1948, pp. 624627.3For 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.Copyright ASTM I
16、nternational, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standar
17、ds, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1D5776 Test Method for Bromine Index of Aromatic Hydro-carbons by Electrometric Titration3. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 bromine numberthe number o
18、f grams of brominethat will react with 100 g of the specimen under the conditionsof the test.4. Summary of Test Method4.1 A known weight of the specimen dissolved in theselected solvent (see 8.1) maintained at 0 C to 5 C (32 F to41 F) is titrated with standard bromide-bromate solution. Theend point
19、is indicated by a sudden change in potential on anelectrometric end point titration apparatus due to the presenceof free bromine.5. Significance and Use5.1 The bromine number is useful as a measure of aliphaticunsaturation in petroleum samples. When used in conjunctionwith the calculation procedure
20、described in AnnexA2, it can beused to estimate the percentage of olefins in petroleum distil-lates boiling up to approximately 315 C (600 F).5.2 The bromine number of commercial aliphatic monoole-fins provides supporting evidence of their purity and identity.6. Apparatus6.1 Electrometric End Point
21、Titration ApparatusAny ap-paratus designed to perform titrations to pre-set end points (seeNote 2) may be used in conjunction with a high-resistancepolarizing current supply capable of maintaining approxi-mately 0.8 V across two platinum electrodes and with asensitivity such that a voltage change of
22、 approximately 50 mVat these electrodes is sufficient to indicate the end point. Othertypes of commercially available electronic titrimeters, includ-ing certain pH meters, have also been found suitable.NOTE 2Pre-set end point indicated with polarized electrodes providesa detection technique similar
23、to the dead stop technique specified inprevious versions of this test method.6.2 Titration VesselA jacketed glass vessel approximately120 mm high and 45 mm in internal diameter and of a formthat can be conveniently maintained at 0 C to 5 C (32 F to41 F).6.3 StirrerAny magnetic stirrer system.6.4 Ele
24、ctrodesA platinum wire electrode pair with eachwire approximately 12 mm long and 1 mm in diameter. Thewires shall be located 5 mm apart and approximately 55 mmbelow the level of the titration solvent. Clean the electrode pairat regular intervals with 65 % nitric acid and rinse withdistilled water be
25、fore use.6.5 BuretAny delivery system capable of measuringtitrant in 0.05 mL or smaller graduations.7. Reagents7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the commit-tee on
26、 Analytical Reagents of the American Chemical Society,where such specifications are available.4Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.7.2 Purity of WaterUnless other
27、wise indicated, referencesto water shall be understood to mean reagent water as definedby Type III of Specification D1193.7.3 Acetic Acid, Glacial(WarningPoison, corrosive-combustible, may be fatal if swallowed. Causes severe burns,harmful if inhaled.)7.4 Bromide-Bromate, Standard Solution(0.2500 M
28、asBr2)Dissolve 51.0 g of potassium bromide (KBr) and 13.92 gof potassium bromate (KBrO3) each dried at 105 C (220 F)for 30 min in water and dilute to 1 L.7.4.1 If the determinations of the bromine number of thereference olefins specified in Section 8 using this solution donot conform to the prescrib
29、ed limits, or if for reasons ofuncertainties in the quality of primary reagents it is considereddesirable to determine the molarity of the solution, the solutionshall be standardized and the determined molarity used insubsequent calculations. The standardization procedure shallbe as follows:7.4.1.1
30、To standardize, place 50 mL of glacial acetic acidand 1 mL of concentrated hydrochloric acid (WarningPoison corrosive. May be fatal if swallowed. Liquid and vaporcauses severe burns. Harmful if inhaled; relative density 1.19.)in a 500 mL iodine number flask. Chill the solution in a bathfor approxima
31、tely 10 min and, with constant swirling of theflask, add from a 10 mL calibrated buret, 5 mL 6 0.01 mL ofthe bromide-bromate standard solution at the rate of 1 or 2drops per second. Stopper the flask immediately, shake thecontents, place it again in the ice bath, and add 5 mL of Klsolution in the li
32、p of the flask. After 5 min remove the flaskfrom the ice bath and allow the Kl solution to flow into theflask by slowly removing the stopper. Shake vigorously, add100 mL of water in such a manner as to rinse the stopper, lipand walls of the flask, and titrate promptly with sodiumthiosulfate (Na2S2O3
33、) solution. Near the end of the titration,add 1 mL of starch indicator solution and titrate slowly todisappearance of the blue color. Calculate the molarity of thebromide-bromate solution as follows:M15AM25!2!(1)where:M1= molarity of the bromide-bromate solution, as Br2,A = millilitres of Na2S2O3sol
34、ution required for titration ofthe bromide-bromate solution, and,M2= molarity of Na2S2O3solution,4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual S
35、tandards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D1159 07 (2017)25 = millilitres of bromidebromate solution, and2 = number of electrons transferred during redox titratio
36、nof bromide-bromate solution.Repeat the standardization until duplicate determinations donot differ from the mean by more than 60.002 M.7.5 Methanol(WarningFlammable. Vapor harmful.Can be fatal or cause blindness if swallowed or inhaled. Cannotbe made non-poisonous.)7.6 Potassium Iodide Solution (15
37、0 g L)Dissolve 150 gof potassium iodide (Kl) in water and dilute to 1 L.7.7 Sodium Thiosulfate, Standard Solution (0.1 M)Dissolve 25 g of sodium thiosulfate (Na2S2O35H2O) in waterand add 0.1 g of sodium carbonate (Na2CO3) to stabilize thesolution. Dilute to 1 L and mix thoroughly by shaking. Stan-da
38、rdize by any accepted procedure that determines the molaritywith an error not greater than 60.0002. Restandardize atintervals frequent enough to detect changes of 0.0005 inmolarity.7.8 Starch Indication Solution Mix 5 g of soluble starchwith about 3 mL to 5 mL of water. If desired, add about 0.65 gs
39、alicylic acid as preservative. Add the slurry to 500 mL ofboiling water and continue boiling for 5 min to 10 min. Allowto cool, and decant the clear, supernatant liquid into glassbottles and seal well. Starch solutions (some preserved withsalicylic acid) are also commercially available and may besub
40、stituted.7.9 Sulfuric Acid (1+5)Carefully mix one volume ofconcentrated sulfuric acid (H2SO4, rel dens 1.84) with fivevolumes of water. (WarningPoison. Corrosive. Strong oxi-dizer. Contact with organic material can cause fire. Can be fatalif swallowed.)7.10 Titration SolventPrepare 1 L of titration
41、solvent bymixing the following volumes of materials: 714 mL of glacialacetic acid, 134 mL of 1,1,1-trichloroethane (ordichloromethane), 134 mL of methanol, and 18 mL ofH2SO4(1 + 5).7.11 1,1,1-Trichloroethane(WarningHarmful if in-haled. High concentrations can cause unconsciousness ordeath. Contact m
42、ay cause skin irritation and dermatitis.)7.12 Dichloromethane(WarningThe replacement of1,1,1-trichloroethane, an ozone-depleting chemical, is neces-sary because its manufacture and import has been discontin-ued. Dichloromethane is temporarily being allowed as analternative to 1,1,1-trichloroethane u
43、ntil a permanent replace-ment can be identified and adopted by ASTM International. Aprogram to identify and evaluate candidate solvents is currentlyunderway in Subcommittee D02.04.)NOTE 3Commercially available reagents can be used in place oflaboratory preparations.8. Check Procedure8.1 In case of d
44、oubt in applying the procedure to actualsamples, the reagents and techniques can be checked by meansof determinations on freshly purified cyclohexene or di-isobutene. (WarningThe user of this test method maychoose to use either 1,1,1-trichloroethane or dichloromethaneto the exclusion of the other so
45、lvent. The selected solvent is tobe used for all operations, that is, in the preparation of thetitration solvent, for the dilution of samples, and as the titrationblank.) Proceed in accordance with Section 9, using a sampleof either 0.6 g to 1 g freshly purified cyclohexene or di-isobutene (see Tabl
46、e 1) or 6 g to 10 g of 10 mass percentsolutions of these materials in 1,1,1-trichlorethane.(WarningFlammable.)8.2 If the reagents and techniques are correct, values withinthe following should be obtained:StandardBromineNumberCyclohexene, purified (see 7.4.1, 9.3, and 8.1) 187 to 199 (see 9.5)Cyclohe
47、xene, 10 % solution 18 to 20Diisobutene, purified (see 7.4.1, 8.3, and 8.1) 136 to 144 (see 9.5)Diisobutene, 10 % solution 13 to 15The reference olefins yielding the above results are charac-terized by the properties shown in Table 1. The theoreticalbromine numbers of cyclohexene and diisobutene are
48、 194.6and 142.4, respectively.8.3 Purified samples of cyclohexene and diisobutene can beprepared from cyclohexene and diisobutene,5by the followingprocedure:8.3.1 Add 65 g of activated silica gel, 75 to 150 m (100 to200 mesh) manufactured to ensure minimum olefin polymer-ization6to a column approxim
49、ately 16 mm in inside diameterand 760 mm in length, that has been tapered at the lower endand that contains a small plug of glass wool at the bottom. A100 mL buret, or any column that will give a height-to-diameter ratio of the silica gel of at least 30:1, will be suitable.Tap the column during the adding of the gel to permit uniformpacking.8.3.2 To the column add 30 mL of the olefin to be purified.When the olefin disappears into the gel, fill the column withmethanol. Discard the first 10 mL of percolate and collect thenext 10 mL
