An American National Standard

Designation: D 1159 – 07

Designation: 130/98

Standard Test Method for

Bromine Numbers of Petroleum Distillates and Commercial
Aliphatic Olefins by Electrometric Titration1
This standard is issued under the fixed designation D 1159; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope* 1.3 For petroleum hydrocarbon mixtures of bromine num-

1.1 This test method2 covers the determination of the ber less than 1.0, a more precise measure for bromine-reactive
bromine number of the following materials: constituents can be obtained by using Test Method D 2710. If
1.1.1 Petroleum distillates that are substantially free of the bromine number is less than 0.5, then Test Method D 2710
material lighter than isobutane and that have 90 % distillation or the comparable bromine index methods for industrial
points (by Test Method D 86) under 327°C (626°F). This test aromatic hydrocarbons, Test Methods D 1492 or D 5776 must
method is generally applicable to gasoline (including leaded, be used in accordance with their respective scopes. The
unleaded, and oxygenated fuels), kerosine, and distillates in the practice of using a factor of 1000 to convert bromine number
gas oil range that fall in the following limits: to bromine index is not applicable for these lower values of
90 % Distillation Point, °C (°F) Bromine Number, max2
bromine number.
Under 205 (400) 175 1.4 The values stated in SI units are to be regarded as the
205 to 327 (400 to 626) 10 standard. The values given in parentheses are for information
1.1.2 Commercial olefins that are essentially mixtures of only.
aliphatic mono-olefins and that fall within the range of 95 to 1.5 This standard does not purport to address all of the
165 bromine number (see Note 1). This test method has been safety concerns, if any, associated with its use. It is the
found suitable for such materials as commercial propylene responsibility of the user of this standard to establish appro-
trimer and tetramer, butene dimer, and mixed nonenes, octenes, priate safety and health practices and determine the applica-
and heptenes. This test method is not satisfactory for normal bility of regulatory limitations prior to use. For specific
alpha-olefins. warning statements, see Sections 7, 8, and 9.
NOTE 1—These limits are imposed since the precision of this test 2. Referenced Documents
method has been determined only up to or within the range of these
bromine numbers.
2.1 ASTM Standards:3
D 86 Test Method for Distillation of Petroleum Products at
1.2 The magnitude of the bromine number is an indication Atmospheric Pressure
of the quantity of bromine-reactive constituents, not an iden- D 1193 Specification for Reagent Water
tification of constituents; therefore, its application as a measure D 1492 Test Method for Bromine Index of Aromatic Hy-
of olefinic unsaturation should not be undertaken without the drocarbons by Coulometric Titration
study given in Annex A1. D 2710 Test Method for Bromine Index of Petroleum Hy-
drocarbons by Electrometric Titration
1
This test method is under the jurisdiction of ASTM Committee D02 on D 5776 Test Method for Bromine Index of Aromatic Hy-
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee drocarbons by Electrometric Titration
D02.04.0D on Physical and Chemical Methods.
In the IP, this test method is under the jurisdiction of the Standardization
Committee.
3
Current edition approved May 1, 2007. Published May 2007. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1951. Last previous edition approved in 2001 as D 1159–01. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
2
See Dubois, H. D., and Skoog, D. A., “Determination of Bromine Addition Standards volume information, refer to the standard’s Document Summary page on
Numbers,” Analytical Chemistry, Vol 20, 1948, pp. 624–627. the ASTM website.

*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.

1
 D 1159 – 07
3. Terminology where such specifications are available.4 Other grades may be
used, provided it is first ascertained that the reagent is of
3.1 Definitions of Terms Specific to This Standard:
sufficiently high purity to permit its use without lessening the
3.1.1 bromine number—the number of grams of bromine accuracy of the determination.
that will react with 100 g of the specimen under the conditions 7.2 Purity of Water— Unless otherwise indicated, refer-
of the test. ences to water shall be understood to mean reagent water as
defined by Type III of Specification D 1193.
4. Summary of Test Method 7.3 Acetic Acid, Glacial—(Warning—Poison, corrosive-
4.1 A known weight of the specimen dissolved in the combustible, may be fatal if swallowed. Causes severe burns,
selected solvent (see 8.1) maintained at 0 to 5°C (32 to 41°F) harmful if inhaled.)
is titrated with standard bromide-bromate solution. The end 7.4 Bromide-Bromate, Standard Solution (0.2500 M as
point is indicated by a sudden change in potential on an Br2)— Dissolve 51.0 g of potassium bromide (KBr) and 13.92
electrometric end point titration apparatus due to the presence g of potassium bromate (KBrO3) each dried at 105°C (220°F)
of free bromine. for 30 min in water and dilute to 1 L.
7.4.1 If the determinations of the bromine number of the
5. Significance and Use reference olefins specified in Section 8 using this solution do
not conform to the prescribed limits, or if for reasons of
5.1 The bromine number is useful as a measure of aliphatic uncertainties in the quality of primary reagents it is considered
unsaturation in petroleum samples. When used in conjunction desirable to determine the molarity of the solution, the solution
with the calculation procedure described in Annex A2, it can be shall be standardized and the determined molarity used in
used to estimate the percentage of olefins in petroleum distil- subsequent calculations. The standardization procedure shall
lates boiling up to approximately 315°C (600°F). be as follows:
5.2 The bromine number of commercial aliphatic monoole- 7.4.1.1 To standardize, place 50 mL of glacial acetic acid
fins provides supporting evidence of their purity and identity. and 1 mL of concentrated hydrochloric acid (Warning—
Poison corrosive. May be fatal if swallowed. Liquid and vapor
6. Apparatus causes severe burns. Harmful if inhaled; relative density 1.19.)
in a 500-mL iodine number flask. Chill the solution in a bath
6.1 Electrometric End Point Titration Apparatus—Any ap- for approximately 10 min and, with constant swirling of the
paratus designed to perform titrations to pre-set end points (see flask, add from a 10-mL calibrated buret, 5 6 0.01 mL of the
Note 2) may be used in conjunction with a high-resistance bromide-bromate standard solution at the rate of 1 or 2 drops
polarizing current supply capable of maintaining approxi- per second. Stopper the flask immediately, shake the contents,
mately 0.8 V across two platinum electrodes and with a place it again in the ice bath, and add 5 mL of Kl solution in
sensitivity such that a voltage change of approximately 50 mV the lip of the flask. After 5 min remove the flask from the ice
at these electrodes is sufficient to indicate the end point. Other bath and allow the Kl solution to flow into the flask by slowly
types of commercially available electronic titrimeters, includ- removing the stopper. Shake vigorously, add 100 mL of water
ing certain pH meters, have also been found suitable. in such a manner as to rinse the stopper, lip and walls of the
NOTE 2—Pre-set end point indicated with polarized electrodes provides flask, and titrate promptly with sodium thiosulfate (Na 2S2O3)
a detection technique similar to the dead stop technique specified in solution. Near the end of the titration, add 1 mL of starch
previous versions of this test method. indicator solution and titrate slowly to disappearance of the
blue color. Calculate the molarity of the bromide-bromate
6.2 Titration Vessel— A jacketed glass vessel approximately solution as follows:
120 mm high and 45 mm in internal diameter and of a form that
AM2
can be conveniently maintained at 0 to 5°C (32 to 41°F). M1 5 (1)
~5! ~2!
6.3 Stirrer—Any magnetic stirrer system.
6.4 Electrodes—A platinum wire electrode pair with each where:
wire approximately 12 mm long and 1 mm in diameter. The M 1 = molarity of the bromide-bromate solution, as Br2,
wires shall be located 5 mm apart and approximately 55 mm A = millilitres of Na2S2O3 solution required for titration
below the level of the titration solvent. Clean the electrode pair of the bromide-bromate solution, and,
at regular intervals with 65 % nitric acid and rinse with M 2 = molarity of Na2S2O 3 solution,
5 = millilitres of bromide—bromate solution, and
distilled water before use.
2 = number of electrons transferred during redox titra-
6.5 Buret—Any delivery system capable of measuring ti- tion of bromide-bromate solution.
trant in 0.05 mL or smaller graduations.

7. Reagents 4
Reagent Chemicals, American Chemical Society Specifications, American
7.1 Purity of Reagents—Reagent grade chemicals shall be Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
listed by the American Chemical Society, see Annual Standards for Laboratory
used in all tests. Unless otherwise indicated, it is intended that
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
all reagents shall conform to the specifications of the commit- and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
tee on Analytical Reagents of the American Chemical Society, MD.

2
 D 1159 – 07
Repeat the standardization until duplicate determinations do TABLE 1 Physical Properties of Purified Olefins
not differ from the mean by more than 60.002 M. Boiling Point, Density at
Index of
7.5 Methanol—(Warning—Flammable. Vapor harmful. Compound Refraction,
°C 20°C, g/mL
D Line at 20°C
Can be fatal or cause blindness if swallowed or inhaled. Cannot Cyclohexene 82.5 to 83.5 0.8100 1.4465
be made non-poisonous.) DiisobuteneA 101 to 102.5 0.7175 6 0.0015 1.4112
7.6 Potassium Iodide Solution (150 g/L)—Dissolve 150 g of A
Only the 2,4,4-trimethyl-1-pentene isomer.
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 (Na2S2O3·5H2O) in water 8.2 If the reagents and techniques are correct, values within
and add 0.1 g of sodium carbonate (Na2CO3) to stabilize the the following should be obtained:
Bromine
solution. Dilute to 1 L and mix thoroughly by shaking. Standard Number
Standardize by any accepted procedure that determines the Cyclohexene, purified (see 7.4.1, 9.3, and 8.1) 187 to 199 (see 9.5)
molarity with an error not greater than 60.0002. Restandardize Cyclohexene, 10 % solution 18 to 20
Diisobutene, purified (see 7.4.1, 8.3, and 8.1) 136 to 144 (see 9.5)
at intervals frequent enough to detect changes of 0.0005 in Diisobutene, 10 % solution 13 to 15
molarity.
7.8 Starch Indication Solution— Mix 5 g of soluble starch The reference olefins yielding the above results are charac-
with about 3 to 5 mL of water. If desired, add about 0.65 g terized by the properties shown in Table 1. The theoretical
salicylic acid as preservative. Add the slurry to 500 mL of bromine numbers of cyclohexene and diisobutene are 194.6
boiling water and continue boiling for 5 to 10 min. Allow to and 142.4, respectively.
cool, and decant the clear, supernatant liquid into glass bottles 8.3 Purified samples of cyclohexene and diisobutene can be
and seal well. Starch solutions (some preserved with salicylic prepared from cyclohexene and diisobutene,5 by the following
acid) are also commercially available and may be substituted. procedure:
7.9 Sulfuric Acid (1 + 5)—Carefully mix one volume of 8.3.1 Add 65 g of activated silica gel, 75 to 150 µm (100 to
concentrated sulfuric acid (H2SO4, rel dens 1.84) with five 200 mesh) manufactured to ensure minimum olefin polymer-
volumes of water. (Warning—Poison. Corrosive. Strong oxi- ization6 to a column approximately 16 mm in inside diameter
dizer. Contact with organic material can cause fire. Can be fatal and 760 mm in length, that has been tapered at the lower end
if swallowed.) and that contains a small plug of glass wool at the bottom.
7.10 Titration Solvent—Prepare 1 L of titration solvent by A100-mL buret, or any column that will give a height-to-
mixing the following volumes of materials: 714 mL of glacial diameter ratio of the silica gel of at least 30:1, will be suitable.
acetic acid, 134 mL of 1,1,1-trichloroethane (or dichlo- Tap the column during the adding of the gel to permit uniform
romethane), 134 mL of methanol, and 18 mL of H2SO 4(1 + 5). packing.
7.11 1,1,1-Trichloroethane—(Warning—Harmful if in- 8.3.2 To the column add 30 mL of the olefin to be purified.
haled. High concentrations can cause unconsciousness or When the olefin disappears into the gel, fill the column with
death. Contact may cause skin irritation and dermatitis.) methanol. Discard the first 10 mL of percolate and collect the
next 10 mL that is the purified olefin for test of the bromine
7.12 Dichloromethane—(Warning—The replacement of
number procedure. Determine and record the density and
1,1,1-trichloroethane, an ozone-depleting chemical, is neces-
refractive index of the purified samples at 20°C. Discard the
sary because its manufacture and import has been discontin-
remaining percolate. (Warning—If distillation of impure ole-
ued. Dichloromethane is temporarily being allowed as an
fins is needed as a pre-purification step, a few pellets of
alternative to 1,1,1-trichloroethane until a permanent replace-
potassium hydroxide should be placed in the distillation flask
ment can be identified and adopted by ASTM International. A
and at least 10 % residue should remain to minimize the
program to identify and evaluate candidate solvents is currently
hazards from decomposition of any peroxides that may be
underway in Subcommittee D02.04.)
present.)
NOTE 3—Commercially available reagents can be used in place of
laboratory preparations. 9. Procedure
9.1 Place 10 mL of 1,1,1-trichloroethane or dichlo-
8. Check Procedure
romethane in a 50-mL volumetric flask and, by means of a
8.1 In case of doubt in applying the procedure to actual pipet, introduce a test specimen as indicated in Table 2. Either
samples, the reagents and techniques can be checked by means
of determinations on freshly purified cyclohexene or di-
isobutene. (Warning—The user of this test method may 5
The sole source of supply of No. 13019 (cyclohexene) and No. P2125
choose to use either 1,1,1-trichloroethane or dichloromethane (diisobutene) known to the committee at this time is Eastman, Rochester, NY. If you
to the exclusion of the other solvent. The selected solvent is to are aware of alternative suppliers, please provide this information to ASTM
International Headquarters. Your comments will receive careful consideration at a
be used for all operations, that is, in the preparation of the meeting of the responsible technical committee,1 which you may attend.
titration solvent, for the dilution of samples, and as the titration 6
The sole source of supply of the apparatus known to the committee at this time
blank.) Proceed in accordance with Section 9, using a sample is Code 923, available from W.R. Grace and Company, Davison Chemical Division,
Baltimore, MD 21203. If you are aware of alternative suppliers, please provide this
of either 0.6 to 1 g freshly purified cyclohexene or diisobutene information to ASTM International Headquarters. Your comments will receive
(see Table 1) or 6 to 10 g of 10 mass percent solutions of these careful consideration at a meeting of the responsible technical committee,1 which
materials in 1,1,1-trichlorethane. (Warning—Flammable.) you may attend.

3
 D 1159 – 07
TABLE 2 Specimen Size 10. Calculation
Bromine Number Specimen Size, g 10.1 Calculate the bromine number as follows:
0 to 10 20 to 16
Over 10 to 20 10 to 8
~A 2 B! ~M1! ~15.98!
bromine number 5 W (2)
Over 20 to 50 5 to 4
Over 50 to 100 2 to 1.5
Over 100 to 150 1.0 to 0.8 where:
Over 150 to 200 0.8 to 0.6 A = millilitres of bromide-bromate solution required
for titration of the test aliquot,
B = millilitres of bromide-bromate solution required
for titration of the blank,
obtain the weight of specimen introduced by difference be- M1 = molarity of the bromide-bromate solution, as Br2,
tween the weight (to the nearest 1 mg) of the flask before and W = grams of test specimen in the aliquot, and
after addition of specimen or, if the density is known accu- 15.98 = factor for converting g of bromine per 100 g of
rately, calculate the weight from the measured volume. Fill the specimen and incorporating molecular weight of
flask to the mark with the selected solvent and mix well. bromine (as Br 2) and conversion of mL to L.
(Warning—Hydrocarbons, particularly those boiling below
205°C (400°F), are flammable.) 11. Precision and Bias 7
9.1.1 Frequently, the order of magnitude of the bromine 11.1 Precision—The precision of this test method as deter-
number of a specimen is unknown. In this case, a trial test is mined by the statistical examination of interlaboratory test
results is as follows:
recommended using a 2-g specimen in order to obtain the
11.1.1 Repeatability— The difference between successive
approximate magnitude of the bromine number. This explor-
results obtained by the same operator with the same apparatus
atory test shall be followed with another determination using
under constant operating conditions on identical test material
the appropriate specimen size as indicated in Table 2. would, in the long run, in the normal and correct operation of
9.1.2 The test specimen taken shall not exceed 20 mL and the test method, exceed the following values only in one case
the volume of bromide-bromate titrant used shall not exceed 10 in twenty.
mL and no separation of the reaction mixture into two phases Petroleum distillates:
shall occur during the titration. Difficulty may be experienced
90 % distillation point under 205°C r 5 0.11 ~X0.70! (3)
in dissolving specimen of the high boiling ranges in the
titration solvent; this can be prevented by the addition of a
90 % distillation point between 205 and 327°C r 5 0.11 ~X 0.67!
small quantity of toluene.
(4)
9.2 Cool the titration vessel to 0 to 5°C (32 to 41°F) and
where: X = sample mean.
maintain the contents at this temperature throughout the
Commercial olefins:
titration. Switch on the titrimeter, and allow the electrical
circuit to become stabilized. r 53 (5)

9.3 Introduce 110 mL of titration solvent into the vessel and 11.1.2 Reproducibility— The difference between two single
pipet in a 5-mL aliquot of the sample solution from the 50-mL and independent results obtained by different operators work-
volumetric flask. Switch on the stirrer and adjust to a rapid ing in different laboratories on identical test material would, in
stirring rate, but avoid any tendency for air bubbles to be drawn the long run, exceed the following values only in one case in
down to the solution. twenty:
Petroleum Distillates:
9.4 Set the end point potential. With each instrument, the
manufacturer’s instructions should be followed for end point 90 % distillation point under 205°C R 5 0.72 ~X0.70! (6)
setting and to achieve the sensitivity in the platinum electrode
circuit specified in 6.1. 90 % distillation point between 205 and 327°C R 5 0.78 ~X 0.67!
(7)
9.5 Depending on the titrator apparatus, add the bromide-
bromate solution manually or by microprocessor control in where: X = sample mean.
small increments from the buret. The endpoint of the titration Commercial olefins 8
is achieved when the potential reaches the pre-set value (see R 5 12 (8)
9.4) and persists for more than 30 s.
9.6 Blanks—Perform duplicate blank titrations of each 11.2 Bias—The procedure for measuring bromine number
batch of titration solvent. Do this by repeating 9.3 through 9.5 has no bias because the value of bromine number can be
for each blank determination, substituting 5 mL of the selected defined only in terms of a test method.
solvent (1,1,1-trichloroethane or dichloromethane) in place of
the sample solution. Less than 0.1 mL of bromide-bromate
7
solution should be required. If more than 0.1 mL is used, Supporting data (round robin data and statistical analysis for products having
90 % distillation points under 205°C) have been filed at ASTM International
discard the analysis, prepare fresh titration solvent and fresh Headquarters and may be obtained by requesting Research Report RR:D02-1290.
reagents and repeat the analysis. 8
Provisional value obtained from a limited amount of data.

4
 D 1159 – 07
NOTE 4—The precision of this test method was determined using 12. Keywords
1,1,1-trichloroethane as the sample dilution solvent and as a a component
of the titration solvent. It is not known whether the precision estimates are 12.1 aliphatic olefins; bromine number; electrometric titra-
applicable when using dichloromethane in place of 1,1,1-trichloroethane. tion; petroleum distillates

ANNEXES

(Mandatory Information)

A1. REPORTED BEHAVIOR OF COMPOUNDS BY THE ELECTROMETRIC BROMINE NUMBER METHOD

A1.1 Technically, the bromine number is the number of A1.3 The possibility of multiple reactions occurring con-
grams of bromine reacting with 100 g of the sample under currently and the variable behavior to certain materials in the
prescribed conditions. By this definition, bromine consumed by presence of bromine imposes an element of uncertainty in the
addition, substitution, oxidation, and reactions with sulfur, interpretation of results. A knowledge of the material being
nitrogen, and oxygen-containing compounds is included in the handled and its response to bromine greatly reduces the risk of
bromine number of the material. The use of the bromine misinterpretation.
number under determination in the estimation of olefinic
unsaturation depends on the fact that the addition reaction A1.4 Bromine number data have been obtained for a
proceeds rapidly and completely under most conditions. The variety of petroleum hydrocarbons and certain nonhydrocar-
addition of bromine proceeds readily at temperatures down to bons associated with petroleum, by the electrometer bromine
or below 0°C. Decreasing temperature of reaction, time of number procedure. These data, which were submitted by
contact, and concentration of free bromine tend to retard both cooperators, are presented in Table A1.1.
substitution and oxidation reactions. Other factors, such as
solvent medium, extent of agitation, and exposure to actinic
A1.5 It is intended that this information serve as a general
light, also influence the rate of the various reactions.
guide in the interpretation of bromine numbers on petroleum
A1.2 Experience has shown that no single set of test products. It is recognized that the bromine number data
conditions will direct the reaction of bromine in one manner to recorded in this table are of limited value owing to incomplete-
the exclusion of the others. For this reason, the conditions of ness; however, it is considered that their usefulness will be
bromine number tests are usually established on an empirical amplified as more bromine number data are contributed by
basis to give reasonable values with representative materials. cooperators.

5
 D 1159 – 07
TABLE A1.1 Reported Behavior of Compounds by the Electrometric Bromine Number Method

Bromine Number
Compound Purity, %A
Theory Found Deviation
Paraffins
Hexane 99.96B 0.0 0.0 0.0
2-Methylhexane 99.88 0.0 0.0 0.1
C
Heptane 0.0 0.1 + 0.1
Octane 99.94 0.0 0.0 0.0
2,2,4-Trimethylpentane 99.96 0.0 0.1 + 0.1
Straight Chain Olefins
1-Pentene 99.7 228.0 208 −20
trans-2-Pentene 99.91 228.0 235 +7
1-Hexene 99.80 189.9 181 −9
cis-2-Hexene 99.83 189.9 189 −1
trans-2-Hexene 99.87 189.9 189 −1
cis-3-Hexene 99.94 189.9 193 +3
trans-3-Hexene ... 189.9 191.4 + 1.5
1-Heptene 99.8 162.8 136 −27
trans-2-Heptene 99.85 162.8 163 0
trans-3-Heptene 99.80 162.8 163 0
1-Octene 99.7 142.4 132 −10
2-Octene ... 142.4 139 −3
trans-4-Octene 99.84 142.4 149 +7
1-Decene 99.89 114.1 111.4 − 2.7
1-Dodecene 99.9 95.1 82.9 − 12.2
1-Tridecene 99.8 87.7 81.4 −6 .3
1-Tetradecene 99.7 81.4 70.8 − 10.6
1-Pentadecene 99.8 76.0 62.9 − 13.1
1-Hexadecene 99.84 71.2 62.8 − 8.4
Branched Chain Olefins
2-Methyl-1-butene 99.90 228.0 231.8 + 3.8
2-Methyl-2-butene 99.94 228.0 235 7
2,3-Dimethyl-1-butene 99.86 189.9 194 +4
3,3-Dimethyl-1-butene 99.91 189.9 167 − 23
2-Ethyl-1-butene 99.90 189.9 198 +8
2,3-Dimethyl-2-butene 99.90 189.9 191 +1
2-Methyl-1-pentene 99.92 189.9 182 −8
3-Methyl-1-pentene 99.70 189.9 152 − 38
4-Methyl-1-pentene 99.82 189.9 176 − 14
2-Methyl-2-pentene 99.91 189.9 190 0
3-Methyl-cis-2-pentene 99.85 189.9 193.7 + 3.8
3-Methyl-trans-2-pentene 99.86 189.9 191 +1
4-Methyl-cis-2-pentene 99.92 189.9 190 0
4-Methyl-trans-2-pentene 99.75 189.9 190 0
2,3,3-Trimethyl-1-butene 99.94 162.8 161 −2
3-Methyl-2-Ethyl-1-butene 99.8 162.8 165.4 + 2.6
2,3-Dimethyl-1-pentene 99.80 162.8 158.5 − 4.3
2,4-Dimethyl-1-pentene 99.87 162.8 152.8 − 10.0
2,3-Dimethyl-2-pentene 99.6 162.8 162.3 − 0.5
4,4-Dimethyl-cis-2-pentene 99.79 162.8 159 −4
4,4-Dimethyl-trans-2-pentene 99.91 162.8 158 −5
3-Ethyl-1-pentene 99.85 162.8 173.1 + 10.3
3-Ethyl-2-pentene 99.80 162.8 165 +2
2-Methyl-1-hexene 99.88 162.8 161 −2
5-Methyl-1-hexene 99.80 162.8 154 −9
3-Methyl-cis-2-hexene 99.8 162.8 163.6 + 0.8
2-Methyl-trans-3-hexene 99.9 162.8 163.4 + 0.6
2-Methyl-3-Ethyl-1-pentene 99.81 142.4 139.8 − 2.6
2,4,4-Trimethyl-1-pentene 99.91 142.4 137.0 − 5.4
2,4,4-Trimethyl-2-pentene 99.92 142.4 141.2 − 1.2
D
Diisobutene 142.4 139.8D − 2.6
E
2-Ethyl-1-hexene 142.4 140.2 − 2.2
2,3-Dimethyl-2-hexene 99.71 142.4 143 +1
2,5-Dimethyl-2-hexene 99.8 142.4 142.8 + 0.4
2,2-Dimethyl-trans-3-hexene 99.80 142.4 139 −3
Triisobutene 99.0F 95 57.5 − 37.5
Nonconjugated Cyclic Diolefins
4-Ethenyl-1-cyclohexene (4-vinyl-1-cyclohexene) 99.90 295.5 210G (− 85)
di-1,8(9)-p-Menthadiene (dipentene) 98–100H 234.6 225.2 − 9.4
Conjugated Diolefins
2-Methyl-1,3-butadiene (isoprene) 99.96 470 235.7 − 234

6
 D 1159 – 07

TABLE A1.1 Continued

Bromine Number
Compound Purity, %A
Theory Found Deviation
cis-1,3-Pentadiene 99.92 470 285.3 − 185
trans-1,3-Pentadiene 99.92 470 234 − 236
2-Methyl-1,3-Pentadiene 95 + I 389 197.3 − 192
2,3-Dimethyl-1,3-Butadiene 99.93 389 186.1 − 203
Nonconjugated Diolefins
1,2-Pentadiene 99.66 470 230 − 240
1,4-Pentadiene 99.93 470 185 − 285
2,3-Pentadiene 99.85 470 227 − 243
1,5-Hexadiene 99.89 389 352 − 37
Aromatics with Unsaturated Side Chains
J
Phenylethylene (styrene) 153.4 123.6 − 29.8
J
Methylphenylethylene (a-methylstyrene) 135.3 133.2 − 2.1
K
Amylbenzene 97.8 135.2 0.0 135.2
Cyclic Olefins
Cyclopentene 99.97 234.6 237 +2
Cyclohexene 99.98 194.6 193.2 − 1.4
D
Cyclohexene 194.6 192.8D − 1.8
1-Methylcyclopentene 99.86 194.6 209 + 14
1-Methylcyclohexene 99.82 166 162 −4
Ethenylcyclopentane (Vinylcyclopentane) 99.91 166 164 −2
Ethylidenecyclopentane 99.96 166.2 167.7 + 1.5
1,2-Dimethylcyclohexene 99.94 145.0 150.9 + 5.9
3-Cyclopentyl-1-propene 99.87 145.0 140.9 − 4.1
Ethylidenecyclohexane 99.86 145.0 147.0 + 2.0
Ethenylcyclohexane (Vinylcyclohexane) 99.95 145 139 −6
1-Ethylcyclohexene 99.83 145 146.6 + 1.6
Indene ... 137.7 134 −4
Aromatics, Monocyclic
Benzene 99.98 0.0 0.1 + 0.1
Toluene 99.97 0.0 0.1 + 0.1
o-Xylene 99 + L 0.0 0.0 0.0
m-Xylene 99 + L 0.0 0.0 0.0
p-Xylene 99 + L 0.0 0.0 0.0
isoopropylbenzene (Cumene) 99.95 0.0 0.0 0.0
1,2,4-Trimethylbenzene (Pseudocumene) 99.67 0.0 0 0
M
1,3,5-Trimethylbenzene (Mesitylene) 0.0 0.3 + 0.3
1,3-Dimethyl-4-ethylbenzene 99.9 0.0 0.0 0.0
1,2,4,5-Tetramethylbenzene (Durene) 99.86 0.0 0.1 + 0.1
M
1,2,3,5-Tetramethylbenzene (Isodurene) 0.0 0.3 + 0.3
t-Butylbenzene 99.73B 0.0 0.0 0.0
F
t-Amylbenzene 0.0 0.7 + 0.7
Aromatics, Bicyclic
M
Phenylbenzene (Biphenyl) 0.0 0.0 0.0
Naphthalene 99.96 0.0 0 0
1, 2,3,4-Tetrahydronaphthalene (Tetralin) 99.9 0.0 0.2 + 0.2
1-Methylnaphthalene 99.78 0.0 0.0 0.0
2-Methylnaphthalene 99.91 0.0 0.0 0.0
2,3-Dihydroindene (Indan) 99.9 0.0 0.0 0.0
Cyclohexylbenzene 99.93 0.0 0 0
Aromatics, Polycyclic
M
Athracene 0.0 11.8 + 11.8
M
Phenanthrene 0.0 3.9 + 3.9
Cycloparaffins
Methylcyclopentane 99.99B 0.0 0.0 0.0
Methylcyclohexane 99.97 0.0 0 0
Isopropylcyclopentane 99.8 0.0 0.0 0.0
cis-Hexahydroindan (cis-Hydrindan) 99.94 0.0 0.0 0.0
trans-Hexahydroindan (trans-Hydrindan) 99.71 0.0 0.0 0.0
tert-Butylcyclohexane 99.95 0.0 0 0
Cyclopentylcyclopentane 99.95 0.0 0.0 0.0
cis-Decahydronaphthalene (cis-decalin) 98 + I 0.0 0.11 + 0.11
trans-Decahydronaphthalene (trans-decalin) 98 + I 0.0 1.64 + 1.64
Sulfur Compounds
Ehanethiol (ethyl mercaptan) 99.95 0.0 209 + 209

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 D 1159 – 07

TABLE A1.1 Continued

Bromine Number
Compound Purity, %A
Theory Found Deviation
3-Thiapentane (ethyl sulfide) 99.94 0.0 184 + 184
2,3-Dithiabutane (methyldisulfide) 99.97 0.0 1.1 + 1.1
Thiacyclobutane (trimethylene sulfide) 99.95 0.0 214 + 214
Thophene 99.99 0.0 0.4 + 0.4
Thiacyclopentane (tetrahydrothiophene) 99.95 0.0 183 + 183
3,4-Dithiahexane (diethyldisulfide) 99.90 0.0 0.4 + 0.4
2-Methyl 2-propanethiol (tert-butyl mercaptan) 99.92 0.0 141 + 141
1-Pentanethiol (amyl mercaptan) 99.92 0.0 83 + 83
Nitrogen Compounds
Broidine 99.85 0.0 11.8 + 11.8
N
iodine 0.0 1.4 + 1.4
2-Methylpyridine 99.90 0.0 0.9 + 0.9
4-Methylpyridine 99 + O 0.0 1.7 + 1.7
2.4,6-Trimethylpyridine 99 + O 0.0 2.7 + 2.7
M
2-(5-nonyl) pyridine 0.0 1.4 + 1.4
Pyrrole 99.99 0.0 873 + 873
2-Methylpyrrole 98 + N 0.0 708 + 708
2,4-Dimethylpyrrole 98 + N 0.0 484 + 484
2,5-Dimethylpyrrole 99.9P 0.0 869 + 869
2,4-Dimethyl-3-ethylpyrrole 98 + N 0.0 248 + 248
1-Butyl 1-(1) pyrrole 98 + N 0.0 472 + 472
Oxygen Compounds
Q
Acetone 0.0 0.0 0.0
R
Methylethylketone 0.0 0.0 0.0
Miscellaneous
M
Ethanolamine 0.0 1.5 +5
O
Ethylene dichloride 0.0 0.0 0.0
O
Ethylene dibromide 0.0 0.0 0.0
S
Tetraethyllead (TEL) (49.5)T 52.7 (+ 3.2)
S
Tetramethyllead (TML) (59.8)T 62.6 (+ 2.8)
S
AK 33X (73.4)T 0.6 (−72.8)
S
“Ethyl” orange dye ... 0.0 ...
A
API Standard Samples, unless otherwise noted.
B
Phillips research grade product.
C
Phillips pure grade product, distilled, heart-cut percolated through Si gel.
D
Average value obtained in September 1957 Cooperative Program on purified Eastman product.
E
Dow Research Chemical.
F
Purity not stated.
G
Approximate value.
H
Hercules Inc., experimental sample.
I
From Penn State University.
J
Eastman white label product, distilled, 50-mm pressure just prior to test.
K
M C and B chemical. Purity determined by GC, impurities not identified.
L
Phillips pure grade product.
M
Eastman white label product.
N
Samples supplied by API Project 52.
O
Purity estimated by spectra and GLC.
P
Purity estimated from freezing point.
Q
B and A Reagent chemical (Code No. 1004).
R
M C and B chemical (Code No. 2609).
S
Ethyl Corporation products.
T
Calculated values based on the reaction of one mole of bromine with the organometallic compound.

A2. CALCULATION OF OLEFIN CONTENT

A2.1 Scope and turbine fuel and kerosine etc., boiling below 315°C
A2.1.1 This procedure covers the calculation of the vol- (600°F) and having a bromine number of less than 20.
ume percentage of olefins from the bromine number in A2.1.2 The procedure is not intended for synthetic olefinic
straight-run, reformed, cracked gasolines and commercial blends of pure or nearly pure compounds having a boiling
gasolines that have a 90 % boiling point below 200°C (392°F); range of less than 14°C (25°F).

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 D 1159 – 07
TABLE A2.1 Boiling Range Corrections for Olefins
Boiling Range Boiling Range, °C (°F) Initial
Correction, * to End, (see Test Method D 86)
1.00 0 (0)
0.975 7 (13)
0.950 14 (25)
0.925 21 (38)
0.900 28 (50)
0.875 38 (68)
0.850 43 (78)
0.825 53 (95)
0.800 62 (112)
0.775 72 (130)
FIG. A2.1 Boiling Range Correction 0.750 95 (152)
0.725 99 (178)
A2.1.3 Sulfur, nitrogen, or oxygen compounds, if present in 0.700 125 or greater (225)

concentrations of 1 volume % or greater will reduce the

accuracy (see Note A2.1).
TABLE A2.2 Relation of Average Relative Molecular Mass
A2.2 Procedure (Molecular Weight) to 50 % Boiling Point by Test Method D 86
A2.2.1 Determine the bromine number in accordance with 50 % Boiling Point, Average Molecular
°C (°F) Weight of Olefins
this test method.
38 (100) 72
NOTE A2.1—For information on types of compounds that may yield 66 (150) 83
anomalous data in the bromine number test, see Annex A1. In the case of 93 (200) 96
special samples that contain high concentrations of certain hydrocarbon 121 (250) 110
149 (300) 127
types, caution in the interpretation of the bromine number is needed. 177 (350) 145
A2.2.2 Calculate the concentration of olefins from the 204 (400) 164
232 (450) 186
bromine number as follows:
olefins, mass % 5 * BM/160 (A2.1)

where:
* = boiling range correction (see Fig. A2.1 and Table
A2.1),
B = bromine number expressed as grams of bromine/100
g of sample, and
M = molecular weight (relative molecular mass) of olefins
(see Table A2.2).

NOTE A2.2—The boiling range correction is needed for cracked naph- FIG. A2.2 Relation of Density to the 50 % Boiling Point
thas since it is an empirical fact that the percentage by volume of olefins
is higher in the lower boiling fractions and that these olefins are also of
lower relative molecular mass (molecular weight).
A2.3.1.1 Repeatability—The difference between successive
A2.2.3 Using the 50 % boiling point (see Test Method
test results obtained by the same operator with the same
D 86), estimate the average density of the olefins using Fig.
apparatus under constant operating conditions on identical test
A2.2. Multiply the mass percentage of olefins (as calculated in
material would, in the long run, in the normal and correct
A2.2.2) by the ratio of the density of the original sample to the
density of the olefins to obtain percentage by volume as operation of the test method, exceed the following values only
follows: in one case in twenty:
Straight-Run Fuels Cracked Gasolines
olefins, volume % 5 ~A/B! 3 C (A2.2) (less than 1 volume % olefins) (1 to 25 volume % olefins)
0.2 0.6
where:
A = density of the sample, A2.3.1.2 Reproducibility— The difference between two
B = average density of the olefins, and single and independent results, obtained by different operators,
C = mass percentage of olefins. working in different laboratories on identical test material
A2.3 Precision9 would, in the long run, in the normal and correct operation of
the test method, exceed the following values only in one case
A2.3.1 The precision of this test method as obtained by
in twenty:
statistical examination of interlaboratory test results is as
Straight-Run Fuels Cracked Gasolines
follows: (less than 1 volume % olefins) (1 to 25 volume % olefins)
0.4 3
9
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR: D02–0036.

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 D 1159 – 07
A2.3.2 Bias—The procedure for calculating olefin content NOTE A2.3—The precision for this test method was not obtained in
has no bias because the value obtained can be defined only in accordance with RR: D02-1007.
terms of a procedure.

SUMMARY OF CHANGES

Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D 1159–01) that may impact the use of this standard.

(1) Revised 9.1.2 to change the maximum volume of the test

specimen from 10 to 20 mL.

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10