ASTM D1159-07(2017)
(Test Method)Standard Test Method for Bromine Numbers of Petroleum Distillates and Commercial Aliphatic Olefins by Electrometric Titration
Standard Test Method for Bromine Numbers of Petroleum Distillates and Commercial Aliphatic Olefins by Electrometric Titration
SIGNIFICANCE AND USE
5.1 The bromine number is useful as a measure of aliphatic unsaturation in petroleum samples. When used in conjunction with the calculation procedure described in Annex A2, it can be used to estimate the percentage of olefins in petroleum distillates boiling up to approximately 315 °C (600 °F).
5.2 The bromine number of commercial aliphatic monoolefins provides supporting evidence of their purity and identity.
SCOPE
1.1 This test method2 covers the determination of the bromine number of the following materials:
1.1.1 Petroleum distillates that are substantially free of material lighter than isobutane and that have 90 % distillation points (by Test Method D86) under 327 °C (626 °F). This test method is generally applicable to gasoline (including leaded, unleaded, and oxygenated fuels), kerosine, and distillates in the gas oil range that fall in the following limits:
90 % Distillation Point, °C (°F)
Bromine Number, max2
Under 205 (400)
175
205 to 327 (400 to 626)
10
1.1.2 Commercial olefins that are essentially mixtures of aliphatic mono-olefins and that fall within the range of 95 to 165 bromine number (see Note 1). This test method has been found suitable for such materials as commercial propylene trimer and tetramer, butene dimer, and mixed nonenes, octenes, and heptenes. This test method is not satisfactory for normal alpha-olefins.
Note 1: These limits are imposed since the precision of this test method has been determined only up to or within the range of these bromine numbers.
1.2 The magnitude of the bromine number is an indication of the quantity of bromine-reactive constituents, not an identification of constituents; therefore, its application as a measure of olefinic unsaturation should not be undertaken without the study given in Annex A1.
1.3 For petroleum hydrocarbon mixtures of bromine number less than 1.0, a more precise measure for bromine-reactive constituents can be obtained by using Test Method D2710. If the bromine number is less than 0.5, then Test Method D2710 or the comparable bromine index methods for industrial aromatic hydrocarbons, Test Methods D1492 or D5776 must be used in accordance with their respective scopes. The practice of using a factor of 1000 to convert bromine number to bromine index is not applicable for these lower values of bromine number.
1.4 The values stated in SI units are to be regarded as the standard.
1.4.1 Exception—The values given in parentheses are for information only.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific warning statements, see Sections 7, 8, and 9.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
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This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation:D1159 −07 (Reapproved 2017)
Designation: 130/98
Standard Test Method for
Bromine Numbers of Petroleum Distillates and Commercial
Aliphatic Olefins by Electrometric Titration
This standard is issued under the fixed designation D1159; 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 U.S. Department of Defense.
1. Scope constituents can be obtained by using Test Method D2710.If
2 the bromine number is less than 0.5, then Test Method D2710
1.1 This test method covers the determination of the
or the comparable bromine index methods for industrial
bromine number of the following materials:
aromatic hydrocarbons, Test Methods D1492 or D5776 must
1.1.1 Petroleum distillates that are substantially free of
be used in accordance with their respective scopes. The
material lighter than isobutane and that have 90 % distillation
practice of using a factor of 1000 to convert bromine number
points (by Test Method D86) under 327 °C (626 °F). This test
to bromine index is not applicable for these lower values of
method is generally applicable to gasoline (including leaded,
bromine number.
unleaded,andoxygenatedfuels),kerosine,anddistillatesinthe
gas oil range that fall in the following limits: 1.4 The values stated in SI units are to be regarded as the
standard.
90 % Distillation Point, °C (°F) Bromine Number, max
Under 205 (400) 175
1.4.1 Exception—The values given in parentheses are for
205 to 327 (400 to 626) 10
information only.
1.1.2 Commercial olefins that are essentially mixtures of
1.5 This standard does not purport to address all of the
aliphatic mono-olefins and that fall within the range of 95 to
safety concerns, if any, associated with its use. It is the
165 bromine number (see Note 1). This test method has been
responsibility of the user of this standard to establish appro-
found suitable for such materials as commercial propylene
priate safety and health practices and determine the applica-
trimerandtetramer,butenedimer,andmixednonenes,octenes,
bility of regulatory limitations prior to use. For specific
and heptenes. This test method is not satisfactory for normal
warning statements, see Sections 7, 8, and 9.
alpha-olefins.
1.6 This international standard was developed in accor-
NOTE 1—These limits are imposed since the precision of this test dance with internationally recognized principles on standard-
method has been determined only up to or within the range of these
ization established in the Decision on Principles for the
bromine numbers.
Development of International Standards, Guides and Recom-
1.2 The magnitude of the bromine number is an indication mendations issued by the World Trade Organization Technical
of the quantity of bromine-reactive constituents, not an iden-
Barriers to Trade (TBT) Committee.
tification of constituents; therefore, its application as a measure
2. Referenced Documents
of olefinic unsaturation should not be undertaken without the
study given in Annex A1.
2.1 ASTM Standards:
D86 Test Method for Distillation of Petroleum Products and
1.3 For petroleum hydrocarbon mixtures of bromine num-
Liquid Fuels at Atmospheric Pressure
ber less than 1.0, a more precise measure for bromine-reactive
D1193 Specification for Reagent Water
D1492 Test Method for Bromine Index of Aromatic Hydro-
This test method is under the jurisdiction of ASTM Committee D02 on carbons by Coulometric Titration
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
D2710 Test Method for Bromine Index of Petroleum Hydro-
Subcommittee D02.06 on Analysis of Liquid Fuels and Lubricants.
carbons by Electrometric Titration
In the IP, this test method is under the jurisdiction of the Standardization
Committee.
CurrenteditionapprovedMay1,2017.PublishedJuly2017.Originallyapproved
in 1951. Last previous edition approved in 2012 as D1159 – 07 (2012). DOI: For referenced ASTM standards, visit the ASTM website, www.astm.org, or
10.1520/D1159-07R17. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
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.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D1159−07 (2017)
D5776 Test Method for Bromine Index of Aromatic Hydro- all reagents shall conform to the specifications of the commit-
carbons by Electrometric Titration tee onAnalytical Reagents of theAmerican Chemical Society,
where such specifications are available. Other grades may be
3. Terminology
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
3.1 Definitions of Terms Specific to This Standard:
accuracy of the determination.
3.1.1 bromine number—the number of grams of bromine
that will react with 100 g of the specimen under the conditions
7.2 Purity of Water—Unless otherwise indicated, references
of the test.
to water shall be understood to mean reagent water as defined
by Type III of Specification D1193.
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 °C to 5 °C (32 °F to
harmful if inhaled.)
41 °F) is titrated with standard bromide-bromate solution. The
7.4 Bromide-Bromate, Standard Solution(0.2500 M as
end point is indicated by a sudden change in potential on an
Br )—Dissolve51.0 gofpotassiumbromide(KBr)and13.92 g
electrometric end point titration apparatus due to the presence
of potassium bromate (KBrO ) 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
5.1 The bromine number is useful as a measure of aliphatic
not conform to the prescribed limits, or if for reasons of
unsaturation in petroleum samples. When used in conjunction
uncertainties in the quality of primary reagents it is considered
withthecalculationproceduredescribedinAnnexA2,itcanbe
desirable to determine the molarity of the solution, the solution
used to estimate the percentage of olefins in petroleum distil-
shall be standardized and the determined molarity used in
lates boiling up to approximately 315 °C (600 °F).
subsequent calculations. The standardization procedure shall
5.2 The bromine number of commercial aliphatic monoole- be as follows:
fins provides supporting evidence of their purity and identity.
7.4.1.1 To standardize, place 50 mL of glacial acetic acid
and 1 mL of concentrated hydrochloric acid (Warning—
6. Apparatus
Poison corrosive. May be fatal if swallowed. Liquid and vapor
causes severe burns. Harmful if inhaled; relative density 1.19.)
6.1 Electrometric End Point Titration Apparatus—Any ap-
in a 500 mL iodine number flask. Chill the solution in a bath
paratus designed to perform titrations to pre-set end points (see
for approximately 10 min and, with constant swirling of the
Note 2) may be used in conjunction with a high-resistance
flask, add from a 10 mL calibrated buret, 5 mL 6 0.01 mL of
polarizing current supply capable of maintaining approxi-
the bromide-bromate standard solution at the rate of 1 or 2
mately 0.8 V across two platinum electrodes and with a
drops per second. Stopper the flask immediately, shake the
sensitivity such that a voltage change of approximately 50 mV
contents, place it again in the ice bath, and add 5 mL of Kl
at these electrodes is sufficient to indicate the end point. Other
solution in the lip of the flask. After 5 min remove the flask
types of commercially available electronic titrimeters, includ-
from the ice bath and allow the Kl solution to flow into the
ing certain pH meters, have also been found suitable.
flask by slowly removing the stopper. Shake vigorously, add
NOTE 2—Pre-set end point indicated with polarized electrodes provides
100 mL of water in such a manner as to rinse the stopper, lip
a detection technique similar to the dead stop technique specified in
and walls of the flask, and titrate promptly with sodium
previous versions of this test method.
thiosulfate (Na S O ) solution. Near the end of the titration,
2 2 3
6.2 Titration Vessel—Ajacketed glass vessel approximately
add 1 mL of starch indicator solution and titrate slowly to
120 mm high and 45 mm in internal diameter and of a form
disappearance of the blue color. Calculate the molarity of the
that can be conveniently maintained at 0 °C to 5 °C (32 °F to
bromide-bromate solution as follows:
41 °F).
AM
6.3 Stirrer—Any magnetic stirrer system. M 5 (1)
5 2
~ !~ !
6.4 Electrodes—A platinum wire electrode pair with each
where:
wire approximately 12 mm long and 1 mm in diameter. The
M = molarity of the bromide-bromate solution, as Br ,
wires shall be located 5 mm apart and approximately 55 mm 1 2
A = millilitres of Na S O solution required for titration of
2 2 3
below the level of the titration solvent. Clean the electrode pair
the bromide-bromate solution, and,
at regular intervals with 65 % nitric acid and rinse with
M = molarity of Na S O solution,
2 2 2 3
distilled water before use.
6.5 Buret—Any delivery system capable of measuring
titrant in 0.05 mL or smaller graduations. 4
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
7. Reagents listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
7.1 Purity of Reagents—Reagent grade chemicals shall be
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
used in all tests. Unless otherwise indicated, it is intended that MD.
D1159−07 (2017)
TABLE 1 Physical Properties of Purified Olefins
5 = millilitres of bromide—bromate solution, and
Index of
2 = number of electrons transferred during redox titration
Boiling Point, Density at
Compound Refraction,
of bromide-bromate solution. °C 20 °C, g/mL
D Line at 20°C
Cyclohexene 82.5 to 83.5 0.8100 1.4465
Repeat the standardization until duplicate determinations do
A
Diisobutene 101 to 102.5 0.7175 ± 0.0015 1.4112
not differ from the mean by more than 60.002 M.
A
Only the 2,4,4-trimethyl-1-pentene isomer.
7.5 Methanol—(Warning—Flammable. Vapor harmful.
Canbefatalorcauseblindnessifswallowedorinhaled.Cannot
be made non-poisonous.)
choose to use either 1,1,1-trichloroethane or dichloromethane
to the exclusion of the other solvent. The selected solvent is to
7.6 Potassium Iodide Solution (150 g⁄L)—Dissolve 150 g
be used for all operations, that is, in the preparation of the
of potassium iodide (Kl) in water and dilute to 1 L.
titration solvent, for the dilution of samples, and as the titration
7.7 Sodium Thiosulfate, Standard Solution (0.1 M)—
blank.) Proceed in accordance with Section 9, using a sample
Dissolve 25 g of sodium thiosulfate (Na S O ·5H O) in water
2 2 3 2
of either 0.6 g to 1 g freshly purified cyclohexene or di-
and add 0.1 g of sodium carbonate (Na CO ) to stabilize the
2 3
isobutene (see Table 1) or 6 g to 10 g of 10 mass percent
solution. Dilute to 1 L and mix thoroughly by shaking. Stan-
solutions of these materials in 1,1,1-trichlorethane.
dardizebyanyacceptedprocedurethatdeterminesthemolarity
(Warning—Flammable.)
with an error not greater than 60.0002. Restandardize at
8.2 If the reagents and techniques are correct, values within
intervals frequent enough to detect changes of 0.0005 in
the following should be obtained:
molarity.
Bromine
7.8 Starch Indication Solution — Mix 5 g of soluble starch
Standard Number
with about 3 mLto 5 mLof water. If desired, add about 0.65 g
Cyclohexene, purified (see 7.4.1, 9.3, and 8.1) 187 to 199 (see 9.5)
Cyclohexene, 10 % solution 18 to 20
salicylic acid as preservative. Add the slurry to 500 mL of
Diisobutene, purified (see 7.4.1, 8.3, and 8.1) 136 to 144 (see 9.5)
boiling water and continue boiling for 5 min to 10 min. Allow
Diisobutene, 10 % solution 13 to 15
to cool, and decant the clear, supernatant liquid into glass
The reference olefins yielding the above results are charac-
bottles and seal well. Starch solutions (some preserved with
terized by the properties shown in Table 1. The theoretical
salicylic acid) are also commercially available and may be
bromine numbers of cyclohexene and diisobutene are 194.6
substituted.
and 142.4, respectively.
7.9 Sulfuric Acid (1+5)—Carefully mix one volume of
8.3 Purified samples of cyclohexene and diisobutene can be
concentrated sulfuric acid (H SO , rel dens 1.84) with five
2 4 5
prepared from cyclohexene and diisobutene, by the following
volumes of water. (Warning—Poison. Corrosive. Strong oxi-
procedure:
dizer.Contactwithorganicmaterialcancausefire.Canbefatal
8.3.1 Add 65 g of activated silica gel, 75 to 150 µm (100 to
if swallowed.)
200 mesh) manufactured to ensure minimum olefin polymer-
7.10 Titration Solvent—Prepare 1 L of titration solvent by
ization to a column approximately 16 mm in inside diameter
mixing the following volumes of materials: 714 mL of glacial
and 760 mm in length, that has been tapered at the lower end
acetic acid, 134 mL of 1,1,1-trichloroethane (or
and that contains a small plug of glass wool at the bottom. A
dichloromethane), 134 mL of methanol, and 18 mL of
100 mL buret, or any column that will give a height-to-
H SO (1 + 5).
2 4 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 uniform
7.11 1,1,1-Trichloroethane—(Warning—Harmful if in-
packing.
haled. High concentrations can cause unconsciousness or
8.3.2 To the column add 30 mL of the olefin to be purified.
death. Contact may cause skin irritation and dermatitis.)
When the olefin disappears into the gel, fill the column with
7.12 Dichloromethane—(Warning—The replacement of
methanol. Discard the first 10 mL of percolate and collect the
1,1,1-trichloroethane, an ozone-depleting chemical, is neces-
next 10 mL that is the purified olefin for test of
...
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D1159 − 07 (Reapproved 2017)
Designation: 130/98
Standard Test Method for
Bromine Numbers of Petroleum Distillates and Commercial
Aliphatic Olefins by Electrometric Titration
This standard is issued under the fixed designation D1159; 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 U.S. Department of Defense.
1. Scope constituents can be obtained by using Test Method D2710. If
2 the bromine number is less than 0.5, then Test Method D2710
1.1 This test method covers the determination of the
or the comparable bromine index methods for industrial
bromine number of the following materials:
aromatic hydrocarbons, Test Methods D1492 or D5776 must
1.1.1 Petroleum distillates that are substantially free of
be used in accordance with their respective scopes. The
material lighter than isobutane and that have 90 % distillation
practice of using a factor of 1000 to convert bromine number
points (by Test Method D86) under 327 °C (626 °F). This test
to bromine index is not applicable for these lower values of
method is generally applicable to gasoline (including leaded,
bromine number.
unleaded, and oxygenated fuels), kerosine, and distillates in the
gas oil range that fall in the following limits: 1.4 The values stated in SI units are to be regarded as the
standard.
90 % Distillation Point, °C (°F) Bromine Number, max
Under 205 (400) 175
1.4.1 Exception—The values given in parentheses are for
205 to 327 (400 to 626) 10
information only.
1.1.2 Commercial olefins that are essentially mixtures of
1.5 This standard does not purport to address all of the
aliphatic mono-olefins and that fall within the range of 95 to
safety concerns, if any, associated with its use. It is the
165 bromine number (see Note 1). This test method has been
responsibility of the user of this standard to establish appro-
found suitable for such materials as commercial propylene
priate safety and health practices and determine the applica-
trimer and tetramer, butene dimer, and mixed nonenes, octenes,
bility of regulatory limitations prior to use. For specific
and heptenes. This test method is not satisfactory for normal
warning statements, see Sections 7, 8, and 9.
alpha-olefins.
1.6 This international standard was developed in accor-
dance with internationally recognized principles on standard-
NOTE 1—These limits are imposed since the precision of this test
method has been determined only up to or within the range of these
ization established in the Decision on Principles for the
bromine numbers.
Development of International Standards, Guides and Recom-
1.2 The magnitude of the bromine number is an indication
mendations issued by the World Trade Organization Technical
of the quantity of bromine-reactive constituents, not an iden- Barriers to Trade (TBT) Committee.
tification of constituents; therefore, its application as a measure
2. Referenced Documents
of olefinic unsaturation should not be undertaken without the
study given in Annex A1.
2.1 ASTM Standards:
D86 Test Method for Distillation of Petroleum Products and
1.3 For petroleum hydrocarbon mixtures of bromine num-
Liquid Fuels at Atmospheric Pressure
ber less than 1.0, a more precise measure for bromine-reactive
D1193 Specification for Reagent Water
D1492 Test Method for Bromine Index of Aromatic Hydro-
carbons by Coulometric Titration
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
D2710 Test Method for Bromine Index of Petroleum Hydro-
Subcommittee D02.06 on Analysis of Liquid Fuels and Lubricants.
carbons by Electrometric Titration
In the IP, this test method is under the jurisdiction of the Standardization
Committee.
Current edition approved May 1, 2017. Published July 2017. Originally approved
in 1951. Last previous edition approved in 2012 as D1159 – 07 (2012). DOI: For referenced ASTM standards, visit the ASTM website, www.astm.org, or
10.1520/D1159-07R17. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
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.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D1159 − 07 (2017)
D5776 Test Method for Bromine Index of Aromatic Hydro- all reagents shall conform to the specifications of the commit-
carbons by Electrometric Titration tee on Analytical Reagents of the American Chemical Society,
where such specifications are available. Other grades may be
3. Terminology
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
3.1 Definitions of Terms Specific to This Standard:
accuracy of the determination.
3.1.1 bromine number—the number of grams of bromine
that will react with 100 g of the specimen under the conditions
7.2 Purity of Water—Unless otherwise indicated, references
of the test.
to water shall be understood to mean reagent water as defined
by Type III of Specification D1193.
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 °C to 5 °C (32 °F to
harmful if inhaled.)
41 °F) is titrated with standard bromide-bromate solution. The
7.4 Bromide-Bromate, Standard Solution(0.2500 M as
end point is indicated by a sudden change in potential on an
Br )—Dissolve 51.0 g of potassium bromide (KBr) and 13.92 g
electrometric end point titration apparatus due to the presence
of potassium bromate (KBrO ) 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
5.1 The bromine number is useful as a measure of aliphatic
not conform to the prescribed limits, or if for reasons of
unsaturation in petroleum samples. When used in conjunction
uncertainties in the quality of primary reagents it is considered
with the calculation procedure described in Annex A2, it can be
desirable to determine the molarity of the solution, the solution
used to estimate the percentage of olefins in petroleum distil-
shall be standardized and the determined molarity used in
lates boiling up to approximately 315 °C (600 °F).
subsequent calculations. The standardization procedure shall
5.2 The bromine number of commercial aliphatic monoole-
be as follows:
fins provides supporting evidence of their purity and identity. 7.4.1.1 To standardize, place 50 mL of glacial acetic acid
and 1 mL of concentrated hydrochloric acid (Warning—
6. Apparatus
Poison corrosive. May be fatal if swallowed. Liquid and vapor
causes severe burns. Harmful if inhaled; relative density 1.19.)
6.1 Electrometric End Point Titration Apparatus—Any ap-
in a 500 mL iodine number flask. Chill the solution in a bath
paratus designed to perform titrations to pre-set end points (see
for approximately 10 min and, with constant swirling of the
Note 2) may be used in conjunction with a high-resistance
flask, add from a 10 mL calibrated buret, 5 mL 6 0.01 mL of
polarizing current supply capable of maintaining approxi-
the bromide-bromate standard solution at the rate of 1 or 2
mately 0.8 V across two platinum electrodes and with a
drops per second. Stopper the flask immediately, shake the
sensitivity such that a voltage change of approximately 50 mV
contents, place it again in the ice bath, and add 5 mL of Kl
at these electrodes is sufficient to indicate the end point. Other
solution in the lip of the flask. After 5 min remove the flask
types of commercially available electronic titrimeters, includ-
from the ice bath and allow the Kl solution to flow into the
ing certain pH meters, have also been found suitable.
flask by slowly removing the stopper. Shake vigorously, add
NOTE 2—Pre-set end point indicated with polarized electrodes provides
100 mL of water in such a manner as to rinse the stopper, lip
a detection technique similar to the dead stop technique specified in
and walls of the flask, and titrate promptly with sodium
previous versions of this test method.
thiosulfate (Na S O ) solution. Near the end of the titration,
2 2 3
6.2 Titration Vessel—A jacketed glass vessel approximately
add 1 mL of starch indicator solution and titrate slowly to
120 mm high and 45 mm in internal diameter and of a form
disappearance of the blue color. Calculate the molarity of the
that can be conveniently maintained at 0 °C to 5 °C (32 °F to
bromide-bromate solution as follows:
41 °F).
AM
6.3 Stirrer—Any magnetic stirrer system.
M 5 (1)
~5! ~2!
6.4 Electrodes—A platinum wire electrode pair with each
where:
wire approximately 12 mm long and 1 mm in diameter. The
M = molarity of the bromide-bromate solution, as Br ,
1 2
wires shall be located 5 mm apart and approximately 55 mm
A = millilitres of Na S O solution required for titration of
2 2 3
below the level of the titration solvent. Clean the electrode pair
the bromide-bromate solution, and,
at regular intervals with 65 % nitric acid and rinse with
M = molarity of Na S O solution,
2 2 2 3
distilled water before use.
6.5 Buret—Any delivery system capable of measuring
titrant in 0.05 mL or smaller graduations.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
7. Reagents listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
7.1 Purity of Reagents—Reagent grade chemicals shall be
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
used in all tests. Unless otherwise indicated, it is intended that MD.
D1159 − 07 (2017)
TABLE 1 Physical Properties of Purified Olefins
5 = millilitres of bromide—bromate solution, and
Index of
2 = number of electrons transferred during redox titration
Boiling Point, Density at
Compound Refraction,
of bromide-bromate solution. °C 20 °C, g/mL
D Line at 20°C
Cyclohexene 82.5 to 83.5 0.8100 1.4465
Repeat the standardization until duplicate determinations do
A
Diisobutene 101 to 102.5 0.7175 ± 0.0015 1.4112
not differ from the mean by more than 60.002 M.
A
Only the 2,4,4-trimethyl-1-pentene isomer.
7.5 Methanol—(Warning—Flammable. Vapor harmful.
Can be fatal or cause blindness if swallowed or inhaled. Cannot
be made non-poisonous.)
choose to use either 1,1,1-trichloroethane or dichloromethane
to the exclusion of the other solvent. The selected solvent is to
7.6 Potassium Iodide Solution (150 g ⁄L)—Dissolve 150 g
be used for all operations, that is, in the preparation of the
of potassium iodide (Kl) in water and dilute to 1 L.
titration solvent, for the dilution of samples, and as the titration
7.7 Sodium Thiosulfate, Standard Solution (0.1 M)—
blank.) Proceed in accordance with Section 9, using a sample
Dissolve 25 g of sodium thiosulfate (Na S O ·5H O) in water
2 2 3 2
of either 0.6 g to 1 g freshly purified cyclohexene or di-
and add 0.1 g of sodium carbonate (Na CO ) to stabilize the
2 3
isobutene (see Table 1) or 6 g to 10 g of 10 mass percent
solution. Dilute to 1 L and mix thoroughly by shaking. Stan-
solutions of these materials in 1,1,1-trichlorethane.
dardize by any accepted procedure that determines the molarity
(Warning—Flammable.)
with an error not greater than 60.0002. Restandardize at
8.2 If the reagents and techniques are correct, values within
intervals frequent enough to detect changes of 0.0005 in
the following should be obtained:
molarity.
Bromine
7.8 Starch Indication Solution — Mix 5 g of soluble starch
Standard Number
with about 3 mL to 5 mL of water. If desired, add about 0.65 g
Cyclohexene, purified (see 7.4.1, 9.3, and 8.1) 187 to 199 (see 9.5)
Cyclohexene, 10 % solution 18 to 20
salicylic acid as preservative. Add the slurry to 500 mL of
Diisobutene, purified (see 7.4.1, 8.3, and 8.1) 136 to 144 (see 9.5)
boiling water and continue boiling for 5 min to 10 min. Allow
Diisobutene, 10 % solution 13 to 15
to cool, and decant the clear, supernatant liquid into glass
The reference olefins yielding the above results are charac-
bottles and seal well. Starch solutions (some preserved with
terized by the properties shown in Table 1. The theoretical
salicylic acid) are also commercially available and may be
bromine numbers of cyclohexene and diisobutene are 194.6
substituted.
and 142.4, respectively.
7.9 Sulfuric Acid (1 + 5)—Carefully mix one volume of
8.3 Purified samples of cyclohexene and diisobutene can be
concentrated sulfuric acid (H SO , rel dens 1.84) with five
2 4
prepared from cyclohexene and diisobutene, by the following
volumes of water. (Warning—Poison. Corrosive. Strong oxi-
procedure:
dizer. Contact with organic material can cause fire. Can be fatal
8.3.1 Add 65 g of activated silica gel, 75 to 150 µm (100 to
if swallowed.)
200 mesh) manufactured to ensure minimum olefin polymer-
7.10 Titration Solvent—Prepare 1 L of titration solvent by
ization to a column approximately 16 mm in inside diameter
mixing the following volumes of materials: 714 mL of glacial
and 760 mm in length, that has been tapered at the lower end
acetic acid, 134 mL of 1,1,1-trichloroethane (or
and that contains a small plug of glass wool at the bottom. A
dichloromethane), 134 mL of methanol, and 18 mL of
100 mL buret, or any column that will give a height-to-
H SO (1 + 5).
diameter ratio of the silica gel of at least 30:1, will be suitable.
2 4
Tap the column during the adding of the gel to permit uniform
7.11 1,1,1-Trichloroethane—(Warning—Harmful if in-
packing.
haled. High concentrations can cause unconsciousness or
8.3.2 To the column add 30 mL of the olefin to be purified.
death. Contact may cause skin irritation and dermatitis.)
When the olefin disappears into the gel, fill the column with
7.12 Dichloromethane—(Warning—The replacement of
methanol. Discard the first 10 mL of percolate and collect the
1,1,1-trichloroethane, an ozone-depleting chemical, is neces-
next 10 mL that is the purified olefin for test of the bromine
sary because
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D1159 − 07 (Reapproved 2012) D1159 − 07 (Reapproved 2017)
Designation: 130/98
Standard Test Method for
Bromine Numbers of Petroleum Distillates and Commercial
Aliphatic Olefins by Electrometric Titration
This standard is issued under the fixed designation D1159; 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 U.S. Department of Defense.
1. Scope*Scope
1.1 This test method covers the determination of the bromine number of the following materials:
1.1.1 Petroleum distillates that are substantially free of material lighter than isobutane and that have 90 % distillation points (by
Test Method D86) under 327°C (626°F).327 °C (626 °F). This test method is generally applicable to gasoline (including leaded,
unleaded, and oxygenated fuels), kerosine, and distillates in the gas oil range that fall in the following limits:
90 % Distillation Point, °C (°F) Bromine Number, max
Under 205 (400) 175
205 to 327 (400 to 626) 10
1.1.2 Commercial olefins that are essentially mixtures of aliphatic mono-olefins and that fall within the range of 95 to 165
bromine number (see Note 1). This test method has been found suitable for such materials as commercial propylene trimer and
tetramer, butene dimer, and mixed nonenes, octenes, and heptenes. This test method is not satisfactory for normal alpha-olefins.
NOTE 1—These limits are imposed since the precision of this test method has been determined only up to or within the range of these bromine numbers.
1.2 The magnitude of the bromine number is an indication of the quantity of bromine-reactive constituents, not an identification
of constituents; therefore, its application as a measure of olefinic unsaturation should not be undertaken without the study given
in Annex A1.
1.3 For petroleum hydrocarbon mixtures of bromine number less than 1.0, a more precise measure for bromine-reactive
constituents can be obtained by using Test Method D2710. If the bromine number is less than 0.5, then Test Method D2710 or the
comparable bromine index methods for industrial aromatic hydrocarbons, Test Methods D1492 or D5776 must be used in
accordance with their respective scopes. The practice of using a factor of 1000 to convert bromine number to bromine index is
not applicable for these lower values of bromine number.
1.4 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
1.4.1 Exception—The values given in parentheses are for information only.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use. For specific warning statements, see Sections 7, 8, and 9.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D86 Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.06 on Analysis of Liquid Fuels and Lubricants.
In the IP, this test method is under the jurisdiction of the Standardization Committee.
Current edition approved April 15, 2012May 1, 2017. Published April 2012July 2017. Originally approved in 1951. Last previous edition approved in 20072012 as
D1159D1159 – 07 (2012).–07. DOI: 10.1520/D1159-07R12.10.1520/D1159-07R17.
Dubois, H. D., and Skoog, D. A., “Determination of Bromine Addition Numbers,” Analytical Chemistry, Vol 20, 1948, pp. 624–627.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on 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
D1159 − 07 (2017)
D1193 Specification for Reagent Water
D1492 Test Method for Bromine Index of Aromatic Hydrocarbons by Coulometric Titration
D2710 Test Method for Bromine Index of Petroleum Hydrocarbons by Electrometric Titration
D5776 Test Method for Bromine Index of Aromatic Hydrocarbons by Electrometric Titration
3. Terminology
3.1 Definitions of Terms Specific to This Standard:
3.1.1 bromine number—the number of grams of bromine that will react with 100 g 100 g of the specimen under the conditions
of the test.
4. Summary of Test Method
4.1 A known weight of the specimen dissolved in the selected solvent (see 8.1) maintained at 00 °C to 5°C (325 °C (32 °F to
41°F)41 °F) is titrated with standard bromide-bromate solution. The end point is indicated by a sudden change in potential on an
electrometric end point titration apparatus due to the presence of free bromine.
5. Significance and Use
5.1 The bromine number is useful as a measure of aliphatic unsaturation in petroleum samples. When used in conjunction with
the calculation procedure described in Annex A2, it can be used to estimate the percentage of olefins in petroleum distillates boiling
up to approximately 315°C (600°F).315 °C (600 °F).
5.2 The bromine number of commercial aliphatic monoolefins provides supporting evidence of their purity and identity.
6. Apparatus
6.1 Electrometric End Point Titration Apparatus—Any apparatus designed to perform titrations to pre-set end points (see Note
2) may be used in conjunction with a high-resistance polarizing current supply capable of maintaining approximately 0.8 V 0.8 V
across two platinum electrodes and with a sensitivity such that a voltage change of approximately 50 mV 50 mV at these electrodes
is sufficient to indicate the end point. Other types of commercially available electronic titrimeters, including certain pH meters,
have also been found suitable.
NOTE 2—Pre-set end point indicated with polarized electrodes provides a detection technique similar to the dead stop technique specified in previous
versions of this test method.
6.2 Titration Vessel—A jacketed glass vessel approximately 120 mm 120 mm high and 45 mm 45 mm in internal diameter and
of a form that can be conveniently maintained at 00 °C to 5°C (325 °C (32 °F to 41°F).41 °F).
6.3 Stirrer—Any magnetic stirrer system.
6.4 Electrodes—A platinum wire electrode pair with each wire approximately 12 mm 12 mm long and 1 mm 1 mm in diameter.
The wires shall be located 5 mm 5 mm apart and approximately 5555 mm below the level of the titration solvent. Clean the
electrode pair at regular intervals with 65 % nitric acid and rinse with distilled water before use.
6.5 Buret—Any delivery system capable of measuring titrant in 0.05 mL 0.05 mL or smaller graduations.
7. Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
7.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water as defined by
Type III of Specification D1193.
7.3 Acetic Acid, Glacial—(Warning—WarningPoison,—Poison, corrosive-combustible, may be fatal if swallowed. Causes
severe burns, harmful if inhaled.)
7.4 Bromide-Bromate, Standard Solution(0.2500 M M as Br )—Dissolve 51.0 g 51.0 g of potassium bromide (KBr) and 13.92
g 13.92 g of potassium bromate (KBrO ) each dried at 105°C (220°F) for 30 min 105 °C (220 °F) for 30 min in water and dilute
to 1 L.1 L.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed by
the American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D1159 − 07 (2017)
7.4.1 If the determinations of the bromine number of the reference olefins specified in Section 8 using this solution do not
conform to the prescribed limits, or if for reasons of uncertainties in the quality of primary reagents it is considered desirable to
determine the molarity of the solution, the solution shall be standardized and the determined molarity used in subsequent
calculations. The standardization procedure shall be as follows:
7.4.1.1 To standardize, place 50 mL 50 mL of glacial acetic acid and 1 mL 1 mL of concentrated hydrochloric acid (Warning—
WarningPoison —Poison corrosive. May be fatal if swallowed. Liquid and vapor causes severe burns. Harmful if inhaled; relative
density 1.19.) in a 500-mL500 mL iodine number flask. Chill the solution in a bath for approximately 10 min 10 min and, with
constant swirling of the flask, add from a 10-mL10 mL calibrated buret, 55 mL 6 0.01 mL 0.01 mL of the bromide-bromate
standard solution at the rate of 1 or 2 drops per second. Stopper the flask immediately, shake the contents, place it again in the
ice bath, and add 5 mL 5 mL of Kl solution in the lip of the flask. After 5 min 5 min remove the flask from the ice bath and allow
the Kl solution to flow into the flask by slowly removing the stopper. Shake vigorously, add 100 mL 100 mL of water in such a
manner as to rinse the stopper, lip and walls of the flask, and titrate promptly with sodium thiosulfate (Na S O ) solution. Near
2 2 3
the end of the titration, add 1 mL 1 mL of starch indicator solution and titrate slowly to disappearance of the blue color. Calculate
the molarity of the bromide-bromate solution as follows:
AM
M 5 (1)
~5! ~2!
where:
where:
M = molarity of the bromide-bromate solution, as Br ,
1 2
A = millilitres of Na S O solution required for titration of the bromide-bromate solution, and,
2 2 3
M = molarity of Na S O solution,
2 2 2 3
5 = millilitres of bromide—bromate solution, and
2 = number of electrons transferred during redox titration of bromide-bromate solution.
Repeat the standardization until duplicate determinations do not differ from the mean by more than 60.002 M.60.002 M.
7.5 Methanol—(Warning—WarningFlammable.—Flammable. Vapor harmful. Can be fatal or cause blindness if swallowed or
inhaled. Cannot be made non-poisonous.)
7.6 Potassium Iodide Solution (150 (150 g g/L)⁄L)—Dissolve 150 g 150 g of potassium iodide (Kl) in water and dilute to 1
L.1 L.
7.7 Sodium Thiosulfate, Standard Solution (0.1 (0.1 M)—Dissolve 25 g 25 g of sodium thiosulfate (Na S O ·5H O) in water
2 2 3 2
and add 0.1 g 0.1 g of sodium carbonate (Na CO ) to stabilize the solution. Dilute to 1 L 1 L and mix thoroughly by shaking.
2 3
Standardize by any accepted procedure that determines the molarity with an error not greater than 60.0002. Restandardize at
intervals frequent enough to detect changes of 0.0005 in molarity.
7.8 Starch Indication Solution — Mix 5 g 5 g of soluble starch with about 33 mL to 5 mL 5 mL of water. If desired, add about
0.65 g 0.65 g salicylic acid as preservative. Add the slurry to 500 mL 500 mL of boiling water and continue boiling for 55 min
to 10 min. 10 min. Allow to cool, and decant the clear, supernatant liquid into glass bottles and seal well. Starch solutions (some
preserved with salicylic acid) are also commercially available and may be substituted.
7.9 Sulfuric Acid (1 + 5)—Carefully mix one volume of concentrated sulfuric acid (H SO , rel dens 1.84) with five volumes of
2 4
water. (Warning—WarningPoison.—Poison. Corrosive. Strong oxidizer. Contact with organic material can cause fire. Can be fatal
if swallowed.)
7.10 Titration Solvent—Prepare 1 L 1 L of titration solvent by mixing the following volumes of materials: 714 mL 714 mL of
glacial acetic acid, 134 mL 134 mL of 1,1,1-trichloroethane (or dichloromethane), 134 mL 134 mL of methanol, and 18 mL 18 mL
of H SO (1 + 5).
2 4
7.11 1,1,1-Trichloroethane—(Warning—WarningHarmful—Harmful if inhaled. High concentrations can cause unconscious-
ness or death. Contact may cause skin irritation and dermatitis.)
7.12 Dichloromethane—(Warning—WarningThe—The replacement of 1,1,1-trichloroethane, an ozone-depleting chemical, is
necessary because its manufacture and import has been discontinued. Dichloromethane is temporarily being allowed as an
alternative to 1,1,1-trichloroethane until a permanent replacement can be identified and adopted by ASTM International. A program
to identify and evaluate candidate solvents is currently underway in Subcommittee D02.04.)
NOTE 3—Commercially available reagents can be used in place of laboratory preparations.
8. Check Procedure
8.1 In case of doubt in applying the procedure to actual samples, the reagents and techniques can be checked by means of
determinations on freshly purified cyclohexene or diisobutene. (Warning—WarningThe—The user of this test method may choose
to use either 1,1,1-trichloroethane or dichloromethane to the exclusion of the other solvent. The selected solvent is to be used for
D1159 − 07 (2017)
TABLE 1 Physical Properties of Purified Olefins
Index of
Boiling Point, Density at
Compound Refraction,
°C 20°C,20 °C, g/mL
D Line at 20°C
Cyclohexene 82.5 to 83.5 0.8100 1.4465
A
Diisobutene 101 to 102.5 0.7175 ± 0.0015 1.4112
A
Only the 2,4,4-trimethyl-1-pentene isomer.
all operations, that is, in the preparation of the titration solvent, for the dilution of samples, and as the titration blank.) Proceed
in accordance with Section 9, using a sample of either
...
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