ASTM D5799-95(2004)

Standard Test Method for Determination of Peroxides in Butadiene

SIGNIFICANCE AND USE
Due to the inherent danger of peroxides in butadiene, specification limits are usually set for their presence. This test method will provide values that can be used to determine the peroxide content of a sample of commercial butadiene.
Butadiene polyperoxide is a very dangerous product of the reaction between butadiene and oxygen that can occur. The peroxide has been reported to be the cause of some violent explosions in vessels that are used to store butadiene.
SCOPE
1.1 This procedure covers the determination of peroxides in butadiene.
1.2 This test method covers the concentrations range of 1 to 10 ppm by mass (ppmw) as available oxygen.
1.3 The values stated in SI units are to be regarded as the standard.
1.4 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.

General Information

• Status: Historical
• Publication Date: 31-Oct-2004
• ICS: 71.080.10 - Aliphatic hydrocarbons
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.D0.04 - C4 and C5 Hydrocarbons

Relations

• Replaces: ASTM D5799-95(2000)e1 - Standard Test Method for Determination of Peroxides in Butadiene
• Effective Date: 01-Nov-2004
• Replaced By: ASTM D5799-95(2009) - Standard Test Method for Determination of Peroxides in Butadiene
• Effective Date: 01-Jul-2009
• Referred By: ASTM D5274-00(2019) - Standard Guide for Analysis of 1,3–Butadiene Product
• Effective Date: 01-Nov-2004

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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:D5799–95 (Reapproved 2004)
Standard Test Method for
Determination of Peroxides in Butadiene
This standard is issued under the fixed designation D5799; 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.
1. Scope 4.2 Butadiene polyperoxide is a very dangerous product of
the reaction between butadiene and oxygen that can occur.The
1.1 This test method covers the determination of peroxides
peroxide has been reported to be the cause of some violent
in butadiene.
explosions in vessels that are used to store butadiene.
1.2 This test method covers the concentrations range of 1 to
10 ppm by mass (ppmw) as available oxygen.
5. Apparatus
1.3 The values stated in SI units are to be regarded as the
5.1 Condensers, Liebig, with 24/40 standard-tapered
standard.
ground-glass joint connections.
1.4 This standard does not purport to address all of the
5.2 Cylinders, graduated, 100-mL capacity.
safety concerns, if any, associated with its use. It is the
5.3 Flask, Erlenmeyer, 250-mL capacity, with 24/40
responsibility of the user of this standard to establish appro-
standard-tapered ground-glass connections with marking at
priate safety and health practices and determine the applica-
100 mL.
bility of regulatory limitations prior to use.
5.4 Heating Mantle, electric, for 250-mLErlenmeyer flasks.
2. Referenced Documents 5.5 Microburette, 10-mL capacity, graduated in 0.02-mL
divisions.
2.1 ASTM Standards:
5.6 Water Bath, a thermostatically controlled liquid bath
D1265 Practice for Sampling Liquefied Petroleum (LP)
capable of maintaining a water temperature of 60 6 1°C (140
Gases, Manual Method
6 2°F).
D3700 Practice for Obtaining LPG Samples Using a Float-
ing Piston Cylinder
6. Reagents
3. Summary of Test Method 6.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
3.1 A known mass of the butadiene sample is placed in a
all reagents shall conform to the specifications of the Commit-
flask and evaporated. The residue is then refluxed with acetic
tee onAnalytical Reagents of theAmerican Chemical Society,
acid and sodium iodide reagents. The peroxides react to
where such specifications are available. Other grades may be
liberate iodine which is titrated with standard sodium thiosul-
used, provided it is first ascertained that the reagent is of
fatesolutionusingvisualend-pointdetection.Interferingtraces
sufficiently high purity to permit its use without lessening the
of iron are complexed with sodium fluoride.
accuracy of the determination.
4. Significance and Use 6.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean deionized or distilled
4.1 Due to the inherent danger of peroxides in butadiene,
water.
specification limits are usually set for their presence. This test
6.3 Acetic Acid, 94 % by volume. Mix 60 mLof water with
method will provide values that can be used to determine the
940 mL of glacial acetic acid (CH COOH). (Warning—
peroxide content of a sample of commercial butadiene.
Poisonous and corrosive. Combustible. May be fatal if swal-
lowed. Causes severe burns. Harmful if inhaled.)
This test method is under the jurisdiction of ASTM Committee D02 on 6.4 Carbon Dioxide,solid(dryice).(Warning—Usegloves
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
to avoid frostbite when handling.)
D02.D0 on Hydrocarbons for Chemical and Special Uses.
Current edition approved Nov. 1, 2004. Published November 2004. Originally
´1 3
approved in 1995. Last previous edition approved in 2000 as D5799 – 95 (2000) . Reagent Chemicals, American Chemical Society Specifications, American
DOI: 10.1520/D5799-95R04. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.
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D5799–95 (2004)
6.5 Potassium Dichromate Solution, Standard (0.1 N)— Immediately add 100 mL of water through the top of the
Dissolve 2.452 g of potassium dichromate (K Cr O ) in water condenser followed by several pellets of dry ice.
2 2 7
and dilute to 500 mL in a volumetric flask.(Warning—Avoid 8.7 Maintaining an inert atmosphere with CO pellets,
contact with eyes and skin and avoid breathing of dust.) remove the flask from the condenser and allow to cool to
6.6 Sodium Fluoride. ambient temperature. Cold water may be used to assist in this
6.7 Sodium Iodide. step. Titrate the liberated iodine with 0.1 N sodium thiosulfate
6.8 Sodium Thiosulfate Solution, Standard (0.1 N)— until a clear endpoint is reached.
Dissolve 12.5 g of so
...