ASTM D5799-95(2009)

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 test method 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 standard. No other units of measurement are included in this 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: 30-Jun-2009
• 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(2004) - 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-Jul-2009

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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 2009)
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope method will provide values that can be used to determine the
peroxide content of a sample of commercial butadiene.
1.1 This test method covers the determination of peroxides
in butadiene. 4.2 Butadiene polyperoxide is a very dangerous product of
thereactionbetweenbutadieneandoxygenthatcanoccur.The
1.2 This test method covers the concentrations range of 1 to
peroxide has been reported to be the cause of some violent
10 ppm by mass (ppmw) as available oxygen.
explosions in vessels that are used to store butadiene.
1.3 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
5. Apparatus
standard.
5.1 Condensers, Liebig, with 24/40 standard-tapered
1.4 This standard does not purport to address all of the
ground-glass joint connections.
safety concerns, if any, associated with its use. It is the
5.2 Cylinders, graduated, 100-mL capacity.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 5.3 Flask, Erlenmeyer, 250-mL capacity, with 24/40
bility of regulatory limitations prior to use. standard-tapered ground-glass connections with marking at
100 mL.
2. Referenced Documents
5.4 Heating Mantle,electric,for250-mLErlenmeyerflasks.
2.1 ASTM Standards:
5.5 Microburette, 10-mL capacity, graduated in 0.02-mL
D1265Practice for Sampling Liquefied Petroleum (LP)
divisions.
Gases, Manual Method
5.6 Water Bath, a thermostatically controlled liquid bath
D3700Practice for Obtaining LPG Samples Using a Float-
capable of maintaining a water temperature of 60 6 1°C.
ing Piston Cylinder
6. Reagents
3. Summary of Test Method
6.1 Purity of Reagents—Reagent grade chemicals shall be
3.1 A known mass of the butadiene sample is placed in a
used in all tests. Unless otherwise indicated, it is intended that
flask and evaporated. The residue is then refluxed with acetic
all reagents shall conform to the specifications of the Commit-
acid and sodium iodide reagents. The peroxides react to
tee onAnalytical Reagents of theAmerican Chemical Society,
liberate iodine which is titrated with standard sodium thiosul-
where such specifications are available. Other grades may be
fatesolutionusingvisualend-pointdetection.Interferingtraces
used, provided it is first ascertained that the reagent is of
of iron are complexed with sodium fluoride.
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
4. Significance and Use
6.2 Purity of Water—Unless otherwise indicated, references
4.1 Due to the inherent danger of peroxides in butadiene,
to water shall be understood to mean deionized or distilled
specification limits are usually set for their presence. This test
water.
6.3 Acetic Acid, 94% by volume. Mix 60 mLof water with
This test method is under the jurisdiction of ASTM Committee D02 on
940 mL of glacial acetic acid (CH COOH). (Warning—
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.D0.04 on C4 Hydrocarbons.
Current edition approved July 1, 2009. Published November 2009. Originally
approved in 1995. Last previous edition approved in 2004 as D5799–95(2004). Reagent Chemicals, American Chemical Society Specifications, American
DOI: 10.1520/D5799-95R09. 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 Annual 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 (2009)
Poisonous and corrosive. Combustible. May be fatal if swal- 8.6 At the end of the reaction period, turn off the heating
lowed. Causes severe burns. Harmful if inhaled.) mantle and remove the flask with condenser from the mantle.
Immediately add 100 mL of water through the top of the
6.4 Carbon Dioxide,solid(dryice).(Warning—Usegloves
condenser followed by several pellets of dry ice.
to avoid frostbite when handling.)
8.7 Maintaining an inert atmosphere with CO pellets,
6.5 Potassium Dichromate Solution, Standard (0.1 N)—
remove the flask from the condenser and allow to cool to
Dissolve 2.452 g of potassium dichromate (K Cr O ) in water
2 2 7
ambient temperature. Cold water may be used to assist in this
and dilute to 500 mL in a volumetric flask.(Warning—Avoid
step. Titrate the liberated iodine with 0.1 N sodium thiosulfate
contact with eyes and skin and avoid breathing of dust.)
until a clear endpoint is reached.
6.6 Sodium Fluoride.
8.8 Repe
...