ASTM D5799-95

Standard Test Method for Determination of Peroxides in 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 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-Dec-1999
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.D0 - Hydrocarbons for Chemical and Special Uses

Relations

• Replaced By: ASTM D5799-95(2000)e1 - Standard Test Method for Determination of Peroxides in Butadiene
• Effective Date: 10-Nov-2000
• Referred By: ASTM D5274-00(2019) - Standard Guide for Analysis of 1,3–Butadiene Product
• Effective Date: 01-Jan-2000

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
Designation: D 5799 – 95
Standard Test Method for
Determination of Peroxides in Butadiene
This standard is issued under the fixed designation D 5799; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope 5.2 Cylinders, graduated, 100-mL capacity.
5.3 Flask, Erlenmeyer, 250-mL capacity, with 24/40
1.1 This procedure covers the determination of peroxides in
standard-tapered ground-glass connections with marking at
butadiene.
100 mL.
1.2 This test method covers the concentrations range of 1 to
5.4 Heating Mantle, electric for 250-mL Erlenmeyer flasks.
10 ppm by mass (ppmw) as available oxygen.
5.5 Microburette, 10-mL capacity, graduated in 0.02-mL
1.3 This standard does not purport to address all of the
divisions.
safety concerns, if any, associated with its use. It is the
5.6 Water Bath, a thermostatically controlled liquid bath
responsibility of the user of this standard to establish appro-
capable of maintaining a water temperature of 60 6 1°C (140
priate safety and health practices and determine the applica-
6 2°F).
bility of regulatory limitations prior to use.
6. Reagents
2. Referenced Documents
6.1 Purity of Reagents—Reagent grade chemicals shall be
2.1 ASTM Standards:
used in all tests. Unless otherwise indicated, it is intended that
D 1265 Practice for Sampling Liquefied Petroleum (LP)
all reagents shall conform to the specifications of the Commit-
Gases–Manual Method
tee on Analytical Reagents of the American Chemical Society,
D 3700 Practice for Containing Hydrocarbons Fluid
where such specifications are available. Other grades may be
Samples Using a Floating Piston Cylinder
used, provided it is first ascertained that the reagent is of
3. Summary of Test Method
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
3.1 A known mass of the butadiene sample is placed in a
6.2 Purity of Water—Unless otherwise indicated, references
flask and evaporated. The residue is then refluxed with acetic
to water shall be understood to mean deionized or distilled
acid and sodium iodide reagents. The peroxides react to
water.
liberate iodine which is titrated with standard sodium thiosul-
6.3 Acetic Acid, 94 % by volume. Mix 60 mL of water with
fate solution using visual end-point detection. Interfering traces
940 mL of glacial acetic acid (CH COOH).
of iron are complexed with sodium fluoride. 3
NOTE 1—Warning: Danger—Poisonous and corrosive. Combustible.
4. Significance and Use
May be fatal if swallowed. Causes severe burns. Harmful if inhaled.
4.1 Due to the inherent danger of peroxides in butadiene,
6.4 Carbon Dioxide, solid (dry ice).
specification limits are usually set for their presence. This test
NOTE 2—Warning: Use gloves to avoid frostbite when handling.
method will provide values that can be used to determine the
peroxide content of a sample of commercial butadiene.
6.5 Potassium Dichromate Solution, Standard (0.1 N)—
4.2 Butadiene polyperoxide is a very dangerous product of
Dissolve 2.452 g of potassium dichromate (K Cr O ) in water
2 2 7
the reaction between butadiene and oxygen that can occur. The
and dilute to 500 mL in a volumetric flask.
peroxide has been reported to be the cause of some violent
NOTE 3—Warning: Avoid contact with eyes and skin and avoid breath-
explosions in vessels that are used to store butadiene.
ing of dust.
5. Apparatus
6.6 Sodium Fluoride.
6.7 Sodium Iodide.
5.1 Condensers, Liebig, with 24/40 standard-tapered
6.8 Sodium Thiosulfate Solution, Standard (0.1 N)—
ground-glass joint connections.
Dissolve 12.5 g of sodium thiosulfate (Na S O 3 5H O) plus
2 2 3 2
1 4
This test method is under the jurisdiction of ASTM Committee D-2 on Reagent Chemicals, American Chemical Society Specifications, American
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee Chemical Society, Washington, DC. For suggestions on the testing of reagents not
D02.D on Hydrocarbons for Chemical and Special Uses. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved Oct. 10, 1995. Published December 1995. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Annual Book of ASTM Standards, Vol 05.01. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
Annual Book of ASTM Standards, Vol 05.02. MD.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
D 5799
0.1 g of sodium carbonate (Na CO ) in 500 mL of water (the ambient temperature. Cold water may be used to assist in this
2 3
Na CO is added to stabilize the Na S O solution). Let this step. Titrate the liberated iodine with 0.1 N sodium thiosulfate
2 3 2 2 3
solution stand a week or more before using. Standardize until a clear endpoint is reached.
against 0.1 N K Cr O solution. Restandardize at frequencies 8.8 Repeat 8.4 through 8.7 for the reagent blank.
2 2 7
to detect changes of 0.0005 in nor
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