ASTM D5799-23

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: D5799 − 19 D5799 − 23
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*
1.1 This test method covers the determination of peroxides in butadiene.
1.2 This test method covers the concentrations range of 1 mg ⁄kg to 10 mg ⁄kg 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, health, and environmental practices and determine the applicability of
regulatory limitations prior to use.
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, health, and environmental practices and determine the applicability of
regulatory limitations prior to use.
1.4.1 The user is advised to obtain LPG safety training for the safe operation of this test method procedure and related activities.
1.5 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:
D1265 Practice for Sampling Liquefied Petroleum (LP) Gases, Manual Method
D3700 Practice for Obtaining LPG Samples Using a Floating Piston Cylinder
3. Summary of Test Method
3.1 A known mass of the butadiene sample is placed in a flask and evaporated. The residue is then refluxed with acetic acid and
sodium iodide reagents. The peroxides react to liberate iodine which is titrated with standard sodium thiosulfate solution using
visual end-point detection. Interfering traces of iron are complexed with sodium fluoride.
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.D0.04 on C4 and C5 Hydrocarbons.
Current edition approved Dec. 1, 2019March 1, 2023. Published January 2020June 2023. Originally approved in 1995. Last previous edition approved in 20142019 as
D5799 – 95 (2014).D5799 – 19. DOI: 10.1520/D5799-19.10.1520/D5799-23.
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
D5799 − 23
4. Significance and Use
4.1 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.
4.2 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.
5. Apparatus
5.1 Condensers, Liebig, with 24/40 standard-tapered ground-glass joint connections.
5.2 Cylinders, graduated, 100 mL capacity.
5.3 Flask, Erlenmeyer, 250 mL capacity, with 24/40 standard-tapered ground-glass connections with marking at 100 mL.
5.4 Heating Mantle, electric, for 250 mL Erlenmeyer flasks.
5.5 Microburette, 10 mL capacity, graduated in 0.02 mL divisions.
5.6 Water Bath, a thermostatically controlled liquid bath capable of maintaining a water temperature of 60 °C 6 1 °C.
6. Reagents
6.1 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.
6.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean deionized or distilled water.
6.3 Acetic Acid, 94 % by volume. Mix 60 mL of water with 940 mL of glacial acetic acid (CH COOH). (Warning—Poisonous
and corrosive. Combustible. May be fatal if swallowed. Causes severe burns. Harmful if inhaled.)
6.4 Carbon Dioxide, solid (dry ice). (Warning—Use gloves to avoid frostbite when handling.)
6.5 Potassium Dichromate Solution, Standard (0.1 N)—Dissolve 2.452 g of potassium dichromate (K Cr O ) in water and dilute
2 2 7
to 500 mL in a volumetric flask. (Warning—Avoid contact with eyes and skin and avoid breathing of dust.)
6.6 Sodium Fluoride.
6.7 Sodium Iodide.
6.8 Sodium Thiosulfate Solution, Standard (0.1 N)—Dissolve 12.5 g of sodium thiosulfate (Na S O × 5H O) plus 0.1 g of
2 2 3 2
sodium carbonate (Na CO ) in 500 mL of water (the Na CO is added to stabilize the Na S O solution). Let this solution stand
2 3 2 3 2 2 3
a week or more before using. Standardize against 0.1 N K Cr O solution. Restandardize at frequencies to detect changes of 0.0005
2 2 7
in normality.
ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference Materials, American Chemical Society, Washington, DC. For
suggestions on the testing of re
...