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: D5799 − 23

Standard Test Method for

Determination of Peroxides in Butadiene1
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* acid and sodium iodide reagents. The peroxides react to

1.1 This test method covers the determination of peroxides liberate iodine which is titrated with standard sodium thiosul-
in butadiene. fate solution using visual end-point detection. Interfering traces
of iron are complexed with sodium fluoride.
1.2 This test method covers the concentrations range of
1 mg ⁄kg to 10 mg ⁄kg as available oxygen. 4. Significance and Use
1.3 The values stated in SI units are to be regarded as 4.1 Due to the inherent danger of peroxides in butadiene,
standard. No other units of measurement are included in this specification limits are usually set for their presence. This test
standard. method will provide values that can be used to determine the
1.4 This standard does not purport to address all of the peroxide content of a sample of commercial butadiene.
safety concerns, if any, associated with its use. It is the 4.2 Butadiene polyperoxide is a very dangerous product of
responsibility of the user of this standard to establish appro- the reaction between butadiene and oxygen that can occur. The
priate safety, health, and environmental practices and deter- peroxide has been reported to be the cause of some violent
mine the applicability of regulatory limitations prior to use. explosions in vessels that are used to store butadiene.
1.4.1 The user is advised to obtain LPG safety training for
the safe operation of this test method procedure and related 5. Apparatus
activities. 5.1 Condensers, Liebig, with 24/40 standard-tapered
1.5 This international standard was developed in accor- ground-glass joint connections.
dance with internationally recognized principles on standard- 5.2 Cylinders, graduated, 100 mL capacity.
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom- 5.3 Flask, Erlenmeyer, 250 mL capacity, with 24/40
mendations issued by the World Trade Organization Technical standard-tapered ground-glass connections with marking at
Barriers to Trade (TBT) Committee. 100 mL.
5.4 Heating Mantle, electric, for 250 mL Erlenmeyer flasks.
2. Referenced Documents
5.5 Microburette, 10 mL capacity, graduated in 0.02 mL
2.1 ASTM Standards:2 divisions.
D1265 Practice for Sampling Liquefied Petroleum (LP)
Gases, Manual Method 5.6 Water Bath, a thermostatically controlled liquid bath
D3700 Practice for Obtaining LPG Samples Using a Float- capable of maintaining a water temperature of 60 °C 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-
tee on Analytical Reagents of the American Chemical Society,
1
where such specifications are available.3 Other grades may be
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
used, provided it is first ascertained that the reagent is of
Subcommittee D02.D0.04 on C4 and C5 Hydrocarbons.
Current edition approved March 1, 2023. Published June 2023. Originally
3
approved in 1995. Last previous edition approved in 2019 as D5799 – 19. DOI: ACS Reagent Chemicals, Specifications and Procedures for Reagents and
10.1520/D5799-23. Standard-Grade Reference Materials, American Chemical Society, Washington,
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or DC. For suggestions on the testing of reagents not listed by the American Chemical
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
Standards volume information, refer to the standard’s Document Summary page on U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
the ASTM website. copeial Convention, Inc. (USPC), Rockville, MD.

*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

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 D5799 − 23
sufficiently high purity to permit its use without lessening the 8.4 Remove the flask from the water bath and allow to cool
accuracy of the determination. to ambient temperature. Add 50 mL of 94 % acetic acid and
6.2 Purity of Water—Unless otherwise indicated, references 0.20 g 6 0.02 g of sodium fluoride. Add several more pellets of
to water shall be understood to mean deionized or distilled dry ice to the flask and allow to stand for 5 min.
water. 8.5 Add 6.0 g 6 0.2 g of sodium iodide to the flask and
immediately connect to the Liebig condenser. Turn on the
6.3 Acetic Acid, 94 % by volume. Mix 60 mL of water with
heating mantle and reflux the solution for 25 min 6 5 min.
940 mL of glacial acetic acid (CH3COOH). (Warning—
Keep the equipment away from strong light during refluxing.
Poisonous and corrosive. Combustible. May be fatal if swal-
lowed. Causes severe burns. Harmful if inhaled.) 8.6 At the end of the reaction period, turn off the heating
mantle and remove the flask with condenser from the mantle.
6.4 Carbon Dioxide, solid (dry ice). (Warning—Use gloves Immediately add 100 mL of water through the top of the
to avoid frostbite when handling.) condenser followed by several pellets of dry ice.
6.5 Potassium Dichromate Solution, Standard (0.1 N)— 8.7 Maintaining an inert atmosphere with CO2 pellets,
Dissolve 2.452 g of potassium dichromate (K2Cr2O7) in water remove the flask from the condenser and allow to cool to
and dilute to 500 mL in a volumetric flask. (Warning—Avoid ambient temperature. Cold water may be used to assist in this
contact with eyes and skin and avoid breathing of dust.) step. Titrate the liberated iodine with 0.1 N sodium thiosulfate
6.6 Sodium Fluoride. until a clear endpoint is reached.
6.7 Sodium Iodide. 8.8 Repeat 8.4 through 8.7 for the reagent blank.
6.8 Sodium Thiosulfate Solution, Standard (0.1 N)— 9. Calculation
Dissolve 12.5 g of sodium thiosulfate (Na2S2O3 × 5H2O) plus
0.1 g of sodium carbonate (Na2CO3) in 500 mL of water (the 9.1 Calculate the peroxide content as follows:
Na2CO3 is added to stabilize the Na2S2O3 solution). Let this ~ A 2 B ! × N × 16 000
peroxide, as O 2 , mg/kg 5 (1)
solution stand a week or more before using. Standardize W
against 0.1 N K2Cr2O7 solution. Restandardize at frequencies
where:
to detect changes of 0.0005 in normality.
A = Na2S2O3 solution required for titration of the
7. Sampling sample, mL,
B = Na2S2O3 solution required for titration of the
7.1 Butadiene should be sampled in a metal container of a blank, mL,
type which ensures maximum safety and which is resistant to N = normality of the Na2S2O3 solution,
butadiene corrosion. The size of the container is dependent W = sample weight, g, and
upon the number of times the test is to be performed according 16 000 = milliequivalents of oxygen.
to this test method. Refer to Practice D1265 or Practice D3700
for instructions on sampling. 10. Precision and Bias4
10.1 Precision—The precision of this test method as deter-
8. Procedure mined by statistical examination of interlaboratory results is as
8.1 Remove the oxygen from a 250 mL Erlenmeyer flask by follows:
adding several pellets (approximately 1 cm in size) of dry ice 10.1.1 Repeatability—The difference between two test re-
and allowing the CO2 to displace the air. This will take sults obtained by the same operator with the same apparatus
approximately 5 min. under constant operating conditions on identical test materials
would, in the long run, in the normal and correct operation of
8.2 Record the weight to one decimal place of the sample
the test method, exceed the following values only in one case
cylinder, and then transfer approximately 100 mLs of butadi-
of twenty:
ene sample from the cylinder to the 250 mL Erlenmeyer flask
containing several pellets of dry ice. Reweigh the sample R 5 1.4 mg/kg
cylinder and record the weight of the sample as the difference 10.1.2 Reproducibility—The difference between two single
of the two weights. (Warning—Butadiene is a flammable gas and independent results, obtained by different operators work-
under pressure.) ing in different laboratories on identical test material, would, in
8.3 Place the flask in a water bath at 60 °C in a well the long run and in the normal and correct operation of the test
ventilated hood. Allow the butadiene to evaporate while method, exceed the following values only in one case in
keeping an inert atmosphere above the liquid butadiene by twenty.
continuing to add pellets of dry ice at intervals until all the R 5 3.4 mg/kg
butadiene has evaporated. (Warning—Peroxides are unstable
and react violently when taken to dryness. Peroxides at the
levels experienced during the test method evaluation have not 4
Supporting data have been filed at ASTM International Headquarters and may
caused a problem, but caution needs to be exhibited in handling be obtained by requesting Research Report RR:D02-1372. Contact ASTM Customer
by the use of personal protective equipment.) Service at service@astm.org.

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 D5799 − 23
10.2 Bias—As no reliable source of butadiene polyperoxide 11. Keywords
is available, the actual bias of the test method is unknown; but 11.1 butadiene; butadiene polyperoxide; peroxide
published data reports that this test method determines 90 % of
the polyperoxide.5

5
For a discussion of the background for this test method, see Mayo, Hendry,
Jones, and Scheatzle, Industrial and Engineering Chemical, Product Research, Vol
7, 1968, p. 145.

SUMMARY OF CHANGES

Subcommittee D02.D0.04 has identified the location of selected changes to this standard since the last issue
(D5799 – 19) that may impact the use of this standard. (Approved March 1, 2023.)

(1) Added subsection 1.4.1.

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