ASTM D5799-95(2014)

Standard Test Method for Determination of Peroxides in Butadiene

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.
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-Apr-2014
• ICS: 71.080.10 - Aliphatic hydrocarbons
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.D0.04 - C4 and C5 Hydrocarbons

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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 2014)
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, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.D0.04 on C4 Hydrocarbons.
CurrenteditionapprovedMay1,2014.PublishedJuly2014.Originallyapproved
in 1995. Last previous edition approved in 2009 as D5799–95(2009). DOI: Reagent Chemicals, American Chemical Society Specifications, American
10.1520/D5799-95R14. 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.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5799 − 95 (2014)
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 mLin 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 Repeat 8.4 through 8.7 for the reagent b
...

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 − 95 (Reapproved 2009) D5799 − 95 (Reapproved 2014)
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 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.
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.
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 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
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.D0.04 on C4 Hydrocarbons.
Current edition approved July 1, 2009May 1, 2014. Published November 2009July 2014. Originally approved in 1995. Last previous edition approved in 20042009 as
D5799–95(2004).D5799 – 95 (2009). DOI: 10.1520/D5799-95R09.10.1520/D5799-95R14.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5799 − 95 (2014)
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.(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.
7. Sampling
7.1 Butadiene should be sampled in a metal container of a type which ensures maximum safety and which is resistant to
butadiene corrosion. The size of the container is dependent upon the number of times the test is to be performed according to this
test method. Refer to Practice D1265 or Practice D3700 for instruct
...