ASTM E299-08

Standard Test Method for Trace Amounts of Peroxides In Organic Solvents

SIGNIFICANCE AND USE
Dilute solutions of peroxides in various organic solvents frequently are used as catalysts or reaction initiators. Peroxides also can be formed through autoxidation in certain classes of compounds including ethers, acetals, dienes, and alkylaromatic hydrocarbons and present a potential safety hazard. This test method provides a procedure for determining the peroxide or active oxygen level.
SCOPE
1.1 This test method , covers organic solvents containing active oxygen in the range from 5 to 80 μg/g (ppm) or higher. By using a special reaction-absorption cell, the test method can be extended to cover the range from 0 to 5 ppm. The test method can be used to determine numerous peroxide classes of varying reactivity such as hydroperoxides, diacyl peroxides, diaroyl peroxides, peresters, and ketone peroxides. The stable di-tert-alkyl peroxides do not react under the conditions of analysis.
1.2 Solvents that can be analyzed successfully include saturated and aromatic hydrocarbons, alcohols, ethers, ketones, and esters. In addition, the test method is applicable to olefinic solvents and to certain compounds that contain α, β, and conjugated unsaturation. Solid samples that are soluble in the acetic acid-chloroform solvent also can be analyzed.
1.3 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.4 This standard does not purport to address 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.
1.5 Review the current Material Safety Data Sheets (MSDS) for detailed information concerning toxicity, first aid practices, and safety precautions.

General Information

• Status: Historical
• Publication Date: 31-Mar-2008
• ICS: 71.100.99 - Other products of the chemical industry
• Technical Committee: D16 - Aromatic, Industrial, Specialty and Related Chemicals

Relations

• Replaced By: ASTM E299-17 - Standard Test Method for Trace Amounts of Peroxides In Organic Solvents
• Effective Date: 01-Feb-2017
• Referred By: ASTM D7125-23 - Standard Specification for Cumene (Isopropylbenzene) Manufactured Via a Zeolite Process
• Effective Date: 01-Apr-2008
• Referred By: ASTM D4077-23 - Standard Specification for Cumene (Isopropylbenzene)
• Effective Date: 01-Apr-2008
• Referred By: ASTM C1572/C1572M-23 - Standard Guide for Dry Lead Glass and Oil-Filled Lead Glass Radiation Shielding Window Components for Remotely Operated Facilities
• Effective Date: 01-Apr-2008
• Referred By: ASTM D1353-13(2021) - Standard Test Method for Nonvolatile Matter in Volatile Solvents for Use in Paint, Varnish, Lacquer, and Related Products
• Effective Date: 01-Apr-2008
• Referred By: ASTM D1078-11(2019) - Standard Test Method for Distillation Range of Volatile Organic Liquids
• Effective Date: 01-Apr-2008

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: E299 − 08
Standard Test Method for
1
Trace Amounts of Peroxides In Organic Solvents
This standard is issued under the fixed designation E299; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope* 2. Referenced Documents
2,3 4
1.1 This test method covers organic solvents containing 2.1 ASTM Standards:
active oxygen in the range from 5 to 80 µg/g (ppm) or higher. D1193 Specification for Reagent Water
By using a special reaction-absorption cell, the test method can E180 Practice for Determining the Precision of ASTM
be extended to cover the range from 0 to 5 ppm. The test Methods for Analysis and Testing of Industrial and Spe-
5
method can be used to determine numerous peroxide classes of cialty Chemicals (Withdrawn 2009)
varying reactivity such as hydroperoxides, diacyl peroxides,
diaroyl peroxides, peresters, and ketone peroxides. The stable
3. Summary of Test Method
di-tert-alkyl peroxides do not react under the conditions of
3.1 A sample is dissolved in a mixture of acetic acid and
analysis.
chloroform. The solution is deaerated and potassium iodide
1.2 Solvents that can be analyzed successfully include reagentsolutionisadded.Themixtureisallowedtoreactinthe
saturatedandaromatichydrocarbons,alcohols,ethers,ketones, dark for 1 h, thereby releasing an equivalent amount of iodine.
and esters. In addition, the test method is applicable to olefinic The absorbance of the solution is measured at 470 nm and the
solvents and to certain compounds that contain α, β, and amount of active oxygen present in the sample is determined
conjugated unsaturation. Solid samples that are soluble in the by reference to a calibration curve prepared from iodine.
acetic acid-chloroform solvent also can be analyzed.
3.2 Forsamplescontaining0to5µg/g(ppm)activeoxygen,
1.3 The values stated in SI units are to be regarded as a special reaction-absorption cell is employed. The sample is
standard. The values given in parentheses are for information de-aerated and the reaction is carried out within the cell.
only.
Absorbance measurements are made at 410 nm to increase the
sensitivity.
1.4 This standard does not purport to address the safety
concerns, if any, associated with its use. It is the responsibility
4. Significance and Use
of the user of this standard to establish appropriate safety and
health practices and determine the applicability of regulatory
4.1 Dilute solutions of peroxides in various organic solvents
limitations prior to use.
frequently are used as catalysts or reaction initiators. Peroxides
1.5 ReviewthecurrentMaterialSafetyDataSheets(MSDS)
also can be formed through autoxidation in certain classes of
for detailed information concerning toxicity, first aid practices,
compounds including ethers, acetals, dienes, and alkylaromatic
and safety precautions.
hydrocarbons and present a potential safety hazard. This test
method provides a procedure for determining the peroxide or
1
active oxygen level.
This test method is under the jurisdiction of ASTM Committee D16 on
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of
Subcommittee D16.15 on Industrial and Specialty General Standards.
Current edition approved April 1, 2008. Published May 2008. Originally
4
approved in 1966. Last previous edition approved in 2002 as E299 – 97 (2002). For referenced ASTM standards, visit the ASTM website, www.astm.org, or
DOI: 10.1520/E0299-08. contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
2
Banerjee, D. K., and Budke, C. C.,Analytical Chemistry, ANCHAM, Vol 36, Standards volume information, refer to the standard’s Document Summary page on
1964, pp. 792–796. the ASTM website.
3 5
Banerjee, D. K., and Budke, C. C.,Analytical Chemistry, ANCHAM, Vol 36, The last approved version of this historical standard is referenced on
1964, pp. 2367–2368. www.astm.org.
*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
1

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E299 − 08
7.4 Acetic Acid-Chloroform Solvent (Containing Approxi-
mately 4 % Water)—Add 40 mL of water to 1 L of solvent
prepared as described in 7.3.
7.5 Iodine.
7.6 Nitrogen Cylinder.
7.7 Potassium Iodide Solution (50 %)—Dissolve 20 g of
potassium iodide (KI) in 20 mL of de-aerated water. This
reagent should be freshly prepared just prior to use.
7.8 Water, De-aerated—Pass nitrogen through distill
...

This document is not anASTM standard and is intended only to provide the user of anASTM 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:E299–97 (Reapproved 2002) Designation:E299–08
Standard Test Method for
1
Trace Amounts of Peroxides In Organic Solvents
This standard is issued under the fixed designation E 299; 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*
,
2 3
1.1 This test method covers organic solvents containing active oxygen in the range from 5 to 80 µg/g (ppm) or higher. By
using a special reaction-absorption cell, the test method can be extended to cover the range from 0 to 5 ppm. The test method can
be used to determine numerous peroxide classes of varying reactivity such as hydroperoxides, diacyl peroxides, diaroyl peroxides,
peresters, and ketone peroxides. The stable di-tert-alkyl peroxides do not react under the conditions of analysis.
1.2 Solvents that can be analyzed successfully include saturated and aromatic hydrocarbons, alcohols, ethers, ketones, and
esters. In addition, the test method is applicable to olefinic solvents and to certain compounds that contain a, b, and conjugated
unsaturation. Solid samples that are soluble in the acetic acid-chloroform solvent also can be analyzed.
1.3
1.3 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.4 This standard does not purport to address 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.
1.45 Review the current Material Safety Data Sheets (MSDS) for detailed information concerning toxicity, first aid practices,
and safety precautions.
2. Referenced Documents
4
2.1 ASTM Standards:
D 1193 Specification for Reagent Water
E 180 Practice for Determining the Precision ofASTM Methods forAnalysis andTesting of Industrial and Specialty Chemicals
3. Summary of Test Method
3.1 A sample is dissolved in a mixture of acetic acid and chloroform. The solution is deaerated and potassium iodide reagent
solution is added. The mixture is allowed to react in the dark for 1 h, thereby releasing an equivalent amount of iodine. The
absorbanceofthesolutionismeasuredat470nmandtheamountofactiveoxygenpresentinthesampleisdeterminedbyreference
to a calibration curve prepared from iodine.
3.2 For samples containing 0 to 5 µg/g (ppm) active oxygen, a special reaction-absorption cell is employed. The sample is
de-aerated and the reaction is carried out within the cell.Absorbance measurements are made at 410 nm to increase the sensitivity.
4. Significance and Use
4.1 Dilutesolutionsofperoxidesinvariousorganicsolventsfrequentlyareusedascatalystsorreactioninitiators.Peroxidesalso
can be formed through autoxidation in certain classes of compounds including ethers, acetals, dienes, and alkylaromatic
hydrocarbons and present a potential safety hazard. This test method provides a procedure for determining the peroxide or active
oxygen level.
5. Interferences
5.1 Oxidizing or reducing substances present in the sample will interfere. Colored solutions can be analyzed if an absorbance
correction is made.
1
This test method is under the jurisdiction of ASTM Committee E15 on Industrial and Specialty Chemicals and is the direct responsibility of Subcommittee E15.01 on
General Standards.
Current edition approved Dec. 10, 2002.April 1, 2008. Published May 2003.2008. Originally approved in 1966. Last previous edition approved in 19972002 as
E 299 – 97(2002).
2
Banerjee, D. K., and Budke, C. C., Analytical Chemistry , ANCHAM, Vol 36, 1964, pp. 792–796.
3
Banerjee, D. K., and Budke, C. C., Analytical Chemistry , ANCHAM, Vol 36, 1964, pp. 2367–2368.
4
Annual Book of ASTM Standards, Vol 11.01.
4
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at [e-mail]. ForAnnualBookofASTMStandards
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.
1

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E299–08
6. Apparatus
6.1 Spectrophotometer—Beckman Model DU or equivalent with matched 1-cm cells.
6.2 SpecialReac
...