ASTM E299-17a

Standard Test Method for Trace Amounts of Peroxides In Organic Solvents

SIGNIFICANCE AND USE
4.1 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 method2,3 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 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid practices, and safety precautions.  
1.4 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.  
1.5 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.  
1.6 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.

General Information

• Status: Published
• Publication Date: 30-Jun-2017
• ICS: 71.100.99 - Other products of the chemical industry
• Technical Committee: D16 - Aromatic, Industrial, Specialty and Related Chemicals
• Drafting Committee: D16.12 - Caustics and Peroxides

Relations

• Refers: ASTM D6809-02(2016) - Standard Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
• Effective Date: 01-Nov-2016
• Refers: ASTM D6809-02(2007) - Standard Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
• Effective Date: 01-Jun-2007
• Refers: ASTM D1193-06 - Standard Specification for Reagent Water
• Effective Date: 01-Mar-2006
• Refers: ASTM D6809-02 - Standard Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
• Effective Date: 10-Jun-2002
• Refers: ASTM D1193-99e1 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999
• Refers: ASTM D1193-99 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999

Overview

ASTM E299-17a, "Standard Test Method for Trace Amounts of Peroxides In Organic Solvents," is a critical standard developed by ASTM International. It outlines a spectrophotometric test method for determining trace amounts of peroxides (active oxygen content) in various organic solvents. This method supports laboratories and manufacturers in assessing peroxide contamination, ensuring material safety, and maintaining compliance with industry best practices.

Monitoring and quantifying peroxides is essential for chemical manufacturing, storage, and application scenarios because certain peroxides can form spontaneously through autoxidation, particularly in ethers, acetals, dienes, and alkylaromatic hydrocarbons. Uncontrolled peroxide formation poses significant safety hazards, including potential fire and explosion risks. ASTM E299-17a offers a reliable and standardized approach to detecting peroxides at levels from sub-ppm to high ppm.

Key Topics

• Detection Range: The method covers detection of active oxygen (as peroxides) from 5 to 80 μg/g (ppm) and can be extended to 0-5 ppm using specialized techniques.
• Applicable Compounds: Suitable for hydroperoxides, diacyl peroxides, diaroyl peroxides, peresters, and ketone peroxides. However, certain stable di-tert-alkyl peroxides do not react under the test conditions.
• Sample Compatibility: Can be applied to a wide variety of organic solvents, including:
  • Saturated and aromatic hydrocarbons
  • Alcohols, ethers, ketones, and esters
  • Olefinic solvents and compounds with α,β, and conjugated unsaturation
  • Solid samples soluble in the acetic acid-chloroform medium
• Spectrophotometric Procedure: Involves dissolving the sample, allowing reaction with potassium iodide, and measuring absorbance to quantify peroxide content.
• Quality Assurance: Laboratories are expected to adopt comprehensive QA/QC protocols, referencing related ASTM guidance for quality control in chemical analysis.

Applications

• Catalyst and Initiator Quality Control: Chemical processes frequently use dilute peroxide solutions as catalysts or polymerization initiators. Accurate quantification prevents underperformance or hazardous excess peroxide levels.
• Safety in Storage and Handling: Ethers and other organic solvents can form peroxides during storage. Routine monitoring using ASTM E299-17a helps minimize accident risks, supporting safe storage protocols in research and industrial environments.
• Regulatory Compliance: Many industries, including pharmaceuticals and petrochemicals, must comply with limits on residual peroxides. This test method aids in verifying compliance with regulatory requirements.
• Research and Development: Scientists analyzing or synthesizing new solvents or intermediates can use this method to assess the peroxide-forming tendency and stability of materials.
• Environmental and Waste Management: Quantifying peroxide content assists in characterizing hazardous waste streams and informing appropriate disposal or treatment strategies.

Related Standards

• ASTM D1193: Specification for Reagent Water - fundamental for accurate chemical analysis.
• ASTM D6809: Guide for QA/QC Procedures in analysis of aromatic hydrocarbons and related materials; provides broader context for quality management referenced in ASTM E299-17a.
• General Spectrophotometric Test Methods: ASTM E180 (Withdrawn) for determining precision in analytical procedures.
• International Standards Alignment: ASTM E299-17a was developed according to WTO principles, ensuring international applicability and recognition.

Keywords: peroxide assay, organic solvents, peroxide detection, spectrophotometric analysis, chemical safety, ASTM E299-17a, trace peroxides, active oxygen quantification, laboratory QA/QC

ASTM E299-17a offers a reliable and practical approach to detecting trace peroxide levels, enhancing safety, compliance, and quality across chemical industries.

Standards Content (Sample)

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: E299 − 17a
Standard Test Method for
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* mendations issued by the World Trade Organization Technical
2,3 Barriers to Trade (TBT) Committee.
1.1 This test method covers organic solvents containing
active oxygen in the range from 5 to 80 µg/g (ppm) or higher.
2. Referenced Documents
By using a special reaction-absorption cell, the test method can
2.1 ASTM Standards:
be extended to cover the range from 0 to 5 ppm. The test
D1193 Specification for Reagent Water
method can be used to determine numerous peroxide classes of
D6809 Guide for Quality Control and Quality Assurance
varying reactivity such as hydroperoxides, diacyl peroxides,
Procedures for Aromatic Hydrocarbons and Related Ma-
diaroyl peroxides, peresters, and ketone peroxides. The stable
terials
di-tert-alkyl peroxides do not react under the conditions of
E180 Practice for Determining the Precision of ASTM
analysis.
Methods for Analysis and Testing of Industrial and Spe-
1.2 Solvents that can be analyzed successfully include
cialty Chemicals (Withdrawn 2009)
saturatedandaromatichydrocarbons,alcohols,ethers,ketones,
and esters. In addition, the test method is applicable to olefinic
3. Summary of Test Method
solvents and to certain compounds that contain α, β, and
3.1 A sample is dissolved in a mixture of acetic acid and
conjugated unsaturation. Solid samples that are soluble in the
chloroform. The solution is deaerated and potassium iodide
acetic acid-chloroform solvent also can be analyzed.
reagentsolutionisadded.Themixtureisallowedtoreactinthe
1.3 Review the current Safety Data Sheets (SDS) for de-
dark for 1 h, thereby releasing an equivalent amount of iodine.
tailed information concerning toxicity, first aid practices, and
The absorbance of the solution is measured at 470 nm and the
safety precautions.
amount of active oxygen present in the sample is determined
1.4 The values stated in SI units are to be regarded as
by reference to a calibration curve prepared from iodine.
standard. The values given in parentheses are for information
3.2 Forsamplescontaining0to5µg/g(ppm)activeoxygen,
only.
a special reaction-absorption cell is employed. The sample is
1.5 This standard does not purport to address the safety
de-aerated and the reaction is carried out within the cell.
concerns, if any, associated with its use. It is the responsibility
Absorbance measurements are made at 410 nm to increase the
of the user of this standard to establish appropriate safety,
sensitivity.
health, and environmental practices and determine the appli-
cability of regulatory limitations prior to use.
4. Significance and Use
1.6 This international standard was developed in accor-
4.1 Dilute solutions of peroxides in various organic solvents
dance with internationally recognized principles on standard-
frequently are used as catalysts or reaction initiators. Peroxides
ization established in the Decision on Principles for the
also can be formed through autoxidation in certain classes of
Development of International Standards, Guides and Recom-
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
This test method is under the jurisdiction of ASTM Committee D16 on
active oxygen level.
Aromatic, Industrial, Specialty and Related Chemicals and is the direct responsi-
bility of Subcommittee D16.12 on Caustics and Peroxides.
Current edition approved July 1, 2017. Published July 2017. Originally approved
in 1966. Last previous edition approved in 2017 as E299 – 17. DOI: 10.1520/ For referenced ASTM standards, visit the ASTM website, www.astm.org, or
E0299-17a. contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
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
E299 − 17a
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 distilled wa-
ter for several minutes prior to use.
8. Procedure
8.1 High Range—0 to 400 µg of Active Oxygen:
8.1.1 Preparation of Calibration Curve:
8.1.1.1 Dissolve 0.1270 g of iodine in acetic acid-
chloroform solvent (2 + 1) and dilute to 100 mL in a volumet-
ric flask. This solution contains 1.27 mg of iodine/mL, which
is equivalent to 80.0 µg of active oxygen/mL.
FIG. 1 Absorption Cell for Low-Active Oxygen
8.1.1.2 Transfer 0, 1, 2, 3, 4, and 5-mL aliquots of this
solution to 25-mL volumetric flasks and dilute each to volume
with the acetic acid-chloroform solvent. Mix thoroughly.
8.1.1.3 Usingahypodermicneedleorglasscapillary,sparge
5. Interferences
the solution with nitrogen for 1 to 1.5 min, add 1 mLof freshly
5.1 Oxidizing or reducing substances present in the sample
prepared KI solution, and continue the nitrogen flow for 1 min.
will interfere. Colored solutions can be analyzed if an absor-
Stopper and mix well.
bance correction is made.
8.1.1.4 Measure the absorbance of each solution at 470 nm,
using 1-cm cells and a water reference.
6. Apparatus
8.1.1.5 Subtract the absorbance of the blank and plot the
absorbance of each standard against micrograms of active
6.1 Spectrophotometer—Beckman Model DU or equivalent
with matched 1-cm cells. oxygen per 25 mL.
8.1.2 Analysis of Sample:
6.2 Special Reaction-Absorption Cell (Fig. 1)—When this
8.1.2.1 Transfer a sample containing up to 400 µg of active
cellisused,theregularBeckmancellcarriageshallbereplaced
oxygen to a 25-mL volumetric flask and dilute to volume with
with the attachment provided for measuring the absorbance in
acetic acid-chloroform solvent (2 + 1) (Note 1). Mix thor-
test tubes.
oughly.
7. Reagents
NOTE 1—A sample volume up to 15 mL may be used provided it is
miscible with the amount of acetic acid-chloroform solvent required to
7.1 Purity of Reagents—Reagent grade chemicals shall be
dilute the sample to 25 mL.
used in all tests. Unless otherwise indicated, it is intended that
8.1.2.2 Sparge the solution with nitrogen for 1 to 1.5 min,
all reagents shall conform to the specifications of the Commit-
add 1 mL of freshly prepared KI solution, and continue the
tee onAnalytical Reagents of theAmerican Chemical Society,
6 nitrogen flow for an additional 1 min.
where such specifications are available. Other grades may be
8.1.2.3 Stopper, mix well, and allow the solution to stand in
used, provided it is first ascertained that the reagent is of
the dark for 1 h.
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
NOTE 2—Very reactive peroxides react within less than 10 min, while
less reactive peroxides require up to 1 h for complete reaction. A general
7.2 Purity of Water—Unless otherwise indicated, references
reaction time for1his therefore specified.
to water shall be understood to mean Type II or Type III
8.1.2.4 Measure the absorbance of the solution at 470 nm
reagent water conforming to Specification D1193.
using 1-cm cells and a water reference.
7.3 Acetic Acid-Chloroform Solvent (2+1)—Mix 2 vol-
NOTE 3—Depending on the amount and type of sample present, some
umes of acetic acid with 1 volume of chloroform.
precipitation of KI may occur. However, the KI crystals readily settle to
the bottom in absorbance measurement.
8.1.2.5 Subtract the absorbance of a blank carried through
Reagent Chemicals, American Chemical Society Specifications, American
the entire procedure, and obtain the micrograms of active
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laborator
...

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: E299 − 17 E299 − 17a
Standard Test Method for
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*
2,3
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 α,β, and conjugated
unsaturation. Solid samples that are soluble in the acetic acid-chloroform solvent also can be analyzed.
1.3 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid practices, and safety
precautions.
1.4 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.5 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 Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid practices, and safety
precautions.
1.6 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:
D1193 Specification for Reagent Water
D6809 Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
E180 Practice for Determining the Precision of ASTM Methods for Analysis and Testing of Industrial and Specialty Chemicals
(Withdrawn 2009)
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
absorbance of the solution is measured at 470 nm and the amount of active oxygen present in the sample is determined by reference
to a calibration curve prepared from iodine.
This test method is under the jurisdiction of ASTM Committee D16 on Aromatic Hydrocarbons Aromatic, Industrial, Specialty and Related Chemicals and is the direct
responsibility of Subcommittee D16.15 on Industrial and Specialty General Standards.
Current edition approved Feb. 1, 2017July 1, 2017. Published February 2017July 2017. Originally approved in 1966. Last previous edition approved in 20082017 as
E299 – 08.E299 – 17. DOI: 10.1520/E0299-17.10.1520/E0299-17a.
Banerjee, D. K., and Budke, C. C., Analytical Chemistry, ANCHAM, Vol 36, 1964, pp. 792–796.
Banerjee, D. K., and Budke, C. C., Analytical Chemistry, ANCHAM, Vol 36, 1964, pp. 2367–2368.
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.
The last approved version of this historical standard is referenced on 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
E299 − 17a
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 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.
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.
6. Apparatus
6.1 Spectrophotometer—Beckman Model DU or equivalent with matched 1-cm cells.
6.2 Special Reaction-Absorption Cell (Fig. 1)—When this cell is used, the regular Beckman cell carriage shall be replaced with
the attachment provided for measuring the absorbance in test tubes.
7. Reagents
7.1 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.
7.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean Type II or Type III reagent
water conforming to Specification D1193.
7.3 Acetic Acid-Chloroform Solvent (2 + 1)—Mix 2 volumes of acetic acid with 1 volume of chloroform.
7.4 Acetic Acid-Chloroform Solvent (Containing Approximately 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.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
FIG. 1 Absorption Cell for Low-Active Oxygen
E299 − 17a
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 distilled water for several minutes prior to use.
8. Procedure
8.1 High Range—0 to 400 μg of Active Oxygen:
8.1.1 Preparation of Calibration Curve:
8.1.1.1 Dissolve 0.1270 g of iodine in acetic acid-chloroform solvent (2 + 1) and dilute to 100 mL in a volumetric flask. This
solution contains 1.27 mg of iodine/mL, which is equivalent to 80.0 μg of active oxygen/mL.
8.1.1.2 Transfer 0, 1, 2, 3, 4, and 5-mL aliquots of this solution to 25-mL volumetric flasks and dilute each to volume with the
acetic acid-chloroform solvent. Mix thoroughly.
8.1.1.3 Using a hypodermic needle or glass capillary, sparge the solution with nitrogen for 1 to 1.5 min, add 1 mL of freshly
prepared KI solution, and continue the nitrogen flow for 1 min. Stopper and mix well.
8.1.1.4 Measure the absorbance of each solution at 470 nm, using 1-cm cells and a water reference.
8.1.1.5 Subtract the absorbance of the blank and plot the absorbance of each standard against micrograms of active oxygen per
25 mL.
8.1.2 Analysis of Sample:
8.1.2.1 Transfer a sample containing up to 400 μg of active oxygen to a 25-mL volumetric flask and dilute to volume with acetic
acid-chloroform solvent (2 + 1) (Note 1). Mix thoroughly.
NOTE 1—A sample volume up to 15 mL may be used provided it is miscible with the amount of acetic acid-chloroform solvent required to dilute the
sample to 25 mL.
8.1.2.2 Sparge the solution with nitrogen for 1 to 1.5 min, add 1 mL of freshly prepared KI solution, and continue the nitrogen
flow for an additional 1 min.
8.1.2.3 Stopper, mix well, and allow the solution to stand in the dark for 1 h.
NOTE 2—Very reactive peroxides react within less than 10 min, while less reactive peroxides require up to 1 h for complete reaction. A general reaction
time for 1 h is therefore specified.
8.1.2.4 Measure the absorbance of the solution at 470 n
...