ASTM E299 Standard Test Method for Trace Amounts of Peroxides in Organic Solvents

Get Certified ASTM E299 Peroxide Testing

The ASTM E299 method applies to active oxygen levels in the range of 5 to 80 μg/g (ppm) or higher, and it can be adapted to 0 to 5 ppm using a special reaction-absorption cell. ASTM E299 certification allows chemical suppliers, solvent manufacturers, and quality professionals to measure peroxide concentration in peroxide-forming products that may form peroxides during storage, processing, or application. In some classes of compounds (e.g., ethers, acetals, dienes, and alkylaromatic hydrocarbons), peroxide formation may also occur by autoxidation, and the peroxide levels are relevant for the assessment of solvents for application and also for process safety considerations.

• Material Type: Organic solvents and some samples of soluble solids.
• Purpose: To determine the amount of trace peroxide or active oxygen. 
• Property Measured: Active oxygen/peroxide concentration. 
• Chemical reaction and spectrophotometric absorbance measurement. 
• Result: Concentration of peroxide/active oxygen (usually in μg/g or ppm).
• Test Limitations: In the specified analytical conditions, stable di-tert-alkyl peroxides do not react, and oxidizing or reducing substances may interfere with the determination. 
• Environmental Conditions: Testing is conducted according to the requirements of reagents, reaction, deaeration, temperature, and reaction time.

What are the uses of ASTM E299 testing?

The ASTM E299 test measures the presence of trace peroxide formation in organic solvents. Compounds that contain ethers, acetals, dienes, and alkylaromatic hydrocarbons can form peroxides via autoxidation, which may pose a safety risk. The test helps to:

• Monitor Peroxide Formation: Detect trace active oxygen in susceptible organic solvents. 
• Support Quality Control: Carry out solvent quality assessment per relevant specification. 
• Evaluate Storage Conditions: Determine if there are storage and handling conditions that lead to the accumulation of peroxides. 
• Support Process Control: Analytical information for chemical manufacturing and processing. 
• Enhance Safety Evaluation: Detect peroxide in materials that may create a hazard due to peroxide formation.

Which Materials Can Be Tested According to ASTM E299?

ASTM E299 covers a variety of organic solvents. The standard lists saturated hydrocarbons, aromatic hydrocarbons, alcohols, ethers, ketones, and esters as classes of solvents that are appropriate and provides guidelines for the applicability of the standard to olefinic solvents and to some compounds with α, β, and conjugated unsaturation. The method applies to:

• Hydrocarbon Solvents: Saturated and aromatic hydrocarbons.
• Oxygenated Solvents: Alcohols, ethers, ketones, and esters.
• Unsaturated Solvents: Olefinic solvents and selected compounds containing α, β, or conjugated unsaturation.
• Other Samples: Solid samples that are soluble in the specified acetic acid-chloroform solvent.

Why is ASTM E299 Testing Important?

Trace peroxide testing is important because organic solvents can accumulate peroxides through chemical oxidation during storage and use. ASTM E299 provides a standardized approach for determining peroxide or active oxygen levels so technicians can evaluate solvent condition using reproducible analytical measurements.

ASTM E299 Testing Process and Data Collection

The ASTM E299 testing process determines the trace amount of peroxide or active oxygen present in an organic solvent through a controlled chemical reaction and analytical measurement. Technicians prepare the sample and required reagents, perform the specified reaction, and measure the resulting analytical response using the applicable spectrophotometric procedure. ASTM E299 covers active oxygen concentrations from 5 μg/g (ppm) to 80 μg/g (ppm) or higher, while the special reaction-absorption cell extends the method to the 0-5 ppm range.

Common Challenges and Troubleshooting

Technicians performing ASTM E299 testing might face problems which can impact the results’ accuracy, sensitivity, or repeatability in measuring peroxide or active oxygen. Sample interference, reagent condition, calibration and handling of very low levels of peroxide are common problems. If the sample contains oxidising or reducing materials, they can affect the peroxide determination. The result should be interpreted with caution in consideration of the applicable interference factors and the composition of the sample analyzed. Variations in reaction conditions, measurement technique, or instrument operation can reduce repeatability. For the analysts, the test conditions should be kept constant and the spectrophotometer should be checked prior to measurement.

• The report expresses the active oxygen result as μg/g (ppm) for the applicable concentration range. The standard covers approximately 5 to 80 μg/g (ppm) or higher, while the special reaction-absorption cell can extend the measurement range down to 0 ppm to 5 ppm.
• The technician records the sample identification, sample preparation details, reagent information, reaction conditions, and applicable spectrophotometric measurement wavelength.
• The analyst documents the measured absorbance and determines the corresponding active oxygen concentration using the applicable calibration curve.
• Analysts record calibration information, sample condition, analytical observations, interference corrections when applicable, and other required test information.
• Engineers and quality professionals compare the measured peroxide or active oxygen concentrations with applicable specifications or internal requirements to support solvent quality control, process monitoring, storage evaluation, and safety-related decisions.

Link to ASTM E299