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Updated: Jun 10, 2026

Research and Development of High-performance Explosives
Published on: February 20, 2016
One-electron standard reduction potentials of nitroaromatic and cyclic nitramine explosives
Minori Uchimiya1, Leonid Gorb, Olexandr Isayev
1Environmental Laboratory, U.S. Army Engineer Research and Development Center, Vicksburg, MS 39180, USA. sophie.uchimiya@ars.usda.gov
This study determined one-electron standard reduction potentials (Eo(R-NO2/R-NO2-)) for explosives. Values decrease from nitroaromatics to nitramines, predicting environmental reductive transformation rates.
Area of Science:
- Environmental Chemistry
- Computational Chemistry
- Energetic Materials Science
Background:
- Nitroaromatic and nitramine explosives pose environmental risks, necessitating understanding of their redox fate.
- One-electron standard reduction potentials (Eo(R-NO2/R-NO2-)) are critical for predicting reductive transformation but are poorly characterized.
- Energetic residues from military sites and emerging contaminants require accurate thermodynamic data for risk assessment.
Purpose of the Study:
- To experimentally and theoretically determine the one-electron standard reduction potentials (Eo(R-NO2/R-NO2-)) for various explosives.
- To establish thermodynamic parameters essential for predicting the rate and extent of reductive degradation of energetic materials.
- To investigate the trend of Eo(R-NO2/R-NO2-) across different classes of explosives, including nitroaromatics, nitramines, and nitroimino compounds.
Main Methods:
- Employed experimental linear free energy relationships (LFERs) to determine reduction potentials.
- Utilized theoretical ab initio calculations for complementary determination of reduction potentials.
- Focused on nitroaromatic, cyclic nitramine, and nitroimino compounds relevant to military sites and environmental contamination.
Main Results:
- Achieved close agreement between experimental and theoretical Eo(R-NO2/R-NO2-) values.
- Identified a clear trend: Eo(R-NO2/R-NO2-) decreases from nitroaromatics to nitramines to nitroimino compounds.
- Observed correlation between the determined Eo(R-NO2/R-NO2-) trend and reported reductive degradation rates.
Conclusions:
- The one-electron standard reduction potential (Eo(R-NO2/R-NO2-)) is a key thermodynamic parameter for predicting explosive transformation.
- Thermodynamic control, as indicated by the Eo(R-NO2/R-NO2-) trend, governs the rate of reductive degradation under anoxic/suboxic conditions.
- The findings provide crucial data for assessing the environmental fate and remediation strategies for energetic residues.
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