Mechanisms and kinetics of alkaline hydrolysis of the energetic nitroaromatic compounds 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroanisole (DNAN)

Alexandra J. Salter-Blanc, Eric J. Bylaska, Julia J. Ritchie, Paul Tratnyek

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The environmental impacts of energetic compounds can be minimized through the design and selection of new energetic materials with favorable fate properties. Building predictive models to inform this process, however, is difficult because of uncertainties and complexities in some major fate-determining transformation reactions such as the alkaline hydrolysis of energetic nitroaromatic compounds (NACs). Prior work on the mechanisms of the reaction between NACs and OH- has yielded inconsistent results. In this study, the alkaline hydrolysis of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroanisole (DNAN) was investigated with coordinated experimental kinetic measurements and molecular modeling calculations. For TNT, the results suggest reversible formation of an initial product, which is likely either a Meisenheimer complex or a TNT anion formed by abstraction of a methyl proton by OH-. For DNAN, the results suggest that a Meisenheimer complex is an intermediate in the formation of 2,4-dinitrophenolate. Despite these advances, the remaining uncertainties in the mechanisms of these reactions-and potential variability between the hydrolysis mechanisms for different NACs-mean that it is not yet possible to generalize the results into predictive models (e.g., quantitative structure-activity relationships, QSARs) for hydrolysis of other NACs.

Original languageEnglish (US)
Pages (from-to)6790-6798
Number of pages9
JournalEnvironmental Science and Technology
Volume47
Issue number13
DOIs
StatePublished - Jul 2 2013

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Trinitrotoluene
trinitrotoluene
hydrolysis
Hydrolysis
energetics
kinetics
Kinetics
Molecular modeling
Anions
Environmental impact
Protons
anion
environmental impact
2,4-dinitroanisole
modeling
hydroxide ion
Uncertainty

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry

Cite this

Mechanisms and kinetics of alkaline hydrolysis of the energetic nitroaromatic compounds 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroanisole (DNAN). / Salter-Blanc, Alexandra J.; Bylaska, Eric J.; Ritchie, Julia J.; Tratnyek, Paul.

In: Environmental Science and Technology, Vol. 47, No. 13, 02.07.2013, p. 6790-6798.

Research output: Contribution to journalArticle

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