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 G.

doi:10.1021/es304461t

Title: Mechanisms and Kinetics of Alkaline Hydrolysis of the Energetic Nitroaromatic Compounds 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN)

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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.

Authors:: Salter-Blanc, Alexandra J.; Bylaska, Eric J.; Ritchie, Julia J.; Tratnyek, Paul G.

Publication Date:: Tue Jul 02 00:00:00 EDT 2013

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1092648

Report Number(s):: PNNL-SA-93956
Journal ID: ISSN 0013-936X; 40016; 400403209

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Environmental Science and Technology

Additional Journal Information:: Journal Volume: 47; Journal Issue: 13; Journal ID: ISSN 0013-936X

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: Hydrolysis mechanism; Rate constants; Activation energy; Free energy; Environmental Molecular Sciences Laboratory

Citation Formats


                    Salter-Blanc, Alexandra J., Bylaska, Eric J., Ritchie, Julia J., and Tratnyek, Paul G. Mechanisms and Kinetics of Alkaline Hydrolysis of the Energetic Nitroaromatic Compounds 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN).  United States: N. p., 2013. 
        Web.  doi:10.1021/es304461t.

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                    Salter-Blanc, Alexandra J., Bylaska, Eric J., Ritchie, Julia J., & Tratnyek, Paul G. Mechanisms and Kinetics of Alkaline Hydrolysis of the Energetic Nitroaromatic Compounds 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN).  United States.  https://doi.org/10.1021/es304461t

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                    Salter-Blanc, Alexandra J., Bylaska, Eric J., Ritchie, Julia J., and Tratnyek, Paul G. 2013.  
        "Mechanisms and Kinetics of Alkaline Hydrolysis of the Energetic Nitroaromatic Compounds 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN)".  United States.  https://doi.org/10.1021/es304461t.

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@article{osti_1092648,

  title        = {Mechanisms and Kinetics of Alkaline Hydrolysis of the Energetic Nitroaromatic Compounds 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN)},

  author       = {Salter-Blanc, Alexandra J. and Bylaska, Eric J. and Ritchie, Julia J. and Tratnyek, Paul G.},

  abstractNote = {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.},

  doi          = {10.1021/es304461t},

  url          = {https://www.osti.gov/biblio/1092648},
  journal      = {Environmental Science and Technology},

  issn         = {0013-936X},

  number       = 13,

  volume       = 47,

  place        = {United States},

  year         = {Tue Jul 02 00:00:00 EDT 2013},

  month        = {Tue Jul 02 00:00:00 EDT 2013}

}

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