Predicting Reduction Rates of Energetic Nitroaromatic Compounds Using Calculated One-Electron Reduction Potentials

Salter-Blanc, Alexandra; Bylaska, Eric J.; Johnston, Hayley; Tratnyek, Paul G.

doi:10.1021/es505092s

Title: Predicting Reduction Rates of Energetic Nitroaromatic Compounds Using Calculated One-Electron Reduction Potentials

Journal Article · Wed Feb 11 00:00:00 EST 2015 · Environmental Science & Technology, 49(6):3778-3786

DOI:https://doi.org/10.1021/es505092s· OSTI ID:1184952

Salter-Blanc, Alexandra; Bylaska, Eric J.; Johnston, Hayley; Tratnyek, Paul G.

The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. The susceptibility of energetic NACs to nitro reduction might be predicted from correlations between rate constants (k) for this reaction and one-electron reduction potentials (E1NAC) / 0.059 V, but the mechanistic implications of such correlations are inconsistent with evidence from other methods. To address this inconsistency, we have reevaluated existing kinetic data using a (non-linear) free-energy relationship (FER) based on the Marcus theory of outer-sphere electron transfer. For most reductants, the results are inconsistent with rate limitation by an initial, outer-sphere electron transfer, suggesting that the strong correlation between k and E1NAC is justified only as an empirical model. This empirical correlation was used to calibrate a new quantitative structure-activity relationship (QSAR) using previously reported values of k for non-energetic NAC reduction by Fe(II) porphyrin and newly reported values of E1NAC determined using density functional theory at the B3LYP/6-311++G(2d,2p) level with the COSMO solvation model. The QSAR was then validated for energetic NACs using newly measured kinetic data for 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), and 2,4-dinitroanisole (DNAN). The data show close agreement with the QSAR, supporting its applicability to energetic NACs.

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

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1184952

Report Number(s):: PNNL-SA-106393; 40016; 400403209

Journal Information:: Environmental Science & Technology, 49(6):3778-3786, Journal Name: Environmental Science & Technology, 49(6):3778-3786

Country of Publication:: United States

Language:: English

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Title: Predicting Reduction Rates of Energetic Nitroaromatic Compounds Using Calculated One-Electron Reduction Potentials

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