Journal
ENVIRONMENTAL SCIENCE & TECHNOLOGY
Volume 49, Issue 6, Pages 3778-3786Publisher
AMER CHEMICAL SOC
DOI: 10.1021/es505092s
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Funding
- Strategic Environmental Research and Development Program (SERDP) [ER-1735]
- OHSU
- Department of Energy's Office of Biological and Environmental Research located at Pacific Northwest National Laboratory [DE-AC06-76RLO 1830]
- EMSL
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The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental f4te. Previously invoked linear free energy relationships (LFER) relating the log of the rate constant for this reaction (log(k)) and one-electron reduction potentials for the NAC (E-NAC(1)) normalized to 0.059 V have been re-evaluated and compared to a new analysis using a (nonlinear) free-energy relationship (FER) based On the Marcus theory of outersphere electron transfer. For most reductants, the results are inconsistent with simple rate limitation by an initial, outer-sphere electron transfer, suggesting that the linear correlation between log(k) and E-NAC(1) is best regarded as an empirical model. This correlation was used to calibrate a new quantitative structure-activity relationship (QSAR) using previously reported values of log(k) for nonehergetic NAC reduction by Fe(II) porphyrin and newly reported values of E-NAC(1) determined using density functional theory at the M06-2X/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-trinitrotoluehe (TNT), 2,4-dinitrotoluene (2,4-DNT), and 2,4-dinitroanisole (DNAN). The data show close agreement with the QSAR, supporting its applicability to other energetic NACs.
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