Predicting reduction rates of energetic nitroaromatic compounds using calculated one-electron reduction potentials

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

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. 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 (E1 NAC) 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 outer-sphere 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 E1 NAC 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 nonenergetic NAC reduction by Fe(II) porphyrin and newly reported values of E1 NAC 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-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 other energetic NACs.

Original languageEnglish (US)
Pages (from-to)3778-3786
Number of pages9
JournalEnvironmental Science and Technology
Volume49
Issue number6
DOIs
StatePublished - Mar 17 2015

Fingerprint

2,4-dinitrotoluene
energetics
electron
Free energy
Electrons
Trinitrotoluene
trinitrotoluene
porphyrin
environmental fate
Reducing Agents
Porphyrins
Solvation
Density functional theory
energy
Rate constants
kinetics
Kinetics
rate
structure-activity relationship
2,4-dinitroanisole

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry

Cite this

Predicting reduction rates of energetic nitroaromatic compounds using calculated one-electron reduction potentials. / Salter-Blanc, Alexandra J.; Bylaska, Eric J.; Johnston, Hayley J.; Tratnyek, Paul.

In: Environmental Science and Technology, Vol. 49, No. 6, 17.03.2015, p. 3778-3786.

Research output: Contribution to journalArticle

Salter-Blanc, Alexandra J. ; Bylaska, Eric J. ; Johnston, Hayley J. ; Tratnyek, Paul. / Predicting reduction rates of energetic nitroaromatic compounds using calculated one-electron reduction potentials. In: Environmental Science and Technology. 2015 ; Vol. 49, No. 6. pp. 3778-3786.
@article{abfed8d497864cde92df90e46558a6b7,
title = "Predicting reduction rates of energetic nitroaromatic compounds using calculated one-electron reduction potentials",
abstract = "The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. 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 (E1 NAC) 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 outer-sphere 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 E1 NAC 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 nonenergetic NAC reduction by Fe(II) porphyrin and newly reported values of E1 NAC 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-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 other energetic NACs.",
author = "Salter-Blanc, {Alexandra J.} and Bylaska, {Eric J.} and Johnston, {Hayley J.} and Paul Tratnyek",
year = "2015",
month = "3",
day = "17",
doi = "10.1021/es505092s",
language = "English (US)",
volume = "49",
pages = "3778--3786",
journal = "Environmental Science & Technology",
issn = "0013-936X",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Predicting reduction rates of energetic nitroaromatic compounds using calculated one-electron reduction potentials

AU - Salter-Blanc, Alexandra J.

AU - Bylaska, Eric J.

AU - Johnston, Hayley J.

AU - Tratnyek, Paul

PY - 2015/3/17

Y1 - 2015/3/17

N2 - The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. 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 (E1 NAC) 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 outer-sphere 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 E1 NAC 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 nonenergetic NAC reduction by Fe(II) porphyrin and newly reported values of E1 NAC 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-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 other energetic NACs.

AB - The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. 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 (E1 NAC) 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 outer-sphere 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 E1 NAC 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 nonenergetic NAC reduction by Fe(II) porphyrin and newly reported values of E1 NAC 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-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 other energetic NACs.

UR - http://www.scopus.com/inward/record.url?scp=84925002443&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84925002443&partnerID=8YFLogxK

U2 - 10.1021/es505092s

DO - 10.1021/es505092s

M3 - Article

C2 - 25671710

AN - SCOPUS:84925002443

VL - 49

SP - 3778

EP - 3786

JO - Environmental Science & Technology

JF - Environmental Science & Technology

SN - 0013-936X

IS - 6

ER -