Hydrogen Atom Transfer Reaction Free Energy as a Predictor of Abiotic Nitroaromatic Reduction Rate Constants: A Comprehensive Analysis.

A linear free energy model is presented that predicts the second-order rate constant for the abiotic reduction of nitroaromatic compounds (NACs). Previously presented models use the one-electron reduction potential E H 1 ( ArNO 2 ) of the NAC reaction ArNO 2 + e - → ArNO 2 • - . If E H 1 ( ArNO 2 ) is not available, it has been proposed that E H 1 ( ArNO 2 ) be computed directly or estimated from the gas-phase electron affinity (EA). The model proposed uses the Gibbs free energy of the hydrogen atom transfer (HAT) reaction ArNO 2 + H • → ArNOOH • as the parameter in the linear free energy model. Both models employ quantum chemical computations for the required thermodynamic energies. The available and proposed models are compared using experimentally determined second-order rate constants from 5 investigations from the literature in which a variety of NACs were exposed to a variety of reductants. A comprehensive analysis utilizing all the NACs and reductants demonstrate that the HAT energy model and the experimental one-electron reduction potential model have similar root mean square errors and residual error probability distributions. In contrast, the model using the computed EA has a more variable residual error distribution with a significant number of outliers. The results suggest that a linear free energy model utilizing computed HAT reaction free energy produces a more reliable prediction of the NAC abiotic reduction second-order rate constant than previously available methods. The advantages of the proposed HAT energy model and its mechanistic implications are discussed as well. Environ Toxicol Chem 2020;39:1678-1684. © 2020 SETAC.
(© 2020 SETAC.)