Controlling Factors in the Rates of Oxidation of Anilines and Phenols by Triplet Methylene Blue in Aqueous Solution

Paul R. Erickson, Nicolas Walpen, Jennifer J. Guerard, Soren N. Eustis, J. Samuel Arey, Kristopher McNeill

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

Anilines and phenols are structurally similar compound classes that both are susceptible to oxidation by excited state triplet sensitizers but undergo oxidation by different mechanisms. To gain an understanding of the factors that control the rate of oxidation of anilines and phenols by triplet excited states, a kinetic study was performed on the oxidation of substituted anilines and phenols by methylene blue. The rate constants of one-electron transfer from anilines to triplet state methylene blue and their dependence on the reaction free energy are well fit to a Sandros-Boltzmann model. The observed rate constants are also well modeled when aniline oxidation potentials derived computationally are used. For phenols, the proton-coupled electron transfer rate constants were found to correlate primarily with O-H bond dissociation free energy and secondarily with phenol pKa. Rate constants for phenols could be modeled using computed bond dissociation free energies. These results provide a basis for predicting aniline and phenol oxidation rates, which could be valuable, for example, in assessing the likely persistence and fate of aniline- and phenol-based aqueous environmental pollutants. (Figure Presented).

Original languageEnglish (US)
Pages (from-to)3233-3243
Number of pages11
JournalJournal of Physical Chemistry A
Volume119
Issue number13
DOIs
StatePublished - Apr 2 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

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