000206155 001__ 206155
000206155 005__ 20181203023813.0
000206155 0247_ $$2doi$$a10.1021/jp511408f
000206155 022__ $$a1089-5639
000206155 02470 $$2ISI$$a000352331600010
000206155 037__ $$aARTICLE
000206155 245__ $$aControlling Factors in the Rates of Oxidation of Anilines and Phenols by Triplet Methylene Blue in Aqueous Solution
000206155 260__ $$bAmerican Chemical Society$$c2015$$aWashington
000206155 269__ $$a2015
000206155 300__ $$a11
000206155 336__ $$aJournal Articles
000206155 520__ $$aAnilines 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 SandrosBoltzmann 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 pK(a center dot) 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.
000206155 700__ $$aErickson, Paul R.
000206155 700__ $$aWalpen, Nicolas
000206155 700__ $$0242212$$g198259$$aGuerard, Jennifer J.
000206155 700__ $$aEustis, Soren E.
000206155 700__ $$g169370$$aArey, J. Samuel$$0240042
000206155 700__ $$aMcNeill, Kristopher
000206155 773__ $$j119$$tJournal of Physical Chemistry A$$k13$$q3233-3243
000206155 909C0 $$0252024$$pLMCE$$xU11955
000206155 909CO $$particle$$ooai:infoscience.tind.io:206155
000206155 917Z8 $$x169370
000206155 917Z8 $$x169370
000206155 917Z8 $$x169370
000206155 937__ $$aEPFL-ARTICLE-206155
000206155 973__ $$rREVIEWED$$sPUBLISHED$$aOTHER
000206155 980__ $$aARTICLE