Water Vapor Does Not Catalyze the Reaction between Methanol and OH Radicals

Angewandte Chemie
Wen ChaoChrista Fittschen

Abstract

Recent reports [Jara-Toro et al., Angew. Chem. Int. Ed. 2017, 56, 2166 and PCCP 2018, 20, 27885] suggest that the rate coefficient of OH reactions with alcohols would increase by up to two times in going from dry to high humidity. This finding would have an impact on the budget of alcohols in the atmosphere and it may explain differences in measured and modeled methanol concentrations. The results were based on a relative technique carried out in a small Teflon bag, which might suffer from wall reactions. The effect was reinvestigated using a direct fluorescence probe of OH radicals, and no catalytic effect of H2 O could be found. Experiments in a Teflon bag were also carried out, but the results of Jara-Toro et al. were not reproducible. Further theoretical calculations show that the water-mediated reactions have negligible rates compared to the bare reaction and that even though water molecules can lower the barriers of reactions, they cannot make up for the entropy cost.

References

Jan 27, 2007·Science·E Vöhringer-MartinezB Abel
Aug 21, 2012·Physical Chemistry Chemical Physics : PCCP·Ditte Linde ThomsenHenrik G Kjaergaard
Oct 18, 2016·Nature Communications·Jean-François MüllerJozef Peeters
Sep 28, 2017·Physical Chemistry Chemical Physics : PCCP·B NarayanT Nakanishi
Oct 21, 2018·Nature Communications·Rebecca L CaravanCraig A Taatjes
Nov 1, 2018·Physical Chemistry Chemical Physics : PCCP·Rafael A Jara-ToroGustavo A Pino
Sep 1, 2012·Atmospheric Chemistry and Physics·K E Cady-PereiraJ Worden

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Citations

Apr 2, 2020·Physical Chemistry Chemical Physics : PCCP·Isabelle WeberChrista Fittschen
Aug 6, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Mei-Tsan KuoJim Jr-Min Lin
Dec 23, 2021·Physical Chemistry Chemical Physics : PCCP·Manas Ranjan Dash, Mohamad Akbar Ali

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