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

被引：22

作者：

Chao, Wen ^{[2
]}

Lin, Jim Jr-Min ^{[2
]}

Takahashi, Kaito ^{[2
]}

Tomas, Alexandre ^{[3
]}

Yu, Lu ^{[4
]}

Kajii, Yoshizumi ^{[4
]}

Batut, Sebastien ^{[1
]}

Schoemaecker, Coralie ^{[1
]}

Fittschen, Christa ^{[1
]}

机构：

[1] Univ Lille, CNRS, UMR 8522, Phys Chem Combust & Atmospher Proc, Bat C11, F-59655 Villeneuve Dascq, France

[2] Acad Sinica, Inst Atom & Mol Sci, Taipei 10617, Taiwan

[3] IMT Lille Douai, SAGE, 941 Rue Charles Bourseul, F-59508 Douai, France

[4] Kyoto Univ, Dept Nat Sources, Atmospher Chem, Kyoto 6068501, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 15期

关键词：

alcohols; atmospheric chemistry; fluorescence; radical reactions; reaction mechanisms; ATMOSPHERIC CHEMISTRY; ORGANIC-COMPOUNDS; KINETICS; PHOTOLYSIS; CH3OH;

D O I：

10.1002/anie.201900711

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Recent reports [Jara-Toro etal., Angew. Chem. Int. Ed. 2017, 56, 2166 and PCCP2018, 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 H2O could be found. Experiments in a Teflon bag were also carried out, but the results of Jara-Toro etal. 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.

引用

页码：5013 / 5017

页数：5

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