The effects of water vapor on the CH3O2 self-reaction and reaction with HO2

The Journal of Physical Chemistry. a
Alecia M EnglishM Matti Maricq

Abstract

The gas phase reactions of CH3O2 + CH3O2, HO2 + HO2, and CH3O2 + HO2 in the presence of water vapor have been studied at temperatures between 263 and 303 K using laser flash photolysis coupled with UV time-resolved absorption detection at 220 and 260 nm. Water vapor concentrations were quantified using tunable diode laser spectroscopy operating in the mid-IR. The HO2 self-reaction rate constant is significantly enhanced by water vapor, consistent with what others have reported, whereas the CH3O2 self-reaction and the cross-reaction (CH3O2 + HO2) rate constants are nearly unaffected. The enhancement in the HO2 self-reaction rate coefficient occurs because of the formation of a strongly bound (6.9 kcal mol(-1)) HO2 x H2O complex during the reaction mechanism where the H2O acts as an energy chaperone. The nominal impact of water vapor on the CH3O2 self-reaction rate coefficient is consistent with recent high level ab initio calculations that predict a weakly bound CH3O2 x H2O complex (2.3 kcal mol(-1)). The smaller binding energy of the CH3O2 x H2O complex does not favor its formation and consequent participation in the methyl peroxy self-reaction mechanism.

References

Jan 20, 2006·The Journal of Physical Chemistry. a·Mikhail G BryukovVadim D Knyazev
May 26, 2006·The Journal of Physical Chemistry. a·Lance E ChristensenJoseph S Francisco
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Citations

May 9, 2012·The Journal of Physical Chemistry. a·Robert J BuszekJoseph S Francisco
Jul 20, 2011·The Journal of Chemical Physics·Veronica Vaida
Sep 30, 2017·Physical Chemistry Chemical Physics : PCCP·Junyao LiLin Du
Oct 19, 2011·Physical Chemistry Chemical Physics : PCCP·Tianlei ZhangYue Zhang
Sep 5, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Junyao LiLin Du
Sep 29, 2009·The Journal of Physical Chemistry. a·Nadezhda ButkovskayaGeorges Le Bras
Jun 8, 2010·The Journal of Physical Chemistry. a·A C NoellS P Sander
Jun 13, 2015·The Journal of Physical Chemistry. a·Matthew K Sprague, Karl K Irikura

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