Issue 9, 2006

Tunneling in the reaction of acetone with OH

Abstract

Based on recent detailed quantum mechanical computations of the mechanism of the title reaction (Phys. Chem. Chem. Phys., 2003, 5, 333) and (J. Chem. Phys., 2003, 119, 10 600), this paper presents kinetics analysis of the overall rate constant and its temperature dependence, for which ample experimental data are available for comparison. The analysis confirms that the principal channel is the formation of acetonyl radical + H2O, while the channel leading to acetic acid is of negligible importance. It is shown that the unusual temperature dependence of the overall rate constant, as observed experimentally, is well accounted for by standard RRKM treatment that includes tunneling. This treatment is applied at the microcanonical level, with chemically activated distribution of entrance species, i.e. using a stationary rather than a thermal distribution that incorporates collisional energy transfer and competition between the redissociation and exit channel. A similar procedure is applied to the isotopic reaction acetone-d6 + OH with equally satisfying results, so that the experimental temperature dependence of the KIE (kinetic isotope effect) is perfectly reproduced. This very good agreement between calculation and experiment is obtained without any fitting to experimental values and without any adjustment of the parameters of calculation.

Graphical abstract: Tunneling in the reaction of acetone with OH

Supplementary files

Article information

Article type
Paper
Submitted
25 Oct 2005
Accepted
16 Jan 2006
First published
06 Feb 2006

Phys. Chem. Chem. Phys., 2006,8, 1072-1078

Tunneling in the reaction of acetone with OH

F. Caralp, W. Forst, E. Hénon, A. Bergeat and F. Bohr, Phys. Chem. Chem. Phys., 2006, 8, 1072 DOI: 10.1039/B515118J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements