In:
Zeitschrift für Physikalische Chemie, Walter de Gruyter GmbH, Vol. 219, No. 9 ( 2005-9-1), p. 1205-1222
Abstract:
Rate coefficients of β-scission reactions in tertiary alkoxy radicals, R(CH 3 ) 2 CO (R = methyl, ethyl, tert -butyl and neo -pentyl) have been estimated via density functional theory (DFT) calculations in conjunction with statistical unimolecular rate theory. For tert -butoxy, results obtained by employing different basis sets are compared with experimental values, indicating that UB3LYP/6-31G(d,p) excellently predicts kinetic data. Rate coefficients for inter- and intramolecular hydrogen abstraction are also reported. Depending on R, the β-scission rate may vary by orders of magnitude. The predicted temperature dependence of the alcohol-to-ketone product ratios for alkoxy radical decomposition in a hydrocarbon environment is in remarkably close agreement with the corresponding ratios measured on the product mixtures from decomposition of tert -butyl and tert -amyl peroxyacetates in solution of n -heptane.
Type of Medium:
Online Resource
ISSN:
2196-7156
,
0942-9352
DOI:
10.1524/zpch.2005.219.9.1205
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
2005
detail.hit.zdb_id:
201103-7
Bookmarklink