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Reaction of excited oxygen atoms, O(^1D_2), with cyclobutane

Colussi, A. J. and Cvetanović, R. J. (1975) Reaction of excited oxygen atoms, O(^1D_2), with cyclobutane. Journal of Physical Chemistry, 79 (18). pp. 1891-1899. ISSN 0022-3654.

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Gas and liquid phase reaction of singlet oxygen atoms O(^1D_2) with cyclobutane has been studied at room temperature (25 ± 2°). The effects of pressure and of O_2 on the yields of the main products show that the reaction mechanism is basically the same as found in related reactions of O(^1D_2) with saturated hydrocarbons. The insertion product, excited cyclobutanol, is only partly stabilized in the gas phase at pressures below 15 atm. Its decomposition products are ethylene and acetaldehyde. From the pressure dependence of the yields of ethylene a lifetime of 8 x 10^(-12) sec is estimated for the excited cyclobutanol, assuming that deactivation occurs at each collision. This result is used to evaluate approximately the Arrhenius A factor for unimolecular decomposition of cyclobutanol. The calculated value is consistent with the literature value of A for pyrolysis of cyclobutanol, in agreement with the postulate that the “hot” intermediate is vibrationally excited cyclobutanol in the ground electronic state.

Item Type:Article
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Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1975 American Chemical Society. (Received January 6, 1975) Publication costs assisted by the National Research Council of Canada. The authors are grateful to Mr. R. S. Irwin for carrying out the experiments in Table II.
Funding AgencyGrant Number
National Research Council of CanadaUNSPECIFIED
Comisión Nacional de Investigación Científica y Tecnológica (CONICYT)UNSPECIFIED
Issue or Number:18
Record Number:CaltechAUTHORS:20150623-154816985
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Official Citation:Reaction of excited oxygen atoms, O(1D2), with cyclobutane A. J. Colussi and R. J. Cvetanovic The Journal of Physical Chemistry 1975 79 (18), 1891-1899 DOI: 10.1021/j100585a001
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58555
Deposited By: George Porter
Deposited On:24 Jun 2015 14:57
Last Modified:03 Oct 2019 08:37

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