Volume 75, 1983
From the journal:

Faraday Discussions of the Chemical Society

Unimolecular decomposition of t-butylhydroperoxide by direct excitation of the 6–0 O—H stretching overtone

Mei-Chen Chuang,   James E. Baggott,   David W. Chandler,   William E. Farneth  and  Richard N. Zare  

Abstract

The kinetics of the unimolecular decomposition of t-butylhydroperoxide [(CH3)3COOH] have been investigated when energy is deposited into 6 quanta of the O—H stretch, causing fission of the O—O bond. The 6–0 O—H overtone is pumped at 532 nm and the appearance of one of the ultimate products, t-butyl alcohol, is detected using optoacoustic spectroscopy to follow the reaction in situ. The results of the present work are compared with previous dissociation studies using direct overtone pumping at both 532 and 619 nm. The appearance rate of t-butyl alcohol as a function of pressure is not consistent with an R.R.K.M. treatment based on simple Stern–Volmer kinetics, but can be adequately fit by invoking collisional transfer to an electronic state, which decomposes more rapidly than the ground state, and/or invoking non-statistical behaviour.

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Article information

DOI
https://doi.org/10.1039/DC9837500301
Article type
Paper

Faraday Discuss. Chem. Soc., 1983,75, 301-313

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Unimolecular decomposition of t-butylhydroperoxide by direct excitation of the 6–0 O—H stretching overtone

M. Chuang, J. E. Baggott, D. W. Chandler, W. E. Farneth and R. N. Zare, Faraday Discuss. Chem. Soc., 1983, 75, 301 DOI: 10.1039/DC9837500301

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