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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 11, Number 4
BKCSDE 11(4)
April 20, 1990 

The Pressure Dependence of the Rate Constant for the t-Butoxy Radical Decomposition Reaction
Jung Mee Park, Nam Woong Song, Kwang Yul Choo*
A thermal decomposition of the tert-butoxy radical has been studied in the gas phase over the pressure range of 1-200 torr at 413。K using di-tert-butyl peroxide + trimethylsilane mixtures. The relative rate constants were obtained by studying the competitive reactions between tert-butoxy radical decomposition (t-BuO·→ CH3COCH3 + CH3·) and hydrogen abstraction reaction from trimethylsilane (t-BuO·+ HSi(CH3)3 → t-BuOH + Si(CH3)3)·). The conventional RRKM calculations were carried out to compare the observed fall-off behavior of the decomposition rate constant (kd) with the theoretical predictions using reasonable values of input parameters. In all cases the calculated half-rate pressure (P1/2) were significantly higher than those observed. The failure of RRKM to reproduce the fall-off behavior led us to suggest that not all of vibrational modes contribute to excitation (leading to decomposition) on the same time scale.
343 - 347
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