Kinetics of solvolysis in water of four secondary alkyl nitrates

Kinetic data are reported for the solvolysis in water of propane-2-nitrate, butane-2-nitrate, cyclopentyl nitrate, and cyclohexyl nitrate. In each case, the dependence of rate constant on temperature is analysed in terms of two mechanisms for the solvolytic reaction. First it is assumed that the rat...

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Bibliographic Details
Published in:Canadian journal of chemistry 1982-07, Vol.60 (13), p.1780-1785
Main Authors: Robertson, Ross Elmore, Koshy, Kalvelil Matthew, Annessa, Adrianne, Ong, Jan N, Scott, John Marshall William, Blandamer, Michael Jesse
Format: Article
Language:English
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Summary:Kinetic data are reported for the solvolysis in water of propane-2-nitrate, butane-2-nitrate, cyclopentyl nitrate, and cyclohexyl nitrate. In each case, the dependence of rate constant on temperature is analysed in terms of two mechanisms for the solvolytic reaction. First it is assumed that the rate constant describes a single step reaction, the analysis leading to estimates of the heat capacity of activation ΔC p ≠ . Three different analytical methods are discussed in this regard. Second it is assumed that the rate constant describes a two stage mechanism, the first stage being reversible. In this case the explanation of the ΔC p ≠ term calculated according to the first mechanism is quite different. We comment on the alternative explanations of trends in activation parameters.
ISSN:0008-4042
1480-3291
DOI:10.1139/v82-244