Statistical Thermodynamic Description of Homogeneous Dispersive Kinetics

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• 作者：Peter J. Skrdla
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：May 24, 2007
• 年：2007
• 卷：111
• 期：20
• 页码：4248 - 4251
• 全文大小：41K
• 年卷期：v.111,no.20(May 24, 2007)
• ISSN：1520-5215

文摘

A statistical thermodynamic interpretation of homogeneous dispersive kinetics (which assumes theexistence of a pseudo-equilibrium between a distribution of reagent states and a single activated state, whichtogether define the rate-determining step), coupled with a previous "quantum kinetic" description forthis same type of system (Skrdla, P. J. J. Phys. Chem. A 2006, 110, 11494), is found to provide new insightsinto the kinetics of these conversions. In particular, the change in the (apparent) activation energy withconversion time is shown to be a function of the entropy change associated with the ensemble of reagentmolecules as they traverse the activation energy barrier. Using these two "orthogonal" stochastic interpretationsof dispersive kinetics, a fundamental physical description of the rate parameter in the author's model isobtained.