NDLI: Thermodynamics of the transition state and the application to interfacial reactions

Content Provider	Royal Society of Chemistry (RSC)
Author	Hall, Denver G.
Copyright Year	1989
Abstract	According to transition-state theory, when the equilibrium hypothesis is valid, activated complexes formed from reactants may be treated thermodynamically in the same way as other species present in very small amounts. Inclusion of these complexes in the Gibbs–Duhem equation for the solution enables an expression to be derived for the dependence of the equilibrium concentration of activated complexes on the solution composition. When the transmission coefficient of the reaction is insensitive to the reaction environment this expression leads directly to the effect of solution composition on the reaction rate. For bulk solutions, this approach is entirely equivalent to that published recently based on the Kirkwood–Buff theory of solutions. For reactions at interfaces the Gibbs adsorption equation plays the same role as the Gibbs–Duhem equation for reactions in bulk and similar arguments apply. These arguments are used to obtain a general expression for the transfer coefficient β in the Butler–Volmer equation of electrode kinetics and for the dependence of β on solution composition. A similar treatment can also be applied to the effects on reaction rates of macromolecules which interact with reactants. Finally, the situation in which adsorbed material is not in equilibrium with that in the bulk solution immediately adjacent to the interface is considered and general guidelines for dealing with this type of situation are forwarded.
Starting Page	1881
Ending Page	1895
Page Count	15
File Format	PDF
ISSN	03009599
Volume Number	85
Issue Number	8
Journal	Journal of the Chemical Society, Faraday Transactions 1
DOI	10.1039/F19898501881
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Electrode Dependent and independent variables Interaction Gibbs Volmer Gibbs\u2013Duhem equation Buff Reaction rate Heat transfer coefficient Butler\u2013Volmer equation Kirkwood Transition state theory Adsorption Transmission coefficient
Content Type	Text
Resource Type	Article
Subject	Chemistry

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