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• W112016711 abstract "As rate constants for reactions occurring on repulsive potential-energy surfaces show an Arrhenius-type temperature dependence, what correspondingly may be said for reactions occurring on attractive surfaces? Experiment reveals no general answer to that question. Here a limited answer is sought for a restricted family of exoergic reactions (ΔE°0 < 0) occurring on surfaces which are similar and reasonably well defined. (A glossary of energy terminology is given in the Appendix.) The reactions involve proton transfer between reactants with filled electronic shells, where reaction proceeds via two intermediates, which correspond to two basins on the potential-energy surface. The description is extended to include multichannel isotope-exchange reactions, for which there are several practical examples and which can involve as many as ten intermediates. For the multichannel reactions, reaction proceeds as the intermediates interconvert by a sequence of proton (or deuteron) transfers. The key kinetic parameter is K, the average number of transfers during the lifetime of the collision. Kinetic analysis expresses the collision efficiency η (reaction rate constant / collisional rate constant) as a function of K; the temperature dependence of K is discussed phenomenologically; and the dependence of the rate constant on the temperature is expressed as an η / Θ plot in reduced variables, where the reduced temperature Θ is defined as -RT/ΔE°0. A single plot, using the reduced variables, is able to describe schematically the behavior of many reactions with widely different ergicities expressed as an equivalent temperature 10 < -ΔE°0 /R (K) < 25, 000. For two ranges of Θ, η shows no temperature dependence and for the two remaining ranges of Θ, η shows a negative temperature dependence. The description has a heuristic purpose. By identifying patterns, it attempts to generalize. It can never be better than semiquantitative since it considers only the gross features of the potential-energy surface and not the individual molecular parameters which distinguish the details of one particular reaction from another." @default.
• W112016711 created "2016-06-24" @default.
• W112016711 creator A5055046220 @default.
• W112016711 date "1994-01-01" @default.
• W112016711 modified "2023-10-16" @default.
• W112016711 title "Rate Constants and Their Temperature Dependences: A Kinetic Description Using Simple Model Potential-Energy Surfaces" @default.
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• W112016711 doi "https://doi.org/10.1016/b978-1-55938-553-4.50011-9" @default.
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