By J Gray, H Hammond, G Dence

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The study of exceedingly fast reactions in solution has become an active field of research in the last decade. Indeed, it was for their pioneering efforts in this field that Manfred Eigen, George Porter, and Ronald G. W. Norrish won the 1967 Nobel prize in chemistry. Aided by increased familiarity with electronic instrumentation, chemists are able to study reactions, for example, involving only the transfer of an electron in reactions between gaseous ions and molecules. Results obtained from these studies have immediate implications in the field of electrochemical rate processes.

Table 6-2 gives some typical lifetimes for excited addition products. 5 x lo-7 -3 x lo-7 \ / 0 - -- - - -- -- a Data taken from R. J. Cvetanovic in W. A. , G. S. Hammond, and J. N. Pitts, Jr. ), Advances in Photochemistry, Vol. 1, p. 125, Interscience, New York, 1963. [ 54 I CHEMICAL DYNAMICS stabilized addition products in the cases of ethylene and butadiene; isobutene and 1-butene should be more favorable in this respect. If two species collide, but do not react, there may be a transfer of energy from one to the other.

Solvation of the Participants in the Reaction, Inclading the Intermediates The term solvation, as it is commonly used, is actually vague because of our ignorance of the detailed structure of liquids. In a general sense solvation refers to any binding of solvent molecules with solute molecules, without necessarily specifying the nature of the interaction. Consider a general bimolecular reaction in solution represented by A+BGC+D A more detailed description of this process includes at least three steps : A.

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