Theory of the Influence of the Dielectric Constant on the Rate of Reaction in Solution with Application to Enzyme Reactions. I. Development of the Theory and its Application to Some Simple Systems
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A theory has been developed on the relationship between the equilibrium constant or the rate constant of a reaction and the dielectric constant of the solvent based on the Kirkwood's model. It is applicable to equilibrium states or reaction processes in which ions or molecules having arbitrary charge distributions are involved, including enzyme reactions. The theory predicts that there is a linear relationship between the logarithm of the equilibrium or rate constant and the reciprocal of the dielectric constant of the solvent. The slope is determined by the new parameter <I>L</I>, termed the charge configuration function, and the radius of each species involved. <I>L</I> of a species is a function of the magnitudes and the relative positions of charges in it and its radius. Tables have been presented in order to facilitate the evaluation of <I>L</I>.<BR>The applicability of the theory has been tested for the dissociation of carboxylic acids, the S<SUB>N</SUB>1 solvolysis of organic halides, and the acid and base hydrolyses of esters, amides and anilides, and the results are found to be satisfactory.<BR>The influence of ionic strength on the theoretical expressions has also been discussed.
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- Theory of the Influence of the Dielectric Constant on the Rate of Reaction in Solution with Application to Enzyme Reactions. I. Development of the Theory and its Application to Some Simple Systems