Abstract
A study of the kinetics of the reaction between mercaptoacetic acid and chloroacetamide shows that the reaction proceeds via the RS" form. A similar study for B-mercaptoethylamine and cysteine shows conclusively that, when the reactivity of the sulfhydryl group is considered, the assignment of pK values given by Cohn and Edsall (1943) is incorrect. The kinetic data for B-mercaptoethylamine and cysteine do not permit differentiation between the ionization schemes proposed by Calvin and Edsall. Kinetic data permit accurate estimates of titration pK values to be made. The problem of the determination of intrinsic dissociation constants is discussed with reference to cysteine.

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