ABSTRACT

I. Introduction ...................................................................................................................... 451

II. General Kinetic Models for Acid-Base Reactions in Solutions .................................... 452

A. The Two-State Proton-Transfer Reaction Model

(The Eigen-Weller Model) ..................................................................................... 452

B. Free-Energy Correlations of the Proton (Deuteron) Transfer Rates....................... 454

C. The Isotope Effect in a Series of Similar Reactions ............................................... 455

III. The Isotope Effect in the Equilibrium Constant of Photoacids ...................................... 456

IV. The KIE in Photoacid Dissociation ................................................................................. 459

V. Concluding Remarks on the KIE in Photoacid (Phenol-Type) Dissociation ................. 462

References..................................................................................................................................... 462

The effect of isotope substitution (H/D) on the kinetics of acid-base reactions has long been

a primary mechanistic tool in proton-transfer research.