Kinetics of the Proton-transfer Reactions between 2,4-Dinitrophenol and Tertiary Amines: Possible Influence of Rotation in the Encounter Complex

Abstract

Kinetic and equilibrium data are reported for the proton-transfer reactions in chlorobenzene between 2,4-dinitrophenol and triethylamine, tri-n-propylamine, tri-n-pentylamine, tri-n-nonylamine and triethylenediamine. The forward rate constants are a factor of 5-35 below the limit predicted by simple diffusion theory. These results are interpreted by means of a theory which takes account of rotation of the reactants within the encounter complex during the period of an encounter.