The Deduction of Reaction Mechanisms from the Theory of Absolute Rates

摘要

The limitations of the simple collision theory for reactions are discussed. The Menschutkin and related reactions are shown to involve the formation of an activated complex with an electric moment of a magnitude which is calculated for the various cases. The free energy of activation for proton transfer is found from the experiments on conductance in water and the dispersion effects on polarization in ice. A partition function for liquid H2O and D2O based upon experimental quantities is given. The abnormal rapidity of the denaturation of proteins in spite of an enormous activation energy is typical of reactions, involving the simultaneous breaking of many bonds.