Determination of thermodynamic and kinetic parameters for equilibria between two diastereoisomers by a polarimetric temperature-jump method. The application to five- and six-co-ordinate phosphorus compounds

Abstract

The usefulness of a polarimetric temperature-jump method for the determination of thermodynamic and kinetic parameters for equilibrium reactions between optically active compounds has been demonstrated for five- and six-co-ordinated phosphorus compounds. Even when the equilibrium constant (K_e) for the reaction cannot be accurately determined, it is shown that, with an approximate value of K_e at one temperature, the dependence of K_e on temperature (ΔH^⊖ and ΔS^⊖) can be accurately determined using the above method.