New three-parameter empirical extension of the arrhenius equation suitable for the precise evaluation of pseudo-thermodynamic activation parameters in chemical kinetics

Abstract

An empirical extension of the logarithmic form of the classical Arrhenius equation is written as a simple three-parameter equation which fits precise experimental data on the variation of rate-constant with temperature better than any three-parameter extension of the Arrhenius equation yet proposed.

The proposed equation has been compared with the three and four parameter equations of Hyne and Robertson for a series of sets of rate-constant against temperature data on solvolysis systems. The equation proposed here is simpler to apply, and provides at least as good a statistical fit to the data as does the three-parameter equation of Hyne and Robertson.