Test of the formal basis of Arrhenius law with heat capacities

Abstract

The exponential factor of Arrhenius satisfactorily quantifies the energetic restriction of chemical reactions but is still awaiting a rigorous basis. Assuming that the Arrhenius equation should be based on statistical mechanics and is probabilistic in nature, two structures for this equation are compared, depending on whether the reactant energies are viewed as the mean values of specific energy distributions or as particular levels in a global energy distribution. In the first version, the Arrhenius exponential factor would be a probability that depends once on temperature, while in the second it is a ratio of probabilities that depends twice on temperature. These concurrent equations are tested using experimental data for the isomerization of 2-butene. This comparison reveals the fundamental structure of the Arrhenius law in isothermal systems and overlooked properties resulting from the introduction of reactant energies into the equation.