Équation d'Eyring

The Eyring equation (occasionally also known as Eyring–Polanyi equation) is an equation used in chemical kinetics to describe changes in the rate of a chemical reaction against temperature. It was developed almost simultaneously in 1935 by Henry Eyring, Meredith Gwynne Evans and Michael Polanyi. The equation follows from the transition state theory, also known as activated-complex theory. If one assumes a constant enthalpy of activation and constant entropy of activation, the Eyring equation is similar to the empirical Arrhenius equation, despite the Arrhenius equation being empirical and the Eyring equation based on statistical mechanical justification. The general form of the Eyring–Polanyi equation somewhat resembles the Arrhenius equation: where is the rate constant, is the Gibbs energy of activation, is the transmission coefficient, is the Boltzmann constant, is the temperature, and is the Planck constant. The transmission coefficient is often assumed to be equal to one as it reflects what fraction of the flux through the transition state proceeds to the product without recrossing the transition state. So, a transmission coefficient equal to one means that the fundamental no-recrossing assumption of transition state theory holds perfectly. However, is typically not one because (i) the reaction coordinate chosen for the process at hand is usually not perfect and (ii) many barrier-crossing processes are somewhat or even strongly diffusive in nature. For example, the transmission coefficient of methane hopping in a gas hydrate from one site to an adjacent empty site is between 0.25 and 0.5. Typically, reactive flux correlation function (RFCF) simulations are performed in order to explicitly calculate from the resulting plateau in the RFCF. This approach is also referred to as the Bennett-Chandler approach, which yields a dynamical correction to the standard transition state theory-based rate constant.