Accuracy
Transition state theory requires a value of the transmission coefficient as a prefactor in the Eyring equation above. This value is usually taken to be unity (i.e., the transition state always proceeds to products and never reverts back to reactants and ). As discussed by Winzor and Jackson in 2006, this assumption invalidates the description of an equilibrium between the transition state and the reactants and therefore the empirical Arrhenius equation is preferred with a phenomenological interpretation of the prefactor and activation energy . For more details, see discussion in Winzor and Jackson (2006) pages 399-400 in section "Transition-state theory."
To avoid specifying a value of the ratios of rate constants can be compared to the value of a rate constant at some fixed reference temperature (i.e., ) which eliminates the term in the resulting expression.
Read more about this topic: Eyring Equation
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