The impact of overpotential on the enthalpy of activation and pre-exponential factor of electrochemical redox reactions

Abstract

The kinetics of the V⁵⁺/V⁴⁺ redox reaction is investigated in a three-electrode configuration on a Vulcan XC-72 modified glassy carbon rotating disk electrode at four different temperatures (25 to 40 °C, with 5 °C interval). The values of enthalpy of activation (ΔH^#) and pre-exponential factor (A_f) estimated using the Eyring equation are in the range of 0.25–0.53 eV (24–51 kJ mol⁻¹) and −1.3 to 5, respectively. The Eyring plots tend to diverge with overpotential, causing an increase in the values of the estimated ΔH^# and A_f. This is perhaps due to the retarding effect of the precipitates/adsorbates on the electrode surface. The investigation of the kinetics suggests that the V⁵⁺/V⁴⁺ redox reaction is electrocatalysed through an increase in the entropy of activation (ΔS^#).