Temperature Dependence of the Proton‐Discharge Reaction at Gold and Silver Electrodes

The kinetics of the Volmer reaction, which is the first step in the hydrogen evolution reaction, have been investigated by means of potentiostatic pulses. Measurements were performed in liquid and frozen HClO4 · 5.5 H2O in the temperature range 180 to 300 K. The apparent transfer coefficient is found to depend strongly on temperature. Classical theories of heterogeneous charge transfer reactions are unable to explain this result. A new model for a “field assisted proton transfer” is presented, which results in a temperature dependent charge transfer coefficient.