Electrolytic water splitting: Indications for the existence of protonic quantum interferences

Abstract

Electrolysis of acidic H₂O–D₂O mixtures has been performed using the well established mercury drop electrode. The experiment was done in order to study, for the first time in a chemical reaction, possible quantum behaviour of hydrogen species which is evident from neutron and Raman light scattering studies. Rate constants and the Tafel slope of the examined reaction show striking deviations from the expected conventional behaviour for the nominal D and H concentrations. Limitations of the applicability of simple reversible thermodynamics and equilibrium statistical mechanics to the electrochemical process under consideration are revealed.