ABSTRACT A recently reported non-linear Tafelian dependence for the hydrogen evolution reaction at low overvoltages has encouraged us to carry out a revision of the theory of charge transfer reactions and Tafel’s law by analyzing the implications that the electric polarization of the metal, described by the modified Rice model, has on the electron emission from the electrode. The analysis of the water percolation entropy and of the X-ray and neutron diffraction data has led us to the conclusion that chains of molecules exist in liquid water and that protons show correlated long-range vibrations in the hydrogen bonds. On the other hand, after fitting the bands of the Raman spectra of HCl and KOH to the Fermi-Dirac and the Bose-Einstien distributions, we conclude that the high mobility of the hydrogen ion in aqueous solutions is explained as a free motion of three correlated protons along water chains, as well as the high mobility of the hydroxyl ion is also explained by the formation of protons pairs stabilized by the negative charge of water chains. Finally, it is shown that water chains are adsorbed parallel to electrode surfaces with outer protons oriented to the metal at negative metal charges or to the solution with partial ionization at positive metal charges.
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