Proton Conductance and the Existence of the H3O· Ion

Measurements of the conductance of HCl in water, methanol, ethanol, n‐propanol, ethylene glycol, glycerol, 1:4 dioxane, acetone, formic, and acetic acids and the respective aqueous‐nonaqueous systems have been made as a function of concentration of water and HCl. The degree of anomalous proton conductance decreases with increasing n in CnH2n+1OH, and conductance minima occur in aqueous alcoholic HCl solutions of low H2O content.Former theories of proton conductance have permitted no quantitative distinction to be made between the rates of classical proton transfer, quantum‐mechanical tunneling transfer, and water rotation as rate determining stages. If resonance in H3O· is set up sufficiently quickly after arrival of a given proton at a water molecule, rotation of H3O· cannot be a rate determining step.Detailed calculations of the rates of classical proton transfer, tunnel transfer, and the rate of rotation of water are made. Classical transfer is much slower and tunnel transfer much faster than correspon...

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