The d-Band Character of Metals and the Rate and Mechanism of the Electrolytic Hydrogen Evolution Reaction


IT is known empirically1 that for the hydrogen evolution reaction, log i 0 (where i 0, the exchange current density, is directly proportional to the rate constant of the reaction) increases linearly with increase of ϕ, the thermionic work function of the electrode substrate, for most metals, but may decrease with increase of ϕ for mercury, thallium and lead. The work function is eliminated in the potential terms governing the rate of hydrogen evolution in an actual cell. The origin of the dependence of rate constant upon ϕ must therefore be sought in the relation to ϕ of some other parameter upon which the rate of evolution of hydrogen depends.

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