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- W2014432009 abstract "Under most conditions in electrode kinetics, the slopes of Tafel relationships for a given electrode process are dependent on temperature. Tafel lines determined at different temperatures therefore intersect at some singular potential, Ecr, for which the Gibbs energy of activation must be zero. The absolute value of the Gibbs energy of activation can then be evaluated by reference to this critical potential. For the oxygen reduction reaction at Pt electrodes in acid solutions, Ecr = 0.36 E vs. RHE. This critical potential yields a value of the Gibbs energy of activation at 0.8 V vs. RHE of 21 kJ mol-1. A comparison of this energy with the apparent enthalpies of activation Δ≠Hap (= 21 and 24 kJ mol-1), obtained previously from the Arrhenius plots at the same potential and in the same solution, shows that TΔS≠ is small. The values for the enthalpic component, βH (= 0.44), and entropic component, Tβs (= 0.07 at room temperature), of the overall symmetry factor, β, are determined. They show that, in this case, the kinetics are controlled mainly by the effect of electrode potential on the enthalpic component of the Gibbs energy of activation. It is shown that the electron energy level, ϵ0, of the reacting complex in the ground-state can be obtained from Ecr. For oxygen reduction at Pt, it is -4.72 eV with respect to the electron energy in vacuum." @default.
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- W2014432009 date "1989-04-01" @default.
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- W2014432009 title "Energetics of an Electrochemical Reaction Derived from the Intersection of Tafel Lines Determined at Different Temperatures" @default.
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