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- W1968650130 abstract "In order to provide new information on the potential-modulated activation process in the elementary proton- and electron-transfer step of proton discharge in the hydrogen evolution reaction (h.e.r.), the enthalpic (βH) and entropic (TβS) components of the overall charge-transfer symmetry factor, β, have been evaluated. These data are obtained from polarization curves for the h.e.r. at Hg from a series of oxonium, ammonium and molecular acid type proton donors in various solvents over a wide range of temperature through the m.p. of Hg. βS and βH define the form of the Tafel slope b as a function of temperature: b = RT/(βH + TβS) F.βS and βH are not related to dielectric polarizability of the solvent but may depend on its proton affinity. However, clear linear relations are demonstrated between βS and the log of the electrochemical Arrhenius factor containing the entropy of activation, and between βHNH+ and Δ H≠. These relations have different slopes for proton discharge from OH+ proton donors. Also Δ H≠ and δ S≠ are linearly related for the series of proton donors in the way familiar in “compensation effect” plots between ΔH and ΔS quantities in condensed media.βS and βH usually change discontinuously, for a given system, through the m.p. of Hg." @default.
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- W1968650130 date "1983-02-01" @default.
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- W1968650130 title "The effect of temperature on the adsorption of trifluoromethanesulfonate anions on mercury from constant ionic strength solutions" @default.
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- W1968650130 doi "https://doi.org/10.1016/0013-4686(83)85103-2" @default.
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