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- W2498606123 abstract "The paper presents theoretical methodology that allows determination of thermodynamic state functions of the under-potential deposition of hydrogen, UPD H, and semiconductor or metallic species, UPD M. The experimental approach involves temperature dependence of the UPD by application of cyclic-voltammetry or chronocoulometry. The theoretical approach is based on a general electrochemical adsorption isotherm and numerical calculations which lead to determination of the Gibbs free energy of adsorption, ΔG°ads, as a function of T and θ. Temperature dependence of ΔG°ads, (for θ = const) leads to appraisal of the entropy of adsorption, ΔS°ads, whereas coverage dependence of ΔG°ads (for T = const) allows assessment of the nature of the lateral interactions between the adsorbed species; knowledge of ΔG°ads and ΔS°ads leads to determination of ΔH°ads. The paper presents new approach which permits elucidation of the bond energy between the substrate, S, and HUPD or S and MUPD, ES-HUPD and ES-MUPD, respectively. Comprehension of ES-HUPD is essential in assessment of the strength of the S-HUPD bond and the adsorption site of HUPD. Knowledge of ES-MUPD is of importance in: (i) evaluation of the strength of the cohesive forces acting between S and MUPD that are responsible for the adhesion of the adsorbate to the substrate; and (ii) comparison of the S-MUPD bond with that observed for the 3-D bulk deposit of M. The UPD H on Rh and Pt electrodes from aqueous H2SO4 solution is discussed as an example of application of this methodology." @default.
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- W2498606123 date "1997-02-28" @default.
- W2498606123 modified "2023-09-27" @default.
- W2498606123 title "Fundamental Thermodynamic Aspects of the Underpotential Deposition of Hydrogen, Semiconductors, and Metals" @default.
- W2498606123 doi "https://doi.org/10.1021/bk-1997-0656.ch004" @default.
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