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Determination of the Frumkin and Temkin Adsorption Isotherms of Hydrogen at Nickel/Acidic and Alkaline Aqueous Solution Interfaces Using the Phase-Shift Method and Correlation Constants

천장호
한국전기화학회 (The Korean Electrochemical Society)|2012.02|전기화학회지 (Journal of the Korean Electrochemical Society)|제15권 제1호|pp. 54-66

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참고문헌

키워드

NickelPhase-shift methodCorrelation constantsHydrogen adsorptionFrumkinLangmuirTemkin adsorption isotherms
주제분류화학

초록

The phase-shift method and correlation constants, which are unique electrochemical impedance spectroscopy techniques for studying the linear relationship between the phase shift (90o ≥ −ϕ ≥ 0o) vs. potential (E) behavior for the optimum intermediate frequency (fo) and the fractional surface coverage (0 ≤ θ ≤ 1) vs. E behavior, are proposed and verified to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and the related electrode kinetic and thermodynamic parameters. At Ni/0.5 M H2SO4 and 0.1M LiOH aqueous solution interfaces,the Frumkin and Temkin adsorption isotherms (θ vs. E) of H for the cathodic hydrogen (H2)evolution, interaction parameters (g), equilibrium constants (K), standard Gibbs energies (ΔGθo)of H adsorption, and rates of change (r) of ΔGθo with θ have been determined using the phaseshift method and correlation constants. A lateral repulsive interaction (g > 0) between the adsorbed H species appears. The value of K in the alkaline aqueous solution is much greater than that in the acidic aqueous solution.

Abstract

The phase-shift method and correlation constants, which are unique electrochemical impedance spectroscopy techniques for studying the linear relationship between the phase shift (90o ≥ −ϕ ≥ 0o) vs. potential (E) behavior for the optimum intermediate frequency (fo) and the fractional surface coverage (0 ≤ θ ≤ 1) vs. E behavior, are proposed and verified to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and the related electrode kinetic and thermodynamic parameters. At Ni/0.5 M H2SO4 and 0.1M LiOH aqueous solution interfaces,the Frumkin and Temkin adsorption isotherms (θ vs. E) of H for the cathodic hydrogen (H2)evolution, interaction parameters (g), equilibrium constants (K), standard Gibbs energies (ΔGθo)of H adsorption, and rates of change (r) of ΔGθo with θ have been determined using the phaseshift method and correlation constants. A lateral repulsive interaction (g > 0) between the adsorbed H species appears. The value of K in the alkaline aqueous solution is much greater than that in the acidic aqueous solution.

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