Determination of Adsorption Isotherms of Hydrogen on Zirconium in Sulfuric Acid Solution Using the Phase-Shift Method and Correlation Constants
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The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior (−ϕ vs. E) of the phase shift (90° ≥ -ϕ≥ 0°) for the optimum intermediate frequency and that (θ vs. E) of the fractional surface coverage (0 ≤ θ ≤ 1), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M H2SO4 aqueous solution interface, the Frumkin and Temkin adsorption isotherms (θ vs. E), equilibrium constants (K = 1.401 × 10-17 exp(-3.5θ) mol-1 for the Frumkin and K = 1.401 × 10-16 exp(-8.1θ) mol-1 for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = 8.7 kJ mol-1 for g = 3.5 and r = 20 kJ mol-1 for g = 8.1) of H with θ, and standard free energies (96.13≤ΔG<수식> ≤ 104.8 kJ mol-1 for K= 1.401 × 10-17 exp(-3.5θ) mol-1 and 0 ≤ θ ≤ 1 and 94.44 < ΔG<수식> < 106.5 kJ mol-1 for K= 1.401×10-16 exp(-8.1θ) mol-1 and 0.2 < θ < 0.8) of H are determined using the phase-shift method and correlation constants. At 0.2 < θ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.
Abstract
The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior (−ϕ vs. E) of the phase shift (90° ≥ -ϕ≥ 0°) for the optimum intermediate frequency and that (θ vs. E) of the fractional surface coverage (0 ≤ θ ≤ 1), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M H2SO4 aqueous solution interface, the Frumkin and Temkin adsorption isotherms (θ vs. E), equilibrium constants (K = 1.401 × 10-17 exp(-3.5θ) mol-1 for the Frumkin and K = 1.401 × 10-16 exp(-8.1θ) mol-1 for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = 8.7 kJ mol-1 for g = 3.5 and r = 20 kJ mol-1 for g = 8.1) of H with θ, and standard free energies (96.13≤ΔG<수식> ≤ 104.8 kJ mol-1 for K= 1.401 × 10-17 exp(-3.5θ) mol-1 and 0 ≤ θ ≤ 1 and 94.44 < ΔG<수식> < 106.5 kJ mol-1 for K= 1.401×10-16 exp(-8.1θ) mol-1 and 0.2 < θ < 0.8) of H are determined using the phase-shift method and correlation constants. At 0.2 < θ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.
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