화학공학소재연구정보센터
Journal of Electroanalytical Chemistry, Vol.756, 124-130, 2015
Thermodynamic aspects of hydrogen electrosorption into Pd-Rh alloys
Pd-Rh alloys were electrodeposited potentiostatically from baths containing a mixture of aqueous solutions of PdCl2, RhCl3 and HCl in various proportions. The thickness of the deposited layers was ca. 1 mu m. The processes of hydrogen electrosorption were studied in 0.5 M H2SO4 solution in the temperature range of 283-328 K, using chronoamperomety and cycling voltammetry. Thermodynamic parameters of hydride formation and decomposition (Gibbs energy -Delta G(alpha ->) (beta), Delta G(beta ->) (alpha), enthalpy Delta H-alpha -> beta, Delta H(beta -> alpha)and entropy -Delta S-alpha -> beta, Delta H-beta -> alpha) were calculated from the potentials of the alpha -> beta and beta -> alpha phase transitions. The absolute values of Gibbs energy and enthalpy distinctly decrease with increasing bulk content of Rh, while the entropy values are only slightly affected by the alloy bulk composition. It means that with increasing bulk content of Rh the hydride phase formation in Pd-Rh alloys becomes less exothermic and the hydride itself becomes thermodynamically less stable. Absorbed hydrogen probably occupies both Pd and Rh neighboring interstices. (C) 2015 Elsevier B.V. All rights reserved.