Mechanism of adsorption, electroreduction and hydrogenation of compounds with ethylenic bonds on platinum and rhodium: Part II. Comparison of the electroreduction and catalytic hydrogenation processes

Abstract

The catalytic liquid-phase hydrogenation of maleic acid on platinum and rhodium has been investigated. It is shown that the rate-determining step of this process as well as of the electroreduction process of maleic acid is the interaction of the chemisorbed particle of maleic acid with the adsorbed hydrogen which is formed at the preceding rapid stage of either the dissociative adsorption of molecular hydrogen, or the electrochemical stage of hydrogen ion discharge. The rate of the process with the same degree of surface coverage with hydrogen and chemisorbed particles of maleic acid does not depend on whether the process is carried out catalytically or electrochemically, on whether maleic acid and hydrogen were preliminarily adsorbed on the surface of the electrode-catalyst or not. With due regard for the mutual influence of chemisorbed particles participating in the rate-determining stage, the main kinetic equations for the electroreduction and catalytic hydrogenation processes have been derived. The difference in the rates of electroreduction of maleic acid on platinum and rhodium, with the same degree of electrode surface coverage with reactants, is shown to be the result of differences in the adsorption heats (or bonding strength with the surface) of hydrogen and maleic acid on these two metals. Experimental procedures are described in Part I [1].