The work is concerned with structure effects exerted by molecules of alkylvinylethers and allylalkylethers in heterogeneously catalysed hydrogenation on platinum and palladium catalysts. The method of a competitive hydrogenation is suggested as a suitable kinetic tool for discussion of stability of surface complexes and of a rate of surface reactions in terms of structures of reacting molecules. Experimental data, represented here by parameters of adsorptivity and reactivity, are interpreted with the help of molecular modelling. (C) 2002 Elsevier Science B.V. All rights reserved.