A theor. discussion is given of the changes in the heat of chemisorption of a H atom upon alloying a group-VIII metal with a group-IB metal. The emphasis is on 2 concepts: the ensemble effect and the ligand effect. The ensemble effect ascribes the changes in the heat of chemisorption primarily to changes in the geometry of the adsorption complex, whereas the ligand effect also considers changes in bond strength due to different intrinsic activity of the bonding metal atom