The heats of adsorption of the adsorbed CO species on Ni supported catalysts are rarely studied by using classical analytical methods (i.e. microcalorimetry and temperature programmed desorption (TPD)) due to experimental difficulties linked to different parallel surface reactions to the adsorption/desorption processes. In the present study, the heats of adsorption of the linear and bridged CO species (denoted L and B CO, respectively) on a reduced 20% Ni/Al2O3 catalyst are studied by using the adsorption equilibrium infra red method developed previously. After a stabilization procedure of the catalyst, the evolutions of the IR bands of the L and B CO species: 2053 and 1927 cm(-1), respectively, at T-a = 500 K and P-a = 1 kPa, with the adsorption temperature T-a are studied at a constant adsorption pressure P-a. These data provide the evolutions of the coverages theta(L) = f(T-a) and BB = f(T-a) of the two adsorbed CO species with the increase in Ta in isobar conditions. These curves allow us to determine the heats of adsorption EL theta L and EL theta B of the L and B CO species for several values of the coverage theta(L) and BB according to an adsorption model, i.e. EL1 = 100, EL0 = 153, EB1 = 106 and EB0 = 147 kJ/mol at coverages 1 and 0, respectively. These values are consistent with literature data on Ni single crystals. In particular, it is shown that the mathematical formalism of the AEIR method can be applied to literature data on Ni(1 1 1) providing ECO theta values similar to those of the present study showing the limited impact of the Ni particle size on the CO adsorption properties. The presence of hydrogen (2% CO/10% H-2/He) during the measurement decreases slightly the coverages of the two CO species at high temperatures due to either a decrease in the heats of adsorption (i.e. EL1 = 97, EL0 = 131, EB1 = 89 and EB0 = 138 kJ/mol) or the perturbation of the adsorption equilibrium by hydrogenation of the adsorbed CO species. (c) 2006 Elsevier B.V. All rights reserved.