Calorimetric investigation of NO and CO adsorption on Pd(100) and the influence of preadsorbed carbon

The coverage dependencies of the differential heats of adsorption for CO and NO on Pd{100}, at room temperature, are reported using single crystal adsorption calorimetry (SCAC). The initial heat for CO is 165 kJ/mol, falling markedly with increasing coverage due to anomalously strong repulsive interactions between molecules. The formation of a c(2 x 4) overlayer at half monolayer coverage places severe constraints on the magnitudes of lateral interactions between adsorbates which can fit the data. A realistic lateral interaction model is proposed. The influence of predosed carbon on the heat of adsorption of CO was also investigated. As little as 0.05 ML of C causes a decrease in the initial heat of about 20 kJ/mol; 0.2 ML reduces the heat to 120 kJ/mol. The results suggest long range interactions between C atoms and CO molecules. The initial heat for NO is 155 kJ/mol, decreasing smoothly to about 105 kJ/mol at saturation. The coverage dependencies of the sticking probabilities for both NO and CO exhibits precursor behavior which is considerably diminished in the presence of a high C precoverage