Journal of Chemical Physics, Vol.106, No.5, 1990-1996, 1997
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.