Although CO-Ni(111) is a relatively simple adsorption system, a description that is complete enough to predict both equilibrium phenomena and kinetic behaviour in terms of tabulated surface properties and controllable experimental variables has not been available. Statistical Rate Theory is being developed to fulfill these needs. In applying Statistical Rate Theory, the chemical potential is a fundamental quantity needed to make a prediction.

A previously developed expression for the chemical potential of adsorbed diatomic molecules is used that is based on a quantum mechanical model of weakly interacting molecules. A new procedure is presented for inferring unknown properties appearing in the chemical potential expression from equilibrium adsorption isotherm measurements. The chemical potential is then used to predict several equilibrium properties. A new equation is presented for the heat of adsorption that takes into account the change in the solid as a result of the adsorption. The heat of adsorption prediction for CO-Ni(111) is found to have the same coverage dependence as measurements reported in the literature and the measurements are used to infer a value for the adsorption-induced enthalpy change of the solid. The procedure for examining isotherms is also used to show that two sets of measured isotherms for similarly prepared CO-Ni(111) surfaces are in agreement and that isotherms measured for a surface with a different preparation are statistically different.

The chemical potential relation, along with the properties found from the equilibrium adsorption isotherms for CO-Ni(111), is then used with Statistical Rate Theory to predict adsorption kinetics. Statistical Rate Theory is then extended to systems which are neither isolated nor at steady state by using it to formulate fundamental equations for both beam-dosing adsorption (in which the pressure is changing as a function of time) and temperature programmed desorption. The theoretical predictions are compared with measurements reported in the literature. The temperature programmed desorption application represents the most complete test to date of Statistical Rate Theory in that all of the properties required to make a prediction are obtained from independent experiments. The predictions agree well with experimental measurements, indicating that Statistical Rate Theory contains all of the required temperature and coverage dependence necessary to predict CO-Ni(111) kinetics.