Heats of adsorption of the linear CO species adsorbed on a Ir/Al2O3 catalyst using in situ FTIR spectroscopy under adsorption equilibrium

The adsorption of CO on a reduced 1% Ir/Al2O3 catalyst has been studied by using Fourier transform infrared spectroscopy (FTIR) at two constant CO partial pressures P-a (200 and 2000 Pa) in the adsorption temperature (denoted by T-a) range of 300-740 K. At 300 K, it is observed a strong IR band at 2044 cm(-1) ascribed to linear CO species (denoted by L) associated to weak shoulders at approximate to2080 and approximate to2000 cm(-1). The FTIR spectra show how the coverage theta(L) of the L CO species evolves with T-a for the two P-a values. At T > 580 K, the Curves theta(L)=f(T-a) are in very good agreement with an adsorption model based on Temkin's approximations indicating that the heat of adsorption linearly increases with the decrease in theta(L) from E-1 to E-0 at theta(L)= 1 and 0, respectively. This allows us to evaluate the ratio E-0/(E-0 - E-1) approximate to 2.1 and then E-0 - E-1 approximate to 115 kJ/mol. Moreover, it is shown that, in the Ta range of 300-740 K, the curves theta(L)= f(T-a) for the two CO partial pressures are in very good agreement with an adsorption model considering the following: (a) an immobile adsorbed species and (b) a linear decrease in the heat of adsorption with the increase in theta(L) from E-0= 225 kJ/mol at theta(L)= 0 to E-1= 115 kJ/mol at theta(L)= 1. Finally the two isobars are used to determine the isosteric heats of adsorption at several coverages in the range of 1-0.8 from the Clausius-Clapeyron equation. A good agreement is observed with the values determined using the adsorption model and this validates the various assumptions involved in the model. The heat of adsorption values are compared to the literature data on single crystals and supported Ir catalysts. Moreover, it is shown that the heat of adsorption values allow us to quantify several quantitative data found in the literature on the stability of the L CO species on Ir-containing solids either in a vacuum or in an inert gas.