Energetics of Adsorbed CH3 on Pt(111) by Calorimetry

The enthalpy and sticking probability for the dissociative adsorption of methyl iodide were measured on Pt(111) at 320 K and at low coverages (up to 0.04 ML, where 1 ML is equal to one adsorbate molecule for every surface Pt atom) using single crystal adsorption calorimetry (SCAC). At this temperature and in this coverage range, methyl iodide produces adsorbed methyl (CH3,ad) plus an iodine adatom (I-ad). Combining the heat of this reaction with reported energetics for I-ad gives the standard heat of formation of adsorbed methyl, Delta H-f(0)(CH3,ad), to be -53 kJ/mol and a Pt(111)-CH3 bond energy of 197 kJ/mol. (The error bar of +/- 20 kJ/mol for both values is limited by the reported heat of formation of I-ad.) This is the first direct measurement of these values for any alkyl fragment on any surface.