Reactions of adsorbed N atoms on Rh(111) to N2 and NH3 were studied with temperature programmed desorption, temperature programmed reaction spectroscopy, and static secondary ion mass spectrometry. For N-atom coverages below ≈0.15 monolayers, desorption of N2 follows simple second-order kinetics, but at higher coverages the desorption traces broaden to higher temperatures. Hydrogenation to NH3 can be described by a stepwise addition of H atoms to Nads in which the reaction from NH2,ads+Hads to NH3,ads determines the rate. The activation energy for the rate determining step is 76 kJ/mol. The desorption of NH3 from Rh(111) was studied separately. The kinetic parameters for desorption at low NH3 coverage are 81 kJ/mol and 1013s−1, but the rate of desorption increases rapidly with increasing NH3 coverage. It is argued that the remarkable coverage dependence of the desorption rate is unlikely to be caused by lateral repulsive interactions but may be due to a coverage dependence of the pre-exponential factor.

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