Both gas-phase kinetic processes and heterogeneous surface processes assume an important role in affecting the flow field in the boundary layer of re-entry vehicles. In this work a N 2 , N, O 2 , O, NO mixture hitting either a non-catalytic surface or a SiO 2 partially catalytic one has been theoretically analysed. Vibrational distributions far from equilibrium have been obtained both for different surface conditions and for different boundary layer edge temperature and wall temperature pairs and finally for different flow residence times.