The effects of non-equilibrium in a quasi-one-dimensional nozzle flow are investigated by means of a collisional-radiative model. The gas undergoing the expansion is an air plasma and consists of atoms, molecules, and free electrons. In the present analysis, the electronic excited states of atomic and molecular species are treated as separate pseudo-species. Rotational and vibrational energy modes are assumed to be populated according to Boltzmann distributions. The coupling between radiation and gas dynamics is accounted for, in simplified manner, by using escape factors. The flow governing equations for the steady quasi-one-dimensional flow are written in conservative form and discretized in space by means of a finite volume method. Steady-state solutions are obtained by using a fully implicit time integration scheme. The analysis of the evolution of the electronic distribution functions reveals a substantial over-population of the high-lying excited levels of atoms and molecules in correspondence of the nozzle exit. The influence of optical thickness is also studied. The results clearly demonstrate that the radiative transitions, within the optically thin approximation, drastically reduce the over-population of high-lying electronic levels.