We study the behavior of the excited electronic states of atoms in the relaxation zone of one-dimensional airflows obtained in shock-tube facilities. A collisional-radiative model is developed, accounting for thermal nonequilibrium between the translational energy mode of the gas and the vibrational energy mode of individual molecules. The electronic states of atoms are treated as separate species, allowing for non-Boltzmann distributions of their populations. Relaxation of the free-electron energy is also accounted for by using a separate conservation equation. We apply the model to three trajectory points of the Fire II flight experiment. In the rapidly ionizing regime behind strong shock waves, the electronic energy level populations depart from Boltzmann distributions because the highlying bound electronic states are depleted. To quantify the extent of this nonequilibrium effect, we compare the results obtained by means of the collisional-radiative model with those based on Boltzmann distributions. For the earliest trajectory point, we show that the quasi-steady-state assumption is only valid for the high-lying excited states and cannot be extended to the metastable states.