In this paper, we analyze the departure from equilibrium in two specific types of thermal plasmas. The first type deals with the plasma produced during the atmospheric entry of a spatial vehicle in the upper layers of an atmosphere, specifically the one of Mars. The second type concerns the plasma produced during the laser-matter interaction above the breakdown threshold on a metallic sample. We successively describe the situation and give the way along which modeling tools are elaborated by avoiding any assumption on the thermochemical equilibrium. The key of the approach is to consider the excited states of the different species as independent species. Therefore, they obey to conservation equations involving collisional-radiative contributions related to the other excited states. These contributions are in part due to the influence of electrons and heavy particles having a different translation temperature. This ‘state-to-state’ approach then enables the verification of the excitation equilibrium by analyzing Boltzmann plots. This approach leads finally to a thorough analysis of the progressive coupling until the equilibrium asymptotically observed.