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A comprehensive state-to-state (StS) model for air was formed -including vibrationvibration-translation (VVT) reactions. The generated VVT reaction rates were compared to available first principles calculations and reasonable agreement was obtained. The influence of multi-quantum transitions revealed that the possible reduction on the number of VVT transitions depends on the application. The influence of VV transitions revealed that the vibrational excitation becomes too fast if VVT transitions are reduced to VT transitions, invalidating this approximation. Comparisons were made with existing NO emission measurements in the UV and mid-IR spectrum. At velocities of 3 -4 km/s, some of the current O2 dissociation rates may be inaccurate. At a higher velocity of 6.81 km/s, the NO mole fraction predicted by the StS model is around an order of magnitude greater than that predicted by

Thermochemical nonequilibrium in expansion tunnel nozzles is investigated numerically using a state-to-state description in one-dimension for representative air conditions. Limiting the multi-quantum jumps of VVT transitions to 3 in both N2 and O2 can accurately simulate the nonequilibrium nozzle flow. The reduction of VVT transitions to VT transitions works well. State-to-state modelling of an actual expansion tunnel nozzle condition yielded agreement with the measured static pressure. A study on the influence of different thermochemical excitation in the freestream at the test section shows that the post-shock radiation emissions can differ by more than 50 %. However, the non-Boltzmann distributions in the freestream has no influence. An evaluation of the discrepancy between the twotemperature and state-to-state models shows that the former generally predicts a faster thermochemical relaxation. Furthermore, the state-to-state results indicate that, in general, the molecular species all have a different vibrational temperature.

This thesis presents an experimental study of high temperature CO2 flowsfocusing on CO2 flows subjected to rapidly expanding conditions relevant to Mars entry and representative of the corner expansion around the shoulder, between the windward and leeward flows, on an entry capsule. This is an important but poorly understood aspect of spacecraft design. Past numerical research showed that, during Mars entry, the CO2 4.3 µm and 2.7 µm band radiation from the aforementioned expanding flow produce non-negligible contributions to the heating of the capsule afterbody.Consequently, this radiative heating should be considered in the sizing of the afterbody thermal protection systems (TPS). However, due to a lack of experimental research, the nonequilibrium characteristics of CO2 expanding flows are not well understood. Therefore, to help with the design of future Mars entry vehicles, it is necessary to investigate such flows.The X2 expansion tube was used to facilitate the current study. Three expansion tube test conditions with differing velocitiesnominally 2.8 km/s, 3.4 km/s, and 4.0 km/swere developed. Using a two-dimensional wedge model with a 54° convex corner along with the new conditions, flows with similarities to the expanding flow around the shoulder of an aeroshell at certain Mars entry conditions were created. Mid-wavelength infrared emission spectroscopy of the 4.3 μm and 2.7 μm bands were performed on the flow. The spectroscopic measurements were used to estimate the rotational and vibrational temperatures and the CO2 number densities using a spectral fitting method. Supplementing the spectroscopic measurements, filtered images of the 4.3 μm and 2.7 μm bands were taken to provide a two-dimensional spatial map of the band radiance in the flow around the wedge. Estimates of the experimental inflow conditions were produced by solving for the intermediate test gas states using measurements of various properties of the operating condition. CO2 spectroscopic measurements of the inflow along with measurements of the wedge model shock location and deduced post-shock conditions were also used to help characterize the test conditions. Using estimated inflow conditions, three-dimensional CFD simulations of the experiments were conducted using a two-temperature model. The computed results were compared to the available measurements to examine the appropriateness of the current numerical model at simulating the CO2 flow.Important qualitative results were obtained in this thesis in regards to the high temperature CO2expanding flow. The temperatures estimated in the wedge flow using both the 2.7 and 4.3 µm spectroscopic measurements were found to be the same. This provides some confidence to the validity of NEQAIR, using CDSD-4000, at predicting CO2 radiation under gas-dynamic conditions which are more relevant to Mars entry. Using the estimated rotational and vibrational temperatures, the CO2 II thermal non-equilibrium in the expanding flow was shown to be smallless than 10%. As the experiments simulate the expanding fl...