The paper presents results of a numerical simulation of a supersonic two-dimensional (2D) viscous flow containing CO2 molecules near a spacecraft entering the Mars atmosphere. The gas–dynamic equations in the shock layer are coupled to the equations of non-equilibrium vibrational and chemical kinetics in the five-component mixture CO2/CO/O2/C/O. Transport and relaxation processes in the flow are studied on the basis of the rigorous kinetic theory methods; the developed transport algorithms are incorporated in the numerical scheme. The influence of the vibrational excitation of CO2 and chemical reactions on the gas flow parameters and heat transfer is analyzed. The obtained results are compared with those found using two simplified models based on the two-temperature and one-temperature vibrational distributions in CO2. The accuracy of the simplified models and the limits of their validity within the shock layer are evaluated. The effect of bulk viscosity in a flow near a re-entry body is discussed. The role of different diffusion processes, chemical reactions, and surface catalytic properties in a flow of the considered mixture in the shock layer is estimated.