Aerothermodynamic characteristics of re-entry vehicles in hypersonic speed regimes are investigated by applying CFD methods based on the Navier-Stokes-Fourier equations. A special emphasis is placed on the effects of high temperature chemically reacting gases on shock stand-off distance and thermal characteristics of the flowfields. A ten species model is used for describing the kinetic mechanism for high temperature air. In particular, the hypersonic flows around a cylinder are computed with and without chemically reacting effects. It is shown that, when the chemically reacting effects are taken into account, the shock stand-off distance and temperature are significantly reduced.