Compressible mixtures in supersonic flows are subject to significant temperature changes via shock-waves and expansions, which affect several properties of the flow. Besides the widely-studied variable transport effects such as temperature-dependent viscosity and conductivity, vibrational and rotational molecular energy storage is also modified through the variation of the heat capacity c p and heat capacity ratio γ, specially in hypersonic flows. Changes in the composition of the mixture may also modify its value through the species mass fraction Y α , thereby affecting the compression capacity of the flow. Canonical configurations are studied here to explore their sharply-conditioned mechanical equilibrium under variations of these thermal models. In particular, effects of c p (T, Y α ) and γ(T, Y α ) on the stability of shock-impinged supersonic shear and mixing layers is addressed, on condition that a shock wave is refracted. It is found that the limits defining regular structures are affected (usually broadened out) by the dependence of heat capacities with temperature. Theoretical and high-fidelity numerical simulations exhibit a good agreement in the prediction of regular shock reflections and their post-shock aerothermal properties.