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Partially‐decoupled upwind‐based total‐variation‐diminishing (TVD) finite‐difference schemes for the solution of the conservation laws governing two‐dimensional non‐equilibrium vibrationally relaxing and chemically reacting flows of thermally‐perfect gaseous mixtures are presented. In these methods, a novel partially‐decoupled flux‐difference splitting approach is adopted. The fluid conservation laws and species concentration and vibrational energy equations are decoupled by means of a frozen flow approximation. The resulting partially‐decoupled gas‐dynamic and thermodynamic subsystems are then solved alternately in a lagged manner within a time marching procedure, thereby providing explicit coupling between the two equation sets. Both time‐split semi‐implicit and factored implicit flux‐limited TVD upwind schemes are described. The semi‐implicit formulation is more appropriate for unsteady applications whereas the factored implicit form is useful for obtaining steady‐state solutions. Extensions of Roe's approximate Riemann solvers, giving the eigenvalues and eigenvectors of the fully coupled systems, are used to evaluate the numerical flux functions. Additional modifications to the Riemann solutions are also described which ensure that the approximate solutions are not aphysical. The proposed partially‐decoupled methods are shown to have several computational advantages over chemistry‐split and fully coupled techniques. Furthermore, numerical results for single, complex, and double Mach reflection flows, as well as corner‐expansion and blunt‐body flows, using a five‐species four‐temperature model for air demonstrate the capabilities of the methods.

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