State-resolved chemical reactions in CO2 are studied by taking into account excitation of all vibrational modes and preferential reaction mechanisms. The effect of several parameters on the reaction rate coefficients is discussed; it is shown that the nonequilibrium factor in the expression for the rate coefficients of exchange reactions is much less sensitive to the number of accounted vibrational states and model parameters than that of dissociation. On the other hand, the choice of thermal equilibrium Arrhenius law parameters is crucial for the correct prediction of rate coefficients for both reactions. Developed models are implemented to the one-dimensional boundary layer code for coupled state-to-state simulations of nonequilibrium CO2 flows under Mars entry conditions. Vibrational distributions, mixture composition, flow variables, and heat flux are studied for several kinetic schemes and different models of chemical reactions. Whereas including the exchange reactions weakly affects the flow, switching between the Park and McKenzie sets of parameters results in significant modification of the kinetic mechanisms; for the McKenzie model, recombination near the wall is a dominating reaction, whereas for the Park model, chemical reactions are frozen. Different contributions to the heat flux are evaluated and a satisfactory agreement with experiments is shown.