The flows of CO2/CO/O2/O/C mixture in the relaxation zone behind shock waves are studied on the basis of the kinetic theory multi-temperature approaches taking into account vibrational and chemical non-equilibrium. The vibrational temperatures are introduced for the coupled (symmetric-bending) and asymmetric modes of CO2 as well as for diatomic species. Governing equations of the flow are written in the five-temperature approximation and solved numerically for different conditions in the free stream. Vibrational energy transitions, dissociation, recombination and exchange reactions are included to the kinetic scheme. The obtained results are compared with those found with the use of simplified three-temperature, two-temperature and one-temperature kinetic models. The influence of vibrational distributions on gas flow parameters and dissociation rates behind the shock front is shown. Along with the equilibrium conditions before the shock front the case of weakly non-equilibrium CO2 distributions in the free stream is also considered in calculations. The peculiarities of the results obtained for this case are discussed.