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of CO2 provides the most effective pathway for dissociation. However not only must vibrational excitation be stimulated, but the population of vibrationally excited species must also be maintained. In order to maintain this population, there must be thermal non-equilibrium between translational and vibrational temperatures. Under these conditions the vibrational-translational (VT) relaxation rate coefficient is relatively slow compared to vibrational excitation. The VT relaxation rate coefficient can be approximated by Equation 6.4, assuming relaxation is primarily related to the symmetric vibrational modes [37]: k ≈10−10 ·exp−72/T1/3 cm3/s. (6.4) VTg When the gas temperature is close to room temperature in thermal non-equilibrium with Tv, kV T ≈ 2 × 10−14 cm3/s. Using the gas temperature measured from the C2 spectra of 6000 K, the rate coefficient increases two orders of magnitude to kVT ≈2×10−12 cm3/s. In addition to the influence of gas temperature on VT relaxation rates that affect dissociation, higher gas temperatures also leave the dissociation products unprotected against reverse reactions. High gas temperature leads to the oxidation reaction of CO, CO + O2 → CO2 + O. The reaction rate coefficient for CO oxidation can be computed as a function of gas temperature using the Arrhenius rate equation cited previously in Equation 5.19. Tabulated values of the empirical values A and Ea relevant to CO2 reactions can be found in Appendix C. When the CO oxidation occurs at room temperature, the reaction rate coefficient is insignificant, k = 5×10−31 cm3/s. However when the rate coefficient is calculated for Tg = 6000 K, the rate becomes much more important as a reaction mechanism for CO2 generation: k = 1 × 10−13 cm3/s. In order to prevent this reverse reaction from occurring in high temperature discharges, substantial quenching on the order of 108 − 109 K/s must be used. Thus the result of 124PDF Image | CO2 Conversion in a Microwave Plasma Catalyst System
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