QRRK theory bimolecular reactions

To illustrate the utility of the bimolecular QRRK theory, consider the recombination of CHjCl and CHjCl radicals at temperatures in the range 800-l,5(X) C. This recombination process is important in the chlorine-catalyzed oxidative pyrolytic (CCOP) conversion of methane into more valuable C2 products, and it has been studied recently by Karra and Senkan (1988a). The following composite reaction mechanism represents the complex process ... 

This section treats the theory of chemical activation reactions more rigorously, at the same level of approximation as in the discussion of unimolecular reactions in Section 10.4.4. That is, the QRRK theory of chemical activation reactions is developed here. This theory for bimolecular reactions was set out by Dean and coworkers [93,428],... 

In summary, the QRRK theory result for the observed bimolecular reaction rate constant fcbimol was given by Eq. 10.198 as... 

Multifrequency Quantum Rice-Ramsperger-Kassel (QRRK) is a method used to predict temperature and pressure-dependent rate coefficients for complex bimolecular chemical activation and unimolecular dissociation reactions. Both the forward and reverse paths are included for adducts, but product formation is not reversible in the analysis. A three-frequency version of QRRK theory is developed coupled with a Master Equation model to account for collisional deactivation (fall-off). The QRRK/Master Equation analysis is described thoroughly by Chang et al. [62, 63]. 

Using the results obtained on the phenyl system for the dibenzofuran + O2 system, kinetics of each path, as a function of temperature and pressure are determined using bimolecular chemical activation analysis. The high-pressure-limit kinetic parameters from the calculation results are again obtained with cannonical Transition State Theory. QRRK analysis is utilized to obtain k(E) and master analysis is used to evaluate the fall-off behaviour of this complex bimolecular chemical activation reaction [34]. 

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