Advances in modeling hydrocarbon cracking kinetic predictions by quantum chemical theory: A review

摘要

Summary In the modeling of hydrocarbon thermal cracking processes, complicated reaction networks of multicomponent reactants make kinetic parameter predictions very challenging. To solve this problem, the additivity method and Evans‐Polanyi equation were proposed for the prediction of kinetic factors. As the calculation of kinetic parameters using quantum chemical theory was used for higher accuracy, new additivity methods at the quantum theory level were developed for the prediction of thermodynamic kinetic parameters. At the same time, a reaction class transition state theory RC‐TST, analogous to the Evans‐Polanyi equation, was proposed by considering quantum factors for kinetic constant evaluation. Quantum calculation methods promoted mechanistic studies of electronic effects to accurately reveal the kinetic constant rules with different structural factors. Under these circumstances, kinetic parameter predictions by different quantum chemical computation methods were firstly introduced and reviewed. Meanwhile, development of the new additivity method and RC‐TST theory at the quantum chemistry level were summarized, and the new outlook on electronic effects with an appropriate quantum chemical computational method into the new additivity method was conducted to develop more perspicuous and accuracy in a simplified method for the calculation of complicated thermal cracking reaction.