Pyrolysis mechanism of carbon matrix precursor cyclohexane—The formation of condensed-ring aromatics and the growing process of molecules

Abstract Based on the experiments, the UAM1 method was adopted to investigate benzene condensation of an important intermediate and the molecule growing mechanism during the cyclohexane pyrolysis process. The conclusions were drawn as follows: (1) from the viewpoint of thermodynamics, the condensation of benzene and C 4 H 5 is a spontaneous reaction and the rising temperature will increase the spontaneous tendency of the reaction. (2) From the viewpoint of kinetic, the condensation of benzene and C 4 H 5 is a two-step reaction. The rate-determining step is step 2 of hydrogen removal from intermediate C 10 H 10 (I1) with the activation energy of 350.61 kJ/mol below 1473 K while the rate-determining step is step 1 that free radical C 4 H 5 attacks benzene to form intermediate C 10 H 10 (I1) with the activation energy Δ E 0 ≠ θ = 31.74  kJ/mol above 1473 K. (3) The space structure, electronic structure and thermodynamics parameters of molecular reaction of dense-ring aromatizing compounds can be used to replace the resonance energy and free valence to judge the activation of thermodynamic reaction of compounds. And (4) the analysis of the space structure, electronic structure and thermodynamic parameters show that the growing process of molecules with benzene used as initial reactants becomes more easier as the multi-ring aromatizing molecular system increases.