A comprehensive study on low-temperature oxidation chemistry of cyclohexane. I. Conformational analysis and theoretical study of first and second oxygen addition

Abstract

To understand the low-temperature oxidation chemistry of cyclohexane, conformational analysis and theoretical study of the first and second oxygen addition are performed using quantum chemical calculations and kinetic calculations. Pressure- and temperature-dependent rate constants and branching ratios for major reaction channels are determined with RRKM/master-equation simulations over 298–2000 K and 0.01–1000 bar. The theoretical results indicate that the rapid inversion-topomerization processes facilitate fast equilibrium between axial and equatorial conformers. This can greatly counterbalance the influence of initial positions of side-chain groups in ROO, QOOH, cis-OOγQOOH and trans-OOγQOOH conformers. Conformational effects are found to be influential on the chain branching reaction sequences in second oxygen addition. The carbon ring prevents the conventional intramolecular H-transfer of cis-OOγQOOH conformers to yield ketohydroperoxides, as well as the inversion-topomerization from cis-OOγQOOH conformer to trans-OOγQOOH conformers. cis-OOγQOOH conformers mainly undergo alternative isomerization channel (cis-OOγQOOH→γP(OOH)2→alkenylhydroperoxides+OH→oxy radical+OH+OH), while trans-OOγQOOH conformers have both conventional isomerization channel (trans-OOγQOOH→ketohydroperoxides+OH→oxy radical+OH+OH) and alternative isomerization channel (trans-OOγQOOH→γP(OOH)2→alkenylhydroperoxides+OH→oxy radical+OH+OH). Kinetic calculation results also support the application of the thumb rule widely used in acyclic alkane oxidation that the rate constant of QOOH+O2 is roughly half of that of R+O2 in cyclic alkane oxidation, while it is indicated that estimating the rate constants of OOQOOH reactions from similar reactions of ROO may cause significant uncertainties.