Abstract
This publication describes the kinetics of the one-step liquid-phase oxidation of cyclohexane to cyclohexanone and cyclohexanol in solutions. Effects of the solvents were examined on the selectivity/conversion relation with regard to the intermediates cyclohexanol and cyclohexanone and their ratio in the reaction mixture. Measurements were carried out in a semibatch reactor at constant temperature (165 °C), and pressure (20 bar) without adding any catalysts. The experimental results can be modeled using a simplified reaction-network. Two models, specific- and unspecific-solvation, were employed to describe the influence of solvents on the different pathways of the developed oxidation network. The specific solvation model is based on the equilibrium between associated and free intermediates. Unspecific influence of the solvents on the reaction-rate can be explained by modeling the reaction-rate constants on the basis of the Kirkwood equation using the dielectric constant of the reaction mixture.
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