Intrinsic reaction kinetics and mechanism for the reverse disproportionation reaction to methyl phenyl carbonate.

Highlights • The reverse disproportionation process is proofed in transesterification system. • An existing conclusion about a constant rate of reverse disproportionation was break. • An more accurate information about the thermodynamic and kinetic was offered. • The available Sn-based intermediate is demonstrated to play a real catalytic role. Abstract The extensive researches about the thermodynamic and intrinsic kinetic of disproportionation reaction of methyl phenyl carbonate to diphenyl carbonate were investigated independently with dibutyltin oxide as a catalyst, at a temperature range of 433.15–473.15 K and different catalyst concentrations in a stirred batch reactor, for a deeper knowledge of reaction essence. This reaction was found endothermic and showed hardly any reaction in the absence of catalyst which indicate an inferior kinetic characteristics. The reaction rate increases with an increasing catalyst concentration until the concentration went to 8.08 × 10−4 mol mol−1. A possible mechanism involving an in-situ Sn-based species was proposed and finally verified by a good agreement between experimental and simulated data. The available Sn-based species was then demonstrated to play a real catalytic role by extra experiments. All results can also be further utilized to explore the essence of transesterification reaction network. [ABSTRACT FROM AUTHOR]