Cation-Exchange Resin Catalyzed Ketalization Reaction of Cyclohexanone with 1,4-Butanediol: Thermodynamics and Kinetics

The thermodynamics and kinetics for the ketalization reaction of cyclohexanone with 1,4-butanediol catalyzed by 732 cation-exchange resin were studied for the first time. The reaction equilibrium compositions were obtained from 293.15 to 333.15 K at atmospheric pressure, and the equilibrium constants was estimated using the UNIFAC model. The thermodynamic properties of the ketalization reaction were evaluated: Δ<i>H</i>⁰ = −12.85 kJ mol^–1, Δ<i>G</i>⁰ = −1.04 kJ mol^–1, Δ<i>S</i>⁰ = −39.61 J K^–1 mol^–1. The influences of various experimental parameters like agitation speed, initial molar ratio of reactants, temperature, catalyst loading, and particle size on the conversion of limiting reactant were studied. Different kinetic models were tested against the experimentally measured kinetic data and the results show that the Eley–Rideal model with chemisorption of 1,4-butanediol on the active sites predict the kinetics best. The <i>E</i>_a value for the overall ketalization reaction is found to be 43.89 kJ mol^–1