AbstractThe synthesis of solketal is one of the innovative routes of glycerol valorization to value‐added products, and the simulation of the process requires the knowledge of thermodynamic properties that are not still available in the literature. In this work, the specific heat capacity as a function of temperature and the enthalpy and entropy of formation of all compounds involved in the reaction were calculated by employing a second‐order group‐additivity method. Expressions for the enthalpy of reaction and equilibrium constant as a function of temperature were also obtained. The glycerol conversion at equilibrium was calculated at different temperatures, pressures, acetone/glycerol molar ratios, and initial water contents, considering the nonideality of the liquid phase.