title: Theoretical estimation of kinetic parameters for nucleophilic substitution reactions in solution: an application of a solution translational entropy model.
abstract: The kinetic parameters, such as activation entropy, activation enthalpy, activation free-energy, and reaction rate constant, for a series of nucleophilic substitution (SN) reactions in solution, are investigated using both a solution-phase translational entropy model and an ideal gas-phase translational entropy model. The results obtained from the solution translational entropy model are in excellent agreement with the experimental values, while the overestimation of activation free-energy from the ideal gas-phase translational entropy model is as large as 6.9 kcal mol(-1). For some of the reactions studied, such as and in methanol, and and in aqueous solution, the explicit + implicit model, namely, a cluster-continuum type model, should be employed to account for the strong solvent-solute interactions. In addition, the explicit + implicit models have also been applied to the DMSO-H2O mixtures, which would open up a door to investigate the reactions in a mixed solvent using density functional theory (DFT) methods.
authors: College of Chemistry, Beijing Normal University, Beijing, 100875, China. dcfang@bnu.edu.cn and Department of Chemistry and Chemical Engineering, Jining University, Qufu, 273155, Shandong, China.
authors: Ling-Li
authors: LL
authors: Han
authors: College of Chemistry, Beijing Normal University, Beijing, 100875, China. dcfang@bnu.edu.cn.
authors: Shi-Jun
authors: SJ
authors: Li
authors: College of Chemistry, Beijing Normal University, Beijing, 100875, China. dcfang@bnu.edu.cn.
authors: De-Cai
authors: DC
authors: Fang