Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 18, Issue 8, Pages 6182-6190Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5cp07803b
Keywords
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Funding
- National Nature Science Foundation of China [91541114]
- Natural Science Foundation of Shandong Province [ZR2014BL013]
- Education Department of Shandong Province [J14LC58]
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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 1b+2b and 1c+2b in methanol, and 1d+2d and 1d+2e 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.
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