The role of nonelectrostatic solvation to chemical reactions in liquid phase

Journal of the Brazilian Chemical Society

Josefredo R. Pliego Jr.¹ 

[1] ,Universidade Federal de Santa Catarina Departamento de Química Florianópolis SC ,Brazil

关键词: solvent effect;    continuum model;    reaction kinetics;   

DOI  :  10.1590/S0103-50532005000200016

来源: SciELO

【 摘 要 】

The relative importance of cavity formation and dispersion-repulsion contributions to the activation free energy of chemical reactions in liquid phase is discussed, taken as example the reaction of one and two H2O molecules with CCl2 in aqueous solution. The solvent effect on these systems was investigated by free energy perturbation in previous publications. In the present report, were used the Pierotti scaled particle theory and the Claverie-Pierotti method to compute the free energy of cavity formation, while the dispersion-repulsion contribution was determined by the Floris and Tomasi method. We have found that the cavity term is the most important nonelectrostatic contribution of the solvent to the activation free energy, while the dispersion-repulsion contribution accounts for 25% to 35% of that term. In addition, we have observed that the direct Pierotti formula is more accurate than the Claverie-Pierotti method for the present system.

【 授权许可】

CC BY   
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