ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Nucleophilic substitution reactions in the alkyl halides, RX + Y- → RY + X-, proceeding in polar media are considered on the basis of the theory presented in Part A. It is shown that the solvent reorganization energy is the main part of the activation energy for this processes. According to calculations performed, the values of the solvent reorganization energy equal ∼2.5-3 eV for H2O and ∼ 1.8-2.3 eV for acetone. From experimental data on the kinetic isotope effect, an estimate for the splitting of nonadiabatic terms and for the slope of the potential curve v′ of the intermolecular interaction between halide ion and methyl halide near transition configuration is made. Further, the parameter v′ is used for calculating the activation entropy of substitution reactions in the methyl halides. Theoretical activation energies and activation entropies agree with experimental values. In the framework of theory presented an interpretation of change of Ea and the preexponential factor with the type of alkyl halide is given.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550060403
