STUDY OF INITIAL-STATE AND TRANSITION-STATE SOLVATION IN THE SOLVOLYSIS OF TERT-BUTYL HALIDES IN ALCOHOLS FROM INFINITE DILUTION ACTIVITY-COEFFICIENTS

• Type: Article in International Scientific Journal
• Date: 1993

Authors

GONCALVES, RMC (Author) Other; SIMOES, AMN (Author) Other; ALBUQUERQUE, LMPC (Author) Other; Maria Eugénia Macedo (Author) FEUP

Journal

Title: Journal of Physical Organic Chemistry

Vol. 6

Pages: 133-138

ISSN: 0894-3230

Publisher: Wiley-Blackwell

Indexing

ISI Web of Knowledge - 8 Citations

Other information

Authenticus ID: P-001-NAP

DOI: 10.1002/poc.610060302

Abstract (EN): The Gibbs energies of activation of the solvolytic reactions of tert-butyl halides (chloride, bromide and iodide) in eight mono-alcohols and eight di-alcohols were dissected into contributions from the initial state and transition state. The unified approach proposed by Abraham was applied and the various factors making up the overall solvent effect in both states were identified and compared. To perform this study, the Gibbs energies of transfer of the initial state were calculated using the infinite dilution activity coefficient values of the solutes in the solvents, gamma(infinity). These values were determined from the UNIFAC group-contribution method, with the modified Flory-Huggins equation in the combinatorial term and with group interaction parameters from the Parameter Table exclusively based on experimental gamma(infinity) data reported in the literature. It is concluded that solvent polarizability and polarity-HBD acidity and cavity effects during the activated process are mainly due to transition-state contributions.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 6