{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,23]],"date-time":"2026-01-23T12:12:01Z","timestamp":1769170321406,"version":"3.49.0"},"reference-count":25,"publisher":"Wiley","issue":"3","license":[{"start":{"date-parts":[[2004,10,12]],"date-time":"2004-10-12T00:00:00Z","timestamp":1097539200000},"content-version":"vor","delay-in-days":4243,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J of Physical Organic Chem"],"published-print":{"date-parts":[[1993,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The Gibbs energies of activation of the solvolytic reactions of <jats:italic>tert<\/jats:italic>\u2010butyl halides (chloride, bromide and iodide) in eight mono\u2010alcohols and eight di\u2010alcohols 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, \u03b3<jats:sup>\u221e<\/jats:sup>. These values were determined from the UNIFAC group\u2010contribution method, with the modified Flory\u2013Huggins equation in the combinatorial term and with group interaction parameters from the Parameter Table exclusively based on experimental \u03b3<jats:sup>\u221e<\/jats:sup> data reported in the literature. It is concluded that solvent polarizability and polarity\u2013HBD acidity and cavity effects during the activated process are mainly due to transition\u2010state contributions.<\/jats:p>","DOI":"10.1002\/poc.610060302","type":"journal-article","created":{"date-parts":[[2005,1,7]],"date-time":"2005-01-07T04:37:35Z","timestamp":1105072655000},"page":"133-138","source":"Crossref","is-referenced-by-count":7,"title":["Study of initial\u2010 and transition\u2010state solvation in the solvolysis of <i>tert<\/i>\u2010butyl halides in alcohols from infinite dilution activity coefficients"],"prefix":"10.1002","volume":"6","author":[{"given":"Raquel M. C.","family":"Gon\u00e7lalves","sequence":"first","affiliation":[]},{"given":"Ana M. N.","family":"Sim\u00f5es","sequence":"additional","affiliation":[]},{"given":"L\u00eddia M. P. 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