Bond-dissociation enthalpies in the gas phase and in organic solvents: Making ends meet

被引：14

作者：

Borges dos Santos, Rui M.

Costa Cabral, Benedito J.

Martinho Simoes, Jose A. ^{[1
]}

机构：

[1] Univ Lisbon, Fac Sci, Dept Chem & Biochem, P-1749016 Lisbon, Portugal

[2] Univ Algarve, Ctr Mol & Struct Biomed, Inst Biotechnol & Bioengn, P-8005139 Faro, Portugal

[3] Univ Lisbon, Grp Math Phys, P-1649003 Lisbon, Portugal

来源：

PURE AND APPLIED CHEMISTRY | 2007年 / 79卷 / 08期

关键词：

thermochemistry; solvation; photoacoustic calorimetry; bond-dissociation enthalpy; quantum chemistry; O-H BOND; DENSITY-FUNCTIONAL THEORY; RESOLVED PHOTOACOUSTIC CALORIMETRY; HOMOLYTIC DISSOCIATION; THERMOCHEMICAL PROPERTIES; DIFFERENTIAL SOLVATION; SUBSTITUTED PHENOLS; HYDROGEN-BOND; FREE-RADICALS; ENERGETICS;

D O I：

10.1351/pac200779081369

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Solvent effects are responsible for the difference between gas- and solution-phase bond-dissociation enthalpies (BDEs), and are thus crucial for understanding reactivity in solution. While solvation effects can be negligible (e.g., in reactions involving carbon-centered radicals), they may be rather significant (e.g., when oxygen-centered radicals are formed). This paper reviews a number of models which have been proposed to deal with the difference between the solvation energetics of a radical and its parent molecule. It is concluded that the radical-solvent interaction may be larger than previously anticipated.

引用

页码：1369 / 1382

页数：14

共 67 条

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