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Pure and Applied Chemistry

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Volume 79, Issue 8

Issues

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

Rui M. Borges dos Santos
  • Corresponding author
  • Institute for Biotechnology and Bioengineering, Centre for Molecular and Structural Biomedicine, University of Algarve, Gambelas Campus, 8005-139 Faro, Portugal
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/ Benedito J. Costa Cabral
  • Corresponding author
  • Department of Chemistry and Biochemistry, Faculty of Science, University of Lisbon, 1749-016 Lisbon, Portugal
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/ José A. Martinho Simões
  • Corresponding author
  • Department of Chemistry and Biochemistry, Faculty of Science, University of Lisbon, 1749-016 Lisbon, Portugal
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Published Online: 2009-01-01 | DOI: https://doi.org/10.1351/pac200779081369

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.

Keywords: bond-dissociation enthalpy; photoacoustic calorimetry; quantum chemistry; solvation; thermochemistry

Conference

International Conference on Chemical Thermodynamics (ICCT-19), Conference on Chemical Thermodynamics, ICCT, Chemical Thermodynamics, 19th, Boulder, CO, USA, 2006-07-30–2006-08-04

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About the article

Published Online: 2009-01-01

Published in Print: 2007-01-01


Citation Information: Pure and Applied Chemistry, Volume 79, Issue 8, Pages 1369–1382, ISSN (Online) 1365-3075, ISSN (Print) 0033-4545, DOI: https://doi.org/10.1351/pac200779081369.

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