The role of nonelectrostatic solvation to chemical reactions in liquid phase

Detalhes bibliográficos
Autor(a) principal: Pliego Jr.,Josefredo R.
Data de Publicação: 2005
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Journal of the Brazilian Chemical Society (Online)
Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532005000200016
Resumo: The relative importance of cavity formation and dispersion-repulsion contributions to the activation free energy of chemical reactions in liquid phase is discussed, taken as example the reaction of one and two H2O molecules with CCl2 in aqueous solution. The solvent effect on these systems was investigated by free energy perturbation in previous publications. In the present report, were used the Pierotti scaled particle theory and the Claverie-Pierotti method to compute the free energy of cavity formation, while the dispersion-repulsion contribution was determined by the Floris and Tomasi method. We have found that the cavity term is the most important nonelectrostatic contribution of the solvent to the activation free energy, while the dispersion-repulsion contribution accounts for 25% to 35% of that term. In addition, we have observed that the direct Pierotti formula is more accurate than the Claverie-Pierotti method for the present system.
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spelling The role of nonelectrostatic solvation to chemical reactions in liquid phasesolvent effectcontinuum modelreaction kineticsThe relative importance of cavity formation and dispersion-repulsion contributions to the activation free energy of chemical reactions in liquid phase is discussed, taken as example the reaction of one and two H2O molecules with CCl2 in aqueous solution. The solvent effect on these systems was investigated by free energy perturbation in previous publications. In the present report, were used the Pierotti scaled particle theory and the Claverie-Pierotti method to compute the free energy of cavity formation, while the dispersion-repulsion contribution was determined by the Floris and Tomasi method. We have found that the cavity term is the most important nonelectrostatic contribution of the solvent to the activation free energy, while the dispersion-repulsion contribution accounts for 25% to 35% of that term. In addition, we have observed that the direct Pierotti formula is more accurate than the Claverie-Pierotti method for the present system.Sociedade Brasileira de Química2005-04-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532005000200016Journal of the Brazilian Chemical Society v.16 n.2 2005reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0103-50532005000200016info:eu-repo/semantics/openAccessPliego Jr.,Josefredo R.eng2005-05-24T00:00:00Zoai:scielo:S0103-50532005000200016Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2005-05-24T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv The role of nonelectrostatic solvation to chemical reactions in liquid phase
title The role of nonelectrostatic solvation to chemical reactions in liquid phase
spellingShingle The role of nonelectrostatic solvation to chemical reactions in liquid phase
Pliego Jr.,Josefredo R.
solvent effect
continuum model
reaction kinetics
title_short The role of nonelectrostatic solvation to chemical reactions in liquid phase
title_full The role of nonelectrostatic solvation to chemical reactions in liquid phase
title_fullStr The role of nonelectrostatic solvation to chemical reactions in liquid phase
title_full_unstemmed The role of nonelectrostatic solvation to chemical reactions in liquid phase
title_sort The role of nonelectrostatic solvation to chemical reactions in liquid phase
author Pliego Jr.,Josefredo R.
author_facet Pliego Jr.,Josefredo R.
author_role author
dc.contributor.author.fl_str_mv Pliego Jr.,Josefredo R.
dc.subject.por.fl_str_mv solvent effect
continuum model
reaction kinetics
topic solvent effect
continuum model
reaction kinetics
description The relative importance of cavity formation and dispersion-repulsion contributions to the activation free energy of chemical reactions in liquid phase is discussed, taken as example the reaction of one and two H2O molecules with CCl2 in aqueous solution. The solvent effect on these systems was investigated by free energy perturbation in previous publications. In the present report, were used the Pierotti scaled particle theory and the Claverie-Pierotti method to compute the free energy of cavity formation, while the dispersion-repulsion contribution was determined by the Floris and Tomasi method. We have found that the cavity term is the most important nonelectrostatic contribution of the solvent to the activation free energy, while the dispersion-repulsion contribution accounts for 25% to 35% of that term. In addition, we have observed that the direct Pierotti formula is more accurate than the Claverie-Pierotti method for the present system.
publishDate 2005
dc.date.none.fl_str_mv 2005-04-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532005000200016
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532005000200016
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.1590/S0103-50532005000200016
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv text/html
dc.publisher.none.fl_str_mv Sociedade Brasileira de Química
publisher.none.fl_str_mv Sociedade Brasileira de Química
dc.source.none.fl_str_mv Journal of the Brazilian Chemical Society v.16 n.2 2005
reponame:Journal of the Brazilian Chemical Society (Online)
instname:Sociedade Brasileira de Química (SBQ)
instacron:SBQ
instname_str Sociedade Brasileira de Química (SBQ)
instacron_str SBQ
institution SBQ
reponame_str Journal of the Brazilian Chemical Society (Online)
collection Journal of the Brazilian Chemical Society (Online)
repository.name.fl_str_mv Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)
repository.mail.fl_str_mv ||office@jbcs.sbq.org.br
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