Source:http://linkedlifedata.com/resource/pubmed/id/11741433
| Subject | Predicate | Object | Context |
|---|---|---|---|
| pubmed-article:11741433 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:11741433 | lifeskim:mentions | umls-concept:C0016693 | lld:lifeskim |
| pubmed-article:11741433 | lifeskim:mentions | umls-concept:C0678599 | lld:lifeskim |
| pubmed-article:11741433 | lifeskim:mentions | umls-concept:C0599530 | lld:lifeskim |
| pubmed-article:11741433 | pubmed:issue | 50 | lld:pubmed |
| pubmed-article:11741433 | pubmed:dateCreated | 2001-12-19 | lld:pubmed |
| pubmed-article:11741433 | pubmed:abstractText | The photolysis reaction of di-tert-butylperoxide was studied in various solvents by photoacoustic calorimetry (PAC). This technique allows the determination of the enthalpy of this homolysis reaction, which by definition corresponds to the O-O bond dissociation enthalpy of the peroxide in solution, DHsin(degrees)(O-O). The derived value from these experiments in benzene, 156.7 +/- 9.9 kJ mol(-1), is very similar to a widely accepted value for the gas-phase bond dissociation enthalpy, DH(degrees)(O-O) = 159.0 +/- 2.1 kJ mol(-1). However, when the PAC-based value is used together with auxiliary experimental data and Drago's ECW model to estimate the required solvation terms, it leads to 172.3 +/- 10.2 kJ mol(-1) for the gas-phase bond dissociation enthalpy. This result, significantly higher than the early literature value, is however in excellent agreement with a recent gas-phase determination of 172.5 +/- 6.6 kJ mol(-1). The procedure to derive the gas-phase DH(degrees)(O-O) was tested by repeating the PAC experiments in carbon tetrachloride and acetonitrile. The average of the values thus obtained was DH(degrees)(O-O) = 179.6 +/- 4.5 kJ mol(-1), confirming that the early gas-phase result is a lower limit. More importantly, the present study questions the usual assumption that the solvation terms of homolysis reactions producing free radicals in solution should cancel, and suggests a methodology to estimate solvation enthalpies of free radicals. | lld:pubmed |
| pubmed-article:11741433 | pubmed:language | eng | lld:pubmed |
| pubmed-article:11741433 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:11741433 | pubmed:status | PubMed-not-MEDLINE | lld:pubmed |
| pubmed-article:11741433 | pubmed:month | Dec | lld:pubmed |
| pubmed-article:11741433 | pubmed:issn | 0002-7863 | lld:pubmed |
| pubmed-article:11741433 | pubmed:author | pubmed-author:Martinho... | lld:pubmed |
| pubmed-article:11741433 | pubmed:author | pubmed-author:Borges Dos... | lld:pubmed |
| pubmed-article:11741433 | pubmed:author | pubmed-author:MuralhaV SVS | lld:pubmed |
| pubmed-article:11741433 | pubmed:author | pubmed-author:CorreiaC FCF | lld:pubmed |
| pubmed-article:11741433 | pubmed:issnType | lld:pubmed | |
| pubmed-article:11741433 | pubmed:day | 19 | lld:pubmed |
| pubmed-article:11741433 | pubmed:volume | 123 | lld:pubmed |
| pubmed-article:11741433 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:11741433 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:11741433 | pubmed:pagination | 12670-4 | lld:pubmed |
| pubmed-article:11741433 | pubmed:dateRevised | 2003-10-31 | lld:pubmed |
| pubmed-article:11741433 | pubmed:year | 2001 | lld:pubmed |
| pubmed-article:11741433 | pubmed:articleTitle | Solvation enthalpies of free radicals: O-O bond strength in di-tert-butylperoxide. | lld:pubmed |
| pubmed-article:11741433 | pubmed:affiliation | Faculdade de Engenharia de Recursos Naturais, Universidade do Algarve, Campus de Gambelas, 8000-810 Faro, Portugal. | lld:pubmed |
| pubmed-article:11741433 | pubmed:publicationType | Journal Article | lld:pubmed |