FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2003758420> ?p ?o ?g. }

• W2003758420 endingPage "6609" @default.
• W2003758420 startingPage "6600" @default.
• W2003758420 abstract "Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the apparent combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5+C2H3-->1-butene, (2c) C2H5 + C2H5-->n-butane, and (3c) C2H3+C2H3-->1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [1-C4H8]/[C4H10] ratio was reduced from approximately 1.2 at 760 Torr (101 kPa) to approximately 0.5 at 100 Torr (13.3 kPa) and approximately 0.1 at pressures lower than about 5 Torr (approximately 0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3-->C3H5+CH3. This reaction occurs even at moderate pressures of approximately 200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(-3)-10(5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3+/-0.1." @default.
• W2003758420 created "2016-06-24" @default.
• W2003758420 creator A5008244247 @default.
• W2003758420 creator A5049317394 @default.
• W2003758420 creator A5085299535 @default.
• W2003758420 date "2007-06-22" @default.
• W2003758420 modified "2023-10-14" @default.
• W2003758420 title "Calculational and Experimental Investigations of the Pressure Effects on Radical−Radical Cross Combination Reactions: C2H5+ C2H3†" @default.
• W2003758420 cites W1963722261 @default.
• W2003758420 cites W1965454628 @default.
• W2003758420 cites W1968433238 @default.
• W2003758420 cites W1983488780 @default.
• W2003758420 cites W2002418337 @default.
• W2003758420 cites W2008480228 @default.
• W2003758420 cites W2012831305 @default.
• W2003758420 cites W2018043796 @default.
• W2003758420 cites W2022239234 @default.
• W2003758420 cites W2029101044 @default.
• W2003758420 cites W2046161498 @default.
• W2003758420 cites W2048264410 @default.
• W2003758420 cites W2065176860 @default.
• W2003758420 cites W2069709184 @default.
• W2003758420 cites W2069971899 @default.
• W2003758420 cites W2095416067 @default.
• W2003758420 cites W2114514241 @default.
• W2003758420 cites W2144273704 @default.
• W2003758420 cites W2291801456 @default.
• W2003758420 cites W2748171212 @default.
• W2003758420 cites W4213115811 @default.
• W2003758420 doi "https://doi.org/10.1021/jp067357v" @default.
• W2003758420 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/17585737" @default.
• W2003758420 hasPublicationYear "2007" @default.
• W2003758420 type Work @default.
• W2003758420 sameAs 2003758420 @default.
• W2003758420 citedByCount "2" @default.
• W2003758420 countsByYear W20037584202012 @default.
• W2003758420 countsByYear W20037584202019 @default.
• W2003758420 crossrefType "journal-article" @default.
• W2003758420 hasAuthorship W2003758420A5008244247 @default.
• W2003758420 hasAuthorship W2003758420A5049317394 @default.
• W2003758420 hasAuthorship W2003758420A5085299535 @default.
• W2003758420 hasConcept C113196181 @default.
• W2003758420 hasConcept C121332964 @default.
• W2003758420 hasConcept C134121241 @default.
• W2003758420 hasConcept C139066938 @default.
• W2003758420 hasConcept C161790260 @default.
• W2003758420 hasConcept C17365422 @default.
• W2003758420 hasConcept C178790620 @default.
• W2003758420 hasConcept C185592680 @default.
• W2003758420 hasConcept C191897082 @default.
• W2003758420 hasConcept C192562407 @default.
• W2003758420 hasConcept C2777954637 @default.
• W2003758420 hasConcept C2778597550 @default.
• W2003758420 hasConcept C30646810 @default.
• W2003758420 hasConcept C54582936 @default.
• W2003758420 hasConcept C75473681 @default.
• W2003758420 hasConcept C97355855 @default.
• W2003758420 hasConceptScore W2003758420C113196181 @default.
• W2003758420 hasConceptScore W2003758420C121332964 @default.
• W2003758420 hasConceptScore W2003758420C134121241 @default.
• W2003758420 hasConceptScore W2003758420C139066938 @default.
• W2003758420 hasConceptScore W2003758420C161790260 @default.
• W2003758420 hasConceptScore W2003758420C17365422 @default.
• W2003758420 hasConceptScore W2003758420C178790620 @default.
• W2003758420 hasConceptScore W2003758420C185592680 @default.
• W2003758420 hasConceptScore W2003758420C191897082 @default.
• W2003758420 hasConceptScore W2003758420C192562407 @default.
• W2003758420 hasConceptScore W2003758420C2777954637 @default.
• W2003758420 hasConceptScore W2003758420C2778597550 @default.
• W2003758420 hasConceptScore W2003758420C30646810 @default.
• W2003758420 hasConceptScore W2003758420C54582936 @default.
• W2003758420 hasConceptScore W2003758420C75473681 @default.
• W2003758420 hasConceptScore W2003758420C97355855 @default.
• W2003758420 hasIssue "29" @default.
• W2003758420 hasLocation W20037584201 @default.
• W2003758420 hasLocation W20037584202 @default.
• W2003758420 hasOpenAccess W2003758420 @default.
• W2003758420 hasPrimaryLocation W20037584201 @default.
• W2003758420 hasRelatedWork W1973280242 @default.
• W2003758420 hasRelatedWork W1978932292 @default.
• W2003758420 hasRelatedWork W2001182836 @default.
• W2003758420 hasRelatedWork W2043669071 @default.
• W2003758420 hasRelatedWork W2047760200 @default.
• W2003758420 hasRelatedWork W2073304781 @default.
• W2003758420 hasRelatedWork W2084013633 @default.
• W2003758420 hasRelatedWork W2093514150 @default.
• W2003758420 hasRelatedWork W2952237605 @default.
• W2003758420 hasRelatedWork W81629588 @default.
• W2003758420 hasVolume "111" @default.
• W2003758420 isParatext "false" @default.
• W2003758420 isRetracted "false" @default.
• W2003758420 magId "2003758420" @default.
• W2003758420 workType "article" @default.