Theoretical study of the thermal decomposition of the 5-methyl-2-furanylmethyl radical.
Identifieur interne : 000069 ( PubMed/Curation ); précédent : 000068; suivant : 000070Theoretical study of the thermal decomposition of the 5-methyl-2-furanylmethyl radical.
Auteurs : Baptiste Sirjean [France] ; René FournetSource :
- The journal of physical chemistry. A [ 1520-5215 ] ; 2012.
Descripteurs français
- KwdFr :
- MESH :
English descriptors
- KwdEn :
- MESH :
- chemical , chemistry : Free Radicals, Furans.
- Molecular Structure, Quantum Theory, Thermodynamics.
Abstract
The thermal decomposition of the 5-methyl-2-furanylmethyl radical (R(1)), the most important primary radical formed during the combustion and thermal decomposition of 2,5-dimethylfuran (a promising next-generation biofuel), was studied using CBS-QB3 calculations and master equation (ME)/RRKM modeling. Because very little information is available in the literature, the detailed potential energy surface (PES) was investigated thoroughly. Only the main pathways, having a kinetic influence on the decomposition of R(1), were retained in the final ME/RRKM model. Among all the channels studied, the ring-opening of the 5-methyl-2-furanylmethyl radical, followed by ring enlargement to form cyclohexadienone molecules is predicted to be the easiest decomposition channel of R(1). The C(6) cyclic species formed can undergo unimolecular reactions to yield phenol and to a lesser extent cyclopentadiene and CO. Our calculations predict that these species are important products formed during the pyrolysis of 2,5-dimethylfuran (DMF). Other channels involved in the decomposition of R(1) lead directly to the formation of linear and cyclic unsaturated C(5) species and constitute an additional source of cyclopentadiene and CO. High-pressure limit rate constants were computed as well as thermochemical properties for important species. ME/RRKM analysis was performed to probe the influence of pressure on the rate coefficients and pressure dependent rate coefficients were proposed for pressures and temperatures ranging, respectively, from 10(-2) bar to 10 bar and 1000 to 2000 K.
DOI: 10.1021/jp303680h
PubMed: 22650318
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Because very little information is available in the literature, the detailed potential energy surface (PES) was investigated thoroughly. Only the main pathways, having a kinetic influence on the decomposition of R(1), were retained in the final ME/RRKM model. Among all the channels studied, the ring-opening of the 5-methyl-2-furanylmethyl radical, followed by ring enlargement to form cyclohexadienone molecules is predicted to be the easiest decomposition channel of R(1). The C(6) cyclic species formed can undergo unimolecular reactions to yield phenol and to a lesser extent cyclopentadiene and CO. Our calculations predict that these species are important products formed during the pyrolysis of 2,5-dimethylfuran (DMF). Other channels involved in the decomposition of R(1) lead directly to the formation of linear and cyclic unsaturated C(5) species and constitute an additional source of cyclopentadiene and CO. High-pressure limit rate constants were computed as well as thermochemical properties for important species. ME/RRKM analysis was performed to probe the influence of pressure on the rate coefficients and pressure dependent rate coefficients were proposed for pressures and temperatures ranging, respectively, from 10(-2) bar to 10 bar and 1000 to 2000 K.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="MEDLINE"><PMID Version="1">22650318</PMID><DateCreated><Year>2012</Year><Month>06</Month><Day>28</Day></DateCreated><DateCompleted><Year>2012</Year><Month>10</Month><Day>31</Day></DateCompleted><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1520-5215</ISSN><JournalIssue CitedMedium="Internet"><Volume>116</Volume><Issue>25</Issue><PubDate><Year>2012</Year><Month>Jun</Month><Day>28</Day></PubDate></JournalIssue><Title>The journal of physical chemistry. A</Title><ISOAbbreviation>J Phys Chem A</ISOAbbreviation></Journal><ArticleTitle>Theoretical study of the thermal decomposition of the 5-methyl-2-furanylmethyl radical.</ArticleTitle><Pagination><MedlinePgn>6675-84</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1021/jp303680h</ELocationID><Abstract><AbstractText>The thermal decomposition of the 5-methyl-2-furanylmethyl radical (R(1)), the most important primary radical formed during the combustion and thermal decomposition of 2,5-dimethylfuran (a promising next-generation biofuel), was studied using CBS-QB3 calculations and master equation (ME)/RRKM modeling. Because very little information is available in the literature, the detailed potential energy surface (PES) was investigated thoroughly. Only the main pathways, having a kinetic influence on the decomposition of R(1), were retained in the final ME/RRKM model. Among all the channels studied, the ring-opening of the 5-methyl-2-furanylmethyl radical, followed by ring enlargement to form cyclohexadienone molecules is predicted to be the easiest decomposition channel of R(1). The C(6) cyclic species formed can undergo unimolecular reactions to yield phenol and to a lesser extent cyclopentadiene and CO. Our calculations predict that these species are important products formed during the pyrolysis of 2,5-dimethylfuran (DMF). Other channels involved in the decomposition of R(1) lead directly to the formation of linear and cyclic unsaturated C(5) species and constitute an additional source of cyclopentadiene and CO. High-pressure limit rate constants were computed as well as thermochemical properties for important species. 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