Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical
Identifieur interne : 000734 ( Hal/Checkpoint ); précédent : 000733; suivant : 000735Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical
Auteurs : René Fournet [France] ; Baptiste Sirjean [France]Source :
- Journal of Physical Chemistry A [ 1089-5639 ] ; 2012-06-08.
English descriptors
- mix :
Abstract
The thermal decomposition of the 5-methyl-2furanylmethyl radical (R,), 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/RRKIvl model. Among all the channels studied, the ring-opening of the 5-methyl-2-furanylmethyl radical, followed by ring enlargement to form c-yclohexadienone 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 Cs 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.
Url:
DOI: 10.1021/jp303680h
Links toward previous steps (curation, corpus...)
Links to Exploration step
Hal:hal-00777859Le document en format XML
<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical</title>
<author><name sortKey="Fournet, Rene" sort="Fournet, Rene" uniqKey="Fournet R" first="René" last="Fournet">René Fournet</name>
<affiliation wicri:level="1"><hal:affiliation type="laboratory" xml:id="struct-211875" status="VALID"><idno type="IdRef">153068876</idno>
<idno type="RNSR">201320573K</idno>
<idno type="IdUnivLorraine">[UL]RQC--</idno>
<orgName>Laboratoire Réactions et Génie des Procédés</orgName>
<orgName type="acronym">LRGP</orgName>
<date type="start">2013-01-01</date>
<desc><address><addrLine>Université de Lorraine - ENSIC, 1 rue de Grandville BP 20451, 54001 Nancy Cedex</addrLine>
<country key="FR"></country>
</address>
<ref type="url">http://lrgp.univ-lorraine.fr/</ref>
</desc>
<listRelation><relation active="#struct-413289" type="direct"></relation>
<relation name="UMR7274" active="#struct-441569" type="direct"></relation>
</listRelation>
<tutelles><tutelle active="#struct-413289" type="direct"><org type="institution" xml:id="struct-413289" status="VALID"><idno type="IdRef">157040569</idno>
<idno type="IdUnivLorraine">[UL]100--</idno>
<orgName>Université de Lorraine</orgName>
<orgName type="acronym">UL</orgName>
<date type="start">2012-01-01</date>
<desc><address><addrLine>34 cours Léopold - CS 25233 - 54052 Nancy cedex</addrLine>
<country key="FR"></country>
</address>
<ref type="url">http://www.univ-lorraine.fr/</ref>
</desc>
</org>
</tutelle>
<tutelle name="UMR7274" active="#struct-441569" type="direct"><org type="institution" xml:id="struct-441569" status="VALID"><idno type="ISNI">0000000122597504</idno>
<idno type="IdRef">02636817X</idno>
<orgName>Centre National de la Recherche Scientifique</orgName>
<orgName type="acronym">CNRS</orgName>
<date type="start">1939-10-19</date>
<desc><address><country key="FR"></country>
</address>
<ref type="url">http://www.cnrs.fr/</ref>
</desc>
</org>
</tutelle>
</tutelles>
</hal:affiliation>
<country>France</country>
<placeName><settlement type="city">Nancy</settlement>
<settlement type="city">Metz</settlement>
<region type="region" nuts="2">Grand Est</region>
<region type="old region" nuts="2">Lorraine (région)</region>
</placeName>
<orgName type="university">Université de Lorraine</orgName>
</affiliation>
</author>
<author><name sortKey="Sirjean, Baptiste" sort="Sirjean, Baptiste" uniqKey="Sirjean B" first="Baptiste" last="Sirjean">Baptiste Sirjean</name>
<affiliation wicri:level="1"><hal:affiliation type="laboratory" xml:id="struct-211875" status="VALID"><idno type="IdRef">153068876</idno>
<idno type="RNSR">201320573K</idno>
<idno type="IdUnivLorraine">[UL]RQC--</idno>
<orgName>Laboratoire Réactions et Génie des Procédés</orgName>
<orgName type="acronym">LRGP</orgName>
<date type="start">2013-01-01</date>
<desc><address><addrLine>Université de Lorraine - ENSIC, 1 rue de Grandville BP 20451, 54001 Nancy Cedex</addrLine>
<country key="FR"></country>
</address>
<ref type="url">http://lrgp.univ-lorraine.fr/</ref>
</desc>
<listRelation><relation active="#struct-413289" type="direct"></relation>
<relation name="UMR7274" active="#struct-441569" type="direct"></relation>
</listRelation>
<tutelles><tutelle active="#struct-413289" type="direct"><org type="institution" xml:id="struct-413289" status="VALID"><idno type="IdRef">157040569</idno>
<idno type="IdUnivLorraine">[UL]100--</idno>
<orgName>Université de Lorraine</orgName>
<orgName type="acronym">UL</orgName>
<date type="start">2012-01-01</date>
<desc><address><addrLine>34 cours Léopold - CS 25233 - 54052 Nancy cedex</addrLine>
<country key="FR"></country>
</address>
<ref type="url">http://www.univ-lorraine.fr/</ref>
</desc>
</org>
</tutelle>
<tutelle name="UMR7274" active="#struct-441569" type="direct"><org type="institution" xml:id="struct-441569" status="VALID"><idno type="ISNI">0000000122597504</idno>
<idno type="IdRef">02636817X</idno>
<orgName>Centre National de la Recherche Scientifique</orgName>
<orgName type="acronym">CNRS</orgName>
<date type="start">1939-10-19</date>
<desc><address><country key="FR"></country>
</address>
<ref type="url">http://www.cnrs.fr/</ref>
</desc>
</org>
</tutelle>
</tutelles>
</hal:affiliation>
<country>France</country>
<placeName><settlement type="city">Nancy</settlement>
<settlement type="city">Metz</settlement>
<region type="region" nuts="2">Grand Est</region>
<region type="old region" nuts="2">Lorraine (région)</region>
</placeName>
<orgName type="university">Université de Lorraine</orgName>
</affiliation>
</author>
</titleStmt>
<publicationStmt><idno type="wicri:source">HAL</idno>
<idno type="RBID">Hal:hal-00777859</idno>
<idno type="halId">hal-00777859</idno>
<idno type="halUri">https://hal.archives-ouvertes.fr/hal-00777859</idno>
<idno type="url">https://hal.archives-ouvertes.fr/hal-00777859</idno>
<idno type="doi">10.1021/jp303680h</idno>
<date when="2012-06-08">2012-06-08</date>
<idno type="wicri:Area/Hal/Corpus">000B47</idno>
<idno type="wicri:Area/Hal/Curation">000B47</idno>
<idno type="wicri:Area/Hal/Checkpoint">000734</idno>
<idno type="wicri:explorRef" wicri:stream="Hal" wicri:step="Checkpoint">000734</idno>
</publicationStmt>
<sourceDesc><biblStruct><analytic><title xml:lang="en">Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical</title>
<author><name sortKey="Fournet, Rene" sort="Fournet, Rene" uniqKey="Fournet R" first="René" last="Fournet">René Fournet</name>
<affiliation wicri:level="1"><hal:affiliation type="laboratory" xml:id="struct-211875" status="VALID"><idno type="IdRef">153068876</idno>
<idno type="RNSR">201320573K</idno>
<idno type="IdUnivLorraine">[UL]RQC--</idno>
<orgName>Laboratoire Réactions et Génie des Procédés</orgName>
<orgName type="acronym">LRGP</orgName>
<date type="start">2013-01-01</date>
<desc><address><addrLine>Université de Lorraine - ENSIC, 1 rue de Grandville BP 20451, 54001 Nancy Cedex</addrLine>
<country key="FR"></country>
</address>
<ref type="url">http://lrgp.univ-lorraine.fr/</ref>
</desc>
<listRelation><relation active="#struct-413289" type="direct"></relation>
<relation name="UMR7274" active="#struct-441569" type="direct"></relation>
</listRelation>
<tutelles><tutelle active="#struct-413289" type="direct"><org type="institution" xml:id="struct-413289" status="VALID"><idno type="IdRef">157040569</idno>
<idno type="IdUnivLorraine">[UL]100--</idno>
<orgName>Université de Lorraine</orgName>
<orgName type="acronym">UL</orgName>
<date type="start">2012-01-01</date>
<desc><address><addrLine>34 cours Léopold - CS 25233 - 54052 Nancy cedex</addrLine>
<country key="FR"></country>
</address>
<ref type="url">http://www.univ-lorraine.fr/</ref>
</desc>
</org>
</tutelle>
<tutelle name="UMR7274" active="#struct-441569" type="direct"><org type="institution" xml:id="struct-441569" status="VALID"><idno type="ISNI">0000000122597504</idno>
<idno type="IdRef">02636817X</idno>
<orgName>Centre National de la Recherche Scientifique</orgName>
<orgName type="acronym">CNRS</orgName>
<date type="start">1939-10-19</date>
<desc><address><country key="FR"></country>
</address>
<ref type="url">http://www.cnrs.fr/</ref>
</desc>
</org>
</tutelle>
</tutelles>
</hal:affiliation>
<country>France</country>
<placeName><settlement type="city">Nancy</settlement>
<settlement type="city">Metz</settlement>
<region type="region" nuts="2">Grand Est</region>
<region type="old region" nuts="2">Lorraine (région)</region>
</placeName>
<orgName type="university">Université de Lorraine</orgName>
</affiliation>
</author>
<author><name sortKey="Sirjean, Baptiste" sort="Sirjean, Baptiste" uniqKey="Sirjean B" first="Baptiste" last="Sirjean">Baptiste Sirjean</name>
<affiliation wicri:level="1"><hal:affiliation type="laboratory" xml:id="struct-211875" status="VALID"><idno type="IdRef">153068876</idno>
<idno type="RNSR">201320573K</idno>
<idno type="IdUnivLorraine">[UL]RQC--</idno>
<orgName>Laboratoire Réactions et Génie des Procédés</orgName>
<orgName type="acronym">LRGP</orgName>
<date type="start">2013-01-01</date>
<desc><address><addrLine>Université de Lorraine - ENSIC, 1 rue de Grandville BP 20451, 54001 Nancy Cedex</addrLine>
<country key="FR"></country>
</address>
<ref type="url">http://lrgp.univ-lorraine.fr/</ref>
</desc>
<listRelation><relation active="#struct-413289" type="direct"></relation>
<relation name="UMR7274" active="#struct-441569" type="direct"></relation>
</listRelation>
<tutelles><tutelle active="#struct-413289" type="direct"><org type="institution" xml:id="struct-413289" status="VALID"><idno type="IdRef">157040569</idno>
<idno type="IdUnivLorraine">[UL]100--</idno>
<orgName>Université de Lorraine</orgName>
<orgName type="acronym">UL</orgName>
<date type="start">2012-01-01</date>
<desc><address><addrLine>34 cours Léopold - CS 25233 - 54052 Nancy cedex</addrLine>
<country key="FR"></country>
</address>
<ref type="url">http://www.univ-lorraine.fr/</ref>
</desc>
</org>
</tutelle>
<tutelle name="UMR7274" active="#struct-441569" type="direct"><org type="institution" xml:id="struct-441569" status="VALID"><idno type="ISNI">0000000122597504</idno>
<idno type="IdRef">02636817X</idno>
<orgName>Centre National de la Recherche Scientifique</orgName>
<orgName type="acronym">CNRS</orgName>
<date type="start">1939-10-19</date>
<desc><address><country key="FR"></country>
</address>
<ref type="url">http://www.cnrs.fr/</ref>
</desc>
</org>
</tutelle>
</tutelles>
</hal:affiliation>
<country>France</country>
<placeName><settlement type="city">Nancy</settlement>
<settlement type="city">Metz</settlement>
<region type="region" nuts="2">Grand Est</region>
<region type="old region" nuts="2">Lorraine (région)</region>
</placeName>
<orgName type="university">Université de Lorraine</orgName>
</affiliation>
</author>
</analytic>
<idno type="DOI">10.1021/jp303680h</idno>
<series><title level="j">Journal of Physical Chemistry A</title>
<idno type="ISSN">1089-5639</idno>
<imprint><date type="datePub">2012-06-08</date>
</imprint>
</series>
</biblStruct>
</sourceDesc>
</fileDesc>
<profileDesc><textClass><keywords scheme="mix" xml:lang="en"><term>5-DIMETHYLFURAN</term>
<term>AB-INITIO</term>
<term>AUTOIGNITION</term>
<term>COMBUSTION</term>
<term>ENGINE</term>
<term>KINETICS</term>
<term>LAMINAR BURNING VELOCITIES</term>
<term>PROGRESS</term>
<term>QUALITY</term>
<term>TEMPERATURE</term>
</keywords>
</textClass>
</profileDesc>
</teiHeader>
<front><div type="abstract" xml:lang="en">The thermal decomposition of the 5-methyl-2furanylmethyl radical (R,), 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/RRKIvl model. Among all the channels studied, the ring-opening of the 5-methyl-2-furanylmethyl radical, followed by ring enlargement to form c-yclohexadienone 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 Cs 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>
<hal api="V3"><titleStmt><title xml:lang="en">Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical</title>
<author role="crp"><persName><forename type="first">René</forename>
<surname>Fournet</surname>
</persName>
<email>rene.fournet@univ-lorraine.fr</email>
<idno type="halauthor">807196</idno>
<affiliation ref="#struct-211875"></affiliation>
</author>
<author role="aut"><persName><forename type="first">Baptiste</forename>
<surname>Sirjean</surname>
</persName>
<email></email>
<idno type="halauthor">807197</idno>
<affiliation ref="#struct-211875"></affiliation>
</author>
<editor role="depositor"><persName><forename>Gabriel</forename>
<surname>Wild</surname>
</persName>
<email>gabriel.wild@univ-lorraine.fr</email>
</editor>
</titleStmt>
<editionStmt><edition n="v1" type="current"><date type="whenSubmitted">2013-01-18 11:38:40</date>
<date type="whenWritten">2012</date>
<date type="whenModified">2016-05-11 01:05:31</date>
<date type="whenReleased">2013-01-18 11:38:40</date>
<date type="whenProduced">2012-06-08</date>
</edition>
<respStmt><resp>contributor</resp>
<name key="179637"><persName><forename>Gabriel</forename>
<surname>Wild</surname>
</persName>
<email>gabriel.wild@univ-lorraine.fr</email>
</name>
</respStmt>
</editionStmt>
<publicationStmt><distributor>CCSD</distributor>
<idno type="halId">hal-00777859</idno>
<idno type="halUri">https://hal.archives-ouvertes.fr/hal-00777859</idno>
<idno type="halBibtex">fournet:hal-00777859</idno>
<idno type="halRefHtml">Journal of Physical Chemistry A, American Chemical Society, 2012, 116 (25), pp.6675-6684. <10.1021/jp303680h></idno>
<idno type="halRef">Journal of Physical Chemistry A, American Chemical Society, 2012, 116 (25), pp.6675-6684. <10.1021/jp303680h></idno>
</publicationStmt>
<seriesStmt><idno type="stamp" n="CNRS">CNRS - Centre national de la recherche scientifique</idno>
<idno type="stamp" n="LRGP-UL">LRGP</idno>
<idno type="stamp" n="UNIV-LORRAINE">Université de Lorraine</idno>
</seriesStmt>
<notesStmt><note type="audience" n="2">International</note>
<note type="popular" n="0">No</note>
<note type="peer" n="1">Yes</note>
</notesStmt>
<sourceDesc><biblStruct><analytic><title xml:lang="en">Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical</title>
<author role="crp"><persName><forename type="first">René</forename>
<surname>Fournet</surname>
</persName>
<email>rene.fournet@univ-lorraine.fr</email>
<idno type="halAuthorId">807196</idno>
<affiliation ref="#struct-211875"></affiliation>
</author>
<author role="aut"><persName><forename type="first">Baptiste</forename>
<surname>Sirjean</surname>
</persName>
<idno type="halAuthorId">807197</idno>
<affiliation ref="#struct-211875"></affiliation>
</author>
</analytic>
<monogr><idno type="halJournalId" status="VALID">6357</idno>
<idno type="issn">1089-5639</idno>
<idno type="eissn">1520-5215</idno>
<title level="j">Journal of Physical Chemistry A</title>
<imprint><publisher>American Chemical Society</publisher>
<biblScope unit="volume">116</biblScope>
<biblScope unit="issue">25</biblScope>
<biblScope unit="pp">6675-6684</biblScope>
<date type="datePub">2012-06-08</date>
</imprint>
</monogr>
<idno type="doi">10.1021/jp303680h</idno>
</biblStruct>
</sourceDesc>
<profileDesc><langUsage><language ident="en">English</language>
</langUsage>
<textClass><keywords scheme="author"><term xml:lang="en">LAMINAR BURNING VELOCITIES</term>
<term xml:lang="en">AB-INITIO</term>
<term xml:lang="en">5-DIMETHYLFURAN</term>
<term xml:lang="en">KINETICS</term>
<term xml:lang="en">AUTOIGNITION</term>
<term xml:lang="en">TEMPERATURE</term>
<term xml:lang="en">COMBUSTION</term>
<term xml:lang="en">PROGRESS</term>
<term xml:lang="en">QUALITY</term>
<term xml:lang="en">ENGINE</term>
</keywords>
<classCode scheme="halDomain" n="chim.theo">Chemical Sciences/Theoretical and/or physical chemistry</classCode>
<classCode scheme="halTypology" n="ART">Journal articles</classCode>
</textClass>
<abstract xml:lang="en">The thermal decomposition of the 5-methyl-2furanylmethyl radical (R,), 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/RRKIvl model. Among all the channels studied, the ring-opening of the 5-methyl-2-furanylmethyl radical, followed by ring enlargement to form c-yclohexadienone 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 Cs 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.</abstract>
</profileDesc>
</hal>
</record>
Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/Lorraine/explor/LrgpV1/Data/Hal/Checkpoint
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 000734 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Hal/Checkpoint/biblio.hfd -nk 000734 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien |wiki= Wicri/Lorraine |area= LrgpV1 |flux= Hal |étape= Checkpoint |type= RBID |clé= Hal:hal-00777859 |texte= Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical }}
![]() | This area was generated with Dilib version V0.6.32. | ![]() |