A computational study on the kinetics of unimolecular reactions of ethoxyethylperoxy radicals employing CTST and VTST

Diethyl ether (DEE) has favorable properties as a diesel fuel component, including its outstanding cetane number. To utilize this promising fuel, more and more knowledge on the chemical kinetics of DEE oxidation will be required. For the present article, the rate constants of unimolecular reactions...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Proceedings of the Combustion Institute 2015-01, Vol.35 (1), p.161-169
Hauptverfasser: Sakai, Yasuyuki, Ando, Hiromitsu, Chakravarty, Harish Kumar, Pitsch, Heinz, Fernandes, Ravi X.
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 169
container_issue 1
container_start_page 161
container_title Proceedings of the Combustion Institute
container_volume 35
creator Sakai, Yasuyuki
Ando, Hiromitsu
Chakravarty, Harish Kumar
Pitsch, Heinz
Fernandes, Ravi X.
description Diethyl ether (DEE) has favorable properties as a diesel fuel component, including its outstanding cetane number. To utilize this promising fuel, more and more knowledge on the chemical kinetics of DEE oxidation will be required. For the present article, the rate constants of unimolecular reactions of ethoxyethylperoxy radicals, which are main intermediates in the oxidation of DEE under the engine relevant conditions, have been computationally investigated and compared with those of alkanes. Geometries, vibrational frequencies, and energies of reactants, products, and transition states with pronounced barrier were calculated according to the procedure of the CBS-QB3 method. The high-pressure limiting rate constants were calculated in the temperature range of 500−2000K by using a conventional transition state theory with hindered rotor approximation for low frequency torsional mode. The oxygen dissociation reactions have been investigated by using a variational transition state theory based on the CASPT2(7,5)/aug-cc-pvdz single point calculations at UB3LYP/CBSB7 geometries and vibrational frequencies. It was found that the oxidation pathways are equal to those of alkane oxidations, however, the rate constants are significantly different from those of alkanes due to the oxygen vicinity. The rate constants of intramolecular hydrogen shift reactions are from 3 to 8 times larger at 700K than those of alkylic peroxy radical when the abstracted hydrogen is in the β-position of the ether. The rate constant of β-scission reactions for 1,5-intramolecular hydrogen shift products of 1-ethoxyethylperoxy radial is 163 times larger at 700K than that of alkylic hydroperoxy radical, and this reaction becomes a main reaction pathway, whereas cyclic-ether is a main product in alkane oxidation. These characteristic rate constants are given in three-parameter modified Arrhenius form for the refinement of predictive chemical kinetic models being developed.
doi_str_mv 10.1016/j.proci.2014.05.099
format Article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1677913801</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><els_id>S1540748914001023</els_id><sourcerecordid>1677913801</sourcerecordid><originalsourceid>FETCH-LOGICAL-c509t-9619af80387c8101b94fd340eafbd7c03d22757f5c0ae36207e2f8b8071422c03</originalsourceid><addsrcrecordid>eNp9kD9PwzAQxSMEEqXwCVg8siSc4yROBoaq4p9UiYHCarnOhbokcbAdRL49bsvMcvekd--k94uiawoJBVrc7pLBGqWTFGiWQJ5AVZ1EM1pyFqccstOg8wxinpXVeXTh3A6AcWD5LBoXRJluGL302vSyJc6P9URMT_wWyafu0WvliGnI2OvOtKjGVlpiUap94OCg35qfKcypHdAGSaystZKtI9gNrZl0_0GW69c1kX1N3oO4jM6aYOPV355Hbw_36-VTvHp5fF4uVrHKofJxVdBKNiWwkqsyFN1UWVOzDFA2m5orYHWa8pw3uQKJrEiBY9qUmxI4zdI0-PPo5vg34Pka0XnRaaewbWWPZnSCFpxXlJVAwyk7niprnLPYiMHqTtpJUBB7yGInDpDFHrKAXATIIXV3TGFo8a3RCqc09gprbVF5URv9b_4XIsmIVw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1677913801</pqid></control><display><type>article</type><title>A computational study on the kinetics of unimolecular reactions of ethoxyethylperoxy radicals employing CTST and VTST</title><source>Access via ScienceDirect (Elsevier)</source><creator>Sakai, Yasuyuki ; Ando, Hiromitsu ; Chakravarty, Harish Kumar ; Pitsch, Heinz ; Fernandes, Ravi X.</creator><creatorcontrib>Sakai, Yasuyuki ; Ando, Hiromitsu ; Chakravarty, Harish Kumar ; Pitsch, Heinz ; Fernandes, Ravi X.</creatorcontrib><description>Diethyl ether (DEE) has favorable properties as a diesel fuel component, including its outstanding cetane number. To utilize this promising fuel, more and more knowledge on the chemical kinetics of DEE oxidation will be required. For the present article, the rate constants of unimolecular reactions of ethoxyethylperoxy radicals, which are main intermediates in the oxidation of DEE under the engine relevant conditions, have been computationally investigated and compared with those of alkanes. Geometries, vibrational frequencies, and energies of reactants, products, and transition states with pronounced barrier were calculated according to the procedure of the CBS-QB3 method. The high-pressure limiting rate constants were calculated in the temperature range of 500−2000K by using a conventional transition state theory with hindered rotor approximation for low frequency torsional mode. The oxygen dissociation reactions have been investigated by using a variational transition state theory based on the CASPT2(7,5)/aug-cc-pvdz single point calculations at UB3LYP/CBSB7 geometries and vibrational frequencies. It was found that the oxidation pathways are equal to those of alkane oxidations, however, the rate constants are significantly different from those of alkanes due to the oxygen vicinity. The rate constants of intramolecular hydrogen shift reactions are from 3 to 8 times larger at 700K than those of alkylic peroxy radical when the abstracted hydrogen is in the β-position of the ether. The rate constant of β-scission reactions for 1,5-intramolecular hydrogen shift products of 1-ethoxyethylperoxy radial is 163 times larger at 700K than that of alkylic hydroperoxy radical, and this reaction becomes a main reaction pathway, whereas cyclic-ether is a main product in alkane oxidation. These characteristic rate constants are given in three-parameter modified Arrhenius form for the refinement of predictive chemical kinetic models being developed.</description><identifier>ISSN: 1540-7489</identifier><identifier>EISSN: 1873-2704</identifier><identifier>DOI: 10.1016/j.proci.2014.05.099</identifier><language>eng</language><publisher>Elsevier Inc</publisher><subject>Alkanes ; CBS-QB3 ; Chemical kinetic modeling ; Combustion ; Computation ; Diethyl ether ; High-pressure limiting rate constant ; Low-temperature oxidation ; Mathematical models ; Oxidation ; Pathways ; Radicals ; Rate constants ; Reaction kinetics</subject><ispartof>Proceedings of the Combustion Institute, 2015-01, Vol.35 (1), p.161-169</ispartof><rights>2014 The Combustion Institute</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c509t-9619af80387c8101b94fd340eafbd7c03d22757f5c0ae36207e2f8b8071422c03</citedby><cites>FETCH-LOGICAL-c509t-9619af80387c8101b94fd340eafbd7c03d22757f5c0ae36207e2f8b8071422c03</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.proci.2014.05.099$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3550,27924,27925,45995</link.rule.ids></links><search><creatorcontrib>Sakai, Yasuyuki</creatorcontrib><creatorcontrib>Ando, Hiromitsu</creatorcontrib><creatorcontrib>Chakravarty, Harish Kumar</creatorcontrib><creatorcontrib>Pitsch, Heinz</creatorcontrib><creatorcontrib>Fernandes, Ravi X.</creatorcontrib><title>A computational study on the kinetics of unimolecular reactions of ethoxyethylperoxy radicals employing CTST and VTST</title><title>Proceedings of the Combustion Institute</title><description>Diethyl ether (DEE) has favorable properties as a diesel fuel component, including its outstanding cetane number. To utilize this promising fuel, more and more knowledge on the chemical kinetics of DEE oxidation will be required. For the present article, the rate constants of unimolecular reactions of ethoxyethylperoxy radicals, which are main intermediates in the oxidation of DEE under the engine relevant conditions, have been computationally investigated and compared with those of alkanes. Geometries, vibrational frequencies, and energies of reactants, products, and transition states with pronounced barrier were calculated according to the procedure of the CBS-QB3 method. The high-pressure limiting rate constants were calculated in the temperature range of 500−2000K by using a conventional transition state theory with hindered rotor approximation for low frequency torsional mode. The oxygen dissociation reactions have been investigated by using a variational transition state theory based on the CASPT2(7,5)/aug-cc-pvdz single point calculations at UB3LYP/CBSB7 geometries and vibrational frequencies. It was found that the oxidation pathways are equal to those of alkane oxidations, however, the rate constants are significantly different from those of alkanes due to the oxygen vicinity. The rate constants of intramolecular hydrogen shift reactions are from 3 to 8 times larger at 700K than those of alkylic peroxy radical when the abstracted hydrogen is in the β-position of the ether. The rate constant of β-scission reactions for 1,5-intramolecular hydrogen shift products of 1-ethoxyethylperoxy radial is 163 times larger at 700K than that of alkylic hydroperoxy radical, and this reaction becomes a main reaction pathway, whereas cyclic-ether is a main product in alkane oxidation. These characteristic rate constants are given in three-parameter modified Arrhenius form for the refinement of predictive chemical kinetic models being developed.</description><subject>Alkanes</subject><subject>CBS-QB3</subject><subject>Chemical kinetic modeling</subject><subject>Combustion</subject><subject>Computation</subject><subject>Diethyl ether</subject><subject>High-pressure limiting rate constant</subject><subject>Low-temperature oxidation</subject><subject>Mathematical models</subject><subject>Oxidation</subject><subject>Pathways</subject><subject>Radicals</subject><subject>Rate constants</subject><subject>Reaction kinetics</subject><issn>1540-7489</issn><issn>1873-2704</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNp9kD9PwzAQxSMEEqXwCVg8siSc4yROBoaq4p9UiYHCarnOhbokcbAdRL49bsvMcvekd--k94uiawoJBVrc7pLBGqWTFGiWQJ5AVZ1EM1pyFqccstOg8wxinpXVeXTh3A6AcWD5LBoXRJluGL302vSyJc6P9URMT_wWyafu0WvliGnI2OvOtKjGVlpiUap94OCg35qfKcypHdAGSaystZKtI9gNrZl0_0GW69c1kX1N3oO4jM6aYOPV355Hbw_36-VTvHp5fF4uVrHKofJxVdBKNiWwkqsyFN1UWVOzDFA2m5orYHWa8pw3uQKJrEiBY9qUmxI4zdI0-PPo5vg34Pka0XnRaaewbWWPZnSCFpxXlJVAwyk7niprnLPYiMHqTtpJUBB7yGInDpDFHrKAXATIIXV3TGFo8a3RCqc09gprbVF5URv9b_4XIsmIVw</recordid><startdate>20150101</startdate><enddate>20150101</enddate><creator>Sakai, Yasuyuki</creator><creator>Ando, Hiromitsu</creator><creator>Chakravarty, Harish Kumar</creator><creator>Pitsch, Heinz</creator><creator>Fernandes, Ravi X.</creator><general>Elsevier Inc</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>H8D</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20150101</creationdate><title>A computational study on the kinetics of unimolecular reactions of ethoxyethylperoxy radicals employing CTST and VTST</title><author>Sakai, Yasuyuki ; Ando, Hiromitsu ; Chakravarty, Harish Kumar ; Pitsch, Heinz ; Fernandes, Ravi X.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c509t-9619af80387c8101b94fd340eafbd7c03d22757f5c0ae36207e2f8b8071422c03</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Alkanes</topic><topic>CBS-QB3</topic><topic>Chemical kinetic modeling</topic><topic>Combustion</topic><topic>Computation</topic><topic>Diethyl ether</topic><topic>High-pressure limiting rate constant</topic><topic>Low-temperature oxidation</topic><topic>Mathematical models</topic><topic>Oxidation</topic><topic>Pathways</topic><topic>Radicals</topic><topic>Rate constants</topic><topic>Reaction kinetics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Sakai, Yasuyuki</creatorcontrib><creatorcontrib>Ando, Hiromitsu</creatorcontrib><creatorcontrib>Chakravarty, Harish Kumar</creatorcontrib><creatorcontrib>Pitsch, Heinz</creatorcontrib><creatorcontrib>Fernandes, Ravi X.</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Aerospace Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Proceedings of the Combustion Institute</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Sakai, Yasuyuki</au><au>Ando, Hiromitsu</au><au>Chakravarty, Harish Kumar</au><au>Pitsch, Heinz</au><au>Fernandes, Ravi X.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A computational study on the kinetics of unimolecular reactions of ethoxyethylperoxy radicals employing CTST and VTST</atitle><jtitle>Proceedings of the Combustion Institute</jtitle><date>2015-01-01</date><risdate>2015</risdate><volume>35</volume><issue>1</issue><spage>161</spage><epage>169</epage><pages>161-169</pages><issn>1540-7489</issn><eissn>1873-2704</eissn><abstract>Diethyl ether (DEE) has favorable properties as a diesel fuel component, including its outstanding cetane number. To utilize this promising fuel, more and more knowledge on the chemical kinetics of DEE oxidation will be required. For the present article, the rate constants of unimolecular reactions of ethoxyethylperoxy radicals, which are main intermediates in the oxidation of DEE under the engine relevant conditions, have been computationally investigated and compared with those of alkanes. Geometries, vibrational frequencies, and energies of reactants, products, and transition states with pronounced barrier were calculated according to the procedure of the CBS-QB3 method. The high-pressure limiting rate constants were calculated in the temperature range of 500−2000K by using a conventional transition state theory with hindered rotor approximation for low frequency torsional mode. The oxygen dissociation reactions have been investigated by using a variational transition state theory based on the CASPT2(7,5)/aug-cc-pvdz single point calculations at UB3LYP/CBSB7 geometries and vibrational frequencies. It was found that the oxidation pathways are equal to those of alkane oxidations, however, the rate constants are significantly different from those of alkanes due to the oxygen vicinity. The rate constants of intramolecular hydrogen shift reactions are from 3 to 8 times larger at 700K than those of alkylic peroxy radical when the abstracted hydrogen is in the β-position of the ether. The rate constant of β-scission reactions for 1,5-intramolecular hydrogen shift products of 1-ethoxyethylperoxy radial is 163 times larger at 700K than that of alkylic hydroperoxy radical, and this reaction becomes a main reaction pathway, whereas cyclic-ether is a main product in alkane oxidation. These characteristic rate constants are given in three-parameter modified Arrhenius form for the refinement of predictive chemical kinetic models being developed.</abstract><pub>Elsevier Inc</pub><doi>10.1016/j.proci.2014.05.099</doi><tpages>9</tpages></addata></record>
fulltext fulltext
identifier ISSN: 1540-7489
ispartof Proceedings of the Combustion Institute, 2015-01, Vol.35 (1), p.161-169
issn 1540-7489
1873-2704
language eng
recordid cdi_proquest_miscellaneous_1677913801
source Access via ScienceDirect (Elsevier)
subjects Alkanes
CBS-QB3
Chemical kinetic modeling
Combustion
Computation
Diethyl ether
High-pressure limiting rate constant
Low-temperature oxidation
Mathematical models
Oxidation
Pathways
Radicals
Rate constants
Reaction kinetics
title A computational study on the kinetics of unimolecular reactions of ethoxyethylperoxy radicals employing CTST and VTST
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-24T18%3A51%3A46IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=A%20computational%20study%20on%20the%20kinetics%20of%20unimolecular%20reactions%20of%20ethoxyethylperoxy%20radicals%20employing%20CTST%20and%20VTST&rft.jtitle=Proceedings%20of%20the%20Combustion%20Institute&rft.au=Sakai,%20Yasuyuki&rft.date=2015-01-01&rft.volume=35&rft.issue=1&rft.spage=161&rft.epage=169&rft.pages=161-169&rft.issn=1540-7489&rft.eissn=1873-2704&rft_id=info:doi/10.1016/j.proci.2014.05.099&rft_dat=%3Cproquest_cross%3E1677913801%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1677913801&rft_id=info:pmid/&rft_els_id=S1540748914001023&rfr_iscdi=true