Direct Observation of H2O2 during Alcohol Oxidation by O2 in Supercritical Water

Direct Observation of H2O2 during Alcohol Oxidation by O2 in Supercritical Water

This paper presents the direct quantitative measurement of the presence of hydrogen peroxide as an intermediate produced during the oxidation of methanol, ethanol, and 1-propanol by oxygen in supercritical water. The concentration of H2O2 is measured as a function of reaction time in an optically ac...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Industrial & engineering chemistry research 1998-05, Vol.37 (5), p.1755-1760
Hauptverfasser: Croiset, Eric, Rice, Steven F
Format: Artikel
Sprache:eng
Schlagworte:
Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 1760
container_issue 5
container_start_page 1755
container_title Industrial & engineering chemistry research
container_volume 37
creator Croiset, Eric
Rice, Steven F
description This paper presents the direct quantitative measurement of the presence of hydrogen peroxide as an intermediate produced during the oxidation of methanol, ethanol, and 1-propanol by oxygen in supercritical water. The concentration of H2O2 is measured as a function of reaction time in an optically accessible, high-pressure flow reactor by monitoring the intensity of a strong resonance in the Raman spectrum at 874 cm-1 that is characteristic of the O−O vibrational stretch. Transient concentrations of H2O2 as high as 0.0065 mol/L (0.1% mole fraction) are measured during the oxidation of ethanol at feed mole fractions of 0.4% at 430 °C and 24.5 MPa. Significantly lower transient concentrations of H2O2 are observed during methanol oxidation. The experimentally observed transient H2O2 concentration during methanol oxidation is compared to that predicted by two similar elementary reaction mechanisms and found to be distinctly lower than the models predict.
doi_str_mv 10.1021/ie970711e
format Article
fullrecord <record><control><sourceid>acs_pasca</sourceid><recordid>TN_cdi_pascalfrancis_primary_2236032</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>f5944371</sourcerecordid><originalsourceid>FETCH-LOGICAL-a165t-281c43fa3cff6d8f38e34ad2cae43578399af68dc07974ab21abbfa5e090c75c3</originalsourceid><addsrcrecordid>eNo90MtOwzAQBVALgUQpLPgDL2AZ8COOnWUpjyJVpKLlsbMmjg0uIansFLV_T1BRV7O4RzOai9A5JVeUMHrtbS6JpNQeoAEVjCSCpOIQDYhSKhFKiWN0EuOSECJEmg7Q7NYHazpclNGGH-h82-DW4QkrGK7WwTcfeFSb9rOtcbHx1Q6UW9zHvsHz9coGE3znDdT4DTobTtGRgzras_85RC_3d4vxJJkWD4_j0TQBmokuYYqalDvgxrmsUo4ry1OomAGbciEVz3NwmaoMkblMoWQUytKBsCQnRgrDh-hit3cFsT_uAjTGR70K_hvCVjPGM8JZz5Id87Gzm30M4UtnkkuhF7O5nj_f3E6e3oV-7f3lzoOJetmuQ9M_oSnRf-3qfbv8F5TKa2E</addsrcrecordid><sourcetype>Index Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Direct Observation of H2O2 during Alcohol Oxidation by O2 in Supercritical Water</title><source>American Chemical Society Journals</source><creator>Croiset, Eric ; Rice, Steven F</creator><creatorcontrib>Croiset, Eric ; Rice, Steven F</creatorcontrib><description>This paper presents the direct quantitative measurement of the presence of hydrogen peroxide as an intermediate produced during the oxidation of methanol, ethanol, and 1-propanol by oxygen in supercritical water. The concentration of H2O2 is measured as a function of reaction time in an optically accessible, high-pressure flow reactor by monitoring the intensity of a strong resonance in the Raman spectrum at 874 cm-1 that is characteristic of the O−O vibrational stretch. Transient concentrations of H2O2 as high as 0.0065 mol/L (0.1% mole fraction) are measured during the oxidation of ethanol at feed mole fractions of 0.4% at 430 °C and 24.5 MPa. Significantly lower transient concentrations of H2O2 are observed during methanol oxidation. The experimentally observed transient H2O2 concentration during methanol oxidation is compared to that predicted by two similar elementary reaction mechanisms and found to be distinctly lower than the models predict.</description><identifier>ISSN: 0888-5885</identifier><identifier>EISSN: 1520-5045</identifier><identifier>DOI: 10.1021/ie970711e</identifier><identifier>CODEN: IECRED</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Chemistry ; Exact sciences and technology ; Kinetics and mechanisms ; Organic chemistry ; Reactivity and mechanisms</subject><ispartof>Industrial &amp; engineering chemistry research, 1998-05, Vol.37 (5), p.1755-1760</ispartof><rights>Copyright © 1998 American Chemical Society</rights><rights>1998 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ie970711e$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ie970711e$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>309,310,314,780,784,789,790,23930,23931,25140,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&amp;idt=2236032$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Croiset, Eric</creatorcontrib><creatorcontrib>Rice, Steven F</creatorcontrib><title>Direct Observation of H2O2 during Alcohol Oxidation by O2 in Supercritical Water</title><title>Industrial &amp; engineering chemistry research</title><addtitle>Ind. Eng. Chem. Res</addtitle><description>This paper presents the direct quantitative measurement of the presence of hydrogen peroxide as an intermediate produced during the oxidation of methanol, ethanol, and 1-propanol by oxygen in supercritical water. The concentration of H2O2 is measured as a function of reaction time in an optically accessible, high-pressure flow reactor by monitoring the intensity of a strong resonance in the Raman spectrum at 874 cm-1 that is characteristic of the O−O vibrational stretch. Transient concentrations of H2O2 as high as 0.0065 mol/L (0.1% mole fraction) are measured during the oxidation of ethanol at feed mole fractions of 0.4% at 430 °C and 24.5 MPa. Significantly lower transient concentrations of H2O2 are observed during methanol oxidation. The experimentally observed transient H2O2 concentration during methanol oxidation is compared to that predicted by two similar elementary reaction mechanisms and found to be distinctly lower than the models predict.</description><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Kinetics and mechanisms</subject><subject>Organic chemistry</subject><subject>Reactivity and mechanisms</subject><issn>0888-5885</issn><issn>1520-5045</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1998</creationdate><recordtype>article</recordtype><recordid>eNo90MtOwzAQBVALgUQpLPgDL2AZ8COOnWUpjyJVpKLlsbMmjg0uIansFLV_T1BRV7O4RzOai9A5JVeUMHrtbS6JpNQeoAEVjCSCpOIQDYhSKhFKiWN0EuOSECJEmg7Q7NYHazpclNGGH-h82-DW4QkrGK7WwTcfeFSb9rOtcbHx1Q6UW9zHvsHz9coGE3znDdT4DTobTtGRgzras_85RC_3d4vxJJkWD4_j0TQBmokuYYqalDvgxrmsUo4ry1OomAGbciEVz3NwmaoMkblMoWQUytKBsCQnRgrDh-hit3cFsT_uAjTGR70K_hvCVjPGM8JZz5Id87Gzm30M4UtnkkuhF7O5nj_f3E6e3oV-7f3lzoOJetmuQ9M_oSnRf-3qfbv8F5TKa2E</recordid><startdate>19980504</startdate><enddate>19980504</enddate><creator>Croiset, Eric</creator><creator>Rice, Steven F</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope></search><sort><creationdate>19980504</creationdate><title>Direct Observation of H2O2 during Alcohol Oxidation by O2 in Supercritical Water</title><author>Croiset, Eric ; Rice, Steven F</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a165t-281c43fa3cff6d8f38e34ad2cae43578399af68dc07974ab21abbfa5e090c75c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1998</creationdate><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Kinetics and mechanisms</topic><topic>Organic chemistry</topic><topic>Reactivity and mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Croiset, Eric</creatorcontrib><creatorcontrib>Rice, Steven F</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><jtitle>Industrial &amp; engineering chemistry research</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Croiset, Eric</au><au>Rice, Steven F</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Direct Observation of H2O2 during Alcohol Oxidation by O2 in Supercritical Water</atitle><jtitle>Industrial &amp; engineering chemistry research</jtitle><addtitle>Ind. Eng. Chem. Res</addtitle><date>1998-05-04</date><risdate>1998</risdate><volume>37</volume><issue>5</issue><spage>1755</spage><epage>1760</epage><pages>1755-1760</pages><issn>0888-5885</issn><eissn>1520-5045</eissn><coden>IECRED</coden><abstract>This paper presents the direct quantitative measurement of the presence of hydrogen peroxide as an intermediate produced during the oxidation of methanol, ethanol, and 1-propanol by oxygen in supercritical water. The concentration of H2O2 is measured as a function of reaction time in an optically accessible, high-pressure flow reactor by monitoring the intensity of a strong resonance in the Raman spectrum at 874 cm-1 that is characteristic of the O−O vibrational stretch. Transient concentrations of H2O2 as high as 0.0065 mol/L (0.1% mole fraction) are measured during the oxidation of ethanol at feed mole fractions of 0.4% at 430 °C and 24.5 MPa. Significantly lower transient concentrations of H2O2 are observed during methanol oxidation. The experimentally observed transient H2O2 concentration during methanol oxidation is compared to that predicted by two similar elementary reaction mechanisms and found to be distinctly lower than the models predict.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ie970711e</doi><tpages>6</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0888-5885
ispartof Industrial & engineering chemistry research, 1998-05, Vol.37 (5), p.1755-1760
issn 0888-5885
1520-5045
language eng
recordid cdi_pascalfrancis_primary_2236032
source American Chemical Society Journals
subjects Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
title Direct Observation of H2O2 during Alcohol Oxidation by O2 in Supercritical Water
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-29T12%3A53%3A24IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs_pasca&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Direct%20Observation%20of%20H2O2%20during%20Alcohol%20Oxidation%20by%20O2%20in%20Supercritical%20Water&rft.jtitle=Industrial%20&%20engineering%20chemistry%20research&rft.au=Croiset,%20Eric&rft.date=1998-05-04&rft.volume=37&rft.issue=5&rft.spage=1755&rft.epage=1760&rft.pages=1755-1760&rft.issn=0888-5885&rft.eissn=1520-5045&rft.coden=IECRED&rft_id=info:doi/10.1021/ie970711e&rft_dat=%3Cacs_pasca%3Ef5944371%3C/acs_pasca%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true