Unimolecular thermal decomposition of phenol and d5-phenol: direct observation of cyclopentadiene formation via cyclohexadienone
The pyrolyses of phenol and d(5)-phenol (C(6)H(5)OH and C(6)D(5)OH) have been studied using a high temperature, microtubular (μtubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting th...
Saved in:
Published in | The Journal of chemical physics Vol. 136; no. 4; p. 044309 |
---|---|
Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
28.01.2012
|
Subjects | |
Online Access | Get more information |
Cover
Loading…
Abstract | The pyrolyses of phenol and d(5)-phenol (C(6)H(5)OH and C(6)D(5)OH) have been studied using a high temperature, microtubular (μtubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting the heated reactor (375 K-1575 K) is subject to a free expansion after a residence time in the μtubular reactor of approximately 50-100 μs. The expansion from the reactor into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. We find that the initial decomposition steps at the onset of phenol pyrolysis are enol/keto tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C(6)H(5)OH → c-C(6)H(6) = O → c-C(5)H(6) + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C(5)H(6) → c-C(5)H(5) + H → HC≡CH + HCCCH(2). At higher temperatures, hydrogen loss from the PhO-H group to form phenoxy radical followed by CO ejection to generate the cyclopentadienyl radical likely contributes to the product distribution; C(6)H(5)O-H → C(6)H(5)O + H → c-C(5)H(5) + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C(6)H(4)-OH) and hydroquinone (p-HO-C(6)H(4)-OH) are shown to undergo decarbonylation at the onset of pyrolysis to form hydroxycyclopentadiene. In the case of catechol, we observe that water loss is also an important decomposition channel at the onset of pyrolysis. |
---|---|
AbstractList | The pyrolyses of phenol and d(5)-phenol (C(6)H(5)OH and C(6)D(5)OH) have been studied using a high temperature, microtubular (μtubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting the heated reactor (375 K-1575 K) is subject to a free expansion after a residence time in the μtubular reactor of approximately 50-100 μs. The expansion from the reactor into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. We find that the initial decomposition steps at the onset of phenol pyrolysis are enol/keto tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C(6)H(5)OH → c-C(6)H(6) = O → c-C(5)H(6) + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C(5)H(6) → c-C(5)H(5) + H → HC≡CH + HCCCH(2). At higher temperatures, hydrogen loss from the PhO-H group to form phenoxy radical followed by CO ejection to generate the cyclopentadienyl radical likely contributes to the product distribution; C(6)H(5)O-H → C(6)H(5)O + H → c-C(5)H(5) + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C(6)H(4)-OH) and hydroquinone (p-HO-C(6)H(4)-OH) are shown to undergo decarbonylation at the onset of pyrolysis to form hydroxycyclopentadiene. In the case of catechol, we observe that water loss is also an important decomposition channel at the onset of pyrolysis. |
Author | Carstensen, Hans-Heinrich Robichaud, David J Nimlos, Mark R Scheer, Adam M Ellison, G Barney Mukarakate, Calvin |
Author_xml | – sequence: 1 givenname: Adam M surname: Scheer fullname: Scheer, Adam M organization: National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, Colorado 80401-3393, USA – sequence: 2 givenname: Calvin surname: Mukarakate fullname: Mukarakate, Calvin – sequence: 3 givenname: David J surname: Robichaud fullname: Robichaud, David J – sequence: 4 givenname: Mark R surname: Nimlos fullname: Nimlos, Mark R – sequence: 5 givenname: Hans-Heinrich surname: Carstensen fullname: Carstensen, Hans-Heinrich – sequence: 6 givenname: G Barney surname: Ellison fullname: Ellison, G Barney |
BackLink | https://www.ncbi.nlm.nih.gov/pubmed/22299873$$D View this record in MEDLINE/PubMed |
BookMark | eNo1kM1KAzEUhYMo9kcXvoDkBaYmd34ycSfFqlBwY9flTnJDIzPJMDMtduejO7R2dTh8h8PhzNh1iIEYe5BiIUWRPslFWqhcC7hiUylKnahCiwmb9f23EEIqyG7ZBAC0LlU6Zb-b4JtYk9nX2PFhR12DNbdkYtPG3g8-Bh4db3cUYs0xWG7z5OyeufUdmYHHqqfugJesOZo6thQGtJ4CcRfHzhM8eDzTHf2c4Dj9jt04rHu6_9c526xev5bvyfrz7WP5sk7MODZNCuFUiVVeSgAlCFRhtNAGHJCDLCutdoUDJZURRqJVGsGkMlN5XjkUgDBnj-fedl81ZLdt5xvsjtvLFfAHCABh2g |
CitedBy_id | crossref_primary_10_1016_j_jphotochem_2023_114577 crossref_primary_10_1002_sia_5147 crossref_primary_10_1016_j_jaap_2021_105410 crossref_primary_10_1021_acs_energyfuels_2c02042 crossref_primary_10_1021_acs_jpca_2c06670 crossref_primary_10_1016_j_combustflame_2017_05_015 crossref_primary_10_1016_j_fuproc_2018_09_022 crossref_primary_10_1063_1_4879615 crossref_primary_10_1002_ange_202107553 crossref_primary_10_1063_1_4906156 crossref_primary_10_1021_acs_jpca_2c00766 crossref_primary_10_1021_acs_jpca_5b06779 crossref_primary_10_1021_acs_analchem_7b00853 crossref_primary_10_1021_acs_jpca_7b08112 crossref_primary_10_1039_C5CP02953H crossref_primary_10_1038_s41586_024_07210_9 crossref_primary_10_1039_C9CP03519B crossref_primary_10_1002_wene_326 crossref_primary_10_1016_j_pecs_2023_101076 crossref_primary_10_1016_j_scitotenv_2022_160359 crossref_primary_10_1021_jp511390f crossref_primary_10_1002_qua_25342 crossref_primary_10_1002_kin_21164 crossref_primary_10_3389_fchem_2019_00326 crossref_primary_10_1016_j_fuel_2018_05_162 crossref_primary_10_1038_ncomms15946 crossref_primary_10_1063_1_4954895 crossref_primary_10_1021_jp5036579 crossref_primary_10_1021_acs_energyfuels_2c01455 crossref_primary_10_1016_j_jaap_2019_05_009 crossref_primary_10_1039_D2CP02741K crossref_primary_10_1039_C5CP05346C crossref_primary_10_1016_j_jaap_2015_09_004 crossref_primary_10_1002_dta_2572 crossref_primary_10_1016_j_fuel_2018_09_025 crossref_primary_10_1021_acs_jpca_5b10984 crossref_primary_10_1039_D1RA06743E crossref_primary_10_1039_D1SC00654A crossref_primary_10_1021_acs_jpca_8b03201 crossref_primary_10_1002_chem_201404271 crossref_primary_10_1021_acs_jpca_7b01656 crossref_primary_10_1016_j_molstruc_2018_05_098 crossref_primary_10_1021_acs_jpca_1c05907 crossref_primary_10_1007_s41061_019_0260_5 crossref_primary_10_1016_j_enconman_2018_10_099 crossref_primary_10_1063_1_4759050 crossref_primary_10_1021_jp5001804 crossref_primary_10_1021_acs_energyfuels_1c01712 crossref_primary_10_1016_j_jms_2021_111453 crossref_primary_10_1039_C9RE00418A crossref_primary_10_1002_aic_15588 crossref_primary_10_1002_adsu_201900140 crossref_primary_10_3390_polym11071119 crossref_primary_10_1039_C9CY02587A crossref_primary_10_1021_acs_jpca_7b02639 crossref_primary_10_1063_1_4867896 crossref_primary_10_1002_chem_201903937 crossref_primary_10_1002_anie_202107553 crossref_primary_10_1021_jp411257k crossref_primary_10_1016_j_jhazmat_2022_128640 crossref_primary_10_1002_chem_201700639 |
ContentType | Journal Article |
Copyright | 2012 American Institute of Physics |
Copyright_xml | – notice: 2012 American Institute of Physics |
DBID | CGR CUY CVF ECM EIF NPM |
DOI | 10.1063/1.3675902 |
DatabaseName | Medline MEDLINE MEDLINE (Ovid) MEDLINE MEDLINE PubMed |
DatabaseTitle | MEDLINE Medline Complete MEDLINE with Full Text PubMed MEDLINE (Ovid) |
DatabaseTitleList | MEDLINE |
Database_xml | – sequence: 1 dbid: NPM name: PubMed url: https://proxy.k.utb.cz/login?url=http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed sourceTypes: Index Database – sequence: 2 dbid: EIF name: MEDLINE url: https://proxy.k.utb.cz/login?url=https://www.webofscience.com/wos/medline/basic-search sourceTypes: Index Database |
DeliveryMethod | no_fulltext_linktorsrc |
Discipline | Chemistry Physics |
EISSN | 1089-7690 |
ExternalDocumentID | 22299873 |
Genre | Research Support, U.S. Gov't, Non-P.H.S Journal Article |
GroupedDBID | --- -DZ -ET -~X 123 1UP 2-P 29K 4.4 53G 5VS 85S AAAAW AAEUA AAPUP AAYIH ABPPZ ABRJW ABZEH ACBRY ACNCT ACZLF ADCTM AENEX AFHCQ AGLKD AJQPL ALEPV ALMA_UNASSIGNED_HOLDINGS AQWKA AWQPM BPZLN CGR CS3 CUY CVF D-I DU5 EBS ECM EIF EJD ESX F5P FDOHQ FFFMQ HAM M6X M71 M73 N9A NPM NPSNA O-B P0- P2P RIP RNS ROL RQS TN5 TWZ UPT UQL WH7 YQT YZZ ~02 |
ID | FETCH-LOGICAL-c2223-60f78ab5812270e276c909c2f2ef2448d9f6f2717c0c1ad79a2c314755bfa02a2 |
IngestDate | Thu May 23 23:15:48 EDT 2024 |
IsPeerReviewed | true |
IsScholarly | true |
Issue | 4 |
Language | English |
License | 2012 American Institute of Physics |
LinkModel | OpenURL |
MergedId | FETCHMERGED-LOGICAL-c2223-60f78ab5812270e276c909c2f2ef2448d9f6f2717c0c1ad79a2c314755bfa02a2 |
PMID | 22299873 |
ParticipantIDs | pubmed_primary_22299873 |
PublicationCentury | 2000 |
PublicationDate | 2012-Jan-28 |
PublicationDateYYYYMMDD | 2012-01-28 |
PublicationDate_xml | – month: 01 year: 2012 text: 2012-Jan-28 day: 28 |
PublicationDecade | 2010 |
PublicationPlace | United States |
PublicationPlace_xml | – name: United States |
PublicationTitle | The Journal of chemical physics |
PublicationTitleAlternate | J Chem Phys |
PublicationYear | 2012 |
SSID | ssj0001724 |
Score | 2.0652652 |
Snippet | The pyrolyses of phenol and d(5)-phenol (C(6)H(5)OH and C(6)D(5)OH) have been studied using a high temperature, microtubular (μtubular) SiC reactor. Product... |
SourceID | pubmed |
SourceType | Index Database |
StartPage | 044309 |
SubjectTerms | Alkenes - chemistry Cyclohexenes - chemistry Cyclopentanes - chemistry Hot Temperature Molecular Structure Phenol - chemistry Spectrophotometry, Infrared |
Title | Unimolecular thermal decomposition of phenol and d5-phenol: direct observation of cyclopentadiene formation via cyclohexadienone |
URI | https://www.ncbi.nlm.nih.gov/pubmed/22299873 |
Volume | 136 |
hasFullText | |
inHoldings | 1 |
isFullTextHit | |
isPrint | |
link | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwnV1ZbxMxELZSEIIXBOW-5Afeoi2O7fXBG4pAFVIjJFqpb5XXaytRc1QoqVqe-E_8QcbHHgmHgJdVspOsop0v48-z38wg9JpRgK7iGjY5cOCuLAsdNq6CMC-tFLUjoTj5aCIOT_jH0_J0MPjeUy1t1tWB_frLupL_8SqcA7-GKtl_8Gx7UTgBr8G_cAQPw_GvfAyEcdGMtw0MEoLsfFi7IBPPWqwoaJ665Sp1BKjLIr0LiYC0mg1XVZuYjRrzazsPI7XWUQvmuurG4eXMJOvUXUXjarmlI-qqzCK_tU0rgpQ8abn7ZzDkEdq1WXTZ2KPNuflizk2a1zc288vZVpWanZpNJ8PvHmdNZot50gqGuqMsgMx5jCgIaerCXYq9ROlCijQ9tA3OqT1KRiHvhVrCOYudFX5eBYB2hYTEAYPdkI4F3eseGi4WEQ5hkLlWaY7Kn607Dbkb0x7akyoE1UlIEOXFH_ggbxpYCfam_Q2h6XT-3s4GJhKZ43vobvYQfpfgdB8N3HIf3R43g__20a1PyWEP0Lc-wHAGGN4CGF55nCCFAWC4BdhbnOCFe_AKn92BF27hhQFeeBdeD9HJh_fH48Mij-wobCCa8Bf3UpmqBNpIJXFUCquJttRT54FIqlp74akcSUvsyNRSG2rZiMuyrLwh1NBH6Ea4_BOEjVVVYOO1IoZ7IirmTWWUKZljzgn6FD1Ot_HsIvVlOWtu8LPfWp6jOx30XqCbHgKBewmscl29in78AQBQfOk |
link.rule.ids | 786 |
linkProvider | National Library of Medicine |
openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Unimolecular+thermal+decomposition+of+phenol+and+d5-phenol%3A+direct+observation+of+cyclopentadiene+formation+via+cyclohexadienone&rft.jtitle=The+Journal+of+chemical+physics&rft.au=Scheer%2C+Adam+M&rft.au=Mukarakate%2C+Calvin&rft.au=Robichaud%2C+David+J&rft.au=Nimlos%2C+Mark+R&rft.date=2012-01-28&rft.eissn=1089-7690&rft.volume=136&rft.issue=4&rft.spage=044309&rft_id=info:doi/10.1063%2F1.3675902&rft_id=info%3Apmid%2F22299873&rft_id=info%3Apmid%2F22299873&rft.externalDocID=22299873 |