Theoretical study on reaction pathways leading to CO and CO2 in the pyrolysis of resorcinol

Yuki Furutani, Shinji Kudo, Hayashi Jun-Ichiro, Koyo Norinaga

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Possible pathways for the pyrolysis of resorcinol with the formation of CO and CO2 as final products were proposed and evaluated using ab initio calculations. Our experimental study revealed that large quantities of CO2 are generated in the pyrolysis of 1,3-dihydroxybenzene (resorcinol), while the pyrolysis of the dihydroxybenzene isomers 1,2-dihydroxybenzene (catechol) and 1,4-dihydroxybenzene (hydroquinone) produces little CO2. The fate of oxygen atoms in catechol and hydroquinone was essentially the formation of CO. In the proposed pathways, the triplet ground state m-benzoquinone was generated initially from simultaneous cleavage of the two O-H bonds in resorcinol. Subsequently, the direct cleavage of a C-C bond of the m-benzoquinone diradical yields 2-oxidanylcyclopenta-2,4-dien-1-yl-methanone, which can be converted via two channels: release of CO from the aldehyde radical group and combination of the ketone radical and carbon atom in the aldehyde radical group to form the 6-oxabicyclo[3.2.0]hepta-2,4-dien-7-one, resulting in the release of CO2. Potential energy surfaces along the proposed reaction pathways were calculated employing the CBS-QB3 method, and the rate constants at the high-pressure limit were also evaluated based on transition-state theory to assess the feasibility of the proposed reaction pathways.

Original languageEnglish
Pages (from-to)631-637
Number of pages7
JournalJournal of Physical Chemistry A
Volume121
Issue number3
DOIs
Publication statusPublished - Jan 1 2017

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Carbon Monoxide
pyrolysis
Pyrolysis
quinones
aldehydes
cleavage
Aldehydes
ketones
Atoms
Potential energy surfaces
oxygen atoms
isomers
Ketones
potential energy
Isomers
Ground state
Rate constants
ground state
Carbon
carbon

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Theoretical study on reaction pathways leading to CO and CO2 in the pyrolysis of resorcinol. / Furutani, Yuki; Kudo, Shinji; Jun-Ichiro, Hayashi; Norinaga, Koyo.

In: Journal of Physical Chemistry A, Vol. 121, No. 3, 01.01.2017, p. 631-637.

Research output: Contribution to journalArticle

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AB - Possible pathways for the pyrolysis of resorcinol with the formation of CO and CO2 as final products were proposed and evaluated using ab initio calculations. Our experimental study revealed that large quantities of CO2 are generated in the pyrolysis of 1,3-dihydroxybenzene (resorcinol), while the pyrolysis of the dihydroxybenzene isomers 1,2-dihydroxybenzene (catechol) and 1,4-dihydroxybenzene (hydroquinone) produces little CO2. The fate of oxygen atoms in catechol and hydroquinone was essentially the formation of CO. In the proposed pathways, the triplet ground state m-benzoquinone was generated initially from simultaneous cleavage of the two O-H bonds in resorcinol. Subsequently, the direct cleavage of a C-C bond of the m-benzoquinone diradical yields 2-oxidanylcyclopenta-2,4-dien-1-yl-methanone, which can be converted via two channels: release of CO from the aldehyde radical group and combination of the ketone radical and carbon atom in the aldehyde radical group to form the 6-oxabicyclo[3.2.0]hepta-2,4-dien-7-one, resulting in the release of CO2. Potential energy surfaces along the proposed reaction pathways were calculated employing the CBS-QB3 method, and the rate constants at the high-pressure limit were also evaluated based on transition-state theory to assess the feasibility of the proposed reaction pathways.

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