title: Theoretical Study on Reaction Pathways Leading to CO and CO2in the Pyrolysis of Resorcinol.
abstract: Possible pathways for the pyrolysis of resorcinol with the formation of CO and CO2as final products were proposed and evaluated using ab initio calculations. Our experimental study revealed that large quantities of CO2are 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.
authors.affiliation: Interdisciplinary Graduate School of Engineering Sciences, Kyushu University , Kasuga 816-8580, Japan.
authors.forename: Yuki
authors.initials: Y
authors.lastname: Furutani
authors.affiliation: Interdisciplinary Graduate School of Engineering Sciences, Kyushu University , Kasuga 816-8580, Japan.|Institute for Materials Chemistry and Engineering, Kyushu University , Kasuga 816-8580, Japan.
authors.forename: Shinji
authors.identifier: http://orcid.org/0000-0003-0002-796X
authors.initials: S
authors.lastname: Kudo
authors.affiliation: Interdisciplinary Graduate School of Engineering Sciences, Kyushu University , Kasuga 816-8580, Japan.|Institute for Materials Chemistry and Engineering, Kyushu University , Kasuga 816-8580, Japan.|Research and Education Centre of Carbon Resources, Kyushu University , Kasuga 816-8580, Japan.
authors.forename: Jun-Ichiro
authors.initials: JI
authors.lastname: Hayashi
authors.affiliation: Interdisciplinary Graduate School of Engineering Sciences, Kyushu University , Kasuga 816-8580, Japan.|Institute for Materials Chemistry and Engineering, Kyushu University , Kasuga 816-8580, Japan.
authors.forename: Koyo
authors.identifier: http://orcid.org/0000-0002-3251-3535
authors.initials: K
authors.lastname: Norinaga