Theoretical Study on Reaction Pathways Leading to CO and CO2 in the Pyrolysis of Resorcinol

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• 作者：Yuki Furutani ; Shinji KudoJun-ichiro Hayashi ; Koyo Norinaga
• 刊名：Journal of Physical Chemistry A
• 出版年：2017
• 出版时间：January 26, 2017
• 年：2017
• 卷：121
• 期：3
• 页码：631-637
• 全文大小：491K
• ISSN：1520-5215

文摘

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.