Unimolecular Thermal Decomposition of Phenol and d5-Phenol: Direct Observation of Cyclopentadiene Formation via Cyclohexadienone

Scheer, Adam M.; Mukarakate, Calvin; Robichaud, David J.; Nimlos, Mark R.; Carstensen, Hans Heinrich; Ellison, G. Barney

doi:10.1063/1.3675902

Unimolecular Thermal Decomposition of Phenol and d5-Phenol: Direct Observation of Cyclopentadiene Formation via Cyclohexadienone

Journal Article · Sat Jan 28 04:00:00 EST 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3675902· OSTI ID:1045748

Scheer, Adam M.; Mukarakate, Calvin; Robichaud, David J.; Nimlos, Mark R.; Carstensen, Hans Heinrich; Ellison, G. Barney

The pyrolyses of phenol and d{sub 5}-phenol (C{sub 6}H{sub 5}OH and C{sub 6}D{sub 5}OH) have been studied using a high temperature, microtubular ({mu}tubular) 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 {mu}tubular reactor of approximately 50-100 {micro}s. 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{sub 6}H{sub 5}OH {yields} c-C{sub 6}H{sub 6} = O {yields} c-C{sub 5}H{sub 6} + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C{sub 5}H{sub 6} {yields} c-C{sub 5}H{sub 5} + H {yields} HC {triple_bond} CH + HCCCH{sub 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{sub 6}H{sub 5}O-H {yields} C{sub 6}H{sub 5}O + H {yields} c-C{sub 5}H{sub 5} + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C{sub 6}H{sub 4}-OH) and hydroquinone (p-HO-C{sub 6}H{sub 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.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy Biomass Program; National Science Foundation

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 1045748

Report Number(s):: NREL/JA-5100-54348

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 136; ISSN JCPSA6; ISSN 0021-9606

Country of Publication:: United States

Language:: English

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Unimolecular Thermal Decomposition of Phenol and d5-Phenol: Direct Observation of Cyclopentadiene Formation via Cyclohexadienone

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