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

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

Research output: Contribution to journalArticlepeer-review

69 Scopus Citations

Abstract

The pyrolyses of phenol and d 5-phenol (C 6H 5OH and C 6D 5OH) 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 enolketo tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C 6H 5OH → c-C 6H 6 O → c-C 5H 6 CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C 5H 6 → c-C 5H 5 H → HCCH 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 6H 5O-H → C 6H 5O H → c-C 5H 5 CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C 6H 4-OH) and hydroquinone (p-HO-C 6H 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.

Original languageAmerican English
Article number044309
Number of pages11
JournalThe Journal of Chemical Physics
Volume136
Issue number4
DOIs
StatePublished - 28 Jan 2012

NREL Publication Number

  • NREL/JA-5100-54348

Keywords

  • biomass
  • biopolymer lignin
  • thermal decomposition

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