Direct Detection of Products from the Pyrolysis of 2-Phenethyl Phenyl Ether

Mark W. Jarvis, John W. Daily, Hans Heinrich Carstensen, Anthony M. Dean, Shantanu Sharma, David C. Dayton, David J. Robichaud, Mark R. Nimlos

Research output: Contribution to journalArticlepeer-review

166 Scopus Citations

Abstract

The pyrolysis of 2-phenethyl phenyl ether (PPE, C 6H 5C 2H 4OC 6H 5) in a hyperthermal nozzle (300-1350 °C) was studied to determine the importance of concerted and homolytic unimolecular decomposition pathways. Short residence times (<100 μs) and low concentrations in this reactor allowed the direct detection of the initial reaction products from thermolysis. Reactants, radicals, and most products were detected with photoionization (10.5 eV) time-of-flight mass spectrometry (PIMS). Detection of phenoxy radical, cyclopen-tadienyl radical, benzyl radical, and benzene suggest the formation of product by the homolytic scission of the C 6H 5C 2H 4-OC 6H 5 and C 6H 5CH 2-CH 2OC 6H 5 bonds. The detection of phenol and styrene suggests decomposition by a concerted reaction mechanism. Phenyl ethyl ether (PEE, C 6H 5OC 2H 5) pyrolysis was also studied using PIMS and using cryogenic matrix-isolated infrared spectroscopy (matrix-IR). The results for PEE also indicate the presence of both homolytic bond breaking and concerted decomposition reactions. Quantum mechanical calculations using CBS-QB3 were conducted, and the results were used with transition state theory (TST) to estimate the rate constants for the different reaction pathways. The results are consistent with the experimental measurements and suggest that the concerted retro-ene and Maccoll reactions are dominant at low temperatures (below 1000 °C), whereas the contribution of the C 6H 5C 2H 4-OC 6H 5 homolytic bond scission reaction increases at higher temperatures (above 1000 °C).

Original languageAmerican English
Pages (from-to)428-438
Number of pages11
JournalJournal of Physical Chemistry A
Volume115
Issue number4
DOIs
StatePublished - 3 Feb 2011

NREL Publication Number

  • NREL/Ja-510-49208

Keywords

  • concerted reactions
  • decomposition
  • PEE
  • PIMS
  • pyrolysis

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