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

Jarvis, Mark W. and Daily, John W. and Carstensen, Hans-Heinrich and Dean, Anthony M. and Sharma, Shantanu and Dayton, David C. and Robichaud, David J. and Nimlos, Mark R. (2011) Direct Detection of Products from the Pyrolysis of 2-Phenethyl Phenyl Ether. Journal of Physical Chemistry A, 115 (4). pp. 428-438. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20110303-095335941

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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, cyclopentadienyl 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).


Item Type:Article
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http://dx.doi.org/10.1021/jp1076356DOIUNSPECIFIED
http://pubs.acs.org/doi/abs/10.1021/jp1076356PublisherUNSPECIFIED
Additional Information:© 2011 American Chemical Society. Received: August 12, 2010; Revised Manuscript Received: October 29, 2010. This work was supported by the U.S. Department of Energy’s Biomass Program, under Contract No. DE-AC36-99GO10337 with the National Renewable Energy Laboratory. We would like to thank Professor G. Barney Ellison, Angayle Vasiliou, and Adam M. Scheer, University of Colorado, and Calvin Mukarakate, National Renewable Energy Laboratory.
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Funding AgencyGrant Number
Department of Energy's Biomass Program/National Renewable Energy LaboratoryDE-AC36-99GO10337
Issue or Number:4
Record Number:CaltechAUTHORS:20110303-095335941
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110303-095335941
Official Citation: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, and Mark R. Nimlos pp 428–438 Publication Date (Web): January 10, 2011 (Article) DOI: 10.1021/jp1076356
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:22623
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:03 Mar 2011 19:20
Last Modified:03 Oct 2019 02:39

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