Title page for ETD etd-10012010-210318

Type of Document Dissertation
Author Brooks, John Daniel
URN etd-10012010-210318
Title Model Chromia Surface Chemistry: C2 Alkyl Fragment Reactions and Probe Molecule Interactions
Degree PhD
Department Chemical Engineering
Advisory Committee
Advisor Name Title
Cox, David F. Committee Chair
Davis, Richey M. Committee Member
Hanson, Brian E. Committee Member
Morris, John R. Committee Member
Oyama, Shigeo Ted Committee Member
  • ethyl
  • ethylidene
  • ethylidyne
  • dehydrogenation
  • water
  • chromia
Date of Defense 2010-09-29
Availability unrestricted
The thermally induced reaction of chlorinated ethanes on the nearly-stoichiometric α-Cr2O3 (102) surface results in the formation of gas phase hydrocarbons including ethylene, ethane, acetylene, 2-butene, 2-butyne and dihydrogen, and deposition of surface chlorine adatoms. No surface carbon or combustion products are observed in any reactions indicating that no thermally induced C-C bond cleavage occurs and surface lattice oxygen is not incorporated into surface intermediates. A combination of photoemission and Auger electron spectroscopies indicates the surface reactions of the chlorinated ethanes proceed via C-Cl bond cleavage to form surface chlorine adatoms and surface C2-alkyl hydrocarbon fragments (i.e. ethyl, ethylidene and ethylidyne). Temperature programmed desorption studies indicate that both ethyl and ethylidene intermediates are selective towards ethylene. However, ethylidyne is more selective towards acetylene, but also produces ethylene in significant quantities. Chlorine adatom deposition leads to deactivation of surface Cr reaction centers by simple site blocking.

The interaction of water with nearly-stoichiometric α-Cr2O3 (001) and (102) surfaces is structure sensitive. Water is sensitive to the difference in coordination number of Cr surface cations between the two surfaces, and on the α-Cr2O3 (001) surface, water has also demonstrated sensitivity to the degree of surface Cr cation reduction (and/or reduced coordination). These observations allowed for the development of a surface treatment recipe for the nearly-stoichiometric (001) surface.

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