Reactions of Ethylidene on a Model Chromia Surface: 1 1-Dichloroethane on Stoichiometric alpha-Cr2O3 (1012)
The reaction of CH{sub 3}CHCl{sub 2} over the nearly-stoichiometric {alpha}-Cr{sub 2}O{sub 3} (10{sub {bar 1}} > 2) surface produces an ethylidene intermediate that yields primarily gas phase CH{sub 2}{double_bond}CH{sub 2} and surface chlorine adatoms; however, trace amounts of HC{triple_bond}CH, CH{sub 3}CH{sub 3}, H{sub 2} and CH{sub 3}CH{double_bond}CHCH{sub 3} are also observed. A rate-limiting intramolecular isomerization (2,1-hydrogen shift) in the surface ethylidene species produces gas phase CH{sub 2}{double_bond}CH{sub 2}. The chlorine freed from the dissociation of CH{sub 3}CHCl{sub 2} binds at the five-coordinate surface Cr{sup 3+} sites on the stoichiometric surface, completing the octahedral coordination sphere, and inhibits the surface chemistry by simple site blocking. No surface carbon deposition is observed from the thermal reaction of 1,1-dichloroethane under the conditions of this study, demonstrating that the ethylidene intermediate is not a primary coke forming intermediate over (10{sub {bar 1}} > 2) facets of {alpha}-Cr{sub 2}O{sub 3} under the conditions of this study.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE SC OFFICE OF SCIENCE (SC)
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 1041901
- Report Number(s):
- BNL-97579-2012-JA; SUSCAS; TRN: US201212%%312
- Journal Information:
- Surface Science, Vol. 605, Issue 13-14; ISSN 0039-6028
- Country of Publication:
- United States
- Language:
- English
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