Turnover Rate, Reaction Order, and Elementary Steps for the Hydrodechlorination of Chlorofluorocarbon Compounds on Palladium Catalysts

C. D. Thompson, R. M. Rioux, N. Chen, F. H. Ribeiro

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The rates of hydrodechlorination catalyzed by Pd supported on carbon for four chlorofluorocarbons spanned a range of 7 orders of magnitude. The rates scaled up to the bond strength of the carbon-chlorine bond for the gas-phase reactant. This finding demonstrates that the rate-determining step involves the scission of the C-Cl bond and suggests, through Polanyi and linear free-energy relationships, that rates for other compounds can be estimated if the C-Cl bond strength is known. The reaction orders for the most abundant products are approximately first-order for the chlorine-containing compound, half-order in H2, and inverse first-order in HCl. The reaction steps consistent with these orders include a rate-determining step involving the adsorption of the chlorofluorocarbon to a single site (which could be a single surface palladium atom) and equilibrated steps between gas-phase H2, gas-phase HCl, and adsorbed hydrogen and chlorine atoms. The rates on the supported catalysts are comparable to the ones reported before on a Pd foil, indicating that the support does not play a role in the reaction. The product distribution is independent of conversion, implying that the various products are formed from a single visit of the reactant on the surface and not from readsorption of gas-phase products. The four compounds studied were chloropentafluoroethane (CF3-CF2Cl), 2-chloro-1,1,1,2-tetrafluoroethane (CF3-CFClH), 1,1-dichlorotetrafluoroethane (CF3-CFCl2), and 1,1,1-trichloro-2,2,2-trifluoroethane (CF3-CCl3).

Original languageEnglish (US)
Pages (from-to)3067-3077
Number of pages11
JournalJournal of Physical Chemistry B
Issue number14
StatePublished - Apr 13 2000


All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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