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• W1966048864 abstract "Abstract Minor changes or substitutions in the structure or composition of reactants can have profound effects on reaction kinetics. The effects of substituents on surface and catalytic reaction kinetics can be understood through the use of semi-quantitative empirical correlations such as the Hammett relation. These correlations provide a basis for comparison of reaction kinetics in varying environments. For example, comparisons can be made between reaction kinetics measured on single crystals under ultra-high vacuum (UHV) conditions and reaction kinetics measured on catalysts at high pressures. Doing so offers a means of translating insights obtained from studies of surface chemistry into the field of catalysis. One such insight is into the nature of the transition states for heterogeneously catalyzed reactions. An example discussed in this article compares β -hydride elimination of alkoxides on Cu(111) with alcohol dehydrogenation over ZnO–Cr 2 O 3 . In both systems inductive substituents (R) decrease the reaction rate suggesting that the transition state for the rate limiting step in both reactions has an electron deficient carbon atom (RC δ + ⋯H). A second example, phenyl coupling on the Ag(111) surface exhibits an increase in rate due to inductive substituents. This observation is consistent with observations of homogeneously catalyzed phenyl coupling described in the literature. These comparisons demonstrate the potential for using Hammett correlations measured in surface science studies to understand important issues in catalysis." @default.
• W1966048864 created "2016-06-24" @default.
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• W1966048864 creator A5045876769 @default.
• W1966048864 date "1998-05-01" @default.
• W1966048864 modified "2023-09-27" @default.
• W1966048864 title "Correlations between substituent effects for surface reactions and catalytic reactions" @default.
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• W1966048864 doi "https://doi.org/10.1016/s1381-1169(97)00256-2" @default.
• W1966048864 hasPublicationYear "1998" @default.
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