Energetics of cyclohexene adsorption and reaction on Pt(111) by low-temperature microcalorimetry

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Lytken, Ole [1 ]
Lew, Wanda [1 ]
Harris, Jonathan J. W. [1 ]
Vestergaard, Ebbe K. [1 ]
Gottfried, J. Michael [1 ,2 ]
Campbell, Charles T. [1 ]
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[1] Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195-1700, United States
[2] Lehrstuhl fuer Physikalische Chemie II, Universitaet Erlangen, Egerlandstr. 3, 91058 Erlangen, Germany
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The heat of adsorption and sticking probability of cyclohexene on Pt(111) were measured as a function of coverage using single-crystal adsorption calorimetry in the temperature range from 100 to 300 K. At 100 K; cyclohexene adsorbs as intact di-σ bonded cyclohexene on Pt(111); and the heat of adsorption is well described by a second-order polynomial (130 - 47 θ - 1250 θ2) kJ/mol; yielding a standard enthalpy of formation of di-σ bonded cyclohexene on Pt(111) at low coverages of -135 kJ/mol and a C-Pt σ bond strength of 205 kJ/mol. At 281 K; cyclohexene dehydrogenates upon adsorption; forming adsorbed 2-cyclohexenyl (c-C6H 9; a) and adsorbed hydrogen; and the heat of adsorption is well described by another second-order polynomial (174 - 700 θ + 761 θ2) kJ/mol. This yields a standard enthalpy of formation of adsorbed 2-cyclohexenyl on Pt(111) at a low coverage of -143 kJ/mol. At coverages below 0.10 ML; the sticking probability of cyclohexene on Pt(111) is close to unity (>0.95); independent of temperature. © 2008 American Chemical Society;
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页码:10247 / 10257
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