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By W. Nicholas Delgass
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Additional info for Spectroscopy in Heterogeneous Catalysis
Example text
The more weakly bound hydrogen is thought to be active in catalytic hydrogenation and from infrared determined isotherms, the reversibly adsorbed hydrogen was shown to be the result of dissociative adsorption with a heat of adsorption of 12 kcal/mole [19]. While the intensity of a normal infrared active band may be increased or decreased upon adsorption relative to that in the gas phase, a totally symmetric vibration would not change the dipole moment and would therefore not absorb in the infrared (it would be Raman active).
When the vibrational quantum number n = 0, the system retains jhv of energy. This is the zero point energy. One implication of the zero point energy is that the dissociation energy E of isotopic species will be different since E = Ee — ^hv and v will be different because of the mass effect, see Fig. 2-3. 2 29 Theory O « w 55 H < H W tr* O Fig. 2-3 Potential-energy function for a real diatomic molecule with a dissociation energy of E and equilibrium bond length re. The dashed line is the harmonic oscillator potential that approximates the actual potential at small displacements from re.
Then from the intensities measured at room temperature surface equilibrium, the ratio of trans:eis: 1-butene 50 2. 3100 -JL 2900 3000 Infrared Spectroscopy 2800 cm Fig. 2-10 Spectrum of chemisorbed propylenes on ZnO in the C-H stretching region: (a) CH 3 —CH=CH 2 , (b) CH 3 - C D = C H 2 , (c) CD 3 —CH=CH 2 , (d) CD 3 —CH=CD 2 . From Dent and Kokes [16]. was found to be 30:100:10. This is quite different from the gas phase where the ratio is 100:26:4. While in principle both the syn and anti π-allyl could be formed from 1-butene, only anti π-allyl is observed.