Chemisorption surface-energy change

Vibrational energy states are too well separated to contribute much to the entropy or the energy of small molecules at ordinary temperatures, but for higher temperatures this may not be so, and both internal entropy and energy changes may occur due to changes in vibrational levels on adsoiption. From a somewhat different point of view, it is clear that even in physical adsorption, adsorbate molecules should be polarized on the surface (see Section VI-8), and in chemisorption more drastic perturbations should occur. Thus internal bond energies of adsorbed molecules may be affected. 

In our view the final verification was given to this conclusion in paper [66] in which simultaneous O2 adsorption on partially reduced ZnO and resultant change in electric conductivity was studied. It was established in this paper that the energies of activation of chemisorption and that of the change of electric conductivity fully coincide. The latter is plausible only in case when localization of free electron on SS is not linked with penetration through the surface energy barrier which is inherent to the model of the surface-adjacent depleted layer. 

Mineral grinding leads to distorsion of chemical and ionic bonds between atoms and ions. In the fracture areas binding and coordination states get asymmetric, and new electron and electric valences occur. Spontaneous reactions in the crystalline structure and with contact phases are the consequence of the distorsion. Surface distorsion of the crystalline structure may be diminished or completely abolished. At the same time, the free surface energy decreases due to polarization of surface ions. These ions are redistributed in the inner or outer layer of the crystalline surface and/or due to chemisorption of molecules and ions1. All these changes occur side by side, but one of them can suppress the effect of the others in a decisive manner. 

Adsorption of atoms and molecules on surfaces plays a fundamental role in catalysis a distinction can be made between physisorption, in which weak Van der Waals forces bind the atom/molecule to the surface, and chemisorption in which chemical bonds dominate. Much experimental and theoretical work is devoted to studying energy changes as a molecule approaches the surface and dissociates (or doesn t) into separate atoms on the surface. Here we concentrate on the relation between structure and bonding for chemisorbed atoms in their equilibrium sites on the surface (ch. 1, sect. 2.4). 

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