Coverage monolayer

Infrared Spectroscopy. The infrared spectroscopy of adsorbates has been studied for many years, especially for chemisorbed species (see Section XVIII-2C). In the case of physisorption, where the molecule remains intact, one is interested in how the molecular symmetry is altered on adsorption. Perhaps the conceptually simplest case is that of H2 on NaCl(lOO). Being homo-polar, Ha by itself has no allowed vibrational absorption (except for some weak collision-induced transitions) but when adsorbed, the reduced symmetry allows a vibrational spectrum to be observed. Fig. XVII-16 shows the infrared spectrum at 30 K for various degrees of monolayer coverage [96] (the adsorption is Langmuirian with half-coverage at about 10 atm). The bands labeled sf are for transitions of H2 on a smooth face and are from the 7 = 0 and J = 1 rotational states Q /fR) is assigned as a combination band. The bands labeled... 

If the desorption rate is second-order, as is often the case for hydrogen on a metal surface, so that appears in Eq. XVIII-1, an equation analogous to Eq. XVIII-3 can be derived by the Redhead procedure. Derive this equation. In a particular case, H2 on Cu3Pt(III) surface, A was taken to be 1 x 10 cm /atom, the maximum desorption rate was at 225 K, 6 at the maximum was 0.5. Monolayer coverage was 4.2 x 10 atoms/cm, and = 5.5 K/sec. Calculate the desorption enthalpy (from Ref. 110). 

Forces of Adsorption. Adsorption may be classified as chemisorption or physical adsorption, depending on the nature of the surface forces. In physical adsorption the forces are relatively weak, involving mainly van der Waals (induced dipole—induced dipole) interactions, supplemented in many cases by electrostatic contributions from field gradient—dipole or —quadmpole interactions. By contrast, in chemisorption there is significant electron transfer, equivalent to the formation of a chemical bond between the sorbate and the soHd surface. Such interactions are both stronger and more specific than the forces of physical adsorption and are obviously limited to monolayer coverage. The differences in the general features of physical and chemisorption systems (Table 1) can be understood on the basis of this difference in the nature of the surface forces. 

Near-monolayer coverage (/covered 0.95) can be achieved only at surf This can pose problems for surfactants, since solution... 

There are several requirements for a good sensitizing dye. A good dye is adsorbed strongly to silver haUde. The dye molecules attach themselves to the surface of the silver haUde crystals, usually up to monolayer coverage. This amount can be deterrnined by measuring the adsorption isotherm for the... 

The water removal mechanism is adsorption, which is the mechanism for ad Class 4 drying agents. The capacity of such materials is often shown in the form of adsorption isotherms as depicted in Figures 9a and 9b. The initial adsorption mechanism at low concentrations of water is beheved to occur by monolayer coverage of water on the adsorption sites. As more water is adsorbed, successive layers are added until condensation or capidary action takes place at water saturation levels greater than about 70% relative humidity. At saturation, ad the pores are fided and the total amount of water adsorbed, expressed as a Hquid, represents the pore volume of the adsorbent. 

Figure 3 The modulus of the Fourier transform of the SEXAFS spectrum for the half-monolayer coverage on Ni(IOO) The SEXAFS spectrum itself is shown in the inset with the background removed.

Raman spectroscopy has provided information on catalytically active transition metal oxide species (e. g. V, Nb, Cr, Mo, W, and Re) present on the surface of different oxide supports (e.g. alumina, titania, zirconia, niobia, and silica). The structures of the surface metal oxide species were reflected in the terminal M=0 and bridging M-O-M vibrations. The location of the surface metal oxide species on the oxide supports was determined by monitoring the specific surface hydroxyls of the support that were being titrated. The surface coverage of the metal oxide species on the oxide supports could be quantitatively obtained, because at monolayer coverage all the reactive surface hydroxyls were titrated and additional metal oxide resulted in the formation of crystalline metal oxide particles. The nature of surface Lewis and Bronsted acid sites in supported metal oxide catalysts has been determined by adsorbing probe mole-... 

In this section we review several studies of phase transitions in adsorbed layers. Phase transitions in adsorbed (2D) fluids and in adsorbed layers of molecules are studied with a combination of path integral Monte Carlo, Gibbs ensemble Monte Carlo (GEMC), and finite size scaling techniques. Phase diagrams of fluids with internal quantum states are analyzed. Adsorbed layers of H2 molecules at a full monolayer coverage in the /3 X /3 structure have a higher transition temperature to the disordered phase compared to the system with the heavier D2 molecules this effect is... 

At high alkali coverages (near monolayer coverage), when the adsorbed alkali overlayer shows a metal-like character, alkali-methoxy species are formed. As shown by TPD experiments in the system K/Ru(001) these alkali-methoxy species are more stable than the methoxy species on clean Ru(001) and adsorbed methanol on 0.1K/Ru(001). On metal surfaces inactive for methanol decomposition, e.g. Cu(lll), these alkali-methoxy species are formed even at low alkali coverages, due to the weaker interaction of the alkali atoms with the metal surface. The formation of these species stabilizes the methoxy species on the metal surface and enhances the activity of the metal surface for methanol decomposition. 

Stimulated by these observations, Odelius et al. [73] performed molecular dynamic (MD) simulations of water adsorption at the surface of muscovite mica. They found that at monolayer coverage, water forms a fully connected two-dimensional hydrogen-bonded network in epitaxy with the mica lattice, which is stable at room temperature. A model of the calculated structure is shown in Figure 26. The icelike monolayer (actually a warped molecular bilayer) corresponds to what we have called phase-I. The model is in line with the observed hexagonal shape of the boundaries between phase-I and phase-II. Another result of the MD simulations is that no free OH bonds stick out of the surface and that on average the dipole moment of the water molecules points downward toward the surface, giving a ferroelectric character to the water bilayer. 

These observations were regarded as providing evidence that doublet corresponds to FePc preadsorbed at monolayer coverages on Che carbon surface. 

Figure 9. Cyclic voltammogram of Fe-TsPc adsorbed on Vulcan XC-72 at monolayer coverages. This measurement was obtained with the material In the form of a thin porous coating. Scan rate 50 mV s. Other conditions are the same as those In caption of Fig. 6.

The relative product yields depend on the CHa to Cl ratio on the surface. In the studies reported here, this ratio has been adjusted to 1 1 (consistent with the CHa Cl stoichiometry in CHaCl) on the basis of a Cl(181 eV) C(272 eV) Auger peak ratio of 6.5 which is the same as that measured for physisorbed monolayers of dimethyldichlorosilane. Monolayer coverages of CHa + Cl having 1 1 stoichiometry were obtained by a 20 L exposure from the methyl radical source (approximately sahiration coverage) followed by a 9.5 L dose of CI2. 

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