Surface acidity, monolayer dispersion

Acidity, 27 284, 285 catalytic performance, 30 121 crystalline titanium silicates, 41 319-320 estimating, 37 166 heteropoly compounds, 41 139-150 ion exchange and, zeolites, 31 5-6 sulfate-supported metal oxides, 37 186-187 surface, monolayer dispersion, 37 34-35 tin-antimony oxide, 30 114-115, 125-1256 Acids, see also specific compounds adsorption of, on oxide surfaces, 25 243-245... 

Interactions between crossed cylinders of mica in air, uncoated or coated with fatty acid monolayers, are described in J. N. Israelachvili and D. Tabor, "The measurement of van der Waals dispersion forces in the range 1.5 to 130 nm," Proc. R. Soc. London Ser. A, 331, 19-38 (1972). An excellent review of this and related work is given in J. N. Israelachvili and D. Tabor, Van der Waals Forces Theory and Experiment, Vol. 7 of Progress in Surface and Membrane Science Series (Academic Press, New York and London, 1973). Later reconciliation of theory and experiment required taking note of cylinder radius L. R. White, J. N. Israelachvili, and B. W. Ninham, "Dispersion interaction of crossed mica cylinders A reanalysis of the Israelachvili-Tabor experiments," J. Chem. Soc. Faraday Trans. 1, 72, 2526-36 (1976). 

The ability of IR spectroscopy to probe the environment in which bonds vibrate allows it to be used to examine structural ordering of surface modifier molecules. If alkyl chains for example are in a liquid-like state of disorder the dispersion forces of attraction between chains are not maximised and vibration of the C-H bonds is influenced almost solely by the bond stiffness. If on the other hand the chains are in an ordered crystalline array, dispersion forces are maximised. This causes the C-H bonds to become very slightly longer (and therefore weaker) than when in the liquid state. This reduction in stiffness causes the asymmetric C-H stretching vibration frequency of a Cjg alkyl chain to reduce by 3-5 cm. Such frequency shifts have been used by Kellar and co-workers [48] to investigate ordering of oleic acid monolayers and by Liauw and co-workers [13, 49]. Vaia and co-workers [50] have also used this approach to examine the order of alkyl chains of quaternary alkyl ammonium intercalants in organo-clays for nanocomposite applications. 

For stearic acid monolayers formed at the pure water surface, we were able to observe densely packed dispersions of ultra-thin CaC03 crystals, which were adsorbed below... 

Surfactants adsorb on solid surfaces due to hydrophobic bonding, electrostatic interaction, acid-base interaction, polarisation of rr electrons and dispersion forces. Hydrophobic bonding occurs between the hydrophobic surfactant tail and the hydrophobic solid surface (tail down adsorption with monolayer structure) or between the hydrophobic tails of the surfactant adsorbed on the hydrophilic solid surface and the hydrophobic tails of the surfactant from the liquid phase (head down adsorption with bilayer structure) [54, 55]. 

Electrostatic interactions occur between the ionic head groups of the surfactant and the oppositely charged solid surface (head down adsorption with monolayer structure) [56]. Acid-base interactions occur due to hydrogen bonding or Lewis acid-Lewis base reactions between solid surface and surfactant molecules (head down with monolayer structure) [57]. Polarisation of jt electrons occurs between the surfactant head group which has electron-rich aromatic nuclei and the positively charged solid surface (head down with monolayer structure) [58]. Dispersion forces occur due to London-van der Waals forces between the surfactant molecules and the solid surface (hydrophobic tail lies flat on the hydrophobic solid surface while hydrophilic head orients towards polar liquid) [59]. 

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