Surface solids

Adsorption. Adsorption involves the transfer of a component onto a solid surface. An example is the adsorption of organic vapors by activated carbon. Activated carbon is a highly porous form of carbon manufactured from a variety of carbonaceous raw materials such as coal or wood. The adsorbent may need to be... 

Langmuir adsorption isotherm A theoretical equation, derived from the kinetic theory of gases, which relates the amount of gas adsorbed at a plane solid surface to the pressure of gas in equilibrium with the surface. In the derivation it is assumed that the adsorption is restricted to a monolayer at the surface, which is considered to be energetically uniform. It is also assumed that there is no interaction between the adsorbed species. The equation shows that at a gas pressure, p, the fraction, 0, of the surface covered by the adsorbate is given by ... 

The capillary effect is apparent whenever two non-miscible fluids are in contact, and is a result of the interaction of attractive forces between molecules in the two liquids (surface tension effects), and between the fluids and the solid surface (wettability effects). 

In Chapter VII, the solid surface is introduced. Stmcture is as important in... 

In the case of solids, there is no doubt that a lateral tension (which may be anisotropic) can exist between molecules on the surface and can be related to actual stretching or compression of the surface region. This is possible because of the immobility of solid surfaces. Similarly, with thin soap films, whose thickness can be as little as 100 A, stretching or extension of the film may involve a corresponding variation in intermolecular distances and an actual tension between molecules. 

The interface between a solid and its vapor (or an inert gas) is discussed in this chapter from an essentially phenomenological point of view. We are interested in surface energies and free energies and in how they may be measured or estimated theoretically. The study of solid surfaces at the molecular level, through the methods of spectroscopy and diffraction, is taken up in Chapter VIII. 

Surface defects (Section VII-4C) are also influenced by the history of the sample. Such imperfections may to some extent be reversibly affected by processes such as adsorption so that it is not safe to regard even a refractory solid as having fixed surface actions. Finally, solid surfaces are very easily contaminated detection of contamination is aided by ultra-high-vacuum techniques and associated cleaning protocols [24]. 

Most solid surfaces are marred by small cracks, and it appears clear that it is often because of the presence of such surface imperfections that observed tensile strengths fall below the theoretical ones. For sodium chloride, the theoretical tensile strength is about 200 kg/mm [136], while that calculated from the work of cohesion would be 40 kg/mm [137], and actual breaking stresses are a hundreth or a thousandth of this, depending on the surface condition and crystal size. Coating the salt crystals with a saturated solution, causing surface deposition of small crystals to occur, resulted in a much lower tensile strength but not if the solution contained some urea. 

Perhaps the simplest case of reaction of a solid surface is that where the reaction product is continuously removed, as in the dissolving of a soluble salt in water or that of a metal or metal oxide in an acidic solution. This situation is discussed in Section XVII-2 in connection with surface area determination. 

P. P. Ewald and H. Juretschke, Structure and Properties of Solid Surfaces, University of Chicago Press, Chicago, 1953. 

W. T. Read, Jr., Dislocations in Crystals, McGraw-Hill, New York, 1953. Solid Surfaces, ACS Symposium Series No. 33, American Chemical Society, Washington, DC, 1961. 

A number of methods that provide information about the structure of a solid surface, its composition, and the oxidation states present have come into use. The recent explosion of activity in scanning probe microscopy has resulted in investigation of a wide variety of surface structures under a range of conditions. In addition, spectroscopic interrogation of the solid-high-vacuum interface elucidates structure and other atomic processes. 

J. J. Burton and G. Jura, Structure and Chemistry of Solid Surfaces, G. Somoijai, ed., Wiley, New York, 1969. 

A heat of immersion may refer to the immersion of a clean solid surface, qs.imm. or to the immersion of a solid having an adsorbed film on the surface. If the immersion of this last is into liquid adsorbate, we then report qsv.imm if tbe adsorbed film is in equilibrium with the saturated vapor pressure of the adsorbate (i.e., the vapor pressure of the liquid adsorbate P ), we will write It follows from these definitions... 

It is important to keep in mind that the phases are mutually in equilibrium. In particular, the designation is a reminder that the solid surface must be in equilibrium with the saturated vapor pressure and that there must therefore be an adsorbed film of film pressure (see Section X-3B). Thus... 

D. Y. Kwok, F. Y. H. Lin, and A. W. Neumann, Contact Angle Studies on Perfect and Imperfect Solid Surfaces, in Proc. 30th Int. Adhesion Symp., Yokohama Japan, 1994. 

The polymer concentration profile has been measured by small-angle neutron scattering from polymers adsorbed onto colloidal particles [70,71] or porous media [72] and from flat surfaces with neutron reflectivity [73] and optical reflectometry [74]. The fraction of segments bound to the solid surface is nicely revealed in NMR studies [75], infrared spectroscopy [76], and electron spin resonance [77]. An example of the concentration profile obtained by inverting neutron scattering measurements appears in Fig. XI-7, showing a typical surface volume fraction of 0.25 and layer thickness of 10-15 nm. The profile decays rapidly and monotonically but does not exhibit power-law scaling [70]. 

This chapter and the two that follow are introduced at this time to illustrate some of the many extensive areas in which there are important applications of surface chemistry. Friction and lubrication as topics properly deserve mention in a textbook on surface chemistiy, partly because these subjects do involve surfaces directly and partly because many aspects of lubrication depend on the properties of surface films. The subject of adhesion is treated briefly in this chapter mainly because it, too, depends greatly on the behavior of surface films at a solid interface and also because friction and adhesion have some interrelations. Studies of the interaction between two solid surfaces, with or without an intervening liquid phase, have been stimulated in recent years by the development of equipment capable of the direct measurement of the forces between macroscopic bodies. 

TWo limiting conditions exist where lubrication is used. In the first case, the oil film is thick enough so that the surface regions are essentially independent of each other, and the coefficient of friction depends on the hydrodynamic properties, especially the viscosity, of the oil. Amontons law is not involved in this situation, nor is the specific nature of the solid surfaces. 

D. W. Dwight, M. E. Counts, and J. P. Wightman, Colloid and Interface Science, Vol. ni. Adsorption, Catalysis, Solid Surfaces, Wetting, Surface Tension, and Water, Academic, New York, 1976, p. 143. 

Clearly, it is important that there be a large contact angle at the solid particle-solution-air interface. Some minerals, such as graphite and sulfur, are naturally hydrophobic, but even with these it has been advantageous to add materials to the system that will adsorb to give a hydrophobic film on the solid surface. (Effects can be complicated—sulfur notability oscillates with the number of preadsoibed monolayers of hydrocarbons such as n-heptane [76].) The use of surface modifiers or collectors is, of course, essential in the case of naturally hydrophilic minerals such as silica. 

The cleaning process proceeds by one of three primary mechanisms solubilization, emulsification, and roll-up [229]. In solubilization the oily phase partitions into surfactant micelles that desorb from the solid surface and diffuse into the bulk. As mentioned above, there is a body of theoretical work on solubilization [146, 147] and numerous experimental studies by a variety of spectroscopic techniques [143-145,230]. Emulsification involves the formation and removal of an emulsion at the oil-water interface the removal step may involve hydrodynamic as well as surface chemical forces. Emulsion formation is covered in Chapter XIV. In roll-up the surfactant reduces the contact angle of the liquid soil or the surface free energy of a solid particle aiding its detachment and subsequent removal by hydrodynamic forces. Adam and Stevenson s beautiful photographs illustrate roll-up of lanoline on wood fibers [231]. In order to achieve roll-up, one requires the surface free energies for soil detachment illustrated in Fig. XIII-14 to obey... 

All gases below their critical temperature tend to adsorb as a result of general van der Waals interactions with the solid surface. In this case of physical adsorption, as it is called, interest centers on the size and nature of adsorbent-adsorbate interactions and on those between adsorbate molecules. There is concern about the degree of heterogeneity of the surface and with the extent to which adsorbed molecules possess translational and internal degrees of freedom. 

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