Solid at the surface

A vacuum rotary-drum filter consists of a porous septum that surrounds an empty rotating drum. The bottom of the drum is immersed in the sludge liquor. A vacuum pulled on the inside of the drum causes the water to enter the drum through the filter medium. The solids that cannot pass through are retained on the surface of the medium. As the drum rotates, the solids at the surface of the septum are lifted out of... 

The symbol (s) designates a solid. At the surface of the precipitate, Ag+ anc Cl ions are constantly going into solution and redepositing from the solution. Because this is an equilibrium process, we can apply the mathematical relation... 

The increased rapidity of solution of a solid at the surface of a liquid solvent, resulting in the etching away of that part of a rod of solid at the place where it is surrounded by the liquid surface, was noticed with camphor in water it is a real effect and is not due to convection currents of denser solution falling away from the surface. It seems to be caused by surface forces causing a direct passage of molecules from the solid to the liquid surface, since it is shown by benzo-phenone in contact with mercury, in which benzophenone is insoluble. ... 

Boundary conditions with distribution coefficient. When Eq. (6.6-7) was derived, the distribution coefficient K between the liquid and the solid at the surface interface was 1.0. The distribution coelTicient as shown in Fig. 6.6-3 is defined as... 

In Fig. 7.1-3a the concentration c, in the liquid adjacent to the solid and c,- in the solid at the surface are in equilibrium and also equal. However, unlike heat transfer, where the temperatures are equal, the concentrations are in equilibrium and are related by... 

Fig. 13.11. A schematic representation of the complex situation near a crystal-solution interface. Shows solute molecnles with variable conformation in the bulk solution, partial structuring of solute molecules near the interface, and solute, solvent and impurity particles adsorbed on the solid surface. The structure of the solid at the surface may be different from the bulk solid structure.

In this subclass of reactions, solid A reacts with a liquid. However, if the newly produced solid is soluble in the liquid, the reaction does not belong to the class of reactions characterized by the formation of a new solid at the surface of the first one. As a matter of fact, in this case the reaction proceeds as the dissolution and then the... 

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 ... 

We suppose that the Gibbs dividing surface (see Section III-5) is located at the surface of the solid (with the implication that the solid itself is not soluble). It follows that the surface excess F, according to this definition, is given by (see Problem XI-9)... 

A still different approach to multilayer adsorption considers that there is a potential field at the surface of a solid into which adsorbate molecules fall. The adsorbed layer thus resembles the atmosphere of a planet—it is most compressed at the surface of the solid and decreases in density outward. The general idea is quite old, but was first formalized by Polanyi in about 1914—see Brunauer [34]. As illustrated in Fig. XVII-12, one can draw surfaces of equipo-tential that appear as lines in a cross-sectional view of the surface region. The space between each set of equipotential surfaces corresponds to a definite volume, and there will thus be a relationship between potential U and volume 0. 

A monolayer can be regarded as a special case in which the potential is a square well however, the potential well may take other forms. Of particular interest now is the case of multilayer adsorption, and a reasonable assumption is that the principal interaction between the solid and the adsorbate is of the dispersion type, so that for a plane solid surface the potential should decrease with the inverse cube of the distance (see Section VI-3A). To avoid having an infinite potential at the surface, the potential function may be written... 

Since solids do not exist as truly infinite systems, there are issues related to their temiination (i.e. surfaces). However, in most cases, the existence of a surface does not strongly affect the properties of the crystal as a whole. The number of atoms in the interior of a cluster scale as the cube of the size of the specimen while the number of surface atoms scale as the square of the size of the specimen. For a sample of macroscopic size, the number of interior atoms vastly exceeds the number of atoms at the surface. On the other hand, there are interesting properties of the surface of condensed matter systems that have no analogue in atomic or molecular systems. For example, electronic states can exist that trap electrons at the interface between a solid and the vacuum [1]. 

The three-dimensional synnnetry that is present in the bulk of a crystalline solid is abruptly lost at the surface. In order to minimize the surface energy, the themiodynamically stable surface atomic structures of many materials differ considerably from the structure of the bulk. These materials are still crystalline at the surface, in that one can define a two-dimensional surface unit cell parallel to the surface, but the atomic positions in the unit cell differ from those of the bulk structure. Such a change in the local structure at the surface is called a reconstruction. 

In order to understand the tendency to fomi a dipole layer at the surface, imagine a solid that has been cleaved to expose a surface. If the truncated electron distribution originally present within the sample does not relax, this produces a steplike change in the electron density at the newly created surface (figme B1.26.19(A)). 

Krypton clathrates have been prepared with hydroquinone and phenol. 85Kr has found recent application in chemical analysis. By imbedding the isotope in various solids, kryptonates are formed. The activity of these kryptonates is sensitive to chemical reactions at the surface. Estimates of the concentration of reactants are therefore made possible. Krypton is used in certain photographic flash lamps for high-speed photography. Uses thus far have been limited because of its high cost. Krypton gas presently costs about 30/1. 

Sodium cyanide does not dissolve m butyl bromide The two reactants contact each other only at the surface of the solid sodium cyanide and the rate of reaction under these con ditions IS too slow to be of synthetic value Dissolving the sodium cyanide m water is of little help because butyl bromide is not soluble m water and reaction can occur only at the interface between the two phases Adding a small amount of benzyltrimethyl ammonium chlonde however causes pentanemtnle to form rapidly even at room temper ature The quaternary ammonium salt is acting as a catalyst it increases the reaction rate How7... 

The enhanced concentration at the surface accounts, in part, for the catalytic activity shown by many solid surfaces, and it is also the basis of the application of adsorbents for low pressure storage of permanent gases such as methane. However, most of the important applications of adsorption depend on the selectivity, ie, the difference in the affinity of the surface for different components. As a result of this selectivity, adsorption offers, at least in principle, a relatively straightforward means of purification (removal of an undesirable trace component from a fluid mixture) and a potentially useflil means of bulk separation. 

Filtered-Particle Inspection. Solids containing extensive inteiconnected porosity, eg, sintered metallic or fired ceramic bodies formed of particles that ate typically of 0.15-mm (100-mesh) screen size, are not inspectable by normal Hquid penetrant methods. The preferred test medium consists of a suspension of dyed soHd particles, which may be contained in a Hquid vehicle dyed with a different color. Test indications can form wherever suspensions can enter cracks and other discontinuities open to the surface and be absorbed in porous material along interior crack walls. The soHd particles that form test indications ate removed by filtration along the line of the crack at the surface where they form color or fluorescent indications visible under near-ultraviolet light (1,3). 

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