Solid-solution

CaTiOs-LnAlOs (Ln = Nd, Sm, La) sohd solution ceramics have attracted much interest due to their broad and promising application perspectives as dielectric ceramics used in resonators. 

When most of the water in the solution was evaporated, the sol transformed into a gel. Then, the gel was dried at 180 °C for hours to become a dark brown sponge xerogel. Finally, the xerogel was pulverized and thermally treated at 600-900 °C for 3 h to obtain fine powders. 

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Vegard s law In phases in which there is a range of composition of solid solution then the cell dimensions vary linearly with the molar proportions of the constituents. The (aw is rarely followed exactly. 

The solid phase can be considered as a pure substance or a solid solution. 

Metals A and B form an alloy or solid solution. To take a hypothetical case, suppose that the structure is simple cubic, so that each interior atom has six nearest neighbors and each surface atom has five. A particular alloy has a bulk mole fraction XA = 0.50, the side of the unit cell is 4.0 A, and the energies of vaporization Ea and Eb are 30 and 35 kcal/mol for the respective pure metals. The A—A bond energy is aa and the B—B bond energy is bb assume that ab = j( aa + bb)- Calculate the surface energy as a function of surface composition. What should the surface composition be at 0 K In what direction should it change on heaf)pg, and why ... 

The adsorption of nonelectrolytes at the solid-solution interface may be viewed in terms of two somewhat different physical pictures. In the first, the adsorption is confined to a monolayer next to the surface, with the implication that succeeding layers are virtually normal bulk solution. The picture is similar to that for the chemisorption of gases (see Chapter XVIII) and arises under the assumption that solute-solid interactions decay very rapidly with distance. Unlike the chemisorption of gases, however, the heat of adsorption from solution is usually small it is more comparable with heats of solution than with chemical bond energies. 

There is a number of very pleasing and instructive relationships between adsorption from a binary solution at the solid-solution interface and that at the solution-vapor and the solid-vapor interfaces. The subject is sufficiently specialized, however, that the reader is referred to the general references and, in particular, to Ref. 153. Finally, some studies on the effect of high pressure (up to several thousand atmospheres) on binary adsorption isotherms have been reported [154]. Quite appreciable effects were found, indicating that significant partial molal volume changes may occur on adsorption. 

There is a large volume of contemporary literature dealing with the structure and chemical properties of species adsorbed at the solid-solution interface, making use of various spectroscopic and laser excitation techniques. Much of it is phenomenologically oriented and does not contribute in any clear way to the surface chemistry of the system included are many studies aimed at the eventual achievement of solar energy conversion. What follows here is a summary of a small fraction of this literature, consisting of references which are representative and which also yield some specific information about the adsorbed state. 

The adsorption of detergent-type molecules on fabrics and at the solid-solution interface in general shows a complexity that might be mentioned briefly. Some fairly characteristic data are shown in Fig. XlIl-15 [242]. There is a break at point A, marking a sudden increase in slope, followed by a maximum in the amount adsorbed. The problem is that if such data represent true equilibrium in a two-component system, it is possible to argue a second law violation (note Problem Xni-14) (although see Ref. 243). 

Contact angle is proportional to (ysv - 7sl), therefore addition of a surfactant that adsorbs at the solid-solution interface should decrease ysL d therefore increase the quantity above and make 6 smaller. Yet such addition in flotation systems increases 6. Discuss what is inconect or misleading about the opening statement. 

Another method by which metals can be protected from corrosion is called alloying. An alloy is a multicomponent solid solution whose physical and chemical properties can be tailored by varying the alloy composition. 

Cizeron J and Pileni MP 1997 Solid solution of Cd ZnS nanosized partioles photophysioal properties J. Phys. Chem. B 101 8887... 

System in which the two components form a continuous series of solid solutions. In all the preceding examples the individual components (A or B or A By) form separate crystals when solidifying from the melt. There are, however, a number of examples of the separation of a homogeneous solid solution of A and B (or A and A By, etc.). 

The general case of two compounds forming a continuous series of solid solutions may now be considered. The components are completely miscible in the sohd state and also in the hquid state. Three different types of curves are known. The most important is that in which the freezing points (or melting points) of all mixtures lie between the freezing points (or melting points) of the pure components. The equilibrium diagram is shown in Fig. 7, 76, 1. The hquidus curve portrays the composition of the hquid phase in equihbrium with sohd, the composition of... 

Two other types of equilibrium curves are occasionally encountered with the system of two components forming a continuous series of solid solutions. These are shown in Figs. 1,16, 3 and 1,16, 4. In the former the freezing or melting curve passes through a minimum (examples p-chloroiodobenzene, m.p. 57° - p-dichlorobenzene, m.p. 53° naphtha-... 

The tables in this section contain values of the enthalpy and Gibbs energy of formation, entropy, and heat capacity at 298.15 K (25°C). No values are given in these tables for metal alloys or other solid solutions, for fused salts, or for substances of undefined chemical composition. 

The stoichiometry must be exact. Coprecipitation by solid-solution formation, foreign ion entrapment, and adsorption are possible sources of error. 

Schematic model of the solid-solution interface at a particle of AgCI in a solution containing excess AgNOa.

The ablated vapors constitute an aerosol that can be examined using a secondary ionization source. Thus, passing the aerosol into a plasma torch provides an excellent means of ionization, and by such methods isotope patterns or ratios are readily measurable from otherwise intractable materials such as bone or ceramics. If the sample examined is dissolved as a solid solution in a matrix, the rapid expansion of the matrix, often an organic acid, covolatilizes the entrained sample. Proton transfer from the matrix occurs to give protonated molecular ions of the sample. Normally thermally unstable, polar biomolecules such as proteins give good yields of protonated ions. This is the basis of matrix-assisted laser desorption ionization (MALDI). 

This is an expression of Raoult s law which we have used previously. Freezing point depression. A solute which does not form solid solutions with the solvent and is therefore excluded from the solid phase lowers the freezing point of the solvent. It is the chemical potential of the solvent which is lowered by the solute, so the pure solvent reaches the same (lower) value at a lower temperature. At equilibrium... 

Forms series of solid solutions forms Na202 at 250°C. Value is estimated. 

Binary Alloys. Aluminum-rich binary phase diagrams show tliree types of reaction between liquid alloy, aluminum solid solution, and otlier phases eutectic, peritectic, and monotectic. Table 16 gives representative data for reactions in tlie systems Al—Al. Diagrams are shown in Figures 10—19. Compilations of phase diagrams may be found in reference 41. 

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