Solids as solution

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

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). 

The distribution-coefficient concept is commonly applied to fractional solidification of eutectic systems in the ultrapure portion of the phase diagram. If the quantity of impurity entrapped in the solid phase for whatever reason is proportional to that contained in the melt, then assumption of a constant k is valid. It should be noted that the theoretical yield of a component exhibiting binary eutectic behavior is fixed by the feed composition and position of the eutectic. Also, in contrast to the case of a solid solution, only one component can be obtained in a pure form. 

The dominant mechanism of purification for column ciystallization of sohd-solution systems is reciystallization. The rate of mass transfer resulting from reciystallization is related to the concentrations of the solid phase and free hquid which are in intimate contac t. A model based on height-of-transfer-unit (HTU) concepts representing the composition profQe in the purification sec tion for the high-melting component of a binaiy solid-solution system has been reported by Powers et al. (in Zief and Wilcox, op. cit., p. 363) for total-reflux operation. Typical data for the purification of a solid-solution system, azobenzene-stilbene, are shown in Fig. 22-10. The column ciystallizer was operated... 

Questions of the analytic control of maintenance of the bivalent metals cations to their joint presence in materials of diverse fixing always were actual. A simultaneous presence in their composition of two cations with like descriptions makes analysis by sufficiently complicated process. Determination of composition still more complicates, if analyzed object is a solid solution, in which side by side with pair of cations (for example, Mg " -Co ", Mn -Co, Zn -Co ) attends diphosphate anion. Their analysis demands for individual approach to working of methods using to each concrete cations pair. 

An effect which is frequently encountered in oxide catalysts is that of promoters on the activity. An example of this is the small addition of lidrium oxide, Li20 which promotes, or increases, the catalytic activity of dre alkaline earth oxide BaO. Although little is known about the exact role of lithium on the surface structure of BaO, it would seem plausible that this effect is due to the introduction of more oxygen vacancies on the surface. This effect is well known in the chemistry of solid oxides. For example, the addition of lithium oxide to nickel oxide, in which a solid solution is formed, causes an increase in the concentration of dre major point defect which is the Ni + ion. Since the valency of dre cation in dre alkaline earth oxides can only take the value two the incorporation of lithium oxide in solid solution can only lead to oxygen vacaircy formation. Schematic equations for the two processes are... 

In the examples given below, the physical effects are described of an order-disorder transformation which does not change the overall composition, the separation of an inter-metallic compound from a solid solution the range of which decreases as the temperature decreases, and die separation of an alloy into two phases by spinodal decomposition. 

These two processes provide examples of the moving boundary problem in diffusing systems in which a solid solution precedes the formation of a compound. The diickness of the separate phase of the product, carbide or... 

In the kinetics of formation of carbides by reaction of the metal widr CH4, the diffusion equation is solved for the general case where carbon is dissolved into tire metal forming a solid solution, until the concentration at the surface reaches saturation, when a solid carbide phase begins to develop on the free surface. If tire carbide has a tirickness at a given instant and the diffusion coefficient of carbon is D in the metal and D in the carbide. Pick s 2nd law may be written in the form (Figure 8.1)... 

The equation for the rate of oxidation of the transition metals at high temperatures, which form a solid solution of oxygen before the oxide appears at the surface has die same form as that derived for die carburizing of die metal, and... 

A phase is a region of material that has uniform physical and chemical properties. Phases are often given Greek symbols, like a or fi. But when a phase consists of a solid solution of an alloying element in a host metal, a clearer symbol can be used. As an example, the phases in the lead-tin system may be symbolised as (Pb) - for the solution of tin in lead, and (Sn) - for the solution of lead in tin. 

Fig. 3.1. The phase diagram for the lead-tin alloy system. There ore three phases L - a liquid solution of lead and tin (Pb) - a solid solution of tin in lead and (Sn) - o solid solution of lead in tin. The diagram is divided up into six fields - three of them are single-phase, and three ore two-phose.

When other elements dissolve in a metal to form a solid solution they make the metal harder. The solute atoms differ in size, stiffness and charge from the solvent atoms. Because of this the randomly distributed solute atoms interact with dislocations and make it harder for them to move. The theory of solution hardening is rather complicated, but it predicts the following result for the yield strength... 

The alloy aluminium-4 wt% copper forms the basis of the 2000 series (Duralumin, or Dural for short). It melts at about 650°C. At 500°C, solid A1 dissolves as much as 4 wt% of Cu completely. At 20°C its equilibrium solubility is only 0.1 wt% Cu. If the material is slowly cooled from 500°C to 20°C, 4 wt% - 0.1 wt% = 3.9 wt% copper separates out from the aluminium as large lumps of a new phase not pure copper, but of the compound CuAlj. If, instead, the material is quenched (cooled very rapidly, often by dropping it into cold water) from 500°C to 20°C, there is not time for the dissolved copper atoms to move together, by diffusion, to form CuAlj, and the alloy remains a solid solution. 

A new, low-pressure, plasma-assisted proeess for synthesising diamonds has been found by Roy et al [83,84]. An intimate mixture of various forms of carbon with one of many metals (e.g., Au, Ag, Fe, Cu, Ni) is exposed to a microwave plasma derived from pure hydrogen at temperatures ranging from 600-1000 °C. Roy et al postulate a mechanism in which a solid solution of atomic hydrogen and the metal. Me, facilitates dissolution of carbon to form molten droplets of Me -Cj,-H. Diamonds nucleate at the surface of the droplets as the temperature is reduced. 

Parting—the selective attack of one or more constituents of a solid solution alloy. 

The morphology of globular type is the most favourable when superplastic deformation is to occur in AI78wt%Zn alloy. This type of structure is formed by decomposition of the a solid solution a -> a + P However, plates usually dominate in the structure of this alloy. To obtain the non-plate or globular type, a special heat treatment is neccesary i.e. the optimal cooling rate as well as the temperature and time of ageing. 

In more recent years two new types of antifouling composition have been developed, using organometallic compounds as poisons. In one type, based chiefly on vinyl resin and organotin compounds (e.g. tributyltin fluoride), the poison and resin form a solid solution. As the poison dissolves from the surface of the film, more poison diffuses from deeper in the film to... 

When a pure metal A is alloyed with a small amount of element B, the result is ideally a homogeneous random mixture of the two atomic species A and B, which is known as a solid solution of in 4. The solute B atoms may take up either interstitial or substitutional positions with respect to the solvent atoms A, as illustrated in Figs. 20.37a and b, respectively. Interstitial solid solutions are only formed with solute atoms that are much smaller than the solvent atoms, as is obvious from Fig. 20.37a for the purpose of this section only three interstitial solid solutions are of importance, i.e. Fc-C, Fe-N and Fe-H. On the other hand, the solid solutions formed between two metals, as for example in Cu-Ag and Cu-Ni alloys, are always substitutional (Fig. 20.376). Occasionally, substitutional solid solutions are formed in which the... 

At the same time it is recognized that the pairs of substances which, on mixing, are most likely to obey Raoult s law are those whose particles are most nearly alike and therefore interchangeable. Obviously no species of particles is likely to fulfill this condition better than the isotopes of an element. Among the isotopes of any element the only difference between the various particles is, of course, a nuclear difference among the isotopes of a heavy element the mass difference is trivial and the various species of particles are interchangeable. Whether the element is in its liquid or solid form, the isotopes of a heavy element form an ideal solution. Before discussing this problem we shall first consider the solution of a solid solute in a liquid solvent. 

Plouvier then prepared the previously unknown racemic form of proto-quercitol by mixing equal weights of the two enantiomers. The melting point (237°C.) of the mixture was not depressed, and its (presumably solid state) infrared spectrum reportedly (36) was identical with that of either active form. It thus appears that DL-proto-quercitol exists as a solid solution, not a racemic compound or conglomerate. 

We have already learned that metals may be deformed easily and we have explained this in terms of the absence of directional character in metallic bonding. In view of this principle, it is not surprising that two-element or three-element metallic crystals exist. In some of these, regular arrangements of two or more types of atoms are found. The composition then is expressed in simple integer ratios, so these are called metallic compounds. In other cases, a fraction of the atoms of the major constituent have been replaced by atoms of one or more other elements. Such a substance is called a solid solution. These metals containing two or more types of atoms are called alloys. 

A solid solution of starch in urea may also be employed. Reflux 1 g of soluble starch and 19 g of urea with xylene. At the boiling point of the organic solvent the urea melts with little decomposition, and the starch dissolves in the molten urea. Allow to cool, then remove the solid mass and powder it store the product in a stoppered bottle. A few milligrams of this solid added to an aqueous solution containing iodine then behaves like the usual starch indicator. 

A common feature of all clathrates discussed so far is a host lattice, by itself thermodynamically unstable, which is stabilized by inclusion of the second component. The forces binding this component must be similar in nature to the intermolecular forces in liquids. It seems natural, therefore, to regard a clathrate compound as a solid solution of the second component in the (meta-stable) host lattice. 

The deviation of the heat capacity of a solid solution from the heat capacity calculated by the additivity hypothesis (Kopp-Neumann rule), a quantity of importance for the evaluation of the... 

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