Types of Phases in Binary Systems

Types of Phases in Binary Systems.—A two-component system, like a system with a single component, can exist in solid, liquid, and gaseous phases. The gas phase, of course, is perfectly simple it is simply a mixture of the gas phases of the two components. Our treatment of chemical equilibrium in gases, in Chap. X, includes this as a special case. Any two gases can mix in any proportions in a stable way, so long as they cannot react chemically, and we shall assume only the simple case where the two components do not react in the gaseous phase. 

Different dipole liquids, similarly, attract each others molecules by suitable orientation of the dipoles and form stable solutions. We have already mentioned the case of alcohol and water. In ammonia and water, the interaction between neighboring ammonia and water molecules is so strong that they form the ammonium complex, leading to NH4OH 

In the metals, the same type of interatomic force acts between atom of different metals that acts between atoms of a single element. We have already stated that for this reason liquid solutions of many metals with each other exist in wide ranges of composition. There, are many other cases in which two substances ordinarily solid at room temperature are soluble in each other when liquefied. Thus, a great variety of molten ionic crystals are soluble in each other. And among the silicates and other substances held by valence bonds, the liquid phase permits a wide range of compositions. This is familiar from the glasses, which can have a continuous variability of composition and which can then supercool to essentially solid form, still with quite arbitrary compositions, and yet perfectly homogeneous structure. 

Solid phases of binary systems, like the liquid phases, are very commonly of variable composition. Here, as with the liquid, the stable range of composition is larger, the more similar the two components are. This of course is quite c-ontrary to the chemists notion of definite chemical composition, definite structural formulas, etc., but those notions are really of extremely limited application. It happens that the solid phases in the system water—ionic compound are often of rather definite composition, and it is largely from this rather special case that the idea of definite compositions in solids has become so firmly rooted. In such a system, there are normally two solid phases ice and the crystalline ionic compound. Ice can take up practically none of any ionic compound, so that it has practically no range of compositions. And many ionic crystals 

Water and ionic compounds are very different types of substances, and it is not unnatural that they do not form solids of variable composition. The reason why water solutions of ionic substances exist is that the water molecules can rotate so as to be attracted to the ions this is not allowed in the solid, where the ice structure demands a fairly definite orientation of the molecule. But as soon as we think about solid phases of a mixture of similar components, we find that almost all the solid phases exist over quite a range. Such phases are often called by the chemists solid solutions, to distinguish them from chemical compounds. This distinction is valid if we mean by a chemical compound a phase which really exists at only a quite definite composition. But the chemists, and particularly the metallurgists, are not always careful about making this distinction for this reason the notation is misleading, and we shall not often use it. 

---