Class-I SOLID SOLUTION

SOLUTION: In chemistry, a solution is a homogeneous mixture composed of only one phase. In such a mixture, a solute is dissolved in another substance, known as a solvent. The solvent does the dissolving. Types of solution (mixtures of solvents and solutes): Homogeneous solution or mixture means that the components of the mixture form a single phase. The properties of the mixture (concentration, temperature, density, etc) can be uniformly distributed through the volume but only in absence of diffusion phenomena or after their completion. Usually, the substance present in the greatest amount is considered the solvent. Solvents can be gases, liquids, or solids. One or more components present in the solution other than the solvent are called solutes. The solution has the same physical state as the solvent. There are three possible conditions for solid solution: 1) Unsaturated Solution: If the solvent is dissolving less of the solute than it could dissolve at a given temperature and pressure, it is said to be unsaturated. 2) Saturated Solution: If it is dissolving the limiting amount of solute, it is saturated 3) Supersaturated Solution: If it is dissolving more of the solute than it should, under equilibrium conditions, the solution is super saturated. This condition may be accomplished by doing work on the solution, such as stirring or preventing equilibrium conditions by rapidly cooling the solution. The separated condition is an unstable one and it becomes stable if

a) Given enough time or b) Little energy The supersaturated solution become stable or started by rejecting or precipitating the excess solute. Gas: If the solvent is a gas, only gases are dissolved under any given set of conditions. An example of a gaseous solution is air (oxygen and other gases dissolved in nitrogen). Since interactions between molecules play almost no role, dilute gases form rather trivial solutions. In part of the literature, they are not even classified as solutions, but addressed as mixtures. Liquid: If the solvent is a liquid, then gases, liquids, and solids can be dissolved. Examples are: 1) Gas in liquid: a) Oxygen in water. b) Carbon dioxide in water is a less simple example, because the solution is accompanied by a chemical reaction (formation of ions). Note also that the visible bubbles in carbonated water are not the dissolved gas, but only an effervescence of carbon dioxide that has come out of solution; the dissolved gas itself is not visible since it is dissolved on a molecular level. 2) Liquid in liquid: a) The mixing of two or more substances of the same chemistry but different concentrations to form a constant (Homogenization of solutions) b) Alcoholic beverages are basically solutions of ethanol in water. 3) Solid in liquid: a) Sucrose (table sugar) in water b) Sodium chloride or any other salt in water forms an electrolyte: When dissolving, salt dissociates into ions. 2

Counter examples are provided by liquid mixtures that are not homogeneous: colloids, suspensions, emulsions are not considered solutions. Body fluids are examples for complex liquid solutions, containing many different solutes. They are electrolytes since they contain solute ions (e.g. potassium and sodium). Furthermore, they contain solute molecules like sugar and urea. Oxygen and carbon dioxide are also essential components of blood chemistry, where significant changes in their concentrations can be a sign of illness or injury. Solid: If the solvent is a solid then the gases, liquids, and solids can be dissolved. 1) Gas in solid: Hydrogen dissolves rather well in metals, especially in palladium; this is studied as a means of hydrogen storage. 2) Liquid in solid: a) Mercury in gold, forming an amalgam b) Hexane in paraffin wax 3) Solid in solid: a) Steel, basically a solution of carbon atoms in a crystalline matrix of iron atoms. b) Alloys like bronze and many others. c) Polymers containing plasticizers. SOLID SOLUTION INTRODUCTION A solid solution is a solid-state solution of one or more solutes in a solvent. Such a mixture is considered a solution rather than a compound when the crystal structure of the solvent remains unchanged by addition of the solutes, and when the mixture remains in a single homogeneous phase. This often happens when the two elements (generally metals) involved are close together on the periodic table; conversely, a chemical compound is generally a result of the non proximity of the two metals involved on the periodic table. 3

DETAILS The solute may incorporate into the solvent crystal lattice substitutionally, by replacing a solvent particle in the lattice, or interstitially, by fitting into the space between solvent particles. Both of these types of solid solution affect the properties of the material by distorting the crystal lattice and disrupting the physical and electrical homogeneity of the solvent material. Some mixtures will readily form solid solutions over a range of concentrations, while other mixtures will not form solid solutions at all. The propensity for any two substances to form a solid solution is a complicated matter involving the chemical, crystallographic, and quantum properties of the substances in question. Solid solutions, in accordance with the Hume-Rotherys rules, may form if the solute and solvent have:

Similar atomic radii (15% or less difference) Same crystal structure Similar electronegativities Similar valency

Fig. 1 A binary phase diagram displaying Fig. 2 This binary phase diagram shows two solid solutions over The full range of Solid solutions: and . relative concentrations

The phase diagram in Fig. 1 displays an alloy of two metals which forms a solid solution at all relative concentration of the two species. In this case, the pure phase of each element is of the same crystal structure, and the similar properties of the two elements allow for unbiased substitution through the full range of relative concentrations. Solid solutions have important commercial and industrial application, as such mixtures often have superior properties to pure materials. Many metal alloys are solid solutions. Even small amounts of solute can affect the electrical and physical properties of the solvent. The binary phase diagram in Fig. 2 at right shows the phases of a mixture of two substances in varying concentrations, and . The region labeled "" is a solid solution, with

acting as the solute in a matrix of . On the other end of the concentration scale,

the region labeled "" is also a solid solution, with acting as the solute in a matrix of . The large solid region in between the and solid solutions, labeled " and ", is not a solid solution. Instead, an examination of the microstructure of a mixture in this range would reveal two phases, solid solution separate phases, perhaps lamella or grains. The extent to which the components of an alloy are miscible depends on the interaction between the atoms. 1) if the elements do not tend to bond to each other, then separate phases will form with limited miscibility 2) If strong mutual attraction occurs, a single crystal of a different structure can form, such as in intermetallic compounds. 3) It there is little difference in like and unlike bonds, then a solid solution can occur, over a wide range of chemical compositions. In this solid solution, different types of atoms/molecules exist in the same crystal lattice. Eg. Of solid solution: Cu-Ni system

-in- and solid solution -in- would form

Cu-Ni phase diagram: Both the metals are completely soluble in each other. The phase is a substitutional solid solution. This occurs because both the Cu and Ni form FCC structure, and have similar atomic radii, electronegativities and valences. Cu and Ni show very different physical properties in their pure states, and the phase provides a continuous change between the extremes. Other systems can exist as multiple phases, and revert to a single solid solution at high temperature. The thermodynamic factors influencing such transitions are discussed. With a liquid, it is easy to visualize the atoms or molecules moving past one another. With solids, the crystalline lattice is not completely static. Atom can move through the lattice by solid state diffusion. This involves swapping of atoms, interstitial atoms and motion of vacancies. These mechanisms are thermally activated. The lattice structure of solid solution is basically that of the solvent with slight changes in lattice parameter. An expansion results if the solute atom is lager than the solvent atom and a contraction if the solute atom is smaller. There is usually a considerable difference in the solubility of the solute in the liquid and solid states of the solution. The solutes are more stable in the liquid than in the solid state. TYPES OF SOLID SOLUTION:

1) Substitutional solid solution: In this type of solution, the atoms of the solute substitute for atoms of the solvent in the lattice structure of the solvent. eg.: Ag atoms may substitute for Au atoms without loosing the FCC structure of Au and vice-versa.

There are four factors that affect the solid solubility limit: a) Crystal Structure Factor: Complete solid solubility is never attained unless the elements have the same type of crystal lattice structure. b) Relative Size Factor: It is said by Hume-Rothery that the atomic size difference in between constituent elements should be < 15%. i) It is observed that if the relative size factor is > 8% but <15% then the alloy system shows a minimum. ii) If the atomic size difference between solute and solvent is > 15% then solid solution formation is very limited. eg: Ag (FCC) and Pb (FCC) system: The relative size factor between them is about 20%. The solubility of Pb in solid Ag is 1.5 and the solubility of Ag in solid Pb is 0.1%. Sb(rhombohedral) and Bi(rhombohedral) are completely soluble in each other. The relative size factor is about 7%. However, the solubility of Sb in FCC Al is less than 0.1%, although the relative size factor is only about 2. c) Chemical Affinity Factor: The greater the chemical affinity of two metals, the more restricted is their solid solubility and greater in the tendency toward compound formation. Generally, the further apart the elements are in the periodic table, the greater is their chemical affinity. d) Relative Valence Factor: If the solute metal has a different valence from that of the solvent metal, the number of valence electrons per atom, called the electron ratio, will be changed. A metal of lower valence tends to dissolve more o the metal of higher valence than vice versa.

eg.: Al-Ni alloy system Ni-1.24 Al- 1.43 Relative size factor is about 14%. Ni is lower in valence than Al. Ni dissolves 5% Al and Al dissolves 0.04% Ni. Lattice Changes: An expansion results if the solute atom is larger than solvent atoms. A contradiction results if the solute atom is smaller than solvent atoms. 2) Interstitial Solid Solution: Solute atoms occupy the interstices of solvent lattice. Solute atom with size < 1 are likely to form interstitial solid solutions. Eg.: H (0.46 ), B (0.97 ) C (0.77 ) N2 (0.71 ) and O2 ( 0.60 ) SOLUBILITY The ability of one compound to dissolve in another compound is called solubility. When a liquid is able to completely dissolve in another liquid the two liquids are miscible. Two substances that can never mix to form a solution are called immiscible. All solutions have positive entropy of mixing. The interactions between different molecules or ions may be energetically favored or not. If interactions are unfavorable, then the free energy decreases with increasing solute concentration. At some point the energy loss outweighs the entropy gain, and no more solute particles can be dissolved; the solution is said to be saturated. However, the point at which a solution can become saturated can change significantly with different environmental factors, such as temperature, pressure, and contamination. For some solute-solvent combinations a supersaturated solution can be prepared by raising the solubility (for example by increasing the temperature) to dissolve more solute, and then lowering it (for example by cooling).

Usually, the greater the temperature of the solvent, the more of a given solid solute it can dissolve. However, most gases and some compounds exhibit solubilities that decrease with increased temperature. Such behavior is a result of an exothermic enthalpy of solution. Some surfactants exhibit this behaviour. The solubility of liquids in liquids is generally less temperature- sensitive than that of solids or gases. APPLICATION In the phase diagram, the unalloyed extreme left and right concentrations, and the dip in the center, the material will be solid and become liquid as heat is added, where at other proportions the material will enter a mushy or pasty phase. The mixture at dip point of the diagram is called a eutectic alloy. Lead-tin mixtures formulated at that point (37/63 mixture) are useful when soldering electronic components, particularly if done manually, since the solid phase is quickly entered as the solder cools. In contrast, when lead-tin mixtures were used to solder seams in automobile bodies a pasty state enabled a shape to be formed with a wooden paddle or tool, so a 70-30 lead to tin ratio was used. (Lead is being removed from such applications owing to its toxicity and consequent difficulty in recycling devices and components that include lead.) EXSOLUTION When a solid solution becomes unstable due to a lower temperature, for example, exsolution occurs and the two phases separate into distinct microscopic to megascopic lamellae. This is mainly caused due to difference in cation size. Cations that have a large difference in radii are not likely to readily substitute. Take the alkali feldspar minerals for example, albite, NaAlSi3O8 and microcline, KAlSi3O8. At high temperatures Na+ and K+ readily substitute for each other and so the minerals will form a solid solution, yet at low temperatures albite can only substitute a small amount of K+ and the same applies for Na+ in the microcline, this leads to exsolution where they will separate into two separate phases. In the case of the alkali feldspar minerals, thin white albite layers will alternate between typically pink microcline.