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Short Answer:
Two materials are said to be miscible if when combined they will form a homogeneous mixture. Immiscible refers to inability to mix two liquids or even two solids completely. Gases are always miscible. Oil and water are immiscible and, if mixed, separate into two different phases, the oil phase and the water phase.
Long Answer:
Immiscible means that 2 phases will form - instead of a single homogeneous phase - when mixing 2 components. The thermodynamics of equilibrium tells us that there is no such thing as completely immiscible, but that the 2 phases will always consists of :
- a phase practically composed entirely of the the first component, and containing a small amount of the second component
- a phase practically composed entirely of the the second component, and containing a small amount of the first component
This can be understood intuitively by considering the dynamics of equilibrium formation. Consider water and oil for example. When water is mixed with oil, an interface between the two liquids forms. Because all of the molecules are moving due to thermal motion, at the interface some water molecules will move from the water phase to the oil phase. As soon as there is water in the oil phase, there will be a tendency for this water to return back to the water phase. The water molecules are more strongly attracted to other water molecules than they are to the oil molecules, so it takes some kinetic energy for a water molecule to leave a region where all the neighbors are water and enter a region where all the neighbors are oil. The molecule has lost kinetic energy but gained potential energy due to the intermolecular forces. (The same is true for oil molecules which are more attracted to each other than to water.) Once a water molecule is away from the water region, it undergoes diffusion and randomly moves about in the oil. When that moving about happens to take is close to the interface again, the forces of the other water molecules affect is and its movements are pulled towards the water region again.
The equilibrium will be characterized by equal tendencies for
- the water to leave the water phase
- the water to return from the oil phase to the water phase.
The same reasoning applies to the oil component.
Exactly the same process takes place when we consider a saturated solution of a solid substance in a liquid, while there is still undissolved solid present : at saturation, the tendency of the solid to dissolve into the liquid equals the tendency for the dissolved solid to return to the solid phase.
Scientifically, the magnitude of these tendencies is called the chemical potential - and it is indeed a potential similar to electrical potential. It is a potential that can result in a driving force.
So at equilibrium, the chemical potential for a given component is equal in both phases. Note that the higher the concentration of a component in a given phase, the higher the tendency for it to move to the other phase. In other words : the chemical potential of a given component depends on its concentration.
Thermodynamics enables us to understand this process in detail. Chemical potential turns out to be nothing else than the so-called Gibbs free energy of the component in solution.
Solids can also consist of more than one phase. Since the mobility of components is very low in solids, the time required to reach equilibrium can be very long, even years. The making of alloys of metals for example needs to take this into account as the actual microscopic structure of an alloy may change in time - and as a consequence also its properties - as time goes by. The chemical potential usually depends on temperature, so the equilibrium compositions of phases in 'solid solutions' can change in function of temperature, and so does the microscopic make-up of alloys.
immiscible means the incapable of mixing or attaining homogeneity.
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