THE PHASE RULE

(SOLID SOLUTIONS)
 INTRODUCTION
• In many cases, cooling a molten solution does not result in the formation of a pure
crystal or in the formation of a compound, but a solid solution is obtained.
• The solid solution has the characteristic of a liquid solution in the sense that
particles of one component are distributed at random among the particles of the
other component. But the particles cannot move at random atmost they can
vibrate about fix positions.
• Here, we shall discuss only the substitutional solid solutions.
• This results when particles of one substance are replaced in their latest position by
atoms of another substance.
• In a true substitutional solid solutions, the replacement of atoms of one substance
by atoms of another substrate is at random.
• There is no order such as replacement of every second atom or every third atom.
Such a solid solution is formed by Nickel and copper.
 Factors Influencing Substitution In Solid Solution

1. Size of the atom of the metal.

2. Chemical nature of the metal.

3. Ratio of the number of electrons to atom in the mixture.

 Factors Influencing Substitution In Solid Solution
SIZE OF THE ATOM OF THE METAL
• To form a substitutional solid solution, an atom of one metal must take the place of an atom of another
metal.
• Thus the atomic size of the two metals must be almost the same.
• Only atoms whose radii fall within a certain range can be expected to be accommodated in a particular
lattice.
• Examination of known two-component solid solution indicates that the radii of the two atoms never differ
by more than 15%.
• This does not mean that solid solutions are always formed if the atomic radii are in the desired range;
there are certain other Factors which prevent the formation of solid solution.
• However, if the size of the atoms differ by more than 15%, this alone is sufficient to prevent the formation
of substitutional solid solutions.
• Explanation: If the atom of one metal (solute) were too large, the lattice of the other metal (solvent)
would have to expand to accommodate it. If the atoms were two small, the regularity of the latest would
have to be distorted.
• In either case, there is a limit to the amount of expansion or distortion that a lattice can undergo.
 Factors Influencing Substitution In Solid Solution
CHEMICAL NATURE OF THE METAL

• The two metals should not have very much different first ionization
potentials.
• If the ionization potential values are widely different then crystals of
a compound of the metals are formed (intermetallic crystals).
 Factors Influencing Substitution In Solid Solution
RATIO OF THE NUMBER OF ELECTRONS IN THE OUTER ORBITALS TO THE
NUMBER OF ATOMS IN THE MIXTURE
• If the atoms of two elements in the solid solution are approximately of the same size and if
the elements have similar first ionization potential the electron/atom ratio determines the
nature of the solid solution.
• For the Formation of substitutional solid solution ratio (e/A) of the two metals should be of
the order of 1.4.
 PHASE DIAGRAMS FOR SOLID SOLUTIONS
• Since the two components are miscible
in solid and liquid phases.
• The maximum number of phases which
can exist at equilibrium would be only
two, and phase rule for such a system
will give the minimum number of
degree of freedom at constant pressure
as:
F = 3 ꟷ P = 3 ꟷ 2 = 1.
• Hence an invariant system is impossible
and there will be no singular point that
is discontinued such as eutectic point Fig 1: A continuous series of solid solution.
At point P’ a solid solution of A+B separates out
on the phase diagram. containing larger amount of B as shown by point Q.
 PHASE DIAGRAMS FOR SOLID SOLUTIONS

The completely miscible solid solutions are classified as:

1. Continuous series

2. With maximum melting point (very rare)

3. With minimum melting point.

 PHASE DIAGRAMS FOR SOLID SOLUTIONS
CONTINUOUS SERIES OF SOLID SOLUTIONS
• Fig 1 shows the phase diagram of this type of system.
• The solution has the freezing point between the freezing points of the two components.
• As the liquid solution is cooled the solid separates as a homogenous mixture of the components (A+B).
• The temperature at which the first crop of the Crystal appears is Marked as the freezing point of the solution (first
break in the cooling curve).
• The temperature at which the last trace of the liquid solution disappears is the melting point of the solid solution
(second break in the cooling curve).
• The curve obtained by the plot of the first break versus mole fraction is called the freezing curve or liquidus curve
and the other obtained on potting the second break versus mole fractions is called the melting curve or solidus curve.
• Above the temperature of the liquidus curve (upper one) the system is in the liquid phase, below the solidus the
system is in the solid form.
• Between the liquidus and solidus curve both liquid and solid phase coexist.
• Any point (c) within the region enclosed by the two curves consist of a solid place which is richer in the component
with higher melting point (point b) and a liquid phase richer in the component with lower melting point (point a).
• the relative amount of the two phases is given by the ratio of the segments of the tie line.
 FRACTIONAL CRYSTALLIZATION
• As shown in Fig 1. on cooling a liquid solution with the composition corresponding to point P, the first crop of solid
solution appears at a temperature corresponding to the point P’.
• This solid place has the composition corresponding to point Q. much richer in component B (high melting point) than
the original liquid solution.
• Suppose the solid solution Q is removed from the system and heated to a temperature represented by point R when it
liquefies. when this liquid is allowed to cool upto temperature R’ a solid solution with composition S (much richer in
component B) separate out.
• On Repeating this process it is possible to separate the pure component B in the solid form.
• The remaining liquid left Behind every solidification will be more and more richer in component A (low melting point).
• Thus the method of the fractional crystallization will enable us to separate pure A and B.
• In actual practice the melt is allowed to cool till half of the amount is crystallized.
• The Crystal form is separated and then heated and allowed to cool till half of the liquid has solidified.
• This is repeated many time to get pure solid of high melting point.
• The half of the liquid left in the first crystallization is cooled till half is crystallized; the crystals are removed and the
liquid is allowed to cool till half of it is solidified.
• On Repeating this process the low melting component is obtained in the pure form.
• By this method the separation of Co ꟷ Ni, Au ꟷ Ag, Au ꟷ Pt, Naphthalene ꟷ β-Naphthanol etc. is carried out.