Phase Diagrams

Show the ranges of temperatures (and/or P) and composition over which phases or mixtures of phases of a compound or compounds are stable. Can also show existence of allotropes or polymorphism (solids having same composition, but different structure). Each phase occupies an area of the diagram.

Phase Diagrams
Phase Rule: P + F = C + 2
P = # of phases present in equilibrium. C = # of components needed to describe system. F = degrees of freedom = # of independent variables that can be varied without changing the # or composition of the existing phases.

e.g. to right is 1 component (H2O) phase diagram. P + F = 1 + 2 = 3

A at that point one phase (gas), so 2 degrees of freedom; can change T or P. B at interface of liquid and vapor there are two phases, so 1 degree of freedom; if change T, must also change P. C triple point, so no degrees of freedom; changing either T or P changes composition. D critical point; (vapor) = (liquid). C

Phase Diagrams
First-order phase transition. Move from liquid to vapor; temperature will stop changing at this point until all of the liquid becomes vapor and only then will continue to increase.

Binary Phase Diagram

Phase diagram for two similar components; Tm(B) aka Solid Solution. Assume Pressure = 1 atm, so 2D rather than 3D plot. Two components, so F + P = 2 + 2 = 4 Composition = mole fraction; 100% B to 100% A. Tm(B) = melting point of pure B. Tm(A) = melting point of pure A. Liquidous = boundary between liquid and mixed phase; gives liquid composition. Solidous = boundary between solid and mixed phase; gives solid composition.

Tm(A)

Binary Phase Diagram

Heat mixture of A & B (at mole fraction indicated) to temperature 1. Then cool. At temperature 1, liquid phase has composition = mole fraction. At temperature 2, solid begins to ppt out; solid is mostly B mixed crystal (composition b1). At temperature 3, solid has composition b2 and liquid has composition a2; note different mole fractions! at a given temperature, the liquid and solid that are in equilibrium with each other have different compositions. At temperature 4, solid formed has composition = b3 = original mole fractions.

1 2 3 4

Binary Phase Diagram

Note that on cooling, the solid will change composition from almost pure B to more and more A composition. Coring: freeze in tube from outside; core will have different composition.

mole fraction

Heat & Beat: heat above liquidous, cool below solidous (but not too far), then beat (to make deformities), then reheat almost to solidous (increase diffusion), beat and repeat. Like? Blacksmith.

Binary Phase Diagram

Example of a system involving the formation of mixed crystals with temperature minimum: special point for which the compositions of the solid and liquid are the same. It is possible to have the special point at a temperature maximum.

liquid (1-phase) liquid composition special point solid composition

solid (1-phase)

Eutectic Phase Diagram

What if two substances are NOT similar at all? They wont want to mix in the solid state, but will in the liquid; e.g. NaF & PbF2.
Tm(NaF) liquid

Eutectic Point (cusp) -eutectic mixture has lower

mp than either of the pure components or any other Tm(PbF2) mixture.

NaF(s) + liquid NaF(s) + PbF2(s) dont mix NaF mole fraction

PbF2(s) + liquid

liquidous curve -highest temp. at which

crystals can exist.

PbF2

solidous curve = Eutectic Temperature -lowest temp. at which

liquids can exist.

Eutectic Phase Diagram

Heat above liquidous and cool; first solid is pure NaF; below Eutectic Temperature both solids appear.

Tm(NaF) solid is pure NaF liquid has increasing PbF2 fraction solid PbF2 begins to ppt NaF

liquid Tm(PbF2) NaF(s) + liquid NaF(s) + PbF2(s) dont mix mole fraction PbF2

PbF2(s) + liquid

particles of NaF & PbF2

pure NaF

Phase Diagrams
Have seen two extremes: solid solution, where the two compounds like each other & eutectic mixture, where the two compounds hate each other.

Solid Solution

Eutectic Mixture

What happens as the two compounds get away from these extremes?

Phase Diagram For Two Almost Immiscible Solids

region of solubility of A in B

region of solubility of A in B

always some width

e.g. most soldier is 50:50 Pb/Sn; heat to solid/liquid region; get solid particles in slushy soldier liquid

Phase Diagram If Two Components Form 3rd Compound

Looks like two Eutectic Diagrams next to each other.
new compound melts congruently

Two Eutectic Points

Compound Forms; called line compound