Content

1.0 Introduction
Thermodynamic
2.0 Thermodynamically stable phase
of 3.0 Unary Heterogeneous Systems
Phase Diagram 3.1 P - T Diagram -Unary, Single Component Phase Diagram
3.2 logP – 1/T Diagram -Unary, Single Component Phase Diagram
3.3 Conclusion-Unary p - T Diagrams
3.4 G-T Phase Diagrams
3.4.1 G - T Diagram - Unary, Single Component Phase Diagram – V
3.4.2 - T Diagram - Unary, Single Component Phase Diagram - L, V
3.4.3 - T Diagram - Unary, Single Component Phase Diagram-, L,V
by 3.4.4 - T Diagram - Single Component Phase Diagram -, L, V

Dr. Srimala
1 2

1.0 Introduction
3.5 Metastability
3.6 Chemical Potential and Gibbs Free Energy of Single Component Phases • A phase diagram is a graphical
3.7 Enthalpy & Entropy of Transformation representation of all the
3.8 Compute Phase Equilibria from Free Energy Relations equilibrium phases as a function
of temperature, pressure, and
4.0 Binary System
composition.
4.1 Binary liquid system
4.2 Binary solutions with total solid solubility
4.3 Binary systems without solid solution • Phase diagrams arise from
5.0 Free Energy-Composition (G-X) Diagram
minimizing free energies for each
5.1 Free energy diagrams of total solubility systems phase. They can be used to
5.2 Free energy diagram for binary solutions with a miscibility gap describe gas - liquid – solid
5.3 Free energy diagram of binary systems without solid solution transitions, polymorphic solid-to-
(eutectic system) solid transitions, stable phases in
6.0 Phase boundary Calculations
alloys of different composition,
etc.
3 4

1
 2.0 Thermodynamically Stable Phases
Thermodynamics can be used to predict
weather the system is
in equilibrium and to analyze the
phase stability and phase transformations.
For example, for transformation occurring at constant T and P
the relative stability of the phases in a system is determined by
their Gibbs free energies, ∆G = Gfinal - Ginitial = ∆ H - T ∆ S
∆G < 0 => process is allowed
∆G > 0 => process is forbidden
∆G = 0 => equilibrium
3.0 Unary Heterogeneous Systems
A system is considered to be unary if it consists of a single
chemical component for the range of states under study.
Example CO2 or H2O
Homogeneous system - consists of a single phase
Heterogeneous system - consists of more than one phase
All the elements may exists in at least 3 distinct states of matter or
phase- solid, liquid and gas
Cont….
• Usually, only one phase of a given substance is stable at any
given temperature and pressure.
• At some conditions of temperature and pressure, two or more
phases may exist in equilibrium.
• A slight change in temperature or pressure will favor one phase
over others. The conversion of one phase to another is a phase
transition.
• Phase transitions occur with a decrease (spont.) or no change
(equil.) in Gibbs energy.
5 6
Cont…
Many element exhibit more than one phase form in solid state-
called Allotropes
Example : BCC and FCC structures are allotropic forms of iron
The BCC phase change to FCC iron at 910oC, 1 atm pressure-
called allotropic transformation
In general, Phase Transformation- any change in the phase form
of a system
Example :
•melting or fusion-which change solid to liquid
•boiling or vaporization-which change from liquid to vapour
7 8
2
3. 1 P - T Diagram -Unary, Single Component
Phase Diagram Cont..
Consider phase stability and phase transformation at a
constant pressure, Po, eg. one-atm.

L, liquid Show regions of

, solid L, liquid
, solid stability of crystal
crystal phases in terms
of the state
variables T & P. +L+V
+L+V
V, vapor
V, vapor

TM TV
T (K) T (K)
9 10

Cont….. Cont…
Can change temperature and pressure independently Can pick temperature or pressure (not both)
and remain in region. and the other is fixed by the phase boundary.

L, liquid Two
Single phase
phase
L, liquid
(L,
(, L, V) , solid L+V,
, solid stability
crystal crystal +V)
regions stability
+L+V are 2-D, +L+V regions
an area. V, vapor are 1-D,
a line.
V, vapor
T (K) T (K)
11 12

3
 Cont….. Cont….
Cannot pick temperature or pressure. Both are Metastable extensions of two-phase stability lines extrapolate into
fixed by the triple point. opposite single phase regions.

L, liquid Three
, solid phase L, liquid
(+L+V) , solid
crystal stability crystal
regions
are 0-D,
+L+V V, vapor a point.
+L+V V, vapor

T (K) Note: More than three phases cannot exist

at equilibrium for a unary system. 13 T (K) 14

3.2 logP – 1/T Diagram -Unary, Single Component

Cont…. Phase Diagram
Note the critical point where the properties of the T (K)
liquid and vapor phases merge.
L, liquid
C.P.
X , solid
L, liquid crystal
, solid
crystal
+L+V
V, vapor
+L+V V, vapor

1/T (K-1)
On a plot of logP vs. 1/T the lines for two-phase equilibrium become
T (K) (approx.) straight.
15 16

4
 Cont…. Cont…
Again, consider stability regions for constant pressure conditions. Again, note metastable extensions of two-phase equilibrium
boundaries.
T (K)
T (K)

, solid L, liquid L, liquid

crystal
, solid
TM
TV crystal
1 atm
1 atm
+L+V +L+V
V, vapor V, vapor

1/T (K-1)
1/T (K-1)
17 18

Cont…. Recall Gibbs Phase Rule

Slopes of lines for two-phase equilibria are inversely proportional
to magnitude of volume expansion on heating.
T (K)
For a system at equilibrium,
L, liquid
F=C-P+2
, solid
crystal C = the number of components (1 so far in this chapter)
P = the number of phases present
1 atm F = the number of degrees of freedom (the number of intensive
+L+V variables such as temp, pres, or mol frac that can be changed
V, vapor without disturbing the number of phases in equilibrium)

1/T (K-1) 19 20

5
 Cont …… 3.3 Conclusion-Unary p - T Diagrams
For a one-component system the phase rule becomes
F=3-P
Single phase regions are represented by an area: 2-D & 2 degrees of
freedom.

Degrees of Freedom Components

Two phase equilibria are represented by a line: 1-D & 1 degree of
Phases freedom.
1 2 1 2
Three phase equilibria are represented by a point (the triple point): 0-
2 1 1 2 D & no degrees of freedom.
3 0 1 2
No regions on a P - T diagram show more than 3 phases coexisting at
equilibrium.

Properties of the liquid and vapor phases merge at the critical point.

21 22

Cont… 3.4 G-T Phase Diagrams

Two phase equilibrium boundaries extend into stable single phase G = H - TS,
regions & indicate potential metastable equilibria. so the slope of the lines at left

Slopes of two-phase equilibrium lines increase as the volume = (dG/dT) = -S

Gibbs energy, G
expansion on heating decreases.
This assumes that H and S are
constant with temp.
Slopes of two-phase equilibrium lines are positive for volume
expansions on heating and slopes are negative for volume
contractions. Since S is positive for all phases
of all substances, the slopes are
Two-phase equilibrium boundaries are approximately straight on all negative.
log P vs. I/T diagrams.
Note that the gas phase has the 
steepest slope; the solid phase, the
Temperature least steep.
23 24

6
 Change in Entropy 3.4.1 G - T Diagram - Unary, Single Component Phase
Diagram - V

Relative Entropy Example:

V
Ssteam > Sliquid water > Sice Fixed P

-SV

Third Law Entropies:

All crystals become increasingly ordered as absolute zero is

approached (0K = -273.15°C) and at 0K all atoms are fixed in space
so that entropy is zero.

T (K)
25 26

3.4.2 G - T Diagram - Unary, Single Component Phase

Diagram - L, V Cont….

V Fixed P V/ Fixed P

-SV

L L/
-SL

L L L L/
V V
T (K) T (K) TV
27 28

7
3.4.3 G - T Diagram - Unary, Single Component Phase
Diagram - , L, V Cont…

Fixed P V/ Fixed P

-SV V

 L/
-S  /
L
/
-SL L L/
V
T (K) T (K) TV
29 30

3.4.4 G - T Diagram - Single Component Phase Diagram -

Cont… , L, V

V/ Fixed P V/ Fixed P

L/ L/
TM
/ TS TS
 / /

/  /
L L/ L  / L/

TM
V T / TM V
T (K) T (K) TV
TV
31 32

8
 Cont… Exercise 1.1
Fixed P

Equilibrium Phases and

Transformations, Only Sketch curves representing the variation of the molar Gibbs free
energy with temperature at the pressure corresponding to triple
point for an element. Repeat this sketch for a pressure slightly
above and below the triple point.
 
L
V
/
T TV
T M
T (K)

33 34

Solution 1.1
Solution 1.1
P - T Diagram based on the question

V P (triple pt.)
L, liquid
, solid
Triple
crystal
L Point:
P>Ptriple point a+L+V
+L+V P=Ptriple point 
V, vapor 
P<Ptriple point
L
V

T (K) T (K)
35 36

9
 Solution 1.1 Solution 1.1

V P > P (triple pt.) V P < P (triple pt.)

Melting Boiling Sublimation

L Point: Point: L Point: + V
a+L L+V
  
L 
 L
L V V

T (K) T (K)
37 38

3.5 Metastability
In systems at constant T & P Gibbs free energy is a minimum at
equilibrium.
The phase with the lowest Gibbs free energy is the most stable.
When phases with higher Gibbs free energies form, they are
metastable.
The greater the deviation of their free energies from the stable
phase, the lower the stability of the metastable phase.
Exercise 1.2
• The standard Gibbs energy of formation of metallic white tin (-
tin) is 0 at 25 oC and that of nonmetallic gray tin (-tin) is +0.13
kJ mol-1 at the same temperature. Which is the thermo-
dynamically stable phase at 25 oC?
Solution 1.2:
• The thermodynamically stable phase is the one with the lower
Gibbs energy, which would be the - (white) tin at 25 oC.

39 40

10
 Exercise 1.3 Solution 1.3:

L/

Compute G-T diagram to show the stable region of ,  and L

based on the information given.
G <G at T<Tt and hence  is more stable /
Tt
G <G at T>Tt and hence  is more stable  /
/
Gliq <G at T>Tm and hence liquid is more stable  /
Tt <Tm L
Tm
T (K)

41 42

Exercise 1.4 Solution 1.4

Recall :
(dG/dT) = -S
 = the slope of the free
energy curve
 and  are 2 solid phases which are possible to appear in the 
substance A. At low temperature  is more stable. Prove Thus the slope of the curve is the
negative entropy of the phase.
thermodynamically requirements for the appearance of In order for  phase to appear at
allotropic transformation form  to  at constant pressure is higher temperatures the free
energy of  should fall rapidly
Entropy of  > Entropy of  than the as the temperature is
raised . In other words, the free
T (K) energy curve for  is steeper than
the this means the entropy of 
should be larger than 

43 44

11
 3.6 Chemical Potential and Gibbs Free
Energy of Single Component Phases
Extensive enthalpy: dH  dU  PdV  V dP

Substitute for dU/ in enthalpy expression: dH  TdS  V dP  dn

Combined 1st & 2nd law with extensive functions:
dU  TdS - PdV  dn
Extensive Gibbs free energy: dG   dH  TdS  SdT
By definition (recall gibbs free energy function):
/
  U n 
S ,V Substitute for dH/ in free energy expression: dG   - SdT  V dP  dn

45 46

dG   - SdT  VdP  dn

3.7 Enthalpy & Entropy of Transformation

For constant T & P (set dT=0, dP=0, & rearrange): At equilibrium --- G=H -TS
   
/
  and G G
   G 
n T , P
 H   TS   H   TS 
Note G’ is the gibbs free energy of the system and G is the gibbs free energy per mole
of the system (molar Gibbs free energy). Therefore G  nG H   H   T S   S  
   nG  
 G /  Thus,
 n 
  n T , P H  / 
T ,P
H  /
T  /
S  / S  /  
   nG     T/
/
    G   G n G
  n    n T , P n T , P
T ,P
Yielding: H  / L H L /V
 G S  / L  S L /V 
TM TV
In a unary system the chemical potential of a phase is equal to its molar Gibbs
free energy at that T & P. 47 48

12
 Chemical Potential Surface and the structure of the Unary Phase
Diagram

Because of
 G in a unary system
3.8 Compute Phase Equilibria from
d  dG   SdT  VdP
Free Energy Relations (7.4)
The coefficients are the molar entropy and molar volume of the phase.
example for  phase,
    (7.5)
d  dG   S dT  V dP
The molar entropy and molar volume for
phase can be computed as function of temperature
and pressure from heat capacity, expansion and
compressibility data.

Integration of Equation 7.5 yield a function

     (T  , P  )
T
can be visualized graphically in Fig 7.3a. Fig 7.3a
49 50

Fig 7.3b
The two surfaces intersect along a space curve AB-at any point on this curve, T, P,
Similar argument for other phase in the system  of the two phases are identical.
For liquid,
 L   L (T L , P L ) Ts = TL Ps= PL s= L

can be visualized graphically in Fig 7.3b
The chemical potential of these 2 phase can be
compared at any given (T,P)
combination if and only if the reference state
used in their computation is the same.
This is the conditions that must be met in order for the solid and liquid phase to
coexist in equilibrium
The projection of this line onto (P, T) plane is the phase boundary that defines the
(s+L) two phase equilibrium and the limit of stability of the solid and liquid phases.

The reference state is chosen to be the

solid phase at (To, Po) and now it is possible
to construct surfaces for both surface
on one graph Fig 7.3 c

The two surfaces intersect along a space curve

AB-at any point on this curve, T, P,  of the
two phases are identical. Fig 7.3c
T
T
Fig 7.3c 51 52

13
 4.0 Binary systems
Fig 7.4 shows the construction when the chemical
potential surface for the gas phase is added.
• Binary liquid system
Intersection of solid and gas (COD)-represents • Binary system without solid solution
the (s+G) two phase equilibrium
C’O’D’ on the (P, T) plane- sublimation curve • Binary system with solid solution

Intersection of liquid and gas (EOF)-represents the

(L+G) equilibrium
E’O’F’ on the (P, T) plane- vaporization curve

All three surface intersect at a single point O. At

this point T, P,  of all the 3 phases are the same
and all 3 phases coexist in equilibrium. The Fig 7.4
projection onto (T,P) plane, O’ is the triple point for
the 3 phases (s+L+G)

53

Partially Immiscible
4.1 Binary liquid system
Species A
When two liquid are brought together,
Total miscibility
they may

• Totally dissolve in one another in all

proportions (total miscibility),
• Partially dissolve in one another or
Immiscible
• Be completely immiscible  Species B

55

14
 Immiscible Mixtures Partially-Miscible Liquid Systems
These are equivalent
• The hexane-nitrobenzene system is seen at
Fully left. This system has an upper critical
temperature.
We may regard this Gas miscible
A and B in gas
mixture as PAsat • The region of miscibility is outside the
PBsat dome-shaped area. When the components
= are miscible there is only one phase present.

• For any given temp inside the dome shaped

Immiscible
Pure B Pure A area, forms two liquid solution

• The relative amounts of the two phases

A (droplets) + (continuous)
in separate phases
The liquid A is in equilibrium with its vapour at present will be given by the lever rule.
the vapour pressure of PA and The liquid B is in
equilibrium with its vapour at the vapour
pressure of PB
Total pressure= PA + PB

Other Partially-Miscible 4.2 Binary solutions with total solid solubility

Systems
For binary system in which two components are mutually soluble in all
proportion in both liquid and solid state, the possible phase diagram are as
• Two other types of partially-miscible systems
shown below
are seen at left.
Azeotropes, high-boiling
• The triethylamine-water system has a lower
critical temperature. That is, the components
get more miscible as the temperature gets lower.

• The nicotine-water system has both an upper

and a lower critical temperature. Only between
61 and 210 oC are there two phases present.

Azeotropes, low-boiling

15
 T-x Diagrams
• For an ideal solution the T-x diagram looks
like that at left.
heating
• Here the liquid phase lies below the vapor.
• As the temp is raised from a starting point
at a1, boiling occurs at a2 , with the vapor
comp’n being at a2. The distillate is
richer in the more volatile component.
• Successive distillations will separate the
pure components.
Azeotropes, high-boiling
• Unfortunately, not all solutions are ideal.
Often there is a maximum or minimum in
the boiling-point curve.
• Note that the liquid and vapor curves
converge at the maximum (composition b)
• Once this composition is reached, no further
separation is possible by simple distillation.
• Composition b is called an azeotrope.
• The system HCl-H2O exhibits this behavior.
High efficient Fractional Distillations
• The horizontal lines in the two-phase region, joining
condensation
boiling
liquid and vapor phases in equilibrium but of
different composition, are called tie lines.
• These are labeled 1, 2, 3, etc. at left.
• A fractional distillation consists of starting with
liquid, heating to boiling, condensing the distillate,
less efficient and repeating.
• The efficiency is quantified by the number of the
theoretical plates, the number of effective
vaporisation and condensation steps that are
required. The closer together the liquid and vapor
curves are, the more theoretical plates are needed to
achieve a given degree of separation of components.
Azeotropes, low-boiling
• In the high-boiling azeotrope, a pure
component could be separated in the
distillate, and the residue approached the
azeotropic composition.
• There are also low-boiling azeotropes, in
which pure components can be separated in
the residue but the distillate approaches the
azeotropic composition.
• A well-known system with a low-boiling
azeotrope is EtOH- H2O. The azeotropic
comp’n is 95% EtOH.
16
 4.3 Binary systems without solid
solution
Eutectic System

• It is commonly found that many materials are highly

miscible in the liquid state, but have very limited mutual
miscibility in the solid state. Thus much of the phase
diagram at low temperatures is dominated by a 2-phase
field of two different solid structures-one that is highly
enriched in component A (the α phase) and one that is
highly enriched in component B (the β phase). These
binary systems, with unlimited liquid state miscibility
and low or negligible solid state miscibility, are referred
to as eutectic systems.

• The behavior just described, where the two components
are completely miscible at high temperatures in the liquid
state and phase-separated into two solids at low
temperatures would be represented by a phase diagram as
follows:
• The solid forms of A and B are essentially
immiscible.
• Their liquids are complete miscible.
• No solid-state compounds are formed between A and B.

5.0 Free Energy-Composition (G-X Diagram)

liquid T1
• For a binary alloy consisting of components A and B, we fix the T1
G
T2 =Tm
pressure (typically P = 1 atm). T B

tie line
liquid T1
T3 solid

T2 =Tm
T B T mA
solid A liquid
tie line
T3 T4

B
T mA 0 1
0 Xl Xs 1 Xl XB
XB
solid
T4
At T1 the free energy of the liquid is everywhere below that of the
0 Xl Xs 1 solid. The graphical construction yields the values for the liquid
XB
phase chemical potentials.
67 68

17
 liquid
liquid T2 =TmB T1 T3
T1
T2 =Tm G
T2=Tm G T B
T B
solid B
tie line solid
tie line T3
T3
B
T mA
liquid
T mA liquid
solid
solid
T4
T4 liquid + solid
A
0 Xl Xs 1 0 Xl Xs 1
0 Xl Xs 1 XB
XB 0 XB 1
At T3 the “common tangent” 
construction shows that a mixed-
phase region exists between Xl and Xs, between which the
At T2 the free energy of the liquid coincides with that of the solid at
chemical potentials of A and B in each phase are equal. Single
the single point X=1. The graphical construction yields the values for
phase regions—either solid or liquid—exist outside those
the solid-phase chemical potentials.
composition limits.
69 70

• Common tangents to free energy curves define composition regions where

phase separation (two phase equilibria) occurs.
liquid T1 T4
• Phase separation lowers the overall free energy by splitting the homogenous T2=TmB G
system into a weighted mix of two separate phases, which each have lower T
free energy than the starting homogeneous phase. liquid
tie line
T3

Compositions of the phases in T mA

two-phase regions are given by solid
the tangent points, and the T4
amount of each phase is solid
determined by the lever rule.
0 Xl XB Xs 1 0 1
XB

At T4, the solid phase everywhere has a lower free energy than does
the liquid, and is the stable phase at all compositions.

72

18
5.1 Free energy diagrams of total solubility systems
We have 2 phases – liquid and solid. Let’s consider Gibbs free energy
Based on the Gibbs free energy curves we can construct a phase curves for the two phases at different T
diagram for a binary isomorphous systems
T1 is above the equilibrium melting temperatures of both pure
components:
Example :
T1 > Tm(A) > Tm(B) > the liquid phase will be the stable phase for any
Let’s construct a binary phase diagram for the simplest case: A and B composition
components are mutually soluble in any amounts in both solid
(isomorphous system) and liquid phases, and form ideal solutions.

Decreasing the temperature below T1 will have two effects:

GAliquid and GBliquid will increase more rapidly than GAsolid and GBsolid For even lower temperature T3 <
The curvature of the G(XB) curves will decrease. T2=Tm(A) the Gibbs free energy
curves for the liquid and solid
Eventually we will reach T2 – melting point of pure component A, phases will cross
where GAliquid = GBsolid

As temperature decreases below T3 GAliquid and GBliquid continue to

increase more rapidly than GAsolid and GBsolid

Therefore, the intersection of the Gibbs free energy curves, as well as

points X1 and X2 are shifting to the right, until, at T4 = Tm(B) the curves
will intersect at X1 = X2 = 1

19
 Construction of the phase diagram

At T4 and below this temperature the Gibbs free energy of the

solid phase is lower than the G of the liquid phase in the whole
range of compositions – the solid phase is the only stable phase.

5.2 Free energy diagram for binary solutions with a

miscibility gap

Let’s consider a system in which the liquid phase is approximately

ideal, but for the solid phase we have .Hmix > 0

At low temperatures, there is a region where the solid solution

is most stable as a mixture of two phases α1 and α2 with
compositions X1 and X2.

This region is called a miscibility gap.

20
5.3 Free energy diagram of binary systems without solid
solution (Eutectic System)
Eutectic phase diagram with different crystal structures of
pure phases
• It is commonly found that many materials are highly miscible in the liquid
state, but have very limited mutual miscibility in the solid state. Thus much of
the phase diagram at low temperatures is dominated by a 2-phase field of two
different solid structures-one that is highly enriched in component A (the α
phase) and one that is highly enriched in component B (the β phase). These
binary systems, with unlimited liquid state miscibility and low or negligible
solid state miscibility, are referred to as eutectic systems.

• The behavior just described, where the two components are completely
miscible at high temperatures in the liquid state and phase-separated into two
solids at low temperatures would be represented by a phase diagram as
follows:

Cont… Cont…

21
 Cont… Cont…

Eutectic phase diagram with same crystal structures of pure

Cont…
phases

22
 Cont…
6.0 Phase boundary Calculations
T m (A)
L XAL

XAs


XBS

A B
XB

For the phase equilibrium of  and liquid as shown in the figure, we

have  with composition XAS in equilibrium with liquid of
composition XAL .

90

Cont… (S  L)
G O
A  free energy change of fusion at T o K
At equilibrium, partial molal Gibbs free energy for each
(S  L)
component is the same in both the phase G O
A  H  TS S H/T

S L (S  L)   H M ( A) 
GA  GA G O
A  H M ( A)  T  
Free energy axis  TM ( A) 
S L  
G A  G oA( S )  G A  G oA( L )  (G oA( L )  G Ao(S ) )
G Ao(L ) (S  L)  a AS 
G OA  RT ln a SA  RT ln a AL  RT ln 
represent free energy
 a AL 

change in melting RT ln a AL
G oA(S )  H M ( A)   S 
(fusion).
 H M ( A)  T    RT ln  a A 
 TM ( A)   aL 
RT ln a SA GRT ln a LA  G o( S L)
o (S )
A
RT ln a SA    A 
 T   S 
with ref to pure Free energy (S ) ( L) H M 1    RT ln  a A 
solid A change on GA  GA  T   aL 
 M ( A)   A 
with ref to pure fusion at ToK
liquid A
Using this we have
Note :Gi=Gio + RTln ai
91 92

23
 Defination of ideal & non ideal
 a AS  H M ( A)  1 1 
ln  L     Species A Species B Ideal Mixture: = 1
 aA  R T TM ( A ) 
   
And if the solutions are assumed ideal  +
 X AS  H M ( A)  1 1 
ln     
 X AL  R T TM ( A) 
   
Similarly for the component B

 X BS  H M (B )  1 1 
ln     
 X BL  R T TM ( B ) 
   
Non-Ideal Mixture of A and B: > 1

A-B Repulsive Interactions

93 Exaggerated

Further if the diagram indicates no solid solubility, we have Phase diagram of full solid solubility is shown below. Calculation
H M ( A)  1 1  of the solidus and liquidus of this type of diagram can be made as
ln X AL     
R T T M ( A )  follows, using the assumption of ideal solution for solid and liquid

state.
In several cases, for the region close to the melting point, one can
state as an approximation, As per equations derived before,
T m (B)
H M ( A)  T 
ln X AL    
R T2 
 M  XAs  X AS   H  1 
Also noting that ln(1-x)-x when x<<1, we can say   M ( A)  1 
T m (A) ln   
 X AL  R T
 T M ( A)


H M ( A)  1 1  XBL XAL  
ln X BL    
R T TM ( A)  A
  B  X BS  H
XB   M ( B )  1 1 
H M ( A)  T  ln  L   
 XB  R  T TM ( B ) 
ln X BL   
   
R T 2 
 M 
95 96

24
 cont….

Effects of relative values of

X AS X BS entropy of fusion of the
Let k1  and k 2  components
X AL X BL  H (1  m )
 S1o 
Also X AS  X BS  1 and X AL  X BL  1 T m (1)

L k2  1 on the shape of the phase

Solving algebraically, X A  diagram with full solid and
k 2  k1
liquid solubility
S L
X A  k1 . X A

X BL  1  X L
A

X BS  1  X S
A

97

Exercise 1.1 Solution (1.1a)

a) Pure iron has melting point 1539oC and on addition of 1% Tm (pure Fe) =1539+273=1812K, Tm (with Si)=1527+273=1800K
(weight) of silicon lowers it to 1527oC. Find the silicon content 1 / 28
in solid iron in equilibrium with liquid at 1527oC. Heat of fusion X SiL   0.0198
(1 / 28)  (99 / 56)
of iron is 15490 J/mol L
X Fe  1  0.0198  0.9802

b) At 1492oC, delta iron contains a maximum of 0.10% (by  X S  H M ( Fe )  1 

ln  Fe    1 
weight) of carbon. What is the carbon content of the liquid iron L   
X
 Fe  R  T TM ( Fe ) 
in equilibrium with this solid? S
 X Fe  15490  1 1 
ln      
 0.9802  8.314  1800 1812 

99

25
 Solution (1.1b)
0 . 001 / 12
S
X CS 
 X Fe  ( 0 . 001 / 12 )  ( 0 . 999 / 56 )
ln    6.855 x 10  3
 0.9802  X CS  4 . 65 x 1 0  3
 
S
X Fe  1.0069 x 0.9802  0.9870
S
X Fe  1  4 . 65 x 1 0  3  0 . 9954

X SiS  1  0.9870  0.013

XS   H M ( Fe ) 1 
ln  Fe     1 
L T T 
(0.013)(28)  X Fe  R  M ( Fe ) 
wt %  x100%
(0.013)(28)  (0.9870)(56)  0 . 9954  15490  1 1 
ln  L
    
 0.65 %  X Fe  8 . 314  1765 1812 

Exercise 1.2
 0.9954 
ln L
  0.0274
 X Fe  Copper and nickel are fully soluble in each other in solid and liquid
0.9954 states. Assuming ideal solutions, calculate the solidus and liquidus
 1.0278
L
X Fe curves of the Cu-Ni diagram using following data : (calculate at
L 0.9954 1400, 1500, 1600 and 1700K).
X Fe   0.9685
1.0278
Cu (A) Ni (B)
X CL  1  0.9685  0.0315
Melting point, K 1356 1728
(0.0315)(12) Heat of fusion (J/mole) 12,790 17,154
wt %  x100%
(0.0315)(12)  (0.9685)(56)
 0.692 %

104

26
 Solution 1.2
 X AS  H M ( A)  1 1   X BS  H M (B)  1 1 
Temp ln      ln     
 X AL  R T TM ( A)   X BL  R T TM ( B ) 
       

1400
 X AS   H M ( A)  1 1 
ln     
 X AL  R T T 
   M ( A)  1500
 X BS  H M (B)  1 1 
ln     
 X BL  R T T 
   M (B )  1600

1700

105 106

 X AS  H M ( A)  1 1   X BS  H M (B)  1 1 
Temp ln      ln     
 X AL  R T TM ( A)   X BL  R T T 
       M (B)  X AS X BS L k2  1
X AS  k1.X AL
Temp k1  k2  X A  X BS  1  X AS X BL  1  X AL
X AL X BL k 2  k1
 X AS   X BS  17154  1 1 
  12790  1 1 
ln  L    0 .2797
  8.314  1400  1356   0.0357  8 .314  1400 1728 
1400 ln L
 X  XB
 A   
1400
XS   X BS  17154  1 1 
 A  12790  1 1  ln  L    0 .1815
1500 ln
 X AL
     0.1089
 8.314  1500 1356   XB  8.314  1500 1728 
    1500
 XS  S
 A  12790  1 1  X B
 17154  1 1 
ln       0.1730 ln  L    0. 0955
1600  X AL  8.314  1600 1356   XB  8 .314  1600 1728  1600
   

 X AS 
  12790  1 1   X BS  17154  1 1 
ln  L   8. 314  1700  1356   0.2296 ln L    0.0197 1700
1700  XA
   XB  8.314  1700 1728 
 

107 108

27
 X AS X BS k2  1 1800
k1  k2  X L
A  X AS  k1.X AL X BS  1  X AS X BL  1  X AL 1728 K
Temp X AL X BL k 2  k1 1700 liquid

1400 0.965 1.323 0.870 0.902 0.130 0.098 1600

Temperature/K 1500
1500 0.897 1.199 0.591 0.659 0.409 0.341
1400
1358 K
1600 0.841 1.100 0.325 0.386 0.675 0.614 1300 solid

1200
0.2 0.4 0.6 0.8 1.0
1700 0.795 1.020 0.071 0.089 0.929 0.911 Cu Ni
Ni composition

109 110

Exercise 1.3 Solution 1.3:

The compound Ca2B2O5-CaSiO3 form a simple eutectic system with no
solid solubility. Using the following data and assuming the liquid
solutions to be ideal, calculate the phase boundaries.
 H M ( A)  1 1 
ln X L
   
Ca2B2O5 (A) CaSiO3
A
R T T 
(B)  M ( A) 
Melting point, K 1583 1813 H M (B)  1 1 
ln X BL     
Heat of fusion (J/mole) 100,834 56,066 R T T 
 M (B) 

111 112

28
  H M ( A)  1 1  H M (B)  1 1 
Temp ln X L
    Temp ln X BL      H M (A)  1 
A
R T TM ( A )  R T TM ( B )  L  1  H M (B)  1 1 
    Temp ln X   Temp ln X BL     
A
R T TM ( A )  R T TM ( B ) 
   
1300 1400 56066  1 1 
100834  1 1  ln X BL       0 .334
1300 ln X AL       0.189 1400 8.314  1400 1813 
8.314  1300 1583 

1350 1500 100834 1 1  56066  1 1 

1350 ln X AL       0.267 1500 ln X BL       0 .460
8.314  1350 1583 8.314  1500 1813 

1400 1600 100834  1 1  56066  1 1 

1400 ln X AL       0.367 1600 ln X BL       0 .609
8.314  1400 1583  8.314  1600 1813 

1450 1700 100834  1 1  56066  1 1 

1450 ln X AL       0.495 1700 ln X BL       0.781
8.314  1450 1583  8.314  1700 1813 

1500 1800 100834  1 1  56066  1 1 

1500 ln X AL       0.654 1800 ln X BL       0 .973
8.314  1500 1583  8.314  1800 1813 

1550 100834  1 1 
1550 ln X AL       0.849
8.314  1550 1583 
113 114

1900
1813 K
1800

1700

1600 1583 K
Below this
1500
Temperature /K point no liquid
phase can exist
1400

1300

1200
0.2 0.4 0.6 0.8 1.0
Ca2B2O5 CaSiO3
CaSiO3 composition

The phase boundary exist at 1480K with Ca2B2O5 = 58% and

CaSiO3= 42% 115

29