MME 2004

Thermodynamic of Solutions
Gibbs Free Energy-Composition
and
Phase Diagrams of Binary Systems
Assist. Prof. Dr. Esra Dokumacı
Assist. Prof. Dr. Murat Alkan
09.04.2020
In Previous Weeks (The Gibbs Free Energy of Binary Solutions)
• The Gibbs free energy of a binary solution of A and B atoms can be calculated
from the free energies of pure A and pure B in the following way.

2
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (The Gibbs Free Energy of Binary Solutions)
• GA and GB are the molar free energies of pure A and pure B. G1, molar free
energy, is plotted as a function of XB or XA. For all alloy compositions G1 lies on the
straight line between GA and GB.

3
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (Ideal Solutions)
• The simplest type of mixing to treat first is when ΔHmix = 0, in which case the
resultant solution is said to be ideal and the free energy change on mixing is only
due to the change in entropy: ΔGmix = – T ΔSmix
• ΔSmix = – R (XA lnXA + XB lnXB) GB
• ΔGmix = RT (XA lnXA + XB lnXB)
GA
GB

GA

4
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (Chemical Potential)
• In alloys it is of interest to know how the free energy of a given phase will change
when atoms are added or removed. If a small quantity of A, dnA mol, is added to a
large amount of a phase at constant temperature and pressure, the size of the
system will increase by dnA and therefore the total free energy of the system will
also increase by a small amount dG'. If dnA is small enough dG' will be
proportional to the amount of A added. Thus we can write
dG' = µA dnA (T, P, nB constant)
• The proportionality constant µA is called the chemical potential of A in the phase.

• For a binary solution at constant temperature and pressure the separate

contributions can be summed:
• If T and P changes:

5
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (Chemical Potential)
• XA mol A and XB mol B must be added and the free energy of the system will
increase by the molar free energy G.
• G = µAXA + µBXB
• When G is known as a function of XA and XB, µA and µB can be obtained by
extrapolating the tangent to the G curve to the sides of the molar free energy
diagram.

6
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (Regular Solutions)
• In the quasi-chemical model it is assumed that the heat of mixing, ΔHmix, is only
due to the bond energies between adjacent atoms. For this assumption to be
valid it is necessary that the volumes of pure A and B are equal and do not change
during mixing so that the interatomic distances and bond energies are
independent of composition.
• Three types of interatomic bonds are present:
1. A-A bonds each with an energy EAA,
2. B-B bonds each with an energy EBB,
3. A-B bonds each with an energy EAB.
• The internal energy of the solution E
• will depend on the number of bonds of
• each type PAA, PBB and PAB such that
E = PAAEAA + PBBEBB + PABEAB

7
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (Regular Solutions)
• In internal energy on mixing is given by ΔHmix = PABE where E = EAB – ½ (EAA + EBB)
• E is the difference between the A-B bond energy and the average of the A-A and
B-B bond energies.
• If E = 0, ΔHmix = 0 and the solution is ideal. In this case the atoms are completely
randomly arranged.
• In such a solution it can also be shown that PAB = NazXAXB where Na is Avogadro's
number, and z is the number of bonds per atom.
• If E < 0 the atoms in the solution will prefer to be surrounded by atoms of the
opposite type and this will increase PAB, whereas, if E > 0, PAB will tend to be less
than in a random solution.
• Real solutions that closely obey: ΔHmix = ΩXAXB known as regular solutions.
• The free energy change on mixing a regular solution is

8
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (Regular Solutions)
• For exothermic solutions ΔHmix
< 0 and mixing results in a free
energy decrease at all
temperatures (a and b).

• When ΔHmix > 0, however, the

situation is more complicated.
At high temperatures TΔSmix is
greater than ΔHmix for all
compositions and the free
energy curve has a positive
curvature at all points (c).
• At low temperatures, on the
other hand, TΔSmix is smaller
and ΔGmix develops a negative
curvature in the middle (d).

9
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (Regular Solutions)
• The actual free energy of the alloy depends on the values chosen for GA and GB
and is

• For a regular solution, the chemical potentials of A and B in the solution are:

10
Source: Porter, D. A., & Easterling, K. E. (1992). Phase transformation in materials. Chapman & Hall, London
In Previous Weeks (Gibbs Free Energy – Compositions)
• If liquid solutions are stable over the entire
range of composition, then the Gibbs free
energies of the liquid states are lower than
those of any possible solid state.
• At intermediate temperatures, the variation
of Gibbs free energy with composition will
identify ranges of composition over which
liquid states are stable, ranges over which
solid states are stable, and intermediate
ranges in which solid and liquid phases
coexist in equilibrium with one another.
• If the temperature of the system is lower
than the lowest solidus temperature, then
the Gibbs free energies of the solid states
are everywhere lower than those of liquid
states.
11
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
In Previous Weeks (Gibbs Free Energy – Compositions)

ideal behavior (I)

positive deviation from ideal behavior (II)
negative deviation from ideal behavior (III)
ΔGM,id = 𝑅𝑅𝑅𝑅(𝑋𝑋𝐴𝐴𝑙𝑙𝑙𝑙𝑙𝑙𝐴𝐴 + 𝑋𝑋𝐵𝐵𝑙𝑙𝑙𝑙𝑙𝑙𝐵𝐵)

12
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Criteria for Phase Stability in Regular Solutions
• For a given temperature, a critical value (αcritical) occurs, and below
this value a homogeneous solution is stable over the entire range of
composition and above which phase separation occurs.
• The criteria used to determine this critical value are obtained by the
variations of ∆𝐺𝐺 𝑀𝑀 , 𝜕𝜕∆𝐺𝐺 𝑀𝑀 ⁄𝜕𝜕𝑋𝑋𝐵𝐵 , 𝜕𝜕 2 ∆𝐺𝐺 𝑀𝑀 ⁄𝜕𝜕𝑋𝑋𝐵𝐵 2 , 𝑎𝑎𝑎𝑎𝑎𝑎 𝜕𝜕 3 ∆𝐺𝐺 𝑀𝑀 ⁄𝜕𝜕𝑋𝑋𝐵𝐵 3
with composition for α<αcritical, α=αcritical, and α>αcritical respectively.

13
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Criteria for Phase Stability in Regular Solutions

At XA=XB=0.5, the third derivative 𝜕𝜕 3 ∆𝐺𝐺 𝑀𝑀 ⁄𝜕𝜕𝑋𝑋𝐵𝐵 3 = 0. Thus, at XA = XB = 0.5, the

second derivative also 𝜕𝜕 2 ∆𝐺𝐺 𝑀𝑀 ⁄𝜕𝜕𝑋𝑋𝐵𝐵 2 = 0.
α=2, which is thus the critical value of α above which phase separation occurs.

The critical temperature, Tcr, is

14
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Criteria for Phase Stability in Regular Solutions
The variation, with temperature, of the
Gibbs free energy of mixing curve for a
regular solution which has a positive
molar heat of mixing (Ω=16630 J/mol)
and a critical temperature of
Tcr=16630/2R=1000 K.

15
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Criteria for Phase Stability in Regular Solutions

• The Gibbs free energy expression contains

a negative logarithmic term, the
magnitude of which is proportional to
temperature, and a positive parabolic
term which is independent of
temperature.

• At high enough temperature, the

logarithmic contribution predominates
and the Gibbs free energy of mixing is
convex downwards at all compositions.

16
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Criteria for Phase Stability in Regular Solutions
• However, with decreasing temperature,
the contribution of the logarithmic term
decreases, and eventually the positive
parabolic term predominates and
produces a range of composition centered
on XB=0.5 over which the Gibbs free
energy curve is convex upwards.
• The logarithmic term still requires that the
tangents to the curve at XA=1 and XB=1 be
vertical.
• Fig. b shows the phase diagram for the
system, in which the miscibility curve
bounding the two-phase region is simply
the locus of the double tangent
compositions in Fig. a.
17
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Criteria for Phase Stability in Regular Solutions
• The influence of temperature on the
variations of the activity of component B
with composition is shown in Fig.c. The
activities are obtained from the
intercepts, with the XB=1 axis, of tangents
drawn to the free energy ∆𝐺𝐺̅𝐵𝐵 = 𝑅𝑅𝑅𝑅 𝑙𝑙𝑙𝑙𝑎𝑎𝐵𝐵 .
• At TCr the activity exhibits a horizontal
inflexion at XB=0.5.

• At TCr and XB=0.5 both the second and third derivatives of ΔGM with
respect to XB are zero, and thus, the first and second derivatives of aB
with respect to XB are zero, which produces a horizontal inflexion point on
the activity curve at XB=0.5 and TCr.

18
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Criteria for Phase Stability in Regular Solutions
• At T<TCr the activity curve has a maximum
800 K
and a minimum, which occur at the spinodal
compositions, the points b and c on the
activity curve at 800 K shown in Fig.
• The portion of the curve given by ab in Fig.
represents the activity of B in phase I which
is supersaturated with B and the portion of
the activity curve given by cd represents the
activity of B in phase II which is
supersaturated with A.

• The value of 𝜕𝜕aB/𝜕𝜕XB is negative between b and c, and this violates an

intrinsic criterion for stability which requires that 𝜕𝜕ai/𝜕𝜕Xi always be
positive.

19
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Criteria for Phase Stability in Regular Solutions
• Thus the derived activity curve between b
800 K
and c, and, consequently, the Gibbs free
energy of mixing curve between the
spinodal compositions, have no physical
significance.

• The horizontal line drawn between a and d

in Fig. represents the actual constant activity
of B in the two-phase region, and the
compositions a and d are those of the
double tangents to the Gibbs free energy of
mixing curve.

20
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• Consider the binary system A–B at a
temperature T which is below Tm(B),
the melting temperature of B, and
above Tm(A), the melting temperature
of A. Consider, further, that this
system forms Raoultian ideal liquid
solutions and Raoultian ideal solid
solutions.
• The phase diagram for the system and
the temperature of interest, T, are
shown in Fig.a.
• Fig.b shows the two Gibbs free energy
of mixing curves of interest, curve I
drawn for liquid solutions and curve II
drawn for solid solutions.
21
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• At the temperature T, the stable states
of pure A and B are located at ΔGM=0,
with pure liquid A located at XA=1 (the
point a) and pure solid B located at
XB=1 (the point b).
• The point c represents the molar
Gibbs free energy of solid A relative to
that of liquid A at the temperature T,
° °
and T>Tm(A), 𝐺𝐺𝐴𝐴(𝑠𝑠) − 𝐺𝐺𝐴𝐴(𝑙𝑙) then is a
positive quantity which is equal to the
negative of the molar Gibbs free
energy of melting of A at the
temperature T.
°
𝐺𝐺𝐴𝐴(𝑠𝑠) − 𝐺𝐺𝐴𝐴° 𝑙𝑙
°
= −∆𝐺𝐺𝑚𝑚 𝐴𝐴
°
= −(∆𝐻𝐻𝑚𝑚 𝐴𝐴
°
− 𝑇𝑇∆𝑆𝑆𝑚𝑚 𝐴𝐴 )

22
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
°
𝐺𝐺𝐴𝐴(𝑠𝑠) − 𝐺𝐺𝐴𝐴° 𝑙𝑙
°
= −∆𝐺𝐺𝑚𝑚 𝐴𝐴
°
= −(∆𝐻𝐻𝑚𝑚 𝐴𝐴
°
− 𝑇𝑇∆𝑆𝑆𝑚𝑚 𝐴𝐴 )
°
• and if Cp,A(s) = Cp,A(l) that is, ∆𝐻𝐻𝑚𝑚 𝐴𝐴 and
°
∆𝑆𝑆𝑚𝑚 𝐴𝐴 are independent of
temperature, then
° °
𝑇𝑇𝑚𝑚(𝐴𝐴) − 𝑇𝑇
∆𝐺𝐺𝑚𝑚 𝐴𝐴 = ∆𝐻𝐻𝑚𝑚 𝐴𝐴
𝑇𝑇𝑚𝑚(𝐴𝐴)
• Similarly, the point d represents the
molar Gibbs free energy of liquid B
relative to that of solid B at the
temperature T, and, as T<Tm(B), then
° °
𝐺𝐺𝐵𝐵(𝑙𝑙) − 𝐺𝐺𝐵𝐵(𝑠𝑠) is a positive quantity,
°
equal to ∆𝐺𝐺𝑚𝑚 𝐵𝐵 .

23
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• The straight line joining a and d
represents the Gibbs free energy of
unmixed liquid A and liquid B relative
to that of the standard state of
unmixed liquid A and solid B, and the
straight line joining c and b represents
the Gibbs free energy of unmixed solid
A and solid B relative to that of the
standard state.
• The straight line cb has the equation
°
∆𝐺𝐺 = −𝑋𝑋𝐴𝐴 ∆𝐺𝐺𝑚𝑚 𝐴𝐴
• and the equation for the straight line
ad is
°
∆𝐺𝐺 = 𝑋𝑋𝐵𝐵 ∆𝐺𝐺𝑚𝑚 𝐵𝐵

24
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• the molar Gibbs free energy of
formation of an ideal liquid solution,
∆𝐺𝐺 𝑀𝑀𝑙𝑙 from liquid A and solid B is given
by

• Similarly, at any composition, the

formation of an ideal solid solution,
∆𝐺𝐺 𝑀𝑀𝑙𝑙 , from liquid A and solid B
involves a change in Gibbs free energy
of

25
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• At the composition e, the tangent to the
curve for the liquid solutions is also the
tangent to the solid solution at the
composition f.
• Thus, at the temperature T, liquid of
composition e is in equilibrium with solid
of composition f (e is the liquidus
composition and f is the solidus
composition)
• As the temperature is lowered, the
magnitude of ca decreases and the
magnitude of db increases.

26
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• The consequent movement of the
positions of curves I and II relative to
one another is such that the positions
e and f of the double tangent to the
curves shift to the left.
• Correspondingly, if the temperature is
increased, the relative movement of
the Gibbs free energy curves is such
that e and f shift to the right.
• For equilibrium between the solid and
liquid phases,

and

27
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States

28
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• The activity-composition relationships for
component B are shown in Fig.c.
• As two standard states are available,
• the point b for solid B
• and the point d for liquid B,
• the lengths of the tangential intercepts with
the XB=1 axis can be measured from b, in which
case the activities of B are obtained with
respect to solid B as the standard state,
• or the lengths can be measured from d, which
gives the activities with respect to liquid B as
the standard state.

29
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• If pure solid B is chosen as the standard state
and is located at the point g, then the length gn
is, by definition, unity, and this defines the
solid standard state activity scale.
• The line ghij then represents aB in the solutions
with respect to solid B having unit activity at g.
• The line is obtained from the variation of the
tangential intercepts from the curve aefb to
the XB=1 axis, measured from the point b.
• On this activity scale Raoult’s law is given by jg,
and the points i and h represent, respectively,
the activity of B in the coexisting liquid solution
e and solid solution f.

30
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• The point m represents the activity of pure
liquid B measured on the solid standard state
activity scale of B.
• This activity is less than unity, being given by
the ratio mn/gn.
• For B in any state along the aefb Gibbs free
energy curve, in which state the partial molar
Gibbs free energy of B 𝐺𝐺̅𝐵𝐵 is the following
relations hold:

31
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
°
• As T<Tm(B), ∆𝐺𝐺𝑚𝑚 𝐵𝐵 is a positive quantity, and
thus the activity of B in any solution with
respect to solid B as the standard state is less
than the activity of B with respect to liquid B as
the standard state, where both activities are
measured on the same (solid or liquid) activity
scale.
• For pure B aB(s)>aB(l) (gn>mn), and, if gn=1, then
°
mn=exp(−∆𝐺𝐺𝑚𝑚 𝐵𝐵 /𝑅𝑅𝑅𝑅).

32
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• If pure liquid B is chosen as the standard state
and is located at the point m, then the length
mn is, by definition, unity, and this defines the
liquid standard state activity scale.
• Raoult’s law on this scale is given by the line
jm, and the activities of B in solution, with
respect to pure liquid B having unit activity, are
represented by the line mlkj.

33
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• The activity of solid B, located at g, is greater
than unity on the liquid standard state activity
°
scale, being equal to exp(∆𝐺𝐺𝑚𝑚 𝐵𝐵 /𝑅𝑅𝑅𝑅).
• When measured on one or the other of the
two activity scales, the lines jihg and jklm vary
°
in the constant ratio exp(∆𝐺𝐺𝑚𝑚 𝐵𝐵 /𝑅𝑅𝑅𝑅) but jihg
measured on the solid standard state activity
scale is identical with jklm measured on the
liquid standard state activity scale.

34
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• The variation of aA with composition is shown
°
in Fig.d. In this case, as T>Tm(A), ∆𝐺𝐺𝑚𝑚 𝐴𝐴 is a
negative quantity, and,
aA (with respect to liquid A) > aA (with respect to solid A)
• when measured on the same activity scale.
• If pure liquid A is chosen as the standard state
and is located at the point p, then the length of
pw is, by definition, unity, and the line pqrs
represents the activity of A in the solution with
respect to the liquid standard state.

35
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• On the liquid standard state activity scale, the
activity of pure solid A, located at the point v,
°
has the value exp(∆𝐺𝐺𝑚𝑚 𝐴𝐴 /𝑅𝑅𝑅𝑅).
• If, on the other hand, pure solid A is chosen as
the standard state, then the length of vw is, by
definition, unity, and Raoult’s law is given by
vs.
• The line vuts represents the activities of A in
the solutions with respect to pure solid A.
• On the solid standard state activity scale, liquid
A, located at the point p, has the value
°
exp(−∆𝐺𝐺𝑚𝑚 𝐴𝐴 /𝑅𝑅𝑅𝑅).

36
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• Again, the two lines, measured on one or the
other of the two activity scales, vary in the
°
constant ratio exp( ∆𝐺𝐺𝑚𝑚 𝐴𝐴 /𝑅𝑅𝑅𝑅 ) and when
measured on their respective scales, are
identical.
• If the temperature of the system is decreased
to a value less than T indicated in Fig.a, then
°
the length of ac, being equal to ∆𝐺𝐺𝑚𝑚 𝐴𝐴 ,
°
decreases, and, the magnitude of ∆𝐺𝐺𝑚𝑚 𝐵𝐵 ,
the length of bd, increase.
• The consequent change in the positions of the
Gibbs free energy of mixing curves I and II in
Fig.b causes the double tangent points e and f
to shift to the left toward A.
37
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
Liquid and Solid Standard States
• The effect on the activities is as follows. In the case of
both components,

• With respect to component B, if the temperature, which

is less than Tm(B), is decreased, the ratio aB(solid)/aB(liquid),
which is greater than unity, increases.
• Thus, the ratio gn/mn increases. With respect to the
component A, if the temperature, which is higher than
Tm(A), is decreased, then the ratio aA(solid)/aA(liquid), which is
less than unity, increases.
• Thus the ratio vw/pw increases. At the temperature Tm(B),
°
solid and liquid B coexist in equilibrium, ∆𝐺𝐺𝑚𝑚 𝐴𝐴 = 0 and
the points p and v intersect.
°
• Similarly, at the temperature 𝑇𝑇𝑚𝑚 𝐵𝐵 the points m and g
intersect.
38
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.