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
02.04.2020
GIBBS FREE ENERGY-COMPOSITION
• At constant temperature and pressure, the stable state of
existence of a system is that which has the minimum
possible value of Gibbs free energy.
• Thus, phase stability in a
system, as normally presented
on an isobaric phase diagram,
can be determined from
knowledge of the variations of
the Gibbs free energies of the
various possible phases with
composition and
temperature.
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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-COMPOSITION
• When a liquid solution is cooled,
a liquidus temperature is
eventually reached, at which
point a solid phase begins to
separate from the liquid solution.
• This solid phase could be a
virtually pure component / a
solid solution of the same or
different composition from the
liquid / a chemical compound
formed by reaction between two
or more of the components.

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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-COMPOSITION
• In all possible cases the
composition of the solid
phase which is in
equilibrium with the liquid
solution is that which
minimizes the Gibbs free
energy.
• 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.
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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-COMPOSITION
• 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.

5
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-COMPOSITION
• 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.

6
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-COMPOSITION
• There are two main rule to determine stable phases by
Gibbs free energy-component relation:
(1) The state of lowest Gibbs free energy is the stable
state
(2) When phases coexist in equilibrium has the same
value in all of the coexisting phases, there must exist
a quantitative correspondence between Gibbs free
energy-composition diagrams and “phase diagrams.”

7
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-ACTIVITY
• The free energy of mixing of the component A and B to
form a mole of a solution is given as:
ΔGM = 𝑅𝑅𝑅𝑅(𝑋𝑋𝐴𝐴 𝑙𝑙𝑙𝑙𝑎𝑎𝐴𝐴 + 𝑋𝑋𝐵𝐵 𝑙𝑙𝑙𝑙𝑙𝑙𝐵𝐵)
ΔGM :the difference between the Gibbs free energy of a mole
of the homogeneous solution and the Gibbs free energy of
the corresponding numbers of moles of the unmixed
components.
As only changes in Gibbs free energy can be measured, the
Gibbs free energies of the pure unmixed components are
assigned the value of zero.

8
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-ACTIVITY
If the solution is ideal, i.e., if ai=Xi, then the molar Gibbs free
energy of mixing, given by
ΔGM,id = 𝑅𝑅𝑅𝑅(𝑋𝑋𝐴𝐴𝑙𝑙𝑙𝑙𝑙𝑙𝐴𝐴 + 𝑋𝑋𝐵𝐵𝑙𝑙𝑙𝑙𝑙𝑙𝐵𝐵 )
ΔHM,id =0
ΔGM,id = −TΔSM,id
has the characteristic shape
shown, at the temperature T,
as curve I in Figure given
below.

ideal behavior (I)

positive deviation from ideal behavior (II)
negative deviation from ideal behavior (III)

9
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-ACTIVITY
Curve I: The shape of the variation of
ΔGM,id with composition depends only
on temperature.
Curve II: The solution exhibits a slight
positive deviation from ideal mixing,
i.e., if γi>1 and ai>Xi.
Curve III: The solution shows a slight negative deviation from ideal
mixing, i.e., if γi<1 and ai<Xi.

The tangent drawn to the ΔGM curve at any composition intersects

the XA=1 and XB=1 axes at ∆𝐺𝐺𝐴𝐴̅ and ∆𝐺𝐺̅𝐵𝐵 , respectively, and, as
∆𝐺𝐺̅𝑖𝑖 =RTInai, a correspondence is provided between the ΔGM-
composition and activity-composition curves.
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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-ACTIVITY

At the composition Y,
tangents drawn to curves I,
II, and III intersect the XB=1
axis at a, b, and c,
respectively.

11
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY-ACTIVITY
The variation, with composition, of
the tangential intercepts generates
the variations of activity with
composition is given in Figure.

As Xi → 0, ai → 0, and hence the

tangential intercept which indicates
that all Gibbs free energy of mixing
curves have vertical tangents at
their extremities. By virtue of being
logarithmic, the entropy of the
mixing curve which has vertical
tangents at its extremities.

12
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION
All solutions studied so far are single-phase homogeneous solutions.
However, this may not always happen depending on the system and
ambient conditions. Depending on the composition at constant
temperature, it is necessary to look at the 1st order derivative of the
ΔGM-XB change in order to understand in which direction the
equilibrium of the solution will change. If;

the system will be in much more equilibrium state.

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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION
In regular solutions, we can express the mixture free energy with the
following relations:

𝑋𝑋𝐴𝐴 = (1 − 𝑋𝑋𝐵𝐵 ) 𝑋𝑋𝐴𝐴 = (1 − 𝑋𝑋𝐵𝐵 )

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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION

Since

the activity coefficient is independent of the composition in

accordance with Henry Law, and ∆𝐻𝐻 �𝐵𝐵 is independent of the
composition. In this case the above relation will be;

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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION
This indicates that the change will approach the ordinate axis
tangentially when XB → 0 that is, in these extremely diluted extreme
areas, the mixture free energy will fall to the negative rapidly.
In this case, the ΔGM–XB curve falls with a very large slope on both
ends of the composition axis and the solution is be more stable than
the pure substance.
This explains why a substance in nature is never truly pure and
contains a small amount of impurities. It is therefore very difficult
to obtain extremely pure metals.

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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
HUME-ROTHERY RULES!
• The addition of impurity atoms to a metal will result in the
formation of a solid solution and/or a new second phase,
depending on the kinds of impurity, their concentrations, and the
temperature of the alloy.
• Solvent represents the element or compound that is present in
the greatest amount.
• Solute is used to denote an element or compound present in a
minor concentration.
• A solid solution forms when, as the solute atoms are added to the
host material, the crystal structure is maintained and no new
structures are formed.
• Impurity point defects are found in solid solutions, of which there
are two types: substitutional and interstitial.
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Source: Callister, W. D. (2009). An introduction to materials science and engineering. John Wiley and Sons Inc.
HUME-ROTHERY RULES!
• For the substitutional type, solute or
impurity atoms replace or substitute for the
host atoms. Several features of the solute
and solvent atoms determine the degree to
which the former dissolves in the latter, as
follows:
1. Atomic size factor. the difference in atomic radii between the two
atom types is less than about ±15%.
2. Crystal structure. the crystal structures of both atom types must
be the same.
3. Electronegativity. the electronegativity values should be closer
otherwise intermediate compounds will be occured.
4. Valences. a metal can dissolve another metal of higher valency.
18
Source: Callister, W. D. (2009). An introduction to materials science and engineering. John Wiley and Sons Inc.
GIBBS FREE ENERGY OF REGULAR SOLUTION
If curves II and III are drawn for regular solutions, then deviation of
ΔGM from ΔGM,id is due only to the nonzero heat of mixing and the
difference between the two curves,

ΔGM-ΔGM,id = GXS = RTαXAXB = ΩXAXB = ΔHM

For curve III, |ΔGM|>|ΔGM,id| and thus ΔHM and Ω are negative
quantities. (Ω is negative if the A-B bond between different atoms is
greater than A-A and B-B bond strength between similar atoms) In
the case that the value of Ω rises negatively or the temperature
rises, the mixture free energy will be greater negative values.

19
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION
For curve II, |ΔGM|<|ΔGM,id|and thus ΔHM is a positive quantity (α
and Ω are positive quantities). (In this case, A-B bond strength
between different atoms is less than A-A and B-B bond strength
between atoms)
As Ω increases positively, mixture free energy will increase. At high
temperatures, ΔGM <0 while at low temperatures, ΔGM >0 .

Curve I is drawn as –ΔSM,id/R = (𝑋𝑋𝐴𝐴𝑙𝑙𝑙𝑙𝑙𝑙𝐴𝐴 + 𝑋𝑋𝐵𝐵𝑙𝑙𝑙𝑙𝑙𝑙𝐵𝐵 )

This curve represents ΔGM,id/RT.

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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION

21
GIBBS FREE ENERGY OF REGULAR SOLUTION

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GIBBS FREE ENERGY OF REGULAR SOLUTION
• This curve is “convex downwards”
only between A and n and between
p and B and is “convex upwards”
between n and p.
The Gibbs free energy of a system
of composition between m and q is
minimized when the system occurs
as two solutions, one of
composition m and the other of
composition q;
e.g., if the homogeneous solution of composition r separates into the
two coexisting solutions m and q, the Gibbs free energy of the system
is decreased from r to s.
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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION
The equilibrium coexistence of two separate solutions at the
temperature T and pressure P requires that

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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION
• Equations are the criteria for
equilibrium coexistence of two
solutions (or phases) at constant T and
P. The positioning of this double
tangent defines the positions of the
points m and q on the Gibbs free
energy of mixing curve.
• The A-B system, is one in which, at the
temperature T, the value of Ω is
sufficiently positive that the
consequent tendency toward
clustering of like atoms is great enough
to cause phase separation.
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Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION
• A homogeneous solution (phase I) is formed when B is initially added to A and
saturation of phase I with B occurs at the composition m.
• Further addition of B causes the appearance of a second solution (phase II) of
composition q (which is phase II saturated with A), and continued addition of B
causes an increase in the ratio of phase II to phase I occurring, until the
overall composition of the two-phase system reaches q, at which point phase I
disappears.
• A homogeneous solution (phase II) occurs between the compositions q and B.

26
Source: Gaskell, D. R. (2003). Introduction to the Thermodynamics of Materials. 4th. New York and London.
GIBBS FREE ENERGY OF REGULAR SOLUTION
• The curve mn represents the
Gibbs free energy of phase I
supersaturated with B, and the
curve qp represents the Gibbs free
energy of phase II supersaturated
with B. As the line AmqB
represents the equilibrium
states of the system.

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