Ana Sofia C. M. d’Oliveira, Ph.D.

Full professor
DEMEC/UFPR

A. S. C. M. D’Oliveira

ØGibbs free energy

– Thermodynamics: what material wants to do

– Kinetics: what it can do, and how quickly

The conditions of equilibrium and stability

– Equilibrium ⇒ no drive for change
– Deviation from equilibrium ⇒ driving force for change
– Beyond limits of stability ⇒ must change

Gibbs free energy, G - defines the state of equilibrium of a system

Available energy to perform work in a system

Gibbs free energy combines enthalpy and entropy into a single value

G = H -TS = E + PV –TS
Enthalpy
Entropy
. A. S. C. M. D’Oliveira

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 ØGibbs free energy

Enthalpy, H Entropy, S
The “heat” of a system
H=E + PV
Measures the (dis)order of a system
At const pressure, in solids and liquids
(condensed phases) PV is very small,
therefore At an atomic level
- configurational desorder (different
H ~ E (internal energy) arrangement of atoms in similar positions)
potential energy (Interaction/bond and
between atoms) - thermal vibrations of atoms
and around their positions.

kinetic energy (Atomic vibrations and

rotation and translational energy (S and L)

A. S. C. M. D’Oliveira

ØGibbs free energy

In a close system (fixed composition and mass) at T and P const equilibrium is

achieved when G is the lowest possible and

dG = 0

At equilibrium G tends to a minimum

G = H -TS

Equilibrium is a compromise between low enthalpy and high entropy

vLow T– solid phase, strong atomic bonds -> low E
vHigh T – entropy predominates; phases with higher freedom of atomic
movements predominate -> entropy (-TS ) “rules”

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 ØGibbs free energy
Equilibrium
Ex: cementite
Metastable equilibium

Stable equilibrium
Ex: graphite Transformations
that result on a
reduction on Gibbs
free energy of the
system are possible

Arrangement of atoms

For a transformation to occur it is required that ΔG reduces

ΔG=G2 -G1 < 0

A. S. C. M. D’Oliveira

ØGibbs free energy

Ø The change in free energy, ΔG, is equal to the sum of the enthalpy plus the product
of the temperature and entropy of the system.
ΔG= ΔH-T ΔS

The reaction is nonspontaneous (i.e., external energy

If ΔG is positive?
input is necessary for the reaction to occur)

If ΔG is negative? The reaction is spontaneous (occurs without external

energy input).

Ø ΔG depends only on the difference in free energy of products and reactants (or final
state and initial state).
Ø ΔG is independent of the path of the transformation and is unaffected by the
mechanism of a reaction.
Ø ΔG cannot tell us anything about the rate of a reaction.

(assume ΔH and ΔS are independent of temperature)

https://www.doitpoms.ac.uk/tlplib/phase-diagrams/index.php A. S. C. M. D’Oliveira

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 ØGibbs free energy
Pure material
Chemical composition does not change; low dependence on pressure ; high dependence on
temperature.

At a given T, the phase with the lowest G exhibits the higher stability

Above Tm L is the
phase with the highest
stability

Transformations
that result on a
reduction on Gibbs
free energy of the
Below Tm, S has
system are
higher stability expontaneous

At Tm, G curves cross and L and

S phases are in equilibrium
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ØGibbs free energy

Binary solutions

Gibbs free energy for the combination of pure A and pure B is a straight line
connecting GA and GB (partition between A and B)

Alloys - atoms A + atoms B mix, DGmix

DGsol = DGmix + DGfus

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 ØGibbs free energy

Mixture of A and B complete solubility, atoms A and B are distributed randomly

in the atomic lattice, DHmix =0

G1 + = G2=G1+ΔGmix

ü Free energy change due to mixing, DGmix = DHmix - TDSmix

üEnthalpy, DHmix, represents the nature of the chemical bonding, or in different words,
the extent to which A prefers B, or A prefers A as a neighbor
üEntropy, DSmix, refers to the increase in disorder in the system as A and B atoms mix. It
is independent of the nature of the chemical bonding.

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ØGibbs free energy

Ideal solution – Complete solubility, atoms A and B are distributed

randomly in the atomic lattice, entalphy is zero

Regular solution - Enthaphy is related to the heat of mixing is only

related to the bond energies between adjacent atoms - random
arrangement of atoms in a solution

Real solution – Entalphy also depends on the strain field cause by

mixing. A random arrangement of atoms in a solution does not reduce the
energy

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 ØGibbs free energy
Ideial solution DHmix =0 DG = - TDSmix

An atom A does not care whether it is sitting next to another A or to a B atom.

DSmix increases as disorder raises during

the mixture of A and B

DSmix

- TDSmix
A B

Entropy :
Thermal contribution, depends on the type of atomic vibration
and
Configurational contribution, depends on the arrangements of atoms

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ØGibbs free energy

Ideial solution DHmix =0 DG = - TDSmix

Gibbs free energy, G , of a systems depends on the G of each component

As T raises,GA and GB decrease

(increase on thermal entropy) and
DGmix decreases ( the free energy
curvature is more significant)

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 ØGibbs free energy
Each phase has a specific G; compare Gsol(XB) with Gliq(XB) for various temperatures

For single phase alloys

solid
molar gibbs free energy,G

High temperature: At temperatures above the melting

point of both pure A and pure B, the liquid is the stable
phase for all compositions.

liquid

composition, XB

liquid
molar gibbs free energy, G

Low temperature: At temperatures below the

melting point of both pure A and pure B, the solid is
solid the stable phase for all compositions.

composition, XB A. S. C. M. D’Oliveira

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ØGibbs free energy

At intermediate T, between Tm of pure A and of pure B

As the temperature is brought down from high to

liquid
low, the Gsol(XB) starts to move below that of
molar gibbs free energy,G

Gliq(XB). The minima in the two curves, in general,

does not occur at the same point

solid
Why the lines do not pass exactly over one another:
• The slope of the line G(pure, combined) will be different for
the solid and liquid, because GA(liquid) ≠GA(solid) and GB(liquid)
composition, XB ≠GB(solid).
• No solution is really ideal, so the enthalpy of mixing needs
to be taken into account.

What are the free energy curves showing ?

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 ØGibbs free energy

Separating in two phases; the overal free

Most stable
phase,lowest G
energy of the system can be reduced

The common tangent construction can link

the GL and GS to minimize the free energy of a
system with composition C. It can identify the
composition of the solid and liquid phase (CS
andDiagrams
MS15a, Gibbs Free Energy and Phase CL) which are in equilibrium at this
temperature
11/00

(2) no solution is really ideal, so the enthalpy of mixing needs to be taken into
account.

What are these last pair of free energy curves telling us? They contain the A. S. C. M. D’Oliveira

information we need to show that we must pass through a two-phase, solid + liquid
23
region as we cool from only liquid to only solid. MS15a,
To facilitate theEnergy
Gibbs Free discussion, let’s
and Phase
the last figure with a few points labeled, and compare it to the phase diagram,
redraw
Diagrams
also
11/00

redrawn with important

(2) no solutionpoints labeled.
is really ideal, so the enthalpy of mixing needs to be taken into
account.

What are these last pair of free energy curves telling us? They contain the
information we need to show that we must pass through a two-phase, solid + liquid
liquid
region as we cool from only liquid to only solid. To facilitate the discussion, let’s redraw
temperature, T

the last figure with a few points labeled, and compare it to the phase diagram, also
redrawn with important points labeled. ØGibbs free energy
To
. Correlation with the phase diagram
liquid
temperature, T

v The Gibbs free energy of the liquid would be

solid To
.
given by point (1)
A X
S
X
O
X
L
B v The system could lower its Gibbs free
B B B
solid energy by transforming to a solid. The gibbs
composition, X B
free energy of that solid would be given by
S O L
A X X X B
B B B point (2)
composition, X B

The system can lower its free energy even

solid further by splitting up into a solid of composition
molar gibbs free energy, g

solid XBS and a liquid of composition XBL

molar gibbs free energy, g

(1)
gs
(4)
(4)
(1) Ø The Gibbs free energy of the solid is given by
gs (2)
(2)
(3)
(3)
point (4) on the g(XB) diagram and that of the
liquid
liquid
liquid by point (5) on the same diagram.
.
(5) gL .
(5) gL

S O L
A X X X B
B B B
S composition,
O L X
A X X X B B
B B B
Let’s say we start out with composition,
a liquid of Xcomposition
B XBO and cool it to To. The
A. S. C. M. D’Oliveira
gibbs free energy of the liquid would be given by point (1) on the g(XB) diagram. The
system realizes it could lower its gibbs free energy by transforming to a solid. The gibbs
Let’s say we start out with a liquid of composition XB)Odiagram.
and coolBut,
it tohow
To.low
The
gibbs free energy
can you go? of25
free energy of that solid would be given by point (2) on the g(XB
the liquid would be given by point (1) on the g(XB) diagram. The
system realizes it could lower its gibbs free energy by transforming to a solid. The gibbs
free energy of that solid would be given by point (2) on the g(XB) diagram. But, how low
6
can you go?

6 8
 ØGibbs free energy

A system with the composition XB L will only

have liquid phase present

A system with the composition XB S will only

have solid phase present

XB L XB S

As T changes, the composition of S and L in equilibrium change, changing the

boundaries between S and L
The boundaries between single and binary regions identify the solidus line
and liquidus line in a phase diagram

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ØGibbs free energy

x y

z k

z k x y

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 Break

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ØGibbs free energy

Ideal solution – Complete solubility, atoms A and B are distributed

randomly in the atomic lattice, entalphy is zero

Regular solution - Enthaphy is related to the heat of mixing is only

related to the bond energies between adjacent atoms - random
arrangement of atoms in a solution

Real solution – Entalphy also depends on the strain field cause by

mixing. A random arrangement of atoms in a solution does not reduce the
energy

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 ØGibbs free energy
Regular solutions
The heat of mixing is only related to the bond energies between adjacent atoms. The
assumption is that the interatomic distances and bond energies are independent of
composition.
DHmix depends on the energy of atomic bonds ∆𝑯𝒎𝒊𝒙 ≠ 𝟎
DHmix <0 mixing is exothermic (heat released)
DHmix >0 mixing is endothermic (heat absorbed)
Alloy system A-B
Bonds between atoms: A – A bond (energy εAA )
A – B bond (energy εAB )
B – B bond (energy εBB )

For PAA, PBB and PAB bonds , the internal energy of the solution is E=PAA εAA + PBB εBB + PAB εAB

Enthalpy changes when the mixture occurs : DHmix = PAB ε

ε = ε AB – ½(ε AA + ε BB)
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ØGibbs free energy

Regular solutions
For small differences between εAB and (ε AA+ ε BB)/2 (and for high T) a random
arrangement of atoms in a solution can be considered - regular solutions.
PAB = Na z XA XB

Na –Avogadro number, Z coordination number

DHmix = WxAxB
W= Nazε

ε AB = ½(ε AA + ε BB ) DHmix = 0 solution is ideal

ε <0 or ε AB < ½(ε AA + ε BB) DHmix < 0 – atoms will tend to be

surrounded by atoms of different type;
A-B bonds favored

ε >0 or ε AB > ½(ε AA + ε BB) DHmix > 0 – atoms will tend to be surrounded
by atoms of the same type;
A-A and B-B bonds favored A. S. C. M. D’Oliveira

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 ØGibbs free energy
Real solutions
When a random arrangement of atoms in a solution does not reduce the energy

ØIf A-A and B-B bonds reduce the internal energy, W > 0, DHmix > 0 clustering may
occur and the system will exhibit rich A regions and rich B regions

ØIf A-B bonds reduce the internal energy, W < 0, DHmix < 0, an ordered solution may
form, the system will exhibit intermetallic compounds.

Fase g`
Fase g``

If atoms A and B have different sizes - The energy of the elastic strain fields due to
the mismatch in atomic sizes should be taken into account. If the size difference is
large, the contribution of the strain energy term could as important as the chemical
(bonding) term
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ØGibbs free energy

DGmix = DHmix - TDSmix = XAXBW + RT (XA lnXA + XBlnXB)

Para W < 0, DHmix <0 – exothermic solution –

mixing is favorable at all T;
At low T, and high │W│ an ordered solution can
form - the assumption of random mixing is not
valid, solution is not regular.

Para W > 0, DHmix>0 - At high T

entropy helps to mix - formation of A-B
pairs
At low T clustering may occur (AA and
BB bonds are favored) - solution is not
regular.

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 ØGibbs free energy
In systems with strong chemical bonding between the atoms there is a tendency for
formation of intermediate phases.
The intermediate phases can have a different crystal structure and may be highly
ordered, and an additional Gibbs free energy curve for the intermediate phase
should be considered.

If an intermediate phase have a specific composition and small deviations from the ideal
composition cause a rapid rise in G, the phase is called compound. Compounds typically have
a stoichiometric composition (AnBm where n and m are integers).

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ØGibbs free energy

Heterogeneous solutions

Systems with two or more phases are

heterogeneous systems. If pure
components A and B have different
equilibrium crystal structures, phase ⍺ and
phase 𝛽, we have to consider two Gibbs
free energy curves, one for each phase

Eutectic and Peritectic

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 ØGibbs free energy

DHmix>0 atoms will tend to be surrounded by

atoms of the same type; A-A and B-B bonds favored)
ØAt low T G assumes a negative curvature stability
increases when a mixture of two phases forms
ØAt high T, entropy increases and the miscibility gap
may be eliminated
Ø Tm has a minimum as the atomic bonds are weak;,
making melting easier

DHmix < 0, atoms will tend to be

surrounded by atoms of different type; A-B
bonds favored – SS or ordered phase can
extend up to Tm

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ØGibbs free energy

Phase diagrams (solid phases with the same crystal structure)

GSB
GSA
GLA GLB

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 ØGibbs free energy
Phase diagrams (solid phases with the different crystal structures)

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ØGibbs free energy

Composition range

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