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A. S. C. M. D’Oliveira
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.
A. S. C. M. D’Oliveira
dG = 0
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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
A. S. C. M. D’Oliveira
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
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.
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
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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)
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4
ØGibbs free energy
G1 + = G2=G1+ΔGmix
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ØGibbs free energy
Ideial solution DHmix =0 DG = - TDSmix
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
Each phase has a specific G; compare Gsol(XB) with Gliq(XB) for various temperatures
liquid
composition, XB
liquid
molar gibbs free energy, G
composition, XB A. S. C. M. D’Oliveira
19
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.
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ØGibbs free energy
(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
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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
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
(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
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can you go?
6 8
ØGibbs free energy
XB L XB S
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x y
z k
z k x y
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9
Break
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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
ε = ε AB – ½(ε AA + ε BB)
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DHmix = WxAxB
W= Nazε
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
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
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GSB
GSA
GLA GLB
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ØGibbs free energy
Phase diagrams (solid phases with the different crystal structures)
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Composition range
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