Introduction to the Equilibrium Phase

First law of thermodynamics : the energy is constant in the thermodynamic universe.

Energy balance
Q
W ∂ U = δ Q− δ W
System δ W =P∗∂ V
∂ U = δ Q−P∗∂V

Second law of thermodynamics : it indicates the most probable way of occuring a

thermodynamic process.

Entropy Balance

∂ ST ≥0

Claussius ' s inequality

δQ
∂ ST ≥
T

1
From energy balance→ δ Q=∂ U + P ∂ V
Replacing into entropy balance→T ∂ S≥∂ U + P ∂ V

∂ U ≤T ∂ S−P ∂ V

From entalphy definition H =U +PV ⇒∂ H =∂U + P ∂ V +V ∂ P

∂ U =∂ H −P ∂ V −V ∂ P
∂ H ≤V ∂ P+T ∂ S

From the same way for G y A ; we have :

∂ G≤V ∂ P−S ∂T
∂ A≤−P∂ V −S ∂ T

At equilibrium or for reversible processes U , H , G y A are equal to zero .

The inequality is used for irreversible processes .
A
V T
V A T +
+
U G

Magic
Square -
U G S H P
Thermodynamic
∂U <T ∂ S−P∂ V
-
S P ∂ U =T ∂ S−P ∂ V
H
2
 Principle of Increase of Entropy

∂ S T >0

∂ S T =0

Irreversible process Reversible process or equilibrium

∂ U <T ∂ S−P ∂V ∂ U =T ∂ S−P ∂ V

∂ H <V ∂ P+T ∂ S ∂ H =V ∂ P+T ∂ S

∂ G<V ∂ P−S ∂ T ∂ G=V ∂ P−S ∂T

∂ A<−P ∂ V −S ∂T ∂ A=−P ∂ V −S ∂ T

3
V A T Maxwell Relations
+
∂V ∂T ∂V ∂T
− ( ) ( ) (
∂S P
=−
∂P S
→ = ) ( )
∂S P ∂ P S
U G ∂S ∂V
( ) ( ∂P T
=− )
∂T P
∂P ∂S

S
-
P
( ) ( =
∂T V ∂V T )
H ∂T ∂P
( ) (
− =
∂V S ∂ T V )
Thermodynamic State Relations

V A T ∂A ∂G
+ ( ) ( )
=
∂T V ∂T P
=−S

∂A ∂U

U G
( ) ( )
=
∂ V T ∂V S
=−P

∂H ∂U
( ) ( )
=
∂S P ∂S V
=T

∂G ∂H
S
-
P
( ) ( )
=
∂P T ∂ P S
=V
H
4
 Chemical Potential (μ)

Third law of thermodynamic shows us that Figure of phase stability of water

the entropy is always positive.

S gas >S líq >S sól

∂G
( )
∂T
=−S

∂G
μ= ( )
∂ n P ,T
=G
∂μ
( ) ∂T
=−S
∂μ ∂μ ∂μ
( ) ( ) ( )
< <
∂ T gas ∂ T líq ∂ T sól

∂ G=∂ μ ≤0
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 Multicomponent Systems

At equilibrium at constant T and P

G=G (T , P , n1 , n2,. .. ,n k )
∂ G=∑ μ i ∂ ni =0
∂G
μi=
( )
∂ ni T , P ,n j≠i
For equilibrium phases
∂A
( )
μi =
∂n T ,V , n j≠ i
Phase β, ni, P, T

nβi
∂U
μ =(
∂n )
i nαi
S , V , n j≠ i Phase α
ni, P,T
∂H
μ =(
i
∂n ) S ,P , n j≠ i
∑ μ i ∂ ni=0
Total differential of the energy Gibbs : ∑ μ i ∂ ni=αμiα ∂ nαi +β μβi ∂ nβi
∂ ni =−∂ ni
α β α
∂G ∂G ∂G (μ i −μ i )∂ n i =0
∂ G= ( )
∂T P
∂T+
∂P ( ) T
∂ P+ ∑
( )
∂ ni P , T ,n j≠i
∂ ni
μ αi =μβi
∂G=−S ∂ T +V ∂ P+ ∑ μi ∂ n i
The above result is the general criteria
of thermodynamic equilibrium

6
 Phases Rule of Gibbs
Intensive property :it is a property that is independent of mass quantity of the system .
Examples : P , T , ρ , x i and son on .

Extensive property :it is a property that is dependent of mass quantity of the system .
Examples :V , U , S , G , H , A and son on .

Experience tells us that we need at least two variables to stablish the state o phase of a pure substance .
Generally the pressure and temperature is enough to determine any other termodynamic property of
a substance pure. In other words, the number minimum of intensive variables or free degrees (F) to de-
fine the thermodynamic state of a pure substance are two.

F =2

Taking account into the number of phases ( Ψ ) for each compound in a mixture, it requires (n-1) com-
sitions for each of them to specify its termodynamic state. Then the number of variables are:

F =2+ Ψ(n−1) .

At thermodynamic equilibrium the system is forced to obey the equilibria criterium, for each substance
can be written one equation of the equilibrium for each ( Ψ -1) phases. This implicate a constraint, then:

F=2+Ψ (n−1)−n(Ψ−1)
F =2+n−Ψ
7
 Phases Rule of Gibbs

Compounds Phases F
1 1 2
F=2+n−Ψ 1 2 1
1 3 0
2 1 3
2 2 2

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