Lecutre 2: Brief Review of Thermodynamics

Review of Equilibrium Thermodynamics:

Equilibrium
Entropy
Solution Thermodynamics
Equilibrium Phase Diagrams
Activity and Activity Coefficients

Lecture 2: Thermodynamic Review

Entropy
Entropy is a state function because the level of disorder of a system only depends on the
current condition of the system. Consequently, the entropy change for any process joining
the same two states is the same, whether the process is reversible or not.

Q S S
a
b
T

rev

To calculate the entropy change for any process we just find a reversible path
connecting the two states and calculate its change in entropy using the above
formula.

Lecture 2: Thermodynamic Review

The Second Law

The Second Law: The entropy of the universe increases for all processes except reversible
ones, for which there is no change in Suniv.
Once disorder is created, it cannot be destroyed.

Q S
univ 0
T

Re v

Suniv Ssys Ssurr

The changes in entropy of the system and surroundings
are balanced for a reversible process. That is entropy
is only transferred, and the original state of the universe
can be obtained by reversing the process.
If a process is not reversible, entropy is created and the disorder of the
universe is increased. The entropy of the universe can never decrease.

Lecture 2: Thermodynamic Review

Entropy
Entropy is a measure of the disorder in a system.

Q S
T

rev

Note that for a given process, the larger the heat flow the greater the increase in S.
Also, that a given heat flow of a process causes a larger change in S at lower Ts.
Also note that if a reversible process is adiabatic, it is isentropic.
Slowly remove mass

Q S
T

rev

Work W

Q S
T

Work W

Re v

Heat Q

Heat Q

Gas

Gas
Isothermal

Lecture 2: Thermodynamic Review

Adiabatic

Criteria for Equilibrium

Ssys

Suniv 0

for irreversible processes

Suniv 0

for reversible processes

Suniv 0

never

Irreversible
processes are also
called spontaneous
or natural

Ssurr

Ssys Screated Stransferred

Definitions:
A chemical system is any system made up of one or more elements.
A phase is any distinguishable region of a chemical system which is in a well-defined state of internal
equilibrium. Phases can be open or closed depending on whether they change or do not change the
amount of material in the phase, respectively.
A component is any independently variable chemical species of the system: For example, P in Si,
(C2H5)OH in H2O.

Lecture 2: Thermodynamic Review

Equilibrium
In a system that is in internal equilibrium, any infinitesimal
process about a point of equilibrium is reversible.
An infinitesimal change in the
system introduces no finite
driving forces and thus no
dissipative processes.
Examples of reversible and irreversible processes:
Heat flow down a temperature gradient
Mixing of NaCl in water
Melting of ice in a glass of water at 273K
Separation of oil and water
For an infinitesimal, reversible process performed on a single-phase closed chemical system
in internal equilibrium we can write:

dU Q W

Q TdS
From our definition
of entropy
Lecture 2: Thermodynamic Review

W PdV
In a chemical system
only mechanical work
is done.

dU TdS PdV i dni

i

Equilibrium Conditions
Consider an isolated chemical system (dV=0, dU=0 and dN=0)
of two phases:

Since the system is isolated, the total volume, internal energy and
number of particles is constant. So any change in these quantities for
one phase must be balanced by an equal and opposite change in the
other phase.
dV 0 dV dV

dU
dn 0 dn dn
dU 0 dU

For phase alpha:

Rearranging:

Likewise:

Lecture 2: Thermodynamic Review

dU

dS

dS

T dS
1

dU

dU

dV dV dV

dS dS dS

dU dU dU

dni dn
i dni

P dV
P

dV
T

dV

i dni
i

dni
T
i

dni

i T
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Equilibrium Conditions

Thus, for the total entropy we obtain the following equation, and since
entropy is a maximum for an isolated system in equilibrium it is equal to zero.

1
1
P
P

dV i i dn
dS
dU

i 0

T
T
T
T
i T
T

Thermal
Equilibrium

Lecture 2: Thermodynamic Review

P P

Mechanical
Equilibrium

Distributive
Equilibrium

Conditions for Phase Stability

Integrate dU

dU TdS PdV idni

i

U TS PV i ni
i

From the definition of G (2nd order

Legendre transform of U)

G U TS PV

Substituting U into our expression

for G

G TS PV i ni TS PV

Gives the Gibbs Free Energy in terms

of chemical potentials and concentrations.

G i ni

Lecture 2: Thermodynamic Review

The Gibbs-Duhem Equation

Starting with our expressions for
the Gibbs free energy

We consider how it changes for

an infinitesimal process
We see that G changes because the
amount of components changes or
because the chemical potential of the
components changes

G i ni

G U TS PV

dG d i ni

dG dU d TS d PV

dG nidi idni
i

dG SdT VdP i dni

i

G changes because T changes

or P changes or because the
composition changes

Since these two expressions for dG are equivalent we can equate them to find:
The Gibbs-Duhem Equation
which relates T, P and at
equilibrium in a single phase
system

Lecture 2: Thermodynamic Review

SdT VdP ni d i 0
i

10

Gibbs Phase Rule

Each phase of a system in internal equilibrium is governed by its own Gibbs-Duhem equation:

SdT VdP nidi 0

i

Each phase is described by C+2 intensive variables:

T, P and the C chemical potentials.
Since the Gibbs-Duhem expression relates these C+2 variables within each phase,
only C+1 of them are independent.
If phases are in equilibrium with each other, then we have only one T and one P for
all the phases, so we still have C+2 variables. However, we now have relationships
between the C+2 variables since we have a Gibbs-Duhem expression for each phase.

Gibbs Phase Rule:

f C 2

Note: F is the number of degrees

of freedom and P is the number of
equilibrium phases.

One can independently vary f intensive variables for a system

of C components and still keep phases in equilibrium.
Lecture 2: Thermodynamic Review

11

Systems at Constant P and T

For systems at constant pressure and temperature, equilibrium is established when the
system has minimized its Gibbs Free Energy:

dG SdT VdP i dni

i

Since a closed system at constant T and P

will minimize its Gibbs free energy at
equilibrium, we determine what equilibrium
phase a material will be in at different conditions
by determining which phase has the lowest G.

vap

The material follows the lowest G curve,

switching from one to another at transition
points.

Lecture 2: Thermodynamic Review

Slope: V

liq

Slope: -S

liq

vap

12

Phase Diagrams
If we consider both changes in T and P, the
material follows the lowest G surface,
switching from one to another at transition
points on a coexistence curve, which is
defined as the intersection of the two Gibbs
free energy surfaces.

G (T ,P)
l

G (T ,P)

coexistence curve

P
T

P
liq
sol
vap

Critical point

Triple point

T
Lecture 2: Thermodynamic Review

13

Construction of a Eutectic Phase Diagram

Below TE

GM

at TE

GM

G' A 0

G' B 0

GM

G' A 0

GA
XB

G' A

GA
XB

at TM(B)

GM

GB

GA
1

G' B 0

GB

G' A 0

G' B 0

Above TE and below

melting points

XB

GB

at TM(A)
GM

G' B 0

G' A 0

G' B

Lecture 2: Thermodynamic Review

+L

+L

+
L

1
XB

L
0

GA

XB

XB

1
14

Vapor Liquid Equilibrium

XB

The equilibrium phase diagram for a vapor-liquid binary system often takes
The form of a lens diagram. The two-phase region is defined by bubble
point and dew point lines which give the compositions of the liquid and vapor
in equilibrium at a particular temperature. The difference between these
compositions provides the driving force for several types of separations methods.

Lecture 2: Thermodynamic Review

15