4.

Thermodynamic potentials
4.1Thermodynamic variables
4.2 Maxwell construction of thermodynamics
4.3 Phase transitions and Phase Equilibrium
4.4 Clausius-Clapeyron Equation
4.5 First and second order phase transition
4.1 Thermodynamic variables
Introduction: Thermodynamics is the study of the inter-relation between heat, work and internal
energy of a system and its interaction with its environment..

Example systems
• Gas in a container
• Magnetization and demagnetization System
• Charging & discharging a battery Environment
• Chemical reactions
• Thermocouple operation
Universe
The energy of a thermodynamic system is a state function. The
variation of such a function depends only on the initial and final state.

A
T
Physical quantities are needed to describe the state of a system:
•Scalars: Volume, pressure, number of moles
•Vectors: Force, electric or magnetic field
•Tensors: Stress, strain
We distinguish extensive (size dependent) and intensive (size
independent) quantities.
Conjugate quantities: product has the dimension of energy.

intensive extensive
Temperature T Entropy S
Pressure P Volume V
Chemical potential m Number of moles n
Electrical field E Displacement D
Stress s Strain e
 Thermodynamic functions:
1. The total (mean) Internal Energy U (E)
2. The Enthalpy H
3. The Helmholtz Free Energy F
4. The Gibbs Free Energy G
• Any one of these functions can be used to characterize the
thermodynamic properties of a macroscopic system. These functions are
sometimes called thermodynamic Potentials (TP).
 Internal Energy U = U(S,V,N)
Enthalpy H = U + pV = H(S,p,N)
Helmholtz Free Energy F = U – TS = F(T,V,N)
Gibbs Free Energy G = U – TS + pV = G(T,p,N)
N  Number of particles in the system.
m  Chemical potential of the system.
Potential Variables
U(S,V,N) S,V,N
H(S,p,N) S,p,N
F(T,V,N) V,T,N
G(T,P,N) P,T,N
• All thermodynamic properties of a system can be found by taking appropriate
partial derivatives of the TP. The total differentials resulting from the combined 1st
& 2nd Laws for each TP are:

dU  S ,V , N   TdS  PdV  mdN

dH S , P, N   T dS  VdP  mdN

dF T ,V , N   SdT  PdV  mdN

dGT , P, N   SdT  VdP  mdN

 Why are thermodynamic potentials useful
Thermodynamic potentials give the complete knowledge about any
thermodynamic system at equilibrium
e.g. U=U(T,V) does not give complete knowledge of the system
and requires in addition
P=P(T,V) equation of state

U=U(T,V) and P=P(T,V) complete knowledge of equilibrium properties

U(T,V) is not a thermodynamic potential

However
We are going to show: U=U(S,V) complete knowledge of equilibrium
properties

U(S,V): thermodynamic potential

The thermodynamic potential U=U(S,V)

Now Consider first law in differential notation dU  dQ  dW 2nd law

dQ dQ  TdS
inexact differentials expressed by exact differentials
dW dW  PdV

Note: exact refers here to the

coordinate differentials dS and dV.
TdS and PdV are inexact
dU  TdS  PdV

So dU is an exact potental.
 By Legendre transformation

(T,V): dU  TdS PdV  d(TS)  SdT  PdV

d(U  TS)  SdT  PdV

from (S,V) to : F Helmholtz free energy

(T,P): dF  SdT  PdV  SdT  d(PV)  VdP

d(F  PV)  SdT  VdP

: G Gibbs free energy

G  F  PV  U  TS PV  H  TS
 Product
dU  TdS dPV  VdP rule

easy check:  dPV  VdP  VdP  PdV  VdP  PdV

dU  dPV  TdS VdP dU  PV  TdS  VdP

=:H (enthalpy)

Enthalpy H=H(S,P) is a thermodynamic potential

dH  TdS VdP
General thermodynamics potential
Internal energy U: Suppose we wish to create a thermodynamic system from scratch. Let’s
imagine that we create it from scratch in a thermally insulated box of volume V .
Suppose that when we spontaneously create our system while it is thermally insulated, but in constant mechanical
contact with a ‘volume bath’ at pressure p.
Suppose that when we spontaneously create our system
while it is in constant contact with a thermal reservoir at
temperature T. Then as we create our system, it will
absorb heat from the reservoir.
•If we create a thermodynamic system at conditions of constant
temperature T and constant pressure p, then it absorbs heat
energy Q = T S from the reservoir and we must expend work
energy pV in order to make room for it. Thus, the total amount
of work we must do in assembling our system is G.
4.2 Maxwell’s relations
•Potentials are functions of state and their differentials are total and
exact.
•Thus, the second derivative of the potentials with respect to the
independent variables does not depend on the order of derivation.
•Some mathematical functions can be employed.
if f  x, y 
f f
and df  dx  dy
x y

 f  f
then 2 2


xy yx
Why Use Maxwell Relations?
• Some variables in thermodynamics are hard to measure experimentally.
For example, the entropy
• The Maxwell Relations provide a way to exchange variables.
• They relate theoretical quantities, such as equations of state & entropy
to more easily measured quantities.
 Deriving Maxwell Relations
• Assume an infinitesimal quasi-static process & express an energy as a function
of the other variables. For the internal energy U as a function of T, S, P, V, we
have

• Next, take the total derivative of the energy with respect to the natural variables. For
example, for the internal energy U, natural variables are entropy S & volume, V.

 U   U 
dU    dS    dV
 S V  V  S
• Now that we have the total derivative with respect to its natural variables, we
can refer back to the original equation for the energy U and define, in this
example, T and P.

 U   U 
dU    dS    dV
 S V  V  S

 U   U 
  T    P
 S V  V  S
 • Next , we take into account a rule about partial derivatives for
analytic functions:

……(1)

which relates the change of the temperature T with the volume V to the (negative of the) change
of the pressure P with the entropy S.
Enthalpy H(S,p,N)
We have already defined enthalpy as H = U + pV .

……(2)
Helmholtz Free Enerygy F(T,V,N)
This time we as we transform from U to F, we replace the independent variable S with its conjugateT.

……(3)
Gibbs Free Energy G(T,p,N)
This time we as we transform from U to G, we replace the independent variables S and
V with their conjugates T and p.

The internal energy U might be thought of as the energy required to create a system in the absence of changes in
temperature or volume. An additional amount of work PV must be done if the system is created from a very small
volume in order to "create room" for the system. A system at constant temperature T will contain an amount of
energy TS Gibbs is the energy in excess of that energy TS.
……(4)
These relations are very important, since they connect changes in one state variables to changes in
another state variable in a different process. They limit the freedom of a system in equilibrium to
respond to external causes. Maxwell relations are easy to derive if you know which state variables
are your basic set, which free energy belongs to that set, and which form the differential has.
 Stability and Gibbs Free Energy G
G = E + PV – TS and we just defined enthalpy H = E + PV so

G(p,T) = H − TS thermal energy minus Temp x disorder

Stable forms of a chemical system have the minimum possible Gibbs Free Energy
H is the Enthalpy, a measure of Thermal Energy.
S is the Entropy, a measure of randomness, of probability.
 4.3 Phase transitions and Phase Equilibrium
What are the States of Matter?

Solid Liquid

31
Gas Plasma
 Phase changes
Reactions that involve formation of inter-molecular interactions are exothermic.
Reactions that involve breaking inter-molecular interactions are endothermic.

35
•A phase diagram is a graphical representation of all the equilibrium phases as a
function of temperature, pressure, and composition.
•Phase diagrams arise from minimizing free energies for each phase. They can be
used to describe gas - liquid – solid transitions, polymorphic solid-to-solid
transitions, stable phases in alloys of different composition, etc.
For a system at equilibrium
 Phase Diagram
• The temperature of a phase transition point is affected by the pressure.
• Therefore, a phase diagram can be drawn in the plane of temperature and
pressure.
• Whether a substance is a solid, liquid or gas depends on the temperature and
pressure.
• Keeping T constant while increasing P usually produces a solid.
• Water is an exception, increasing pressure on ice produces water.
• Phase Diagram:
– Plot of Pressure versus Temperature.
• Triple Point
– A point on the phase diagram at which all three phases exist (solid, liquid and gas)
• Critical Point
– A point on the phase diagram at which the density of the liquid a vapor phases are the
38 same
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 P

• At the critical point c the phase boundary between liquid and gas vanishes.
• The phase boundary between solid and liquid never vanishes.
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 Coexistence of Phases
Solid-to-liquid phase transition:
• In general, the liquid phase has a slightly larger molar volume and a slightly
higher internal energy. The molecules in the liquid require a larger nearest-
neighbor distance to move around, and so the volume expands, and the average
potential energy of interaction is higher. The molecules or atoms in the liquid
phase can be anywhere in the volume, but in the solid phase they can move only
around their lattice points. Therefore, the number of possible microscopic states
is much larger in the liquid phase than in the solid phase, and the entropy of the
liquid phase should be larger. Near the phase transition point, there should be
two local minima of U+PV −S(U, V )T in the U–V plane.

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• The quantity U+PV is lower at the solid-phase local minimum, as explained
above. Therefore, at lower temperatures, where the contribution ST is small,
the solid phase has a lower value of U+PV −ST. As the temperature becomes
higher, the liquid-phase minimum decreases faster than the solid-phase
minimum owing to the larger value of S, and so a transfer of the minimum
from one phase to the other occurs at some temperature.

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Liquid-to-gas phase transition.
In this case the energy is higher in the gas phase because there is practically no
energy gain from the attractive interaction of the molecules. The volume and
entropy are much larger in the gas phase. Therefore, both temperature and pressure
can be effective in causing a transition between the phases. The liquid phase is
favored at high pressure because of the PV term. The gas phase is favored at high
temperature because of the −ST term. These tendencies are in accordance with our
everyday experience.

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 The interpretation of a critical point is as follows. If the temperature is in the
range (Tt, Tc), an increase in pressure will cause a phase transition between two
states. At low pressure the state of the system resembles a gas, at high pressure a
liquid. Since these two states are separated by a phase transition, we can clearly
identify them. If the temperature is above Tc, however, this clear separation
vanishes. At low pressure the system still behaves like a gas, and at high
temperature like a liquid. The change from one to the other is continuous and it is
not possible to uniquely identify where we change from one type of behavior to
another. This continuous change is not possible from liquid to solid, as far as we
know from experiments.
• There are two special points in the phase diagram. One is the triple point, at
which the solid, liquid, and gas phases can coexist. This occurs at T = 273.16K
and P = 611.66 Pa.
• Another is the critical point, beyond which the line separating the gas and liquid
phases disappears. This is the point at T = 647.31K and P = 22.106 MPa. 47
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 4.4 Clausius-Clapeyron Equation

• The slope of the coexistence line in the phase diagram, dP/dT, can be related
to measurable quantities.
• Along the coexistence line, the Gibbs free energies of the two phases are the same. 49
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 The Clausius-Clapeyron Relation P
G1 P, T   G2 P, T 
Along the phase boundary: phase
G1 P, T   G2 P, T  m1 P, T   m2 P, T  P boundary

Consider two distinct displacements along the coexistence

curve, one immediately above the curve (in phase 1), the
other immediately below the curve, in phase 2. Because the T T
chemical potentials remain equal along the curve, dm1 = dm2

For the slope of the boundary we have:  S1dT  V1dP  S2 dT  V2 dP

dP S1 P, T   S 2 P, T 
- the slope is determined by the entropies and volumes of the
 two phases. The larger the difference in entropy between the
dT V1 P, T   V2 P, T  phases – the steeper the coexistence curve, the larger the
difference in molar volumes – the shallower the curve.
(compare the slopes of melting and vaporization curves)

Since S1 - S2 = L/T (L is the latent heat), we dP LT  (applies to all


arrive at the Clausius-Clapeyron Relation : dT T V T  coexistence curves)

Example: - since Vgas > Vliq , and L > 0 for the “liquidgas”
transformation, the boiling temperature increases with

dT T Vgas T   Vliq T 

 pressure. The “freezing” temperature with increasing
LT 
pressure either increases or decreases, depending on the
dP sign Vliq – Vsolid (exception – 3He).
• The Clapeyron equation gives the relationship between the variations
of pressure and temperature required for maintaining equilibrium
between the two phases.

Applications of the Clausius-Clapeyron Equation:

1. Pressure dependence of the melting point
2. Pressure dependence of the boiling point
3. Evaporation and sublimation
 4.5 First and second order phase transition
As the pressure or temperature changes, one phase may be replaced by another phase. This
change of phase is called a phase transition. Phase transitions can be divided into two classes.
In a first-order phase transition, the internal energy per mole changes by a nonzero amount. On
the other hand, in a second-order phase transition, the internal energy changes continuously
through the transition point. The phase transitions between a gas and a liquid, between a liquid
and a solid, and between a solid and a gas are usually of first order.

• A solid can also have different phases. For example, iron is in a paramagnetic
phase at T > Tc and a ferromagnetic phase at T < Tc.
• The magnetic transition and the normal-to superfluid transition of liquid
helium are of second order.
First order phase transition
• Since the entropy changes across the coexistence line, i.e. the line of the first-
order phase transition, a latent heat is always needed for a first-order phase
transition.
When water starts boiling, it undergoes a phase transition from a liquid to a gas phase. For both phases independently, the equation
of state is a well-defined regular function, continuous, with continuous derivatives. However, while going from liquid to gas one
function “abruptly” changes to the other function. Such a transition is of first-order. Gibbs enthalpy. Phase transitions in the P − T
phase diagram are described by the Gibbs enthalpy G(T, P, N), as defined by (5.11), which is itself a function of the pressure P and
of the temperature T. G(T, P, N) changes continuously across the phase boundary when the transition is of first order. The entropy
S and volume V , which are given by the derivatives
Second order phase transition
 At the transition point, S1=S2 and V1= V2.

Thus, second-order phase transition do not involve discontinuity jumps in volume

and in entropy, but involve abrupt changes in heat capacity and compressibility.