CHAPTER 2

Classical Thermodynamics of Phase Equilibria

 Thermodynamics originated during the middle of the

nineteenth century.
 From its Greek root (therme, heat; dynamics, force),
one might wonder what “thermodynamics” has to do
with the distribution of various components between
various phases. Indeed, the early workers in
thermodynamics were concerned only with systems
of one component.
 The original thermodynamic formulas were applied
to only a limited class of phenomena, such as heat
engines. Now they are applicable to a large number
of problems in both physical and biological sciences.

 It was not until the monumental work of J. Willard

Gibbs that thermodynamic methods were shown to
be useful in the study of multi-component systems.

 It was Gibbs who was able to show that a thermo-

dynamic procedure is possible for a variety of
applications, including the behavior of chemical
systems.
Josiah Willard Gibbs
 The chapter briefly reviews the essential
concepts of the classical thermodynamic
description of phase equilibria.

 Heat transfer between

any two phases within the
heterogeneous system.
 Displacement of a phase
boundary.
 Mass transfer of any
component in the system
across a phase boundary.
 A heterogeneous system that is in a state of
internal equilibrium is a system at equilibrium
with respect to each of the three processes.

 The governing potentials in these three

processes are temperature, pressure and
chemical potential.
 It is one of the prime responsibilities of classical
thermodynamics of phase equilibria to “discover”
and exploit the appropriate “chemical potential”.
 2.1 Heterogeneous Closed Systems

 A homogeneous system is one with uniform

properties throughout; i.e., a property such as
density has the same value from point to point,
in a macroscopic sense.
 A phase is a homogeneous phase.
 A closed system is one that does not exchange
matter with its surroundings, although it may
exchange energy.
In a closed system not undergoing chemical
reaction,
the number of moles of each component is constant.
This constraint can be expressed as

dni  0 i  1,2,..., m

where ni is the number of moles of the ith component

and m is the number of components present.
 The Laws of Thermodynamics

 The first law of thermodynamics – Conservation

of Energy

Although energy assumes many forms, the total

equality of energy is constant, and when energy
disappears in one form it appears simultaneously
in other forms.

(Energy of the system)+(Energy of surroundings)=0

 The Laws of Thermodynamics
 The second law of thermodynamics –

All processes proceed in such a direction that the

total entropy change caused by the process is
positive; the limiting value of zero is approached
for processes which approach reversibility.
Mathematically this is expressed as

Stotal  0
 Entropy as Time's Arrow
One of the ideas involved in the concept of entropy is
that nature tends from order to disorder in isolated
systems. This tells us that the right hand box of
molecules happened before the left. Using Newton's
laws to describe the motion of the molecules would
not tell you which came first.
The concept of entropy and the second law of thermo-
dynamics suggests that systems naturally progress from
order to disorder. If so, how do biological systems
develop and maintain such a high degree of order?
Is this a violation of the second law of thermodynamics?

Order can be produced with an expenditure of energy,

and the order associated with life on the earth is
produced with the aid of energy from the sun.
For example, plants use energy from the sun in tiny
energy factories called chloroplasts. Using chlorophyll
in the process called photosynthesis, they convert the
sun's energy into storable form in ordered sugar
molecules. In this way, carbon and water in a more
disordered state are combined to form the more ordered
sugar molecules.
 The Laws of Thermodynamics

 The second law of thermodynamics –

1. No apparatus can operate in such a way that its

only effect is to convert heat absorbed by a system
completely into work done by the system.

2. No process is possible which consists solely in the

transfer of heat from one temperature level to a
higher one.
 Second Law: Heat Engines
Second Law of Thermodynamics: It is impossible to
extract an amount of heat QH from a hot reservoir and
use it all to do work W . Some amount of heat QC must
be exhausted to a cold reservoir. This precludes a
perfect heat engine.
 Second Law: Refrigerator
Second Law of Thermodynamics: It is not possible for
heat to flow from a colder body to a warmer body
without any work having been done to accomplish this
flow. Energy will not flow spontaneously from a low
temperature object to a higher temperature object.
This precludes a perfect refrigerator.
The second law of thermodynamics is a general principle
which places constraints upon the direction of heat
transfer and the attainable efficiencies of heat engines.
In so doing, it goes beyond the limitations imposed by
the first law of thermodynamics.

The First Law is essentially a statement of conservation

of energy and asserts that you can't get more energy out
of a heat engine than you put in. But the Second Law
says that no heat engine can use all the heat produced
by a fuel to do work. The Carnot cycle sets the ideal
efficiency which can be obtained if there is no friction,
mechanical losses, leakage, etc., but real machine
efficiencies are much less.
 The Laws of Thermodynamics

 The third law of thermodynamics –

The absolute entropy is zero for all perfect

crystalline substances at absolute zero
temperature.

S ( 0)  0 for all perfect ordered crystalline

materials
•The vast majority of substances form perfect crystals,
although several substances are known to form crystals
which are not perfect.

•Absolute entropies for these anomalous substances

are found by calculating the entropy of the crystal at
absolute zero through the methods of statistical and
quantum mechanics.

•The first statistical picture of entropy was that of

Boltzmann.
•The function W that represents the number of ways we
can distribute N particles into a number of states. Using
the function W the entropy can be expressed as:

S  k B ln W
•At zero Kelvin the system is its lowest energy state.
For a perfect crystal there is only one way to distribute
the energy and W=1, therefore S=0.

•However, if the substance is not a perfect crystal, W>1,

the entropy will not equal to zero. Although the entropy
in such cases is a small correction, it still leads to an
important concept.
 CO : an Imperfect Crystal
•The molecule CO has a very small dipole moment and
there is a finite chance that CO will crystallize as
CO:CO:CO instead of CO:OC:CO.

•For each CO molecule there are two possible orientation

of the molecule, therefore there are two ways each CO
can exist in the lattice. The number of ways per molecule
is w=2 for each CO.

•If we have N CO molecules there are wN ways or 2N ways

that all of the CO can be distributed. Therefore,

S  k B ln W  k B ln 2  Nk B ln 2
N
For a homogeneous, closed system, taking into
account interactions of the system with its
surroundings in the form of heat transfer and work
of volumetric displacement, a combined statement
of the first and second laws of thermodynamics is

dU  TdS  PdV
where dU, dS, and dV are, respectively, small
changes in energy, entropy, and volume of the
system resulting from the interactions; each of
these properties is a state function.
1st law of thermodynamics
U  Q  W
For infinitesimal changes, we have
dU  dQ  dW
Define entropy change and work as
dQ
dS  and dW   PdV
T
 dU  TdS  PdV
U,S,V,P,T : state function
State Variable : State variable or state function refers
to a variable whose value depends on the state in
which the system exists. Between two states the
change in a state variable is always the same regard-
less of which path the system travels. Temperature,
pressure and volume are examples of state variables.

Path Variables : Changes in path variables depend on

the path traveled by the system. These variables have
meaning only when applied to a process in which the
path between two states is specified. Work and heat are
path variables.
 Concept of Equilibrium State

 Processes such as heat transfer, work of volume

displacement and for open systems, mass
transfer across a phase boundary have no ten-
dency to depart spontaneously.
 The properties are independent of time and of
previous history of the system.
 An equilibrium state can be distinguished from a
steady state by the fact that in an equilibrium
state there are no net fluxes of the kind under
consideration across a plane surface placed
anywhere in the system.
 Concept of Reversible Process

 A change in the equilibrium state of a system is

called a process.
 A reversible process is one where the system is
maintained in a state of virtual equilibrium
throughout the process.
 This requires that the potential difference
between system and surroundings causing the
process to occur be only infinitesimal.
 Any natural or actual process occurs irreversibly.
 Concept of Reversible Process
 We can think of a reversible process as a l
imit approached but never attained.
 The inequality in

dU  TdS - PdV

refers to a natural (irreversible) process an

d the equality to a reversible process.
To obtain the finite change in a thermodynamic
property occurring in an actual process (from equilibrium
state 1 to equilibrium state 2), the integration of equation
must be done over a reversible path using the properties
of the system as
dU  TdS  PdV
S2 V2

U  U 2  U1   TdS   PdV
S1 V1
Because U is a state function, this result is indepen-
dent of the path of integration, and it is independent
of whether the system is maintained in a state of
internal equilibrium or not during the actual process.
 dU  TdS  PdV
This equation represents the fundamental thermody-
namic relation (Gibbs, 1961). If U is considered to be
a function of S and V, and if this function is known,
then all other thermodynamic properties can be ob-
tained by purely mathematical operations on this
function. For example,
T   U / S  V
P   U / V  S
While another pair of independent variables could be used to
determine U, no other pair has this simple physical signifi-
cance. Thus, U, S and V are a fundamental grouping.
 An important aspect of dUTdS-PdV is that it presents
U as a potential function. If the variation dU is constrained
to occur at constant S and V, then

dU S ,V  0
 This implies that at constant S and V, U tends toward a
minimum in an actual or irreversible process in a closed
system and remains constant in a reversible process.

 Because the actual process is one tending toward an

equilibrium state, an approach to equilibrium at constant
entropy and volume is accompanied by a decrease in
internal energy.
 Other extensive thermodynamic potentials for closed
systems and other fundamental groupings can be ob-
tained by using different pairs of the four variables P,
V, T, and S as independent variables. For example,
we define

H  U  PV
dH  dU  PdV  VdP
 TdS  PdV  PdV  VdP
 TdS  VdP
dH S , P  0 H, S, P : fundamental grouping
Similarly, we can define the Helmholtz energy by using
T and V as the independent variables,

A  U  TS
dA  dU  SdT  TdS
 TdS  PdV  SdT  TdS
  SdT  PdV
dAT ,V  0 A, T, V : fundamental grouping
Similarly, we can define the Gibbs energy by using
T and P as the independent variables,

G  H  TS
dG  dH  SdT  TdS
 TdS  VdP  SdT  TdS
  SdT  VdP
dGT , P  0 G, T, P : fundamental grouping
 2.2 Homogeneous Open Systems

 An open system can exchange matter as well as

energy with its surroundings.
 For a closed homogeneous system, we
considered U to be a function only of S and V;
that is, U=U(S,V).
 In an open system, there are additional indepen-
dent variables. We can use the mole numbers of
the various components present,
U=U(S,V,n1,n2,…nm)
where m is the number of components.
 The total differential is then
 U   U   U 
dU    dS    dV     dni
 S V ,ni  V  S ,ni i  ni  S ,V , n
j

 Further, we define the function i as

 U 
i     f (T , P, xi )
 ni  S ,V ,n j
 We may then write
dU  TdS  PdV   i dni
i
This is the fundamental equation for an open system.
 Using the defining equations for H, A, and G, we can
obtain three other fundamental equations for an open
system dU  TdS  PdV   i dni
i
dH  TdS  VdP   i dni
i

dA   SdT  PdV   i dni

i
dG   SdT  VdP   i dni
i

 From the above equations,

 U   H   A   G 
i            
 ni  S ,V ,n j  ni  S , P ,n j  ni T ,V ,n j  ni T , P ,n j
Note : The quantity i is the partial molar Gibbs energy, but it is not the
partial molar internal energy, enthalpy, or Helmholtz energy.
 2.3 Equilibrium in a Heterogeneous
Closed System

 A heterogeneous, closed system is made up of

two or more phases with each phase considered
as an open system within the overall closed
system.
 We now consider the conditions where the
heterogeneous system is in a state of internal
equilibrium with respect to the three processes
of heat transfer, boundary displacement, and
mass transfer.
  The general result for a closed, heterogeneous
system consisting  phases and m components
is that at equilibrium, (1) ( )
T ( 2)
T  ...  T
( )
Overall : heterogeneous closed P (1)
P ( 2)
 ...  P
(1) ( 2) ( )
homogeneous open 1   1  ...  1
(1) ( 2) ( )
2  2  ...   2
homogeneous open
.
homogeneous open .
( )
m  m  ...   m
(1) ( 2)
 2.4 The Gibbs-Duhem Equation

 We may characterize the intensive state of each

phase present in a heterogeneous system at
internal equilibrium by its temperature, pressure
and the chemical potential of each component
present – a total of m+2 variables.
 Those variables are not all independently
variable, and the Gibbs-Duhem equation shows
how the variables are related.
 Consider a particular phase within the heterogeneous
system as an open, homogeneous system. The funda-
mental equation in terms of U is
dU  TdS  PdV   i dni
i
 We may integrate this equation from a state of zero
mass (U=S=V=n1=…=nm=0) to a state of finite mass
(U,S,V,n1,…,nm) at constant temperature, pressure,
and composition; along this path of integration, all
coefficients, including all i are constant; the integ-
ration gives
U  TS  PV   i ni
i
 Differentiation of this equation to obtain a general
expression for dU gives
dU  TdS  SdT  PdV  VdP   i dni   ni di
i i
 Comparing with
dU  TdS  PdV   i dni
i
We have
SdT  VdP   ni di  0 The Gibbs-Duhem Eq.
i

Note that of the m+2 intensive variables that may be used to charac-
terize a phase, only m+1 are independently variable; a phase has
m+1 degrees of freedom.
 2.5 The Phase Rule

 If the heterogeneous system is not in a state of

internal equilibrium, but each phase is, the
number of independent variables is (m+1),
because for each phase there are m+1 degrees
of freedom; a Gibbs-Duhem equation applies to
each phase.
 If the entire system is in a state of internal equili-
brium, then there are (-1)(m+2) equilibrium
relations.
 2.5 The Phase Rule (cont’d)
 The number of degrees of freedom, F, is the
number of intensive variables used to charac-
terize the system minus the number of relations
or restrictions connecting them:

F = (m+1)-(-1)(m+2)
= m+2-

m is the number of independently variable

species and  is the number of phases in the
system.
 2.6 The Chemical Potential
 The task of phase-equilibrium thermodynamics
is to describe quantitatively the distribution at
equilibrium of every component among all the
phases present.
 Gibbs obtained the thermodynamic solution to
the phase-equilibrium problem by introducing the
abstract concept of chemical potential.
 The goal here is to relate the abstract chemical
potential of a substance to physically measur-
able quantities such as temperature, pressure
and composition.
 For a pure substance i, the chemical potential is
related to the temperature and pressure through
the Gibbs-Duhem equation

di   si dT  vi dP
where si and vi are the molar entropy and volume.

 Integrating and solving for i at some T and P, then

T P
i (T , P)   i (T , P )   si dT   vi dP
r r

Tr Pr
where superscript r refers to some arbitrary refer-
ence state.
 T P
i (T , P)   i (T r , P r )   si dT   vi dP
Tr Pr

 The two integrals on the right side can be evaluated

from thermal and volumetric data over the range Tr
to T and Pr to P.
 However, the chemical potential i(Tr, Pr) is unknown.
Hence, the chemical potential at T and P can only be
expressed relative to its value at the arbitrary reference
state designated by Tr and Pr.
 Thus, we use arbitrary reference states that are com-
monly called standard states for successful application
of thermodynamics to real systems.
 2.7 Fugacity and Activity

 In an attempt to simplify the abstract equation of chemical

potential, Lewis first considered the chemical potential for
a pure, ideal gas and then generalized to all systems.
 i 
di   si dT  vi dP   P   vi
 T
 Substituting the ideal-gas equation, vi  RT / P

 And integrating at constant temperature,

P
i    RT ln 0
i
0

P
 P
i    RT ln 0
i
0

P
 The essential value of the above equation is that it
simply relates a mathematical abstraction to a common,
intensive property of the real world. However, it is valid
only for pure, ideal gases.
 To generalize it, Lewis defined a function f, called
fugacity, by writing for an isothermal change for any
component in any system, solid, liquid, or gas, pure or
mixed, ideal or not,
fi
i    RT ln 0
i
0

fi
 For a pure, ideal gas f i  Pi
 For a component i in a mixture of ideal gas f i  yi P
 For all systems, pure or mixed, approach ideal-gas
behavior at very low pressures, the definition of
fugacity is completed by the limit
fi
1 as P0
yi P

 Lewis called the ratio f/f0 the activity, a. The activity

of a substance gives an indication of how “active” a
substance is relative to its standard state.
 For ideal gas For any system
P fi
i    RT ln 0
i
0
i    RT ln 0
i
0

P fi

The relation between fugacity and chemical potential

provides conceptual aid in performing the transition
from thermodynamic to physical variables.

 It is difficult to visualize the chemical potential, but

the concept of fugacity is less so. Fugacity is a
“corrected pressure”; for a component in a mixture
of ideal gases it is equal to the partial pressure of
that component.
The fugacity provides a convenient transformation of
the fundamental equation of phase equilibrium. For
phases  and , respectively
 
 
i i
f i f 
i  i0  RT ln 0 and i  i0   RT ln i0 
fi fi
Suppose that the standard states for the two phases
are the same,
i0  i0  and 0
fi  fi 0

 
 fi  fi
 2.8 A Simple Application: Raoult’s Law
 Consider the equilibrium distribution of a component in a
binary system between a liquid phase and a vapor phase.
For component 1, the equation says f1V  f1L
Assumptions : The fugacity, at constant temperature and
pressure, is proportional to the mole fraction,
f 1
V
 y1 f V
pure1 and f1  x1 f
L L
pure1

Assumption : Pure component 1 vapor at temperature T

and pressure P is an ideal gas,
f V
pure1 P
Assumption : The effect of pressure on the fugacity of a
condensed phase is negligible at moderate
temperatures. We also assume that the
vapor in equilibrium with pure liquid 1 at
temperature T is an ideal gas.
f L
pure1 P 1
s

 y1 P  x P1 1
s
Raoult’s Law

where P1s is the saturation pressure of pure

liquid 1 at temperature T.