EXAMPLE 9.

4 A gas mixture containing 3 mol CO2, 5 mol H2 and 1 mol water is undergoing the
following reactions:
CO2 + 3H2 CH3OH + H2O
CO2 + H2 CO + H2O
Develop expressions for the mole fraction of the species in terms of the extent of reaction.
Solution The total moles initially present,
n0 = 3 + 5 + 1 = 9
For the first reaction,
n1 = – 1 – 3 + 1 + 1 = – 2
For the second reaction,
n2 = – 1 – 1 + 1 + 1 = 0
The mole fractions are calculated using Eq. (9.9)

9.2 CRITERIA OF CHEMICAL REACTION EQUILIBRIUM

We have developed the criteria of phase equilibrium in Chapter 8. At constant temperature and
pressure, the transfer of materials from one phase to another under equilibrium is found to occur with
no change in the free energy. Stated mathematically,
………(9.10)
Here is the total Gibbs free energy of the system at constant temperature and pressure. This
criterion is quite general and is not restricted to physical transformations. When a chemical reaction
occurs at equilibrium there is no change in the Gibbs free energy of the system, provided the change is
taking place at constant temperature and pressure.
Consider a closed system in which a chemical reaction represented by the following general equation
has been allowed to reach a state of equilibrium at a given temperature and pressure.
aA + bB lL + mM………(9.11)
An infinitesimal change is allowed to occur in the system whereby the number of moles of various
species change. The increments in the number of moles are dnA, dnB, dnL and dnM for components
A, B, L and M respectively. The free energy change for the process occurring at constant temperature
and pressure is given by [see Eq. (7.36)]

where mi is the chemical potential of component i. For the reaction under consideration, Eq. (9.12)
takes the form

where – a, – b, l and m are the stoichiometric numbers which are positive for products and negative
for the reactants and e is the extent of reaction. In general, for an infinitesimal change in a reacting
system, we can write Eq. (9.13) as

The left-hand side of Eq. (9.16) is the free energy change DG accompanying the complete reaction
under equilibrium conditions. Hence, DG = 0 under equilibrium.
The physical significance of the criterion of chemical equilibrium can now be examined. Consider a
simple chemical reaction equilibrium: A D B. Let the extent of the reaction be e. The change in the
number of moles of A = – de and the change in the number of moles of B = de. The change in free
energy at constant temperature and pressure is found out by Eq. (9.14)
dGt = (mB – mA) de………(9.17)
This equation can be written in the following form.

Equation (9.18) gives the slope of the curve obtained when the Gibbs free energy is plotted against
8
Phase Equilibria
A system is said to be in a state of equilibrium if it shows no tendency to depart from that state either
by energy transfer through the mechanism of heat and work or by mass transfer across the phase
boundary. Since a change of state is caused by a driving force, we can describe a system at
equilibrium as one in which there are no driving forces for energy or mass transfer. That is, for a
system in a state of equilibrium, all forces are in exact balance. It may be noted here that the state of
equilibrium is different from a steady state condition. Under steady state there exist net fluxes for
material or energy transfer across a plane surface placed anywhere in the system. Under equilibrium
the net flux is zero.
Transfer of material or energy across phase boundaries occurs till equilibrium is established between
the phases. In our daily experience, we come across a number of processes in which materials are
transferred from one phase to another. During breathing we take oxygen from the air through the lungs
and dissolve it in the blood. During the preparation of tea or coffee we extract the soluble
components in the powder into boiling water. Dilute aqueous solution of alcohol is concentrated by
distillation in which a vapour rich in alcohol is produced from the boiling solution. The phase
equilibrium thermodynamics is of fundamental importance in many branches of science, whether
physical or biological. It is particularly important in chemical engineering, because majority of
manufacturing processes involve transfer of mass between phases either during the preparation of the
raw materials or during the purification of the finished products. Gas–liquid absorption, distillation,
liquid–liquid extraction, leaching, adsorption, etc., are some of the important separation techniques
employing mass transfer between phases. In addition to these, many industrial chemical reactions are
carried out under conditions where more than one phase exist. A good foundation in phase
equilibrium thermodynamics is essential for the analysis and design of these processes.
In this chapter due emphasis is given to the development of the relationship between the various
properties of the system such as pressure, temperature and composition when a state of equilibrium is
attained between the various phases constituting the system. The temperature–pressure-composition
relationships in multiphase system at equilibrium form the basis for the quantitative treatment of all
separation processes. The two types of phase equilibrium problems that are frequently encountered
are:
1. The determination of composition of phases which exist in equilibrium at a known temperature
and pressure
2. The determination of conditions of temperature and pressure required to obtain equilibrium
between phases of specified compositions.
The present chapter tries to provide solutions to these problems.

8.1 CRITERIA OF PHASE EQUILIBRIUM

Consider a homogeneous closed system in a state of internal equilibrium. The criteria of internal
thermal and mechanical equilibrium are that the temperature and pressure be uniform throughout the
system. For a system to be in thermodynamic equilibrium, additional criteria are to be satisfied.
Consider a closed system consisting of two phases of a binary solution, for example, the vapour and
liquid phases of an alcohol–water solution. The requirement of uniformity of temperature and
pressure does not preclude the possibility of transfer of mass between the phases. If the system is in
thermodynamic equilibrium, mass transfer also should not occur. It means that additional criteria are
necessary for establishing the state of thermodynamic equilibrium.
A system can interact with the surroundings reversibly or irreversibly. In the reversible process, a
state of equilibrium is maintained throughout the process. So it can be treated as a process connecting
a series of equilibrium states. The driving forces are only infinitesimal in magnitude and the process
can be reversed by an infinitesimal change (either increase or decrease) in the potential for the system
or the surroundings. The irreversible process, in contrast, occurs with a finite driving force, and it
can not be reversed by infinitesimal changes in the external conditions. However, all irreversible
processes tend towards a state of equilibrium. We have shown in Chapter 4 under ‘Clausius
inequality’,

In this equation, the equality sign refers to a reversible process which can be treated as a succession
of equilibrium states and the inequality refers to the entropy change for a spontaneous process whose
ultimate result would be an equilibrium state. The first law of thermodynamics expressed
mathematically by Eq. (2.5) can be rewritten as
dQ = dU + dW………(8.1)
Substituting Eq. (8.1) into Eq. (4.44), we get
T dS ≥ dU + dW
dU T dS – dW………(8.2)
dW in Eq. (8.2) may be replaced by P dV so that
dU T dS – P dV………(8.3)
Equation (8.3) is valid for cases where external pressure is the only force and the work is, therefore,
the work of expansion only. By this, we exclude other effects like those due to gravitational and
electromagnetic fields and surface and tensile forces. Equation (8.3) can be treated as the combined
statement of the first and second law of thermodynamics applied to a closed system which interact
with its surroundings through heat transfer and work of volume displacement. This equation is utilised
for deriving the criteria of equilibrium under various sets of constraints, each set corresponding to a
physically realistic or commonly encountered situation. These different criteria are discussed now.
Constant U and V. An isolated system does not exchange mass, heat or work with the
surroundings. In Eq. (8.1), d Q = 0, d W = 0 and hence d U = 0. A well-insulated vessel of constant
volume would closely approximate this behaviour. Thus in Eq. (8.3) dU = 0 and dV = 0 so that

The entropy is constant in a reversible process and increases in a spontaneous process occurring in a
Differentiating Eq. (7.29) with reference to m,

Partial molar volume of water = 18.05 10–6 m3/mol

Partial molar volume of NaCl = 17.48 10–6 m3/mol

7.2 CHEMICAL POTENTIAL

The chemical potential, denoted by the symbol m, is a widely used thermodynamic property. It is
used as an index of chemical equilibrium in the same manner as temperature and pressure are used as
indices of thermal and mechanical equilibrium. The chemical potential mi of component i in a
solution is the same as its partial molar free energy in the solution, . That is, chemical potential of a
component i in a solution can be defined as

………(7.30)
The total free energy Gt of a solution is a function of pressure, temperature and number of moles of
various components.
Gt = f(P, T, n1, n2, . . ., ni, . . .)………(7.31)

The total differential dGt is

We have shown that for a closed system, when there is no change in the amount of various
constituents,
dG = V dP – S dT (6.18)
Considering the total properties of the system,
dGt = Vt dP – St dT
from which, it follows that

By reasoning analogous to that used in the derivation of Eq. (7.12), we have, at constant temperature
and pressure,
Gt = S mini
For a binary solution, the molar free energy of the solution is
G = x 1m 1 + x 2m 2
The chemical potential of a component is thus seen to be the contribution of that component to the
Gibbs free energy of the solution. The chemical potential is an important property of solution
extensively used in the study of phase and chemical equilibria.
7.2.1 Effect of Temperature and Pressure on Chemical Potential
Effect of temperature. Consider Eqs. (7.30) and (7.34). Differentiate Eq. (7.30) with respect to
temperature. Then
increased to 20 bar at 300 K? What assumption is involved in the solution?
Solution The coefficient of volume expansion is defined as

The change in entropy is

DS = –1.25 10–4 (P2 – P1) = – 1.25 10–4 (20.0 – 1.0) 105 = – 237.5 J/kmol K
It is assumed that the derivative (∂V/∂T)P is constant in the pressure range 1 to 20 bar.

6.4.4 Clapeyron Equation

The Clapeyron equation predicts the dependence of equilibrium pressure on temperature when two
phases of a given substance coexist. It is given by

………(6.25)
where DH and DV are the enthalpy and volume change accompanying a phase change. It can be
derived from Maxwell’s relation Eq. (6.23), which is applicable to any closed, homogeneous or
heterogeneous system in equilibrium, with an external pressure. Consider a single component system
containing two phases, say liquid and vapour, in thermodynamic equilibrium. By the phase rule, the
system is univariant, i.e. only one intensive parameter can be varied independently. The equilibrium
pressure (for the present case, the vapour pressure), is dependent on temperature only and is
independent of volume. Thus, the partial derivative (∂P/∂T)V in Eq. (6.23) can be replaced by
(dP/dT) without the constant volume restriction. Moreover, (∂S/∂V)T = DS/DV, where DS is the
entropy change when a given quantity of the substance is transferred from one phase to the other at
constant temperature and DV is the accompanying volume change. (DS/DV) is a constant at a given
temperature, for both DS and DV are extensive quantities that are proportional to the amount of
material transferred. As we are dealing with equilibrium and therefore with a reversible process, DS
= Q/T = DH/T, where DH is the change in enthalpy during the phase change or the latent heat of phase
change. Substituting these into Eq. (6.23) we get the Clapeyron equation, Eq. (6.25):
Clapeyron equation may be used for various purposes. It can be used to calculate the heat of
vaporisation, if the variation of vapour pressure with temperature is known. Alternatively, if the heat
of vaporisation is available, it is possible to predict the vapour pressure variation with temperature.
[Note: An alternative derivation for the Clapeyron equation is provided in Chapter 8. See
Example 8.3.]
Clausius-Clapeyron equation. If the temperature is not too near the critical point, the volume of
the liquid is small in comparison with the volume of vapour. The volume change accompanying
vaporisation DV = VG – VL is therefore approximately equal to VG, the molar volume of vapour.
Equation (6.25) now becomes

EXAMPLE 6.2 Calculate the vapour pressure of water at 363 K, if the vapour pressure at 373 K is
101.3 kPa. The mean heat of vaporisation in this temperature range is 2275 kJ/kg.
Solution Refer Eq. (6.28). T1 = 363 K; T2 = 373 K; = 101.3 kPa; DH = 2275 18 kJ/kmol; R =
8.314 kJ/kmol K.
Substituting the values in Eq. (6.28), we get
EXAMPLE 6.3 Mercury has a density of 13.69 103 kg/m3 in the liquid state and 14.193
103 kg/m3 in the solid state, both measured at the melting point of 234.33 K at 1 bar. If the heat of
fusion of mercury is 9.7876 kJ/kg, what is the melting point of mercury at 10 bar?
Solution The Clapeyron equation [Eq. (6.25)], can be rearranged as:

6.4.5 Entropy–Heat Capacity Relationships

Maxwell’s equations provide the partial derivatives of entropy with pressure or volume. The partial
derivatives of entropy with temperature are provided by the entropy–heat capacity relationships.
The specific heats at constant pressure (CP) and constant volume (CV) are discussed in
Section 2.7. These are defined as under,
Applications of Equilibrium Criteria:

1. Prediction of Phase Equilibrium

Equilibrium criteria are used to determine conditions for vapor–liquid,
liquid–liquid, and solid–liquid equilibrium in thermodynamic systems.
2. Distillation and Separation Processes
Used in the design and analysis of distillation columns, absorption, and
extraction, where equilibrium relations determine component distribution
between phases.
3. Chemical Reaction Equilibrium
Helps determine the extent of reaction and equilibrium composition using the
condition of minimum Gibbs free energy.
4. Calculation of Equilibrium Constant
Equilibrium criteria are used to relate Gibbs free energy change (ΔG) with the
equilibrium constant (K) for chemical reactions.
5. Stability of Thermodynamic Systems
Determines whether a system is stable, metastable, or unstable by applying
conditions such as minimum energy or Gibbs free energy.
6. Design and Operation of Chemical Processes
Applied in designing reactors, separators, and thermodynamic processes by
predicting the final equilibrium state of the system.

Equilibrium Criteria Conditions:

1. Thermal Equilibrium
A system is in thermal equilibrium when the temperature is the same
throughout the system and no heat transfer occurs between its parts.
Condition: T1=T2=T3
2. Mechanical Equilibrium
Mechanical equilibrium exists when the pressure is equal at all points of the
system, so no unbalanced forces are present.
Condition: P1=P2=P3
3. Chemical Equilibrium
Chemical equilibrium occurs when the chemical potential of each component
is equal in all phases and no chemical reaction proceeds further.
Condition: μiα=μiβ
4. Phase Equilibrium
When a substance exists in more than one phase (solid, liquid, vapor),
equilibrium occurs when temperature, pressure, and chemical potential are
equal in all phases.
5. Overall Thermodynamic Equilibrium
A system is in complete equilibrium only when thermal, mechanical, and
chemical equilibrium conditions are satisfied simultaneously, meaning no
heat, mass, or energy transfer occurs.