Phase Equilibria 1: Problem Formulation (Chapter 6) : Live Your Life. Create Your Destiny

Lesson 2
Live your life. Create your destiny.
PHASE EQUILIBRIA 1: PROBLEM

FORMULATION
(Chapter 6)
Department of Chemical, Metallurgical & Materials Engineering

REMEMBER!!!
• Cellphones on silent or completely off.
• Put away your laptops.
• Settle down, be comfortable and switch on
your MIND.
• Avoid seating next to someone who will
distract your attention.
• Ask questions without shame of what your
classmates will think of you. Remember,
you came to TUT ALONE!!! However, think
carefully before you ask.
PHASE EQUILIBRIA
Objectives of this lesson:
• Explain why it is convenient to use the thermodynamic property Gibbs
energy to determine pure species equilibrium.
• Write the Clapeyron equation and use it to relate T and P for a pure species
in phase equilibrium. Derive the Clausius-Clapeyron equation for vapor-
liquid mixtures.
Introduction
− Phases (solid, liquid, gas).
Homogeneous portion of a system
Uniform chemical and physical properties
Several phases maybe present simultaneously
Phases are recognizable and separable
− Equilibrium represents the state at which the system has no tendency to

change.
− In this chapter, we wish to calculate how species distribute among phases

when more than one phase is present.
• A generic representation of the phase equilibria problem.
− We consider a closed system, since only closed systems can be in
thermodynamic equilibrium.
− In formulating the phase equilibria problem, we need only measure the

temperature and pressure of one phase, and these values must apply to
the entire system.
− This assembly is used to remind us that the system must be able to

change in volume to accommodate thermal and mechanical equilibrium.
This chapter will focus on:
• Establishing the criterion for chemical

equilibrium
• Use this criteria to solve phase
equilibria problems (with T and P
known).
6.2 PURE SPECIES PHASE EQUILIBRIUM
- Our objective for this section is to develop a criterion that tells us when two
or more phases can coexist at equilibrium or when a single phase is stable.
- Criterion for chemical equilibrium is when the Gibbs energy is at the
minimum:
• Roles of Energy and Entropy in Phase Equilibria.
− Self study.
• The Clausius-Clapeyron Equation.
− We now wish to come up with an expression relating the pressure at which

two phases can coexist to the temperature of the system. This expression
will allow us to calculate, for example, how the saturation pressure changes
with temperature.
− We begin with the Clapeyron equation:
− By using the following simplifications Eq. 6.8 can be modified to yield the
Clausius-Clapeyron equation applicable for vapor-liquid equilibria.
1. The latent heat of vaporisation is constant and independent of

temperature.
2. The molar volume of liquid is negligible compared to that of vapor.
3. The vapor behaves as an ideal gas
- Clausius-Clapeyron equation:
Recall that the saturation

pressure, , is defined as
the unique pressure at
which pure species boils
at a given temperature.
• Example 1
Q: The vapor pressure of a substance is 2.8 kPa at 300

K. Calculate the vapor pressure at 310 K if the enthalpy
of vaporisation is 24 kJ/mol.
A:
𝟐𝟒𝟎𝟎𝟎 𝟏 𝟏
− (
𝟖 .𝟑𝟏𝟒 𝟑𝟏𝟎
−
𝟑𝟎𝟎 )
𝑷𝟐= 𝟐𝟖𝟎𝟎 × 𝒆
𝑷𝟐=𝟑 . 𝟖 𝒌𝑷𝒂
• Example 2
Q: The vapor pressure of a substance is 4 kPa at 250 K.

At what temperature will the substance have vapor
pressure of 20 kPa? The enthalpy of vaporisation is 45
kJ/mol.

A:
−𝟏
𝟐𝟎
( )
𝑻𝟐= ( 𝟏
𝟐𝟓𝟎
−
𝟖 . 𝟑𝟏𝟒 × 𝒍𝒏
𝟒𝟓 × 𝟏𝟎
𝟑
𝟒
)
𝑻 𝟐 =𝟐𝟕𝟎 .𝟏 𝑲
6.3 THERMODYNAMICS OF MIXTURES
Objectives of this lesson:
• Apply thermodynamics to mixtures.

• Define a partial molar property and describe its role in determining the
properties of mixtures.
• Relate the volume, enthalpy, and entropy changes of mixing to the relative
intermolecular interactions.
•
− In this chapter we discuss how the thermodynamic properties of a mixture
are determined and introduce certain concepts that are essential to the
study of phase equilibria.
− We now wish to specify the extensive thermodynamic property of the entire

mixture, K, where we use the symbol K to represent any possible extensive
thermodynamic property , that is:
− By dividing K by the total number of moles in the system, we would get the
intensive property:
• Partial molar properties
− We wish to develop a way to account for how much of a solution property ( V, S, G,

U….) can be assigned to each species contributing to the properties of the mixture.
We do this through a new formalism: the partial molar property.
• Example
3
•Q:Consider an ideal gas mixture at 83.14 kPa and 500 K . It contains 2 moles
of species A and 3 moles of species B. Calculate the following:
a) Specific molar volumes: , ,
b) Total volumes ,
•c) Partial molar volumes
A:
a) From the ideal gas law
b) Partial molar volumes

•
Physical interpretation of
• SELF STUDY
• The Gibbs-Duhem Equation
− In a binary mixture, if we know the values for a partial molar property of one
of the species, we can apply the Gibbs-Duhem equation to calculate the
partial molar property values for the other species.
− The Gibbs-Duhem equation is as follows:

•• Property
changes of mixing
− A property change of mixing, , describes how much a given property
changes as a result of the mixing process. Mathematically, the property
change of mixing is given by:
As well as:
− For intensive properties we get:
• Example
4
•Q:Consider an ideal gas mixture at 83.14 kPa and 500 K . It contains 2 moles
of species A and 3 moles of species B. Calculate the following:
•a) Change in specific molar volume and change in total volume
A:
This means for a pure species the partial molar property is merely the pure
molar property.
• Enthalpy of mixing, Enthalpy of solution & Entropy of mixing
− SELF STUDY
• Determination of partial molar properties
− Partial molar property tells us about the contribution of a given species to

the properties of a given mixture.
− The partial molar property change of mixing:
− The partial molar property change of mixing, gives the relative value of how
species i behaves in a mixture to how it behaves by itself as a pure species.
• Determination of Partial Molar Properties
The partial molar property change of mixing for species i can be determined
from the following equation:
-Tangent -intercept method:

• Example
5
Q: The molar volume of a binary mixture consisting of components 1 and 2 at 298 K
and 1 atm is represented by the following empirical relation:
where is in and is the mole fraction of component 2. Develop the expression for the
partial molar volumes for both the components.
A: Following the tangent-intercept method equation we get:

Differentiating the equation of molar volume, we get:
The partial molar volume of component 1 can be expressed as:

For component 2 we get:
The partial molar property expression for component 2:

6.4 MULTICOMPONENT PHASE
EQUILIBRIA
• The chemical potential- the criteria for chemical
equilibrium
− SELF STUDY

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Lesson 2

Live your life. Create your destiny.

PHASE EQUILIBRIA 1: PROBLEM

Department of Chemical, Metallurgical & Materials Engineering

− Equilibrium represents the state at which the system has no tendency to

− In this chapter, we wish to calculate how species distribute among phases

− In formulating the phase equilibria problem, we need only measure the

− This assembly is used to remind us that the system must be able to

This chapter will focus on:

• Establishing the criterion for chemical

− We now wish to come up with an expression relating the pressure at which

1. The latent heat of vaporisation is constant and independent of

Recall that the saturation

Q: The vapor pressure of a substance is 2.8 kPa at 300

Q: The vapor pressure of a substance is 4 kPa at 250 K.

• Apply thermodynamics to mixtures.

− We now wish to specify the extensive thermodynamic property of the entire

− We wish to develop a way to account for how much of a solution property ( V, S, G,

a) From the ideal gas law

b) Partial molar volumes

− The Gibbs-Duhem equation is as follows:

• Determination of partial molar properties

− Partial molar property tells us about the contribution of a given species to

-Tangent -intercept method:

A: Following the tangent-intercept method equation we get:

The partial molar volume of component 1 can be expressed as:

The partial molar property expression for component 2:

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