CHE 312

Chemical Engineering
Thermodynamics II
Credit Hours

30

By
Dr. Qazi Nasir
Lecture # 1

CHE 312 Chemical Engineering

Thermodynamics II

In
nineteenth
century,
the
science
of
thermodynamic was born which describe the
operation of steam engines
The name was given as power developed from
heat is the main application of steam engine
The principle which
generalized as first
thermodynamics

valid
and

for engines are

second laws of

These laws have no mathematical sense

Chemical engineers among other problems ,
calculation of heat and work requirement for
physical and chemical processes, determination
of equilibrium conditions for chemical reactions

CHE 312 Chemical Engineering

Thermodynamics II

The application of thermodynamics to any real

problems starts with the identification of body
Body = system
Thermodynamic state = Measurable macroscopic
properties such as length , time, mass,
temperature and amount of substance (Mass, no
of moles, total volume, specific volume)
Temperature: commonly measured in liquid-inglass thermometer, wherein the liquid expands
when heated
Pressure: The normal force exerted by the fluid
per square meter or Nm-2. (dead-weight gauge)

CHE 312 Chemical Engineering

Thermodynamics II

Work: when a force acts through a distance then

work is performed
A work which accompanies a change in volume
of fluid is often encountered in thermodynamics,
e.g. compression and expansion of fluid in a
cylinder
The force exerted by the piston on the fluid is
equal to the product of the piston area and
pressure of the fluid.
The displacement of the piston is equal to the
total volume change of the fluid divided by area

CHE 312 Chemical Engineering

Thermodynamics II

CHE 312 Chemical Engineering

Thermodynamics II
Area is constant

CHE 312 Chemical Engineering

Thermodynamics II
Heat: Hot object brought in contact with cold
object becomes cooler whereas cooled object
become warmer.
Something is transferred from hot object to cold
object is Heat Q
Temperature is a driving force for the transfer of
energy as heat
Rate of heat transfer from one body to another is
proportional to the temperature difference.
Between two bodies
1/100th quantity of heat which when transferred
to one kilogram mass of water raised its
temperature from 0 to 100 0C

CHE 312 Chemical Engineering

Thermodynamics II
Thermodynamic properties are classified into two
types
Direct measureable properties

Pressure-volume-temperature
relationships

(PVT)

Indirect measureable properties

Determined indirectly using relationships that
express in terms of physical properties
Internal energy, entropy, enthalpy, Helmholtz
free energy, Gibbs free energy and association
properties such as
chemical potential and
fugacity)

CHE 312 Chemical Engineering

Thermodynamics II
Four

quantities

potential

are

called
useful

thermodynamic
in

the

chemical

thermodynamics of reactions and non-cyclic

processes.
Internal energy
Enthalpy
Helmholtz free energy
Gibbs free energy

CHE 312 Chemical Engineering

Thermodynamics II
Helmholtz Free Energy

Internal energy U might be thought of as the

energy required to create the system in the
absence of changes in temperature or volume
But in environment of temperature T, some
the energy can be obtained by spontaneous
heat transfer in TS

CHE 312 Chemical Engineering

Thermodynamics II
Gibbs Free Energy

Internal energy U might be thought of as the

energy required to create the system in the
absence of changes in temperature or volume
Amount of work PV must be done if the
system is created from a very small volume.

CHE 312 Chemical Engineering

Thermodynamics II
Fugacity

In chemical thermodynamics, the fugacity (f) of a

real gas is effective pressure which replaces the true
mechanical
pressure
in
accurate
chemical
equilibrium calculations.
For example, nitrogen gas (N2) at 00C and a pressure
of P = 100 atm has a fugacity of f = 97.03 atm
This also means the chemical potential of real
nitrogen at a pressure of 100 atm is less than if
nitrogen were an ideal gas.
Fugacities are determined
estimated from various model

experimentally

or

The ideal gas pressure and fugacity are related

through fugacity coefficient

CHE 312 Chemical Engineering

Thermodynamics II
Fundamental equations
J. W. Gibbs give the names because they
contain all information needed for the complete
description of the thermodynamic state of a
system.
Fundamental equations for closed system
System that do no exchange mass with the
surroundings is considered as closed system

CHE 312 Chemical Engineering

Thermodynamics II
Fundamental equations for the Internal
Energy
A closed homogenous system which experience
the transfer of a small of heat dQ and an
amount of volumetric work dW. The change in
internal energy according to first law is given as
dU = dQ dW

(1)

If changes are reversible, then:

dW = PdV

dQ = TdS

dU = TdS PdV
U = f(S, V)

CHE 312 Chemical Engineering

Thermodynamics II
Fundamental equations for the Internal
Energy
Consider a differential change in S and V. The
corresponding change in U is given as.

Comparison of equation (1) indicates that

CHE 312 Chemical Engineering

Thermodynamics II
The system enthalpy is also specified from the
definition
H = U + PV
Similarly, the two energy properties
A = U ST
Gibbs free energy
G = U + PV - ST
Therefore, the availability of the functional
relationship U = f(S,V) gives complete
description on the thermodynamic state of the
system i.e. its fundamental equation

CHE 312 Chemical Engineering

Thermodynamics II
The fundamental Equation for H, A, and G
H = U + PV

(2)

The enthalpy differential

dH = dU + PdV + VdP
As, TdS = dU + PdV
dH = TdS + VdP
which indicates that:
H = f(S,P)

(3)

CHE 312 Chemical Engineering

Thermodynamics II
The differential change in S and P leads to
following form

Comparison with Eq (2) indicates that

(4)
Eq (3) and Eq (4) completely describe the
system once S and P are specified. It is
therefore, also a fundamental equation

CHE 312 Chemical Engineering

Thermodynamics II
Similarly, Helmholtz & Gibbs free energy can be
describe as

CHE 312 Chemical Engineering

Thermodynamics II
Recommended Books
Smith J.M., Van Ness H.C., Abbott M.M.
Chemical Engineering Thermodynamics 6th
Ed. 2001. McGraw Hill International Edition.
Daubert Thomas E. Chemical Engineering
Thermodynamics, 1st Ed. 1985, McGraw Hill
Book Company.
Sandler Stanley I. Chemical and Engineering
Thermodynamics 3rd Ed. John Wiley and
sons, Inc.