Kathmandu University

Introduction of Chemical
Engineering Thermodynamics

Dr. Ziaul Haque Ansari

Department of
Chemical Science and Engineering
Personal information
Office: Building 9

Mobile:98418884185

Email: ziaul.ansari@ku.edu.np

Textbook:

J M Smith, H. C. Van Ness, M.M. Abbott;

Introduction of chemical engineering thermodynamics

Course Purpose
The purpose of this course is to have students

acquire the skills and knowledge in chemical thermodynamics that

are necessary for design and simulation of separation and reaction
processes.

This course can be viewed as a prerequisite to the subjects to the

subjects of
• mass transfer,
• heat transfer, and
• reaction engineering.
 Course Objective
1. Learn the first law of thermodynamics and apply the law to solve energy
balance equations for closed and open systems.
2. Learn temperature dependence of heat capacity, latent heat of pure
substances, and how to calculate the heat of reaction at a given
temperature.
3. Learn the second law of thermodynamics and apply the law to entropy
change, ideal work, and lost work for steady-state processes.
4. Understand the concept of Gibbs free energy, residual properties of
volume, internal energy, enthalpy, entropy and Gibbs energy, and learn
how to determine the residual properties using the equation of state.
5. Understand the theories of phase equilibrium, and learn how to draw
phase diagram, and to determine the activity coefficient to modify
Raoult’s law in real phase-equilibria.
6. Understand the principles of chemical reaction equilibrium, learn how to
calculate the equilibrium constant, and learn how to determine
equilibrium composition for gas and liquid phase reactions.
Schedule
 The first law and other basic concepts.
 Heat Effects
 The second law of thermodynamics
 Ideal work and lost work
 Thermodynamic properties of fluids
 Vapor/Liquid Equilibrium: Introduction
 Solutions Thermodynamics: Theory
 Solutions Thermodynamics: Applications
 Chemical Reaction Equilibria in Homogeneous Systems
 Chemical Reaction Equilibria in Heterogeneous Systems
 Review of Phase and Chemical Equilibria
 Basic Concepts

What is thermodynamics?

A field of science and engineering that describes

“the driving forces (thermodynamics variables) for the flow of

energy, such as heat and work, and the condition for equilibrium
within a system (the system has no tendency to change)”.

Thermodynamics does not deal with rates of changes, but only

with the driving forces which cause changes.

To do thermodynamics, we must understand;

(a) Basics physics, such as classical mechanism

(b) To be adept at using and converting units of measurements.
 Basic Concepts

Defines driving forces that enable processes to occur.

Set of principles that allows us to determine the state of a system

under a given set of condition.

Helps us to determine the limits of safe operating conditions.

Under given conditions, thermodynamics shows us whether a

reaction will be spontaneous and which direction it will go.

Thermodynamics does NOT tell us how fast anything will occur.

1.1 The Scope of Thermodynamics
The science of thermodynamics was born in the nineteenth century of the
need to

• describe the operation of steam engines and

• to set forth the limits of what they can accomplish.

Power developed from heat, with obvious application to heat engines.

initial example - steam engine.

However, the principles observed to be valid for engines are readily

generalized, and are known as the first and second law of thermodynamics.
1.1 The Scope of Thermodynamics
Problems of Chemical Engineers

• Calculation of heat and work requirements for physical and chemical

processes, and

• The determination of equilibrium conditions for chemical reactions and

for the transfer of chemical species between phases.

Thermodynamic considerations do not establish the rates of chemical or

physical processes.

Neither can thermodynamics, a macroscopic-property formulation, reveal the

microscopic (molecular) mechanisms of physical or chemical processes.
 1.1 The Scope of Thermodynamics
The application of thermodynamics to any real problem starts
with the identification of a particular body of matter as the focus
of attention. This body of mater is called the system.

Thermodynamic System definition

A quantity of matter or a region in space chosen for study.

Cylinder-piston equipment Steam turbine

1.2 Dimensions and Units
Primary units have been set by international agreement, and are codified as

the International Systems of Units (abbreviated SI, Systeme International).

Time (s)

Length - Meter (m)

Kilogram - kg

Temperature - (kelvin, K)
1.3 Measures of Amount or Size
Three measures of amount or size are in common use :
• Mass, m
• Number of moles, n
• Total volume, Vt

m
• Mass, m n Or m  Mn
M

Vt
• Specific volume V Or V t  mV
m
Vt
• Molar volume V Or V t  nV
n

• Specific or molar density   V 1

1.4 Force
F  ma Newton, N.
Newton : the force which when applied to a mass of kg produces an
acceleration of 1 m s-2
In the metric engineering system of units, force is treated as additional
independent dimension along with length, time, and mass.
1 1
F ma 1kgf  1kg  9.80665ms  2 g c  9.80665kgmkgf 1s 2
gc gc

The kilogram force (kgf) : force which accelerates 1 kilogram mass at

9.80665 meters per second per second.
Newton’s law must here include a dimensional proportionality constant if it is
to reconciled with this definition.
The kilogram force (kgf) is equivalent to 9.80665 N.
1.4 Force
Example 1.1
An astronaut weighs 730 N in Houston, Texas, where the local acceleration of
gravity is g = 9.792 m s-2. What are the astronaut’s mass and weight on the
moon, where g = 1.67 m s-2 .
Solution

With a = g, Newton’s law is: F = mg. Whence

F 730N 1 2
m  2
 74. 55 Nm s
g 9.792ms
Because the newton N has the units kg m s-2. m = 74.55 kg
This mass of the astronaut is independent of location, but weight depends on
the local acceleration of gravity. Thus on the moon the astronaut’s weight is:
F (moon )  mg (moon )  74.55kg 1.67 ms 2
F (moon )  124.5kgms 2  124.5N
State and State Properties
2. Properties

Properties are used to depict any characteristic of a system.

pressure P, enthalpy,

temperature T, entropy,

volume V, viscosity,

mass m, thermal conductivity

internal energy U
Characteristics of State Properties

(1) Properties of a state are determined by the state. If the

state is specified, its properties are fixed, or vise versa.

(2) The magnitude of the change in property is independent

of the path (route), but just depend on the initial and
final states.

x2

 dx x
x1
2  x1
Basic State Properties
Pressure P, temperature T, specific volume V (measurement)

Density
It is defined as mass per unit volume ()

Units: SI (e.g. kg/m3) English (e.g. lb/ft3)

Specific volume is the reciprocal of density and is defined as

volume per unit mass.

Units: SI (e.g. m3/kg) English (e.g. ft3/lb)

V 1
v  3
m / kg
m 
Basic State Properties
Pressure P,

It is defined as the force exerted by a fluid vertically on a surface

of unit area.
F
p
A

Units:
It has the unit of Newtons per square meter (N/m2)
1 Pa = 1 N/m2
1 kPa = 103 Pa
1 MPa = 106 Pa
Basic State Properties
Other units

1 bar = 105 Pa = 100 kPa = 0.1 MPa

Standard atmosphere
1 atm = 101325 Pa = 101.325 kPa

Engineer atmosphere
1 at = 1 kgf/cm2 = 9.807 N/cm2 = 9.807*104 Pa

Height of liquid column

1 atm = 760 mm Hg
1 at = 10 m H2O

1 mmHg = 1 gh = 133.3 Pa

Basic State Properties
The Manometer

Manometers measure a pressure difference by balancing the

weight of a fluid column between the two pressures of
interest.

P1  P2  Patm  gh
Basic State Properties
Temperature

Temperature is an intensive property of matter.

When are two bodies in thermal equilibrium?

What will happen if two bodies not in equilibrium are in contact?

Equality of temperature is a necessary and

sufficient condition for thermal equilibrium,

i.e. no transfer of heat.

Basis for property called Temperature

Basic State Properties
The Zeroth Law of Thermodynamics

If two bodies are in thermal equilibrium with a third body,

they are also in thermal equilibrium with each other.

Perfect insulation between two bodies would prevent any

energy transfer = ADIABATIC process

Process at constant temperature called ISOTHERMAL

Basic State Properties
Temperature scale

Kelvin scale (K) T [ K ]  t[ O C ]  273.15

Celsius scale (°C)

5
t[ C ]  (t[ F ]  32)
O

Temperature 273.16 K 0.01 ℃ 9

The temperature interval on both t[ F ]  t[ R ]  459.67

scales is the same

Fahrenheit scale (German, G. Fahrenheit, 1686-1736)

Rankine scale (W. Rankine, 1820-1872)

Basic State Properties
Relations among temperature scales
Basic State Properties
Work
Mechanical work can be defined as the product of a forces times a
distance or the integral of force over some distance through which it
acts. If F is the component of force along the direction of motion
and dl is a differential displacement in that direction, then the work
can be expressed as:
dW  F * dl
where dW is the differential amount of work performed when
the force F acts through the displacement dl.

units (J or joules)

Work is from energy transfer

Basic State Properties

In thermodynamics, we often deal with the work done by an expanding fluid (or
work done on a fluid to compress it). In this case, the force F is the pressure
multiplied by area over which the pressure is applied (F=PA). If the compression is
done by a cylinder of constant area A then change in total volume of the fluid is
dVt=Adl. Using these expressions for dl and F gives dW   pdV t
Basic State Properties
Energy Kinetic energy
When a body of mass m, acted upon by a force F, is displaced a distance dl
during a differential interval of time dt, the work done is given by

dW = F dl dW = ma dl dW = mu dl
a  du/dt ; u  dl/dt
du dl
dW  m dl  m du
dt dt

Integrating for a finite change in velocity from u1 to u2:

u2
 u 22 u12  mu 22 mu12  mu 2 
W  m  udu  m
 2  2   W    
 

u1   2 2  2 

1
Ek  mu 2 Kg m2 s-2
2
Basic State Properties
Energy Kinetic energy

The work done on a body in accelerating it from an initial velocity u1 to a

final velocity u2 is equal to the change in kinetic energy of the body.

Conversely, if a moving body is decelerated by the action of a resisting force,

the work done by the body is equal to its change in kinetic energy.

In the metric engineering system, kinetic energy is expressed as

1
mu 2 / g c gc, has the value 9.80665 and the units kg m kgf-1 s-2
2

mu 2 kgm 2 s 2 Dimensional consistency here requires

Ek   1  2
 mkgf
2 g c kgmkgf s the inclusion of gc.
Basic State Properties
Energy Potential Energy

If a body of mass m is raised from an initial elevation z1 to a final elevation z2,

an upward force at least equal to the weight of the body must be exerted on it,
and this force must move through the distance z2-z1. because the weight of the
body is the force of gravity on it, the minimum force required is given by
Newton’s law:
F  ma  mg where g is the local acceleration of gravity

The minimum work required to raise the body is the product of this force and
the change in elevation

W  F ( z 2  z1 )  mg ( z 2  z1 )

W  mz2 g  mz1 g   (mzg )

Basic State Properties
Energy Potential Energy

Work done on a body in raising is equal to the change in the quantity mzg.
Conversely, when a body is lowered against a resisting force equal to its
weight, the work done by the body is equal to the change in the quantity mzg.

E p  mzg Kg m2 s-2

In the metric engineering system, kinetic energy is expressed as mzg/gc

mzg kgm 2 s 2
EP   1  2
 mkgf
gc kgmkgf s

Dimensional consistency here requires the inclusion of gc.

Basic State Properties
Energy Conservation
The work of accelerating a body produces a change in its kinetic energy
 mu 2 
W  E K   
 2 

The work done on a body in elevating it produces a change in its potential energy:
W  E P  (mzg )
An elevated body, allowed to fall freely (without friction or other resistance),
gains in kinetic energy what it loses in potential energy. Mathematically,
EK  E P  0 mu22 mu12
  mz2 g  mz1 g  0 Kg m2 s-2
2 2

Dimensional consistency here requires the inclusion of gc.

Basic State Properties
Energy Conservation
The generality of the principle of conservation of energy in mechanics is
increased if we look upon work itself as a form of energy.

This is clearly permissible because both kinetic- and potential-energy changes

are equal to the work done in producing them [Eqs. (1.5) and (1.7)].

However, work is energy in transit and is never regarded as residing in a

body.

When work is done and does not appear simultaneously as work elsewhere, it
is converted into another form of energy.
Basic State Properties
Energy Conservation
In contrast, kinetic and potential energy reside with the system.

Their values, however, are measured with reference to the surroundings;

kinetic energy depends on velocity with respect to the surroundings, and

potential energy depends on elevation with respect to a datum level.

Changes in kinetic and potential energy do not depend on these reference

conditions, provided they are fixed.
Basic State Properties
Example 1.4
An elevator with a mass of 2500 kg rests at a level 10 m above the base of an elevator
shaft. It is raised to 100 m above the base of the shaft, where the cable holding it
breaks. The elevator falls freely to the base of the shaft and strikes a strong spring.
The spring is designed to bring the elevator to rest and, by means of a catch
arrangement, to hold the elevator at the position of maximum spring compression.
Assuming the entire process to be frictionless, and taking g = 9.8 m s-2, calculate: 

(a) The potential energy of the elevator in its initial position relative to its base. 
(b) The work done in raising the elevator. 
(c) The potential energy of the elevator in its highest position. 
(d) The velocity and kinetic energy of the elevator just before it strikes the spring. 
(e) The potential energy of the compressed spring. 
(f) The energy of the system consisting of the elevator and spring
(1) at the start of the process,
(2) when the elevator reaches its maximum height,
(3) just before the elevator strikes the spring,
(4) after the elevator has come to rest.
Basic State Properties
Solution
Initial condition = subscript 1
Elevator at highest position = subscript 2
State just before the elevator strikes the spring = subscript 3

(a) Potential energy is defined by Eq. (1.8):

EP1  = m z1g = 2500 kg × 10 m × 9.8 m·s −2
= 245,000 kg·m2⋅s−2  = 245,000 J

(b) Work is computed by Eq. (1.7).

Units are as in the preceding calculation:

W = mg(z2−z1) = (2500) (9.8) (100−10)

= 2,205,000 J
Basic State Properties
Solution
(c) Again by Eq. (1.8),
EP2 = mz2g = ( 2500 ) ( 100 ) ( 9.8 )  = 2,450,000 J
Note that W = EP2 − EP1 .

(d) The sum of the kinetic- and potential-energy changes

during the process from state 2 to state 3 is zero; that is,

ΔEK2→3 + ΔEP2→3 = 0 or EK3−EK2 + EP3−EP2= 0

However, EK2 and EP3 are zero; EK3=EP2 = 2,450,000 J.

Basic State Properties
Solution
(e) The changes in the potential energy of the spring and the
kinetic energy of the elevator must sum to zero:

ΔEP ( spring )  + ΔEK ( elevator )  = 0

initial potential energy of the spring = 0

final kinetic energy of the elevator = 0

final potential energy of the spring = kinetic

energy of the elevator just before it strikes the spring.

Thus the final potential energy of the spring is 2,450,000 J.

Basic State Properties
Solution
( f ) With the elevator and spring as the system, the initial
energy is the potential energy of the elevator, or 245,000 J.

The only energy change of the system occurs when work is

done in raising the elevator. This amounts to 2,205,000 J.

The energy of the system when the elevator is at maximum

height ( state 2) is 245,000 + 2,205,000 = 2,450,000 J.

The total energy of the system remains constant at

2,450,000 J.

It merely changes from potential energy of position

(elevation) of the elevator to kinetic energy of the elevator
to potential energy of configuration of the spring.