Introduction To

Chemical
Engineering
Thermodynamics I
CHE 325
(3 Units)

Textbooks
1.Introduction
To
Chemical
Engineering
Thermodynamics (J. M. Smith, H. C. Van Ness &
M. M. Abbot)
2.Thermodynamics: An Engineering Approach
(Yunus A. Cengel & Michael A. Boles)
3.Any other relevant thermodynamics text

Grading
Assignments/Tests = 30 marks
Examination
= 70 marks

Module
1: INTRODUCTION

Basic definitions, aim and scope.

PVT system, path dependency.

2:

3:

FIRST LAW OF THERMODYNAMICS

Work and Heat.
Adiabatic work.
Internal Energy.
Enthalpy.
Heat Capacity.
SECOND LAW OF THERMODYNAMICS
Inter-conversion of Work and Heat.
Heat Engines and Cyclic processes.
Refrigeration Cycle.
Coefficient of Performance.

MODULE ONE

BASIC
DEFINITIONS OF
SOME TERMS

Definition of Some Terms

Thermodynamics:
is the science of energy
involves all aspects of energy and
energy transformation.
involves the storage, transformation
& transfer of energy.

Energy is transformed from one form

of energy to another.
it is transferred across a boundary as
either heat or work.

Definition of Some Terms

Classical
Thermodynamics:
is
observation driven (macroscopic)
and
focuses
on
bulk
energy
flow
(transfer/transformation/storage). It has its
applications mostly in Engineering fields.
Statistical Thermodynamics: is theory
driven (microscopic). Focuses on structure
of matters and molecules interaction. It has
its applications mostly in science fields
(physics, chemistry).

Applications of Thermodynamics in Chemical

Engineering

Conversion of chemical stored energy in

fossil fuel to Heat and Work

Determination of properties of
materials/systems

Applications of Thermodynamics
in Chemical Engineering
Conversion of materials to useful
products

Monitoring of chemical reactions

Some of The Future Benefits of

Thermodynamics
Better Industries/Homes construction
due to reduction in the need of heating
or cooling system.
Homes /Industries will have systems
that the energy usage are electronically
monitored and regulated.
Adoption of solar energy in every home.
Improved railway system and the use of
hybrid vehicles that run on biofuels .

Some of the Future Benefits of

Thermodynamics
Internet becomes predominant
business transactions.

means

of

Wind, solar and other renewable technologies will

contribute significantly to nations electricity grid.
Use of telecommuting and teleconferencing by
industries and institutions will be very common.

ENERGY IS LIFE

Revision
System: portion/object to be studied
Surroundings: everything external to the
system
Boundary: what separates a system from
its surroundings.
Open System (control volume):
a
system that allows mass and energy
interaction.

Revision
Closed System: a system with no
mass interaction between the system
and the surroundings
Properties:
What describe a system.
Macroscopic characteristics of
a system and can be assigned
numerical values
State:
condition of a system due
to change in properties

Revision
Process: a series of changes experience by a system
from one state to another.
The path of successive states through which a system
passes when change from one state to another.
Reversible Process: a system undergoes reversible
process when it is restored to its initial state.

Equilibrium: state of balance, a system in equilibrium

experiences no changes when it is isolated from its
surroundings. condition of constant property.

Revision
Isobaric process
o P = constant

Isochoric process
o V = constant

P
V

Isothermal process

Adiabatic process

o T = constant
oQ=0

Example 1
As shown in the figure, water
which circulates between a
storage tank and a solar
collector is used for domestic
purposes. Identify locations on
the system boundary where the
system
interacts
with
the
surroundings
and
describe
events that occur within the
system, if the system is
[a] solar collector
[b] solar collector, storage tank
and connecting pipes.

Solution
[a]
The system (solar
collector)
is
an
open
system.
Warm water enters the
system at the base through
the pump.
The water is heated up as a
result of heat radiation
through the surface of the
system.
Hot
water
leaves
the
system at the top.
Pressure exerted on the

Solution
[b] The system consisting of the
solar collector, the tank and pipes
is an open system.
Cold water enters the tank at the
base and get warm on mixing with
hot water inside the tank.
There is interaction between the
surroundings, surface of the tank,
water inside the tank.
Warm
water
entering
solar
collector
interacts
with
the
surroundings at the surface of the
collector and becomes hot water.
Hot water in the tank leaves the
tank the moment the water level

Example 2
The table below lists temperatures and specific volumes
of water vapor at two different pressures
p = 1.0 MPa
p = 1.5 MPa
T (C)
v (m/kg)
T (C)
v
(m/kg)
200
0.2060
200
0.1325
240
0.2275
240
0.1483
280
0.2480
280
0.1627
Data encountered in solving problems often do not fall
exactly on the grid of values provided by property
tables, and linear interpolation between adjacent table
entries become necessary. Using the data provided

Solution
[a]
At a temperature of 240C, 1.25MPa falls
between 1.0 MPa and 1.5 MPa.
Finding slope will help
Slope =
=
0.5(v 0.1483)
= 0.25 (0.0792)
0.5v = 0.0198 + 0.07415
v = 0.1879 m/kg

Solution
[b]
p = 1.5 Mpa and v = 0.1555 m/kg fall
between
T = 240C and T = 280C.
Slope =
=
T = 260C

Solution
[c] At T = 220 C and p = 1.4 MPa, the
specific volume falls between 1.0 and 1.5
MPa and T = 220 C btw 200 and 240C.
Hence, double interpolation is required.
At 220 C, v at each pressure is the
average over the interval
At 1.0MPa, 220C; v = = 0.21675 m/kg
At 1.5MPa, 220C; v = = 0.1404 m/kg
so as calculated in [a]
= v = 0.15567 m/kg

Assignment

1.
Over a limited temperature range , the
relation between electrical resistance R and
temperature T for a resistance temperature
detector is
[1 + )]
where is the resistance, in ohms (), measured at
reference temperature (C) and is a material constant
with units of . The following data are obtained for
a particular resistance thermometer.
(C)
Test 1 ()
= 51.39
Test 2

0
91

Assignment
2.
As illustrated in
the figure, water
circulates through a
piping
system,
servicing
various
household needs.
Considering the water
heater as a system,
identify locations on
the system boundary
where
the
system
interacts
with
its
surroundings
and
describe
significant
occurrence within the

Exercises
Perform the following unit
conversion
a)122 in to L
b)778.17 ft.ibf to kJ
c)100 hp to kW
d)1000 ib/h to kg/s
e)29.392 ibf/in to bar
f) 650 J to Btu
g)0.135 kW to ft.ibf/s
h)304 kPa to ibf/in
i) 2500 ft/min to m/s

PT Diagram of a Pure
Substance

PT Diagram of a Pure
Substance
Line
1-2:
Solid/Vapour
phase
equilibrium,
Line 2- C:
Liquid/Vapour phase
equilibrium,
Line
2
-3:
Solid/Liquid
phase
equilibrium
Critical point: Highest value of P and T
at which chemical species of the pure
substance
exist
in
liquid/vapour
equilibrium

PT Diagram of a Pure
Substance
Isothermal Process is represented by
vertical line on the PV diagram
Isobaric
Process
is
represented
by
horizontal line on PV diagram
When any of these two lines crosses phase
boundary, there is immediate change of
properties and phase at constant T and P
Transition from A to B is possible, it is
gradual and does not involve vapourisation
step
A fluid existing at above TC is Supercritical
fluid

PV Diagram

PV Diagram
PV shows the existence of regions between two
phases e.g. Soild/Liquid region in equilibrium.
Regions are separated by bounding curves that
represent single phases.
At a fixed Temperature, a bounding curve is
obtained.
Lines labelled T1
and T2 are for subcritical
temperatures, each line consists of three
segments.
The horizontal segments of these lines represent
liquid/vapour mixture at equilibrium (100% liquid
at the extreme left, 100% vapour at the right end).

PV Diagram
The locus of these end points forms a domeshaped curved, BCD.
The left half (BC) represents single-phase
liquids at their vapourisation temperatures.
The right half (CD) represents single-phase
vapours at their condensation temperatures.
Liquids and vapours represented by BCD
are said to be saturated.
Subcooled liquid region lies to the left of
saturated liquid curve, BC.
Superheated vapour region lies to the right
of saturated vapour curve, CD.

MODULE TWO
FIRST LAW OF THERMODYNAMICS
Work and Heat.
Adiabatic work.
Internal Energy.
Enthalpy.
Heat Capacity.

First law of
Thermodynamics
Although energy assumes many forms,
the total quantity of energy is constant,
and when disappears in one form it
appears simultaneously in other forms.

that is during an interaction, energy can change

from one form to another but the total amount of energy
remains constant, that is, energy can neither be created nor
destroyed.

First law of
Thermodynamics

The law implies that

There are different forms of energy
There is conservation of energy
Total energy between a system and its
surroundings is constant (no change in
total energy between a system and its
surroundings)
The last expression can be written as

(Energy of the System) + (Energy

of the Surroundings) = 0
2.1

WORK, W
is a transfer of energy between the
system and surroundings.
It can only be transferred, but not stored
Work is done by a system on its
surroundings if the sole effect on
everything external to the system could
have been the raising of a weight
W is not a point function, but path
function (magnitude depends on the
path).
W= =

Heat, Q
Heat is a form of energy which, when
transferred to or from a system makes it hotter
or colder, respectively.
Heat and work are energy in transit, between
a system and its surroundings.
Energy interaction is heat only if it takes place
because of temperature difference.
There cannot be any heat transfer between two
systems that are at the same temperature.
Heat is recognized only as it crosses the
boundary of a system

Forms of Energy
1. Macroscopic : forms of energy a system
possesses as a whole with respect to some
outside reference frame, such as kinetic and
potential energies (the macroscopic energy of
an object changes with velocity and elevation)
2. Microscopic forms of energy are those related
to the molecular structure of a system and
the degree of the molecular activity, and the are
independent of outside reference frames.
The sum of all the microscopic forms of energy is
called the Internal Energy of a system, U.

Forms of Energy
The macroscopic energy of a system is
related to motion and the influence of some
external effects such as gravity, magnetism,
electricity, and surface tension.
The energy that a system possesses as a
result of its motion relative to some reference
frame is called kinetic energy (KE).
The energy that a system possesses as a
result of its elevation in a gravitational field is
called potential energy (PE).

Other Forms of Energy: Enthalpy, H

Enthalpy is defined using combination of properties.
The enthalpy, H, is defined as:
H
U + PV and
*
H = U + (PV)
**
where U is Internal Energy, P is Pressure and V is
volume.
For a constant P and V process, H = U
***
Recall also that
the product P x V has energy units.
Q = nH
=
nCpdT
****
Read Textbooks for more information on Enthalpy and Heat Capacity
Study Example 2.1 2.14 in Introduction To Chemical Engineering
Thermodynamics (J. M. Smith, H. C. Van Ness & M. M. Abbot).

Energy Balance For A Closed

System
For
a closed system, no form of energy is

transported between the system & surroundings.

The only forms of energy that may be transferred
are Heat (Q) and Work (W).
The second term of Equation 2.1 is now written
as
(Energy of the Surroundings) = Q W
2.2
Q and W denote Heat and Work of the system.
The sign used depends on the nature of the
energy, +ve sign is taken as energy to the
system

Energy Balance For A Closed

System
Hence,

= -Q,
= -W
2.3
Equation 2.1 becomes
(Energy of the System) + - Q - W = 0
(Energy of the System) = Q + W
Change in Total Energy of a closed system equals net
energy transferred to it in form of heat and Work.
Total Energy of a closed system is represented as Total
Internal Energy () of the system.
so

=Q+W
2.4

Examples 2.1
A

non-conducting container filled with 25 kg of water at C

is fitted with a stirrer which is made to turn by gravity
acting on a weight of mass 35 kg. The weight falls slowly
through a distance of 5 m in driving the stirrer. Assuming
that all work
done on the weight is transferred to the water and that
the local acceleration of gravity is 9.8 determine
a) the amount of work done on the water
b) the internal energy change of the water
c) the final temperature of the water, for which C p = 4.18
d) the amount of heat that must be removed from the
water to return it to its initial temperature
e) the total energy change of the universe because of
i.
the process of lowering the weight
ii. the process of cooling the water back to its

Solution to Example 2.1

= 35 kg,

g = 9.8 ,
z = 5 m
[a] Work, W = F.d = . g . z = 35 kg x 9.8 x 5 m
W
= 1715 J =
1.715 kJ
[b] Change in Internal Energy,
No energy loss
= W = 1.715 kJ
[c] Final Temperature of water,
At constant P and V,
[using *** and
****]
U = H = CpdT = x Cp -

Solution to Example 2.1

1.715 = 35 x 4.18 - 20)

hence

= 20.01C, Final
Temperature
[d] Heat removed, Q, to restore (cool)
water to
Q = - U = -1.715
kJ
[e] No change in total energy of the
universal in each of the three cases

Example 2.2

2.3