Cowardice asks the question, ‘Is it safe?

’
Expediency asks the question, ‘Is it politic?’
Vanity asks the question, ‘Is it popular?’
But, conscience asks the question, ‘Is it right?’
And there comes a time when one must take a position
that is neither safe, nor politic, nor popular but one must take
it because one’s conscience tells one that it is right.
—Martin Luther King, Jr

https://en.wikipedia.org/wiki/Martin_Luther_King_Jr.
 ChE 103
Engineering Thermodynamics
ChE 103 - Engineering Thermodynamics
3.00 credits, 3 hours/week
Syllabus
- General: The scope of thermodynamics; Fundamental and secondary
quantities.
- The first law and other basic concepts.
- Volumetric properties of pure fluids: P-V-T behavior of pure substances;
Ideal and non-ideal gas; Equations of state and its applications.
- Heat effects: Heat capacities; Phase changes of pure substances; Standard
heat of reaction and effect of temperature.
- The second law of thermodynamics: Alternative statements; Heat engine;
Entropy changes and irreversibility. The third law of thermodynamics.

- Thermodynamics properties: Single phase and two-phase systems;

Thermodynamic diagrams.
- Conversion of heat into work by power cycles: Vapor cycles; Steam power
plant; Internal combustion engines and gas turbines; Combined gas-vapor
cycle.
1. Course Objectives
• Objective 1: To understand the theory and applications of classical
thermodynamics, thermodynamic properties, equations of state,
methods used to describe and predict phase equilibria.
• Objective 2: To apply the knowledge of thermodynamics, science,
and engineering to analyse and solve physical and chemical
problems encountered in chemical engineering.
2. Lecture Plan
Lec# Lecture Topics Book Chapters
01-04 Introduction to Chemical Engineering Thermodynamics Chapter 1
05-08 The first law and other basic concepts (Class Test #1) Chapter 2
09-12 Volumetric Properties of pure fluids Chapter 3
13-15 Heat Effects (Class Test #2) Chapter 4
16-21 The second law of thermodynamics Chapter 5
22-28 Thermodynamic properties of fluids Chapter 6
29-33 Thermodynamics of flow process (Class Test #3) Chapter 7
34-39 Production of power from heat (Class Test #4) Chapter 8
3. Distribution of Marks
Class Participation 10%
Continuous Assessment 20%
Final Examination 70%
Total 100%

4. Textbooks
1. Smith, Van Ness, Abbott (2018), Introduction to Chemical
Engineering Thermodynamics, 8th Ed., McGraw-Hill [Ch1 – Ch8]
2. Cengel, Boles, Kanoglu (2015), Thermodynamics – An
Engineering Approach, 8th Ed., McGraw-Hill
 Chapter 1
Introduction

Introduction and Basic

Concepts of
Thermodynamics
https://www.youtube.com/watch?v=F_NmS -Wy2lE\
What is Thermodynamics?
Thermodynamics can be defined as the science of energy.
The name thermodynamics stems from the Greek words
therme (heat) and dynamis (power or energy)
Thermodynamics is the branch of physics concerned
with heat and temperature and their relation to energy
and work.
Applications of Thermodynamics

Air-conditioning Airplanes
systems

The human
body

Car radiators Power plants Refrigeration systems

Chemical Engineering & thermodynamics
The main uses of thermodynamics in chemical engineering are to
determine the states of phases and chemical equilibrium necessary
for the design of separations processes (i.e., distillation, absorption,
extraction, etc.) and chemical reactors, and in determining the
thermodynamic (2nd law) efficiency of chemical processes.
Stanley Sandler, 1986
That is,
 Transfer of chemical species between phases (mass transport)
 Determination of equilibrium conditions for chemical reactions
 Calculation of heat and work requirements for physical and chemical processes

In short, thermodynamics is an essential part of chemical engineering.

We need to understand how energy is transferred within a system and to its surroundings.
Without it, we wouldn't be able to analyze or design a chemical process.
Thermodynamics deals with driving force, it does not deal with rate of physical
or chemical phenomena.
 SYSTEMS AND CONTROL VOLUMES

The application of thermodynamics to any real problem starts with the

specification of a particular region of space or body of matter designated
as the system and its surroundings

System: A quantity of matter or a region in

space chosen for study.
Systems may be considered to be
closed or open.
Surroundings: The mass or region outside
the system
Boundary: The real or imaginary surface
that separates the system from its
surroundings.
The boundary of a system can be fixed or
movable.
Closed system:
Material content is fixed
Internal mass changes only due to a chemical reaction
Exchange energy only in the form of heat or work with the surroundings
Open system:
▪ Material and energy content are variable
▪ System freely exchanges mass and energy with its
surroundings
▪ The system can have fixed, moving, real, and imaginary
boundaries.
▪ It usually encloses a device that involves mass flow
such as a compressor, turbine, or nozzle.
What do we mean by the State of a System?
Once a system has been selected, we must describe its state.
The state of a system is fixed by knowing a minimum number of the system
properties
Properties are considered to be either
extensive or intensive.

extensive properties
These are additive and depend
upon the mass of the
system, e.g. m, n, V, H, U, etc.

intensive properties
These are not additive and do not
depend upon the mass of
the system, e.g. P, T, refractive
index, density, thermal
conductivity, etc.
 STATE AND EQUILIBRIUM

Thermodynamics deals with equilibrium

states.
Equilibrium: A state of balance.
In an equilibrium state there are no
unbalanced potentials (or driving forces)
within the system.
Thermal equilibrium: If the temperature is the
same throughout the entire system.
Mechanical equilibrium: If there is no change
in pressure at any point of the system.
Phase equilibrium: If a system involves two
phases and when the mass of each phase
reaches an equilibrium level and stays
there.
Chemical equilibrium: If the chemical
composition of a system does not change
with time, that is, no chemical reactions
occur.
13
Processes
A process takes place in a system!
Energy conversion and degradation → physical and chemical processes
Adiabatic process:
Any process within an adiabatic system (no heat transfer through the
system boundaries)
Steady state process:
- Variables in the system remain constant with time
- System exchanges energy or matter at a constant rate
Unsteady state process (transient process):
Variables in the system change with time
Infinitesimal process:
A process that takes place with only an infinitesimal change in the
macroscopic properties of a system
Processes
 Reversible process is a case between natural and unnatural
processes and proceeds in either direction through a continuous
series of equilibrium states
e.g.

 Irreversible process Irreversible changes are permanent. They

cannot be undone. A change is called irreversible if it cannot be
changed back again.
e.g.
Basic, scientific concepts essential to the subject:
∙ Dimensions and units of measure
∙ Force and pressure
∙ Temperature
∙ Work and heat
∙ Mechanical energy and its conservation

Examples of questions that can be answered on the basis of the laws of

thermodynamics combined with property information include the following:

• What maximum flame temperature can be reached when ethanol is

burned in air?
• If a water/ethanol mixture is partially frozen, what are the
compositions of the liquid and solid phases?
• What volume of solution results from mixing one liter of ethanol with
one liter of water? (It is not exactly 2 liters!)
IMPORTANCE OF DIMENSIONS AND UNITS
Any physical quantity can be characterized by dimensions.

The magnitudes assigned to the dimensions are called units.

Some basic dimensions such as mass m, length L, time t, and

temperature T are selected as primary or fundamental dimensions,
while others such as velocity V, energy E, and volume V are expressed
in terms of the primary dimensions and are called secondary
dimensions, or derived dimensions.

Metric SI system: A simple and logical system based on a decimal

relationship between the various units.

English system: It has no apparent systematic numerical base, and

various units in this system are related to each other rather arbitrarily.
1.2 INTERNATIONAL SYSTEM OF UNITS

Although the SI is well established throughout most of the world, use of the U.S. Customary system of units persists in daily
commerce in the United States.
Even in science and engineering, conversion to SI is incomplete, though globalization is a major incentive.
U.S. Customary units are related to SI units by fixed conversion factors. Those units most likely to be useful are defined in

Appendix A. Conversion factors are listed in Table A.1.

1.3 MEASURES OF AMOUNT OR SIZE
Three measures of amount or size of a homogeneous material are in common
use:
∙ Mass, m
∙ Number of moles, n
∙ Total volume, Vt

Some relations

molar mass, ℳ
(formerly called molecular weight)
1.4 TEMPERATURE
 Zeroth Law of Thermodynamics
Thermal equilibrium
If two bodies are in contact through a thermally-conducting boundary for a
sufficiently long time, no further observable changes take place

Two systems, which are individually in thermal equilibrium with a third are in
thermal equilibrium with each other; all three systems have the same
value of the property called temperature.
1.5 PRESSURE
Force per unit area is called pressure, and its unit is the
pascal.
The actual pressure at a given position is called the
absolute pressure, and it is measured relative to absolute
vacuum (i.e., absolute zero pressure).
The absolute, gage, and vacuum pressures are related by

The Basic Manometer

1 atm = 30 inch hg= 33 ft water

= 1013.25 mbar

Vacuum and Pressure Gauge

Absolute, gage, and vacuum pressures. https://yzhfyb.en.made-in-china.com/product/qFdxEovOSmWy/China-
Mechanical-Pressure-and-Vacuum-Gauge-to-15-Psi-Specification.html
EXAMPLE 1–5 Absolute Pressure of a Vacuum Chamber
A vacuum gage connected to a chamber reads 5.8 psi at a location where the atmospheric
pressure is 14.5 psi. Determine the absolute pressure in the chamber.
SOLUTION

Pabs = Patm - Pvac = 14.5 - 5.8 = 8.7 psi

1 atm = 30 inch hg= 33 ft water = 1013.25 mbar

1.6 WORK, joule, 1 J = 1 kg⋅m2⋅s−2 = 1 N⋅m. [ W = F.s= m.a.s]
Work, W, is performed whenever a force acts through a distance. By its definition, the
quantity of work is given by the equation: dW = F dl (1.2)
where F is the component of force acting along the line of the displacement dl.
An example is the movement of a piston in a cylinder so as to cause compression or expansion
of a fluid contained in the cylinder.

1-2 - work is done on the system, piston moves

down to compress fluid, the work is therefore
positive, volume change is negative
2-1 - work is done on the surroundings, piston
moves up to expand fluid, volume change is
positive, the work is negative

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
1.7 ENERGY, joule, 1 J = 1 kg⋅m 2⋅s−2 = 1 N⋅m.

The sum of all forms of energy of a system is

called total energy, which is considered to consist
of internal, kinetic, and potential energies.
Internal energy represents the molecular energy
of a system and may exist in sensible, latent,
chemical, and nuclear forms.
Potential energy is the capacity for mechanical
work related to the position of a body
Kinetic energy is the capacity for mechanical work
related to the motion of a body
Potential and kinetic energies are external
energies

Energy in Transit: Energy may be transferred in the

form of heat or work through the system boundary
 Internal Energy, U
• No concise thermodynamic definition
• Cannot be directly measured-there are no
internal-energy meters
• It is a thermodynamic primitive.
• Absolute values are unknown.
• Only changes in internal energy are used,
ΔU=U2-U1

FIGURE 2–6
The various forms of microscopic energies that make up sensible energy.

This energy is named internal to distinguish it

FIGURE 2–7 from the kinetic and potential energy
The internal energy of a
system is the sum of all associated with a substance because of its
forms of the microscopic
energies. macroscopic position, configuration, or
motion, which can be thought of as external
forms of energy.
Example 1.5
A team constructs a system to supply water to a mountainside village located 1800 m above
sea level from a spring in the valley below at 1500 m above sea level.
(a) When the pipe from the spring to the village is full of water, but no water is flowing,
what is the pressure difference between the end of the pipe at the spring and the end of the
pipe in the village?
(b) What is the change in gravitational potential energy of a liter of water when it is
pumped from the spring to the village?
(c) What is the minimum amount of work required to pump a liter of water from the;
spring to the village?

Solution 1.5
(a) Take the density of water as 1000 kg⋅m−3 and the acceleration of gravity as 9.8 m⋅s−2. By
Eq. (1.1): P = hρg = 300 m × 1000 kg·m −3 × 9.8 m·s−2 = 29.4 × 105 kg·m−1⋅ s −2
Whence P = 29.4 bar or 2940 kPa

(b) The mass of a liter of water is approximately 1 kg, and its potential-energy change is:
Δ EP = Δ(mzg) = mgΔz = 1 kg × 9.8 m·s−2 × 300 m = 2940 N·m = 2940 J

(c) The minimum amount of work required to lift each liter of water through an elevation
change of 300 m equals the potential-energy change of the water. It is a minimum value
because it takes no account of fluid friction that results from finite-velocity pipe flow.
1.8 HEAT, joule, 1 J = 1 kg⋅m2⋅s−2 = 1 N⋅m.
Heat, like work, is recognized as energy in transit.
Examples
-- braking of an automobile
-- A kitchen refrigerator running on electrical energy must transfer this
energy to the surroundings as heat.
-- A room air conditioner, operating in the same way, extracts heat from the
room, but the heat exchanger is external, exhausting heat to the outside air,
thus cooling the room.

https://www.youtube.com/watch?v=gVLhrLTF878
1-11

Many Ways to Supply the Same

Energy
Ways to supply a room with energy equalling a 300-W electric resistance heater

(Fig. 1-52)
THE END