TDA301T 2023

Lecture Notes
LESSON ONE
Compiled by
Mr. Leshabane LJ
(MEng: Chem Eng TUT)
Department of Chemical, Metallurgical and
Materials Engineering
Please note:
• MyTutor – Official media for academic activities
• Assessment date to follow soon
• Classes every Thursday (9:30 AM) and Friday (11:00 AM)
• Practical's are on Monday – schedule will be posted.
• Consultation – Wednesdays (10:00-15:00PM).
• Cellphones must switched off or on silent mode at all
times during lectures.

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 Course Outline
• LESSON ONE & TWO: Review Of First And Second Laws Of Thermodynamics
-Definitions, Examples of Thermodynamic Systems, First Law, Second Law, Perpetual Motion Machine, Tutorials

• LESSON THREE: Heating And Expansion

-Thermodynamics relations, Tutorials

• LESSON FOUR: Nozzles

-Introduction, Industrial applications, Thermodynamics Relations, Tutorials

• LESSON FIVE: Carnot And Rankine Cycles

-Introduction, Systems based on Carnot and Rankine cycles, p-v Diagram, T-s Diagram, efficiency and performance, Tutorials

• LESSON SIX: Refrigeration And Cooling

• LESSON SEVEN: Steam Generation And Power Plants

• LESSON EIGHT: Any Other Topic Such As Chemical Equilibrium

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 Assessments
– 1. Two major tests : 60 % ( 08th Sept and 20th October)
– 2. Two class test: 20% ( 01st Sept and 13th October)
– 3. One assignments: 10 %( 4th Sept )
– 4. One practical: 10% (compulsory to pass the module)
– 5. Final mark = Mark1+Mark2+Mark3 + Mark4 = 100%

This is a continuous module, all marks count towards your final

mark.

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 Course Content
Any Thermodynamics book with Engineering Approaches
Examples:
– Chemical, Biochemical & Engineering Thermodynamics (Fifth
Edition) by Stanley I. Sandler
– Applied Thermodynamics by Eastop and McConkey
– Fundamentals of Chemical Engineering Thermodynamics by
Themis Matsoukas
– Introduction to Chemical Engineering Thermodynamics by
JM Smith

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 Introduction
What is Thermodynamics ?
 Word: Thermodynamics = Thermo + Dynamics
(Greek) ΘΕΡΜΟ + ΔΥΝΑΜΙΣ
(HEAT) (POWER)
Thermodynamics is the study of energy changes
accompanying physical and chemical changes.
The term itself clearly suggests what is happening --
"thermo", from temperature (heat!) meaning energy,
and "dynamics", which means the change over time.

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 Introduction
•
What is Thermodynamics ?
“Thermodynamics is a funny subject.
 The first time you go through it, you don't understand
it at all.
 The second time you go through it, you think you
understand it, except for one or two small points.
 The third time you go through it, you know you don't
understand it, but by that time you are so used to it, it
doesn't bother you anymore.”
The German physicist Arnold Sommerfeld, (nominated 81 times
for the Nobel Prize!) was asked about Thermodynamics

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 Introduction
• Why is it relevant to you – to Chemical Engineering?
 Applied thermodynamics is the science of the
relationship between heat, work, and systems that
analyze energy processes.
 The energy processes that convert heat energy from
available sources such as chemical fuels into mechanical
work are the major concern of this science.
 Thermodynamics consists of a number of analytical and
theoretical methods which may be applied to machines
for energy conversion

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 Introduction
• The origins of Thermodynamics
 Thermodynamics began as a way to evaluate the
potential of steam engines to provide work.
 In other words: thermodynamics is dealing with the flow
of heat that could be used for industrial processes and
locomotion
 Study of heat engines soon extended from steam engines
to internal combustion engines, turbines, heat pumps,
air conditioners etc.
 Understanding of properties of pure fluids (water &
steam) and refrigerants and gases (oxygen, nitrogen)

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 Introduction
• Thermodynamics:
 Describes macroscopic properties of equilibrium
systems
 Entirely Empirical
 Built on 4 Laws and “simple” mathematics

Zeroth Law ⇒ Defines Temperature (T)

1st Law ⇒ Defines Energy (U)
2nd Law ⇒ Defines Entropy (S)
3rd Law ⇒ Gives Numerical Value to Entropy

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 Revision of Thermodynamics Concepts
• The problem regions
 In attempting to apply the laws of Thermodynamics in such a
way as to solve engineering problems, it is critical that we
define exactly the region of space to which we are applying
those rules.
• The universe is all of space.
 While the laws of thermodynamics could be applied to the
universe, it is usually more convenient to break that space up
into:
• The system is the region of space that is of interest in the
problem.

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 Revision of Thermodynamics Concepts
• The System is a spatial domain bounded for the purpose of
describing a problem; while
• the surroundings are the entire spatial domain outside of the
system.
• The communication between them is established through the
boundaries of the system. The system and the surroundings
make up the universe.
 The surroundings is all of the space which is not contained
within the system.
• The system is enclosed by a boundary (that may be real or
simply a "line"), so that the system can be open, closed, or
isolated.
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Revision of Thermodynamics Concepts

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 Revision of Thermodynamics Concepts
• The System and the surroundings interact with each other.
 Thermodynamic problem : that of predicting changes in a
system due to interactions with its surroundings.
• A system is open if it can exchange mass with the surroundings,
and closed if it does not exchange mass with the surroundings.
• A system is adiabatic if it does not exchange heat energy with
the surroundings.
• We called a system isolated if there is neither heat nor mass
crossing its boundaries
• Distinguish between the universe, system, surroundings, and
boundary

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 Revision of Thermodynamics
Description of System
• Describing systems requires:
1. A few macroscopic properties: p, T, V, n, m, …
2. Knowledge if System is Homogeneous or Heterogeneous
3. Knowledge if System is in Equilibrium State
4. Knowledge of the number of components in the system

Two classes of Properties:

5. Extensive: Depend on the size of the system (n, m, V,…)
6. Intensive: Independent of the size of the system (T, p, V = V ,…)

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 Revision of Thermodynamics
Description of System
• The state is the thermodynamic coordinate of the system,
specified by a number of intensive variables.
• The degree of freedom is the number of intensive variables
needed to define the state of the system.
• State functions are those whose changes depend on their end
states only and are independent of the path between them.
• A process is the series of successive, intermediate states that
the system goes through in order to go from an initial to a final
state.

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 Revision of Thermodynamics
Description of System
• A process is isothermal or isobaric if the temperatures or
pressures of all successive steps are the same, respectively.
• A reversible process is one for which the exchange of energy
between the system and its surroundings takes place under
vanishing gradients or driving forces;
 the properties of the system and surroundings are balanced.
 In a reversible process, each step of the process can be
“reversed” and the original states of the system and
surroundings can be restored.
 Any process that does not take place under infinitesimal
gradients is irreversible.

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 Revision of Thermodynamics
Description of System
• The State of a System at Equilibrium:
 Defined by the collection of all macroscopic properties that are
described by State variables (p, n, T, V,…) [INDEPENDENT of the
HISTORY of the SYSTEM]
Example:
• For a one-component System, all that is required is “n” and 2
variables. All other properties then follow.
V =f(n,p,T) or p = g(n,V,T)
3 H2 (g, 1 bar, 100 °C) means 3 moles; gas; p=1 bar; T=100 °C
2 Cl2 (g, 5 L, 50 °C) means 2 moles; gas; V=5 L; T=50 °C
5 Ar (s, 5 bar, 50 K) means 5 moles; solid; T=50 K

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 Revision of Thermodynamics
Description of System
• Change of State: (Transformations)
 Example:
3 H2 (g, 5 bar, 100 K) = 3 H2 (g, 1 bar, 50 K)
 Path: Sequence of intermediate steps

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 Revision of Thermodynamics
Description of System
• Process: Describes the Path
 Reversible (always in Equilibrium)
 Irreversible (defines direction of time)
 Adiabatic (no heat transfer between system and
surroundings)
 Isobaric (constant pressure)
 Isothermal (constant temperature)
 Isochoric (constant volume)

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 Revision of Thermodynamics
Forms of Energies
• Heat (Q )
• Work (w)
• Internal Energy (U)
• Kinetic Energy (KE)
• Potential Energy (PE)
• Flow Energy (PV)
how do you express the first Law of Thermodynamics?

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 Revision of Thermodynamics
Forms of Energies
1. Heat.
• We use 'Q to denote the total rate of flow of heat into the
system, by both conduction and radiation, so that
• ‘Q is positive if energy in the form of heat flows into the system
and negative if heat flows from the system to its surroundings.
I
• Energy in the form of heat may enter or leave the system
across the system’s boundaries:

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 Revision of Thermodynamics
Forms of Energies
2. Work.
• Energy in the form of work (mechanical, electrical etc.) may
enter or leave the system across the system’s boundaries. The
total energy flow into the system due to work will be divided
into several parts.
i. Shaft work: The first part, called shaft work and denoted by
the symbol Ws is the mechanical energy flow that occurs
without a deformation of the system’s boundaries. The flow
of electrical energy into or out of the system will be included
in the shaft work term.

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 Revision of Thermodynamics
Forms of Energies
ii. Work also results from the movement of the system
boundaries. The rate at which work is done when a force F is
moved through a distance in the direction of the applied
force dL, in the time interval dt:

• Convention: W> 0; if work is added to the system

 An energy flow into the system is positive
 A energy flow out of the system is negative

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 Revision of Thermodynamics
Forms of Energies
• Ẇ <0 if the system is carrying out work
 In the case the system is behaving reversibly, then
F = P A, where
 P is the pressure of the system, which is assumed uniform
over A.
 Then

• The negative value is added because Ẇ > 0 if

<0

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 Revision of Thermodynamics
Forms of Energies
• We recognize that pressure P is a force F per unit area and
write where P is the pressure exerted by the system at its
boundaries.

• The negative sign in this equation arises from the convention

that work done on a system in compression (for which dV/dt
is negative) is positive, and
• Work done by the system on its surroundings in an expansion
(for which dV/dt is positive) is negative.

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 Revision of Thermodynamics
Forms of Energies
 To evaluate this energy flow term, which occurs only in
systems open to the flow of mass, we will compute the net
work done as one fluid element of mass (ΔM1) enters a
system, such as the valve in Fig., and another fluid element
of mass (ΔM2 ) leaves the system.

 The pressure of the fluid at the inlet side of the valve is P1

and the fluid pressure at the outlet side is P2
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 Revision of Thermodynamics
Forms of Energies
• As fluid moves, it does work against the fluid that is ahead of it
(for example in a pipe!)
Work = F dL, but F = P A, and A dL = dV
Work=P dV= P Ṽ ΔM

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 The First Law of Thermodynamics
• We arrive at an alternate representation of the first law by the
following analysis.
• Consider the sketch of Fig. below:
• Now, consider two cycles, each passing through points 1 and
2, albeit via different paths:
 Cycle I: 1 to 2 on Path A followed by 2 to 1 on Path B,
 Cycle II: 1 to 2 on Path A followed by 2 to 1 on Path C.

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 The First Law of Thermodynamics
• We can show that despite the fact that B and C are arbitrary
paths; Eq. below asserts that the integral of δQ − δW from 2 to 1
is path-independent.

• This is in spite of the fact that both W and, as we will see later, Q
are path-dependent quantities.
• This defines Energy:
• Energy: a thermodynamic property which is a theoretical
construct suggested by the first law of thermodynamics as
account for the difference between heat transfer and work in any
process between the same start and end states.
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 The First Law of Thermodynamics
 Energy: new extensive property of the system (denoted by E).
 While we like to think we have intuition for what constitutes
energy: , it really is an elusive quantity.
 viewed at another way, the (Newtonian) mechanical energy is
easily visualized in terms of kinetic and potential energy, but
it is not always conserved!
 Our new energy includes thermal energy, which we think we
can easily feel, so we still have a good intuition for it. So we
have generalized energy so that it is always conserved, at the
expense of losing the ability to easily visualize it.

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 The First Law of Thermodynamics
 Recall that properties depend only on the state and not the
path taken to arrive at the state.
 Let us then take the following definition for the differential of E:

 If we integrate from 1 to 2 we obtain:

 finally yielding:
 alternate representation of the First Law
 For a system undergoing a process, the change in energy is
equal to the heat added to the system minus the work done
by the system.

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 The First Law of Thermodynamics
• Now, we consider E to represent the total energy of the system.
It has units of J. It includes energy which is
 potential,(EP)
 kinetic, (EK)
 thermal, (Q)
 chemical,
 electrical, magnetic,etc.
• We lump all of these other types of energy into a single term U,
which we define as
 Internal energy: that portion of total energy E which is not
kinetic or potential energy. It includes thermal, chemical,
electric, magnetic, and other forms of energy.

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 The First Law of Thermodynamics
• We take U to have units of J. We call the kinetic energy KE and the
potential energy PE.
• So we consider the total energy to consist of:

• We are concerned with changes of U which are associated with

changes of the thermal energy of the system.
• Thermal energy: kinetic energy associated with random motions
of molecules at the microscale.
• We cannot easily observe this microscale kinetic energy; only
consider it in the average. In fact, the temperature is a measure
of the average microscale kinetic energy.
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 The First Law of Thermodynamics
• Each form of energy is an extensive property of the system
(what is an extensive property?).
• Taking differentials of previous Equation, we get
dE = dU + d(KE) + d(PE)

 So the first law, dE = δQ − δW, can be written as

dU + d(KE) + d(PE) = δQ − δW.

In the next two examples, let us consider two special cases which
are familiar from Newtonian mechanics

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 The First Law of Thermodynamics
• Example 1

 Let’s assume a system of mass m for which:

dU = 0, d(PE) = 0, and δQ = 0.
 Physically, this might correspond to a system with constant
internal energy, held at constant height, and with no heat
exchanges with its surroundings.
 For this system, the first law gives a balance between changes
in kinetic energy and work. And let us assume that the system
is being accelerated by a horizontal force F as it acts through a
distance in the x direction. Assume there is no friction force.

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 The First Law of Thermodynamics
• Example 1

• From the First Law we obtain:

d(KE) = −δW
• Newtonian mechanics tells us
δW = −F dx.
 The sign is negative because the system is being worked upon.
It is not doing work. So we get
d(KE) = F dx

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 The First Law of Thermodynamics
• Example 1

 Newton’s second axiom tells us F = m(d2x/dt2)

(Force equals mass X acceleration)
 Since dx/dt = v (velocity) , we can say F = m(dv/dt), so
d(KE) = m (dv/dt) dx
 Note we use ν for velocity and distinguish that from V, the
specific volume.

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 The Kinetic Energy

• If we take v1 = 0 and define the KE1 as zero at this point, and

take 2 to just be a general state, we get the commonly used
equation for the kinetic energy

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 First Law – Potential Energy
• Example 2

 Let’s assume a system of mass m for which:

dU = 0, d(KE) = 0, and δQ = 0.
 Physically, this might correspond to a system with constant
internal energy, held at constant upward velocity, with no
heat exchanges with its surroundings.
 For this system, the first law gives a balance between changes
in potential energy and work.
 Let us assume that the system is being raised at constant
velocity v through distance z against a gravitational force,
where the gravitational acceleration g is constant.

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 First Law – Potential Energy
• Example 2

Sketch of system being raised at constant velocity v

in a gravitational potential
• Newton’s second axiom says that m(d2z/dt2) = F −mg.
 Now, we are told the velocity is constant, so the acceleration
here is zero, so Newton’s second axiom gives a force balance, 0
= F − mg, thus
F=mg
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 First Law – Potential Energy
• Example 2
• If we take PE1 to be zero at z1 = 0, and consider a general z, we
get the commonly used equation for the potential energy
PE = m g z
 Derivation:

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 First Law – Potential Energy
• Example 2
 If we use
• again and by substituting the formulas for the kinetic and
the potential energy as obtained earlier, above equation
becomes:

• Integrating Eq. above from state 1 to state 2 to get

• Substituting in equation

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 First Law – Potential Energy

• Now, if m is a constant, as it will be for a system, we can

divide both sides by m to get

• Here, we have defined the new intensive variables

 u ≡ U/m, the internal energy per unit mass, also known as
the specific internal energy. It has units kJ/kg. It is an
intensive thermodynamic property

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The Conservation Equation: 1st Law of Thermodynamics
W Q

Inlet 1 Outlet 2

system

z2

z1
Datum

Conservation equation: Energy entering the system = energy leaving the

system ( on unit mass basis for steady state flow)
U1 + P1 V1 + u12 /2 + z1g + Q = U2 + P2 V2 + u22 /2 + z2g + W
∆U + ∆PV + ∆EK + ∆EK = Q - W
 The Conservation Equation: Notes

1. For negligible potential, kinetic and flow energies

Q-W = U2-U1 = U

2. H1 =U1 + P1 1 and H2 = U2 + P2 2 (Enthalpies)

3. For negligible potential and kinetic energies only

Q-W = H2-H1 = H
 Applications: 1st Law of Thermodynamics
1. Nozzle
A nozzle is a device that a. Rate of net energy transfer =
increases the velocity of a fluid rate of change of energy
at the expense of pressure
b. For nozzles: Q= 0; w=0, PE=0

c. H2-H1 = u12/2 - u22 /2

u1 u2
 Applications: 1st Law of Thermodynamics
2. Pump
A pump is a device that adds
energy to a fluid (increases fluid
a. Rate of net energy transfer = rate of change
pressure). The energy is of energy
requirement is measured in
terms of shaft work
P2
b. For pump: Q= 0
u2
P1 z2 c. P1 1 + u12/2 + z1g + Win = P2 2 + u22/2 + z2g
u1
z1
Win d. Where pumps are used to transfer fluid over
long distances, energy dissipation interms of
frictional losses must be included in the output
 Applications: 1st Law of Thermodynamics
a. Rate of net energy transfer = rate of
3. Turbine change of energy
A turbine is a device that
extracts energy (Wout) from a b. For turbine: Q= 0
fluid
P1 c. H1 + u12 /2 + z1g = H2 + u22 /2 + z2g + Wout
u1
z1
H1

Wout
P2
u2
z2
H2
 Applications: 1st Law of Thermodynamics
4. Compressor a. Rate of net energy transfer = rate of
change of energy
A compressor is a device that
adds energy (Win) to a fluid i.e it b. For Compressor: Q= 0
increases pressure. Heat transfer
c. H1 + u12 /2 + z1g + Win = H2 + u22 /2 + z2g
is negligible unless otherwise
P2
indicated u2
z2
H2

W in

P1 NOTE: In compressors PE is

u1
z1
negligible i.e. z1 =z2
H1
LeshabaneLJ@tut.ac.za

Department of Chemical, Metallurgical and Materials Engineering

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