TDA301T 2023

Lecture Notes
LESSON TWO
Compiled by
Mr. Leshabane LJ
(MEng: Chem Eng TUT)
Department of Chemical, Metallurgical and
Materials Engineering
 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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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 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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 Entropy
• Second law of thermodynamics:
“Heat cannot, of itself, pass from a colder to a hotter body”

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 Entropy
• Definition of Entropy
• The entropy (symbol S ) is a state function.
 In a system in which there are flows of both heat by
conduction (‘Q ) and work [ Ẇs and P(dV/dt)] across the
system boundaries:
 the conductive heat flow, but not the workflow, is the one
that causes a change in the entropy of the system;
• This rate of entropy change is ‘Q/ T,
 where T is the absolute thermodynamic temperature of the
system at the point of the heat flow.

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 Entropy
• Definition of Entropy
• If, in addition, there are mass flows across the system
boundaries:
 the total entropy of the system will also change due to this
convective*) flow, i.e.
• Each element of mass entering or leaving the system carries
with it its entropy (as well as internal energy, enthalpy etc.]

• *) convective flow : Motion of a fluid due to differences in

density.
These differences in density commonly
occur due to temperature gradients.

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 Entropy Balance
Second Law of Thermodynamics,
Open System

• with

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 Entropy Balance
Second Law of Thermodynamics,
Closed System
• For a system closed to the flow of mass (i.e., all Ṁk = 0), we
have the entropy balance for a closed system:

• Based on the discussion above, we then have

a. The entropy function must be a state variable, and

b. It needs to have a positive rate of internal generation, that is,
Sgen> 0

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 Entropy Balance
Second Law of Thermodynamics,
Closed System

• A and B can interact transferring heat only.

• Heat transfer process occurs in such a way that, at any instant
each subsystem is in a state of internal thermal equilibrium
• Assume now that the heat transfer takes place very slowly so
that no internal generation of entropy takes place (bunch of
successive uniform states, or “equilibrium” states).

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 Entropy Balance
Closed System
• The rate-of-change form of the entropy balances for
subsystems A and B, which are passing through a succession of
equilibrium states and therefore have no internal generation of
entropy, are:

• In writing these equations we accept that the amount of heat

that leaves subsystem A enters subsystem B,
• h is the heat transfer coefficient

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 Entropy Balance
Closed System
• We mentioned that: in writing these equations we have
recognized that
• the amount of heat that leaves subsystem A enters subsystem
B, and
• the heat flow from A to B is proportional to the temperature
difference, ΔT, between the two systems,

• We remember that h is the heat transfer coefficient

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 Entropy Balance
Closed System
• Then for the combined non-equilibrium composite system,
composed of subsystems A and B, (‘Q = 0), we have as entropy
balance:

• And therefore, if we consider that total entropy of the system

is: S = SA + SB we obtain:

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 Entropy Balance
Closed System

• Since h , TA , and TB are positive, above equation establishes that

for this simple example the entropy generation term is positive.
• Also important to note that Śgen is proportional to the second
power of the system's non-uniformity, here (ΔT)2.
• Thus, Śgen , is positive away from equilibrium (when TA TB) and
equal to zero at equilibrium.

Śgen

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 Entropy Balance
Difference Form Balance Equation
• Often one is interested in the change in entropy of a system in
going from state 1 to state 2, rather than the rate of
change of entropy with time.
• This entropy change can be determined by integrating Eq. 4.1-
5 over the time interval t1 to t2 ,
 where (t1 to t2 ) is the time required to go between the two
states.

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 Forms of 2nd Law
• Clausius Formulation of Second Law
“it is not possible to construct a device that operates in a cycle
and whose sole effect is to transfer heat from a colder body to a
hotter body”
• Show from the axiom:
that the process below is impossible, in other words:
• the Clausius statement of the second law is consistent with
what it has been presented thus far!

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 Clausius Form of Second Law
of Thermodynamics
• The entropy balance over one complete cycle,
Sf – Si = 0 = + + Sgen
• By re-arranging we obtain
Sgen
• Remember:
Q1 = - Q2
• Then Sgen = ]

“Heat cannot, of itself, pass from a colder to a hotter body.”

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 Clausius Form of Second Law
of Thermodynamics
• The second-law statement we have used was:
Sgen 0
• Since 1

 It follows from : Sgen that:

• if Q1 were positive (Q1 0), (meaning flow of heat into device from cold
body) and 1

 Then Sgen 0 violation of our axiom

• If, however, Q1 were negative (Q1 0), (meaning flow of heat into
device was from high temperature to low temperature from hot body) or
2 process possible

 Conclusion: process may be possible as long as Sgen 0

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 Kelvin-Planck Statement of the
Second Law of Thermodynamics
• The second-law statement simplified:
“It is impossible for any system to operate in a thermodynamic
cycle and deliver a net amount of work to its surroundings while
receiving an energy transfer by heat from a single thermal
reservoir.”

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 Kelvin-Planck Statement of the
Second Law of Thermodynamics
Alternative Statement:
 It is not possible to construct a device operating in a cycle that
results in no effect other than, the production of work by
transferring heat from a single body.

• Energy Balance:

• We have specified that the process is a cycle, so that

Uf = Ui , and thus the first law holds:
Uf - Ui = 0 = Q + W
Q + W = 0 ; therefore: W = - Q
 Principle of energy conservation satisfied!

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 Kelvin-Planck Statement of the
Second Law of Thermodynamics
• Entropy Balance:
 We have specified that the process is a cycle, therefore entropy
balance: S –S =0= + S
f i gen

or Sgen =
• Since T (absolute temperature) is positive, T
• Q must be negative in order for Sgen [for the entropy
generation to be positive]
• the device cannot absorb heat and convert all of it to work,
however:
• the reverse process in which the device receives work and
converts all that work to heat is possible!

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 Reversibility
of Chemical Processes
• It is useful to remember definitions for so-called reversible and
irreversible processes
 Reversible process: A process in which it is possible to return
both the system and surroundings to their original states.
 Irreversible process: A process in which it is impossible to
return both the system and surroundings to their original
states.
• What happens if we can restore the system to its original state
but not the surroundings? , or
• Restore the surroundings to its original state but not the
system? → Such a process is irreversible.

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 Reversible Processes
• Important Class of Processes for 2nd Law;
• Those for which the rate of generation of entropy is always
zero: Sgen are called:
• Reversible processes: A process that occurs with no
(appreciable) internal temperature, pressure, or velocity
gradients and therefore no internal flows or viscous dissipation
• Examples:
• Fluid flow in a well-designed turbine, compressor, or nozzle
• Uniform and slow expansion or compression of a fluid
• Many processes in which changes occur sufficiently slowly that
gradients do not appear in the system

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 Irreversible Processes
• Irreversible process: A process that occurs with internal
temperature, pressure, or velocity gradients so that there are
internal flows or viscous dissipation
• Examples are:
• Flow in a pipe or duct in which viscous forces are present
• Flow through a constriction such as a partially open valve, a
small orifice, or a porous plug (i.e., the Joule-Thomson
expansion)
• FIow through a sharp gradient such as a shock wave
• Heat conduction process with a temperature gradient
• Any process in which friction is important
• Mixing of fluids of different temperatures, pressures, or
compositions
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 A General Heat Engine

(a) Schematic diagram of a simple heat engine.

(b) Schematic diagram of a fluid flow engine
• Such engines are shown schematically in Fig. , where 'Q is the heat flow rate into the
engine from the surroundings at temperature T1 ; Q2 is the heat flow rate from the
engine to its surroundings at temperature T2, and Ẇ is the rate at which work is done
by the engine. Remember that from the Clausius and Kelvin-Planck statements discussed
earlier that Q2 cannot be zero; that is, some of the heat entering the engine cannot be
converted to work and must be expelled at a lower temperature.

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 A General Heat Engine

• Engine in Fig. above may operate either in a steady-state fashion, in which case 'Q1 ,
'Q 2 and Ẇ are independent of time, or cyclically.
• If the energy and entropy balances for the engine are integrated over a time interval
Δt, which is the period of one cycle of the cyclic engine, or any convenient time
interval for the steady-state engine, one obtains:

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 P-V Diagrams

• Plot of pressure vs the volume is called a p-V diagram.

• On a p-V diagram, lines of constant temperature curve
from the upper left to the lower right → isotherms.

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P-V Diagrams

• Isothermal process: A process

performed at constant temperature
• Adiabatic process: no heat is
transferred to the gas, but the
temperature, pressure, and volume
of the gas change as shown by the
dashed line.
• The area under a process curve on a
p-V diagram is equal to the work
performed by a gas during the
process.

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 T-S Diagrams

• Plot of the temperature

versus the entropy of the gas.
• This plot is called a T-S
diagram.
• Lines of constant pressure
curve from the lower left to
upper right on a T-S diagram.

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T-S Diagrams
• Isobaric process: constant pressure
process ; this type of process occurs
in the combustor of a gas turbine
engine.
• Isentropic process: there is no
change in the entropy of the system
and the process is reversible. An
isentropic process appears as a
vertical line on a T-s diagram.
• The area under a process curve on a
T-s diagram is related to the amount
of heat transferred to the gas.

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 The Carnot Heat Engine

Carnot heat engine is a hypothetical

engine that operates on the reversible
Carnot cycle.
Basically developed by Sadi Carnot
in 1824

Expanded graphically by Clapeyron in 1834;

Finalised by Rudolf Clausius, which introduced the concept of
entropy

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 The Carnot Heat Engine

• A thermodynamic cycle occurs when a system is taken

through a series of different states, and finally returned to
its initial state.
• In the process of going through this cycle, the system may
perform work on its surroundings, thereby acting as a
heat engine.
• A heat engine acts by transferring energy from a warm
region to a cool region of space and, in the process,
converting some of that energy to mechanical work.
• The cycle may also be reversed (examples?)
• If worked upon by an external force, it can transfer
thermal energy from a cooler system to a warmer one

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 The Carnot Heat Engine

Carnot engine diagram

• Here, heat flows from a high temperature TH furnace

through the fluid of the system (“working substance”) into
the cold sink TC thus forcing the working substance to do
mechanical work W on the surroundings, via cycles of
contractions and expansions

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 The Carnot Heat Engine

Carnot engine diagram

• Here, heat flows from a high temperature TH furnace

through the fluid of the system (“working substance”) into
the cold sink TC thus forcing the working substance to do
mechanical work W on the surroundings, via cycles of
contractions and expansions

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The Carnot Heat Engine

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 The Carnot Heat Engine

• We will use a p-V diagram to plot the various processes in

the Carnot Cycle.
• The cycle begins with a gas, colored yellow on the figure,
which is confined in a cylinder, colored blue.
• The volume of the cylinder is changed by a moving red
piston, and the pressure is changed by placing weights on
the piston.
• We have two heat sources; the red one is at a nominal
300 degrees, and the purple one is at 200 degrees.
• Initially, the gas is in State 1 at high temperature, high
pressure, and low volume.

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 The Carnot Heat Engine

• We will use a p-V diagram to plot the various processes in

the Carnot Cycle.
• The cycle begins with a gas, colored yellow on the figure,
which is confined in a cylinder, colored blue.
• The volume of the cylinder is changed by a moving red
piston, and the pressure is changed by placing weights on
the piston.
• We have two heat sources; the red one is at a nominal
300 degrees, and the purple one is at 200 degrees.
• Initially, the gas is in State 1 at high temperature, high
pressure, and low volume.

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 The Carnot Heat Engine
The Carnot Cycle (4 steps)
1. Isothermal (reversible) expansion from Va to Vb adding Q1
2. Adiabatic (reversible) expansion from Vb to Vc reducing m
pressure.
3. Isothermal (reversible) volume reduction from Vc to Vd by
removing Q2
4. Adiabatic (reversible) compression from Vd to Va using a
compressor.

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 The Carnot Heat Engine
1. - Isothermal Expansion
• The first process performed on the gas is an isothermal
expansion.
• The 300 degree heat source is brought into contact with the
cylinder, and weight is removed, which lowers the pressure in
the gas.
• The temperature remains constant, but the volume increases.
• During the process from State 1 to State 2 heat is transferred
from the source to the gas to maintain the temperature.
• We will note the heat transfer by Q1 into the gas.

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 The Carnot Heat Engine
2. - Adiabatic Expansion
• The second process performed on the gas is an adiabatic
expansion.
• During an adiabatic process no heat is transferred to the gas.
• Weight is removed, which lowers the pressure in the gas.
• The temperature decreases and the volume increases as the
gas expands to fill the volume.
• During the process from State 2 to State 3 no heat is
transferred.
• Initially, the gas is in State 1 at high temperature, high
pressure, and low volume.

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 The Carnot Heat Engine
3. - Isothermal Compression
• The third process performed on the gas is an isothermal
compression.
• The 200 degree heat source is brought into contact with the
cylinder, and weight is added, which raises the pressure in the
gas.
• The temperature remains constant, but the volume
decreases.
• During the process from State 3 to State 4 heat is transferred
from the gas to heat source to maintain the temperature.
• We will note the heat transfer by Q2 away from the gas.

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 The Carnot Heat Engine
4.- Adiabatic Compression
• The fourth process performed on the gas is an adiabatic
compression.
• Weight is added, which raises the pressure in the gas.
• The temperature increases and the volume decreases as the
gas is compressed.
• During the process from State 4 to State 1 no heat is
transferred.
• At the end of the fourth process, the state of the gas has
returned to its original state and the cycle can be repeated as
often as required.
• During the cycle, work W has been produced by the gas,
• Total work = area enclosed by the process curves.

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 The Carnot Heat Engine
The Carnot Cycle (4 steps)

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 The Carnot Cycle (4 steps)
a. Reversible isothermal expansion of the gas at the "hot"
temperature, TH (isothermal heat addition/absorption).
During this step (1 to 2 on Figure 1, A to B in Figure 2) the
expanding gas makes the piston work on the surroundings.
The gas expansion is propelled by absorption of quantity Q1
of heat from the high temperature reservoir.
b. Isentropic (reversible adiabatic) expansion of the gas
(isentropic work output). For this step (2 to 3 on Figure 1, B
to C in Figure 2) the piston and cylinder are assumed to be
thermally insulated. The gas continues to expand, working
on the surroundings. The gas expansion causes it to cool to
the "cold" temperature, TC

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 The Carnot Cycle (4 steps)
c. Reversible isothermal compression of the gas at the
"cold" temperature, TC (isothermal heat rejection) (3 to 4 on
Figure 1, C to D on Figure 2) Now the surroundings do work
on the gas, causing quantity Q2 of heat to flow out of the
gas to the low temperature reservoir.
d. Isentropic compression of the gas (isentropic work input).
(4 to 1 on Figure 1, D to A on Figure 2)
• Piston and cylinder are assumed to be thermally insulated.
During this step, the surroundings do work on the gas,
compressing it and causing the temperature to rise to TH. At
this point the gas is in the same state as at the start of step 1.
e have specified that the process is a cycle, therefore entropy
balance:
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 The Carnot Cycle (4 steps)
• We have specified that the process is a cycle, therefore
entropy balance:
or Sgen =
• Since T (absolute temperature is positive, T
• Q must be negative in order for Sgen
• the device cannot absorb heat and convert all of it to work,
however:
• the reverse process in which the device receives work and
converts all that work to heat is possible

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 Heat Engine
• Consider a simplified Power Plant given below
Energy source Highlights:
E.g. Furnace
Qin • The Power Plant uses a working fluid
System
that undergoes a cycle
boundary
Boiler • The Heat Engine receives heat (Qin)
from high temperature source
(Furnace). The furnace in this case is
Pump W thermal energy reservoir
Win Turbin out
• Thermal energy reservoir is a
e
hypothetical body with a relatively
large heat capacity that can supply or
Condenser absorb energy
• Part of heat received is converted to
Qout work (Wout)
Energy sink e.g. • Heat Engine reject the remaining
atms, lake, river
waste heat (Qout) to low temperature
sink
Thermal Efficiency = Net work output/ Total heat input
Th = Wnet,out /Qin OR Th = (Qin – Qout) /Qin = 1- Qout / Qin

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 Heat Pump
• A device that transfers heat from low temperature medium to a high
temperature medium. E.g. a device used to heat a room during winter
Warm heated space
at TH> TL
Highlights:
QH (Desired Output)
• The objective of heat pump is to maintain
heated space at high temp.
• Heat is absorbed from low temperature
Heat environment
Pum Wnet, in • Heat supplied to high temperature
p (Required input) environment
• A measure of performance of heat pump
is expressed in terms of coefficient of
QL
performance ( COP )
Cold environment
at TL Coefficient Of Performance (COP) Of Heat Pump
COPHP = COPHP = COPHP = =

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 Perpetual-Motion Machine
Highlights
-According to this invention, this steam
W out
power uses no fossil or nuclear fuel.
-The boiler is heated by resistance heaters
that extracts part of the generated
Boiler electricity

-Energy balance across the system

boundary indicates that energy is
Pump
Turbin Generator generated by an amount of Qout + W out
e
since there is no energy input to the power
plant.
Condenser
-The above is not possible since according
Qout System boundary to the First Law of Thermodynamics energy
cannot be generated.

-This violates First Law of Thermodynamics

and therefore the device is just a PMMI

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 Perpetual-Motion Machine
Highlights
Energy source According to this invention, this steam
E.g. Furnace
power has only one thermal reservior:
Qin Energy Source
System
boundary
Boiler -Energy balance across the system
boundary indicates that Qin = Wnet, out since
there is no heat wasted to the sink
Pump
Turbin W net,out
e -The above is not possible since according
to the Second Law of Thermodynamics
energy must be exchanged between the
source and the sink.

-This device therefore violates the Second

Law of Thermodynamics and therefore the
device is just a PMMII.

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LeshabaneLJ@tut.ac.za

Department of Chemical, Metallurgical and Materials Engineering

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