Chemical Engineering

Thermodynamics 1

Julius C. Ahiekpor, PhD

Senior Lecturer
Chemical Engineering

[email protected]
Course Content (Syllabus)
● First law of thermodynamics; basic concepts:
reversibility, equilibrium.
● Volumetric properties of fluids
● Second law of thermodynamics; Entropy.
● Thermodynamic properties of fluids
● Thermodynamic of flow processes and applications to
fluids transportation equipment.
● Conversion of heat into work by power cycles.
● Refrigeration and liquefaction
Course Objective
To introduce students to the fundamental concepts of
first and second law of thermodynamics

By the end of the course:

At the end of the course, the student should be able to:

1. Apply the first and second laws of thermodynamics and

their implications.

2. Perform calculations on a process using thermodynamic

principles.
Expectation of students (Analysis of class input)

● Understand and Apply

● Understand and Pass
● Interactive
● Tutorial
● Fairness
Recommended Reference Books

● Smith JM, Van Ness HC, Abbot MM, (2004).

Introduction to Chemical Engineering Thermodynamics,
7th edition, The Mcgraw-Hill Chemical Engineering Series

● Moran MJ, Shapiro HN, et al., (2010). Fundamentals of

Engineering Thermodynamics, 7th edition, Wiley

● PK Nag (2008). Basic and Applied Thermodynamics, 8th

Edition.
Grading

● Assignments 10%
● Mid-sem Exams 20%
● Final Exam 70%
Introduction

Thermodynamics
????
● Thermodynamics is the branch of science
which deals with energy as a property of
matter and its transformation into heat and
work.

● It also deals with various properties of

substances (volume, pressure, concentration,
temperature,) and the changes in these
properties due to energy transformations.
● volume, pressure, concentration,
temperature (STATE PROPERTIES)? We
elaborate later..
Historical Perspective
● Benjamin Thompson, in 1798, proposed a link between
work and heat generated from observing the boring of
cannons
● Nicolas Carnot, in 1824, first proposed the concept of
reversibility
● James Joule (a brewmaster), between 1840-1849
measured rising temperature from mechanical stirring –
quantifying the relation between work and heat
● The term ‘thermodynamics’ was coined by Kelvin in 1849
● The first thermodynamics book was written by Rankine
Where do we use thermodynamics

● Used in day to day activities to describe the

performance of propulsion systems, chemical
reaction systems, power generation systems,
and refrigerators, and to describe fluid flow,
combustion, and many other phenomena.

● It can address ANY geochemical reaction, if

thermo says NO, rest assured the reaction will
not proceed, if thermo says yes, then we can
progress to the next question → how fast
(Kinetics)
 Basic Terminologies and
definitions
To understand the laws of thermodynamics and how they work, first we need
to get the terminology right. Some of the terms may look familiar (as they are
used in everyday language as well)- but their meanings are more ‘technical’
and ‘precise’, when used in TD and hence we should not use them ‘casually’.
❑ System is region where we focus our attention (Au block
in figure).
❑ Surrounding is the rest of the universe (the water bath at
constant ‘temperature’).
❑ Universe = System + Surrounding (the part that is within the dotted
line box in the figure below )
❑ More practically, we can consider the ‘Surrounding’ as the immediate
neighbourhood of the system (the part of the universe at large, with which
the system ‘effectively’ interacts).
In this scheme of things we can visualize: a system, the surrounding and the
universe at large.

In TD we usually
do not worry
about the
universe at large!
 Open, closed and isolated
❑systems
To a thermodynamic system two ‘things’ may be added/removed:
➢ energy (heat, work) ➢ matter.
❑ An open system is one to which you can add/remove matter (e.g. a open
beaker to which we can add water). When you add matter- you also end up
adding heat (which is contained in that matter).
❑ A system to which you cannot add matter is called closed.
Though you cannot add/remove matter to a closed system, you can still add/
remove heat (you can cool a closed water bottle in fridge).
❑ A system to which neither matter nor heat can be added/removed is called
isolated.
A closed vacuum ‘thermos’ flask can be considered as isolated.
Type of boundary Interactions
Open All interactions possible (Mass, Work,
Heat)

Closed Matter cannot enter or leave

Only certain species can enter
Semi-permeable
or leave
Insulated Heat cannot enter or leave
Mechanical work cannot be
Rigid
* By or on the system done*
** Mass, Heat or Work
Isolated No interactions are possible**
Thermodynamic Properties

● A property is a characteristic of a system and it is used

to specify the condition or state of a system
● Pressure, temperature, volume, mass
● Extensive properties ?
● depend on the size of the system and hence the mass of the
system. Examples include mass, volume, and total energy.
● Intensive properties ?
● are independent of the size of the system. They include
pressure and temperature.
● A specific property (denoted by lower case letters)
refers to an extensive property per unit mass. eg. v = V/
m.
State postulate

● The state of a system is described by its properties. In

practice not all properties must be known before the
state is specified. Once a sufficient number of properties
are known, the state is specified and all other properties
are determined.
● The number of properties required to determine the
state of a simple, homogeneous system is given by the
state postulate:

“The thermodynamic state of a simple compressible

system is completely specified by two independent,
intensive properties”
PV Diagram
Thermodynamic process
● Any change from one state to another is called a
process. If the state of a system changes, then it is
undergoing a process.
● The succession of states through which the system
passes defines the path of the process.
 We will deal with some of them in
Processes in detail later on….

Thermodynamic
❑ Here is a brief listing of a few kinds of processes:
➢ Isothermal process → the process takes place at constant temperature
(e.g. freezing of water to ice at –10°C)
➢ Isobaric → constant pressure
(e.g. heating of water in open air→ under atmospheric pressure)
➢ Isochoric (Isovolumetric)→ constant volume
(e.g. heating of gas in a sealed metal container)
➢ Reversible process → the system is close to equilibrium at all times (and
infinitesimal alteration of the conditions can restore the universe (system +
surrounding) to the original state.
➢ Cyclic process → the final and initial state are the same. However, q and w
need not be zero.
➢ Adiabatic process → dq is zero during the process (no heat is added/
removed to/from the system)
❑ A combination of the above are also possible: e.g. ‘reversible adiabatic
process’.
Processes illustrated on a PV diagram. We shall use this to
perform some basic calculations using the first Law
State and path functions

● If the change in value of a function depends

only on it’s initial and final states and not the
path taken, the quantity is a state function.
Eg. Internal energy
● If the change in value is dependent on the
path taken, then the function is path function.
Eg. Work and heat
Equilibrium/ Reversibility

● Anything at equilibrium is theoretically

undergoing forward and reverse reactions:
● A+B↔C
● A + B → C AND C → A +B
● Equilibrium has 2 criteria:
● Reaction does not appreciably change in time
● Perturbation of that equilibrium will result in a
return to the equilibrium
 STABLE VS. METASTABLE
EQUILIBRIUM
● Stable equilibrium - System is at its lowest
possible energy level.
● Metastable equilibrium - System satisfies above
two criteria, but is not at lowest possible energy.
 Spontaneous and Driven
❑processes
A spontaneous process is one which occurs ‘naturally’, ‘down-hill’
in energy*. I.e. the process does not require input of work in any
form to take place.
∙ Melting of ice at 50°C is a spontaneous process.
❑ A driven process is one which wherein an external agent takes the
system uphill in energy (usually by doing work on the system).
∙ Freezing of water at 50°C is a driven process (you need a
refrigerator, wherein electric current does work on the system).

Spontaneous
process
(Click to see)
 Heat and
❑Work
Work (W) in mechanics is displacement (d) against a resisting force (F). W
=F ×d
❑ Work has units of energy (Joule, J).
❑ Work can be expansion work (PΔV), electrical work, magnetic work etc.
(many sets of stimuli and their responses).
❑ Heat as used in TD is a tricky term.
➢ The transfer of energy as a result of a temperature difference is called
heat.
➢ “In TD heat is NOT an entity or even a form of energy; heat is a mode of
transfer of energy” [1].
➢ “Heat is the transfer of energy by virtue of a temperature difference” [1].
➢ “Heat is the name of a process, not the name of an entity” [1].
➢ “Bodies contain internal energy (U) and not heat” [2].
❑ The ‘flow’ of energy down a temperature gradient can be treated
mathematically by considering heat as a mass-less fluid [1] → this does not
To give an example
make (inspired by [1]):
heat a fluid!
assume that you start a rumour that there is ‘lot of’ gold under the class room floor. This
rumour ‘may’ spread when persons talk to each other. The ‘spread of rumor’ with time
may be treated mathematically by equations, which have a form similar to the diffusion
equations
[1] Four Laws that(or heat
Drive the transfer
Universe, equations).
Peter Atkins, Oxford This
University Press, Oxford, 2007.does not
[2] Physical make
Chemistry, ‘rumour’
Ira N Levine, Tata McGrawaHillfluid!
Education Pvt. Ltd., New York (2002).
Expansion work (PV work)

● Along path a: W = 2p 0 (2V 0 – V 0) = 2p 0 v0

● Along path b: W = p 0 (2V 0 – V 0) = p0 v0

P
Things to note !!!!

● An important component to the solution of any engineering

thermodynamic problem is the proper use of units.
● Volume (m3)
● Pressure (Pa, N/m2),
● Temperature (Kelvin)

● ALWAYS REMEMBER TO HAVE YOUR UNITS IN THE SI

SYSTEM
First Law of Thermodynamics
● The first law of thermodynamics is a consequence of the Law of
conservation of energy which states that “Energy can be changed
from one form to another, but it cannot be created or
destroyed. The total amount of energy and matter in the
Universe remains constant, merely changing from one form to
another”.

This implies that the total energy of the universe is conserved

Note that the first law applies to the system and its surroundings
and not the system alone.
 Implications of the first law
“Heat and work are mutually convertible but since energy can
neither be created nor destroyed, the total energy associated
with an energy conversion remains constant”.

“When a system undergoes a “No machine can produce

thermodynamic cycle then the energy without
net heat supplied to the system corresponding expenditure
from the surroundings is equal of energy, i.e., it is
to net work done by the system impossible to construct a
on its surroundings. perpetual motion machine of
first kind”
There can be no machine which would continuously supply
mechanical work without some form of energy disappearing
simultaneously. Such a machine is called a perpetual motion
machine of the first kind
 First Law Equation for Closed Systems

ΔEsystem = Q – W
ΔE = Δ(U+PE+KE) = total energy of the system
Q = heat input to the system
W = work done by the system

For closed systems, no macroscopic transfer of mass,

PE=KE=0

ΔE = Δ(U+PE+KE) = ΔU
Therefore:

ΔU = Q – W
EXAMPLE :
Notes About the First Law
► When a system undergoes an infinitesimal change in state in which a small
amount of energy dQ is transferred by heat and a small amount of work dW is
done, the internal energy changes by a small amount :

(first law of thermodynamics for infinitesimal processes)

► Because dQ and dW are inexact differentials

Application of first law to reversible systems
● A process is reversible when its direction can be
reversed at any point by an infinitesimal change in
external conditions.
The First Law of Thermodynamics. A reversible constant volume
process

If heat is added at constant volume, no

work is done, so the heat added equals
to the increase in thermal energy

Internal Energy is a state function, i.e. it is not

dependent on the process, it only depends of the
initial and final temperature
Reversible Constant Pressure Process

If heat is added at constant pressure the

heat energy transferred will be used to
expand the substance and to increase the
internal energy.
Applying the First Law of Thermodynamics

This introduces the concept of enthalpy,

Which is the sum of Internal energy and PV
work. It is also a state function.
Degrees of Freedom/Phase rule

F = 2-π+N
F is the degrees of freedom
N is the number of chemical species
Π is the number of phases
 Reversible Constant Temperature Process
A process at a constant temperature is called an isothermal process.

When a working substance in a cylinder behind a piston expands from a high pressure
to a low pressure there is a tendency for the temperature to fall. In an isothermal
expansion heat must be added continuously in order to keep the temperature at the
initial value. Similarly in an isothermal compression heat must be removed from the
working substance continuously during the process.
Reversible Constant Temperature Process

Applying the First Law of Thermodynamics

 Adiabatic Process (Q=0)
Adiabatic process: no heat transfer between the system and the environment
Work done in a reversible adiabatic process

The work done is given by the shaded area,

and this area can be evaluated by integration.
The First Law of Thermodynamics- Home Work

A biatomic ideal gas undergoes a cycle starting at point A (2 atm, 1L).

Process from A to B is an expansion at constant pressure until the
volume is 2.5 L, after which, it is cooled at constant volume until its
pressure is 1 atm. It is then compressed at constant pressure until the
volume is again 1L, after which it is heated at constant volume until it is
back to its original state. Find (a) the work, heat and change of internal
energy in each process (b) the total work done on the gas and the total
heat added to it during the cycle.
OPEN SYSTEMS (FLOW SYSTEMS)
Introduction
● The first law of thermodynamics also applies to flow
(open) systems.
● In open systems, there is transfer of both mass and
energy across the boundary of the system.
● The medium through which the fluid flows carrying with
it mass and energy is called the CONTROL VOLUME
(CV) and the boundaries is the CONTROL SURFACE
Energy Balance Equation

ΔE = Q – W

The energy E present within a system per unit mass

can be classified in three ways as;
Potential energy (zg),

Kinetic energy (c 2/2) and

Internal energy (U).

The rate of energy associated with mass flow in a control volume is
given as

Net energy efflux from system

The overall energy balance equation is therefore given as

For steady state, normal unidirectional and uniform flow, we have

The work (W) which is energy per unit time can be divided into purely shaft work (Ws)
and pressure-volume, (pV), that is

Also, the pV term and U term are combined using the definition of enthalpy,
H:
Dividing through by m so that the equation is on mass basis,
Steady State flow Energy Equation is given as

v = velocity
z = height
H = Enthalpy
Q = Heat transferred
Ws = Shaft work
 Summary

At constant volume, no work is done (W = 0), so the heat

added equals to the increase in thermal energy

If heat is added at constant pressure the heat energy transferred

will be used to expand the substance and to increase the internal
energy.
W =PΔV
At constant temperature, there is no change internal energy,
ΔU =0

Adiabatic process: no heat transfer between the system

and the environment (Q = 0)

For steady state flow systems, the energy equation is given as

Applications of the 1 st Law:

Examples
VOLUMETRIC PROPERTIES
OF PURE FLUIDS
Pure Substances (Introduction)
● A pure substance is a system which is
● (i) homogeneous in composition,
● (ii) homogeneous in chemical aggregation, and
● (iii) invariable in chemical aggregation.

● “Homogeneous in composition” means that the

composition of each part of the system is the same as
the composition of every other part

● “Homogeneous in chemical aggregation” means that

the chemical elements must be combined chemically in
the same way in all parts of the system
● Invariable in chemical aggregation” means that the
state of chemical combination of the system does not
change with time

Examples of pure substances include:

• Water (solid, liquid, and vapour phases);

• Mixture of liquid water and water vapour;
• Carbon dioxide, CO 2;
• All elements
• Oxygen, O 2; and
• Mixtures of gases, such as air, as long as there is
no change of phase.
PVT Behaviour of pure substance
● Pressure, Volume, and Temperature (PVT) are
important properties needed for the evaluation
of quantities of heat and work required to carry
out industrial processes

● PVT are related mathematically as equations of

state f(P,V,T)=0

● PVT relations are used in metering of fluids and

the design of vessels and pipelines.
PVT Surface
Let us consider 1 kg of liquid water at a temperature of 20°C in a cylinder
fitted with a piston, which exerts on the water a constant pressure of
one atmosphere (1.0132 bar) as shown in (i).

As the water is heated slowly

its temperature rises until the
temperature of the liquid
water becomes 100°C. During
the process of heating, the
volume slightly increases as
indicated by the line 1-2 on
the temperature-specific
volume diagram.
If the heating of the liquid is continued
it undergoes a change in phase. This
state is described by the line 2-3.

The temperature at which

vapourisation takes place at a given
pressure is called the saturation
temperature and the given pressure is
called the saturation pressure.
During the process represented by the
line 2-3, the volume increases rapidly.
When all the liquid has been evaporated completely and
heat is further added, the temperature of the vapour
increases. The curve 4-5 describes the process
 If this process is repeated for a series of constant
pressures, we would have a curve like this

If all of the saturated liquid states are connected, the saturated

liquid line is established. If all of the saturated vapor states are
connected, the saturated vapor line is established. These two
lines intersect at the critical point and form what is often called
the “steam dome
The region to the left of the saturated liquid line and below the
critical temperature is called the compressed liquid region.

The region to the right of the saturated vapor line and above
the critical temperature is called the superheated region.
● When the temperature increases above the saturation
temperature the vapour is known as the superheated vapour

● The temperature at this state is called the superheated

temperature.

● The difference between the superheated temperature and the

saturation temperature at the given pressure is called the
degree of superheat.

● The specific volume of the saturated liquid and of the saturated

vapour is the same, i.e., vf = vg.

● The parameters like temperature, pressure, volume, at the

critical state are called critical parameters.
 Equation of state (Single phase region)
● An equation of state may be solved for any one of the three
quantities P, V, or T as a function of the other two. WHY?
● For example, if V is considered a function of T and P, then, V=(T,P),
and
Equation of state (Single phase)
Viral Equation
Rubin/Webb Equation
Second Law of Thermodynamics
Limitations of the first law
● The first law tells us that energy is conserved and can
flow from a system as work or heat but it places no limit
on the total energy of a system which can be converted
to work.

● It establishes equivalence between the quantity of heat

used and the mechanical work but does not specify the
conditions under which conversion of heat into work is
possible.

● It does not also tell us the direction in which heat

transfer can take place
Statements of the second law
● Statement 1: It is impossible by a cyclic process to
convert the heat absorbed by a system completely into
work done by the system (Kelvin- Planck statement)

Impossible (Kelvin- Planck)

● Statement 2: No process is possible which
consist solely in the transfer of heat from
lower temperature level to a higher one
(Clausius statement)

Note that the first law of

thermodynamics is not violated if heat
flows from a low temperature to a high
temperature without the expenditure
of work.

For T1 < T 2 , this is impossible (Classius)

The second law thus tells us that we cannot get
work from a single reservoir only.

A process will not occur unless it satisfies both the

first and the second laws of thermodynamics.

Some Definitions
To express the second law in a workable form, we
need to understand certain terminologies
Heat (Thermal) Reservoir
● A heat reservoir is a sufficiently large system in stable
equilibrium to which and from which finite amounts of
heat can be transferred without any change in its
temperature.

● A high temperature heat reservoir from which heat is

transferred is sometimes called a heat source. Eg of
heat source is a constant temperature furnace.

● A low temperature heat reservoir to which heat is

transferred is sometimes called a heat sink. Eg of heat
sink is the sea/river/atmoshere.
 Work (Mechanical energy)
Reservoir

A work reservoir is a sufficiently large

system in stable equilibrium to which and
from which finite amounts of work can be
transferred adiabatically without any change
in its pressure.
 Heat Engines
A heat engine is a device that converts heat into work. A classic example
is the steam engine. Fuel heats the water; the vapor expands and does
work against the piston; the vapor condenses back into water again and
the cycle repeats.

All heat engines have:

- working substance
- high-temperature reservoir
- low-temperature reservoir
- cyclical engine
Thermal Efficiency,
The thermal efficiency is the index of performance of a work-producing device or a
heat engine and is defined by the ratio of the net work output (the desired result) to
the heat input (the costs to obtain the desired result).

For a heat engine the desired result is the net work done and the input is the heat
supplied to make the cycle operate. The thermal efficiency is always less than 1 or
less than 100 percent.
77
wher
e

Now apply the first law to the cyclic heat engine.

0 (Cyclic)

78
The cycle thermal efficiency may be written
as

Cyclic devices such as heat engines, refrigerators, and heat pumps often operate
between a high-temperature reservoir at temperature TH and a low-temperature
reservoir at temperature TL.

79
The thermal efficiency of the above device becomes

Example

A steam power plant produces 50 MW of net work while burning fuel to produce 150
MW of heat energy at the high temperature. Determine the cycle thermal efficiency
and the heat rejected by the cycle to the surroundings.

80
 Heat Pump
A heat pump is a thermodynamic system operating in a thermodynamic cycle that
removes heat from a low-temperature body and delivers heat to a high-
temperature body. To accomplish this energy transfer, the heat pump receives
external energy in the form of work or heat from the surroundings.

While the name “heat pump” is the thermodynamic term used to describe a cyclic
device that allows the transfer of heat energy from a low temperature to a higher
temperature, we use the terms “refrigerator” and “heat pump” to apply to
particular devices.

Here a refrigerator is a device that operates on a thermodynamic cycle and

extracts heat from a low-temperature medium.

The heat pump also operates on a thermodynamic cycle but rejects heat to the
high-temperature medium.

The following figure illustrates a refrigerator as a heat pump operating in a

thermodynamic cycle.
81
Coefficient of Performance, COP

The index of performance of a refrigerator or heat pump is expressed in terms of the

coefficient of performance, COP, the ratio of desired result to input. This measure of
performance may be larger than 1, and we want the COP to be as large as possible.

82
For the heat pump acting like a refrigerator or an air conditioner, the primary function
of the device is the transfer of heat from the low- temperature system.

For the refrigerator the desired result is the heat supplied at the low temperature and
the input is the net work into the device to make the cycle operate.

83
Now apply the first law to the cyclic refrigerator.

and the coefficient of performance

becomes

For the device acting like a “heat pump,” the primary function of the device is the
transfer of heat to the high-temperature system (QH). The coefficient of performance
for a heat pump is

Note, under the same operating conditions the COPHP and COPR are related by

84
 PMM
● Any device that violates the first or second
law of thermodynamics is called a perpetual-
motion machine.

● If the device violates the first law, it is a

perpetual-motion machine of the first kind.

● If the device violates the second law, it is a

perpetual-motion machine of the second
kind.
PMM2
 The Carnot Cycle
● The Carnot cycle is best known reversible cycle; it was
proposed by French soldier Sadi Carnot in 1824.

● The Carnot cycle is the most efficient cycle possible for

converting a given amount of thermal energy into work.

● A Carnot heat engine is a hypothetical engine that

operates on the reversible Carnot cycle.

● A Carnot cycle has four processes.

● There are two adiabatic reversible paths and two

isothermal reversible paths.
 The Carnot Cycle
Process 1-2:Reversible isothermal heat addition at high temperature, TH > TL, to the
working fluid in a piston-cylinder device that does some boundary work.

Process 2-3:Reversible adiabatic expansion during which the system does work as
the working fluid temperature decreases from TH to TL.

Process 3-4:The system is brought in contact with a heat reservoir at TL < TH and a
reversible isothermal heat exchange takes place while work of compression is
done on the system.

Process 4-1:A reversible adiabatic compression process increases the working fluid
temperature from TL to TH

89
You may have observed that power cycles operate in the clockwise direction when
plotted on a process diagram. The Carnot cycle may be reversed, in which it
operates as a refrigerator. The refrigeration cycle operates in the counterclockwise
direction.

90
 Carnot Principles
The second law of thermodynamics puts limits on the operation of cyclic devices as
expressed by the Kelvin-Planck and Clausius statements. A heat engine cannot
operate by exchanging heat with a single heat reservoir, and a refrigerator cannot
operate without net work input from an external source.

Consider heat engines operating between two fixed temperature reservoirs at TH >
TL. We draw two conclusions about the thermal efficiency of reversible and
irreversible heat engines, known as the Carnot principles.

(a)The efficiency of an irreversible heat engine is always less than the

efficiency of a reversible one operating between the same two reservoirs.

(b) The efficiencies of all reversible heat engines operating between the same
two constant-temperature heat reservoirs have the same efficiency.

91
The thermal efficiencies of actual and reversible heat engines operating
between the same temperature limits compare as follows:

The coefficients of performance of actual and reversible (such as Carnot)

refrigerators operating between the same temperature limits compare as
follows:

92
Efficiency of a reversible Heat Engine

● The efficiency of a reversible heat engine in which heat

is received solely at T1 is found to be

● From the above expression, it may be noted that as T2

decreases and T1 increases, The efficiency of the
reversible cycle increases.
● Since η is always less than unity, T2 is always greater
than zero and + ve.
COP for reversible refrigerator
Can the Carnot Cycle be performed
in practice?
Entropy: A measure of Disorder

● The second law of thermodynamics leads to

the definition of a new property called
entropy.
● We will soon see that this property is
quantitative measure of microscopic disorder
for a system.
● Entropy is a measure of energy that is no
longer available to perform useful work
within the current environment.
To obtain the working definition of entropy and, thus, the second law, let's
derive the Clausius inequality.

Consider a heat reservoir giving up heat to a reversible heat engine, which

in turn gives up heat to a piston-cylinder device as shown below.

97
We apply the first law on an incremental basis to the combined system composed of
the heat engine and the system.

where E c is the energy of the combined system. Let Wc be the work done by the
combined system. Then the first law becomes

If we assume that the engine is totally reversible (Carnot cycle), then

The total net work done by the combined system

becomes

98
Now the total work done is found by taking the cyclic integral of the
incremental work.

If the system, as well as the heat engine, is required to undergo a cycle, then

and the total net work becomes

If Wc is positive, we have a cyclic device exchanging energy with a single

heat reservoir and producing an equivalent amount of work; thus, the Kelvin-
Planck statement of the second law is violated. But Wc can be zero (no
work done) or negative (work is done on the combined system) and not
violate the Kelvin-Planck statement of the second law. Therefore, since TR
> 0 (absolute temperature), we conclude:

or
99
Here Q is the net heat added to the system, Qnet.

This equation is called the Clausius inequality.

The equality holds for the reversible process and,

The inequality holds for the irreversible process.

100
Definition of Entropy
● For a reversible cyclic process, the Clausius inequality is ZERO.

● This suggests that the quantity (δQ net/T) is independent of the path
and is a function of the initial and final states of the system and
must be a property of the system just as INTERNAL ENERGY.

● This property is known as the ENTROPY.

● The entropy change occurring during a process is related to the

heat transfer and the temperature of the system. The entropy is
given the symbol S (kJ/K), and the specific entropy is s (kJ/kg⋅K).
In general the entropy change during a process is defined as

where = holds for the internally reversible process

> holds for the irreversible process

102
 Definition of Second Law of Thermodynamics

Now consider an isolated system composed of several subsystems exchanging

energy among themselves. Since the isolated system has no energy transfer across
its system boundary, the heat transfer across the system boundary is zero.

Applying the definition of entropy to the isolated

system

The total entropy change for the isolated system

is

103
This equation is the working definition of the second law of thermodynamics. The
second law, known as the principle of increase of entropy, is stated as

The total entropy change of an isolated system

during a process always increases or, in the limiting
case of a reversible process, remains constant. No
process is possible for which the total entropy
decreases.
Now consider a general system exchanging mass as well as energy with its
surroundings.

where = holds for the totally reversible process

> holds for the irreversible process

104
Since all natural processes are irreversible, the entropy is
increasing continually! This means systems are constantly in a
state of increase disorder or randomization until the systems
reaches a stable equilibrium, where it attains a state of
maximum disorder.

Entropy change is caused by heat transfer and irreversibility.

Heat transfer to a system increases the entropy, and heat
transfer from a system decreases it. The effect of irreversibility
is always to increase the entropy.

The increase in entropy principle can be summarized as

follows:

105
Some Remarks about Entropy

1. Processes can occur in a certain direction only, not in just any direction,
such that S gen≥0.

2. Entropy is a non-conserved property, and there is no such thing as the

conservation of entropy principle. The entropy of the universe is
continuously increasing.

3. The performance of engineering systems is degraded by the presence of

irreversibilities, and entropy generation is a measure of the magnitudes
of the irreversibilities present during that process.

106
 Temperature-Entropy Diagram (T-S Curve)

T Area under the

process curve is the
heat transfer.

1 Qnet

ds s

In the above figure, the heat transfer in an internally

reversible process is shown as the area under the
process curve plotted on the T-S diagram.

107
ENTROPY CHANGE FOR CLOSED
SYSTEM
 Entropy Change: Heating at Constant Volume

Let 1 kg of gas be heated at constant volume and let the change in

entropy and absolute temperature be from s1 to s2 and T1 to T2
respectively.
 Heating a Gas at Constant Pressure

Let 1 kg of gas be heated at constant pressure, so

that its absolute temperature changes from T1 to T2
and entropy s1 to s2.
Isothermal, Reversible Process

HOME WORK!!!!!!

111
 Adiabatic, Reversible (Isentropic) Process

For an adiabatic process, one in which there is no heat transfer, the entropy change
is

If the process is adiabatic and reversible, the equality holds and the entropy change
is

or on a per unit mass

basis

112
Third Law of Thermodynamics

The third law of thermodynamics states that the entropy of a pure crystalline
substance at absolute zero temperature is zero. This law provides an absolute
reference point for the determination of entropy. The entropy determined relative to
this point is called absolute entropy.

Entropy as a Property

Entropy is a property, and it can be expressed in terms of more familiar properties (P,
v,T) through the Tds relations. These relations come from the analysis of a
reversible closed system that does boundary work and has heat added. Writing the
first law for the closed system in differential form on a per unit mass basis
δQ int rev
δW int rev, out

System used to find expressions for ds

113
On a unit mass basis we obtain the first Tds equation, or Gibbs equation, as

Recall that the enthalpy is related to the internal energy by h = u + Pv. Using this
relation in the above equation, the second Tds equation is

These last two relations have many uses in thermodynamics and serve as the
starting point in developing entropy-change relations for processes. The successful
use of Tds relations depends on the availability of property relations. Such relations
do not exist in an easily used form for a general pure substance but are available for
incompressible substances (liquids, solids) and ideal gases. So, for the general pure
substance, such as water and the refrigerants, we must resort to property tables to
find values of entropy and entropy changes.

114
The enthalpy-entropy diagram for water is shown below.

Shown above are the temperature-entropy and enthalpy-entropy diagrams for water.
The h-s diagram, called the Mollier diagram, is a useful aid in solving steam power
plant problems where heat transfer and work may be expressed as enthalpy
changes for steady-flow constant pressure and isentropic processes, respectively.
115
 Summary of Second Law (Highlights)
Clausius statement :

“It is impossible for a self-acting machine working in a cyclic process, unaided by any
external agency, to convey heat from a body at a lower temperature to a body at a
higher temperature.”

Kelvin-Planck statement :
“It is impossible to construct an engine, which while operating in a cycle produces no
other effect except to extract heat from a single reservoir and do equivalent amount of
work”

Although above statements of second law of thermodynamic appear to be different,

they are really equivalent in the sense that violation of either statement implies violation
of other.

Perpetual motion machine of second kind (PMM2) is that imaginary machine

which would continuously absorb heat from a single thermal reservoir and convert
this heat completely into work. The efficiency of such a machine would be 100%.
Entropy’ is a function of a quantity of heat which shows the possibility of
conversion of that heat into work.

The third law of thermodynamics states that the entropy of a pure

crystalline substance at absolute zero temperature is zero.