Professor K.

Srinivasan
Department of Mechanical
Engineering
Indian Institute of Science
Bangalore
 Fundamental Concepts
and Definitions

THERMODYNAMICS:
¾ It is the science of the relations between heat,
Work and the properties of the systems.
¾ How to adopt these interactions to our benefit?
Thermodynamics enables us to answer this
question.
 Analogy

All currencies are not equal

Eg: US$ or A$ or UK£ etc. Have a better purchasing power
than Indian Rupee or Thai Baht or Bangladesh Taka
similarly,all forms of energy are not the same.
Human civilization has always endeavoured to obtain
¾ Shaft work
¾ Electrical energy
¾ Potential energy to make life easier
 Examples
If we like to
¾ Rise the temperature of water in kettle
¾ Burn some fuel in the combustion chamber of an aero
engine to propel an aircraft.
¾ Cool our room on a hot humid day.
¾ Heat up our room on a cold winter night.
¾ Have our beer cool.
What is the smallest amount of electricity/fuel we
can get away with?
 Examples (Contd…)

On the other hand we burn,

¾ Some coal/gas in a power plant to generate electricity.
¾ Petrol in a car engine.
What is the largest energy we can get out of these efforts?
Thermodynamics allows us to answer some of these
questions
 Definitions
¾ In our study of thermodynamics, we will choose a small part of
the universe to which we will apply the laws of thermodynamics.
We call this subset a SYSTEM.
¾ The thermodynamic system is analogous to the free body
diagram to which we apply the laws of mechanics, (i.e.
Newton’s Laws of Motion).
¾ The system is a macroscopically identifiable collection of matter
on which we focus our attention (eg: the water kettle or the
aircraft engine).
¾ The rest of the universe outside the system close enough
to the system to have some perceptible effect on the
system is called the surroundings.
¾ The surfaces which separates the system from the
surroundings are called the boundaries as shown in fig
below (eg: walls of the kettle, the housing of the engine).

System

Boundary Surroundings
 Types of System

¾ Closed system - in which no mass is permitted to cross the

system boundary i.e. we would always consider a system
of constant mass.We do permit heat and work to enter or
leave but not mass.
Boundary Heat/work
Out
system

Heat/work
in
No mass entry or exit
¾ Open system- in which we permit mass to cross the system
boundary in either direction (from the system to surroundings
or vice versa). In analysing open systems, we typically look at
a specified region of space, and observe what happens at the
boundaries of that region.

Most of the engineering devices are open system.

Boundary
Heat/work Mass
Out out
System

Heat/work
Mass in
In
¾ Isolated System- in which there is no interaction between
system and the surroundings. It is of fixed mass and
energy, and hence there is no mass and energy transfer
across the system boundary.

System

Surroundings
 Choice of the System and
Boundaries Are at Our
Convenience
¾ We must choose the system for each and every problem
we work on, so as to obtain best possible information on
how it behaves.
¾ In some cases the choice of the system will be obvious
and in some cases not so obvious.
¾ Important: you must be clear in defining what constitutes
your system and make that choice explicit to anyone else
who may be reviewing your work. (eg: In the exam
paper or to your supervisor in the work place later)
 Choice of the System and
Boundaries Are at
Our Convenience (contd…)
¾ The boundaries may be real physical surfaces or they may
be imaginary for the convenience of analysis.
eg: If the air in this room is the system,the floor,ceiling
and walls constitutes real boundaries.the plane at the open
doorway constitutes an imaginary boundary.
 Choice of the System and
Boundaries Are at Our
Convenience (contd…)
¾ The boundaries may be at rest or in motion.
eg: If we choose a system that has a certain defined
quantity of mass (such as gas contained in a piston
cylinder device) the boundaries must move in such
way that they always enclose that particular quantity
of mass if it changes shape or moves from one place
to another.
 Macroscopic and
Microscopic Approaches

Behavior of matter can be studied by these two

approaches.

¾ In macroscopic approach, certain quantity of

matter is considered,without a concern on the events
occurring at the molecular level. These effects can be
perceived by human senses or measured by
instruments.

¾ eg: pressure, temperature

 Microscopic Approach

¾ In microscopic approach, the effect of molecular

motion is Considered.

eg: At microscopic level the pressure of a gas is not

constant, the temperature of a gas is a function of the
velocity of molecules.

Most microscopic properties cannot be measured with

common instruments nor can be perceived by human
senses
 Property

¾It is some characteristic of the system to which some physically

meaningful numbers can be assigned without knowing the
history behind it.
¾These are macroscopic in nature.
¾Invariably the properties must enable us to identify the system.
¾eg: Anand weighs 72 kg and is 1.75 m tall. We are not
concerned how he got to that stage. We are not interested what
he ate!!.
 Examples (contd...)

We must choose the most appropriate set of properties.

¾ For example: Anand weighing 72 kg and being 1.75 m
tall may be a useful way of identification for police
purposes.
¾ If he has to work in a company you would say Anand
graduated from IIT, Chennai in 1985 in mechanical
engineering.
¾ Anand hails from Mangalore. He has a sister and his
father is a poet. He is singer. ---If you are looking at
him as a bridegroom!!
 Examples (contd…)

¾ All of them are properties of Anand. But you

pick and choose a set of his traits which describe
him best for a given situation.
¾ Similarly, among various properties by which a
definition of a thermodynamic system is possible, a
situation might warrant giving the smallest number
of properties which describe the system best.
 Categories of Properties

¾Extensive property:
whose value depends on the size or extent of the system
(upper case letters as the symbols).
eg: Volume, Mass (V,M).
If mass is increased, the value of extensive property also
increases.
¾Intensive property:
whose value is independent of the size or extent of the
system.
eg: pressure, temperature (p, T).
 Property (contd..)

Specific property:
¾ It is the value of an extensive property per unit mass of
system. (lower case letters as symbols) eg: specific volume,
density (v, ρ).
¾ It is a special case of an intensive property.
¾ Most widely referred properties in thermodynamics:
¾ Pressure; Volume; Temperature; Entropy; Enthalpy; Internal
energy
(Italicised ones to be defined later)
¾State:
It is the condition of a system as defined by the values of all its
properties.
It gives a complete description of the system.
Any operation in which one or more properties of a system
change is called a change of state.

¾Phase:
It is a quantity of mass that is homogeneous throughout in
chemical composition and physical structure.
e.g. solid, liquid, vapour, gas.
Phase consisting of more than one phase is known as
heterogenous system .
 Path And Process

The succession of states passed through during a change of

state is called the path of the system. A system is said to go
through a process if it goes through a series of changes in
state. Consequently:
¾A system may undergo changes in some or all of its
properties.
¾A process can be construed to be the locus of changes of
state
Processes in thermodynamics are like streets in a city
eg: we have north to south; east to west; roundabouts;
crescents
 Types of Processes

¾As a matter of rule we allow •Isothermal (T)

one of the properties to remain a
•Isobaric (p)
constant during a process.
¾Construe as many processes as •Isochoric (v)
we can (with a different property
kept constant during each of •Isentropic (s)
them) •Isenthalpic (h)
¾Complete the cycle by
regaining the initial state •Isosteric (concentration)
•Adiabatic (no heat addition or
removal
 Quasi-static Processes
The processes can be restrained or unrestrained
We need restrained processes in practice.

A quasi-static process is one in which

¾ The deviation from thermodynamic equilibrium is
infinitesimal.
¾ All states of the system passes through are equilibrium
states.

Gas
 Quasi-static Processes
(contd…)
¾ If we remove the weights slowly one by one the
pressure of the gas will displace the piston gradually. It
is quasistatic.
¾ On the other hand if we remove all the weights at
once the piston will be kicked up by the gas
pressure.(This is unrestrained expansion) but we don’t
consider that the work is done - because it is not in a
sustained manner
¾ In both cases the systems have undergone a change
of state.
¾Another eg: if a person climbs down a ladder from
roof to ground, it is a quasistatic process. On the other
hand if he jumps then it is not a quasistatic process.
 Equilibrium State

¾A system is said to be in an equilibrium state if its properties

will not change without some perceivable effect in the
surroundings.
¾Equilibrium generally requires all properties to be uniform
throughout the system.
¾There are mechanical, thermal, phase, and chemical equilibria
 Equilibrium State
(contd)
Nature has a preferred way of directing changes.
eg:
¾water flows from a higher to a lower level
¾ Electricity flows from a higher potential to a lower one
¾ Heat flows from a body at higher temperature to the one at
a lower temperature
¾ Momentum transfer occurs from a point of higher
pressure to a lower one.
¾ Mass transfer occurs from higher concentration to a lower
one
 Types of Equilibrium

Between the system and surroundings, if there is no difference in

ƒPressure Mechanical equilibrium

ƒPotential Electrical equilibrium
ƒConcentration of species Species equilibrium
ƒTemperature Thermal equilibrium

No interactions between them occur.

They are said to be in equilibrium.

Thermodynamic equilibrium implies all those together.

A system in thermodynamic equilibrium does not deliver anything.
 Definition Of Temperature and
Zeroth Law Of
Thermodynamics

¾Temperature is a property of a system which determines the

degree of hotness.
¾Obviously, it is a relative term.
eg: A hot cup of coffee is at a higher temperature than a block of
ice. On the other hand, ice is hotter than liquid hydrogen.

Thermodynamic temperature scale is under evolution. What we

have now in empirical scale.
 Zeroth Law Of Thermodynamics
(Contd…)
¾Two systems are said to be equal in temperature,
when there is no change in their respective observable
properties when they are brought together. In other
words, “when two systems are at the same temperature
they are in thermal equilibrium” (They will not
exchange heat).

Note:They need not be in thermodynamic equilibrium.

 Zeroth Law

¾If two systems (say A and B) are in thermal

equilibrium with a third system (say C) separately (that
is A and C are in thermal equilibrium; B and C are in
thermal equilibrium) then they are in thermal
equilibrium themselves (that is A and B will be in
thermal equilibrium

TA TB

TC
 Explanation of Zeroth Law
¾ Let us say TA,TB and TC are the temperatures of A,B and C
respectively.
¾ A and c are in thermal equilibrium. Ta= tc
¾ B and C are in thermal equilibrium. Tb= tc

Consequence of of ‘0’th law

¾ A and B will also be in thermal
equilibrium TA= TB
¾ Looks very logical
¾ All temperature measurements are based on this LAW.
Module 2

Work and Heat

 We Concentrate On Two
Categories Of Heat And Work

¾ Thermodynamic definition of work:

Positive work is done by a system when the sole
effect external to the system could be reduced to the
rise of a weight.

¾ Thermodynamic definition of heat:

It is the energy in transition between the system and
the surroundings by virtue of the difference in
temperature.
 Traits of Engineers
¾ All our efforts are oriented towards how ¾We require a
to convert heat to work or vice versa: combination of
processes.
Heat to work Thermal power plant ¾Sustainability is
ensured from a cycle
Work to heat Refrigeration ¾A system is said to
have gone through a
¾ Next, we have to do it in a sustained cycle if the initial state
manner (we cant use fly by night has been regained after
techniques!!) a series of processes
 Sign Conventions

¾ Work done BY the system is +ve

¾ Obviously work done ON the system is –ve
¾ Heat given TO the system is +ve
¾ Obviously Heat rejected by the system is -ve

W W
-VE +VE

Q
Q -VE
+VE
 Types of Work Interaction

Types of work interaction

¾ Expansion and compression work

(displacement work)
¾ Work of a reversible chemical cell
¾ Work in stretching of a liquid surface
¾ Work done on elastic solids
¾ Work of polarization and magnetization
 Notes on Heat

¾ All temperature changes need not be due to heat alone

eg: Friction
¾ All heat interaction need not result in changes in temperature
eg: condensation or evaporation
 Various Types of Work

¾ Displacement work (pdV work)

¾ Force exerted, F= p. A
¾ Work done
dW = F.dL = p. A dL = p.dV
¾ If the piston moves through a finite distance say 1-2,Then
work done has to be evaluated by integrating δW=∫pdV
 Work (Contd…)

p
Cross sectional area=A

dl

p p
1 2
1
v
 Discussion on Work Calculation
The system (shown by the dotted line) has gone
through a change of state from 1 to 2.We need to 1 2
know how the pressure and volume change. p

Possibilities:
¾ Pressure might have remained constant v
or
¾ It might have undergone a
2
change as per a relation p (V)
or p
¾ The volume might have remained constant
In general the area under the process on p-V 1
plane gives the work
v
 Other Possible Process
¾ pv=constant (it will be a rectangular hyperbola)
¾ In general pvn= constant
IMPORTANT: always show the states by numbers/alphabet and
indicate the direction.

1 2 Gas
V = constant

p 2
Pv=constant
Gas 2

v
 Various compressions

2 Pv=constant 2 Gas
Gas p

V = constant
2 1

P=constant

¾n= 0 Constant pressure (V2>V1 - expansion)

¾n=1 pv=constant (p2<p1 ;V2>V1 - expansion)
¾n= ∞ Constant volume (p2< p1 - cooling)
 Others Forms Of Work
™ Stretching of a wire:
Let a wire be stretched by dL due to an application of a force F
Work is done on the system. Therefore dW=-FdL
™ Electrical Energy:
Flowing in or out is always deemed to be work
dW= -EdC= -EIdt
™ Work due to stretching of a liquid film due to surface tension:
Let us say a soap film is stretched through an area dA
dW= -σdA
where σ is the surface tension.
 Module 3

First law of thermodynamics

 First Law of Thermodynamics
Statement:
¾When a closed system executes a
1
complete cycle the sum of heat B

interactions is equal to the sum of work Y A 2

interactions.
Mathematically
X
¾ ΣQ=Σ W
The summations being over the entire
cycle
 First Law (Contd…)

Alternate statement:
When a closed system undergoes a cycle the cyclic
integral of heat is equal to the cyclic integral of work.

Mathematically δQ = δW
In other words for a two process cycle
QA1-2+QB2-1=WA1-2+WB 2-1
 First Law (Contd…)

Which can be written as

 First Law (contd…)

¾ Since A and B are arbitrarily chosen, the conclusion is, as far

as a process is concerned (A or B) the difference δQ−δW
remains a constant as long as the initial and the final states are
the same. The difference depends only on the end points of the
process. Note that Q and W themselves depend on the path
followed. But their difference does not.
not
 First Law (contd…)

¾ This implies that the difference between the heat and

work interactions during a process is a property of the
system.
¾ This property is called the energy of the system. It is
designated as E and is equal to some of all the energies
at a given state.
 First Law(contd…)
We enunciate the FIRST LAW for a process as
δQ-δW=dE
E consists of E=U+KE+PE
U -internal energy
KE - the kinetic energy
PE - the potential energy
For the whole process A Q-W=E2-E1
Similarly for the process B Q-W=E1-E2
 First Law(contd…)

¾ An isolated system which does not interact with the

surroundings Q=0 and W=0. Therefore, E remains constant
for such a system.
¾ Let us reconsider the cycle 1-2 along path A and 2-1 along
path B as shown in fig.
¾ Work done during the path A = Area under 1-A-2-3-4
¾ Work done during the path B = Area under 1-B-2-3-4
¾ Since these two areas are not equal, the net work interaction
is that shown by the shaded area.
 First Law (Contd…)

¾The net area is 1A2B1.

¾Therefore some work is derived
by the cycle.
¾First law compels that this is
possible only when there is also
heat interaction between the
system and the surroundings.
¾In other words, if you have to
get work out, you must give heat
in.
 First Law (contd…)
¾ Thus, the first law can be construed to be a statement of
conservation of energy - in a broad sense.
¾ In the example shown the area under curve A < that under B
¾ The cycle shown has negative work output or it will receive
work from the surroundings. Obviously, the net heat
interaction is also negative. This implies that this cycle will heat
the environment. (as per the sign convention).
 First Law(contd…)

¾ For a process we can have Q=0 or W=0

¾ We can extract work without supplying
heat(during a process)
process but sacrificing the energy
of the system.
¾We can add heat to the system without doing
work(in process)
process which will go to increasing the
energy of the system.
¾Energy of a system is an extensive property
 Engineering Implications

¾ When we need to derive some work, we must expend

thermal/internal energy.
¾ Whenever we expend heat energy, we expect to derive
work interaction (or else the heat supplied is wasted or goes
to to change the energy of the system).
¾ If you spend money, either you must have earned it or you
must take it out of your bank balance!!
¾ !!There is nothing called a free lunch!!
 Engineering implications
(contd…)

¾The first law introduces a new property of the system called

the energy of the system.
¾It is different from the heat energy as viewed from physics
point of view.
¾We have “energy in transition between the system and the
surroundings” which is not a property and “energy of the
system” which is a property.
 Engineering Applications
(contd…)

¾ It appears that heat (Q) is not a property of the system but

the energy (E) is.
™ How do we distinguish what is a property of the system
and what is not?
¾ The change in the value of a “property” during a process
depends only on the end states and not on the path taken by a
process.
¾ In a cycle the net in change in “every property” is zero.
 Engineering implications
(contd…)
¾If the magnitude of an entity related to the system changes during
a process and if this depends only on the end states then the entity is
a property of the system. (Statement 3 is corollary of statement 1)

HEAT and WORK are not properties because they depend on the
path and end states.

HEAT and WORK are not properties because their net change
in a cycle is not zero.
 Analogy

¾ Balance in your bank account is a property. The

deposits and withdrawals are not.

¾ A given balance can be obtained by a series of

deposits and withdrawals or a single large credit or
debit!
 Analogy (contd…)

Balance is deposits minus withdrawals Energy is heat minus work

™ If there are no deposits and if you If the system has enough

have enough balance, you can energy you can extract work
withdraw. But the balance will without adding heat.but the
Will diminish energy diminish
™ If you don’t withdraw but keep If you keep adding heat but
depositing your balance will go up. don’t extract any work, the
system energy will go up.
 Analogy(Contd)

¾ Between 2 successive 1 Januarys you had made several

deposits and several withdrawals but had the same balance,
then you have performed a cycle. - it means that they have
been equalled by prudent budgeting!!
™ Energy - balance; Deposits - heat interactions;
Withdrawals - work interactions.
™ Mathematically properties are called point functions or
state functions
™ Heat and work are called path functions.
 Analogy (contd…)

To sum up:
I law for a cycle: δQ = δW
I law for a process is Q-W = ΔE
For an isolated system Q=0 and W=0.
Therefore ΔE=0
 Analogy (contd…)
1

Conducting plane; Insulating rough block in vacuum

System Q W ΔE
Block 0 + -
Plane 0 - +
Block+plane 0 0 0
 Analogy (Contd…)

¾ The first law introduces the concept of energy in the

thermodynamic sense.
¾Does this property give a better description of the system
than pressure, temperature, volume, density?
The answer is yes, in the broad sense.
¾ It is U that is often used rather than E. (Why? - KE and PE
can change from system to system).
¾They have the units of kJ
 First law (Contd…)

¾Extensive properties are converted to specific extensive properties

(which will be intensive properties) ., i.E.., U and E with the units
kJ/kg.

¾A system containing a pure substance in the standard gravitational

field and not in motion by itself, if electrical, magnetic fields are
absent (most of these are satisfied in a majority of situations) ‘u’ will
be ‘e’.
 First law (Contd…)

¾The I law now becomes Q - W = ΔU δQ-δW=δU

¾Per unit mass of the contents of the system (Q - W)/m = Δu
¾If only displacement work is present δQ-pdV=dU
¾Per unit mass basis δq-pdv=du
¾Which can be rewritten as δq = du+pdv
 Flow Process
Steady flow energy equation:

¾ Virtually all the practical systems involve flow of mass across

the boundary separating the system and the surroundings. Whether
it be a steam turbine or a gas turbine or a compressor or an
automobile engine there exists flow of gases/gas mixtures into and
out of the system.

¾ So we must know how the first Law of thermodynamics can be

applied to an open system.
 SFEE (contd…)

¾The fluid entering the system will have its own internal,
kinetic and potential energies.

¾Let u1 be the specific internal energy of the fluid entering

¾ C1be the velocity of the fluid while entering

¾ Z1 be the potential energy of the fluid while entering

¾Similarly let u2 ,C2 and Z2be respective entities while leaving.

 SFEE(Contd…)

Exit Total energy of the slug at entry

2 C2

U2 =Int. E+Kin. E+ Pot. E

=δmu1+δmC12/2+δmgZ1
Entry
=δm(u1+C12/2+gZ1)
c 1
1

u1 Z2
A small slug of mass δm
Z1 W

Datum with reference to which all potential energies are measured

Focus attention on slug at entry-1

 SFEE(Contd…)

¾Initially the system consists of just the large rectangle. Let its
energy (including IE+KE+PE) be E’

¾The slug is bringing in total energy of δm (u1+ C12/2 + gz1)

¾The energy of the system when the slug has just entered will be

E’+ δm (u1+c12/2+gz1).
 SFEE(Contd…)

¾ To push this slug in the surroundings must do some work.

If p1 is the pressure at 1,

v1 is the specific volume at 1,

This work must be -p1dm v1

(-ve sign coming in because it is work done on the system)

 SFEE (contd…)

2 C2
Exit Total energy of the slug at exit
U2
=Int. E+Kin. E+ Pot. E
A small slug of mass δm
=δmu2+δmC22/2+δmgZ2
Entry 1
=δm(u2+C22/2+gZ2)
c 1 Z2
u1

Z1

Datum with reference to which all potential energies are measured

Focus Attention on Slug at Exit-2

 SFEE (contd…)

¾ The energy of the system should have been

= E’+ δm (u2+C22/2+gZ2)

¾ So that even after the slug has left, the original E’

will exist.

¾ We assume that δm is the same. This is because

what goes in must come out.
 SFEE (contd…)

¾ To push the slug out, now the system must do

some work.
If p2 is the pressure at 2,
v2 is the specific volume at 2,
This work must be + p2δm v2
(positive sign coming in because it is work
done by the system)
 SFEE (contd…)

¾ The net work interaction for the system is

¾ W+p2δm v2-p1δm v1=W+δm(p2 v2-p1 v1 )

¾ Heat interaction Q remains unaffected.

¾ Now let us write the First law of

thermodynamics for the steady flow process.

 SFEE (contd…)
Now let us write the First law of thermodynamics for the steady
flow process.
Heat interaction =Q
Work interaction = W+δm(p2 v2 - p1 v1)
Internal energy at 2 (E2) = [E’+ δm (u2 + C22/2 + gZ2)]
Internal energy at 1 (E1) = [E’+ δm (u1+ C12/2 + gZ1)]
Change in internal energy = [E’+ δm (u2 + C22/2 + gZ2)] -
(E2-E1) [E’+ δm (u1+ C12/2 + gZ1)]
= δm[(u2+C22/2+gZ2)-
(u1+C12/2+gZ1)]
 SFEE (contd…)
¾ Q-[W+dm(p2 v2-p1 v1)]= dm [(u2+C22/2+gZ2)- (u1+C12/2+gZ1)]
¾ Q-W= dm[(u2 + C22/2 + gZ2 + p2 v2)- (u1+ C12/2 + gZ1 +p1 v1)]
¾ Recognise that h=u+pv from which u2+ p2 v2=h2 and similarly
u1+ p1 v1=h1
¾ Q-W= dm[(h2 + C22/2 + gZ2) - (h1 + C12/2 + gZ1)]
Per unit mass basis
¾ q-w= [(h2+C22/2+gZ2) - (h1+C12/2+gZ1)] or
= [(h2 - h1)+(C22/2 - C12/2) +g(Z2-Z1)]
¾SFEE
 SFEE (contd…)
¾The system can have any number of entries and exits through
which flows occur and we can sum them all as follows.

¾If 1,3,5 … are entry points and 2,4,6… are exit points.
Q-W= [ m2(h2+C22/2+gZ2)+ m4(h4+C42/2+gZ4)+ m6(h6+C62/2+gZ6)

+…….]

- [ m1(h1+C12/2+gZ1) + m3(h3+C32/2+gZ3)

+ m5(h5+C52/2+gZ5)+…….]

It is required that m1+m3+m5….=m2+m4+m6+…..

which is the conservation of mass (what goes in must come out)

 Some Notes On SFEE

¾ If the kinetic energies at entry and exit are small compared to

the enthalpies and there is no difference in the levels of entry and
exit
¾ q-w=(h2 - h1)=Δh: per unit mass basis or Q-W= mΔh (1)
¾ For a flow process - open system- it is the difference in the
enthalpies whereas for a non-flow processes - closed system - it is
the difference in the internal energies.
 SFEE (contd…)
¾ pv is called the “flow work”. This is not thermodynamic
work and can’t rise any weight, but necessary to establish the
flow.
¾ For an adiabatic process q = 0
¾-w = Δh (2)
¾ ie., any work interaction is only due to changes in enthalpy.
¾ Note that for a closed system it would have been -w = Δu
 SFEE (Contd…)
Consider a throttling process (also referred to as wire drawing
process)
1 2

There is no work done (rising a weight) W=0

If there is no heat transfer Q =0
Conservation of mass requires that C1=C2
Since 1 and 2 are at the same level Z1=Z2
From SFEE it follows that h1=h2
Conclusion: Throttling is a constant enthalpy process
(isenthalpic process)
 Heat Exchanger

Insulated on the outer surface

Hot fluid in g1
W =0

Cold fluid in ( f1) Cold fluid out (f2)

Hot fluid out

(g2)

Hot fluid Cold fluid

Qg=mg(hg2- hg1) Qf=mf(hf2- hf1)
 Heat Exchanger
(contd…)

™ If velocities at inlet and outlet are the same

¾ All the heat lost by hot fluid is received by the cold fluid.
But, for the hot fluid is -ve (leaving the system)
¾ Therefore -Qg= Qf
or mg (hg1-hg2) = mf (hf2- hf1)
¾ You can derive this applying SFEE to the combined
system as well (note that for the combined hot and cold
system Q=0;W=0
¾ 0 - 0 = mf hf2 - mf hf1 +mg hg2- mg hg1
 Adiabatic Nozzle
Normally used in turbine based
power production.
It is a system
where the kinetic energy
is not negligible compared to
enthalpy.
Q=0
W=0
SFEE becomes
0-0=h2-h1+(c22/2-c12/2)

= h1-h2
 Adiabatic Nozzle
(Contd…)
¾ If h1 is sufficiently high we can convert it into kinetic energy
by passing it through a nozzle. This is what is done to steam at
high pressure and temperature emerging out of a boiler or the
products of combustion in a combustion chamber (which will be
at a high temperature and pressure) of a gas turbine plant.
Usually, C1 will be small - but no assumptions can be made.
 Analysis of Air Conditioning
Process

1.Heating of Moist Air

Application of SFEE
(system excluding the
heating element)
q-0= ma(h2-h1)
Air will leave at a higher
enthalpy than at inlet.
 Air Conditioning Process
(Contd…)
2. Cooling of moist air:
Two possibilities:
a) Sensible cooling (the final state is not below the dew point)
-q-0= ma(h2-h1) or q= ma(h1-h2)
Air will leave at a lower enthalpy than at inlet.
 Moist Air (contd…)
b.Moisture separates out

•SFEE yields
-q-0= ma(h2-h1) + mw hw
•Moisture conservation
Humidity ratio of entering air at 1=W1
Moisture content = maW1
Humidity ratio of leaving air at 2 =W2
Moisture content = maW2
Moisture removed = mw
•What enters must go out !
 Moisture Air
(Contd…)
maW1 = maW2 + mw
mw = ma ( W1- W2)
Substituting into SFEE
q = ma[(h1-h2) - ( W1- W2) hw]
 3.Adiabatic Mixture of Two
Streams of Air at Separate
States
SFEE
¾ 0-0=ma3h3-ma1h1-ma2h2
¾Dry air conservation
¾ ma3 = ma1 + ma2
¾Moisture conservation
¾ ma31 w3= ma1 w1+ ma2 w2
¾Eliminate ma3
¾(ma1+ma2)h3=ma1h1+ ma2h2
¾ma1 (h3- h1) =ma2 (h2- h3)
Adiabatic mixture
(contd…)
 Adiabatic mixture (contd…)

Moral: 1. The outlet state lies along the straight

line joining the states of entry streams

Moral: 2. The mixture state point divides the

line into two segments in the ratio of dry air
flow rates of the incoming streams
 4.Spraying of Water Into a Stream
of Air

SFEE
¾0-0= mah2-mah1-mwhw
™Moisture conservation
¾ma w2= ma w1+ mw
¾or mw = ma (w2- w1)
¾Substitute in SFEE
¾ma(h2-h1) = ma (w2- w1) hw
¾or hw = (h2-h1) / (w2- w1)
 Spraying of Water (contd…)

Moral: The final state of air leaving lies along a

straight line through the initial state Whose
direction is fixed by the enthalpy of water
injected
5. Injecting steam into a stream of
air
¾ The mathematical treatment exactly the same as
though water is injected

¾ The value of hw will be the enthalpy of steam

¾ There is problem in cases 4 and 5!

¾We don’t know where exactly the point 2 lies

¾ All that we know is the direction in which 2 lies

with reference to 1.
 Injecting Steam (contd…)

¾ On a Cartesian co-ordinate system that

information would have
been adequate.
¾ !!But, in the psychrometric chart h and w lines
are not right angles!!
¾HOW TO CONSTRUCT THE LINE 1-2
FOR CASES 4 AND 5 ??
 Injecting Stream(contd…)

From the centre of the circle draw a line connecting the value of
which is equal to Δh/Δw. (Note that hw units are kJ/g of water or
steam). Draw a line parallel to it through 1.
 Module 4

Pure substances and

Steam tables and ideal
and real gases
 Properties Of Gases
¾ In thermodynamics we distinguish between
a) perfect gases
b)Ideal gases
c) real gases
¾ The equation pV/T= constant was derived assuming that
Molecules of a gas are point masses
¾ There are no attractive nor repulsive forces between the
molecules
¾ Perfect gas is one which obeys the above equation.
 Perfect Gas(contd…)
¾ Various forms of writing perfect gas equation of state

¾ pV=mRuT/M (p in Pa; V in m3; m n kg :T in K; M kg/kmol)

¾ pv= RT

¾ p=rRT

¾ pV=n RuT

¾ ρ= density (kg/ m3) n= number of moles

¾ Ru = Universal Gas Constant = 8314 J/kmol K

 Perfect Gas
(Contd…)

¾ R = Characteristic gas constant = Ru/M

J/kg K
¾ NA=Avogadro's constant = 6.022 x 1026 k
mol-1
¾ kB=Boltazmann constant = 1.380 x 10-23 J/K
¾ Ru = NA kB
 Deductions

For a perfect gas a constant pv process is also a

constant temperature process; ie., it is an
isothermal process.

Eg 1: Calculate the density of nitrogen at

standard atmospheric condition.

p=1.013x105Pa, T=288.15K; R=8314/28 J/kg K

ρ= p/RT= 1.013x105/ [288.15x( 8314/28)/]

=1.184 kg/ m3
 Perfect Gas (contd…)

Eg 2: What is the volume occupied by 1 mole of nitrogen at

normal atmospheric condition?
1 mole of nitrogen has m=0.028 kg. p= 1.013x105 Pa, T=273.15
K, R=8314/28 J/kg K
V=mRT/p = 0.028 x (8314/28) 273.15/ 1.013x105 =0.0224183
m3
Alternately V= nrut/p=1x 8314x 273.15/ 1.013x105 = 0.0224183
m3
This is the familiar rule that a mole of a gas at NTP will occupy
about 22.4 litres.
Note: NTP refers to 273.15 K and STP to 288.15 k;P=
1.013x105 pa
 Perfect Gas (contd…)

When can a gas be treated as a perfect gas?

A) At low pressures and temperatures far from critical
point
B) At low densities

¾A perfect gas has constant specific heats.

¾An ideal gas is one which obeys the above equation, but
whose specific heats are functions of temperature alone.
 Real Gas
A real gas obviously does not obey the perfect gas equation
because, the molecules have a finite size (however small it may
be) and they do exert forces among each other. One of the
earliest equations derived to describe the real gases is the van
der Waal’s equation

(P+a/v2)(v-b)=RT;

Constant a takes care of attractive forces; B the finite volume of

the molecule.
 Real Gas (contd…)

¾There are numerous equations of state.

¾The world standard to day is the Helmholtz free

energy based equation of state.

¾For a real gas pv ≠ RT;

¾ The quantity pv/RT = z and is called the

“COMPRESSIBILITY”.

¾For a perfect gas always z=1.

 Definitions

¾Specific heat at constant volume cv= (∂u/∂T)v

¾enthalpy h= u+pv
¾Specific heat at constant pressure cp= (∂h/∂T)p
¾u, h, cv and cp are all properties.
¾ Implies partial differentiation.
¾The subscript denotes whether v or p is kept constant.
 Definitions (contd…)
¾For a perfect gas since are constants and do not depend on any
other property, we can write cv= du/dT and cp= dh/dT

¾Since h=u+pv dh/dT=du/dT+d(pv)/dT …….1

¾But pv=RT for a perfect gas.Therefore, d(pv)/dT= d(RT)/dT= R

¾Eq. 1 can be rewritten as cp= cv + R

¾R is a positive quantity. Therefore, for any perfect gas cp > cv

¾Note: Specific heats and R have the same units J/kg K

 Alternate Definitions
From Physics

P=constant V=constant
s.T
h or u

T
hv

s.
uv

T Heat Heat
 Alternate Definitions
From Physics (contd…)
¾cp= amount of heat to be added to raise the
temperature of unit mass of a substance when the
pressure is kept constant

¾cv= amount of heat to be added to raise the

temperature of unit mass of a substance when the
volume is kept constant

¾Physical interpretation of why cp > cv ?

 Alternate Definitions
From Physics(contd…)

¾ When heat is added at const. p, a part of it goes

to raising the piston (and weights) thus doing
some work. Therefore, heat to be added to rise
system T by 1K must account for this.
Consequently, more heat must be added than in
v=const. case (where the piston does not move).
 Alternate Definitions
From Physics (contd…)

¾When heat is added at const v

the whole amount subscribes to
increase in the internal energy.
¾The ratio cp/cv is designated
as γ.
¾cp and cv increase with
temperature
 Alternate Definitions
From Physics (contd…)

Volume Fractions of Components in Sea Level Dry Air

and their ratio of specific heats
γ γ
N2 0.78084 1.40 O2 0.209476 1.40
Ar 9.34x10-3 1.67 CO2 3.14x10-4 1.30
Ne 1.818x10-5 1.67 He 5.24x10-6 1.67
Kr 1.14x10-6 1.67 Xe 8.7x10-8 1.67
CH4 2x10-6 1.32 H2 5x10-7 1.41
 Implications of an Adiabatic
Process for a Perfect Gas in a
Closed System
¾The First Law for a closed system going through an
adiabatic process is
¾-w=du or -pdv=cvdT for a perfect gas
¾From the relation cp-cv=R and γ=cp/cv
¾ cv=R/(γ-1) cp=R γ /(γ-1)
¾Therefore -pdv=RdT /(γ-1) (A)
¾From the perfect gas relation pv=RT;
 Implications (Contd…)

¾Since During an adiabatic process p,v and T can change

simultaneously let dp,dv and dT be the incremental changes.

¾Now the perfect gas relation will be

(p+dp)(v+dv) = R(T+dT)
¾ Which on expansion become pv+vdp+pdv+dp dv=RT+RdT
 Implications (Contd…)

¾Using the condition pv=RT and the fact that product of

increments dp dv can be ignored in relation to the other quantities
¾we get vdp+pdv=RdT
¾Substitute for RdT in eq. (A) -pdv= [vdp+pdv] /(γ-1)
¾Rearrange terms -pdv {1+1 /(γ-1)}=vdp/(γ−1)
¾or - γ pdv=vdp or - γ dv/v=dp/p
 Implications
(Contd…)

¾We will integrate it to obtain

¾const- γ ln (v) = ln (p)
¾const= ln (p) + γln (v) = ln (p)+ ln (vγ) = ln(pvγ)
¾or pvγ = another constant (B)
 Implications (Contd…)

Note: This is an idealised treatment. A rigorous treatment

needs the Second Law of Thermodynamics. Eq (B) holds
good when the process is also reversible. The concept of
reversibility will be introduced later.

The work done during an adiabatic process between states

1-2 will be

W1-2=(p1V1- p2V2) /(g-1)

 Implications (Contd…)

Recapitulate: pvγ = constant

1. Is not an equation of state, but a description of

the path of a specific process - adiabatic and
reversible

2. Holds only for a perfect gas

 Pure Substance

¾ Pure Substance is one with uniform and invariant

chemical composition.

¾ Eg: Elements and chemical compounds are pure

substances. (water, stainless steel)

¾ Mixtures are not pure substances. (eg: Humid

air)
 Pure Substance
(contd…)

¾ Exception!! Air is treated as a pure substance though it

is a mixture of gases.
¾ In a majority of cases a minimum of two properties are
required to define the state of a system. The best choice
is an extensive property and an intensive property
 Properties Of Substance

¾ Gibbs Phase Rule determines what is expected to define

the state of a system
¾ F=C+2-P
¾ F= Number of degrees of freedom (i.e.., no. of properties
required)
¾ C= Number of components P= Number of phases
¾ E.g.: Nitrogen gas C=1; P=1. Therefore, F=2
 Properties of
substance (Contd…)
¾ To determine the state of the nitrogen gas in a cylinder two
properties are adequate.
¾ A closed vessel containing water and steam in equilibrium:
P=2, C=1
¾ Therefore, F=1. If any one property is specified it is sufficient.
¾ A vessel containing water, ice and steam in equilibrium
¾ P=3, C=1 therefore F=0. The triple point is uniquely defined.
 Properties of Liquids

The most common liquid is water. It has peculiar

properties compared to other liquids.

¾ Solid phase is less dense than the liquid phase (ice

floats on water)

¾ Water expands on cooling ( a fully closed vessel

filled with water will burst if it is cooled below the
freezing point).

¾ The largest density of water near atmospheric

pressure is at 4°c.
 Properties of Liquids
(contd…)
¾The zone between the saturated liquid and the saturated vapour
region is called the two phase region - where the liquid and vapour
can co-exist in equilibrium.

¾Dryness fraction: It is the mass fraction of vapour in the mixture.

¾Normally designated by ‘x’.

¾ On the saturated liquid line x=0

¾ On the saturated vapour line x=1

¾ x can have a value only between 0 and 1

 Properties of Liquids
(contd…)
¾Data tables will list properties at the two ends of saturation.
¾To calculate properties in the two-phase region:
¾p,T will be the same as for saturated liquid or saturated
vapour
v = x vg+ (1-x) vf
h = x hg+ (1-x) hf
u = x ug+ (1-x) uf
 Properties of Liquids
(contd…)
¾ One of the important properties is the change in
enthalpy of phase transition hfg also called the latent
heat of vaporisation or latent heat of boiling. It is
equal to hg-hf.

¾ Similarly ufg-internal energy change due to

evaporation and vfg- volume change due to
evaporation can be defined (but used seldom).
 Properties of Liquids
(contd…)

¾The saturation phase depicts some very interesting

properties:
¾The following saturation properties depict a maximum:
1. T ρf 2. T (ρf-ρg) 3. T hfg 4. Tc(pc-p)
5. p(Tc-T) 6. p(vg-vf) 7. T (ρc2- ρfρg) 8. hg
¾The equation relating the pressure and temperature
along the saturation is called the vapour pressure curve.
¾Saturated liquid phase can exist only between the triple
point and the critical point.
 Characteristics of the critical
point
1. It is the highest temperature at which the liquid and
vapour phases can coexist.
2. At the critical point hfg ,ufg and vfg are zero.
3. Liquid vapour meniscus will disappear.
4. Specific heat at constant pressure is infinite.
¾A majority of engineering applications (eg: steam based
power generation; Refrigeration, gas liquefaction) involve
thermodynamic processes close to saturation.
 Characteristics of the
critical point (contd…)
¾The simplest form of vapour pressure curve is

¾ln p= A+B/T valid only near the triple point.(Called

Antoine’s equation)

¾The general form of empirical vapour pressure curve is

¾ln p=ln pc+ [A1(1-T/Tc) + A2(1-T/Tc)1.5+ A3(1-T/Tc)2

+……]/(T/Tc) (Called the Wagner’s equation)

¾Definitions:
Definitions Reduced pressure pr =p/pc;

¾ Reduced temperature Tr =T/Tc

 Characteristics of the
critical point (contd…)

¾For saturated phase often it enthalpy is an important property.

¾Enthalpy-pressure charts are used for refrigeration cycle
analysis.
¾Enthalpy-entropy charts for water are used for steam cycle
analysis.
¾Note: Unlike pressure, volume and temperature which have
specified numbers associated with it, in the case of internal
energy, enthalpy (and entropy) only changes are required.
Consequently, a base (or datum) is defined - as you have seen in
the case of water.
 Characteristics of the
critical point (contd…)
¾For example for NIST steam tables u=0 for water at triple
point. (You can assign any number you like instead of 0).
[Don’t be surprised if two two different sets of steam tables
give different values for internal energy and enthalpy].
¾Since, p and v for water at triple point are known you can
calculate h for water at triple point (it will not be zero).
¾If you like you can also specify h=0 or 200 or 1000 kJ/kg
at the triple point and hence calculate u.
 Pressure-volume-temperature surface
for a substance that contracts on freezing
Note that there is a discontinuity at the phase boundaries
(points a,b,c,d etc.)
International Association for the Properties of
Water and Steam (IAPWS) has provided two formulations
to calculate the thermodynamic properties of ordinary
water substance,
i) “The IAPWS Formulation 1995 for the Thermodynamic
Properties of Ordinary Water Substance for General and
Scientific Use” (IAPWS-95) and
ii) “The IAPWS Industrial Formulation 1997 for the
Thermodynamic Properties of Water and
Steam” (IAPWS-IF97).
 Module 5

Basics of energy conversation

cycles
 Heat Engines and Efficiencies

¾ The objective is to build devices which receive

heat and produce work (like an aircraft engine or a
car engine) or receive work and produce heat (like
an air conditioner) in a sustained manner.
manner

¾ All operations need to be cyclic. The cycle

comprises of a set of processes during which one of
the properties is kept constant (V,p,T etc.)
 Heat Engines (contd…)

¾A minimum of 3 such processes are required to

construct a cycle.

¾All processes need not have work interactions

(eg: isochoric)

¾All processes need not involve heat interactions

either (eg: adiabatic process).
 Heat Engines (Contd…)

¾A cycle will consist of processes: involving some

positive work interactions and some negative.

¾If sum of +ve interactions is > -ve interactions the

cycle will produce work

¾If it is the other way, it will need work to operate.

¾On the same lines some processes may have +ve

and some -ve heat interactions.
 Heat Engines (Contd…)

¾Commonsense tells us that to return to the same point

after going round we need at one path of opposite direction.
¾I law does not forbid all heat interactions being +ve nor
all work interactions being -ve.
¾ But, we know that you can’t construct a cycle with all
+ve or
¾ All -ve Q’s nor with all +ve or all -ve W’s
¾ Any cycle you can construct will have some processes
with
¾ Q +ve some with -ve.
 Heat Engines (Contd…)
¾Let Q1,Q3,Q5 …. be +ve heat interactions (Heat supplied)

¾Q2,Q4,Q6 …. be -ve heat interactions (heat rejected)

¾From the first law we have

¾Q1+Q3+Q5 ..- Q2-Q4-Q6 -... = Net work delivered (Wnet)

¾ΣQ+ve -ΣQ-ve = Wnet

¾The efficiency of the cycle is defined as η = Wnet /ΣQ+ve

¾Philosophy → What we have achieved ÷ what we have

spent to achieve it
Heat Engines (Contd…)
 Otto Cycle
Consider the OTTO Cycle (on which your car engine works)
It consists of two isochores and two adiabatics
• There is no heat interaction during
1-2 and 3-4
• Heat is added during constant
volume heating (2-3) Q2-3= cv
(T3-T2)
• Heat is rejected during constant
volume cooling (4-1) Q4-1= cv
(T1-T4)
• Which will be negative because
T4 >T1
 Otto Cycle (Contd…)

¾ Work done = cv (T3-T2) + cv (T1-T4)

¾ The efficiency = [cv(T3-T2)+cv(T1-T4) ]/[cv(T3-T2)]

= [(T3-T2) + (T1-T4) ]/[(T3-T2)]

=1 - [(T4-T1) / (T3-T2)]
 Carnot Cycle
Consider a Carnot cycle - against which all other cycles are
compared
It consists of two isotherms and two adiabatics

• Process 4-1 is heat

addition because v4 <
v1
• Process 2-3 is heat
rejection because v3 <
v2
 Carnot Cycle (contd..)
Process Work Heat
1-2 (p1v1-p2v2)/(g-1) 0
2-3 p2v2 ln (v3/v2) p2v2 ln (v3/v2)
3-4 (p3v3-p4v4)/(g-1) 0
4-1 p4v4 ln (v1/v4) p4v4 ln (v1/v4)
Sum (p1v1-p2v2 + p3v3-p4v4)/(g-1)
+ RT2 ln (v3/v2) RT2 ln (v3/v2)
+ RT1ln (v1/v4) + RT1ln (v1/v4)
But,p1v1 = p4v4 and p2v2 = p3v3
Therefore the first term will be 0
!!We reconfirm that I law works!!
 Carnot Cycle (contd..)

We will show that (v2/v3) = (v1/v4)

1 and 2 lie on an adiabatic so do 3 and 4
p1v1g = p2v2g p4v4g = p3v3g
Divide one by the other (p1v1g /p4v4g) = (p2v2g
/p3v3g) (A)
(p1/p4 ) (v1g / v4g) = (p2/p3 ) (v2g /v3g)

But (p1/p4 ) = ( v4/ v1) because 1 and 4 are on the same

isotherm
Similarly (p2/p3 ) = ( v3/ v2) because 2 and 3 are on the same
isotherm
 Carnot Cycle (contd..)

Therefore A becomes (v1 / v4)g-1= (v2/v3)g-1

which means (v2/v3) = (v1/v4)
Work done in Carnot cycle = RT1ln (v1/v4) + RT2 ln (v3/v2)
= RT1ln (v1/v4) - RT2 ln (v2/v3)
=R ln (v1/v4) (T1- T2)
Heat supplied = R ln (v1/v4) T1
The efficiency = (T1- T2)/T1
In all the cycles it also follows that Work done=Heat supplied
- heat rejected
 Carnot Cycle (contd..)
Carnot engine has one Q +ve process and one Q -ve
process.This engine has a single heat source at T1 and a single
sink at T2.
If Q +ve > Q -ve; W will be +ve It is a heat engine
 Carnot Cycle (contd..)

It will turn out that Carnot efficiency of (T1- T2)/T1 is the

best we can get for any cycle operating between two fixed
temperatures.
 Carnot Cycle (contd..)
Q +ve < Q -ve W will be - ve It is not a heat engine

Efficiency is defined only for a work producing heat engine

not a work consuming cycle
 Carnot Cycle (contd..)

Note: We can’t draw such a diagram for an Otto cycle

because there is no single temperature at which heat interactions
occur
 Chapter 6
Second Law of Thermodynamics
 Leads Up To Second Law Of
Thermodynamics
It is now clear that we can’t construct a heat engine with just one
+ve heat interaction.

The above engine is not possible.

 Second Law Of Thermodynamics
(contd…)
Is it possible to construct a heat engine with only one -ve
heat interaction?
Is the following engine possible?

The answer is yes, because

This is what happens in a
stirrer
 Second Law Of Thermodynamics
(contd…)
Perpetual motion machine of the second kind is not possible.

Perpetual motion machine of

the first kind violates I LAW W
(It produces work without
receiving heat)
Enunciation of II Law of Thermodynamics

Statement 1: It is impossible to construct a device which

operating in a cycle will produce no effect other than raising of
a weight and exchange of heat with a single reservoir.
Note the two underlined words.
II Law applies only for a cycle - not for a process!! (We already
know that during an isothermal process the system can exchange
heat with a single reservoir and yet deliver work)
!!There is nothing like a 100% efficient heat engine!!
 Enunciation of
II Law of Thermodynamics
™ To enunciate the II law in a different form

¾ !!! We have to appreciate some ground realities !!!

¾ All processes in nature occur unaided or

spontaneously in one direction. But to make the
same process go in the opposite direction one needs
to spend energy.
 Common sense tells us that

1Heat flows from a body at higher A hot cup of coffee left in a room
temperature to a body at lower becomes cold. We have to expend
temperature energy to rise it back to original
temperature

Possible Not possible

(you can’t make room heat up your coffee!!)
 Common sense tells us that

2.Fluid flows from a point of Water from a tank can flow down
higher pressure or potential. To get it back to the tank you have to
to a lower one use a pump i.e, you spend energy

Possible
 Common sense tells us that

3.Current flows from a point of Battery can discharge through

higher potential to lower one a resistance, to get the charge

4. You can mix two gases or liquids. But to separate them you
have to spend a lot of energy. (You mix whisky and soda
without difficulty - but can’t separate the two - Is it
worthwhile?)
5. All that one has to say is “I do”. To get out of it one has to
spend a lot of money
6. When you go to a bank and give 1US$ you may get Rs 49.
But if you give Rs 49 to the bank they will give you only 95
US cents (if you are lucky !!). You spend more.
 Common sense tells us that

6. When you go to a bank and give 1US$ you may get Rs 49.
But if you give Rs 49 to the bank they will give you only
95 US cents (if you are lucky !!). You spend more.
7. You can take tooth paste out of the tube but can’t push it
back!!
Moral:
All processes such as 1-7 occur unaided in one direction
but to get them go in the other direction there is an
expenditure - money, energy, time, peace of mind? ….
They are called irreversible processes
 Definitions of Reversible Process
™A process is reversible if after it, means can be found to
restore the system and surroundings to their initial states.
Some reversible processes:
¾Constant volume and constant pressure heating and
cooling - the heat given to change the state can be rejected
back to regain the state.
 Reversible Process (contd…)

¾ Isothermal and adiabatic processes -the work derived can

be used to compress it back to the original state
¾ Evaporation and condensation
¾ Elastic expansion/compression (springs, rubber bands)
™ Lending money to a friend (who returns it promptly)
 Some Irreversible Process
spontaneous
motion with friction chemical reaction

unrestrained
heat transfer expansion

T1 > T2 P1 > P2

Q
 Irreversible Process (contd…)
mixing .....
.
Flow of current through a resistance - when a battery
discharges through a resistance heat is dissipated. You can’t
recharge the battery by supplying heat back to the resistance
element!!
Pickpocket
!!!Marriage!!!!
 Reversible Cycle

¾A cycle consisting of all reversible processes is a reversible

cycle. Even one of the processes is irreversible, the cycle
ceases to be reversible.

Otto, Carnot and Brayton cycles are all reversible.

A reversible cycle with clockwise processes produces work
with a given heat input. The same while operating with
counter clockwise processes will reject the same heat with
the same work as input.
 Other reversible cycles:

Diesel cycle Ericsson cycle Stirling cycle

 Clausius Statement of II Law of
Thermodynamics

It is impossible to construct a device which operates in a cycle and

produces no effect other than the transfer of heat from a cooler
body to a hotter body.

™Yes, you can transfer heat from a cooler body to a hotter body by
expending some energy.
energy
 Clausius Statement (contd…)

¾ Note : It is not obligatory to expend work, even thermal

energy can achieve it.

¾ Just as there is maximum +ve work output you can derive

out of a heat engine,
engine there is a minimum work you have to
supply (-ve) to a device achieve transfer of thermal energy
from a cooler to a hotter body.
 Carnot Cycle for a
Refrigerator/heat Pump

Heat sink
T1

Q1

T1>T2
T2 Q2
TH=T1
Heat source
TC=T2
 Heat pump

™A device which transfers heat from a cooler to a warmer body

(by receiving energy) is called a heat pump. A refrigerator is a
special case of heat pump.
Just as efficiency was defined for a heat engine, for a heat pump the
coefficient of performance (COP) is a measure of how well it is
doing the job.
 Heat Pump (contd…)

™ A heat pump
• Invoke the definition: what we have achieved ¸ what we
spent for it
• COPHP = heat given out ¸ work done = ½Q1/W½
• Note : The entity of interest is how much heat could be
realised. Work is only a penalty.
 Heat Pump (contd…)

Reverse cycle air conditioners used for winter heating do the

above. Heat from the ambient is taken out on a cold day and put
into the room.

The heat rejected at the sink is of interest in a heat pump , ie., Q1.

In a refrigerator the entity of interest id Q2.

In this case COP R = ⏐ Q2/W ⏐

NOTE: η ,COPHP COP R are all positive numbers η<1 but COPs
can be > or < 1
 Heat Pump (contd…)
Relation between η and COPHP

It is not difficult to see that η COPHP =1

Apply I law to Carnot cycle as a heat pump/refrigerator:

-Q1+Q2 = -W or Q1=Q2+W

Divide both sides with W Q 1 / W = Q2 / W + 1

or COPHP = COPR+1

The highest COPHP obtainable therefore will be T1/(T1-T2)

and highest COPR obtainable therefore will be T2/(T1-T2)

 Examples

Eg: If 10 kw of heat is to be removed from a cold store at -

20oCand rejected to ambient at 30oC.
COPR= 253.15/(303.15-253.15)= 5.063
W= Q2/ COPR ; Q2= 10 kW
Therefore W= 10/5.063 = 1.975 kW
 Examples (contd…)

™Another example: Let us say that the outside temperature on a

hot summer day is 40oC. We want a comfortable 20oC inside the
room. If we were to put a 2 Ton (R) air conditioner, what will be its
power consumption?

Answer: 1 Ton (R) = 3.5 kw. Therefore Q2=7 kW

COPR= 293.15/(313.15-293.15)= 14.66 ie., W=7/14.66 =0.47 kW

Actually a 2 Ton air-conditioner consumes nearly 2.8 kW (much

more than an ideal cycle!!)
 Ideal but possible Real and possible Not possible

HEAT ENGINE
HEAT PUMP
You derive work > what is
This is the best that This is what thermodynamic maximum nor can
can happen happens in reality You expend work < what is
thermodynamic minimum
 Examples (contd…)

Suppose the ambient is at 300 K. We have heat sources

available at temperatures greater than this say 400, 500,
600…..K. How much work ca you extract per kW of heat ?
Similarly, let us say we have to remove 1 kW of heat from
temperatures 250, 200, 150 …. K. How much work should
we put in?
 Examples (contd…)
Work ne e de d /produce d

0
0 200 400 600 800 1000 1200
Tem perature (K)
 Some Interesting Deductions
¾Firstly, there isn’t a meaningful temperature of the source from
which we can get the full conversion of heat to work. Only at ∞
temp. one can dream of getting the full 1 kW work output.
 Some Interesting Deductions
™ Secondly, more interestingly, there isn’t enough work
available to produce 0 K. In other words, 0 K is
unattainable. This is precisely the III LAW.
™ Because, we don’t know what 0 K looks like, we haven’t
got a starting point for the temperature scale!! That is why
all temperature scales are at best empirical.
 Summation of 3 Laws
You can’t get something for nothing
To get work output you must
give some thermal energy
You can’t get something for very little
To get some work output there
is a minimum amount of
thermal energy that needs to
be given
You can’t get every thing
However much work you are
willing to give 0 K can’t be
reached.
Violation of all 3 laws: try to get everything for nothing
 Equivalence of Kelvin-Planck
and Clausius statements

II Law basically a negative statement (like most laws in

society). The two statements look distinct. We shall prove
that violation of one makes the other statement violation too.

Let us suspect the Clausius statement-it may be possible to

transfer heat from a body at colder to a body at hotter
temperature without supply of work
Equivalence of Kelvin-Planck
and Clausius statements

Let us have a heat engine

operating between T1 as source
and T2 as a sink. Let this heat
engine reject exactly the same Q2
(as the pseudo-Clausius device)
to the reservoir at T2. To do this
an amount of Q1 needs to be
drawn from the reservoir at T1.
There will also be a W =Q1-Q2
 Equivalence of Kelvin-Planck
and Clausius statements
Combine the two. The reservoir at T2 has not undergone
any change (Q2 was taken out and by pseudo-Clausius
device and put back by the engine). Reservoir 1 has given
out a net Q1-Q2. We got work output of W. Q1-Q2 is
converted to W with no net heat rejection. This is violation
of Kelvin-Planck statement.
 Equivalence of Kelvin-Planck
and Clausius statements
• Let us assume that Clausius statement is true and suspect
Kelvin-Planck statement
Pseudo Kelvin Planck engine
requires only Q1-Q2 as
the heat interaction to give
out W (because it does not reject
any heat) which drives
the Clausius heat pump
May be possible? Combining the two yields:
ƒThe reservoir at T1 receives Q1
but gives out Q1-Q2 implying a net
delivery of Q2 to it.
ƒ Q2 has been transferred from T2 to
T1 without the supply of any work!!
ƒA violation of Clausius statement
 Equivalence of Kelvin-Planck
and Clausius statements
Moral: If an engine/refrigerator violates one version of II
Law,
it violates the other one too.

All reversible engine operating between the same two fixed

temperatures will have the same η and COPs.
If there exists a reversible engine/ or a refrigerator which
can do better than that, it will violate the Clausius
statement.
 Equivalence of Kelvin-Planck
and Clausius statements
Let us presume that the HP is super
efficient!!
For the same work given out by the engine
E, it can pick up an extra DQ from the low
temperature source and deliver over to
reservoir at T1. The net effect is this extra
DQ has been transferred from T2 to T1
with no external work expenditure.
Clearly, a violation of Clausius
statement!!
 Equivalence of Kelvin-Planck
and Clausius statements (contd…)

SUM UP

¾ Heat supplied = Q1; Source temperature = T1 ;Sink

temperature= T2
¾ Maximum possible efficiency = W/Q1= (T1-T2)/T1
¾ Work done = W= Q1(T1-T2)/T1
 Equivalence of Kelvin-Planck
and Clausius statements (contd…)

Applying I Law
Sum of heat interactions = sum of work interactions
Q1+ Q2=W= Q1 (T1-T2)/T1
Q1 is +ve heat interaction; Q2 is -ve heat interaction
 Equivalence of Kelvin-Planck
and Clausius statements
¾ Heat rejected = -ve heat interaction = -Q2= (Q1-W)=
Q1T2/T1
¾ For a reversible heat engine operating in a cycle Q1/T1+Q2 /
T2= 0
¾ or S(Q/T) = 0

Ideal engine
10,000/600 +(-5000/300)=0

Not so efficient engine

10,000/600+ (-7000/300) < 0
Module 7

Entropy
 Clausius Inequality

Suppose we have an
engine that receives from
several heat reservoirs and
rejects heat to several
reservoirs, we still have
the equation valid.
 Clausius Inequality
(contd…)

™ With reference to previous fig,

¾ Assume that reservoir at T1 gets its Q1 with the help of a
fictitious heat pump operating between a source T0 and T1.
The same for 3,5,7….
¾ Similarly, assume that reservoir at T2 rejects the heat Q2
through a fictitious heat engine to the sink at T0.The same
for 4,6,8….
Clausius Inequality
(contd…)
 Clausius Inequality
(contd…)

¾ Sum of work inputs for = -Q1-Q3…….+Q1 T0 /T1+ Q3T0

/T3…...
All fictitious heat pumps
¾ Sum of work outputs of = Q2+Q4…….-Q2 T0 /T2- Q4T0
/T4…...
All fictitious heat engines
™ [Note that the sign convention for work is already taken
into account]
 Clausius inequality
(contd…)

™ The net of work inputs + work outputs of all the fictitious

units
= -Q1-Q3…….+Q2+Q4…….+To [Q1 /T1+ Q3 /T3...-Q2 /T2-
Q4 /T4 ..]
But we know that for the main engine at the centre
™ W= Q1+Q3…….-Q2-Q4……. [after taking the sign into
account]
 Clausius Inequality
(Contd…)
¾ If we consider the entire system consisting of all the
reservoirs 1-12 and the fictitious source at T0, the work
output of our main engine must be compensated by the
works of fictitious engines (Otherwise the overall system
will be delivering work by interaction with a single source
at T0).
 Clausius Inequality
(Contd…)
This is possible only when
¾ To [Q1 /T1+ Q3 /T3...-Q2 /T2- Q4 /T4 ..]=0
¾ which implies that Q1/T1+Q3 /T3...-Q2/T2- Q4/T4 ..=0

¾ In general, S(Q/T) =0 provided the engine is perfectly

reversible.
If it is not S(Q/T) <0
Therefore in general S(Q/T) ≤ 0
Since, summation can be replaced by an integral (δQ /T) ≤ 0.
 Clausius Inequality
(contd…)
¾ The cyclic integral is to remind us that II Law
holds only for a cycle.
¾ Note: Equality holds when the cycle is reversible.
< sign will be the most probable one for real
cycles.
¾ Just as we had dW= p dV
¾ Can we guess that there is something emerging to
define Q?
 Clausius Inequality
(contd…)

9 Is there (something) which is = dQ/T? Or dQ = T.

(something) ???
9 In W, p, V relation on the right hand side p and V are
properties.
9 Is this (something) also a property?
9 For an adiabatic process we said dQ = 0. Does that
(something) remain invariant during an adiabatic process?
 The Concept Of Entropy

™ Consider a reversible
cycle constructed as
shown. Since we will be
integrating ∫ δQ /T over
the entire process say 1-2
along A or B, processes A
and B need not be
isothermal.
 The Concept of Entropy
(contd…)

¾ (δQ /T) = ∫ δQ /T⏐along 1A2 + ∫ δQ /T⏐along 2B1= 0

¾ If A and B are reversible and <0 if they are not.

¾ ∫ δQ /T⏐along 1A2 = -∫ δQ /T⏐along 2B1

¾ ∫ δQ /T⏐along 1A2 = ∫ δQ /T⏐along 1B2

 The Concept of Entropy
(contd…)
™ In other words the integral remains the same no matter
what the path is. It can be simply written as S2-S1. The
value depends only on the end states and not on the path
followed. So it is a state function or a property.

™ Like energy entropy (s) is also an extensive property. It

will have the units of J/K. Similar to energy where we
converted it into specific property, specific entropy (lower
case s) will have units of J/kg K (same as specific heat)
 The Concept of Entropy
(contd…)
1∫ δQ /T= S2-S1 or 1∫
2 2 δq /T= s2-s1 ⏐ δq /T= δs or δq = T δs

™ Lesson learnt:
¾ Just as we can represent work interactions on P-V plane
¾ we can represent heat interactions on T-S plane.
¾ Naturally, T will be the ordinate and S will be the abscissa.
¾ All constant temperature lines will be horizontal and constant
entropy lines vertical. So Carnot cycle will be just a
rectangle.
 The Concept of Entropy
(contd…)

™Integrals under P-V plane give work interaction

™Integrals under T-S plane give heat interactions
 Calculations

¾ Let us invoke the I law for a process namely δq=δw+du

¾ Substitute for δq=Tds and δw = p dv Tds = pdv +du
¾ For a constant volume process we have Tds = du… (1)
¾ We have by definition h = u+ pv
¾ Differentiating dh=du+pdv+vdp
dh= Tds +vdp
¾ For a constant pressure process Tds = dh…. (2)
 Calculations (contd…)
™ For a perfect gas du=cvdT and dh=cpdT
Substitute for du in (1) and dh in (2)
for v=const Tds = cvdT or dT/ds⏐v=const= T / cv
for p=const Tds = cpdT or dT/ds⏐p=const= T / cp
1. Since cp > cv a constant pressure line on T-s plane will be
flatter than a constant volume line.

2. The both (isobars and isochores) will have +ve slopes and
curve upwards because the slope will be larger as the
temperature increases
Calculations (contd…)

7-1-6 Const V line

9-1-8 Const. p line
 Calculations (contd…)
s T p v
1-2 Isothermal expansion ↑ ⎯ ↓ ↑
1-3 Isothermal compression ↓ ⎯ ↑ ↓
1.4 Isentropic compression ⎯ ↑ ↑ ↓
1-5 Isentropic expansion ⎯ ↓ ↓ ↑
1-6 Isochoric heating ↑ ↑ ↑ ⎯
1-7 Isochoric cooling ↓ ↓ ↓ ⎯
1-8 Isobaric heating/expansion ↑ ↑ ⎯ ↑
1-9 Isobaric cooling/compression ↓ ↓ ⎯ ↓
Comparison Between
p-v and T-s Planes
 Comparison Between
p-v and T-s Planes
(contd…)
¾ A similar comparison can be made for processes going in
the other direction as well.
¾ Note that n refers to general index in pvn=const.
Note:
¾ For 1 < n < g the end point will lie between 2 and 5
¾ For n > g the end point will lie between 5 and 7
 Comparison Between
P-v and T-s Planes (contd…)
Brayton cycle Stirling cycle

Note: All work producing cycles will have a clockwise direction

even on the T-s plane
Consider the Clausius inequality

∫ δQ /T≤ 0
In the cycle shown let A be a
reversible process (R) and B an
irreversible one (ir), such that
1A2B1 is an irreversible cycle.
™ Applying Clausius inequality
δQ /T⏐along 1A2 + ∫ δQ /T⏐along 2B1 < 0
(because the cycle is irreversible < sign applies)
Since A is reversible ∫ δQ /T⏐along 1A2 = S2-S1
S2-S1+ ∫ δQ /T⏐along 2B1 < 0
• Implying that ∫ δQ /T⏐along 2B1 < S1-S2
• Or S1-S2 > ∫ δQ /T⏐along 2B1
• Had B also been reversible ∫ δQ/T⏐along 2B1
would have been equal to S1-S2
Moral 1
(S1-S2)irreversible>(S1-S2)reversible
An irreversible process generates more entropy than a reversible
process.
Moral 2:
If process B is adiabatic but irreversible S1-S2 >0 or S1 > S2
™In general we can say ds ≥δQ /Tor δQ≤T ds
(equality holding good for reversible process)

1-2R Isentropic expansion (reversible)

1-2ir Non-isentropic expansion (irreversible)

3-4R Isentropic compression (reversible)

3-4ir Non-isentropic compression (irreversible)

An irreversible engine can’t produce more work than a
reversible one.

™ An irreversible heat pump will always need more work

than a reversible heat pump.

•An irreversible expansion will produce less work than a

reversible expansion

™ An irreversible compression will need more work than

a reversible compression
 Calculation of change in entropy during various
reversible processes for perfect gases

Starting point of equation δ q-δ w=du

Rewritten as Tds=pdv+cvdT
1. Constant volume process dv=0 ds=cvdT/T
which on integration yields s2-s1= cvln(T2/T1)
2. For constant pressure process ds= cpdT/T
which on integration yields s2-s1= cpln(T2/T1)
3. Constant temperature process (dT=0) Tds=pdv
But p=RT/v ds=Rdv/v
Which on integration yields s2-s1= R ln(v2/v1) = R ln(p1/p2)
 Calculation Of Change In Entropy During Various
Reversible Processes For Perfect Gases

Starting point of equation δ q-δ w=du

Rewritten as Tds=pdv+cvdT
1. Constant volume process dv=0 ds=cvdT/T
which on integration yields s2-s1=cvln(T2/T1)
2. For constant pressure process ds= cpdT/T
which on integration yields s2-s1= cpln(T2/T1)
 Calculation Of Change In Entropy During Various
Reversible Processes For Perfect Gases (contd…)

4. General equation ds=p dv/T+cvdT/T = Rdv/v+ cvdT/T

Which on integration yields s2-s1= R ln(v2/v1) + cvln(T2/T1)
Using Tds=cpdT-vdp (see slide 130) s2-s1= cpln(T2/T1) - Rln(p2/p1)

5. Throttling dT=0 p=RT/v from which s2-s1= R ln(p1/p2)

Since p2< p1 , throttling is always irreversible
 Refrigeration
Processes
• As per II law we need to put in work to transfer heat from
a colder system to a warmer one.
• We need to put in work to remove moisture from air
(unmixing is an energy intensive process).
• Therefore, refrigeration and air conditioning are energy
intensive processes
Refrigeration Processes
(contd…)
To take Q2 out of source at T2 we
need a medium. This is the
refrigerant
The same medium (refrigerant)
will reject Q1 to sink at T1.
In other words, there is a need
for an “agent” to collect heat
from one source to transfer it
over to the other source.
One of the easiest ways of
transferring heat at constant
temperature is by evaporation
and condensation.
 Refrigeration Processes
(contd…)
Technically we should have refrigerant evaporating at T2 and
condensing at T1. The only way to do this is to raise the
pressure.
Vapour pressure curve
 Refrigeration Processes
(contd…)

Raising of the pressure occurs in the compressor

which receives work.
What options are available?
i) Constant volume heating
ii) polytropic compression pvn=const
 Refrigeration Processes
(contd…)

Option 1: T3’>Ta
We like to get the state 3 as close as We are left with no choice but
possible to the saturated vapour (g) to use polytropic
state at pa. compression. Ideally we like
to have n=γ.
Ideally the process should follow
the path 2-g.
 Refrigeration Processes
(contd…)
¾ The process 4-1 is a pressure reduction process.
Possibilities are polytropic or isentropic expansion. State 4
is saturated liquid.
¾ In practice, it is extremely difficult to compress or expand
liquids.
¾ What happens in an actual refrigeration cycle is the liquid
at 4 is throttled from pressure p4 to p1. But throttling is an
irreversible process. Consequently, the cycle is
irreversible.
¾ As a convention we depict irreversible processes by dashed
lines.
¾ The above cycle is called vapour compression refrigeration
cycle.
cycle
 Refrigeration Processes
(contd…)
¾ The working fluid that goes through those cycle changes is
called a refrigerant.
¾ Ammonia (NH3), CO2, SO2, methyl chloride were some of
the early refrigerants.
¾ Chlorofluorocarbons (commonly called as freons)
revolutionalised the refrigeration industry from about late
30’s.
¾ There is a rethinking on them because of their ozone
depletion potential.
¾ General trend is to use naturally occurring substances eg:
NH3, CO2
 Refrigeration Processes
(contd…)
The vapour compression refrigeration cycle is seldom
analyzed on the p-V plane. T-s is slightly better. p-h is the
best.
 Refrigeration Processes
(contd…)
¢ Selection criteria for refrigerants:
9 pb > atm. pr. or else if there is a leak atmospheric air will
enter the system.
9 Heat of vaporization at Tb (or pb) should be large - so that
we can circulate only the minimal amount of refrigerant
9 pa/pb should be small so that the work of compression is
the least.
 Refrigeration Processes
(contd…)
¢ Components of a refrigeration system
¾ The compressor is the heart - Process 2-3 occurs in this. It
is here that we meet the II law requirement of giving the
work input. This is the “black box” at the rear bottom of
your domestic refrigerator. This is the one which makes
noise while running
¾ The evaporator - or the freezer is where process 1-2
occurs. This is where we get the cooling. This is the unit
inside your refrigerator and on which a lot of frost forms.
This serves the role of the low temperature heat source.
 Refrigeration Processes
(contd…)
• The condenser - where the process 3-4 occurs. It is the black
painted serpentine tube with grill on it at the rear of the
refrigerator. Usually it feels warm. This serves the purpose of
high temperature sink. (In the modern refrigerator it is embedded
beneath outer surface of the refrigerator - so don’t be surprised if
you don’t physically see one!!)

• The expansion device - where process 4-1 occurs. It takes the

form of a capillary tube (a small diameter tube) in domestic
refrigerators. In large cold rooms it takes the from of a valve (on
which you may see a lot of frost). The capillary is usually
attached to the end of the condenser tube at the rear of the
refrigerator. (In many units you may not see it as it passes through
the body)
 Application of SFEE to the evaporator
yields

Heat taken out of the source at Tb

Qb= m (h2-h1)
This is the area under the line 1-2 in
the T-s diagram m Tb(s2-s1)
Application of SFEE to the evaporator
yields (contd…)
Application of SFEE to the compressor (assuming it to
be insulated) yields -W=m(h3-h2)
COPR =⏐Q/W⏐= (h2-h1)/(h3-h2)

Application of SFEE to the condenser yields

Qa= m(h4-h3)
(which will be negative because h4<h3 or condenser
rejects heat)
Application of SFEE to the evaporator
yields (contd…)
The above aspects are easy to determine from the
p-h plane. It is not difficult to see that (h2-h1)+(h3-
h2)=h3-h1 (mathematically and on the p-h diagram)
Further, since h4=h1 (for the throttling process)
h3-h1 =h3-h4 (which is exactly the heat
rejected in the condenser)
Moral:
Moral The condenser has to reject the heat taken in
from the evaporator and the work put in at the
compressor
 Irreversibility

‰ The entropy of a system plus its surroundings (i.e. an

isolated system) can never decrease (2nd law).
The second law states:
(ΔS)system + (ΔS)surr. where Δ = final - initial
> 0 irreversible (real world)
= 0 reversible (frictionless, ideal)
 Irreversibility
(contd…)
‰ In an ideal case if Q is the heat supplied from a source at T,
its availability or the maximum work it can deliver is Q(1-
T0/T) where T0 is the temperature of the surroundings.
Invariably it will be less than this value. The difference is
termed as irreversibility

Availability = Maximum possible work-Irreversibility

W useful= W rev- I
 Irreversibility (contd…)

¾ Irreversibility can also be construed as the amount of work

to be done to restore the system to the original state.
¾ Eg: If air at 10 bar is throttled to 1 bar, the irreversibility
will be
¾ pv ln (10) which is the work required to get 10 bar back.
Here p is 1 bar and v is the specific volume at this
condition.
 Irreversibility (contd…)
ƒ Note that the system has been restored to the original state
but not the surroundings Therefore increase in entropy will
be
ƒ R ln 10.
ƒ Combining I & II laws
ƒ TdS ≥ Δu+ δW
ƒ equality sign being for the reversible process. It implies
that the amount of heat energy to be supplied in a real
process is larger than the thermodynamic limit.
 Second Law of Thermodynamics
9 Irreversible Processes increase the entropy of the universe
9 Reversible Processes do not effect the entropy of the universe
9 Impossible Processes decrease the entropy of the universe
ΔS universe = 0
Entropy Generation in the universe is a measure of lost work
ΔS Universe = ΔS System + ΔS Surroundings
The losses will keep increasing
The sin keeps accumulating
Damage to environment keeps increasing
‰ When the entropy of the universe goes so high, then some one has to
come and set it right. HE SAYS HE WILL COME. Every religion
confirms this. Let us all wait.
Cheer up, things are not that bad yet!!
 IRREVERSIBILITY

The entropy of a system plus its surroundings (i.e. an isolated

system) can never decrease (2nd law).
The second law states:
(ΔS)system + (ΔS)surr. = 0 where Δ = final - initial
> 0 irreversible (real world)
= 0 reversible (frictionless, ideal)
In an ideal case if Q is the heat supplied from a source at T, its
availability or the maximum work it can deliver is Q(1-T0/T)
where T0 is the temperature of the surroundings. Invariably it
will be less than this value. The difference is termed as
irreversibility.
Availability = Maximum possible work-Irreversibility
W useful= W rev- I
Irreversibility can also be construed as the amount of work to be done
to restore the system to the original state.
Eg: If air at 10 bar is throttled to 1 bar, the irreversibility will be
pv ln (10) which is the work required to get 10 bar back. Here p is 1
bar and v is the specific volume at this condition.
Note that the system has been restored to the original state but not the
surroundings Therefore increase in entropy will be
R ln 10.
Combining I & II laws
TdS ≥ Δu+δW
equality sign being for the reversible process. It implies that the
amount of heat energy to be supplied in a real process is larger than the
thermodynamic limit.
 Second Law of Thermodynamics
• Irreversible Processes increase the entropy of the universe
• Reversible Processes do not effect the entropy of the universe
• Impossible Processes decrease the entropy of the universe
ΔS universe = 0
Entropy Generation in the universe is a measure of lost work
ΔS Universe = ΔS System + ΔS Surroundings
The losses will keep increasing
The sin keeps accumulating
Damage to environment keeps increasing
When the entropy of the universe goes so high, then some one has to come
and set it right. HE SAYS HE WILL COME. Every religion confirms this.
Let us all wait.
Cheer up, things are not that bad yet!!
 Ideal maximum work –
Availability or Exergy

Consider a fully reversible process with no dissipative effects – that

is all work is transferred without loss and all heat is transferred
using an ideal Carnot process to generate additional work.
 Availability or Exergy (cont…)

The resulting maximum work in Secondary system given by

ΔB = H out − H in − To ( Sout − Sin ) = ΔH − To ΔS

ΔB = change in availability or exergy
= maximum work output or minimum work input

ΔB = ΔH − To ΔS T
Tin , Pin

out , Pout

Normally, Tout , Pout = ambient or dead state condition = T0 , P0

 Availability or Exergy (cont…)

Clearly, the availability B is a state function in the strictest

mathematical sense so the maximum (or minimum) work
associated with any steady state process is also independent
of the path.
Availability:
• Yields the maximum work producing potential or the
minimum work requirement of a process
•Allows evaluation and quantitative comparison of options in
a sustainability context
 Exergy analysis

Exergy analysis is a formalised way of applying availability theory to

engineering installations such as power generating plants. Energy (First
Law) analysis keeps track of the heat and work transfers but does not
indicate the source and magnitude of the irreversible entropy creation.
Exergy (Second Law) analysis provides this information. It is useful in
indicating where research resources can be directed to best advantage.

Steady-flow exergy equation

The specific steady-flow availability function is defined by,

b = h − T0 s
• T0 is the temperature of a heat reservoir (usually the environment).
• The datum level for b (the state at which b = 0) depends on the datum
levels for h and s. These can be chosen arbitrarily because it is only
differences in h, s and b which are meaningful.
 Steady-flow exergy equation….(cont.)

• When a fluid is at equilibrium with the environment, it has zero potential for
doing work
• It would therefore be physically meaningful if b were zero at this condition.
• This will not be so unless h and s also happen to be zero. Rather than change
the h and s datum levels in all the different thermodynamic tables, we choose
instead to replace the availability function with a new quantity called the
exergy.
• When the fluid is at equilibrium with the environment it is said to be in its
dead state (pD, TD).
• The dead state is usually taken as pD = 1 bar and TD = 25 °C (which coincides
with what is known as the ‘standard state’).
• The specific steady-flow exergy e is then defined as the difference between the
actual value of b and its value bD at the dead state,
e = b − bD = ( h − T0 s ) − ( hD − T0 sD )
where hD and sD are the fluid specific enthalpy and entropy at (pD, TD). Hence, eD = 0.
 Steady-flow exergy equation….(cont.)

• The steady-flow exergy of a fluid at a given state is therefore the maximum

power which could be obtained by taking the fluid, in steady-flow, from the given
state to the dead state (allowing heat transfer only with the environment at T0).
• Although this confers a certain absolute status on e, it is important to appreciate
that the only truly meaningful quantities are changes in e and b and that these are
equal, (e2 - e1) = (b2 - b1).

The figure shows a device such as a

turbine, boiler, condenser, etc. The device
may produce shaft power W& X and there
may be a heat transfer dQ& 0 between the
control volume at local temperature T and
the environment at T0.
Also indicated is a possible heat transfer
dQ& S between an unspecified heat source
and the control volume. The work and
heat transfers are positive in the direction
of the arrows.
 Steady-flow exergy equation….(cont.)

Neglecting changes in KE and PE between inlet and oulet states, the steady-flow
energy and entropy equations applied to the control volume are :
2 2
m& ( h2 − h1 ) = ∫ dQ& S − ∫ dQ& 0 −W& X (1)
1 1

2 dQ& S 2 dQ& 0
m& ( s2 − s1 ) = ∫ −∫ + ΔS&irrev ( 2)
1 T 1 T

where ΔS&irrev is the rate of entropy creation in the control volume due to
irreversibilities. Mulyiplying eq. (2) by T0 and subtracting from eq. (1), we
obtain,

⎛ T0 ⎞ & ⎛ T ⎞
m& [( h2 − T0 s2 ) − ( h1 − T0 s1 )] = ∫ ⎜1 − ⎟dQS − WX − T0 ΔSirrev − ∫ ⎜1 − 0 ⎟dQ& 0
2 2
& &
1⎝ T⎠ 1⎝ T⎠
 Second Law Efficiency
The general definition of second law efficiency of a process can be obtained in
terms of change in availability during the process:

Production of availability
Second Law Efficenccy = η II Law =
Destruction of availability

Steam Turbine Heat Exchanger

i
4 3 Hot

wa 1 2 Cold
wa
η II Law =
bi − be m& 1 (b2 − b1 )
η II Law =
m& 3 (b3 − b4 )