Thermodynamics

Chapter 4
THE SECOND LAW OF THERMODYNAMICS
4.1 According to first law of thermodynamics heat and work are mutually convertible during any
cycle of a closed system. This law does not specify the conditions which conversions is possible. It
also does not give any information regarding the direction of heat and work.

The following systems fallow the first law of thermodynamics. However some limitation will be
observed in all such cases.

Example : 1

Fig-1: Example showing the transfer of heat from high

temperature system to low temperature system

Fig-1 shows two systems, one at higher temperature and the other at a lower temperature under
going a process in which heat transferred from the high temperature system to low temperature
system. This process can takes place but it is impossible to complete a cycle by transferring heat
from low temperature system to high temperature system, by heat transfer only.

Example-2

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Fig-2: A closed system that undergoes a cycle involving heat & work

Fig-2 shows a closed system (gas) and the surroundings. Let the gas constitute the system and as per
the discussion of first law, let this system undergoes a cycle in which work is first done on the
system by the paddle wheel as the weight is lowered. Then the cycle is completed by transferring het
to the surroundings. However, these processes cannot be reversed, i.e. if we transfer heat to the gas
(as shown by the dotted arrow), the temperature of the gas will increase, but the paddle wheel will
not turn and raise the weight.

Example-3
Consider the running automobile vehicle is stopped by applying brakes. The breaks get hot and the
kinetic energy lost by the vehicle is gained by the breaks whose temperature increases. The first law
of thermodynamics would be satisfied if the break were to cool off and give back its internal energy
to vehicle causing the vehicle to resume its motion.

Example -4
A hot cup of coffee cools by virtue of heat transfer to the cooler surroundings but once it is cooled, it
can never be heated by addition of heat from the cooler surrounding.

Thermal Reservoir
A thermal reservoir is a body to which and from which heat can be transferred indefinitely without
any appreciable change in its temperature. Thus in general it may be considered as a system in which
any amount of energy may be dumped or extracted ou6t and there shall be no change in its
temperature.
Eg. Atmosphere, large river, sea etc.
Thermal reservoir can be of two types depending upon nature of heat interaction (i.e. heat rejection
or heat absorption) from it. Thermal reservoir which rejects heat from it is called ‘source’. While the
heat reservoir which absorbs heat is called ‘sink’.

4.2 The Second law of Thermodynamics

Statements of Second Law of Thermodynamics:
There are two classical statements of second law of thermodynamics
1) Kelvin – Planck statement
2) Clausius statement

Kelvin – Planck statement

‘It is impossible to construct a heat engine operating on a cycle whose sole effect is transfer of heat
energy from a single heat reservoir and its conversion into equal amount of work’.

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Not Possible

Possible
Fig-10: Illustration of Kelvin-Plank Statement
This statement states that it is impossible to construct a heat engine which operates in a cycle and
receives a given amount of heat from a high temperature body and does an equal amount of work.
The only alternative is that some heat must be transferred from working fluid at a lower temperature
to a low temperature body as shown in fig-4.5
This statement also implies that it is impossible to build a heat engine having a thermal efficiency of
100 percent.

Clausius statement
‘It is impossible to construct a device operating on a cycle whose sole effect is transfer of heat from
a low temperature body to high temperature body.’

Not Possible Possible

Fig-11: Illustration of Clausius statement
This statement is related to the devices converting work into heat i.e. heat pump or refrigerator, says
that it is impossible to construct a heat pump or refrigerator that operates without an input of work.
Hence, external work is necessary to drive a heat pump or refrigerator which in effect transfers heat
from a cooler body to a hotter body or extracts from cooler body to a hotter body.

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Devices Converting Heat into work:

Direct Heat engine

Heat engine is a device used for converting heat into work and it defined as ‘a device operating in a
cycle between high temperature source and low temperature sink and producing work. Heat engine
receives heat from the source, transforms some portion of heat into work and rejects the balance heat
to sink. All process occurring in heat engine constitute cycle.

Fig-3: Heat engine

A schematic diagram of the direct heat engine is shown in the fig-3, where Q1 is the heat received by
the heat engine from the high temperature reservoir (Source at a temperature T1), W is the network
done by the engine and Q2 is the amount of heat transferred to the low temperature reservoir (Sink at
a temperature T2).

The performance of a direct heat engine is assessed quantitatively by using a parameter called
‘Thermal Efficiency’ (η) of the engine, and it is defined as the ratio of network output from the
engine to the heat absorbed by the engine from the source. Symbolically this can be written as.

Net Work W
η th  
Heat Supplied Q1

Where
Net work (W) = (Heat supplied to Heat-engine) – (Heat rejected by Heat-engine)
W = Q1 – Q2
Q1  Q 2 Q
 η th 
Q1
 1 2
Q1

Q rejected
or, in general η HE  1 
Q added

Examples of Heat engine include steam engines, steam and gas turbines, spark-ignition and diesel
engines, and the "external combustion" engine. Such engines can provide motive power for
transportation, to operate machinery, or to produce electricity.
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Steam or Gas Turbine Power Plant

Fig-4: Closed cycle Steam turbine power plant

The Steam turbine plant in fig-4 shows that heat is added to the high pressure water (working fluid)
from 1–2 in a Boiler (Source), the high pressure steam is expanded in a turbine from 2-3 and
produces positive work. After expansion the low pressure and low temperature steam goes to the
Condenser (Sink) where it condenses by giving up the heat to a cooling agent from 3-4. The
condensate coming out of the condenser will be at low pressure. The pressure of this condensate is
increased by means of a Compressor from 4-1, and the high pressure water is sent back to the Boiler.
The work required for compression is quite small as compared to positive available in turbine and is
supplied by the turbine itself.

 Heat Engine model for it shall be as follows,

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Fig-5: Heat engine representation of steam turbine plant

The work output from the plant Wnet is

Wnet = (Work produced by Turbine) – (Work supplied to Compressor)

= WT – WC

Also Wnet = (Heat supplied to Heat-engine) – (Heat rejected by Heat-engine)

Wnet = Qadded – Qrejected

 WT – WC = Qadded – Qrejected

Net Work Wnet

The Efficiency of the Heat-Engine is η HE  
Heat Supplied Q added

WT  WC
=
Q added
Q added  Q rejected
=
Q added

Q rejected
η HE  1 
Q added

Devices Converting work into heat:

a. Heat Pump

Heat pump refers to a device used for extracting heat from a low temperature surroundings and
sending it to high temperature body, while operating in a cycle. In other words heat pump maintains
a body or system at temperature higher than surroundings, while operating in cycle. Working Cycle
for a heat pump is given below (fig-6)

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Fig-6: Heat Pump Working Cycle

Heat pump works by exploiting the physical properties of an evaporating and condensing fluid
known as a refrigerant.
The working fluid, in its gaseous state (1), is pressurized and circulated through the system by a
compressor. On the discharge side of the compressor (2), the now hot and highly pressurized gas is
cooled in a heat exchanger, called a Condenser, until it condenses into a high pressure, moderate
temperature liquid (3) by rejecting heat (Qrejected). The condensed refrigerant then passes through a
pressure-lowering device like an expansion valve. This device then passes the low pressure liquid
refrigerant (4) to another heat exchanger, the evaporator where the refrigerant evaporates into a gas
via heat absorption (Qadded). The refrigerant then returns to the compressor and the cycle is repeated.

The Block Diagram of a Heat Pump is shown in fig-7 below

Fig-7: Heat pump

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As the heat pump transfers heat from low temperature from low temperature to high temperature,
which is non spontaneous process, so external work is required for realizing such heat transfer. Heat
pump shown picks up heat Q2 at temperature T2 and rejects Q1 for maintaining high temperature
body at temperature T1. For causing this heat transfer heat pump is supplied with work W as shown.

Since the heat pump is not work producing device and also its objective is to maintain a body at high
temperature, so its performance is measured through a parameter called ‘Coefficient of Performance’
(C.O.P). The Coefficient of performance is defined by ratio of desired effect and net work done for
getting the desired effect.

Desired Effect
C.O.P 
Net Work Done
For Heat pump:

Net work = W
Desired Effect = Heat transferred Q1 to high temperature body at temperature, T1.

  C.O.P  HP  Q1
W
Also W = Q1 – Q2

Q1
So  C.O.P  HP 
Q1  Q 2
b. Refrigerator

Refrigerator is device similar to heat pump but with reverse objective. It maintains a body at
temperature lower than that of surroundings while operating in a cycle. Working Cycle for a
refrigerator is given below (fig-8)

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Fig-8: Refrigerator Working Cycle

Refrigerator also works by exploiting the physical properties of an evaporating and condensing fluid
known as a refrigerant. (Freon or Ammonia)
The working fluid (refrigerant), in its gaseous state, is pressurized and circulated through the system
by a compressor. As the refrigerant is compressed, it increases in temperature and pressure (1-2).
After the compressor the refrigerant passes through the heat exchanger, called a Condenser, until it
condenses into a high pressure, moderate temperature liquid by rejecting heat (Qrejected) to a
surrounding environment. The condensed refrigerant then passes through a pressure-lowering device
like an expansion valve, which reduces the temperature and pressure of the refrigerant (3-4). This
device then passes the low pressure liquid refrigerant to another heat exchanger called Evaporator
where the refrigerant evaporates into a gas by heat absorption (Qadded). The refrigerant then returns to
the compressor and the cycle is repeated (4-1).

The Block Diagram of a Refrigerator is shown fig-9 below

Fig-9: Refrigerator

Refrigerator also performs a non spontaneous process of extracting heat from low temperature body
for maintaining it cool, therefore external work W is to be done for realizing it.

The block diagram (fig-9) shows that refrigerator extracts heat Q2 for maintaining body at low
temperature T2 at expense of work W and rejects heat Q1 to high temperature surroundings.

Performance of refrigerator is also measured by Coefficient of Performance(C.O.P), which could be

defined as:
 COP  refrigerator  Desired Effect  Q 2
Net Work W

For Heat pump:

Net work = W
Desired Effect = Heat absorbed Q2 from low temperature body at temperature, T2.

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Here W = Q1 – Q2
Q
  C.O.P  refrigerator  Q 2Q
1 2

Note:  Heat pump and Refrigerator are also called as Reversed Heat Engines
 C.O.P values of heat pump and refrigerator can be related as: (COP) HP = (COP)refrigerator + 1
Statements of Second Law of Thermodynamics:
There are two classical statements of second law of thermodynamics
1) Kelvin – Planck statement
2) Clausius statement

Kelvin – Planck statement

‘It is impossible to construct a heat engine operating on a cycle whose sole effect is transfer of heat
energy from a single heat reservoir and its conversion into equal amount of work’.

Not Possible

Possible
Fig-10: Illustration of Kelvin-Plank Statement
This statement states that it is impossible to construct a heat engine which operates in a cycle and
receives a given amount of heat from a high temperature body and does an equal amount of work.
The only alternative is that some heat must be transferred from working fluid at a lower temperature
to a low temperature body as shown in fig-4.5
This statement also implies that it is impossible to build a heat engine having a thermal efficiency of
100 percent.

Clausius statement
‘It is impossible to construct a device operating on a cycle whose sole effect is transfer of heat from
a low temperature body to high temperature body.’

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Not Possible Possible

Fig-11: Illustration of Clausius statement
This statement is related to the devices converting work into heat i.e. heat pump or refrigerator, says
that it is impossible to construct a heat pump or refrigerator that operates without an input of work.
Hence, external work is necessary to drive a heat pump or refrigerator which in effect transfers heat
from a cooler body to a hotter body or extracts from cooler body to a hotter body.
This statement also implies that the coefficient of performance is always than infinity.

Equivalence of the Two Statements:

The Kelvin-Plank and the Clausius statements are equivalent in their consequences, and either
statement can be used as the expression of the second law of thermodynamics. Any device that
violates the Kelvin-Plank statement also violates the Clausius statement, and vice versa. This can be
demonstrated as follows.

Proof of violation of the Kelvin-Plank statement results in violation of the Clausius statement

Fig-12 System based on Violation of Kelvin-Plank Statement

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Consider a heat engine producing net work W by extracting heat with only one reservoir at
temperature T1, thus based on violation of Kelvin-Plank Statement. Let us also have a perfect heat
pump operating between two reservoirs at temperatures T1 and T2 as shown in fig-12 above. Let the
work requirement of heat pump may be met from the work available from heat engine.
From the Fig-12,

The Work output from the Heat engine: W = Q1

The Work input to the Heat pump: W = Q 2 – Q3

Since all the work output from the Heat engine is supplied to the Heat Pump
Therefore for Heat Pump
Q1 = Q2 – Q3

i.e. the combination of heat engine and heat pump shall thus result in a equivalent system working as
heat pump transferring heat from low temperature T2 to high temperature T1 without expense of any
external work. This heat pump is based on the violation of Clausius statement and therefore not
possible.

Proof of violation of the Clausius statement results in violation of the Kelvin-Plank statement

Fig-13 System based on Violation of Clausius Statement

Consider a heat pump which operating in cycle transfers heat from low temperature reservoir to high
temperature reservoir without expense of any work, thus based on violation of Clausius statement.
Heat pump transfers heat Q1 to high temperature reservoir by extracting heat Q2 from low
temperature reservoir.
Mathematically, as no work is done on pump, so
Q2 = Q3

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Let us also have a perfect heat engine operating between two reservoirs at temperatures T1 and T2 as
shown in fig-13 above.

From the Fig-13,

The Work output from the Heat engine: W = Q1 – Q2

The Work input to the Heat pump: W = Q 2 – Q3
= Q2 – Q2 = 0
Let us now devise for heat rejected from heat pump be given directly to heat engine. i.e. the amount
of heat rejected by heat pump Q3(or Q2) is supplied to heat engine. Arrangement is shown by dotted
lines

In such a case, the work done by heat engine will be

W = Q1

Because Q1 is equal to Q3 (i.e heat rejected by heat pump) , and Q3 again equal to Q2 (i.e. heat
supplied to heat pump).

Therefore there is no transfer to the low temperature reservoir, and hence the combination of heat
engine and heat pump thus result in a equivalent system working as heat engine transfers heat T1
from the high temperature reservoir and produces equivalent amount of work.
Perpetual Motion Machine of First Kind (PMM-1)

It is an imaginary device which produces a continuous supply of work without absorbing any energy
from the surrounding or from the system. Such a machine in effect creates energy from nothing and
violates the first law of thermodynamics. (fig-14)

As per the law of conservation of energy, no engine can produce mechanical work continuously
without some other form of energy disappearing simultaneously.

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Perpetual Motion Machine of Second Kind (PMM-2)

Without violating the first law, a machine can be imagined which would continuously absorbs heat
from single thermal reservoir and would convert this heat into work. The efficiency of such machine
would be 100 percent. This machine is called the perpetual motion machine of second kind (PMM2)

Fig-16 shows the PMM2. a machine of this kind will be evidently violates the second law of
thermodynamics.

Reversible and Irreversible process

When the system undergoes change from its initial state to the final state, the system is said to have
undergone a process. During thermodynamic process the one or more of the properties of the system
like temperature, pressure, volume, enthalpy or heat, entropy etc changes. The second law of
thermodynamics enables to classify all the processes under two main categories: reversible or ideal
process and irreversible or natural process.
Reversible Process
A process that, once having taken place, can be reversed and in doing so leaves no change in either
the system or the surroundings is called reversible process. In this process every state along some
path is an equilibrium state. This process is possible if the net of heat and net work exchange
between the system and the surrounding is zero for the combined process.

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Fig-17: Reversible Process

A reversible process is shown in the fig-17; let us suppose that the system has undergone change
from state A to state B. If the system can be restored from state B to state A, and there is no change
in the universe, then the process is said to be reversible process. The reversible process can be
reversed completely and there is no trace left to show that the system had undergone thermodynamic
change.
The phenomenon of a system undergoing reversible change is also called as reversibility. In actual
practice the reversible process never occurs, thus it is an ideal or hypothetical process. All
thermodynamic process are attempted to reach close to the reversible process in order to give best
performance

The following are some of the examples of reversible process

a) Gradual extension of a spring b) Frictionless motion of solids
c) Slow frictionless adiabatic expansion of gas d) Slow frictionless adiabatic expansion of gas

Irreversible Process

A process for which a system cannot be restored to its initial state and in doing so it influences either
the system or surroundings is called irreversible process. In this process the system passes through a
series of non-equilibrium states

An irreversible process is shown in the fig-18; let us suppose that the system has undergone change
from state A to state B, in which the process will not retrace the reverse path to restore the original
state.

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Fig-18: Irreversible process

The irreversible process is also called as natural process because all the processes occurring in the
nature are irreversible processes. The phenomenon of system undergoing irreversible process is
called as irreversibility.
Some of the examples of irreversible process are:
a) Combustion process b) Mixing two fluids
c) Free or unrestricted expansion d) Heat transfer through finite temperature difference
e) Process involving friction f) Plastic Deformation

Factors that make a process Irreversible:

The factors that cause a process to be irreversible are called irreversibilities. They include friction,
unrestrained expansion, mixing of two fluids, heat transfer across a finite temperature difference,
electric resistance, inelastic deformation of solids, and chemical reactions.
Some of the frequently encountered irreversibilities are explained below.

1. Friction

Fig-19: Process involving Friction

Friction is the familiar form of irreversibility associated with the bodies in motion. When two bodies
in contact are forced to move relative to each other, for example consider the piston cylinder
arrangement shown in fig-19, a friction force that opposes the motion develops at the interface of
cylinder and the piston, some work is needed to overcome this friction force. The energy supplied as
work is eventually converted to heat during the process and is transferred to the bodies in contact.

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Even when the direction of motion of the piston is reversed, more of the work is converted to heat
while overcoming the friction force that also opposes the reverse motion of piston.
Friction is also encountered between a fluid and solid and even between the layers of a fluid moving
at different velocities.

2. Unrestrained Expansion or Free Expansion

Fig-20: Unrestrained Expansion

An unstrained expansion is shown in the fig-20, in which a gas is separated from vacuum by a
membrane. When the membrane is ruptured, the gas fills the entire tank (fig-20a). The only way to
restore the system to its original state is to compress it to its initial volume, while transferring heat
from the gas to the surrounding until it reaches the initial temperature (fig-20b). Since the
surroundings are not restored to their initial state, unrestrained expansion is an irreversible process.

3. Heat Transfer through a finite temperature difference

Fig-21: Heat transfer over a finite temperature difference

Heat transfer occurs only when there exist temperature difference between bodies undergoing heat
transfer. Consider the transfer of heat from a high temperature body to a low temperature body as
fig-21(a). The only way of reversing this process, that is, transferring heat from low temperature

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body to high temperature body is by means of heat pump as shown in fig-21(b), which requires some
external work. Hence, the process is an irreversible one.

4. Mixing of two Substances

Let us consider the mixing of any two gases (say oxygen and nitrogen) as shown in fig-22 to form a
mixture by rupturing the membrane.

Fig-22: Illustration of mixing of two substances

Now, if this mixture has to be separated back to oxygen and nitrogen, an air separation plant has to
be used, which requires some amount of work and heat transfer. Hence, we conclude that the mixing
of two substances is an irreversible process since the surroundings are not restored to their initial
state.

5. Electrical resistance

Fig-23: Electrical resistance

The flow electric current (I) through a wire represents work transfer, because the current can drive
motor which can raise a weight. Because of electrical resistance dissipation of electrical work into
internal energy or heat takes place as shown in fig-23. The reverse transformation from heat or
internal energy to electrical work is not possible.

6. Inelastic Solid Deformation

Deformation of solids, which are inelastic type is also irreversible and thus causes irreversibility in
the process. If the deformation occurs within elastic limit then it does not lead to irreversibility as it
is of reversible type.

Difference between Reversible and Irreversible process

Reversible Process Irreversible Process

 Reversible Process can not be realized in
Practice
 The Process can be carried out in a reverse
direction following the same path
 All practical processes occurring are
irreversible processes
 Process, when carried out in reverse direction
follows the path different from that in forward
direction

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 A reversible process leaves no traces of
occurrences of process upon the system and
surroundings after its reversal.
 Such processes can occur in either directions
without violating second law of
thermodynamics
 A system undergoing reversible process has
maximum efficiency. So the systems with
reversible processes are considered as
reference systems. (for comparison)
 Reversible process occurs at infinitesimal rate
i.e. quasi-static process.
 System remains throughout in thermodynamic
equilibrium during occurrence of such process
 Examples:
Frictionless motion, Controlled expansion and
compression, Elastic deformations, Electric
current with no resistance, Electrolysis,
Polarization and magnetization process etc.
 The evidences of process having occurred are
evident even after reversal of irreversible
process
 Occurrence of irreversible processes in either
direction is not possible, as in one direction it
shall be accomplished with violation of second
law of thermodynamics.
 Systems having irreversible processes do not
have maximum efficiency as it is accompanied
by the wastage of energy.
 Irreversible processes occur at finite rate.
 System does not remain in thermodynamic
equilibrium during occurrence of irreversible
processes.
 Examples:
Viscous fluid flow, inelastic deformation and
hysteresis effect, free expansion, Electric
circuit with resistance, Mixing of dissimilar
gases, Throttling process etc.

Reversible Heat Engine

[A theoretical heat engine developed by Sadi Carnot]

A heat engine operating in an ideal, reversible cycle (also called as Carnot cycle) between two
reservoirs without any losses is called reversible heat engine. Eg: Carnot Heat Engine

A reversible heat engine has got significantly higher thermal efficiencies than existing heat engines
operating within the same temperature ranges.

This reversible heat engine can made to operate efficiently as either a forward heat engine or as a
reverse heat engine at any given selected moment; thus, permitting the present heat engine to be
utilized as an air conditioner or heat pump, or, alternatively, if a heat source is provided to the
engine, as a forward heat engine producing a work output.

Carnot Cycle

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Fig-24: Carnot Cycle

The T-s diagram of the Carnot cycle.

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Since area under T-S diagram gives heat transfer

Heat added

ΔQH =TH (sB − sA)

Heat rejected

ΔQC=TC(sB − sA)

efficiencyη=1 -

First and second law of thermodynamics.

Key concepts:
1. The first law of thermodynamics is the same as the law of conservation of energy: The total
energy of a closed system remains constant. Energy can change from one type of energy to another
(for example kinetic to potential) but the total amount remains fixed.
2. In thermodynamics energy is classified into three different types: work, W, heat, Q, and internal
energy, ∆U. This allows us to write a simple form for conservation of energy (the first law of
thermodynamics) as ∆U = Q + W.
3. Heat, Q (in Joules or calories) is a flow of energy. Objects don't have a certain amount of heat in
them but energy can be added or removed. Heat transfer occurs by one of the three mechanisms of
convection, conduction, radiation. Evaporation also transfers heat but since there is a mass transfer
it does not usually apply to a closed system.

4. Work is but since pressure, P = F/A we can also write the work equation as

. If we are referring to the the expansion or contraction of a gas (for example the
hot gases expanding in the cylinder of a car engine) then the surface area A of a piston pushed
through a distance ds results in a change of volume dV = Ads and we can write
hermodynamic work as

(in Joules or calories). Examples of thermodynamic

work for various cases are given below. Note that on a pressure versus volume (P-V) diagram
the work will be the area under the curve.
5. Internal energy, ∆U, (in Joules or calories) is the sum of all of the types of energy the
individual molecules have. It includes rotational energy, vibrational energy, chemical potential

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energy and kinetic energy (average kinetic energy by itself is proportional to temperature; 3/2
kB T = <1/2 m v2>). Chemical potential energy is the energy absorbed or released by chemical
reactions between molecules.
6. In an ideal gas the molecules are non interacting point particles and so do not have
rotational, vibrational or chemical potential energy. The only kind ofenergy an ideal gas can
have is kinetic energy (temperature).
7. Note that the first law of thermodynamics tells us energy is conserved but does not provide
any restrictions about how energy may be converted fromone type to another.

1. The second law of thermodynamics restricts the kinds of energy

transfers that are possible in a closed system.
2. The second law also determines the theoretical efficiency of some kinds of energy transfers.
Efficiency is defined to be e = Eout/Ein x100% where Eout is the output energy or work done
by a process and Ein is the input energy (or work) needed to make the process occur.
3. There are several different ways of stating the second law. Although it might not be obvious
at first glance, each different statement of the second law can be used to prove the others.
4. Version one of the second law: Entropy (another word for disorder) increases.
(see below for explanations)
5. Version two of the second law: In a closed system heat flows from hot to cold, it takes input
energy to make it flow the other way. (see below for explanations)
6. Version three of the second law: The Carnot cycle is the most efficient cycle possible for a
process that involves heat transfer: e = (1 -T2/T1)x 100%. (see below for explanations)
7. A heat engine is a device that converts heat into mechanical work. Because a heat flow is
needed for a heat engine to operate, some energy has to flow out of the system and this outflow
cannot be converted into mechanical work (this is sometimes called 'waste heat'). Heat engines
can never convert 100% of the input energy into useful mechanical work. This limitation is a
consequence of the second law, there is no way to avoid it.
8. One consequence of the second law is that it is not possible, even in theory, to make a heat
engine which is 100% efficient. For example, gasoline engines must have a radiator or cooling
fins where heat is expelled to the environment. Current gasoline engines are only about 25%
efficient as a result (75 %on the dollar goes to heating the air outside the car). The second law
says we can do a little better (the Carnot cycle) but never 100%, even if all friction is
eliminated.
9. This also means that it is impossible to do something like extract heat from the ocean to do
mechanical work. You must have a cool reservoir to expel waste heat to and there isn't a
convenient one available.
10.It is possible to use the so called 'waste heat' from a heat engine in other ways. For example
in the winter time the waste heat from your car engine can be used to warm the people in the
car. Factories and electric generating plants which operate heat engines can sometimes sell or
otherwise use the waste heat (for example for heating homes) making the overall efficiency of
the combined processes more efficient.

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 Thermodynamics

11.Other devices such as fuel cells, batteries and electric engines are not limited in efficiency by
the second law because they are not heat engines, they do not convert heat energy into
mechanical work (they perform other kinds of energy conversions).

Source
Desired
Effect

Qin Heat
Engine W
Required
Effect

Qout

Sink

Figure 4.1 Heat Engine

Wnet

Qin
...(4.1)
From first law of thermodynamics

Q  W

Q in  Qout  Wnet

...(4.2)
Clausius statement : Unaided by an external agency heat can not be transferred
from a body at lower temperature to a body at higher temperature.
Devices that are used to transfer heat from a body at lower temperature to a body
at higher temperature are known as refrigerators (or) heat pumps. If the high
temperature side is atmosphere it is a refrigerator. If the low temperature side is
atmosphere it is known as a heat pump. The performance index here is called
coefficient of performance (COP). In refrigerator (and heat pumps) the performance is
the ratio of two independent parameters and hence the possibility of getting the value

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 Thermodynamics

more than unity is always there. But the term efficiency is restricted to a maximum of
unity. Hence the term efficiency is not used here.
Desired Effect
COP 
Re quired Effect

Q2
COP 
W

Taking work as external agency, for refrigerators (Figure 4.2)

...(4.3)
From first law
Q  W

Q1  Q2  W

Q2
COP 
Q1  Q2

Sink
[Atmosphere]
Required
Effect Q1

Refrig
W erator
Desired
Effect Q2

Source
[conditioned Space]

Figure 4.2 Refrigerator

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 Thermodynamics

Sink
Desired
[Conditioned Space]
Effect
Q1

Heat
W Pump
Required
Effect Q2

Source
[Atmosphere]

Figure 4.3 Heat Pump

Similarly for a heat pumps (Figure 4.3)

Desired Effect
COP 
Re quired Effect

Q1
COP 
W ...(4.4)
Since, Q1  Q2  W
Q1
COP 
Q1  Q2
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 Thermodynamics

...(4.5)

4.3 Equivalence of Kelvin-Planck and Clausius Statements

The Clausius and Kelvin-Planck statements of the second law are entirely
equivalent. This equivalence can be demonstrated by showing that the violation
of either statement can result in violation of the other one.
Referring to Figure 4.4(a) the device marked Clausius violator is pumping
Q1 amount of heat from a low temperature reservoir at T 1 to a high
temperature reservoir at T2 without the aid of any external agency. This is an
impossible arrangement.
If such an arrangement is possible it would also violate Kelvin-Planck
statement. Let a heat engine operating between the same reservoirs at T 2 and
T1 take in Q2 as heat input at T2. It converts a part of this heat into work and
rejects heat Q3to the sink at T1. Since the Clausius violator is rejecting the
same quantity Q2at T2, it can be supplied directly into the heat engine so that
the reservoir at T2 can be eliminated. This combination as shown in Figure 4.4
(b) is producing continuous work with a single reservoir at T 1. Hence it violates
the Kelvin-Planck statement.

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 Thermodynamics

Reservoir
Reservoir
at T2
at T2

Q2
Q2
W
Clausius Heat
violator Engine

Q3
Q1

Reservoir at T1

(a)

Q2
Q2
W
Clausius Heat
violator Engine

Q1 Q3

Reservoir at T1

(b)

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 Thermodynamics

Figure 4.4 Illustration of the equivalence of Clausius and Kelvin-Planck’s

statement

Referring to Figure 4.5 a Kelvin-planck violator is converting all heat Q H taken from
the reservoir at TH into work. If such an impossible heat engine is assumed to exist it
will violate the Clausius statement. Consider a refrigerator pumping Q L heat from the
low temperature reservoir at T L to the reservoir at higher temperature T H. Combined
with the Kelvin-Planck violator, the arrangement is pumping Q L heat from TL to TH,
without any external agency. Hence it violate the Clausius statement.

4.4 Reversible Process

A process is said to be reversible if it can be reversed without leaving any trace on
the surroundings.
For example, let a system be taken from state 1 to state 2 with a work transfer of
+5 kJ and heat transfer of 10 kJ. If the process is reversible, while taking the system
from state 2 to state 1, the work transfer must be 5 kJ and heat transfer must be +10
kJ. So that, both the system and surroundings are returned to their initial states at the
end of the process 2 to 1.

4.5 Irreversibility and Causes of Irreversibility

The factors that make a process irreversible are known as irreversibilities. Various
forms of irreversibilities are listed below.
a) Friction : Friction occurs at the interface of two bodies moving relative to
each other. It is the main cause of irreversibility in many
processes. Energy spent in overcoming friction is dissipated in the
form of heat which can never be restored.

b) Heat transfer: Once heat is transferred from a body at higher temperature to a

body at lower temperature, it can never be reversed without the
aid of an external agency.
through finite
temperature
difference
c) Unresisted expansion :

Consider a vessel with two chambers as given in the

arrangement as shown in Fig. 4.6. If the members separating the
gas from vacuum is removed, gas will expand and occupy the
entire space. Since the expansion has no influence on the
surroundings, there is no work output in this process. But to
restore the initial arrangement, a definite work input is required.
d) Mixing of two gases : Consider a vessel with two chambers, one with O 2 and the
other with N2. When the member separating O 2 & N2 is removed,

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 Thermodynamics

uniform mixing is taking place without any work output. But such
a process can not be reversed without any work input.

e) Throttling : It is a totally irreversible process. Gas or vapour will expand

through a restricted passage with its pressure decreasing rapidly
without any work output. Such an expansion can not be reversed.

4.6 Externally and internally reversible processes

As mentioned earlier if no irreversibilities occur outside the system boundaries
during the process, it is known as externally reversible.
If no irreversibilities occur within the boundary of the system during a process, it
is known as internally reversible process. For such a process, the path of the reverse
process will follow exactly that of the forward process in any property diagram.
To be totally reversible or simply reversible both external and internal
reversibilities must be ensured.

4.7 The Carnot Cycle

In 1824, Nicholas Sadi Carnot proposed a classical ideal cycle consisting of four
processes. All processes are individually reversible and hence the cycle as a whole is a
reversible cycle. The processes that make up the Carnot cycle are :
Process 1-2
The working substance is taken in a piston cylinder arrangement as given in
Figure 4.8(a). Heat is added reversibly and isothermally from a high temperature
reservoir at TH. Since the process is to be reversible, the temperature T H of the reservoir
should be equal to or infinitesimally greater than that of the working substance.

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 Thermodynamics

Figure 4.8(a) Figure 4.8(b)

Process 2-3
The working substance is allowed to expand reversibly and adiabatically until its
temperature falls down to TL. The process is represented by Figure 4.8(b)

Process 3-4
Heat is rejected by the working substance to a low temperature reservoir kept T L
or at temperature infinitesimally smaller than TL.

Process 4-1
The working substance is then compressed reversibly and adiabatically until its
temperature becomes TH and the cycle continues.

The cycle has been represented in a p-V diagram in Figure 4.9. The included area
represents the net work done in the cycle. From first law of thermodynamics net
workdone is equal to net heat transfer in the cycle. Since Q H is the heat added to
system and QL is the heat rejected by the system, the neat heat transfer is Q H  QL.

Isothermal heat Adiabatic compression

addition
1 Isothermal heat
p
rejection
2

Adiabatic
MEMORY expansion
In-Line 4 9040640809,9437635541
INSTITUTION 3 Page 78

v
 Thermodynamics

Wnet
Efficiency of Carnot Engine =
Qin
QH  Q L

Qin

QL
= 1
Qin

Where
QL = 3W4 + U4  U3

Since the process is isothermal U4  U3

 QL  3W4
 p3 
 P3 V3 ln  
 p4 
 p3 
 mRTL ln  
 p4 
 p2 
Similarly QH  mRTH ln  
 p1 

Process 2-3 is reversible adiabatic

  1 
 
T2  p 2     TH
  
T3  p3  TL

Process 4-1 is also reversible adiabatic
  1 

 
 
 T1   p1  TH


T4  p 4  TL

From the above two expressions

p2 p
 1
p3 p4
p2 p
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 3
p1 p4
 Thermodynamics

Substituting the above condition we get

mRTL ln 3 
p
 Carnot  1
QL
 1  p4 
Qin mRTL ln p 2 
 p1 
T
1 L
TH
It shows that efficiency of carnot engine is purely a function of T H and TL.

Since the carnot cycle being completely reversible, if carried out in reverse
direction, the magnitudes of all energy transfers remain the same but their sign
change. This reversed carnot cycle can be applied for a refrigerator or a heat pump.
Figure 4.10 shows the p-V diagram of a reversed carnot cycle.

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