SECOND LAW OF THERMODYNAMICS

1
1.1 Introduction

 First law of thermodynamics deals with conservation and conversion of

energy. It stipulates that when a thermodynamic process is carried out, energy
is neither gained nor lost. Energy only transforms from one form into another
and the energy balance is maintained. The law, however, fails to state the
condition under which energy conversions are possible. The law presumes
that any change of a thermodynamic state can take place in either direction.
 However, this is not true; particularly in the inter-conversion of heat and
work. Processes proceed spontaneously in certain directions but not in
opposite directions, even though the reversal of processes does not violate the
first law.

1.2 Examples of First law

 It is common experience that a cup of hot coffee left in a cooler room eventually
cools off. This process satisfies the first law of thermodynamics since the
amount of energy lost by the coffee is equal to the amount gained by the
surrounding air. Now let us consider the reverse process—the hot coffee getting
even hotter in a cooler room as a result of heat transfer from the room air. We
all know that this process never takes place. Yet, doing so would not violate the
first law as long as the amount of energy lost by the air is equal to the amount
gained by the coffee.

Figure 1 coffee in a cold room

 As another familiar example, consider the heating of a room by the passage of

electric current through a resistor. Again, the first law says that the amount of
electric energy supplied to the resistance wires be equal to the amount of
energy transferred to the room air as heat. Now let us attempt to reverse this
process. It will come as no surprise that transferring some heat to the wires
does not cause an equivalent amount of electric energy to be generated in the
wires.

Figure 2 Transferring heat to a wire will not generate electricity

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 Consider a paddle-wheel mechanism that is operated by the fall of a mass.
The paddle wheel rotates as the mass falls and stirs a fluid within an
insulated container. As a result, the potential energy of the mass
decreases, and the internal energy of the fluid increases in
accordance with the conservation of energy principle. However, the
reverse process, raising the mass by transferring heat from the fluid to
the paddle wheel, does not occur in nature, although doing so
would not violate the first law of thermodynamics.

Figure 3 Transferring heat to a paddle wheel will not cause it to rotate

 Consider a running automobile vehicle stopped by applying brakes, and the

process changes the kinetic energy of the vehicle in to heat and the brakes get
heated up. Thus increase in internal energy of brakes in accordance with the
first law. Now cooling of brakes to their initial state never puts the vehicle in to
motion. Heat in the brake cannot convert to mechanical work even though that
would not violate the principle of energy conversion.
 When a block slides down a rough plane, it warmer. However, the
reverse process where the block slides up the plane and becomes
cooler is not true even though the first law will still hold good.
 Water flows from a higher level to a lower level, and reverse is not
automatically possible. A mechanical energy from an external source
would be required to pump the water back from the lower level to
higher level.
 Fuels (coals, diesel, and petrol) burns with air to form the products of
combustion. Fuels once burnt cannot be restored back to original from.
 When hydrogen and oxygen are kept in an isolated system, they produce
water on chemical reaction. But the water never dissociates into hydrogen and
oxygen again.
 It is clear from these above arguments that processes proceed in a certain
direction and not in the reverse direction.

Figure 4 Processes occur in a certain direction, and not in the reverse direction
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 A process cannot take place unless it satisfies both the first and second
laws of thermodynamics.

Figure 5 A processes must satisfy both the first and second laws of
thermodynamics

1.2.1 Limitations of First Law of Thermodynamics


 First law does not help to predict whether the certain process is possible or not.
 A spontaneous process can proceed in a particular direction only, but first law
does not give information about direction.
 First law not provides sufficient condition for a certain process to take place.
First law establishes equivalence between the amount of heat used and
mechanical work, but does not specify the conditions under which conversion of
heat into work is possible, neither the direction in which heat transfer can take
place.

1.3 Basic Definitions

1.3.1 Thermal Energy Reservoir

 It is defined as sufficiently large system in stable equilibrium that can supply or

absorb finite amount of heat without any change in its temperature.”
 A thermal reservoir is thus characterized by its temperature which remains
constant.
 In practice, large bodies of water such as oceans, lakes, rivers, and atmospheric air can
be considered thermal energy reservoirs.

Figure 6 Thermal energy reservoirs

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Heat Source

 It is defined as the thermal reservoir which is at high temperature and supplies

heat is called a heat source.” i.e. boiler furnace, combustion chamber etc.

Heat Sink

 It is defined as the thermal reservoir which is at low temperature and to which heat
is transferred is called heat sink”. i.e. atmospheric air, ocean, rivers etc.

Figure 7 Heat source and Heat sink

1.3.2 Heat Engine


 It is defined as thermodynamic device used for continuous production of work
from heat when operating in a cyclic process is called heat engine .

Characteristics of Heat Engine

 It receives heat from a high-temperature source at temperatureT1
(furnace, nuclear reactor, solar energy etc.)
 It converts the part of this heat to work (mostly in the form of a rotating shaft).

Figure 8 Heat engine

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 It rejects the remaining waste heat to a low-temperature sink (the atmosphere,
rivers etc.).
 It operates on complete thermodynamic cycle.

Thermal Efficiency

 It is defined as the ratio of the desired net work output to the required heat input is
called thermal efficiency.”

 Thus thermal efficiency of a heat engine can be expressed as,

1.3.3 Refrigerator

 It is defined as the mechanical device that used for the transfer of heat from a
low-temperature medium to a high-temperature medium is called refrigerator.”
 The objective of a refrigerator is to maintain the refrigerated space at a
low temperature by absorbing heat from it and reject to higher-temperature
medium.

Figure 9 Refrigerator

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Coefficient of Performance of Refrigerator

 The COP of a refrigerator can be expressed as the ratio of refrigerating effect to
the work input.

 Mathematically,

1.3.4 Heat Pump


 It is defined as the mechanical device that transfers heat from a low-
temperature medium to a high-temperature is called heat pump.
The objective of heat pump is to maintain a heated space at a high temperature.
This is accomplished by absorbing heat from a low-temperature source and
reject to higher temperature source.

Coefficient of Performance of Heat Pump

The COP of a heat pump can be expressed as the ratio of heating effect to the
work input”.
 Mathematically,

Figure 10 Heat pump

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 The conservation of energy principle for a cyclic device requires that,

1.3.5 Perpetual-Motion Machines (PMM)


 It is defined as the device that violates either law (first or second) is
called a perpetual- motion machine.”

 PMM1 “A device that violates the first law of thermodynamics is called a
perpetual- motion machine of the first kind (PMM1).”

 PMM2 “A device that violates the second law of thermodynamics is called a
perpetual-motion machine of the second kind (PMM2).”

Figure 11 Perpetual motion machine of the second kind

 In above equation, if Q2 0 , then Wnet  Q1 and th 100%. That is, if the
engine exchanges heat only with one thermal reservoir, then the entire heat
supplied to it gets converted into an equivalent amount of work and the efficiency
becomes 100%. Such a heat engine is called a PMM2. The PMM2 is follow first law,
but it violates the Kelvin - Planck statement of second law.

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1.4 The Statements of Second Law of Thermodynamics

1.4.1 Kelvin–Planck Statement


 It is impossible to construct a device that operates in thermodynamic cycle
produce no effect other than work output and exchange heat with a single
reservoir.

(a) Impossible (b) Possible

Figure 12 Schematic representation of heat engine accordance with Kelvin–Planck

statement

1.4.2 Clausius Statement


 It is impossible to construct a device that operates in a cycle and produces no
effect other than the transfer of heat from a lower-temperature reservoir
to a higher- temperature reservoir.
OR
 It is impossible for any system to operate in such a way that the sole result would
be an energy transfer by heat from a cooler to a hotter body.

(a) Impossible (b) Possible

Figure 13 Schematic representation of refrigerator accordance with the Clausius statement

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1.4.3 Equivalency of the Two Statements

(a) Violation of Clausius statement leading to violation of Kelvin-Planck statement.


 As shown in Fig. (14) a refrigerator R that operates in a cycle and transfers QL
amount of heat from low temperature reservoir at TL to a high temperature
reservoir at TH without any work input. This is in violation of the Clausius statement.

Figure 14 Proof of the violation of the Clausius statement leads to the violation of
the Kelvin–Planck statement

 Along with this heat engine H.E , that also operates in a cycle, takes QH amount
of heat from the high temperature reservoir, delivers QH QL amount of
work to the surroundings and rejects the remaining QL amount of heat to the
low temperature reservoir.

 As shown in Fig.(14) the composite system constitutes a device that receives
QH QL amount of heat from the high temperature reservoir and converts it
completely into an equivalent amount of work W  QH QL without
rejecting any heat to the low temperature reservoir. This is violation of the
Kelvin-Planck statement.

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 (b) Violation of Kelvin-Planck statement leading to violation of Clausius statement.

 As shown in Fig. (15) an engine H.E which operates from a single heat
reservoir at temperature TH . It receives QH amount of heat from this
reservoir and converts it completely into an equivalent amount of work W  QH
without rejecting any heat to the low temperature reservoir at T2 . This is violation
of the Kelvin-Planck statement.
 Along with this the refrigerator R which extracts QL amount of heat from the
low temperature reservoir, is supplied with QL amount of work from an external
agency (surroundings) and supplies QH  QL units of heat to the high temperature
reservoir.
 As shown in Fig. ( 15) the work and heat interactions for the refrigerator and heat
engine when coupled together. The output of the engine is utilized to drive the
refrigerator.

Figure 15 Proof of the violation of the Kelvin–Planck statement leads to the violation of the
Clausius statement

This composite system constitutes a device which transfers heat from the
low temperature reservoir to the high temperature reservoir without any work input.
This is in violation of the Clausius statement. Thus violation of Kelvin-Planck
statement leads to violation of Clausius statement also.
Therefore, the Clausius and the Kelvin–Planck statements are two
equivalent expressions of the second law of thermodynamics.

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1.5 Reversible and Irreversible Process
1.5.1 Reversible Process

 Definition: “ A reversible process is defined as a process that can be reversed
without leaving any trace on the surroundings and both the system and the
surroundings are restored to their respective initial states by reversing the
direction of the process ”.

Conditions of Reversible Process


 The process must proceed in a series of equilibrium states.
 Heat transfer should not take place with finite temperature difference.
 The process should be quasi-static and it should proceed at infinitely slow speed.
The process should not involve friction of any kind (mechanical and intermolecular)

Figure 16 Reversible processes deliver the most and consume the least work

 Reversible processes can be viewed as theoretical limits for the

corresponding irreversible ones.
 The more closely we approximate a reversible process, the more work delivered
by a work-producing device or the less work required by a work-consuming
device.

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 It leads to the definition of the second law efficiency for actual processes, which is
the degree of approximation to the corresponding reversible processes. This
enables us to compare the performance of different devices that are designed to
do the same task on the basis of their efficiencies.
 It is idealized process actually do not occur in nature.
 There should be no free or unrestricted expansion and no mixing of the fluids.
 Work done during reversible process is represented by area under process curve
on p-v diagram.

1.5.2 Irreversible Process

 Definition: “ An irreversible process is defined as a process that can be

reversed with permanent leaving any trace on the surroundings and both
the system and the surroundings are not restored to their respective initial
states by reversing the direction of the process ”.

 These processes that occurred in a certain direction, once having taken place,
these processes cannot reverse themselves spontaneously and restore the system
to its initial state.
 For example, once a cup of hot coffee cools, it will not heat up by retrieving the
heat it lost from the surroundings. If it could, the surroundings, as well as the
system (coffee), would be restored to their original condition, and this would be a
reversible process.
 It should be pointed out that a system can be restored to its initial state
following a process, regardless of whether the process is reversible or
irreversible. But for reversible processes, this restoration is made without
leaving any net change on the surroundings, whereas for irreversible
processes, the surroundings usually do some work on the system and therefore
does not return to their original state.

1.5.3 Irreversibilities

 Definition: “ It is defined as the factors that cause a process to be irreversible are
called irreversibilities.”

(A) Causes of Irreversibilities


They include friction, unrestrained expansion, mixing of two fluids, and heat
transfer across a finite temperature difference, electric resistance, inelastic
deformation of solids, and chemical reactions. The presence of any of these effects
renders a process irreversible. A reversible process involves none of these.
Some of the frequently encountered irreversibilities are discussed briefly below.

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1. Friction:
 When two bodies in contact are forced to move relative to each other (a piston
in a cylinder, for example, as shown in Fig. a friction force that opposes the
motion develops at the interface of these two bodies, and 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, as evidenced by
a temperature rise at the interface.

Figure 17 Friction renders a process irreversible

 When the direction of the motion is reversed, the bodies are restored to their
original position, but the interface does not cool, and heat is not converted
back to work. Instead, more of the work is converted to heat while overcoming
the friction forces that also oppose the reverse motion. Since the system
(the moving bodies) and the surroundings cannot be returned to their
original states, this process is irreversible. Therefore, any process that involves
friction is irreversible.

2. Unrestrained expansion.

 Unrestrained expansion of a gas separated from a vacuum by a membrane, as

shown in Fig. When the membrane is ruptured, the gas fills the entire tank.
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 until it reaches its
initial temperature. From the conservation of energy considerations, it can
easily be shown that the amount of heat transferred from the gas equals the
amount of work done on the gas by the surroundings.

Figure 18 Unrestrained expansion of a gas makes the process Irreversible

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 The restoration of the surroundings involves conversion of this heat
completely to work, which would violate the second law. Therefore, unrestrained
expansion of a gas is an irreversible process.

3. Heat transfer through a finite temperature difference:

Figure 19 (a) Heat transfer through a temperature difference is irreversible, and

(b) the reverse process is impossible

 Consider a can of cold soda left in a warm room Fig. Heat is transferred from
the warmer room air to the cooler soda. The only way this process can be reversed
and the soda restored to its original temperature is to provide refrigeration,
which requires some work input. At the end of the reverse process, the soda
will be restored to its initial state, but the surroundings will not be. The internal
energy of the surroundings will increase by an amount equal in magnitude to the
work supplied to the refrigerator. The restoration of the surroundings to the initial
state can be done only by converting this excess internal energy completely to
work, which is impossible to do without violating the second law.
 Since only the system, not both the system and the surroundings, can be restored
to its initial condition, heat transfer through a finite temperature difference is an
irreversible process.

(B) Types of Irreversibilities

 Internally Irreversibilities: These are associated with dissipative effects within

working fluid itself.
 Externally Irreversibilities: These are associated with dissipative effects outside
the working fluid or boundaries of the system. i.e. Mechanical friction
occurring during process.

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Figure 20 A reversible processes involves no internal and external irreversibilities (Totally reversible)

 As shown in Fig. Both processes are internally reversible, since both take
place isothermally and both pass through exactly the same equilibrium states.
 The first process shown is externally reversible also, since heat transfer for this
process takes place through an infinitesimal temperature difference dT. The
second process, however, is externally irreversible, since it involves heat
transfer through a finite temperature difference dT.

Figure 21 Totally and internally reversible heat transfer processes

 Mechanical Irreversibilities: These are associated with fluid friction

(intermolecular friction) between the molecules and mechanical friction
between the molecules and mechanical parts and friction between molecules and
atmosphere.
 Thermal Irreversibilities: These are associated with energy transfer as heat due
to a finite temperature difference between parts of system or between
system and its environment.

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1.6 The Carnot Cycle (Carnot Heat engine)

Assumptions for Carnot cycle

1. The piston moving in a cylinder does not develop any friction during motion.
2. The walls of piston and cylinder are considered as perfect insulators of heat.
3. The cylinder head is so arranged that it can be a perfect heat conductor or perfect
Heat insulator.
4. The transfer of heat does not affect the temperature of source or sink.
5. Working medium is a perfect gas and has constant specific heat.
6. Compression and expansion are reversible.
 The Carnot cycle is composed of four reversible processes—two isothermal and
two adiabatic. Consider a closed system that consists of a gas contained in an
adiabatic piston–cylinder device, as shown in Fig. the insulation of the cylinder
head is such that it may be removed to bring the cylinder into contact with
reservoirs to provide heat transfer.

Figure 22 Carnot Cycle


 Reversible Isothermal Expansion ( process 1-2, TH  constant): In this process,
high temperature energy source is put contact with cylinder cover and QH amount
heat is supplied while the gas expands isothermally at temperature TH . The
amount of heat transferred to the gas during this process is given by,

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 Reversible Adiabatic Expansion (process 2-3 adiabatic process Q=0 ): In this
process the adiabatic cover is put contact on the cylinder head, and the gas
is expanded adiabatically, thus the temperature decreases from TH to TL .
 Reversible Isothermal Compression (process 3-4, T  constant): In this
L

process, low temperature energy sink is put contact with cylinder head cover and
QL amount of heat is rejected while the gas compressed isothermally at
temperature TL The amount of total heat transferred from the gas during this
process is given by,


 Reversible Adiabatic Compression (process 4-1 adiabatic process Q=0 ): In this
process the adiabatic cover is put contact on the cylinder head, and the gas
is compressed adiabatically, thus temperature increases from TL to TH and
returns to its initial state 1 to complete the cycle.

 Thermal efficiency of Carnot cycle is given by,





 As there is not heat interaction along the reversible adiabatic processes 2-3
and 4-1, and application of first law of thermodynamics for the complete cycle
gives,



 Substituting the values of Wnet. in above equation we get

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For the adiabatic expansion and compression process 2-3 and 4-1,

 Substitute the values in above equation, we get,

Conclusions from Carnot heat engine are:

1. The efficiency is independent of the working fluid and depends upon the
temperature of source and sink. Being a reversible cycle, the Carnot cycle is the
most efficient cycle operating between two specified temperature limits.
2. If TL 0, the engine will have an efficiency of 100%. However that means
absence of heat sink which is violation of Kelvin-Plank statement of the second
law.
3. The efficiency is directly proportional with the Temperature difference
TH TL between the source and sink. Thermal efficiency increases with an
increase in the average temperature at which heat is supplied to the system or
with a decrease in the average temperature at which heat is rejected from the
system. If TH  TL , no work will be done and efficiency will be zero.

 Even though the Carnot cycle cannot be achieved in reality, the efficiency of
actual cycles can be improved by attempting to approximate the Carnot cycle
more closely.

The Carnot cycle is impracticable because of the following reasons:


 All the four processes have to be reversible. This necessitates that working fluid
must have no internal friction between the fluid particle and no mechanical
friction between the piston and cylinder wall. It is impossible to perform a
frictionless process.
 The heat absorption and rejection take place with infinitesimal temperature

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 difference. Accordingly the rate of energy transfer will be very low and the engine
will deliver only infinitesimal power. It is impossible to transfer the heat without
temperature potential.

 Isothermal process can be achieved only if the piston moves very slowly to allow
heat transfer so that the temperature remains constant. Also Reversible
isothermal heat transfer is very difficult to achieve in reality because it would
require very large heat exchangers and it would take a very long time (a
power cycle in a typical engine is completed in a fraction of a second).
Therefore, it is not practical to build an engine that would operate on a cycle
that closely approximates the Carnot cycle.

 Adiabatic process can be achieved only if the piston moves as fast as possible so
that the heat transfer is negligible due to very short time available. The
isothermal and adiabatic processes take place during the same stroke therefore
the piston has to move very slowly for part of the stroke and it has to move very
fast during remaining stroke. This variation of motion of the piston during the
same stroke is not possible.

 The source and sink temperatures that can be used in practice are not without
limits, however. The highest temperature in the cycle is limited by the maximum
temperature that the components of the heat engine, such as the piston or the
turbine blades, can withstand. The lowest temperature is limited by the
temperature of the cooling medium utilized in the cycle such as a lake, a river,
or the atmospheric air.

 There is insignificant difference in the slopes of isothermal and adiabatic
lines. Consequently the p-v plot is greatly extended both in horizontal and vertical
directions. The cylinder involves great pressure and volumes, and thus becomes
bulky and heavy.

1.7 The Reversed Carnot Cycle (Carnot Refrigerator or Carnot heat pump) 

 The Carnot heat-engine cycle just described is a totally reversible cycle.
Therefore, all the processes that comprise it can be reversed, in which case it
becomes the Carnot refrigeration cycle. Refrigerator and heat pump are reversed
heat engines.
 This time, the cycle remains exactly the same, except that the directions of any
heat and work interactions are reversed: Heat in the amount of QL is
absorbed from the low-temperature reservoir, heat in the amount of QH is

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 rejected to a high-temperature reservoir, and a work input of Wnet,in is required to
accomplish all this. The P-V diagram of the reversed Carnot cycle is the same as
the one given for the Carnot cycle, except that the directions of the processes are
reversed, as shown in Fig.
 Process 1-2: adiabatic expansion of the working fluid in the clearance space of
the cylinder. The temperature falls from TH to TL .
 Process 2-3: Isothermal expansion during which heat QL is a bsorbed at
temperature TL from the space being cooled.
 Process 3-4: Adiabatic compression of working fluid. The temperature rises from
TL to TH .
 Process 4-1: Isothermal compression of working fluid during which heat QH is
rejected to a high-temperature reservoir.

Figure 23 P-V diagram of the reversed Carnot cycle

 By using equations outlines in Carnot heat engine,


 For Carnot heat pump,

Q H = Q1 & Q L = Q 2
W= Q1 - Q2



 For Carnot refrigerator,

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1.8 The Carnot Theorem and Carnot Corollaries

1.8.1 Carnot Theorem and Its Proof

 “ The efficiency of an irreversible heat engine is always less than the
efficiency of a reversible one operating between the same two reservoirs.”
 Thus if A(rev) B(irev)

Proof of Carnot Theorem

 Consider a reversible engine EA and an irreversible engine EB operating between
the same thermal reservoirs at temperatures T1 and T2 as shown in Fig. For
the same quantity of heat Q withdrawn from the high temperature source,
the work output from these engines is WA and WB respectively. As such the heat
rejected is given by the reversible engine EA is Q  WA and that from irreversible
engine is Q  WB .

Figure 24 The proof of Carnot theorem

 Let us assume that B (irev) A (rev) ; WB  WA ; Q WB  Q  WA (violation of

Carnot theorem). Thus if irreversible engine EB delivered WB  WA more amount
of work than the first reversible engine EA and WA is utilized to run reversible
refrigerator RA by reversing the reversible engine EA then composite system as
shown in Fig. is an engine that produces a net amount of work while
exchanging heat with a single reservoir which is the violation of Kelvin-Plank
statement (PMM-2).
 Therefore, we conclude that no irreversible heat engine can be more efficient
than a reversible one operating between the same two reservoirs, thus our
assumption B (irev) A (rev) is wrong, because A (rev) B (irev) is only true to
satisfy Carnot theorem.

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1.9 Thermodynamic Temperature Scale

 Definition: “A temperature scale that is independent of the properties
of the thermometric substance that are used to measure
temperature is called a thermodynamic temperature scale.”
 A thermodynamic temperature scale is established based on fact that the
thermal efficiency of reversible heat engines is a function of the reservoir
temperatures only. That is,
th,rev  (t1,t2 )
 Where  signify the form of function that connects the temperature with
temperature scale and it independent of the properties of the working fluid. The
nature of  need to be determine to give thermodynamic temperature scale.
 Consider two reversible engines E1 is supplied with Q1 amount of heat from
the high temperature reservoir at t1 and rejects Q2 amount of heat at low
temperature reservoir t2 which is directly receives by reversible heat engine E2
which further rejects Q3 to the low temperature reservoir at t3 as shown in Fig.

Figure 25 Thermodynamics temperature scale

 The amounts of heat rejected by engines E1 and E2 must be the same since
engines E1 and E2 and can be combined into one reversible engine operating
between the same reservoirs as engine E3 and thus the combined engine
will have the same efficiency as engine E3 . Thus we can write for each
reversible engine,






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 Thus we can write for combine reversible engine,


 Thus we can write,


 Now consider the identity,

 Above equation reveals that the left-hand side is a function of t1 and t2 , and
therefore the right-hand side must also be a function of t1 and t2 only. That
is, the value of the product on the right-hand side of this equation is
independent of the value of t2 . This condition will be satisfied only if the
function f has the following form:


 Where  is another function of t . The choice of function depends upon
chosen scale of temperature and has infinite variety of forms. If the single
form is selected it may written as,



 This temperature scale is called the Kelvin scale, and the temperatures on this scale
are called absolute temperatures. On the Kelvin scale, the temperature ratios
depend on the ratios of heat transfer between a reversible heat engine and
the reservoirs and are independent of the physical properties of any substance.

24