Chapter 7

Chapter 7: The Second Law of
Thermodynamics
Thermodynamics 1
Introduction and basis for Second law
 In Chaps. 5 & 6, the first law for processes
involving closed and open systems are based on
the conservation of energy principle.
 Energy is a conserved property.
 A process must satisfy the 1st law to occur.
 But satisfying the 1st law does not mean that the
process will actually occur.
 1st law places no restriction on the direction.
Thermodynamics – Chapter 7 2
 A hot cup of coffee cools by virtue of heat
transfer to the surrounding.
 The heat from the colder surrounding cannot
flow in the cup and make the coffee hot again
automatically.
This process satisfies the first

law of thermodynamics since
the energy lost by the coffee
is equal to the amount gained
by the surrounding air.
 Gasoline is used as a car drives up a hill, but the
fuel level in the gasoline tank cannot be restored
to its original level when the car coasts down
the hill.
 The heating of a room by the passage of electric
current through the resistor.
 The first law dictates the amount of electric
energy supplied to the resistance wires be equal to
the amount of energy transferred to the room air
as heat.
 Transferring heat to a wire will not generate
electricity.
 The paddle wheel rotates as the mass falls and
stirs a fluid within an insulated container.
 The reverse process, raising the mass by
transferring heat from the fluid to the paddle
wheel, does not occur in nature.
 From these examples, it is clear that processes
proceed in a certain direction and not in the
reverse direction.
 The first law places no restriction on the

direction of a process.
 Satisfying the first law does not ensure that the
process can actually occur.
 This inadequacy of the first law to identify
whether a process can take place is remedied by
the second law of thermodynamics.
 The reverse process discussed above violate the
second law of thermodynamics.
 Violation of the 2nd law is detected using a
property called entropy.
 A process cannot occur unless it satisfy the 1st
and 2nd law of thermodynamics.
Use of Second Law of Thermodynamics
 Identifying the direction of the process.
 It also asserts that energy has quality as well as
quantity. The first law is concerned with quantity
of energy and the transformations of energy
from one form to another with no regard to its
quality.
 It is also used to determine the theoretical limits
for performance of various engineering systems
as well as predicting the degree of completion of
various chemical reactions.
Thermal Reservoir (Heat reservoir)
A hypothetical body with a
 Large thermal capacity (mass × specific heat)
 It can supply or absorb finite amounts of heat
without undergoing any change in temperature
Such a body is called a thermal energy reservoir.
A heat reservoir is always characterised by its

temperature.
Examples
 Oceans
 Lakes
 Rivers
 Atmosphere
In practice, large bodies of water such as oceans,

lakes, and rivers as well as the atmospheric air can
be thermal reservoir because of their large thermal
energy storage capabilities or thermal masses.
 A two-phase system:
It can absorb and release large quantities of heat
while remaining at constant temperature.
 Industrial furnace:
Capable of supplying large quantities of thermal
energy as heat in an isothermal manner.
 A body does not actually have to be very large to
be considered a thermal reservoir.
 Any physical body whose thermal energy
capacity is large relative to the amount of energy
it supplies or absorb can be modeled as one.
 Example match stick lit in a room
 The air in the room, in the analysis of the
heat dissipation from a TV set in the room.
 A reservoir that supplies energy in the form of
heat is called a source.
 One that absorbs energy in the form of heat is
called a sink.
Conventions used
Heat supplied by the source → QH
Heat absorbed by the sink → QL
Heat Engines
The work can easily be converted to other forms of
energy, but converting other forms of energy to
work is not that easy.
The work can be converted to heat directly and

completely, but converting heat to work requires the
use of special devices, known as heat engines.
Let the gas in the cylinder constitute the system.
A simple heat engine

The substance to which and from which heat is
transferred is called the working substance or
working fluid.
Definition of Heat Engine
Heat engine is defined as a

device that operates in a
thermodynamic cycle and does
certain amount of net positive
work through heat transfer
from high-temperature body to
low-temperature body.
Characterization of Heat Engines
Heat engines differ considerably from one another,
but all can be characterized by the following
 They receive heat from a high-temperature
source (solar energy, oil furnace, nuclear reactor,
etc.).
 They convert part of this heat to work (usually
in the form of a rotating shaft).
 They reject the remaining waste heat to a low-
temperature sink (the atmosphere, rivers, etc.).
 They operate on a cycle.
 The term heat engine is often used in a border
sense to include all work producing devices that
does not operate in a thermodynamic cycle.
 Eg., Gas turbines and car engines.
 These devices operate in a mechanical cycle
but not in a thermodynamic cycle since the
working fluid does not undergo a complete
cycle.
 In this chapter, we restrict ourselves to heat
engine which operate on a thermodynamic cycle.
Starting position, intake stroke, and compression stroke.
Ignition of fuel, power stroke, and exhaust stroke.

Heat Engine- Steam Power Plant
This is an external combustion engine and the
thermal energy released during this process is
transferred to the steam as heat.
Thermal Efficiency of Heat Engine
Qin = amount of heat supplied to steam in boiler
from a high-temperature source (furnace).
Qout = amount of heat rejected from steam in

condenser to a low- temperature sink (the
atmosphere, a river, etc.).
Wout = amount of work delivered by steam as it

expands in turbine.
Win = amount of work required to compress water to

boiler pressure.
The net out put  Wnet ,out  Wout  Win
Recall that for a closed system undergoing a cycle,
the change in internal energy U is zero, and
therefore the net work output of the system is also
equal to the net heat transfer to the system:
 dW   dQ
Wout  Win  Qin  Qout
The net out put  Wnet ,out  Qin  Qout
Qout represents the magnitude of the energy
wasted in order to complete the cycle. But Qout is
never zero; That is, only part of the heat transferred
to the heat engine is converted to work. Therefore
the thermal efficiency of a heat engine is defined as
Net work output

Thermal efficiency =
Total heat input
Wnet ,out Qin - Qout Qout
th    1-
Qin Qin Qin
The heat engines operate between a high-
temperature medium (or reservoir) at temperature
TH and a low-temperature medium (or reservoir) at
temperature TL.
QH = magnitude of heat transfer between the

cyclic device and the high- temperature
medium at temperature TH.
QL = magnitude of heat transfer between the
cyclic device and the low- temperature medium
at temperature TL.
Wnet ,out
th 
QH
QH  QL
th 
QH
QL
th  1 
QH
Thermal efficiency is a
measure of how efficiently
a heat engine converts the
heat that it receives to
work.
Device /system Thermal efficiency
Power plants 35-50%

Gas-steam power plant 60%
Gasoline engines 25%
Diesel engines 40%
Smaller utility type 20%
engines
Can we save QL
In a steam power plant, the condenser is the device
where large quantities of waste heat is rejected to
rivers, lakes, or the atmosphere. Then one may ask,
can we not just take the condenser out of the plant
and save all that waste energy?
The answer to this question is, unfortunately, a

firm no.
This can be justified by the following example
Every heat engine must waste some energy by
transferring it to a low-temperature reservoir in
order to complete the cycle, even under idealized
conditions.
Second Law of Thermodynamics :
Kelvin-Planck Statement
It is impossible to construct a device that will
operate in a cycle and produce no effect other than
the raising of weight and exchange of heat with a
single reservoir.
or
It is impossible for any device that operates on a
cycle to receive heat from a single reservoir and
produce a net amount of work.
A heat engine must
exchange heat with a
low-temperature sink
as well as a high-
temperature source to
keep operating.
The Kelvin–Planck statement can also be

expressed as no heat engine can have a
thermal efficiency of 100 percent.
(Q) Heat is transferred to a heat engine
from a furnace at a rate of 80 MW.
If the rate of waste heat rejection to
a nearby river is 50 MW, determine
the net power output and the thermal
efficiency for this heat engine.
QH  80 MW and QL  50 MW
The net power out of this engine is

Wnet ,out  QH  QL
 80 - 50  MW  30 MW
Then the thermal efficiency is
Wnet ,out 30 MW
th    0.375  37.5%
QH 80 MW
Discussion: The heat engine converts 37.5
percent of the heat it receives to work.
(Q) A car engine with a power output of
50 kW has a thermal efficiency of
24 percent. Determine the fuel
consumption rate of this car if the
fuel has a heating value of 44,000
kJ/kg (that is, 44,000 kJ of energy is
released for each kg of fuel burned).
The amount of energy imput 
Wnet ,out 50 kW
QH    208.3 kW
th 0.24
To supply energy at this rate, the 50 kW
engine must burn fuel at a rate of
QH 208.3 kW
m   0.00473 kg/s
qH 44,000 kJ/kg
Discussion: The thermal efficiency of the car
could be doubled, the rate of fuel consumption
would be reduced by half.
Refrigerators
 Heat transfer from high to low temperature
reservoir occur without requiring any device.
 The reverse process requires a special devices
called Refrigerators.
 Refrigerators, like heat engines, are cyclic
devices.
 The working fluid used in the refrigeration cycle
is called a refrigerant.
 Most frequently used refrigeration cycle is
vapor-compression cycle.
Objective : To
maintain the
refrigerated
space at a low
temperature
by removing
heat from it.
Basic components of a
refrigeration system
QL is the magnitude of
the heat removed from the
refrigerated space at
temperature TL.
QH is the magnitude of
the heat rejected to the
warm environment at
temperature TH.
Wnet,in is the net work

input to the refrigerator.
Coefficient of Performance (COP)
The efficiency of refrigerator expressed in terms of
Coefficient of Performance (COP). The objective
of a refrigerator is to remove heat (QL) from the
refrigerated space. To accomplish this objective, it
requires a work input of Wnet ,in
Desired output QL
COPR  REF  = 
Required input Wnet ,in
The conservation of energy principle for a cyclic

device requires that Wnet,in  QH  QL
QL QL 1
COPR   
Wnet ,in QH - QL QH  1
QL
 COPR can be greater than unity. That is, the

amount of heat removed from refrigerated space
can be greater than the amount of work input.
 This is contrast to the thermal efficiency, which
can never be greater than 1.
 To avoid the oddity of having efficiencies
greater than unity, another term COP is used .
 COP of a refrigerator decreases with decreasing
refrigeration temperature. Therefore, it is not
economical to refrigerate more than needed.
Item to be refrigerated COPR

Cutting preparation rooms 2.6-3.0
Meat, Deli, Dairy, produce 2.3-2.6
Frozen food 1.2-1.5
Ice cream units 1.0-1.2
Fridge Deep freezer
Heat Pumps
 Is a device that transfer heat from a low-
temperature medium to a high-temperature one.
 The objective of a heat pump is to maintain a
heated space at a high temperature.
 This is accomplished by absorbing heat from a
low-temperature source, such as well water or
cold outside air in winter, and supplying this
heat to the high-temperature medium such as a
house.
Schematic diagram of
a heat pump
Refrigerator Heat pump
1. Maintaining 1. Maintaining heated
refrigerated space space at a high
at low temperature. temperature.
2. Discharging heat to 2. Extracting heat
high temperature from a low
medium is a temperature space
necessary part of is a necessary part
operation. of operation.
The measure of performance of a heat pump is also
expressed in terms of the coefficient of
performance COPHP.
Desired output QH
COPHP  
Required input Wnet ,in
QH 1
COPHP  
QH - QL 1  QL
QH
A comparison of COPR and COPHP for fixed values
of QH and QL reveals that
COPHP  COPR 1
 COPHP is always greater than 1 since COPR is a
positive quantity.
 Worst condition it works as resistance heater,
supplying as much energy to the house as it
consumes.
 It may go below 1, if outside air temperature is
too low.
 Most of the heat pumps available in market are
having COP of 2 to 3.
 Air-source heat pumps and geothermal heat
pumps.
Geothermal Heat Pump
Air-Source Heat Pump

(Q) The food compartment of a refrigerator is
maintained at 4°C by removing heat from it at a rate
of 360 kJ/min. If the required power input to the
refrigerator is 2kW, determine (a) the coefficient
of performance of the refrigerator and (b) the rate
of heat rejection to the room that houses the
refrigerator.
(a) The coefficient of performance of the
refrigerator is
QL 360 kJ/min  1 kW 
COPR    3
Wnet ,in 2 kW  60 kJ/min 
That is, 3 kJ of heat is removed from the
refrigerated space for each kJ of work supplied.
(b) The rate at which heat is rejected to the room is
QH  QL  Wnet ,in
 60 kJ/min 
 360 kJ/min+  2 kW     480 kJ/min
 1 kW 
Discussion: Notice that both
the energy removed from the
refrigerated space as heat and
the energy supplied to the
refrigerator as electrical work
eventually show up in the
room air and become part of
the internal energy of the air.
This demonstrates that energy
can change from one form to
another, can move from one
place to another, but is never
destroyed during a process.
(Q) A heat pump is used to meet the heating
requirements of a house and maintain it at 20°C. On
a day when the outdoor air temperature drops to
2°C, the house is estimated to lose heat at a rate of
80,000 kJ/h. If the heat pump under these
conditions has a COP of 2.5, determine (a) the
power consumed by the heat pump and (b) the rate
at which heat is absorbed from the cold outdoor air.
(a) The power consumed by heat pump is
determined from the COP
QH 80,000 kJ/h
Wnet ,in    32,000 kJ/h
COPR 2.5
(b) The house is losing heat at a rate of 80,000
kJ/h. If the house is to be maintained at a
constant temperature of 20°C, the heat pump
must deliver heat to the house at the same
rate, that is, at a rate of 80,000 kJ/h. Then the
rate of heat transfer from the outdoor becomes
QL  QH  Wnet ,in  80,000  32,000 kJ/h = 48,000 kJ/h
Discussion: Note that 48,000
of the 80,000 kJ/h heat
delivered to the house is
actually extracted from the cold
outdoor air. Therefore, we are
paying only for the 32,000-kJ/h
energy that is supplied as
electrical work to the heat
pump. If an electric resistance
heater were used instead, we
would have to supply the
entire 80,000 kJ/h to the
resistance heater as electric
energy.
Second Law of Thermodynamics :
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 cooler body to a hotter body.
It does not imply that a cyclic device that

transfers heat from a cold medium to a warmer
one is impossible to construct. It simply states that a
refrigerator cannot operate unless its compressor is
driven by an external power source, such as an
electric motor.
The Clausius statement An impossible refrigerator
 Both the Kelvin–Planck and the Clausius
statements of the second law are negative
statements, and a negative statement cannot
be proved.
 Like any other physical law, the second law of
thermodynamics is based on experimental
observations.
 Till date, no experiment has been conducted that
contradicts the second law, and this should be
taken as sufficient proof of its validity.
Equivalence of the Two Statements
 The Kelvin–Planck and the Clausius statements
are equivalent in their consequences.
 Either statement can be used as the expression of
the second law of thermodynamics.
 Any device that violates the Kelvin–Planck
statement also violates the Clausius statement,
and vice versa.
Proof that the violation of the Kelvin-Planck
statement leads to the violation of Clausius statement
Proof that the violation of the Clausius statement
leads to the violation of Kelvin-Planck statement
Perpetual-Motion Machines (PMM)
 A process cannot take place unless it satisfies both
the first and second law of thermodynamics. Any
device that violates either law is called a
perpetual-motion machine.
 A perpetual-motion machine of the first kind
(PMM1) would create work from nothing thus
violating the first law.
 A perpetual-motion machine of second kind
(PMM2) would extract heat from a source and
then convert this heat completely into other forms
of energy, thus violating the second law of
thermodynamics.
Consider the steam power plant as shown below.
A perpetual-motion machine of the first kind
Consider the steam power plant as shown below.
A perpetual-motion machine of second kind
Consider the power plant of a ship.
A perpetual-motion machine of the second kind

Thus, we have a PPM in the sense that work is done
by utilizing freely available sources of energy as the
ocean or atmosphere.
Reversible and Irreversible processes
 The second law states that no heat engine can

have an efficiency of 100 percent.
 What is the highest efficiency that a heat engine
can possibly have?
 Before we can answer this question, we need to
define an idealized process first, which is called
the reversible process.
 A reversible process is defined as a process that
can be reversed without leaving any trace on the
surroundings.
 That is, both the system and the
surroundings are returned to their initial
states at the end of the reverse process.
 This is possible only if the net heat and net
work exchange between the system and the
surroundings is zero for the combined
(original and reverse) process.
 Processes that are not reversible are called
irreversible processes.
 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.
An example of an irreversible process
The initial process is an irreversible process one

because it could not be reversed without leaving a
change in the surroundings.
An example of a process that approaches being reversible
As the weights become very small, the reverse

process can be accomplished is such a manner that
both the system and surroundings are in exactly the
same state they are initially.
Irreversibilities
The factors that cause a process to be irreversible
are called irreversibilities. They are
Friction
Unrestrained expansion of gases
Heat transfer through a finite temperature difference
Mixing of two different substances
Hysteresis effects
I2R losses in electrical circuits
Any deviation from a quasi-static process
The presence of any of these effects renders a
process irreversible. A reversible process involves
none of these.
Irreversibilities : Friction
A block and inclined plane make up a system

The surroundings are not restored to their initial
state at the end of the reserve process, we conclude
that friction has rendered the process irreversible.
Irreversibilities : Unrestrained Expansion
The gas would have to be compressed and heat

transferred from the gas until its state is reached.
Since the work and heat transfer involve a change in
the surroundings, the surroundings are not restored
to their initial state. Therefore unrestrained
expansion is an irreversible process.
Irreversibilities : Heat Transfer through a
Finite Temperature Difference
The only way in which the system can be restored to

its initial state is by refrigeration, which requires
work from the surroundings, and some heat transfer
to the surroundings. Because of work and heat
transfer the surroundings are restored to their
original state.
Irreversibilities : Mixing of Two Different
Substances
A certain amount of work is necessary to separate

these gases. Thus, an air separation plant requires an
input of work to accomplish the separation. This
indicating that mixing of two different gases was an
irreversible process.
Internally and Externally Reversible
Processes
 A process is called internally reversible if
no irreversibilities occur within the boundaries
of the system during the process.
 During an internally reversible process, a
system proceeds through a series of
equilibrium states, and when the process is
reversed, the system passes through exactly
the same equilibrium states while returning
to its initial state.
 The quasi-equilibrium process is an example.
 A process is called externally reversible if no
irreversibilities occur out side the system
boundaries during the process.
 A process is called totally reversible, or simply
reversible, if it involves no irreversibilities
within the system or its surroundings.
 A totally reversible process involves no heat
transfer through a finite temperature
difference, no nonquasi-equilibrium
changes, and no friction or other
dissipative effects.
An example for totally and internally reversible heat
transfer process
 The transfer of heat to two identical system that

are undergoing a constant-pressure phase-change
process.
An example for totally and internally reversible heat
transfer process
 Both processes are internally reversible, since

both take place isothermally and both pass
exactly the same equilibrium states.
 The first process 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 ΔT.
Why to bother with fictitious (reversible)
process?
 First, they are easy to analyze, since a
system passes through a series of equilibrium
states during a reversible process;
 second, they serve as idealized models to which
actual processes can be compared.
 Engineers are interested in reversible
processes because work producing devices that
operate on reversible processes deliver the most
work, and work consuming devices that operate
on reversible processes consume the least work.
 When the compression process is non-
quasiequilibrium, the molecules before the
piston face cannot escape fast enough, forming
a high pressure region in front of the piston. It
takes more work to move the piston against this
high pressure region.
 When an expansion process is non-
quasiequilibrium, the molecules before the
piston face cannot follow the piston fast enough,
forming a low pressure region behind the piston.
The lower pressure that pushes the piston
produces less work.
The Carnot Cycle
 French military engineer Nicolas Sadi Carnot
(1769-1832) was among the first to study the
principles of the second law of
thermodynamics.
 Carnot was the first to introduce the concept
of cyclic operation and devised a reversible
cycle.
 Reversible cycles can be benchmarks for
actual cycles. And it can be limiting case for
both heat engine and refrigerator.
 Probably the best known reversible cycle
is the Carnot cycle, first proposed in 1824
by French engineer Sadi Carnot.
 The theoretical heat engine that operates on
the Carnot cycle is called the Carnot heat
engine.
 The Carnot cycle is composed of four
reversible processes — two isothermal and
two adiabatic and it can be executed either
in a closed or a steady-flow system.
Consider a closed system that consists of a gas
(not necessarily an ideal gas) contained in an
adiabatic piston–cylinder device. 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.
The four reversible processes that make up the

Carnot cycle are as follows:
Reversible Isothermal Expansion (Process 1-2)
Reversible Adiabatic Expansion (Process 2-3)
Reversible Isothermal Compression (Process 3-4)
Reversible Adiabatic Compression (Process 4-1)
The area under curve
1-2-3 is the work done by
the gas during the
expansion part of the
cycle.
The area under curve
3-4-1 is the work done on
the gas during the
compression part of the P – ν diagram of the Carnot
cycle. cycle
The area enclosed by the path of the cycle (area 1-2-3-

4-1) is the net work done during the cycle.
Four processes in a Carnot cycle
Being a reversible cycle, the Carnot cycle is the
most efficient cycle operating between two
specified temperature limits.
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 Reversed Carnot Cycle
The Carnot heat-
engine cycle is a
totally reversible
cycle. Therefore, all
the processes that
comprise it can be
reversed, when all the
process are reversed it
becomes the Carnot
refrigeration cycle. P – ν diagram of the reversed
Carnot cycle
A heat engine that operates on a Carnot cycle
A Refrigerator that operates on a Carnot cycle
The Carnot Principles (Corollaries)
Two conclusions pertain to the thermal efficiency
of reversible and irreversible heat engines, and
they are known as the Carnot principles.
 The efficiency of an irreversible heat engine is

always less than the efficiency of a reversible
one operating between the same two reservoirs.
 The efficiencies of all reversible heat engines

operating between the same two reservoirs are
the same.
The efficiency of an irreversible heat engine is
always less than the efficiency of a reversible one
operating between the same two reservoirs.
The efficiencies of all reversible heat engines
operating between the same two reservoirs are
the same.
These two statements can be proved by
demonstrating that the violation of either statement
results in the violation of the second law of
thermodynamics.

The Thermodynamic Temperature Scale
 The zeroth law of thermodynamics provides

basis for temperature measurement, but that a
temperature scale must be defined in terms of a
particular thermometer substance and device.
 A temperature scale that is independent of the
properties of the substances that are used to
measure temperature is called a thermodynamic
temperature scale.

 The second Carnot principle states that all
reversible heat engines have the same
thermal efficiency when operating between
the same two reservoirs.
 That is, the efficiency of a reversible engine
is independent of the working fluid
employed and its properties, the way the
cycle is executed, or the type of reversible
engine used.
 This fact provides the basis for a

thermodynamic temperature scale.
Since energy reservoirs are characterized by their
temperatures, the thermal efficiency of reversible
engines is a function of the reservoir temperatures
only, this is
QL
th  1   g (TH , TL ) --------- (7.1)
QH
or
QH
  (TH , TL ) --------- (7.2)
QL

Engines A and C are supplied
with the same amount of heat
Q1 from the high-
temperature reservoir at T1.
Engine C rejects Q3 to the
low-temperature reservoir at
T3. Engine B receives the
heat Q2 rejected by engine A
at temperature T2 and rejects
heat in the amount of Q3 to a
reservoir at T3.

Applying this functional relation (Eq. 7.2) to all
three engines separately, we obtain
Q1
  T1 , T2 
Q2
Q2
  T2 , T3  ,
Q3
Q1
and   T1 , T3 
Q3

Now consider the identity
Q1 Q1 Q2

Q3 Q2 Q3
which corresponds to
 (T1 ,T3 )  (T1,T2 )  (T2 ,T3 )
The left-hand side is a function of T1 and T3, and
therefore the right-hand side must also be a function
of T1 and T3 only, and not T2. 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
ψ has the following form
f (T1 ) f (T2 )
 (T1 , T2 )  and  (T2 , T3 ) 
f (T2 ) f (T3 )
So that f(T2) will cancel from the product of
ψ(T1,T2) and ψ(T2,T3), yielding
Q1 f (T1 )
  (T1 , T3 )  --------- (7.3)
Q3 f (T3 )

For a reversible heat
engine operating between
two reservoirs at
temperatures TH and TL,
can be written as
QH f (TH )
 --------- (7.4)
QL f (TL )
This is the only requirement that the second law

places on the ratio of heat transfers to and from the
reversible heat engines.
Several functions f(T) satisfy this equation, and the
choice is completely arbitrary. Lord Kelvin first
proposed taking f(T)=T to define a thermodynamic
temperature scale as
 QH  TH
   --------- (7.5)
 QL rev TL
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.
 On this scale, temperatures vary between zero
and infinity.
 The thermodynamic temperature scale is
not completely defined by Eq. (7.5) since it
gives us only a ratio of absolute
temperatures.

 At the International Conference on Weights and
Measures held in 1954, the triple point of
water was assigned the value 273.16 K.
 The magnitude of a kelvin is defined as
1/273.16 of the temperature interval between
absolute zero and the triple-point temperature of
water.
 The magnitudes of temperature units on the
Kelvin and Celsius scales are identical
(1K =1°C). The temperatures on these two
scales differ by a constant 273.15

A conceptual
experimental setup
to determine
thermodynamic
temperatures on the
Kelvin scale by
measuring QH and
Q L.

Even though the thermodynamic temperature scale
is defined with the help of the reversible heat
engines, it is not possible, nor is it practical, to
actually operate such an engine to determine
numerical values on the absolute temperature scale.
Absolute temperatures can be measured accurately

by other means, such as the constant-volume ideal-
gas thermometer together with extrapolation
techniques.

The Carnot Heat engine
 Hypothetical heat engine

that operates on the
reversible Carnot cycle is
called Carnot heat engine.
 Thermal efficiency of any
heat engine, reversible or
irreversible, is given by
QL
th  1 
QH

 For reversible heat engines, the heat transfer
ratio in the above relation can be replaced by the
ratio of the absolute temperatures of the two
reservoirs.
 Then the efficiency of a Carnot engine, or
any reversible heat engine, becomes
QL TL
th, rev  1  1
QH TH
This is the highest efficiency a heat engine

operating between the two thermal energy
reservoirs at temperatures TL and TH can have.

 The thermal efficiencies of actual and
reversible heat engines operating between the
same temperature limits compare as follows
 th,rev irreversible heat engine


th =th,rev reversible heat engine
>
 th,rev impossible heat engine

The Carnot Refrigerator and Heat Pump
 A refrigerator or a heat pump that operates on
the reversed Carnot cycle is called a Carnot
refrigerator, or a Carnot heat pump.
 The coefficient of performance of any
refrigerator or heat pump, reversible or
irreversible, is given by
1 1
COPR  and COPHP 
QH QL
1 1
QL QH

 The COPs of all reversible refrigerators or
heat pumps can be determined by replacing
the heat transfer ratios by the ratios of the
absolute temperatures of the high- and
low-temperature reservoirs.
 Then the COP relations for reversible
refrigerators and heat pumps become,
1 1
COPR ,rev  and COPHP ,rev 
TH T
1 1 L
TL TH
These are the highest coefficients of performance

that a refrigerator or a heat pump operating between
the temperature limits of TL and TH can have.
 The coefficients of performance of actual
and reversible refrigerators operating between
the same temperature limits can be compared as
follows:
 COPR ,rev irreversible refrigerator


COPR =COPR ,rev reversible refrigerator
>COP
 R , rev impossible refrigerator

The Ideal-Gas Temperature Scale
This temperature scale is based on the observation
that as the pressure of a real gas approaches zero, its
equation of state approaches that of an ideal gas.
Pv  RT
 P 
T  273.16  
 Pt . p. 
 
Constant Volume gas thermometer

The Constant-Volume Gas Thermometer
The standard thermometer, against which all other
thermometers are calibrated, is based on the
pressure of a gas in a fixed volume.
It consists of a gas-filled bulb

connected by a tube to a mercy
manometer. By raising or
lowering R, the mercy level in
the left arm of the U-tube can
always be brought to zero of
the scale to keep the gas
volume constant.
Constant Volume gas thermometer

The temperature of any body in thermal contact
with the bulb (such as liquid surrounding the bulb)
is then defined to be
T  Cp ----------------(1)
Where p is the pressure exerted by the gas and c is
constant. Then the pressure p is
p  po  ρgh
in which po is the atmospheric pressure, ρ is the
density of the mercy in the manometer, and h is the
mercy column height.

If we next put the bulb in a triple-point cell, the
temperature now being measured is
T  Cp3 ----------------(2)
in which p3 is the gas pressure now. Eliminating C
between Eqs. 1 and 2 gives us the temperature as
P  P
T  T3    273.16 K  
 P3   P3 
We still have a problem with this thermometer. If we
used it to measure the boiling point of water, the
different gases in the bulb give slightly different
results.
However, as small and smaller amounts of gas to fill
the bulb, the readings converge nicely to a single
temperature, no matter what gas we use. Below
figure shows this convergence for three gases.
 P
T  273.16  lim  ---------------(3)
gas 0 P
 3 

The recipe instructs us to measure an unknown
temperature T as known: Fill the thermometer bulb
with an arbitrary amount of any gas and measure p3
(using a triple-point cell) and p, the gas pressure at the
temperature being measured (keep the gas volume the
same).
Calculate the ratio p/p3. Then repeat both
measurements with a smaller amount of gas in the
bulb, and again calculate this ratio. Continue this way,
using smaller and smaller amounts of gas, until you
can extrapolate to the ratio p/p3. Calculate the
temperature T by substituting that extrapolated ratio
into Eq. (3). This temperature is called ideal gas
temperature.

Is Ideal-Gas Temperature Scale Identical to
Thermodynamics Temperature Scale
For each of the four processes, the reversible work
done at the moving boundary is given by
 w  Pdv
Similarly, for each process the gas behavior is, from
the ideal gas relation,
Pv  RT
And the internal energy change,
du  Cv 0dT

Assuming no changes in kinetic or potential
energies, then the first law for unit mass is
 q  du   w
RT
 q  Cv 0 dT  dv --------- (7.6)
v

Integrate Eq. 7.6 for each of the four process that
make up the Carnot cycle.
For the isothermal heat addition process 1-2,
v2
qH  1 q 2  0  RTH ln --------- (7.7)
v1
For the adiabatic expansion process 2-3,
TL
Cv 0 v3
0  dT  R ln --------- (7.8)
TH
T v2
For the isothermal heat rejection process 3-4,
v4 v3
qL   3 q 4  0  RTL ln   RTL ln --------- (7.9)
v3 v4

and for the adiabatic compression process 4-1,
TH
Cv 0 v1
0  dT  R ln --------- (7.10)
T TL
v4
From Eq. 7.8 and 7.10, we get
TH
Cv 0 v3 v1
T T dT  R ln v  R ln v
L 2 4
Therefore,
v3 v4 v3 v2
 or  --------- (7.11)
v2 v1 v4 v1

Thus, from Eq. 7.7 and 7.9 and substituting Eq.
7.11, we find that
v2
RTH ln
qH v1 TH
 
qL v3 TL
RTL ln
v4
This demonstrate that the ideal-gas temperature

scale is identical to the thermodynamic temperature
scale.

Chapter 7

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Chapter 7

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Chapter 7: The Second Law of

This process satisfies the first

 The first law places no restriction on the

A heat reservoir is always characterised by its

In practice, large bodies of water such as oceans,

 The air in the room, in the analysis of the

heat dissipation from a TV set in the room.

The work can be converted to heat directly and

A simple heat engine

Heat engine is defined as a

Ignition of fuel, power stroke, and exhaust stroke.

Qout = amount of heat rejected from steam in

Wout = amount of work delivered by steam as it

Win = amount of work required to compress water to

The net out put  Wnet ,out  Wout  Win

Net work output

QH = magnitude of heat transfer between the

Power plants 35-50%

The answer to this question is, unfortunately, a

This can be justified by the following example

The Kelvin–Planck statement can also be

The net power out of this engine is

Wnet,in is the net work

The conservation of energy principle for a cyclic

 COPR can be greater than unity. That is, the

Item to be refrigerated COPR

Air-Source Heat Pump

QL  QH  Wnet ,in  80,000  32,000 kJ/h = 48,000 kJ/h

It does not imply that a cyclic device that

A perpetual-motion machine of the first kind

A perpetual-motion machine of second kind

A perpetual-motion machine of the second kind

 The second law states that no heat engine can

The initial process is an irreversible process one

As the weights become very small, the reverse

A block and inclined plane make up a system

The gas would have to be compressed and heat

The only way in which the system can be restored to

A certain amount of work is necessary to separate

 The transfer of heat to two identical system that

 Both processes are internally reversible, since

The four reversible processes that make up the

Reversible Adiabatic Expansion (Process 2-3)

Reversible Adiabatic Compression (Process 4-1)

The area enclosed by the path of the cycle (area 1-2-3-

Even though the Carnot cycle cannot be

 The efficiency of an irreversible heat engine is

 The efficiencies of all reversible heat engines

Thermodynamics – Chapter 7 101

 The zeroth law of thermodynamics provides

Thermodynamics – Chapter 7 102

 This fact provides the basis for a

Thermodynamics – Chapter 7 104

Thermodynamics – Chapter 7 105

Thermodynamics – Chapter 7 106

Thermodynamics – Chapter 7 108

This is the only requirement that the second law

This temperature scale is called the Kelvin

Thermodynamics – Chapter 7 110

Thermodynamics – Chapter 7 111

Thermodynamics – Chapter 7 112

Thermodynamics – Chapter 7 113

Absolute temperatures can be measured accurately

Thermodynamics – Chapter 7 114