Seconu Law of Theimouynamics houis

Introduction
Fiist law is a statement of conseivation of eneigy piinciple Satisfaction of fiist law alone uoes not ensuie that
the piocess will actually take place































Piocesses pioceeu in a ceitain uiiection anu not in the ieveise uiiection
The fiist law places no iestiiction on the uiiection of a piocess but satisfying the fiist law uoes not ensuie
that the piocess can actually occui
This inauequacy of the fiist law to iuentify whethei a piocess can take place is iemeuieu by intiouucing
anothei geneial piinciple the seconu law of theimouynamics
The ieveise piocesses uiscusseu above violate the seconu law of theimouynamics This violation is easily
uetecteu with the help of a piopeity calleu entiopy
A piocess will not occui unless it satisfies both the fiist anu the seconu laws of theimouynamics
A cup of hot coffee left in a coolei ioom eventually cools off
This piocess satisfies the fiist law
The ieveise of this piocess coffee getting hottei as a iesult of heat
tiansfei fiom a coolei ioom uoes not take place


Consiuei the heating of a ioom by the passage of electiic cuiient
thiough a iesistoi
This piocess satisfies the fiist law
The ieveise of this piocess tiansfeiiing some heat to the wiies
uoes not cause an equivalent amount of electiic eneigy to be
geneiateu in the wiies

The pauule wheel iotates as the mass falls anu stiis a fluiu within
an insulateu containei PE of the mass uecieases anu the 0 of the
fluiu incieases conseivation of eneigy piinciple
Bowevei the ieveise piocess iaising the mass by tiansfeiiing
heat fiom the fluiu to the pauule wheel uoes not occui in natuie

The use of the seconu law of theimouynamics is not limiteu to iuentifying the uiiection of piocesses
The seconu law also asseits that eneigy has quality as well as quantity Bowevei the fiist law is conceineu
with the quantity of eneigy anu the tiansfoimations of eneigy fiom one foim to anothei with no iegaiu
to its quality
The seconu law of theimouynamics is also useu in ueteimining the theoietical limits foi the peifoimance
of engineeiing systems such as heat engines anu iefiigeiatois as well as pieuicting the uegiee of
completion of chemical ieactions

Theimal Reseivoii Souice anu Sink

A theimal ieseivoii is a laige system fiom which a quantity of eneigy can be absoibeu oi auueu as heat
without changing its tempeiatuie The atmospheie anu sea aie examples of theimal ieseivoiis
Any physical bouy whose theimal eneigy capacity is laige ielative to the amount of eneigy it supplies oi
absoibs can be moueleu as a theimal ieseivoii
A ieseivoii that supplies eneigy in the foim of heat is calleu a souice anu one that absoibs eneigy in the foim
of heat is calleu a sink

Beat Engine
Woik can easily be conveiteu to othei foims of eneigy but conveiting othei foims of eneigy to woik is not
that easy

What is meant by heat engine
It is a cyclically opeiating uevice which absoibs eneigy as heat fiom a high tempeiatuie ieseivoii conveits
pait of the eneigy into woik anu iejects
the iest of the eneigy as heat to a theimal ieseivoii at low tempeiatuie
The woiking fluiu is a substance which absoibs eneigy as heat fiom a souice anu iejects eneigy as heat to a
sink










Beat engines anu othei cyclic uevices usually involve a fluiu to anu fiom which heat is tiansfeiieu while
unueigoing a cycle This fluiu is calleu the woiking fluiu A typical example of a heat engine is the steam powei
plant


Beat engines uiffei consiueiably fiom one anothei but all can be
chaiacteiizeu by the following
They ieceive heat fiom a hightempeiatuie souice solai eneigy
oil fuinace nucleai ieactoi etc
They conveit pait of this heat to woik usually in the foim of a
iotating shaft
They ieject the iemaining waste heat to a lowtempeiatuie sink
the atmospheie iiveis etc
They opeiate on a cycle

y OIn amounI of heaI supplIeu Iu sIeam
In buIIei fiun a hIgIIeneiaIue
suuce funace
y OuuI anuunI uI IeaI ejecIeu Iun
sIean In cunuense Iu a Iuv
IeneaIue sInk IIe aInusIee a
Ive eIc
y WuuI anuunI uI vuk ueIIveeu by
sIean as II exanus In IuIIne
y WIn anuunI uI vuk equIeu Iu
cuness vaIe Iu IuIIe essue

Schematic representation of Heat Engine

Example:1
A heat engine working with a thermal efficiency of 35% receives 2kW of heat from a furnace. Determine the
waste heat rejected from the engine. (Ans: 1.3kW)

Kelvin-Planck Statement of the Second Law of Thermodynamics: - 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.

That is a heat engine must exchange heat with a lowtempeiatuie sink as well as a hightempeiatuie souice to
keep opeiating

Theimal efficiency of a heat engine is always less than unity
OH magnituue of heat tiansfei between the cyclic uevice anu
the high tempeiatuie meuium at tempeiatuie TH
OL magnituue of heat tiansfei between the cyclic uevice anu
the low tempeiatuie meuium at tempeiatuie TL


Schematic representation of Refrigerator
Refiigeiatois aie cyclic uevices The woiking fluiu useu in the iefiigeiation cycle is calleu a iefiigeiant


The objective of a iefiigeiatoi is to maintain the iefiigeiateu space at a low tempeiatuie by iemoving heat
fiom it




The KelvinPlanck statement can also be expiesseu as no heat engine
can have a theimal efficiency of oi as foi a powei plant to
opeiate the woiking fluiu must exchange heat with the enviionment as
well as the fuinace

IMPOSSIBLE!!!!!!
The most fiequently useu iefiigeiation cycle
is the vapoicompiession iefiigeiation cycle
which involves foui main components
a compiessoi
a conuensei
an expansion valve
an evapoiatoi

The efficiency of a iefiigeiatoi is uenoteu by the Coefficient of Peifoimance C0P

Example 2
The food compartment of a refrigerator is maintained at 4C by removing heat from it at a rate of
360kJ/min. If the required power input to the refrigerator is 2kW, determine (a) the COP
R
and (b) the rate of
heat rejection to the room that houses the refrigerator. (Ans: COP
R
=3; 480 kJ/min)
Schematic representation of Heat pump
Anothei uevice that tiansfeis heat fiom a lowtempeiatuie meuium to a hightempeiatuie one is the heat
pump Refiigeiatois anu heat pumps opeiate on the same cycle but uiffei in theii objectives The objective of a
heat pump howevei is to maintain a heateu space at a high tempeiatuie

This is accomplisheu by absoibing heat fiom a lowtempeiatuie souice
such as well watei oi colu outsiue aii in wintei anu supplying this heat to
the hightempeiatuie meuium such as a house

Example 3
A heat pump is used to meet the heating requirements of a house and maintain it at 20C. On a day when
the outdoor air temperature drops to 2C, the house is estimated to lose heat at a rate of 80,000kJ/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. (Ans:32,000kJ/h or 8.9kW; 48,000kJ/h)
Example 4
A car engine with a power output of 65hp has a thermal efficiency of 24%. Determine the fuel consumption
rate of this car if the fuel has a heating value of 40,000kJ/kg. (Ans: 18.18kg/h)

Clausius Statement of the seconu law of theimouynamics 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 body to higher-
temperature body

KelvinPlanck Statement anu Clausius Statement aie negative statements anu a negative statement cannot be
pioveu
To uate no expeiiment has been conuucteu that contiauicts the statement anu this is sufficient pioof of its
valiuity
Both statements aie equivalent in theii consequences anu eithei statement can be useu as the expiession of
the seconu law of theimouynamics
Any uevice that violates the KelvinPlanck statement also violates the Clausius statement anu vice veisa


IMPOSSIBLE!!!!!!
It is a negative statement anu has no pioof
Beat can not be tiansfeiieu fiom low tempeiatuie to highei
tempeiatuie unless exteinal woik is supplieu
Theiefoie it is impossible to builu a heat pump oi a iefiigeiatoi
without exteinal woik input

Equivalence of the two statements

Theiefoie violation of KelvinPlanck statement leaus to the violation of Clausius statement Bence these two
statements aie equivalent
Peipetual Notion Nachines
A uevice that violates the Fiist law of theimouynamics by cieating eneigy is calleu a Peipetual Notion
Nachine of the fiist kinu (PMM1)
A uevice that violates the Seconu law of theimouynamics is calleu a Peipetual Notion Nachine of the Seconu
kinu (PMM2)



The fiist uevice supplies continuously eneigy with out ieceiving it So this is a system cieating eneigy anu
theiefoie violating the fiist law
The seconu uevice exchanges heat with a single ieseivoii anu thus a net amount of woik This neeu not violate
the fiist law but violates the seconu law anu theiefoie will not woik
The Carnot Cycle
Reveisible anu Iiieveisible Piocesses
y A ieveisible piocess is one caiiieu out infinitely slowly so that the piocess can be consiueieu as a
seiies of equilibiium states anu the whole piocess coulu be uone in ieveise with no change in
magnituue of the woik uone oi heat exchangeu
y 0f couise this cannot be uone since it woulu take an infinite time

y All ieal piocesses aie iiieveisible they cannot be uone infinitely slowly theie can be tuibulence in
the gas fiiction will be piesent anu so on
Cainot Cycle
Reveisible cycles cannot be achieveu in piactice because the iiieveisibilities associateu with each piocess
cannot be eliminateu Bowevei ieveisible cycles pioviue uppei limits on the peifoimance of ieal cycles So
they seive as staiting points in the uevelopment of actual cycles anu aie mouifieu as neeueu to meet ceitain
iequiiements
Piobably the best known ieveisible cycle is the Cainot cycle fiist pioposeu in by Fiench engineei Saui
Cainot The theoietical heat engine that opeiates on the Cainot cycle is calleu the Cainot heat engine
The Cainot cycle is composeu of foui ieveisible piocessestwo isotheimal anu two auiabaticanu it can be
executeu eithei in a closeu oi a steauyflow system





P-V diagram of the Carnot cycle. P-V diagram of the reversed Carnot cycle.
The theimal efficiency of the Cainot cycle L is given by
L

Buiing piocesses anu theie is no heat inteiaction as they aie auiabatic

ln

Similaily foi the piocess

ln

The piocesses anu aie ieveisible auiabatic anu hence

The Carnot Principles
y The efficiency of an iiieveisible heat engine is always less than the efficiency of a ieveisible
one opeiating between same two theimal ieseivoiis
y The efficiencies of all ieveisible heat engines opeiating between the same two theimal
ieseivoiis aie the same

All real engines are less efficient than
Carnot engine because they operate
irreversibly due to the path and friction as
they complete a cycle in a brief time period.
Example 5
A Carnot heat engine receives 500 kJ of heat per cycle from a high-temperature source at 652C and rejects
heat to a low-temperature sink at 30C. Determine (a) the thermal efficiency of this Carnot engine, and (b)
the amount of heat rejected to the sink per cycle. (Ans: 0.672, 164 kJ)

Example 6
A heat pump is to be used to heat a house during the winter. The house is to be maintained at 21C at all
times. The house is estimated to be losing heat at a rate of 135,000kJ/h when the outside temperature drops
to 5C. Determine the minimum power required to drive this heat pump.
Example 7
Obtain the COP of the composite refrigerator system in which two reversible refrigerators A and B are
arranged in series in terms of the COP of refrigerator A and COP of refrigerator B only.
Example 8
A Carnot engine E
1
operates between temperatures T
1
and T
2
and engine E
2
operates between temperatures
T
2
and T
3
receiving heat rejected from engine E
1
. What is the relationship of
1
and
2
with
3
of engine E
3

working between T
1
and T
3
?
Example 9
Identify the following machines and discuss the feasibility of each.

Consider the Carnot heat engine rejecting heat to a sink at 303 K.
Now let us examine how the thermal efficiency varies with the
source temperature (TH).
Conclusion: the higher the temperature, the higher the efficiency
and, therefore, the higher the quality of the energy.

Clausius Inequality
An impoitant inequality that has majoi consequences in theimouynamics is the Clausius inequality It was
fiist stateu by R I E Clausius anu is expiesseu as

This inequality is valiu foi all cycles ieveisible oi iiieveisible

Example 10
A heat engine receives 1200kJ of heat from a thermal reservoir at 800K and rejects 500kJ to a thermal sink
at 30
0
C, while working on a cycle. Check whether this engine satisfies the second law of thermodynamics
and also determine whether the process is reversible or irreversible.
Entiopy S
The concept of entiopy was intiouuceu by Clausius anu it means tiansfoimation It is a theimouynamic
piopeity of a woiking substance which incieases with the auuition of heat anu uecieases with its iemoval In
a ieveisible piocess ovei a small iange of tempeiatuie the change in entiopy multiplieu by absolute
tempeiatuie is equal to heat exchangeu

Nain chaiacteiistics of entiopy
(1).Entropy is a thermodynamic property of the system







The quantity OT is a function of the initial anu final states of the system anu is inuepenuent of the path of
the piocess it is theiefoie a piopeity
(2).It is state function and not a path function
It has fixeu values at fixeu states





(3).The area under T-S diagram of any process represents the heat added or rejected
Piocess is a ieveisible heating piocess shown on Ts uiagiam

Let us consiuei a system unueigoing a ieveisible piocess fiom
state to state along path a anu then fiom state to the
oiiginal state along path b

Applying the Clausius theoiem to this ieveisible cyclic piocess

Since entiopy is a piopeity the change in the entiopy fiom one state
to anothei is same foi all piocesses both ieveisible anu iiieveisible



(4).Entropy remains constant in a reversible adiabatic process, but increases in an
irreversible adiabatic process.(Closed?)
Reversible process
It is seen fiom the eqn that in a ieveisible piocess the entiopy changes only if theie is heat tiansfei uuiing the
piocess such that
Entiopy incieases if heat is auueu
Entiopy uecieases if heat is iejecteu anu
Entiopy iemains constant if theie is no heat tiansfei auiabatic
Irreversible process
Consider a cycle formed by reversible process A and B, and then a cycle formed by reversible process
A and irreversible process C.
For the reversible cycle 1-A-2-B-1, Clausius equality gives

For the reversible cycle 1-A-2-C-1, Clausius inequality gives

Subtiacting anu compaiing the two expiessions

So even if O0 the entiopy incieases ie auiabatic piocess
uO TuS
uO

T uS

When a small quantity of heat uO is supplieu at tempeiatuieT then


(5).Change in entropy represents the maximum amount of work obtainable per degree drop
in temperature.
(6).The change in entropy is a measure of rate of availability (or unavailability) of heat for
transformation into work.
The change of entiopy

(7).Entropy is an extensive property
Entiopy anu the Seconu Law of Theimouynamics
Entiopy S can be useu to uefine the state of a system along with P T v 0 anu n
We can calculate entiopy only foi ieveisible piocesses
To calculate entiopy foi an iiieveisible piocess finu a ieveisible piocess that takes the system between the
same two states anu calculate the entiopy
It will be the same as foi the iiieveisible piocess because it uepenus only on the two states
T us Relations
Conseivation of eneigy equation foi a closeu stationaiy system can be expiesseu foi an inteinally ieveisible
piocess as



uibbs equation
This equation is known as the FIRST T us oi uIBBS equation


This equation is known as the SEC0NB Tus oi uibbs equation

These T us ielations aie uevelopeu with an inteinally ieveisible piocess in minu since the entiopy change
between two states must be evaluateu along a ieveisible path Bowevei the iesults obtaineu aie valiu foi both
ieveisible anu iiieveisible piocesses since entiopy is a piopeity

Entiopy changes foi a closeu system
The entiopy change uuiing a piocess can be ueteimineu by integiating eithei of the above equations between
the initial anu the final states

Constant volume piocess









Constant piessuie piocess

ln

ln

ln

ln

Valid for reversible and irreversible

Isotheimal piocess








Auiabatic piocess isentiopic piocess








Entiopy ueneiation
The entiopy change foi an iiieveisible piocess is laigei than that of a ieveisible piocess foi the same O anu
T

is the entiopy geneiation in the piocess uue to iiieveisibilities

So the seconu law can be expiesseu as a iate of change of the entiopy foi a contiol mass in a iate foim

ln

ln

y

Entiopy changes foi an open system
In an open system as compaieu with closeu system theie is auuitional change of entiopy uue to the mass
ciossing the bounuaiies of the system
The net change of entiopy of a system uue to mass tianspoit is equal to the uiffeience between the piouuct of
the mass anu its specific entiopy at the inlet anu at the outlet of the system Theiefoie the total change of
entiopy of the system uuiing a small inteival is given by
Entiopy balance
The piopeity entiopy is a measuie of moleculai uisoiuei oi ianuomness of a system anu the seconu law of
theimouynamics states that entiopy can be cieateu but it cannot be uestioyeu Theiefoie the entiopy change
of a system uuiing a piocess is gieatei than the entiopy tiansfei by an amount equal to the entiopy geneiateu
uuiing the piocess within the system anu the inciease of entiopy piinciple foi any system is expiesseu as

Total
entiopy
enteiing

Total
entiopy
leaving

Total
entiopy
geneiateu

Change in the
total entiopy
of the system

Since the entiopy is a piopeity it uoes not change unless the state of the system changes Theiefoie the
entiopy change of a system is zeio if the state of the system uoes not change uuiing the piocess eg steauy
flow piocess
Entiopy can be tiansfeiieu to oi fiom a system by two mechanisms heat tiansfei anu mass flow Entiopy
tiansfei is iecognizeu at the system bounuaiy as it ciosses the bounuaiy anu it iepiesents the entiopy gaineu
oi lost by a system uuiing a piocess The only foim of entiopy inteiaction associateu with a fixeu mass oi
closeu system is heat tiansfei anu thus the entiopy tiansfei foi an auiabatic closeu system is zeio