Chapter 3

Laws of thermodynamics

Julkarnain
Professor
Dept of EEE, RU
Outlines
l Thermodynamics
l Heat and work,
l Thermodynamic system
l The first law of thermodynamics and its applications
l Second law of thermodynamics
l Carnot cycles and Carnot’s theorem
l Entropy and its significance
What is Thermodynamics?
Thermodynamics is a branch of physics
concerned with heat and temperature and their
relation to energy and work on a system.

Thermodynamics is only concerned with

macroscopic (large-scale) changes and
observations
Thermodynamics
l All of thermodynamics can be expressed in terms of
four quantities
l Temperature (T)

l Internal Energy (U)

l Entropy (S)

l Heat (Q)
Heat and Temperature
lHeat is a form of energy whose absorption
makes a body hot and rejection makes a body
cold.
lHeat is a form of energy which produces the
sensation of hotness or coldness of a body.
lHeat is a form of energy which flows from
higher temperature to lower temperature by
conduction, convection and radiation
processes.
Heat and Temperature
lWhen we touch a piece of ice, we feel cold but
if we touch a boiling kettle we feel hot. The
amount of hotness or coldness of a body is
measured by a quantity called temperature.
lApparently, the degree of hotness is expressed
by temperature.
lAlternatively, the temperature of a body is the
property that determines whether or not the
body is in thermal equilibrium with another
body.
Thermodynamic equilibrium
l Thermodynamic equilibrium: the state of a system is an equilibrium state if
the macroscopic variables that characterize the system do not
change in time.

l A gas inside a closed rigid container, completely insulated

from its surroundings, with fixed values of pressure, volume,
temperature, mass and composition that do not change with
time, is in a state of thermodynamic equilibrium.
Thermal equilibrium
l The same systems A and B separated by a diathermic wall – a
conducting wall that allows heat to flow from one to another.
In this case, thermal equilibrium is attained in due course.
Lays of Thermodynamics
l The four laws of thermodynamics define fundamental physical
quantities (temperature, energy, and entropy) that characterize
thermodynamic systems. The laws describe how these
quantities behave under various circumstances, and forbid
certain phenomena (such as perpetual motion).
l The four laws of thermodynamics are-
1. Zeroth law of thermodynamics

2. First law of thermodynamics

3. Second law of thermodynamics

4. Third law of thermodynamics

Zeroth law of thermodynamics
l If two bodies/systems are separately in thermal equilibrium
with a third body/system then the first two bodies/systems
must be in thermal equilibrium with each other”.

The Zeroth Law clearly suggests that when

two systems A and B, are in thermal
equilibrium, there must be a physical quantity
that has the same value for both. This
thermodynamic variable whose value is equal
for two systems in thermal equilibrium is
called temperature (T ). Thus, if A and B are
separately in equilibrium with C, TA = TC and Systems A and B are separated
TB = TC. This implies that TA = TB i.e. the by an adiabatic wall, while each
systems A and B are also in is in contact with a third system
thermal equilibrium. C via a conducting wall.
Internal Energy (U)
We know, every bulk system consists of a large number
of molecules. Internal energy is simply the sum of the
kinetic energies and potential energies of these
molecules.

Internal energy is thus, the sum of molecular kinetic and

potential energies in the frame of reference relative to
which the centre of mass of the system is at rest. Thus, it
includes only the (disordered) energy associated with
the random motion of molecules of the system.
We denote the internal energy of a system by U.
Internal Energy (U)
The important thing about internal energy is that it
depends only on the state of the system, not on how that
state was achieved.

The internal energy of a given mass of gas depends on

its state described by specific values of pressure,
volume and temperature.
Internal Energy (U)
Heat and Work
There are two ways of changing the
state of the gas (and hence its internal
energy). One way is to put the cylinder
in contact with a body at a higher
temperature than that of the gas. The
temperature difference will cause a
flow of energy (heat) from the hotter
body to the gas, thus increasing the
internal energy of the gas. The other
way is to push the piston down i.e. to
do work on the system, which again
results in increasing the internal energy
of the gas.
1st law of thermodynamics
l Joule’s statement: “When work is transformed
into heat or heat is transformed into work, then
work and heat is directly proportional to each
other”.
l Clausius’s statement: “If some heat is supplied
to a system which can do work, then the quantity
of heat (ΔQ) absorbed by the system is equal to
the sum of the increase in internal energy (ΔU)
of the system and the external work (ΔW) done
by the system”.
ΔQ = ΔU+ΔW
1st law of thermodynamics
l The change in internal energy of a system is
equal to the heat added to the system minus the
work done by the system
ΔU = ΔQ - ΔW
l Sign of ΔQ and ΔW depends on which direction of transfer
i. ΔQ is positive when the system absorbs heat
and is negative when it loses heat,
ii. ΔU is positive when the internal energy of
the system increases and is negative when it
decreases,
iii. ΔW is positive when the work done on the
system and is negative when the work done
by the system.
1st law of thermodynamics
1. Calculate the change in the system’s internal energy if 3000 J
of heat is added to a system and a work of 2500 J is done.

2. What is the change in the internal energy of the system if

2000 J of heat leaves the system and 2500 J of work is done
by the system?
Heat Capacity, Specific Heat Capacity,
Molar Specific Heat Capacity
Heat Capacity: Suppose an amount of heat ∆Q supplied to a
substance changes its temperature from T to T + ∆T. We define
heat capacity of a substance to be
S= ∆Q/ ∆T
! # ∆%
Specific Heat Capacity: 𝑠 = " = " ∆&
s depends on the nature of the substance and its temperature. The
unit of specific heat capacity is J kg-1 K-1.
Molar Specific Heat Capacity: If the amount of substance is
specified in terms of moles μ (instead of mass m in kg ), we can
define heat capacity per mole of the substance by
𝑆 1 ∆𝑄
C= =
𝜇 𝜇 ∆𝑇
Different thermodynamic processes
Isothermal process: A process in which the temperature of the
system is kept fixed throughout is called an isothermal process.
Isobaric process: A process in which the pressure of the system
is kept fixed throughout is called an isobaric process.
Isochoric process: A process in which the volume of the system
is kept fixed throughout is called an isochoric process.

Adiabatic process: A process in which the heat of the system is

kept fixed throughout is called an adiabatic process.
If the system is insulated from the surroundings and no heat flows
between the system and the surroundings, the process is
adiabatic.
Different thermodynamic processes
.
 Work done in isothermal process
We now consider these processes in some detail :
11.8.2 Isothermal process
For an isothermal process (T fixed), the ideal gas
equation gives
PV = constant
i.e., pressure of a given mass of gas varies inversely
as its volume. This is nothing but Boyle’s Law.
Suppose an ideal gas goes isothermally (at
temperature T ) from its initial state (P1, V1) to
rature the final state (P2, V 2). At any intermediate stage
d the with pressure P and volume change from V to
imally V + ∆V (∆V small)
of the There is no change in the
∆W = P ∆ V internal energy of an ideal gas
sly a Taking (∆V → 0) and summing the quantity in an isothermal process.
esses ∆W over the entire process,
volve The First Law of
V2
arge W = ∫ P dV Thermodynamics then
nably V1 implies that heat supplied to
cess.
V2 the gas equals the work done
static dV V2 by the gas : Q = W.
= µ RT ∫ = µ RT In (11.12)
wise. V1
V V1
 1 1 2 2
11.8.3
is, in anAdiabatic processthe gas absorbs
isothermal expansion,
heat and does work while in an isothermal
1 ⎡ P2V2 (11.15) P1V1γ ⎤
γ
Incompression,
an adiabatic workprocess,
is done theon thesystem
gas by is theinsulated W = − γ −1 ⎥
⎢
environment
from and heat is released.
the surroundings and heat absorbed or 1 − γ ⎣ V2γ −1γ V
From Eq. (11.14), the constant is P1V1 or P21V2γ ⎦
released is zero.process
11.8.3 Adiabatic From Eq. (11.1), we see that
work
In andone by process,
the gasthe results ininsulated
decrease in its 1 ⎡ P2V2
γ
P1V1γ1⎤ µR(T1 − T2 )
Work done in adiabatic process
adiabatic system is W = ⎢ γ −1 − = γ −1 ⎥ [ P2V2 − P1V1 ] = (11.16)
internal
from theenergy
surroundings (and and henceheatits temperature
absorbed or for 1 − γ ⎣ V2 V1 ⎦
1−γ γ −1
anreleased is zero.
ideal gas). We From
quote Eq. without
(11.1), weproofsee that(the result 1 µR(T1 − T2 )
work done by the gas results in decrease in its
THERMODYNAMICS PAs
V expected, if work(11.16)is done by the gas in an 235
for that for 1 − γ [ 2 2
that youenergy
will learn in higher courses) = − P1V1 ] =
internal (and hence its temperature γ −1
ananadiabatic
ideal gas). We process of anproof
quote without ideal
(thegas.
result adiabatic process (W > 0), from Eq. (11.16),
that you As expected,
T2 if< work
T1We. is
On done the byother
the gashand,
in an if work is done on
where inwill
the
P V
learn
=
in higher
γsecond
const stepcourses)
we havethat for made(11.13)use of can calculate,
adiabatic process (W > 0), from Eq. (11.16),
as before, the work done in
an adiabatic process of an ideal gas.
the ideal gasγ equation
where γ isP Vthe =ratio
PV = µ RT
constof specific heats
and taken T2 < T1.the
(11.13)(ordinary On the gas
an
the other (W if<work
adiabatic
hand, 0),change
is we
donegetonof Tan
2
>ideal
T 1 i.e.,
gas the
from the
constants out of thepressure
integral. Foratan ideal
the gas gas, (Wtemperature
state
< 0), (P1,Tof
we get V >the
,T T 1 )gas rises.
to the
i.e., the state (P , V , T ).
or molar)
where γ isattheconstant
ratio of specific heats and
(ordinary constant 2
1 1 2 2 2
temperature of the gas rises.
internal
or
volume.molar) energy
at constant depends
pressure only
and at on
constanttemperature. 11.8.4 Isochoric process
volume. 11.8.4 Isochoric process V2
Thus, there isC no C p change in the internal energy
In process,
an isochoric
VW is = ∫process,
P dV V is constant. No work
of an idealγγ=gas = p in an isothermal process. In an isochoric
The is done on From
constant.
or by the
No work
gas.theFrom Eq. (11.1), the
CvC is done on or by the gas. V1Eq. (11.1),
First Law of Thermodynamics v then implies that heat
heat absorbed by the gas goes entirely to change
Thus ifif an ideal gasgasundergoes a change in absorbed by the gas goes entirely to change
heatThus suppliedan ideal
to the undergoes
gas equals a
thechange
workits in
done
internal energy and its temperature. The
its state adiabatically from (P1, V1) to (P2, V2) : its internal energy and its temperature. The
its
by state
the gas adiabatically from (P1, V1Eq.
γ : Q = γ W. Note from
) to (P ,V
(11.12) ) : that
change in temperature for a given amount of
P1 V1 = P2 V2 (11.14)
2 2 change
heat is determined by in
thetemperature
specific heat of the for a given amount of
γ γ
for V > V1,1 shows
2 P1 V
Figure11.8
W= P>2 0;V
the
and for Vof<anVideal
2 P-V curves 2 1
,W< 0. atThat
(11.14)
gas heat
constant is determined by the specific heat of the
volume.
is,gasinfor
antwo
Figure11.8 isothermal
adiabatic processes
shows the expansion,
P-Vconnecting
curves the ofgas
two absorbs
an11.8.5
ideal Isobaric gas process
at constant volume.
isotherms.
heat
gas forand does work
two adiabatic while in
processes an isothermal
In two
connecting an isobaric process, P is fixed. Work done by
11.8.5 Isobaric process (11.15)
compression,
isotherms. work is done on the gastheby
gasthe
is
environment and heat is released. W = P (V2 –In
V1an
) = isobaric
µ R (T2 – T1process,
) P is fixed. Work done by
(11.17)
γ γ
From Eq.
the gaschanges,
Since temperature is (11.14),
so does internalconstant is P1V1 or P2V2
the
11.8.3 Adiabatic process energy. The heat absorbed goes partly to
W = P (V2 –partly µ Rwork.
V1) =to do (T
increase internal energy and γ 2 – T1) γ (11.17)
In an adiabatic process, the system is insulated 1 ⎡ P2 V 2 P1 V1
⎤
W for
The change in temperature = a given
Since temperature ⎢ amount
changes,
γ −1
− γ so −1 ⎥does internal
from the surroundings and heat absorbed of heat isor 1 − γ heat
determined by the specific V of the V
energy. The heat ⎣ absorbed 2 ⎦ partly to
1 goes
released is zero. From Eq. (11.1), we gas
seeatthat
constant pressure.
increase internal energy and partly to do work.
work done by the gas results in decrease 11.8.6
in Cyclic
its Theprocess 1 − T2 )
µR(T1amount
change in = temperature
[ P V − P for
V ] a= given (11.16)
2 2 1 1
internal energy (and hence its temperature for process,
In a cyclic
of heat
the system returns to its
is 1−γ
determined by the specific γ − 1of the
heat
initial state. Since internal energy is a state
anFig. 11.8 gas).
ideal We quote
P-V curves without
for isothermal proof (the
and adiabatic result = 0atforconstant
variable, ∆Ugas pressure.
processes of an ideal gas.
that you will learn in higher courses) that for Asa expected,
cyclic process. From
if work is done by the gas in an
Home Work
Derive relation between pressure and volume of a gas in adiabatic
change.

Derive relation between temperature and volume of a gas in

adiabatic change
2nd law of thermodynamics
l Clausius’s statement: It is impossible to make heat flow
from a body at a lower temperature to a body at a higher
temperature without doing external work on the
substance.
l Kelvin’s statement: Continuous flow of energy cannot be
obtained from an object cooling it from its surrounding.
l Plank’s statement: It is impossible to construct an engine
which can extract heat continuously from a heat source
and completely transforms into work.
l Carnot’s statement: No engine can be built which can
extract a fixed amount of heat and will convert totally into
work.
Reversible and irreversible process

Reversible process: A thermodynamic process (state i → state f )

is reversible if the process can be turned back such that both the
system and the surroundings return to their original states, with
no other change anywhere else in the universe. A process is
reversible only if it is quasi-static (system in equilibrium with the
surroundings at every stage) and there are no dissipative effects.
Example:
1. a quasi-static isothermal expansion of an ideal gas in a
cylinder fitted with a frictionless movable piston is a
reversible process.
2. A given mass of ice changes to water when a certain amount
of heat is absorbed by it and the same mass of water changes
to ice when the same quantity of heat is removed from it.
Reversible and irreversible process

Irreversible process: An irreversible process is one which cannot

be retraced in the opposite direction by reversing the controlling
factor. All changes which occur suddenly like the explosion etc
may be considered as irreversible.

Example:
1. Sudden unbalanced explosion of a gas either isothermal or
adiabatic.
2. Heat produced by friction.

3. Heat generated when current flows through an electrical

resistance.
Carnot’s Engine and Carnot’s Cycle

Carnot’s Engine: The device which transforms heat energy into

mechanical energy is called heat engine. In order to explain this
phenomenon theoretically Carnot proposed an ideal engine. This
engine is called Carnot’s engine.
A reversible heat engine operating between two temperatures is
called a Carnot engine.
All practical engines have many defects and limitations, but
Carnot’s engine is free from all defects and limitations. It should
be remembered that Carnot’s engine is an imaginary one. it is
impossible to construct such an engine.

A Carnot’s engine must have the sequence of steps constituting

one cycle, called the Carnot cycle.
Carnot’s Engine and Carnot’s Cycle
Ca e e
Operation of Carnot’s
The device which Engine:
transforms heat The
energy into Carnot’s
mechanical energy cycle andengine.
is called heat the Inwork
order to explain
done can be expressed
this phenomenon by aproposed
theoreticall Carnot diagram. Itengine.
an ideal is called index
This engine diagram.
is called Carnot s engine. All
practical engines have many defects and limitations, but Carnot s engine is free from all defects and
Thelimitations.
Carnot’s cycle
It should and work
be remembered dones are
that Carnot engineexplained
is an imaginar byone.the index to construct
it is impossible
diagram:
such an engine. But it is very easy to explain theoretically its working principle or operation.
A (P1,V1)

B (P2,V2)
Adiabatic
compression Adiabatic
P4 expansion
D (P4,V4)

P3 C (P3,V3)
a d b c
V4 V2 V3

Fig.1: P-V diagram of Carnot s engine

Carnot’s Engine and Carnot’s Cycle

First Step: In this step, the cylinder is placed on the source of

heat. Very quickly the temperature of the working substance (gas)
becomes equal to the temperature T1 of the source. In the index
diagram, it is represented by the point A. let the pressure and
volume in this state are P1 and V1 respectively. Then the gas is
allowed to expand isothermally. During the expansion, it takes Q
amount of heat from the source. After isothermal expansion, the
pressure and volume of the gas become P2 and V2 respectively.
In the figure, it is represented by point B.

l In the index diagram, work done for the isothermal expansion

W1=area ABba.
Carnot’s Engine and Carnot’s Cycle

Second Step: In this step, the cylinder is placed on the insulated

platform and the confined gas is allowed to expand adiabatically.
In the adiabatic expansion, the temperature of the gas becomes
T2. After adiabatic process, the pressure and volume of the gas
are respectively P3 and V3 which is represented by the point C in
the figure.

l In the index diagram, work done by the adiabatic expansion,

W2=area BCcb
Carnot’s Engine and Carnot’s Cycle

Third Step: Now, the cylinder is placed on the heat sink and the
gas is compressed isothermally by the piston. As a result, the
pressure of the gas increases. In this step work is done by the
piston on the gas. During compression, it rejects Q amount of
heat to the sink at temperature T2. The pressure and volume of
the gas in this step are P4 and V4 respectively. This is represented
by point D in the diagram.

l The CD protion of the index diagram represents compression

of the gas at temperature T2 and the work done,
W3=area CcdD
Carnot’s Engine and Carnot’s Cycle

Fourth Step: In this step, the cylinder is placed on the insulated

platform and the confined gas is allowed to compress
adiabatically. Due to the work done on the confined gas the
temperature of the gas increases and becomes equal to the
temperature of the source. In this process, the pressure and
volume of the gas are P1 and V1 respectively i.e., the cycle
returns to its initial state.

l In the diagram, point A represents this state. Graph DA in the

index diagram indicates the adiabatic compression and the
work done in this step, W4= area DdaA.
Carnot’s Engine and Carnot’s Cycle

Now according to the convention, total work done by the

confined gas is
W= W1+W2-W3-W4=area of ABba + area of BCcb - area
of CcdD - area of DdaA= area of ABCD.

From the above discussion, it is evident that in the Carnot’s cycle

the work done by this working substance i.e., gas is represented
by two isothermal graphs and two adiabatic graphs in the index
diagram and is equal to the areas under the graphs.

This cycle is called the Carnot’s cycle.

From the above discussion, it is eviden ha in he Carno s c cle he ork done b his orking form la
substance i.e., gas is represented by two isothermal graphs and two adiabatic graphs in the index diagram
and is eq al o he areas nder he graphs. This c cle is called he Carno s cycle.
Efficiency
f Ca of eCarnot’s
Eff c e c e: Engine
In one cycle, the ratio of the heat converted into work and the amount of heat taken from the source by the
engine is called efficienc of he engine. I is represen ed b
.
Let Q1=heat taken by the working substance (gas)

Q2= heat rejected by the gas

amount of heat converted into work = Q1-Q2

efficienc of he engine, = (Q1-Q2)/ Q1=1- Q2/ Q1 --------------------------(1)

In case of Carno s engine, he amo n of hea aken and rejec ed are respec i el propor ional to the
temperature of the source and the sink i.e., Q/T=constant

So, Q1/T1=Q2/T2

Or, Q1/Q2=T1/T2

from he eq a ion (1) e ge , = (T1-T2)/ T1=1- T2/ T1 ---------------------(2)

In erms of percen age, =(1- T2/ T1)×100% -------------------------------------------(3)

From eq a ion (3), i is seen ha efficienc of he Carno s engine depends on he empera res of he hea
and sink and not on the working substance.
Carnot’s Theorem

v Working between two given temperatures T1 and T2 of the hot

and cold reservoirs respectively, no engine can have efficiency
more than that of the Carnot engine and
v The efficiency of the Carnot engine is independent of the
nature of the working substance.
Entropy
Entropy: Entropy is the physical property of an object which
remains constant in adiabatic reversible process. It is represented
by S.
Entropy has tremendous importance and significance in
thermodynamics. It tells us about the direction of heat flow and helps in
determining the thermodynamic condition. Entropy is measured by the
rate of change of heat absorbed or rejected with respect to temperature
of the system.
The change in entropy (dS) of a system was originally defined for a
thermodynamically reversible process as dS=dQ/T
where T is the absolute temperature of the system, dividing an
incremental reversible transfer of heat into that system (dQ). (If heat is
transferred out the sign would be reversed giving a decrease in entropy
of the system
Entropy
Significance of entropy:
Entropy is very significant in thermodynamics. The significances
are mention below:
§ Entropy is a physical quantity. It is equal to the ratio of heat
absorbed or rejected to the temperature.
§ It indicates the direction of heat flow.

§ It helps in determining the thermodynamic state of an object.

§ Like temperature, pressure, volume, internal energy, magnetic

behavior it expresses the state of a body.
§ The orderliness of an object decreases with the increase of
entropy.
§ Like temperature or pressure it cannot be felt.