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CHAPTER-12 THERMODYNAMIC EQUILIBRIUM:

THERMODYNAMICS If a system is simultaneously in a state of
mechanical equilibrium, chemical
Thermodynamics is that branch of equilibrium and thermal equilibrium then
physics which is concerned with the system is said to be in thermodynamic
transformation of heat into mechanical equilibrium.
work. It deals with the concepts of heat,
 Thermal Equilibrium:
temperature and inter-conversion of heat
When the temperature within the
into other forms of energy i.e., electrical, system is equal to that of the
mechanical, chemical etc. and vice versa. surroundings then the system is said
Thermodynamics does not take any to be in thermal equilibrium with the
account of atomic or molecular surroundings. In thermal equilibrium,
constitution of matter and it deals with the temperature of system and
surroundings are same.
the bulk systems.
 Mechanical Equilibrium:
State of any thermodynamic
When there is no unbalanced force
system can be described in terms of within the system or between the
certain know macroscopic variables system and surroundings then the
known as thermodynamic variables. system is said to be in mechanical
Thermodynamic variables determine the equilibrium. In this system pressure of
thermodynamic behavior of a system. the gas remains same.
 Chemical Equilibrium:
Quantities like pressure (P), volume (V),
When the system does not tend to
and temperature (T) are thermodynamic
undergo chemical reactions or no
variables. Some other thermodynamic transfer of matter from one part to
variables are entropy, internal energy etc. another part, then it is said to be in
described in terms of P, V and T. chemical equilibrium.

THERMODYNAMIC SYSTEM: The portion Adiabatic Wall:

of universe, which is bounded by a closed An insulting wall (can be movable)
surface and is under experimental that does not allow flow of heat energy
observation, is called a thermodynamic from one to another is called adiabatic
system. wall.
There are three types of systems
Diathermic wall:
1. Closed Systems: A system in which
A conducting wall that allows heat
energy will exchange with
energy to flow from one to another is
surroundings but no exchange of
called a Diathermic wall.
matter with surroundings is called a
closed system. EQUATION OF STATE:
2. Open System: A system in which both The mathematical relation
energy and matter will exchange with between the pressure, volume and
surroundings is called an open system. temperature of the thermodynamic
3. Isolated System: An isolated system is system is called equation of state.
one which cannot exchange energy or
matter with its surroundings. 𝑖. 𝑒. , 𝑃𝑉 = 𝑛𝑅𝑇

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ZEROTH LAW OF THERMODYNAMICS: FIRST LAW OF THERMODYNAMICS

“If two systems are in thermal It states that “The amount of heat
equilibrium with a third system then they given to a system is equal to the sum of
must be in thermal equilibrium with each increase in its internal energy and external
work done by the system”.
other”. This law gives the concept of
If dQ is the quantity of heat
temperature. supplied to a system, a part of it is used to
i.e., it implies that temperature is a increase its internal energy dU and the
physical quantity which has the same rest is used in doing external work dw,
value for all systems which are in thermal then,
equilibrium with each other. 𝑑Q = dU + dW
If the pressure remains constant at
HEAT, INTERNAL ENERGY AND WORK: P and a change in volume dV takes place,
then
Heat is a form of energy which d𝑊 = 𝑃d𝑉,
flows from the body at a higher Therefore, dQ = dU + PdV
temperature to the body at lower
temperature. The flow of heat energy SIGN CONVENTION
stops as soon as the temperature of the
1. dw is positive if the work is done by
two bodies becomes equal. Then, the
the system and dw is negative if the
bodies are in thermal equilibrium.
work is done on the system.
2. dQ is positive when heat is supplied to
The internal energy (U) of a
the system and dQ is negative when
system is the sum of potential and kinetic
heat is taken out from the system.
energies of all the molecules in the system
3. When the temperature of the system
in the frame of reference relative to which
increases in a process dU is positive
the centre of mass of the system is at rest.
and when temperature decreases dU
Internal energy is the total energy
is negative.
possessed by all the particles of the
system. When heat flows into the system NOTE: First law of thermodynamics is a
its internal energy increases, when heat consequence of law of conservation of
flows out of the system its internal energy energy.
decreases.
SPECIFIC HEAT OF GASES
The energy that is transferred from
one system to another by a force moving Since gases are highly
its point of application in its own direction compressible and so the change of
is work. When work is done on the system temperatures cause large changes both in
its internal energy increases when work is pressure and volume hence gas has two
done by the system its internal energy specific heats.
decreases.
1. Molar specific heat of a gas at
Thus, internal energy of the system is a constant volume(Cv)
thermodynamic state of variable, but heat 2. Molar specific heat of a gas at
and work are only two modes of energy constant pressure (Cp).
transfer to a system resulting in a change
in its internal energy.

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RELATION BETWEEN MOLAR SPECIFIC HEAT THERMODYNAMIC PROCESSES

OF GASES (MAYER’S EQUATION)
A thermodynamic process is said
Consider one mole of an ideal gas to occur if the thermodynamic variables of
be heated at constant volume so that its a system undergo a change with time.
temperature increases by an amount dT. The different thermodynamic
Since the volume is constant, the heat processes are as follows,
supplied increases its internal energy and
no work is done on the system. 1. ISOTHERMAL PROCESS: During this
process, changes in pressure and volume
The supplied heat is takes place at constant temperature.
dQ′ = cv dT
Since temperature is constant in
Hence increase in internal energy dU = this process, the internal energy remains
cv dT ……….…………………… (1) same. The change in internal energy
dU=0. By applying first law of
Where Cv is Molar specific heat of a gas at
thermodynamics,
constant volume.
we get
Now, one mole of same gas is heated at
𝑑Q = dW = 𝑃𝑑𝑉
constant pressure so that its temperature
increases by dT. When a gas expands isothermally,
an amount of heat equivalent to the work
The supplied heat is
done by the gas has to be given from an
dQ = cp dT…............................. (2)
external source.
Where Cp is Molar specific heat of a gas at
When a gas compressed
constant pressure.
isothermally, an amount of heat
If dV is the increase in volume
equivalent to the work done on the gas
during this process,
has to be removed from the gas.
Work done is dW = 𝑃𝑑𝑉…………………… (3)
The ideal gas equation for n moles
According to the first law of of a gas is,
thermodynamics we have, 𝑃𝑉 = 𝑛𝑅𝑇
𝑑Q = dU + dW ........................ (4)
In the above expression n,R and T
From equation 1, 2, 3 and 4, we get are constant.
cp dT = cv dT + 𝑃𝑑𝑉………….…… (5)
For isothermal process the above
From the ideal gas equation, 𝑃𝑉 = 𝑅𝑇 equation gives,
By differentiating w.r.t T, we get,
𝑑𝑉 𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃 𝑑𝑇 = 𝑅 Or 𝑃𝑑𝑉 = 𝑅𝑑𝑇 ……… (6)
NOTE:
From equation 5 and 6,
 Boyle’s law holds good in this
cp dT = cv dT + RdT process i.e., PV= Constant.
Or 𝒄𝒑 = 𝒄𝒗 + 𝑹  Specific heat of a gas in this
process is infinity.
Or 𝒄𝒑 − 𝒄𝒗 = 𝑹  This process takes place slowly.

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WORK DONE IN ISOTHERMAL PROCESS 2. ADIABATIC PROCESS: During this

process, pressure, volume and
Consider n moles temperature changes such that heat is
of an ideal gas contained neither allowed to leave the system nor
in a cylinder having allowed to enter the system.
conducting walls and
provided with frictionless Since heat energy is constant.
and movable piston of From first law of thermodynamics,
cross sectional area A, as We have,
shown in the figure. Let P 𝑑Q = 0 = dU + dW or dU = −dW
be the pressure of the
gas. When a gas expands adiabatically,
work is done by the gas and its internal
Work done by the gas when piston energy decreases by an equal amount.
moves up by a small distance dx is given Hence temperature decreases.
by,
d𝑊 = 𝑃𝐴𝑑𝑥 = 𝑃d𝑉 (∵ 𝑑𝑉 = 𝐴𝑑𝑥) When a gas compressed
adiabatically, work is done on the gas and
Suppose the gas expands its internal energy increases by an equal
isothermally from initial state (P1,V1) to amount. Hence temperature increases.
the final state (P2,V2), then the total
amount of work done will be, The variation of pressure P and
volume V of a given mass of the gas
𝑉
𝑊 = ∫𝑉 2 𝑃𝑑𝑉 during adiabatic process satisfy the
1
relation,
For n moles of a gas, 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑅𝑇 𝛾 𝛾
𝑃𝑉 = 𝑛𝑅𝑇 Or 𝑃 = 𝑛 Or 𝑃1 𝑉1 = 𝑃2 𝑉2
𝑉

𝑉2 𝑉2 The variation of temperature T and

𝑅𝑇 1 volume V of a given mass of the gas
∴𝑊= ∫𝑛 𝑑𝑉 = 𝑛𝑅𝑇 ∫ 𝑑𝑉
𝑉 𝑉 during adiabatic process satisfy the
𝑉1 𝑉1
relation,
𝑉2
= 𝑛𝑅𝑇[𝑙𝑛𝑉 ] 𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉1
𝛾−1 𝛾−1
= 𝑛𝑅𝑇[𝑙𝑛𝑉2 − 𝑙𝑛𝑉1 ] Or 𝑇1 𝑉1 = 𝑇2 𝑉2
𝑉2
= 𝑛𝑅𝑇𝑙𝑛 The variation of pressure P and
𝑉1
temperature T of a given mass of the gas
𝑉2 during adiabatic process satisfy the
𝑊 = 2.303𝑛𝑅𝑇𝑙𝑜𝑔
𝑉1 relation,
𝑃1 𝑉2 𝑃𝛾−1 𝑇 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
From 𝑃1 𝑉1 = 𝑃2 𝑉2 𝑂𝑟 =
𝑃2 𝑉1 𝛾−1 𝛾 𝛾−1 𝛾
Or 𝑃1 𝑇1 = 𝑃2 𝑇2
𝑃
𝑊 = 2.303𝑛𝑅𝑇𝑙𝑜𝑔 𝑃1 𝐶𝑝
2 Where 𝛾 = is the ratio of the
𝐶𝑣
This is the expression for the work done specific heats of the gas.
during the isothermal expansion of n
moles of an ideal gas.

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WORK DONE IN ADIABATIC PROCESS Also, 𝑃1 𝑉1 = 𝑛𝑅𝑇1 and 𝑃2 𝑉2 = 𝑛𝑅𝑇2

Consider n moles Therefore,

of an ideal gas contained 1
𝑊= [𝑛𝑅𝑇1 − 𝑛𝑅𝑇2 ]
in a cylinder having 𝛾−1
insulating walls and
𝑛𝑅
provided with frictionless 𝑊= [𝑇 − 𝑇2 ]
and movable insulating 𝛾−1 1
piston of cross sectional This equation gives the work done
area A, as shown in the during the adiabatic expansion of n moles
figure. Let P be the of an ideal gas.
pressure of the gas. When work is done by the gas
Work done by the gas when piston moves during expansion, W>0 and T2<T1,
up by a small distance dx is given by, temperature of the gas decreases.
d𝑊 = 𝑃𝐴𝑑𝑥 = 𝑃d𝑉 (∵ 𝑑𝑉 = 𝐴𝑑𝑥) When work is done on the gas
during compression, W<0 and T2>T1,
Suppose the gas expands adiabatically temperature of the gas decreases.
from initial state (P1,V1,T1) to the final
state (P2,V2,T2), then the total amount of
work done will be, 3. ISOBARIC PROCESS: During this
process, changes in volume and
𝑉
𝑊 = ∫𝑉 2 𝑃𝑑𝑉 temperature take place at constant
1
pressure.
For an adiabatic change,
Since volume can change, the gas
𝑃𝑉 𝛾 = 𝐾 Or 𝑃 = 𝐾𝑉 −𝛾
expands and work is done, and also
𝑉 temperature can change, its internal
𝑊 = ∫𝑉 2 𝐾𝑉 −𝛾 𝑑𝑉
1
energy changes. If dQ is the supplied heat
𝑉2 energy a part dW is used to do external
= 𝐾 ∫ 𝑉 −𝛾 𝑑𝑉 work and a part dU is used to raise
internal energy. From first law
𝑉1
We write,
𝑉 𝑑Q = dU + dW.
𝑉 1−𝛾 2
= 𝐾[ ]
1−𝛾 𝑉
1 4. ISOCHORIC PROCESS: During this
𝐾 process, changes in pressure and
= [𝑉 1−𝛾 − 𝑉11−𝛾 ] temperature take place at constant
1−𝛾 2
volume.
1 1−𝛾 1−𝛾 The volume of the system remains
= [𝐾𝑉1 − 𝐾𝑉2 ]
𝛾−1 constant there is no change in volume
(dV=0), no work is done on or by the
But, system.
𝛾 𝛾
𝐾 = 𝑃1 𝑉1 = 𝑃2 𝑉2 From first law 𝑑Q = dU. Hence the
entire heat given to the system is utilized
1 𝛾 1−𝛾 𝛾 1−𝛾 to change in internal energy and
𝑊= [𝑃1 𝑉1 𝑉1 − 𝑃2 𝑉2 𝑉2 ]
𝛾−1 temperature of the system. The change in
1 temperature can be calculated by, 𝑑𝑄 =
𝑊= [𝑃 𝑉 − 𝑃2 𝑉2 ] 𝑛𝐶𝑉 𝑑𝑇.
𝛾−1 1 1

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5. CYCLIC PROCESS: In a cyclic process, the P-V INDICATOR DIAGRAM

system undergoes a series of changes and A graphical representation of the
finally returns to the initial state. state of the system with the help of two
thermo-dynamical variables is called an
For a cyclic process change in indicator diagram.
internal energy is zero. From first law, A curve
We have showing variation
𝑑Q = dW. of volume of a
substance taken
Hence in cyclic process, the total along the X-axis
heat absorbed by a system is equal to the and the variation
work done by the system. of pressure taken
along Y-axis is
6. REVERSIBLE PROCESS: A process that called a P-V diagram. The shape of the
can be retraced back in the opposite indicator diagram shall depend on the
direction in such a way that the system nature of the thermo-dynamical process
passes through the same states as in the the system undergoes.
direct process and finally the system and The area under the curve is numerically
surroundings returns to their original equal to the work done by a system or on
states with no other changes is called a the system.
reversible process.
HEAT ENGINE
Condition for reversible process It is a device which converts heat
continuously into mechanical energy in a
 The process must be infinitely cyclic process.
slow. Heat engine has three essential
 The system should remain in parts as follows,
thermal equilibrium i.e., system 1. Source: It is a heat reservoir at higher
and surrounding should remain at temperature (T1) from which any amount
the same temperature. of heat (Q1) can be drawn from it without
changing its temperature.
EX: A very slow isothermal expansion or
compression of a gas and a very slow 2. Sink: It is a heat reservoir at lower
adiabatic expansion or compression of a temperature (T2) to which any amount
gas is reversible processes. heat (Q2) can be added to it without
changing its temperature.
7. IRREVERSIBLE PROCESS: A process that
cannot be retraced back in the opposite 3. Working substance: It is a material
which performs mechanical work when
direction is called an irreversible process.
heat is supplied to it.
EX: An explosion, Diffusion of gases,
rusting of iron, Dissolution of salt in water.

8. QUASI-STATIC PROCESS: A quasi-static

process is an infinitely slow process such
that the system remains in thermal and
chemical equilibrium with the
surroundings.
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SECOND LAW OF THERMODYNAMICS 4. Insulating stand: when the base of the

It can be stated in a number of cylinder is attached to the insulating
ways as follows, stand, the working substance gets isolated
from the surroundings.
1) Kelvin-Planck statement: It is
impossible to construct an engine, which CARNOT CYCLE:
will produce no effect other than Carnot’s heat engine operates
extracting heat from a reservoir and through a series of two isothermal and
performing an equivalent amount of work. two adiabatic processes called Carnot
cycle. The working substance is carried
2) Clausius statement: It is impossible for a
through a reversible cycle of the following
self-acting machine, unaided by any four steps;
external agency to transfer heat from a
body to another at higher temperature.
SIGNIFICANCE OF SECOND LAW:
 The efficiency of a heat engine can
never be unity, implies that heat
released to the cold reservoir can
never be made zero.
 The coefficient of performance of a
refrigerator can never be infinite,
implies that external work can never
be zero. Step 1: Isothermal expansion:
CARNOT ENGINE: Let us consider an ideal gas
enclosed in the cylinder. The cylinder is
It is an ideal reversible heat engine
placed over the source which is at the
that operates between two temperatures
temperature T1. The piston is allowed to
T1 (source) and T2 (sink).
move slowly outwards, so that the gas
It was first conceived by a French
expands isothermally which takes its state
engineer, Sadi Carnot in 1824.
from (P1, V1, T1) to (P2, V2, T1).
Carnot engine has the following
During this process, the quantity of
main parts,
heat absorbed from the source is Q1 and
1. Cylinder: This is the main part of the
W1 is the corresponding amount of work
engine has conducting base and insulating
done by the gas.
walls. It is fitted with an insulating and 𝑉2
frictionless piston. An ideal gas is taken in 𝑊1 = 𝑄1 = 𝑛𝑅𝑇1 𝑙𝑛
𝑉1
the cylinder as working substance.
Step 2: Adiabatic expansion:
2. Source: It is a heat reservoir at higher The gas is now placed on the
temperature (T1) from which any amount insulating stand and allowed to expand
of heat (Q1) can be drawn from it without slowly till its temperature falls to T2.
changing its temperature. If W2 is work done by the gas in
the adiabatic expansion which takes its
3. Sink: It is a heat reservoir at lower
state from (P2, V2, T1) to (P3, V3, T2) then,
temperature (T2) to which any amount
heat (Q2) can be added to it without 𝑛𝑅
changing its temperature. 𝑊2 = [𝑇 − 𝑇2 ]
𝛾−1 1

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Step 3: Isothermal compression: EFFICIENCY OF CARNOT ENGINE:

The gas is now placed in thermal It is defined as the ratio of the net
contact with the sink at temperature T2. work done per cycle by the engine to the
The gas is slowly compressed so that as amount of heat absorbed per cycle by the
heat is produced, it easily flows to the working substance from the source.
sink. The temperature of the gas remains 𝑖. 𝑒. , 𝑇ℎ𝑒 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝑜𝑓 𝐶𝑎𝑟𝑛𝑜𝑡 𝑒𝑛𝑔𝑖𝑛𝑒
constant at T2.
If Q2 is heat released by the gas to 𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒
𝜂=
the sink and w3 is the work done on the ℎ𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑
gas which takes its state from (P3, V3, T2) 𝑊 𝑄1 −𝑄2 𝑄2
to (P4, V4, T2), then 𝜂= = =1−
𝑄1 𝑄1 𝑄1
𝑉3
𝑊3 = 𝑄2 = 𝑛𝑅𝑇2 𝑙𝑛 𝑉3
𝑉4
𝑇2 𝑙𝑛 𝑉4
Step 4: Adiabatic compression: 𝜂 =1− … … … … (1)
𝑇1 𝑙𝑛 𝑉2
The cylinder is placed again on the 𝑉1
insulating stand. The gas is further From adiabatic expansion,
compressed slowly till it returns to its
𝛾−1 𝛾−1
initial state (P1, V1, T1). 𝑇1 𝑉2 = 𝑇2 𝑉3 … … … … (2)
If W4 is the work done in this
From adiabatic compression,
process from (P4, V4, T2) to (P1, V1, T1),
then 𝛾−1
𝑇1 𝑉1 = 𝑇2 𝑉4
𝛾−1
… … … … (3)
𝑛𝑅
𝑊4 = [𝑇 − 𝑇2 ]
𝛾−1 1 On dividing (2) by (3), we get
Net work done by the gas per cycle, 𝑉2 𝛾−1 𝑉3 𝛾−1
( ) =( )
𝑊 = 𝑊1 + 𝑊2 − 𝑊3 − 𝑊4 𝑉1 𝑉4
𝑉2 𝑉3
But, 𝑊2 = 𝑊4 =
𝑉1 𝑉4
Therefore, 𝑇2
𝑊 = 𝑊1 − 𝑊3 = 𝑄1 − 𝑄2
Hence, 𝜂 = 1−
𝑇1

𝑉2 𝑉3 The efficiency of a Carnot engine,

𝑊 = 𝑛𝑅𝑇1 𝑙𝑛 − 𝑛𝑅𝑇2 𝑙𝑛
𝑉1 𝑉4
 Depends upon the temperature of the
The cyclic change ABCDA of the source and the sink
working substance in the cylinder  Independent on the nature of the
represents Carnot cycle. The area within working substance
the loop ABCDA represents the net  Is the same for all reversible engines
amount of work done by the gas during a working between the same two
cycle. During each cycle, Q1 is the heat temperatures.
absorbed from the source and Q2 is the  Is directly proportional to the
heat rejected to the sink. Therefore the temperature difference(𝑇1 − 𝑇2 ).
net amount of heat converted into work is  Is always less than 100 % because
𝑊=𝑄1 − 𝑄2 . 𝑄1 > 𝑄2 .

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