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Chapter 11
Thermodynamics
Thermodynamics
Thermodynamics is a branch of physics which deals with the study of heat,
temperature and their inter conversion of heat energy into other forms of
energy.

Thermodynamic System
A thermodynamic system is a certain quantity of matter which is
separated from its surroundings by a real or imaginary boundary. This
system may be in solid , liquid or gaseous state.
Surroundings
Everything outside a thermodynamic system is its surrounding.

Boundary
The real or imaginary surface that separates the system from its
surroundings is called boundary.
Boundary can be of two types: Adiabatic , Diathermic
Adiabatic wall (boundary)
An insulating wall that does not allow flow of energy (heat) from one
system to another is called an adiabatic wall.

Diathermic wall
A conducting wall that allows energy flow (heat) from one system to
another is called a diathermic wall.

Thermodynamic State Variables

Every equilibrium state of a thermodynamic system is completely
described by specific values of some macroscopic variables. These are
called thermodynamic state variables.
Eg: pressure, volume, temperature, mass , composition,Entropy, Enthalpy
Thermodynamic Equilibrium
The state of a thermodynamic system is in equilibrium , if the macroscopic
variables that characterise the system do not change in time.
Eg: 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.
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Thermal equilibrium
A system is said to be in thermal equilibrium with itself if the temperature
of the system remains constant.
Two systems are said to be in thermal equilibrium, when there is no flow
of thermal energy between them ,when they are connected by a diathermic
wall. In thermal equilibrium, the temperatures of the two systems are
equal.
If systems A and B (two gases) are separated by an adiabatic wall that
does not allow flow of heat, system A will be in its own thermal
equilibrium, and system B also will be in its own thermal equilibrium. But
systems A and B will not be in thermal equilibrium with each other.

If the same systems A and B separated by a diathermic wall that allows

heat to flow from one to another, thermal equilibrium is attained between
the two systems in due course. In this case the temperature of the two
systems become equal.

Zeroth Law of Thermodynamics

R.H. Fowler formulated this law in 1931 long after the first and second
Laws of thermodynamics were stated and so numbered.
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Systems A and B are separated by an

adiabatic wall, while each is in contact with a
third system C via a conducting wall. In this
case A will be in thermal equilibrium with B.
Zeroth Law of Thermodynamics states that
‘two systems in thermal equilibrium with a third system separately are in
thermal equilibrium with each other’.
Thus if A and B are separately in equilibrium with C, TA = TC and TB = TC .
This implies that TA = TB i.e. the systems A and B are also in thermal
equilibrium.
𝐢. 𝐞, 𝐈𝐟 𝐓𝐀 = 𝐓𝐂 and 𝐓𝐁 = 𝐓𝐂 then 𝐓𝐀 = 𝐓𝐁

The concept of temperature from Zeroth Law

The thermodynamic variable whose value is equal for two systems in
thermal equilibrium is called temperature (T ).
Heat, Internal Energy and Work
Heat and work are two modes of energy transfer to the system . (or )
Heat and work are two modes to change the internal energy of a system.
Heat and work are not thermodynamic state variables, but internal energy
is a thermodynamic state variable.

Internal Energy(U)
Internal energy of a system is the sum of kinetic energies and potential
energies of the molecular constituents of the system.
It does not include the over-all kinetic energy of the system.
Internal energy U of a system is an example of a thermodynamic ‘state
variable’ – its value depends only on the given state of the system, not on
the ‘path’ taken to arrive at that state.
Heat(Q)
Heat is energy transfer due to temperature difference between two
systems.
Heat is certainly energy, but it is the energy in transit.
Heat is not a thermodynamic state variable. its value depends on the ‘path’
taken to arrive a particular state.
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Work (W)
Work is energy transfer brought about by means that do not involve such a
temperature difference(e.g. moving the piston by raising or lowering some
weight connected to it)
Work is not a thermodynamic state variable. its value depends on the
‘path’ taken to arrive a particular state.

First Law of Thermodynamics

The heat supplied supplied to the system is partly used to increase the
internal energy of the system and the rest is used to do work on the
environment .
ΔQ = ΔU + ΔW
ΔQ = Heat supplied to the system by the surroundings
ΔW = Work done by the system on the surroundings
ΔU = Change in internal energy of the system
▪ If work is done by the system against a constant pressure P ,then
ΔW = P ΔV (ΔW=F Δx=PA Δx=P ΔV)
ΔQ = ΔU + P ΔV
▪ If a system is taken through a process in which ΔU = 0
ΔQ = ΔW
Heat supplied to the system is used up entirely by the system in
doing work on the environment.
Eg: Isothermal expansion of an ideal gas
▪ From the First Law of Thermodynamics,
ΔQ - ΔW = ΔU
As ΔU is path independent ( ΔQ - ΔW )should also be path
independent.
i.e., eventhough ΔQ and ΔW are path dependent, their combination
ΔQ – ΔW, is path independent.

Specific Heat Capacities of Gases

As gas is compressible, heat transfer can be achieved by keeping either
pressure or volume constant. So gases have two types of molar specific
heat capacities.
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Molar specific heat capacity at constant pressure Cp
𝟏 𝚫𝐐
𝐂𝐩 = 𝛍 (𝚫𝐓)
𝐩

Molar specific heat capacity at constant volume Cv

𝟏 𝚫𝐐
𝐂𝐯 = 𝛍 (𝚫𝐓)
𝐯

Relation connecting 𝐂𝐩 and 𝐂𝐯 − Mayer’s relation

First law of thermodynamics , ΔQ = ΔU + P ΔV
If ΔQ is absorbed at constant volume, ΔV = 0
ΔQ = ΔU
ΔQ
Cv = ( ) (for 1 mole)
ΔT v
ΔU
Cv = ( ) (U depends only on T .So subscript V can be omitted)
ΔT v
𝚫𝐔
𝐂𝐯 = 𝚫𝐓 ---------(1)
If, on the other hand, ΔQ is absorbed at constant pressure,

ΔQ = ΔU + P ΔV
ΔQ
Cp = ( )
ΔT p
ΔU ΔV
Cp = ( ) + (P ΔT) (U depends only on T .So subscript P can be omitted)
ΔT p p

𝚫𝐔 𝚫𝐕
𝐂𝐩 = 𝚫𝐓+ (𝐏 𝚫𝐓) ------------(2)
𝐩

Now, for a mole of an ideal gas

PV = RT
ΔV ΔT
P ( ) =R( )
ΔT ΔTp
ΔV
P ( ) =R
ΔT p
ΔU
Cp = +R
ΔT

Substituting from eq(1) Cp = Cv +R

𝐂𝐩 − 𝐂𝐯 = 𝐑
This is called Mayer’s relation.
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𝐂𝐩 𝐢𝐬 𝐚𝐥𝐰𝐚𝐲𝐬 𝐠𝐫𝐞𝐚𝐭𝐞𝐫 𝐭𝐡𝐚𝐧 𝐂𝐯 . Why

𝚫𝐔
From eqns (1) and (2) 𝐂𝐯 =
𝚫𝐓
𝚫𝐔 𝚫𝐕
𝐂𝐩 = + (𝐏 )
𝚫𝐓 𝚫𝐓 𝐩

When gas is heated at constant volume, the entire heat is used to increase
the internal energy of the gas. But when the gas is heated at constant
pressure, the heat is used to increase the internal energy and also to do
𝚫𝐔
external work during expansion. is the same in both cases. Hence 𝐂𝐩 is
𝚫𝐓
greater than 𝐂𝐯 .
Thermodynamic State Variables and Equation of State
Every equilibrium state of a thermodynamic system is completely
described by specific values of some macroscopic variables, also called
state variables.
For example, an equilibrium state of a gas is completely specified by the
values of pressure, volume, temperature, and mass (and composition if
there is a mixture of gases).
Equation of state
The connection between the state variables is called the equation of state.
Eg: For an ideal gas, the equation of state is the ideal gas relation
PV=μRT
Extensive and Intensive Variables
The thermodynamic state variables are of two kinds:
Extensive and Intensive.
Extensive Variables
Extensive variables indicate the ‘size’ of the system.
(If we imagine ,to divide a system in equilibrium into two equal parts, the
variables whose values get halved in each part are extensive.)
Eg:Internal energy, Volume , Mass
Intensive Variables
Intensive variables do not indicate the ‘size’ of the system.
(If we imagine, to divide a system in equilibrium into two equal parts, the
variables that remain unchanged for each part are intensive.)
Eg: Pressure, Temperature , Density
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Thermodynamic Process
A thermodynamic process is defined as a change from one equilibrium
state to another.
Quasi-static process
The name quasi-static means nearly static.
A quasi-static process is an infinitely slow process such that the system
remains in thermal and mechanical equilibrium with the surroundings
throughout.
In a quasi-static process, the pressure and temperature of the environment
can differ from those of the system only infinitesimally.
Eg: Processes that are sufficiently slow and do not involve accelerated
motion of the piston, large temperature gradient, etc. are reasonably
approximation to an ideal quasi-static process.
Some special thermodynamic processes

Isothermal process.
A process in which the temperature of the system is kept fixed throughout
is called an isothermal process.
For isothermal process T = constant .
So internal energy does not change, ΔU=0
▪ Eg: Change of state (Melting, fusion, vaporistion..)
▪ The expansion of a gas in a metallic cylinder placed in a large
reservoir of fixed temperature is an example of an isothermal
process.

Equation of state for an isothermal process

For an ideal gas, PV=μRT
If an ideal gas goes isothermally from its initial state to the final state , its
temperature remains constant
PV = constant
This is the equation of state for an isothermal process.
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Work done by an ideal gas during an isothermal process

Consider an ideal gas undergoes a change in its state isothermally (at
temperature T) from (P1 ,V1 ) to the final state (P2 , V2 ).
ΔW = P ΔV
In the limit ΔV → 0
dW = P dV

v
W =∫v 2 P dV
1
P V = μ R T (for 1 mole)
μR T
P=
V
v μR T
W =∫v 2 dV
1 V
v 1
W =μ R T ∫v 2 dV
1 V

v
W = μR T [ln V]v21
W = μR T [ln V2 − ln V1 ]
𝐕
W = 𝛍𝐑𝐓 𝐥𝐧 [ 𝟐 ]
𝐕𝟏
Isothermal expansion,
For Isothermal expansion, V2 > V1 and hence W > 0 (workdone is
positive)
That is, in an isothermal expansion, the gas absorbs heat and work is done
by the gas on the environment.
Isothermal compression
In isothermal compression V2 < V1 and hence W < 0 (workdone is
negative)
That is, In an isothermal compression, work is done on the gas by the
environment and heat is released.

The First Law of Thermodynamics for an isothermal change

For isothermal process ΔU= 0
First Law of Thermodynamics ΔQ = ΔU + ΔW
ΔQ = ΔW
The heat absorbed by the gas is entirely used to do the work on the
environment.

Adiabatic process
In an adiabatic process, the system is insulated from the surroundings and
heat absorbed or released is zero.
ΔQ=0
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Equation of state for an adiabatic process

P𝐕 𝛄 = constant
Or T 𝐕 𝛄−𝟏 = constant
where γ is the ratio of specific heats (ordinary or molar) at constant
𝐂𝐩
pressure and at constant volume. 𝛄=𝐂
𝐯
Workdone by an Ideal gas during an Adiabatic Process
Consider an ideal gas undergoes a change in its state adiabatically from
(P1 ,V1 ) to the final state (P2 , V2 ).
v
W =∫v 2 P dV
1
PV γ = k
k
P= γ
V

P=k V −γ
v
W = k ∫v 2 V −γ dV
1
v2
V−γ+1
W = k[ ]
−γ+1 v
1
k −γ+1
W= [v − v1 −γ+1 ]
1−γ 2
1 k k
W= [ γ−1 − ]
1−γ v2 v1 γ−1
PV γ = k
P1 V1 γ = P2 V2 γ=k
1 P2 V2 γ P1 V1 γ
W= [ − ]
1−γ v2 γ−1 v1 γ−1
𝟏
W= [ 𝐏𝟐 𝐕𝟐 − 𝐏𝟏 𝐕𝟏 ]
𝟏−𝛄
PV=μRT
1
W= [ μ R T2 − μ R T1 ]
1−γ
𝛍𝐑
W = 𝟏−𝛄 [ 𝐓𝟐 − 𝐓𝟏 ]
Or
𝛍𝐑
W = 𝛄−𝟏 [ 𝐓𝟏 − 𝐓𝟐 ]
Adiabatic expansion
In adiabatic expansion, the work is done by the gas (W > 0), we get T2 <
T1 i.e., the temperature of the gas lowers.
Adiabatic compression
In Adiabatic compression, work is done on the gas (W < 0), we get T2 >
T1 . i.e., the temperature of the gas rises.
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First law of thermodynamics for an adiabatic process
Δ Q= ΔU+ ΔW
For adiabatic process, Δ Q=0
ΔW = -ΔU
i.e., Workdone = - change in internal energy

Isochoric process
In an isochoric process, V is constant.

Workdone in an isochoric process

Δ W=P ΔV
For isochoric process, ΔV =0
Δ W =0
In an isochoric process no work is done on or by the gas.

First law of thermodynamics for an isochoric process

Δ Q= ΔU+ ΔW
For isochoric process, Δ W =0
Δ Q= ΔU
The heat absorbed by the gas goes entirely to change its internal energy
and thereby its temperature.

Isobaric Process
In an isobaric process, P is constant.

Work done by the gas in an Isobaric process

Work done by the gas is
Δ W=P ΔV
W = P (𝐕𝟐 − 𝐕𝟏 )
W= μ R (𝐓𝟐 − 𝐓𝟏 )

First Law of Thermodynamics for an Isobaric Process

Since temperature changes, internal energy also changes. The heat
absorbed goes partly to increase internal energy and partly to do work.
Δ Q= ΔU+ ΔW
Cyclic Process
In a cyclic process, the system returns to its initial state.
Since internal energy is a state variable, ΔU = 0 for a cyclic process
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First Law of Thermodynamics for Cyclic Process
Δ Q= ΔU+ ΔW
ΔU = 0
Δ Q= ΔW
The total heat absorbed equals the work done by the system.

P-V curves for isothermal and adiabatic processes of an ideal gas.

Second Law of Thermodynamics

Kelvin-Planck statement
No process is possible whose sole result is the absorption of heat from a
reservoir and the complete conversion of the heat into work.
Clausius statement
No process is possible whose sole result is the transfer of heat from a
colder object to a hotter object.
The two statements above are completely equivalent

Reversible and Irreversible Processes

Reversible Processes
A thermodynamic process 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.
Eg: A quasi-static isothermal expansion of an ideal gas in a cylinder
fitted with a frictionless movable piston is a reversible process.
A process is reversible only if:
1) It is quasi-static i.e., the system in equilibrium with the surroundings
at every stage.
2) There are no dissipative factors such as friction, viscosity, etc.
Irreversible Processes
A thermodynamic process is irreversible if the process cannot 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.
The spontaneous processes of nature are irreversible.
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▪ Eg:The free expansion of a gas
▪ The combustion reaction of a mixture of petrol and air ignited by a
spark .
▪ Cooking gas leaking from a gas cylinder in the kitchen diffuses to the
entire room. The diffusion process will not spontaneously reverse
and bring the gas back to the cylinder.

Irreversibility of a process arises due to:

1) Many processes take the system to non-equilibrium states.
2) Most processes involve friction, viscosity and other dissipative
effects.

Carnot Engine
Sadi Carnot, a French engineer, developed Carnot engine. Carnot engine is
a reversible engine operating between two temperatures T1 (source) and
T2 (sink). The working substance of the Carnot engine is an ideal gas.

Carnot cycle

The four processes involved

in carnot cycle are
1.Isothermal Expansion
2. Adiabatic Expansion
3. Isothermal Compression
4. Adiabatic Compression

Workdone in a Carnot cycle

(a)Step 1 →2 Isothermal expansion of the gas from (𝐏𝟏, 𝐕𝟏, 𝐓𝟏 ) to (𝐏𝟐, 𝐕𝟐, 𝐓𝟏 ).
Since the process is isothermal
The workdone (W1→2 ) =Heat absorbed (Q1 )
Work done by the gas,
𝐕
𝐖𝟏→𝟐 = 𝐐𝟏 = μ 𝐑𝐓𝟏 𝐥𝐧 ⌊ 𝟐⌋ ------------(1)
𝐕𝟏
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(b) Step 2 → 3 Adiabatic expansion of the gas from (𝐏𝟐 ,𝐕𝟐 ,𝐓𝟏 ) to (𝐏𝟑 , 𝐕𝟑 , 𝐓𝟐 ).
Work done by the gas,
𝛍𝐑
𝐖𝟐→𝟑 = [ 𝐓𝟏 − 𝐓𝟐 ] ------------------(2)
𝛄−𝟏

(c)Step 3→4 Isothermal compression of the gas from(𝐏𝟑 ,𝐕𝟑 ,𝐓𝟐 ) to (𝐏𝟒 ,𝐕𝟒 ,𝐓𝟐 ).
The workdone (W3→4 ) =Heat released (Q 2 )
Work done on the gas,
𝐕
𝐖𝟑→𝟒 = 𝐐𝟐 = μ 𝐑𝐓𝟐 𝐥𝐧 ⌊ 𝟒⌋
𝐕𝟑
𝐕
𝐖𝟑→𝟒 = 𝐐𝟐 = − μ 𝐑𝐓𝟐 𝐥𝐧 ⌊ 𝟑⌋ -----------(3)
𝐕𝟒

(d) Step 4 → 1 Adiabatic compression of the gas from (𝐏𝟒 ,𝐕𝟒 ,𝐓𝟐 ) to (𝐏𝟏 ,𝐕𝟏 , 𝐓𝟏 )
Work done on the gas is,
𝛍𝐑
𝐖𝟒→𝟏 = [𝐓𝟐 − 𝐓𝟏 ]
𝛄−𝟏

𝛍𝐑
𝐖𝟒→𝟏 =− [𝐓𝟏 − 𝐓𝟐 ] -----------------(4)
𝛄−𝟏

Total work done by the gas in one complete cycle is

W= W1→2 + W2→3 + W3→4 + W4→1
V μR V μR
W= μ RT1 ln ⌊ 2 ⌋ +γ−1 [ T1 − T2 ] − μ RT2 ln ⌊V3 ⌋ − γ−1 [ T1 − T2 ]
V1 4
𝐕𝟐 𝐕𝟑
W= μ 𝐑𝐓𝟏 𝐥𝐧 ⌊ ⌋ − μ 𝐑𝐓𝟐 𝐥𝐧 ⌊ ⌋ -------------(5)
𝐕𝟏 𝐕𝟒

Efficiency of Carnot Engine

Q2
η=1−
Q1

V
μ RT2 ln⌊V3 ⌋
4
η=1− V2
μ RT1 ln⌊V ⌋
1
V3 V2
As the two processes involved are adiabatic ,we get =
V4 V1

𝐓
𝛈 = 𝟏 − 𝐓𝟐
𝟏
𝐓𝟏 − 𝐓𝟐
𝛈= 𝐓𝟏
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Carnot’s theorem
(a) 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
(b) the efficiency of the Carnot engine is independent of the nature of the
working substance.
Example
Calculate the efficiency of a heat engine working between steam point and
ice point. Can you design an engine of 100% efficiency.
Steam point , T1 =1000 C =100+273=373K
Ice point , T2 = 00 C = 0+273=273K
T1 − T2
η=
T1
373− 273
η= = 0.268
373

𝛈 = 𝟐𝟔. 𝟖%

An ideal engine with η = 1 or (100% ) efficiency is never possible, even if

we can eliminate various kinds of losses associated with actual heat
engines.

Seema Elizabeth
HSST Physics
MARM Govt HSS Santhipuram
Thrissur