THERMODYNAMICS

6KLKDEXGKHHQ0
Assistant Professor in Physics
61*6College, 3DWWDPEL
 Thermodynamic system

THERMODYNAMICS
 Thermodynamics is the study of heat energy and
its transformation.
 Thermodynamics is based on four laws , namely,
the zeroth law , first law , second law and third
law of thermodynamics

Thermodynamic System
 A finite portion of matter or a restricted region of
space ,which is set aside on which our attention
is focused is called a thermodynamic system.
Eg : Air enclosed in a steel tank.
SURROUNDINGS, BOUNDARY AND UNIVERSE

 Surroundings :Everything outside the system which

has a direct bearing on the behavior of the system.
 Boundary :The separation between the system and
surrounding is called the of the system.
 The boundary may be real or imaginary.
 Universe :A finite portion of the world consisting of the
system and those surroundings
 It has no cosmic or celestial implications.
THERMODYNAMIC CO-ORDINATES
 The thermodynamic system is specified by the
thermodynamic co-ordinates
 Pressure

 Volume

 Temperature

 Entropy

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HYDROSTATIC SYSTEMS
 A hydrostatic system is any isotropic system
 of constant mass and constant composition
 that exerts a uniform hydrostatic pressure on the
surroundings
 in the absence of gravitational, electric or magnetic effects
 These systems are divided into the following categories.
 A pure substance:
 A single chemical compound in the pure form of solid , liquid , a gas
 A mixture of any two or all the three

 A homogenous mixture of different compounds:

 Mixture of
 inert gases

 chemically active gases

 liquids or solution

 A heterogeneous mixture:
 mixture of different gases with a mixture of different liquids
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HYDROSTATIC SYSTEMS

 For hydrostatic system,

 Volume expansivity,
1 𝜕𝑉
𝛽=
𝑉 𝜕𝑇 𝑃

 Isothermal Bulk modulus of elasticity

𝜕𝑃
𝐵 = −𝑉
𝜕𝑉 𝑇

 Isothermal compressibility,
1 𝜕𝑉
𝐾=−
𝑉 𝜕𝑃 𝑇
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 THERMODYNAMIC EQUILIBRIUM
If the system satisfies
all the 3 equilibria
 Thermal  Chemical
 Mechanical
Equilibrium Equilibrium
Equilibrium If there are no If there are no
If there are no temperature chemical
unbalanced forces differences reactions within
acting on any part between the the system and
of the system or on different parts of no motion of any
the system as a the system or chemical
whole between the constituent from
system and the one part of the
surroundings system to
another part
QUASI STATIC PROCESS
 If the unbalanced force acting on the system is
infinitesimally small such that
 The system is at all times near to a state of
thermodynamic equilibrium
 All states through which the system passes
can be defined by thermodynamic variables

Then that process is quasi static process

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ZEROTH LAW OF THERMODYNAMICS
 Two systems in thermal
equilibrium with a third
system, all 3 systems are
in equilibrium with each
other

 A in equilibrium with C
 B in equilibrium with C

Then
 A in equilibrium with B

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THERMODYNAMIC PROCESSES
 Thermodynamic state of a system is defined by
thermodynamic co-ordinates
 Any change in thermodynamic co-ordinates of the
thermodynamic system causes change in the
state of a system.
 Such process is Thermodynamic Process
 Isothermal Process
 Adiabatic
 Isochoric
 Isobaric

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ISOTHERMAL PROCESS
 A process in which temperature remains constant
 Pressure and volume changes

 It is a slow process

 Graph between P & V –Isotherm

 Since internal energy depends only on temp,

Internal energy of perfect gas remains constant
in an isothermal process

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ISOTHERMAL PROCESS
 First law of thermodynamics, 𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
𝑑𝑈 = 0, 𝑑𝑄 = 𝑃𝑑𝑉
Heat is completely converted to external work

 Ideal gas equation is 𝑑𝑄= Heat change

𝑑𝑈= internal energy change
PV=nRT 𝑃𝑑𝑉= work done
 Eqn of isothermal process P = Pressure
V = Volume
PV=constant n = no: of moles
R = Universal gas constant
T = Temperature

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 ISOTHERMAL PROCESS
 V-T Diagram  P-T Diagram
V P

T T

 P-V Diagram  T-S Diagram

S
ADIABATIC PROCESS
 The system is isolated from the surroundings
 In a reversible adiabatic process-Entropy is constant

 Pressure, Volume, Temperature may change

 It is a quick and sudden process

Slow process

Quick process
Steeper negative slope
ADIABATIC PROCESS
 First law of thermodynamics, 𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
𝑑𝑄 = 0, 𝑑𝑈 = −𝑃𝑑𝑉
𝑑𝑄= Heat change
𝑑𝑈= internal energy change
𝑃𝑑𝑉= work done
 Eqn of Adiabatic process P = Pressure
V = Volume
𝑃𝑉 𝛾 =constant n = no: of moles
R = Universal gas constant
T = Temperature
 Adiabatic Process,  Isothermal Process,
𝑃𝑉 𝛾 =constant=K 𝑃𝑉=constant=K
𝑃 = 𝐾𝑉 −𝛾 𝑃 = 𝐾𝑉 −1
Slope of the adiabatic Slope of the isothermal
𝜕𝑃
= −𝛾𝐾𝑉 −𝛾−1 = −𝛾𝐾𝑉 −𝛾 𝑉 −1 𝜕𝑃
= −𝐾𝑉 −1−1 = −𝐾𝑉 −1 𝑉 −1
𝜕𝑉 𝑆 𝜕𝑉 𝑇
𝑃 𝑃
= −𝛾𝑃𝑉 −1 = −𝛾 = −𝑃𝑉 −1
= −
𝑉 𝑉
Since 𝛾>1,
Slope of adiabatic curve > slope of isotherm

Slow process

Quick process
Steeper negative slope
 ADIABATIC PROCESS
 V-T Diagram  P-T Diagram

V P
Projection adiabatic in
V-T plane
P-T plane
P-V plane

T
T
 P-V Diagram  T-S Diagram

S
ISOBARIC PROCESS
 Process at constant Pressure
 Equation of Isobaric Process

𝑉 𝑉1 𝑉2
= 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 =
𝑇 𝑇1 𝑇2

 First law of thermodynamics, 𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉

 Heat supplied is utilized for
 Increase in Internal energy
 Do external work
 ISOBARIC PROCESS
 V-T Diagram  P-T Diagram
V P

T T

 P-V Diagram  T-S Diagram

T
P
Isochoric
Isobaric

V S
ISOCHORIC PROCESS
 Process at constant Volume
 Equation of Isochoric Process

𝑃 𝑃1 𝑃2
= 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 =
𝑇 𝑇1 𝑇2

 First law of thermodynamics, 𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉

𝑑𝑉 = 0, 𝑑𝑄 = 𝑑𝑈
 Heat supplied is utilized for
 Increase in Internal energy
 ISOCHORIC PROCESS
 V-T Diagram  P-T Diagram

V P

T
T
 P-V Diagram
 T-S Diagram
P T

Isochoric
Isobaric

V S
INDICATOR DIAGRAM
 Graph between thermodynamic variables for
different thermodynamic process
 P-V Diagram
 P-T Diagram
 V-T Diagram
 T-S Diagram
 P-V DIAGRAM
Work done=Area enclosed by PV diagram

Expansion

Compression

V
V-T DIAGRAM

Isochoric

Adiabatic

Isobaric
Isothermal

T
T-S DIAGRAM
T

Isochoric
Isobaric
Adiabatic

Isothermal

S
P-T DIAGRAM (PHASE DIAGRAM)

Adiabatic
Isochoric
Isothermal

Isobaric

T
 P-T DIAGRAM (PHASE DIAGRAM)

Triple Point:
A point at which three phases of a substance co-exist
CYCLIC PROCESS
 If the system brought back to initial state after
performing series of processes
 Work done=Area enclosed by PV diagram
REVERSIBLE PROCESS
 The process in which system and surroundings
brought back to the initial state at the end without
producing any change in the universe
 The process is performed quasi statically
 System is always pass through states of
thermodynamic equilibrium
 Process is not accompanied by any dissipative effects
 Friction
 Viscosity
 Inelasticity
 Electric resistance
 Magnetic hysteresis
 Since it is impossible to satisfy all the conditions,
 Reversible process-ideal
IRREVERSIBLE PROCESS
 Process does not fulfill the conditions of reversible
process
 Thermodynamic equilibrium is not satisfied
 Process is accompanied by dissipative effects
 Friction
 Viscosity
 Inelasticity
 Electric resistance
 Magnetic hysteresis

 All natural process are irreversible since dissipation

of energy is present
WORK DONE21 A HYDROSTATIC SYSTEM

Cylinder with movable Piston

Applied Force
PA

dx

At equilibrium, 𝐹 = −𝑃𝐴 F=Applied Force

Work done, 𝑑𝑊 = 𝐹𝑑𝑥 = −𝑃𝐴𝑑𝑥 = −𝑃𝑑𝑉 P=Pressure
A=Area
𝑉 𝑉𝑖 =Initial Volume
Total Work done=𝑊 = − ‫𝑉𝑑𝑃 𝑓 𝑉׬‬ 𝑉𝑓 =Final Volume
𝑖
1. ISOTHERMAL PROCESS
𝑛𝑅𝑇
 For an Ideal gas, PV=nRT, 𝑃=
𝑉

𝑉
 Work done, 𝑊= ‫𝑉𝑑𝑃 𝑓 𝑉׬‬
𝑖

𝑉 𝑛𝑅𝑇
= ‫𝑓 𝑉׬‬ 𝑑𝑉
𝑖 𝑉

𝑉 𝑑𝑉
= 𝑛𝑅𝑇 ‫𝑓 𝑉׬‬
𝑖 𝑉

𝑉𝑓 𝑉𝑓
= 𝑛𝑅𝑇[lnV] 𝑉𝑖 = 𝑛𝑅𝑇 𝑙𝑛
𝑉𝑖

𝑉𝑓
Isothermal work = 𝑛𝑅𝑇 𝑙𝑛
𝑉𝑖
ADIABATIC PROCESS
 For an Adiabatic Process, 𝑃𝑉 𝛾 =constant=K
𝑃 = 𝐾𝑉 −𝛾
𝑉𝑓 𝑉𝑓
 Work done, 𝑊= ‫𝑉𝑑𝑃 𝑉׬‬ = ‫ 𝑉𝐾 𝑉׬‬−𝛾 𝑑𝑉
𝑖 𝑖
𝑉
𝑉 −𝛾+1 𝑓 𝐾 −𝛾+1 −𝛾+1
= 𝐾 = 𝑉𝑖 − 𝑉𝑓
−𝛾+1 𝑉 𝛾−1
𝑖
1 −𝛾 −𝛾
= 𝐾𝑉𝑖 𝑉𝑖 − 𝐾𝑉𝑓 𝑉𝑓
𝛾−1
1
Adiabatic Work= 1− 𝛾 𝑃𝑓 𝑉𝑓 − 𝑃𝑖 𝑉𝑖
For an Ideal gas, PV=nRT
𝑛𝑅
Adiabatic Work= 𝑇𝑓 − 𝑇𝑖
1−𝛾
ISOCHORIC PROCESS

 Volume Constant, dV=0

𝑉
 Work done, 𝑊= ‫ = 𝑉𝑑𝑃 𝑓 𝑉׬‬0
𝑖

Isochoric Work=0
ISOBARIC PROCESS
𝑉 𝑉
Work done, 𝑊= ‫= 𝑉𝑑𝑃 𝑓 𝑉׬‬ 𝑃 ‫𝑉𝑑 𝑓 𝑉׬‬
𝑖 𝑖

= P 𝑉𝑓 − 𝑉𝑖

Isobaric Work= P 𝑉𝑓 − 𝑉𝑖

For an Ideal gas, PV=nRT

Isobaric Work= nR 𝑇𝑓 − 𝑇𝑖
FIRST LAW OF THERMODYNAMICS
 In a thermodynamic process involving a closed
system, the increment in the internal energy is
equal to the difference between the heat
accumulated by the system and the work done by
it.
𝑑𝑈 = 𝑑𝑄 − 𝑃𝑑𝑉

𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉

 It is the law of conservation of energy, adapted

for thermodynamic systems
 FIRST LAW OF THERMODYNAMICS
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
 Isothermal Process –T constant
𝑑𝑇 = 0 𝑑𝑈 = 0, 𝑑𝑄 = 𝑃𝑑𝑉
Heat is completely converted to external work

 Adiabatic Process –no heat exchange

𝑑𝑄 = 0, 𝑑𝑈 = −𝑃𝑑𝑉
Internal energy change is converted to external
work

Isobaric Process-𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉

Isochoric Process
Heat supplied is utilized for
𝑑𝑉 = 0, 𝑑𝑄 = 𝑑𝑈
Increase in Internal energy
Heat supplied is utilized for
Do external work
Increase in Internal energy
 APPLICATION OF FIRST LAW –HEAT CAPACITIES
MEYER’S EQUATION

 For a hydrostatic system, 𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉

 U is a function of (P, V, T)
 Choosing T&V
𝜕𝑈 𝜕𝑈
𝑑𝑈 𝑇, 𝑉 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
 First law becomes
𝜕𝑈 𝜕𝑈
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 = 𝑑𝑇 + 𝑑𝑉 + 𝑃𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
𝜕𝑈 𝜕𝑈
= 𝑑𝑇 + +𝑃 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
 Dividing throughout by dT
𝑑𝑄 𝜕𝑈 𝜕𝑈 𝑑𝑉
= + +𝑃
𝑑𝑇 𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝑑𝑇
 𝑑𝑄 𝜕𝑈 𝜕𝑈 𝑑𝑉
= + +𝑃
𝑑𝑇 𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝑑𝑇
Case I
V is constant, dV=0

𝜕𝑄 𝜕𝑈
=
𝜕𝑇 𝑉
𝜕𝑇 𝑉
But
𝜕𝑄
= 𝐶𝑣
𝜕𝑇 𝑉

𝜕𝑄 𝜕𝑈
𝐶𝑣 = =
𝜕𝑇 𝑉
𝜕𝑇 𝑉
 𝑑𝑄 𝜕𝑈 𝜕𝑈 𝑑𝑉
= + +𝑃
𝑑𝑇 𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝑑𝑇
Case 2
P is constant
𝜕𝑄 𝜕𝑈 𝜕𝑈 𝜕𝑉
= + +𝑃
𝜕𝑇 𝑃 𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇 𝑃
But
𝜕𝑄 𝜕𝑈
= 𝐶𝑝 𝐶𝑣 =
𝜕𝑇 𝑃 𝜕𝑇 𝑉

𝜕𝑄 𝜕𝑈 𝜕𝑈 𝜕𝑉
= + +𝑃
𝜕𝑇 𝑃
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇 𝑃
𝜕𝑈 𝜕𝑉
𝐶𝑝 = 𝐶𝑣 + +𝑃
𝜕𝑉 𝑇
𝜕𝑇 𝑃
𝜕𝑈 𝜕𝑉
𝐶𝑝 − 𝐶𝑣 = +𝑃
𝜕𝑉 𝑇
𝜕𝑇 𝑃
 For one mole of gas, PV=RT
 Differentiating, 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑅𝑑𝑇
𝜕𝑉
 But P=constant, 𝑃𝑑𝑉 = 𝑅𝑑𝑇 P =𝑅
𝜕𝑇 𝑃
𝜕𝑈 𝜕𝑉 𝜕𝑈 𝜕𝑉
𝐶𝑝 − 𝐶𝑣 = +𝑃 = +𝑅
𝜕𝑉 𝑇 𝜕𝑇 𝑃 𝜕𝑉 𝑇 𝜕𝑇 𝑃

𝜕𝑈
In an isothermal Process, 𝑑𝑇 = 0 , 𝑑𝑈 = 0, =0
𝜕𝑉 𝑇
𝜕𝑈 𝜕𝑉
𝐶𝑝 − 𝐶𝑣 = +𝑅 =𝑅
𝜕𝑉 𝑇
𝜕𝑇 𝑃

For Isothermal isobaric process

𝐶𝑝 − 𝐶𝑣 = 𝑅
HEAT ENGINE
 It is a machine that converts heat into
mechanical work
 Essential requirements of heat engine
 Source- High Temperature Reservoir
 Working Substance-System
 Sink-Low Temperature Reservoir
HEAT ENGINE
 Heat is absorbed from High Temperature
high temperature Reservoir

reservoir- 𝑄𝐻 𝑄𝐻

 Work is done by the 𝑊

system - 𝑊 System

𝑄𝐿
 Heat is rejected to the
Low Temperature
low temperature
Reservoir
reservoir- 𝑄𝐿

𝑄𝐻 = 𝑊 + 𝑄𝐿
HEAT ENGINE –EFFICIENCY
𝑂𝑢𝑡𝑝𝑢𝑡 𝑊𝑜𝑟𝑘 𝐷𝑜𝑛𝑒 𝑊
 Efficiency=η = = =
𝐼𝑛𝑝𝑢𝑡 𝐻𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑄𝐻

𝑄𝐻 = 𝑊 + 𝑄𝐿 , 𝑊 = 𝑄𝐻 − 𝑄𝐿

𝑊 𝑄𝐻 − 𝑄𝐿 𝑄𝐿
η= = =1−
𝑄𝐻 𝑄𝐻 𝑄𝐻

When 𝑄𝐿 = 0
η = 1 = 100%
But in real case, 𝑄𝐿 ≠ 0 η < 100%
Efficiency of an engine always less than 100%
SECOND LAW OF THERMODYNAMICS
KELVIN-PLANCK STATEMENT
 Based on heat engine

 For heat engine, 𝑄𝐻 = 𝑊 + 𝑄𝐿

 No process when 𝑄𝐿 = 0, 𝑄𝐻 = 𝑊

 No process is possible whose sole result is the

absorption of heat from a reservoir and the
conversion of this heat into work
REFRIGERATOR
 Heat is absorbed from High Temperature
LOW temperature Reservoir

reservoir- 𝑄𝐿 𝑄𝐻

 Work is done ON the 𝑊

system - 𝑊 System

𝑄𝐿
 Heat is rejected to the
Low Temperature
HIGH temperature
Reservoir
reservoir- 𝑄𝐻

𝑄𝐿 + 𝑊 = 𝑄𝐻
REFRIGERATOR–
CO-EFFICIENT OF PERFORMANCE
𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑄𝐿
Co-efficient of Performance =𝜔 = =
𝐼𝑛𝑝𝑢𝑡 𝑝𝑜𝑤𝑒𝑟 𝑊

𝑄𝐿 + 𝑊 = 𝑄𝐻 , 𝑄𝐿 = 𝑄𝐻 − 𝑊

𝑄𝐿 𝑄𝐻 − 𝑊
𝜔= =
𝑊 𝑊
SECOND LAW OF THERMODYNAMICS
CLAUSIUS STATEMENT
 Based on refrigerator

 For Refrigerator, 𝑄𝐿 + 𝑊 = 𝑄𝐻

 No process when 𝑊 = 0, 𝑄𝐿 = 𝑄𝐻

 No process is possible whose sole result is the

transfer of heat from a cooler to a hotter body
  Theoretical engine with
maximum possible
CARNOT’S REVERSIBLE ENGINE efficiency developed by
Carnot
 It is operating in carnot
cycle

Piston
Perfect Cylinder
gas
Diathermic wall

High Temp Non-conducting Low Temp

reservoir stand reservoir
 Cylinder placed on non-conducting stand
 Initially 1(𝑃1 , 𝑉1 , 𝑇𝐿 )

Piston
 Reversible adiabatic compression is
performed
 Volume decreases,
 Pressure increases Perfect Cylinder
gas
 Temperature increases

 2 (𝑃2 , 𝑉2 , 𝑇𝐻 ) Non-conducting
stand
2 (𝑃2 , 𝑉2 , 𝑇𝐻 )

1(𝑃1 , 𝑉1 , 𝑇𝐿 )
 Adiabatic Compression (1-2)

Compression-Work is done on the gas-

negative

𝑅
𝑊1 = − 𝑇𝐻 − 𝑇𝐿
𝛾−1

2 (𝑃2 , 𝑉2 , 𝑇𝐻 )

1(𝑃1 , 𝑉1 , 𝑇𝐿 )
 Piston
 Cylinder placed on high
temperature reservoir
 2(𝑃2 , 𝑉2 , 𝑇𝐻 )

 Reversible Isothermal expansion is Perfect Cylinder

performed gas
 Volume Increases, High
Temp
 Pressure decreases, reservoir
 Temperature constant
 3 (𝑃3 , 𝑉3 , 𝑇𝐻 ) 2 (𝑃2 , 𝑉2 , 𝑇𝐻 )
Isothermal expansion

3 (𝑃3 , 𝑉3 , 𝑇𝐻 )

1(𝑃1 , 𝑉1 , 𝑇𝐿 )
Isothermal Expansion (2-3)

Expansion-Work is done by the gas-positive

𝑉3
𝑊2 = 𝑅𝑇𝐻 𝑙𝑛
𝑉2

2 (𝑃2 , 𝑉2 , 𝑇𝐻 )
Isothermal expansion

3 (𝑃3 , 𝑉3 , 𝑇𝐻 )

1(𝑃1 , 𝑉1 , 𝑇𝐿 )
 Cylinder placed on non-conducting
stand
 3 (𝑃3 , 𝑉3 , 𝑇𝐻 )

Piston
 Reversible Adiabatic expansion is
performed
 Volume Increases,
 Pressure decreases, Perfect Cylinder
gas
 Temperature decreases

 4 (𝑃4 , 𝑉4 , 𝑇𝐿 ) Non-conducting
2 (𝑃2 , 𝑉2 , 𝑇𝐻 ) stand
Isothermal expansion
3 (𝑃3 , 𝑉3 , 𝑇𝐻 )

Adiabatic
1(𝑃1 , 𝑉1 , 𝑇𝐿 ) expansion

4 (𝑃4 , 𝑉4 , 𝑇𝐿 )
 Adiabatic Expansion (3-4)

Expansion-Work is done by the gas-positive

𝑅
𝑊3 = 𝑇𝐻 − 𝑇𝐿
𝛾−1
2 (𝑃2 , 𝑉2 , 𝑇𝐻 )
Isothermal expansion
3 (𝑃3 , 𝑉3 , 𝑇𝐻 )

Adiabatic
1(𝑃1 , 𝑉1 , 𝑇𝐿 ) expansion

4 (𝑃4 , 𝑉4 , 𝑇𝐿 )
 Cylinder placed on low

Piston
temperature reservoir
 4 (𝑃4 , 𝑉4 , 𝑇𝐿 )

 Reversible Isothermal compression

Perfect Cylinder
is performed gas
 Volume decreases, Low
 Pressure increases, Temp
 Temperature constant reservoir

 1(𝑃1 , 𝑉1 , 𝑇𝐿 )
2 (𝑃2 , 𝑉2 , 𝑇𝐻 )
Isothermal expansion

3 (𝑃3 , 𝑉3 , 𝑇𝐻 )

Adiabatic expansion
1(𝑃1 , 𝑉1 , 𝑇𝐿 )
4 (𝑃4 , 𝑉4 , 𝑇𝐿 )
Isothermal compression
Isothermal Compression (4-1)

Compression-Work is done on the gas-negative

𝑉4
𝑊4 = − 𝑅𝑇𝐿 𝑙𝑛
𝑉1

2 (𝑃2 , 𝑉2 , 𝑇𝐻 )
Isothermal expansion

3 (𝑃3 , 𝑉3 , 𝑇𝐻 )

Adiabatic
expansion
1(𝑃1 , 𝑉1 , 𝑇𝐿 )
4 (𝑃4 , 𝑉4 , 𝑇𝐿 )
Isothermal compression
EFFICIENCY
 Net work done, 𝑊 = 𝑊1 + 𝑊2 + 𝑊3 + 𝑊4
𝑅 𝑉3 𝑅 𝑉4
𝑊=− 𝑇𝐻 − 𝑇𝐿 +𝑅𝑇𝐻 𝑙𝑛 + 𝑇𝐻 − 𝑇𝐿 + −𝑅𝑇𝐿 𝑙𝑛
𝛾−1 𝑉2 𝛾−1 𝑉1
𝑉3 𝑉4
𝑊 = 𝑅𝑇𝐻 𝑙𝑛 − 𝑅𝑇𝐿 𝑙𝑛
𝑉2 𝑉1
Adiabatic Process
𝛾−1 𝛾−1
(1-2), 𝑇𝐿 𝑉1 = 𝑇𝐻 𝑉2
𝛾−1 𝛾−1 𝑅
(3-4) 𝑇𝐿 𝑉4 = 𝑇𝐻 𝑉3 𝑊1 = − 𝑇 − 𝑇𝐿
𝛾−1 𝐻
𝑉3
Dividing 𝑊2 = 𝑅𝑇𝐻 𝑙𝑛
𝑉2
𝑅
𝑉4 𝑉3 𝑊3 = 𝑇 − 𝑇𝐿
= 𝛾−1 𝐻
𝑉1 𝑉2 𝑉4
𝑊4 = − 𝑅𝑇𝐿 𝑙𝑛
𝑉1
 𝑊 𝑊
 Efficiency of heat engine, η = =
𝑄𝐻 𝑊2
 Since system is in contact with High temperature
reservoir during Isothermal expansion (2-3), 𝑄𝐻 = 𝑊2

𝑉3 𝑉
𝑅𝑇𝐻 𝑙𝑛 − 𝑅𝑇𝐿 𝑙𝑛 4
𝑉2 𝑉1
η=
𝑉3
𝑅𝑇𝐻 𝑙𝑛
𝑉2

𝑉3 𝑉3
𝑅𝑇𝐻 𝑙𝑛 − 𝑅𝑇𝐿 𝑙𝑛 𝑇𝐻 − 𝑇𝐿 𝑇𝐿
𝑉2 𝑉2
η= = =1−
𝑉3 𝑇𝐻 𝑇𝐻
𝑅𝑇𝐻 𝑙𝑛
𝑉2
CARNOT’S REFRIGERATOR
 Carnot cycle for engine High Temperature
Reservoir
performed in opposite
𝑄𝐻
direction-refrigeration cycle
 Co-efficient of Performance, 𝑊
𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑄𝐿 System
𝜔= =
𝐼𝑛𝑝𝑢𝑡 𝑝𝑜𝑤𝑒𝑟 𝑊
𝑄𝐿
 Since system is in contact with
Low Temperature
Low temperature reservoir Reservoir
during Isothermal compression
(4-1), 𝑄𝐿 = 𝑊4 𝑄𝐿 + 𝑊 = 𝑄𝐻
 𝑉4
𝑊4 𝑅𝑇𝐿 𝑙𝑛
𝑉1
𝜔= =
𝑊 𝑉 𝑉
𝑅𝑇𝐻 𝑙𝑛 3 − 𝑅𝑇𝐿 𝑙𝑛 4
𝑉2 𝑉1
𝑉
𝑅𝑇𝐿 𝑙𝑛 𝑉4
1
=
𝑉4 𝑉4
𝑅𝑇𝐻 𝑙𝑛 − 𝑅𝑇𝐿 𝑙𝑛
𝑉1 𝑉1

𝑇𝐿 𝑄𝐿
𝜔= =
𝑇𝐻 − 𝑇𝐿 𝑄𝐻 − 𝑄𝐿
CARNOT’S THEOREM AND COROLLARY
 No heat engine operating between two given
reservoirs can be more efficient than a Carnot
engine operating between the same two reservoirs

 Imagine
 A Carnot engine-R
 Irreversible engine-I
 Carnot engine-R Irreversible engine-I

Absorbs heat 𝑄𝐻 from High Absorbs heat 𝑄𝐻′ from High

Temperature Reservoir Temperature Reservoir
Performs work 𝑊 Performs work 𝑊
Rejects heat 𝑄𝐿 = 𝑄𝐻 − 𝑊 to Rejects heat 𝑄𝐿′ = 𝑄𝐻′ − 𝑊 to
Low Temperature Reservoir Low Temperature Reservoir
Efficiency, η𝑅 =
𝑊 𝑊
𝑄𝐻 η𝐼 = ′
𝑄𝐻
High Temperature
Reservoir

𝑄𝐻′ 𝑄𝐻

𝑊 𝑊
I R

𝑄𝐻′ − 𝑊 𝑄𝐻 − 𝑊

Low Temperature
Reservoir
 Let us assume 𝜂𝐼 > 𝜂𝑅

𝑊 𝑊
′ >
𝑄𝐻 𝑄𝐻

𝑄𝐻 > 𝑄𝐻′

𝑄𝐻 − 𝑄𝐻′ is positive
 High Temperature
Reservoir
 Let I drive R back ward
as refrigerator 𝑄𝐻′ 𝑄𝐻
 I-Engine
 R-Refrigerator 𝑊
I R
 I&R-Self acting machine System

𝑄𝐻′ − 𝑊 𝑄𝐻 − 𝑊

Low Temperature
Reservoir

Carnot Refrigerator-R Irreversible engine-I

Absorbs heat 𝑄𝐻 − 𝑊 from Absorbs heat 𝑄𝐻′ from High

Low Temperature Reservoir Temperature Reservoir
Work 𝑊 is done on the system Performs work 𝑊
Rejects heat 𝑄𝐻 to High Rejects heat 𝑄𝐿′ = 𝑄𝐻′ − 𝑊 to
Temperature Reservoir Low Temperature Reservoir
 High Temperature
Reservoir
𝑄𝐻′ 𝑄𝐻

𝑊
I R
System

𝑄𝐻′ − 𝑊 𝑄𝐻 − 𝑊
Low Temperature
Reservoir

Carnot Irreversible Self acting machine

Refrigerator-R engine-I
High temperature reservoir
Rejects heat 𝑄𝐻 Absorbs heat 𝑄𝐻′ Rejects heat 𝑄𝐻 − 𝑄𝐻′
Work done
𝑊 - on the system 𝑊 -by the system 𝑊 =0
Low Temperature Reservoir
Absorbs heat Rejects heat Absorbs heat
𝑄𝐿 = 𝑄𝐻 − 𝑊 𝑄𝐿′ = 𝑄𝐻′ − 𝑊 𝑄𝐿 − 𝑄𝐿′ = 𝑄𝐻 − 𝑄𝐻′
 • Self acting machine
transfer 𝑄𝐻 − 𝑄𝐻′ heat
High Temperature from Low to high
Reservoir temperature reservoir
𝑄𝐻′
without work
𝑄𝐻

𝑊
• Violates second law of
I R thermodynamics
System

𝑄𝐻′ − 𝑊 𝑄𝐻 − 𝑊 • So original assumption

• 𝜂𝐼 > 𝜂𝑅 is false
Low Temperature
Reservoir
• 𝜂𝐼 ≤ 𝜂𝑅
COROLLARY
 All Carnot engines operating between the same
two reservoirs have the same efficiency
 Consider 2 Carnot engines R1 & R2

High Temperature
Reservoir

𝑄𝐻′ 𝑄𝐻

𝑊 𝑊
R1 R2

𝑄𝐻′ − 𝑊 𝑄𝐻 − 𝑊

Low Temperature
Reservoir
 High Temperature
Reservoir
Case I
𝑄𝐻′ 𝑄𝐻
 Let R1 drive R2 back ward
as refrigerator R1
𝑊
R2
 R1-Engine System

 R2-Refrigerator 𝑄𝐻 − 𝑊
𝑄𝐻′ − 𝑊

 R1&R2 -Self acting machine Low Temperature

Reservoir

 From Carnot’s Theorem,

𝜂R ≤ 𝜂R
1 2 Carnot’s Theorem
I-Engine
R-Refrigerator
𝜂𝐼 ≤ 𝜂𝑅
 High Temperature
Reservoir
Case II
𝑄𝐻′ 𝑄𝐻
 Let R2 drive R1 back ward
as refrigerator R1
𝑊
R2
 R2-Engine System

 R1-Refrigerator 𝑄𝐻 − 𝑊
𝑄𝐻′ − 𝑊

 R1&R2 -Self acting machine Low Temperature

Reservoir

 From Carnot’s Theorem,

𝜂R ≤ 𝜂R
2 1 Carnot’s Theorem
I-Engine
R-Refrigerator
𝜂𝐼 ≤ 𝜂𝑅
 Case I, 𝜂 R ≤ 𝜂R
1 2
 Case II, 𝜂 R ≤ 𝜂R
2 1

 To satisfy both cases, only possibility is equality

𝜂 R = 𝜂R
1 2

Why maximum efficiency for Carnot Engine?

 Efficiency of Carnot engine is independent of
working substance
 The temperature of reservoirs remains same

 This is not practical case and that is why the

efficiency of practical engines is less than
theoretical Carnot engine