Second law of thermodynamics

Second law of thermodynamics

This law simply ensure the direction of flow of heat , according to which heat always flows
from body at higher temperature to body at lower temperature.
Kelvin’s Statement
It is impossible to get a continuous supply of work from a body by cooling it to a
temperature lower than of its surroundings.

Clausius Statement
It is Impossible to make heat flow from a colder body to a warmer body without doing
external work.
Heat Engine
It is device used for conversion of heat energy into mechanical energy. There are two types
of engine, internal combustion engine ( e.g. petrol engine ) and external combustion engine
( e.g., steam engine).
It consist of three basic parts,
1. The source :-
It provides heat to the working substance. It is at higher temperature.
2. The working substance ( Heat Engine ) :-
It takes heat from source and convert a part of absorbed heat into useful work.
Remaining heat is rejected to the sink.
3. The sink :-
It has fixed low temperature to which any amount of heat can be rejected.
Heat Engine Efficiency of Heat Engine (ƞ)
W=-
Source =
Efficiency (ƞ) =

ƞ = 1- X 100%
Heat W=-
Engine
In terms of temperature,
ƞ = 1- X 100%
Sink
Carnot Engine
A Carnot engine is a theoretical engine which
is used to convert heat into mechanical work. It is
an ideal heat engine with maximum efficiency.
Parts of Carnot Engine
1. The source :-
It has fixed high temperature () from which heat engine draws energy.
2. The working substance ( Heat Engine ) :-
It consist of cylinder with non-conducting sides and conducting bottom containing a
perfect gas as the working substance.
3. The sink :-
It has fixed low temperature () to which any amount of heat can be rejected.
The source and sink have infinite thermal capacities.
A Carnot engine is perfectly reversible engine due to given reasons,

1. No friction between cylinder and piston

2. Operation on ideal gas are performed slowly

3. Loss of heat is prevented by using insulated piston and insulated walls of cylinder.

4. The base of cylinder is conducting such that temperature remains constant due to infinite
thermal capacities of source and sink ( Isothermal process ).
Carnot Cycle :-

Step I :- Isothermal expansion ( to )

= = R ln ( )

Step II :- Adiabatic Expansion ( to ) Fig :- PV Diagram of Carnot cycle

= [- ]

=[ -]
Step III :- Isothermal compression ( to )

= = R ln ( )

Step IV :- Adiabatic Compression ( to ) Fig :- PV Diagram of Carnot cycle

=- [ - ]

Then, total work done by Carnot engine per cycle is,

W= + - - = R ln ( ) - R ln ( )
Here, =

Hence, W= R ln ( ) - R ln ( )

Or, W = R [ - ] ln ( )
Efficiency of Carnot Engine (ƞ)
Efficiency (ƞ) = =

ƞ = 1- X 100%

In terms of temperature,
ƞ = 1- X 100%
Petrol Engine (Otto Engine)
 A petrol engine is heat engine which uses a mixture of air and petrol. It consist of cylinder
having inlet and outlet valve along with spark plug. It is fitted with movable piston.

1. First Stroke (Suction stroke ) :-

The inlet valve opens and outlet valve closes.
Air-petrol mixture is sucked in.

2. Second Stroke (Compression stroke ) :-

Piston moves inward.
Fuel is compressed adiabatically.
Temperature rises to 600 °C.
The fuel is then ignited using spark plug.
heat is absorbed.
3. Third Stroke (Working stroke ) :-
Due to ignition, gas expands rapidly.
The piston is pushed out with great force causing adiabatic expansion.
Some external work is done during this process.

4. Fourth Stroke ( Exhaust stroke ) :-

The outlet valve opens due to high pressure
Inlet valve closes.
The expanded gas is allowed to escape.
The burnt fuel is removed.
heat is rejected to sink.
Working and PV Diagram of a petrol engine
Efficiency (ƞ)
ƞ = 1- x 100%

= 1- x 100%

ƞ = 1- x 100%

Where, ρ = is adiabatic compression ratio

Diesel Engine
 A diesel engine is an internal combustion heat engine that uses air-diesel mixture as fuel.
It consist of cylinder having inlet valve , inlet nozzle N and outlet valve . It is fitted with movable
piston.

1. First Stroke (Intake stroke ) :-

Inlet valve opens.
Air comes in.
Volume increases at constant pressure.

2. Second Stroke (Compression stroke ) :-

Air inside cylinder is compressed to th of its initial volume
Pressure and temperature to increase.
3. Third Stroke (Working stroke ) :-
Increased pressure causes piston to push outward.
Expansion of air at constant pressure.
The diesel is spread through inlet nozzle N,
Diesel burns instantly to produce large amount of heat.
Pressure increases due to heat
Piston is pushed with adiabatic increase of volume.

4. Fourth Stroke ( Exhaust stroke ) :-

The outlet valve opens.
Burnt fuel is removed at constant volume,
Pressure decrease.
heat is rejected to sink.
Remaining gas are forced to move outward and volume decreases to original level.
Working and PV Diagram of a diesel engine
Efficiency (ƞ)
ƞ = 1- x 100%

= 1- x 100%

ƞ = 1- x 100%

Where, ρ = is adiabatic compression ratio

 Petrol Engine
• Less efficient (around 26%) than diesel
engine.
• Petrol is more expensive than diesel.
• Is light weight and can be fitted on two
wheelers and airplanes.
• Requires spark plug so there is risk of
fire due to explosion of petrol vapour
by Spark.
Diesel Engine
• More efficient (around 40%) than petrol
engine.
• Diesel is less expensive than petrol.
• Heavy and cannot be fitted on two
wheelers and airplanes.
• No risk of fire since doesn’t require
spark plug
Refrigerator :-
A refrigerator is a heat engine that operates in reverse direction. In this engine, working
substance take heat from cold body (inside refrigerator) and reject it to hot body ( or external
atmosphere). Thus, external energy is used for this purpose of transfer of heat from cold body to
hot body.
Hot temperature
Coefficient of performance ,
β=

Refrigerant W=-
=
= 1

In winter less work is required to be done to transfer heat

from cold to hot body, compared to that in summer. Low Temperature
Entropy :-
It is the degree of disorder or randomness in the system. It represent the unavailability of a
system's thermal energy for conversion into mechanical work.
It can also be defined as the measure of a system’s thermal energy per unit temperature that
is unavailable for doing useful work.
The change in entropy dS, when system changes from one equilibrium to another is ,
dS = When heat is added, dQ is taken +Ve, when heat is subtracted from
system, dQ is taken –Ve . T is absolute temperature of system.
When system changes from state A, to state B, entropy of state B concerning state A is,
S= =
In terms of entropy, second law of thermodynamics can be stated as, “ Every physical or
chemical process in nature takes place in such a manner that total entropy increases.”