Lecture 3: The Second

Law of
Thermodynamics
 Introduction:The Second Law

All real changes which are natural have a direction:

> A gas expands to fill the available volume.

> A hot body cools to the temperature of the surroundings.
> A chemical reaction runs in one direction rather than the other.

Spontaneous Processes: direction of change which

does not require work to be done to bring it about.
 The First Law

The first law of thermodynamics is the most general statement about

conservation of energy.

There is no notion of direction; both spontaneous and non-spontaneous

processes conserve energy and obey the first law of thermodynamics

It suggests that engine can run in a cycle and can convert heat into useful work.
 The Second Law of Thermodynamics...

• Puts restrictions on useful conversion of heat into work.

• Introduces the notion of directionality in spontaneous
processes.

• Provides a set of principles for

1. determining the direction of spontaneous change.2.
determining the equilibrium state of a system.
Various statements of Second Law

Impossible
Various statements of Second Law

Impossible
 Various Statements of Second law
Entropy: mathematical statement

There is a state function defined as

For an isolated where equality holds

system for reversible and
inequality for
irreversible processes.

The entropy of an isolated system never

decreases
 How to link various statements of second law?

Maximum 1. Kelvin statement

work theorem for engines
Mathematical statement:
Entropy as state function
2.Clausius statement
for refrigerators

1. Kelvin statement
Carnot Cycle Mathematical statement:
for engines
Entropy as state function

2.Clausius statement
for refrigerators
 The Maximum Work Theorem

System
A B

Heat source Work source

The delivered work is maximum and the delivered heat is minimum if the
entire process is reversible,
 The Maximum Work Theorem

First Law: Conservation of Energy

System

Surroundings
 The Maximum Work Theorem
Second Law: The entropy of an isolated system increases.

Reversible
process: =

=
 The Maximum Work Theorem

First Law:

Second Law: =

=
Reversible work
 Engine

Energy Source
(Furnace, Boiler...)
Th

Cooling System
Machinery
Tc
 Engine

work performed
Efficiency =
heat absorbed
 Refrigerator

Ambient
Atmosphere
Th

Refrigerator Power Plant

Tc Rev. Work Source
 Refrigerator

Heat removed
Efficiency =
Work required
 The Carnot Cycle

• It considers a specific reversible cycle

• It considers an ideal gas as a working
substance.

• It shows that entropy is a state function.

The Carnot Cycle
Efficiency of Carnot Cycle
 Carnot cycle for an ideal gas

Isothermal

Adiabatic

Isothermal

Adiabatic
 Carnot cycle:

In the limit of infinite number of cycles

Entropy is a state function, but to calculate change in entropy
requires a reversible path.