Lecture 2 : The Second

Law of Thermodynamics

Arti Dua

Department of Chemistry

IIT Madras

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 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 to determine

1. The direction of spontaneous change.

2. The equilibrium state of a system.
 Sadi Carnot Rudolf Clausius Lord Kelvin

French Physicist and Military Engineer

German Physicist and Mathematician
British Mathematical Physicist and
1796-1832 1822-1888 Engineer

1824-1907
Carnot gave the first successful theoretical
In 1865, he introduced the concept

account of heat engines, now known as
of entropy
Carnot cycle
Various statements of Second Law

Impossible
Various statements of Second Law

Impossible
To obtain the upper limit on the efficiency of a heat engine Sadi Carnot in 1824
considered a theoretical cycle called “The Carnot Cycle”. It represents a perfect
engine that can not be built in practice.

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The Carnot Cycle

• It considers a specific reversible cycle

• Itsubstance.
considers an ideal gas as a working

• It shows that entropy is a state function.

The Carnot Cycle

compression
Efficiency of Carnot Cycle

1
 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.
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If one path of the cycle is made irreversible….

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An irreversible cycle is less efficient than reversible one.
Clausius inequality:

A. System is isolated and irreversibly changes from 1 to 2.

B. System is brought into contact with heat reservoir and changes reversibly from
2 to 1.
 Independent of path
depends on whether the path is reversible or irreversible

Irreversible:

Reversible:
 Mathematical statement 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
 The Second Law (in terms of Entropy)

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.