CY11001  Physical Chemistry 8/9/2019

Fundamental Concepts of 
Thermodynamics

CY 11001 CHEMISTRY
Autumn 2019‐2020

Second Law of Thermodynamics
Entropy

• A state function called entropy, is identified such that

ð
 is an exact differential
ð
 ∆ is independent of the path.

 can be measured for both reversible and irreversible 
processes

 can be estimated using the Third law of thermodynamics

 reflects the degree of disorder in a system

Srabani Taraphder, IIT Kharagpur 1
CY11001  Physical Chemistry 8/9/2019

Combining the 1st and 2nd law of 

thermodynamics

1st law:  ð ð

2nd law:      ð

For ð

Key Questions about Entropy

• Can we estimate the change in entropy, ∆ for different 
processes?

• How is entropy used to predict the following?

 the direction of spontaneous change
 the condition of equilibrium

• Can we use entropy to explain why the heat engines do 
not have the ideal efficiency?

Srabani Taraphder, IIT Kharagpur 2
CY11001  Physical Chemistry 8/9/2019

Entropy and Clausius Inequality 
• For any reversible engine, operating in cycle between two 
temperatures   and  ,  
ð
 

• For any arbitrary engine (NOT reversible) operating in cycle

between the same two temperatures and , with the same
input of

because    
ð

∴         ⇒

Entropy and Clausius Inequality 

ð
For any irreversible cycle                ∮

Irreversible Reversible
State 1 State 2 State 1

ð ð
∴

ð ð
⇒ ∆

Srabani Taraphder, IIT Kharagpur 3
CY11001  Physical Chemistry 8/9/2019

Entropy and Clausius Inequality 
For an irreversible change in state from state 1 to state 2

ð ð
⇒

Mathematical  statement of  2nd law of thermodynamics    

ð

ð Irreversible and spontaneous change in state 

ð Reversible process

ð Process associated with the change in state is NOT permitted 

Application to transformations in real systems
• From Clausius inequality 
ð

• In an isolated system, during an irreversible process,

ð ⇒  0

• For a real transformation in an isolated system, upon withdrawal

of an internal constraint, the system spontaneously changes
towards that direction that increases the entropy.

Srabani Taraphder, IIT Kharagpur 4
CY11001  Physical Chemistry 8/9/2019

Initial equilibrium state       Final equilibrium state       

Isothermal  Isothermal 
irreversible irreversible
compression expansion

What is ∆ as the system goes from    to    ?  

∆ if   
∆
The ideal gas will spontaneously expand 
under the given experimental condition

Initial equilibrium state       Final equilibrium state       

Isothermal 
irreversible
expansion

Under what condition does the gas stop expanding any further so 
that a new equilibrium state is reached?
∆ reaches a maximum when  is maximum 
∆ ⇒ is maximum when    
The ideal gas will spontaneously expand till it 
fills up the entire available volume

Srabani Taraphder, IIT Kharagpur 5
CY11001  Physical Chemistry 8/9/2019

Entropy Change in an Isolated System 
• Any natural change within an isolated system
is accompanied by an increase in entropy

• The entropy continues to increase as long as

the changes occur within the system

• When entropy attains its maximum value,

the system reaches a new equilibrium state.

Irreversible and spontaneous change in state 

No further change, a new equilibrium is reached

Process associated with the change in state is NOT permitted 

For an isolated system..

ENTROPY STATE FUNCTION

Calvin and Hobbes, ©Bill Waterson

Srabani Taraphder, IIT Kharagpur 6
CY11001  Physical Chemistry 8/9/2019

Maximization of Entropy in a closed system 

At equilibrium,  and 

What happens to internal energy when entropy is a maximum?

What happens to  and   when entropy is a maximum?  

What is  in a closed system? 

Since ,

At equilibrium,  ⇒

Srabani Taraphder, IIT Kharagpur 7
CY11001  Physical Chemistry 8/9/2019

What is the nature of the extremum w.r.t. U?

Let us examine the sign of  

At equilibrium
Let     , ) = 

What is the nature of the extremum w.r.t. U?

Let us examine the sign of  

At equilibrium

Srabani Taraphder, IIT Kharagpur 8
CY11001  Physical Chemistry 8/9/2019

Maximization of Entropy 

At equilibrium  and 

What happens to internal energy when entropy is a maximum?

At equilibrium 

When the system exhibits a maximum w.r.t.  , 
it also exhibits a minimum w.r.t. 

Condition of 
Spontaneity and Equilibrium
in an Isolated System 

Irreversible and spontaneous change in state 

No further change, a new equilibrium is reached

Process associated with the change in state is NOT

permitted 

Srabani Taraphder, IIT Kharagpur 9
CY11001  Physical Chemistry 8/9/2019

But real systems are NOT isolated

© Tenor

Calvin and Hobbes, ©Bill Waterson

Spontaneity and Equilibrium
In 
Isolated and non‐Isolated Systems 
How do we find a 
common condition?

Calvin and Hobbes, ©Bill Waterson

Srabani Taraphder, IIT Kharagpur 10