Lecture 3: Consequences of

the second law of

thermodynamics

Arti Dua

Department of Chemistry

IIT Madras

!
Entropy is a state function, but to calculate change in entropy
requires a reversible path.
 Reversible isothermal expansion of an ideal gas

Ideal and isothermal U(T)

Heat Reservoir T

The heat reservoir gives an amount of heat

to the gas at temperature T

The work done is stored in a spring attached to the moving

wall and can be used to compress a gas back to the initial state.
 Irreversible Free Expansion of an ideal gas
Joule’s Experiment p
free expansion

(irreversible)
reversible isothermal

Heat Reservoir T expansion

vacuu V
gas
m
Free expansion:
Since there is no change in temperature:
Heat Reservoir T
Entropy is a state function:
vacuu
gas
m There is no heat transfer between gas and its environment:

No work done in this process: increase in total entropy is a reflection of loss of useful energy
Note: the entropy of a gas is nonzero even though there is no heat transfer between system and
surroundings
 Entropy of Mixing of an Ideal Gas at Constant T

spontaneous,

irreversible (constant T)

reversible demixing

(constant T)

reversible mixing

(constant T)
piston permeable to A piston permeable to B
 Entropy is a function of state

For demixing process:

 To calculate S for any irreversible process, we
should first identify a reversible path.
Examples:

1. Heating (cooling) at constant volume:

2. Reversible phase change at constant T and p:
3. Irreversible phase change at constant T and p:
Carry out the irreversible process by adding up three reversible processes.
Consider the following sequence of processes for substance A: