MSE 203: Thermodynamics of

Materials

CH3

The Second Law of

Thermodynamics
 Introduction
• The 1st law defines the relation between the change in the internal energy , work and
heat.

• Is there a limit on how much work can be done by the system?

• The 2nd law answers this question.
• First we have to define two type of processes (reversible and irreversible)
• Also we will introduce a new state function called the entropy (s)

• Entropy is a state function for reversible and increases as the degree of irreversibility
increases.
• Entropy and Time's Arrow?
 Entropy
• For an isolated system, equilibrium achieved when entropy is maximized

• Cosmology – entropy of black holes

• Information science

• Computer sciences –entropy of an information source

• Linguistics – entropy of a language

 Introduction
• Heat flows from hot to cold bodies

• Gases tend to mix and will not separate naturally

• These natural directions (spontaneous) of change increases the entropy of

an isolated systems.

• Does spontaneous mean immediately?

• Is the transformation of diamond to graphite spontaneous?

 Introduction
• If the system is initially in equilibrium with its surroundings, then, it will
remain in this equilibrium state.

• IF the initial state is not the equilibrium state, the system will
spontaneously (without any external influence) move toward its
equilibrium state.

• The equilibrium state is a state of rest

 Entropy and the Quantification of irreversibility
• There are two types of spontaneous processes:
• Work conversion into heat
• Transfer of heat down a temperature gradient

• Entropy produced by the system, ΔSʹ , is given by

• As the process irreversibility increases the produced entropy increases

• Reversible process is the limit at which no degradation of energy occurs.

 Thought experiment 1
• If we have a metal rod with a uniform temperature as the initial state.

• Can this rod become hot at one end and cold in the other end
spontaneously?

• What about the opposite?

• Why one of them is allowed and not the other? Isn't the 1st law satisfied
for both cases?
 Thought experiment 2
• What about having ideal gas initially occupying the full container to only
occupy half of it. Is this allowed?

• What about the opposite?

• Does any of the two cases violate the 1st law?

• Why one of them is allowed and not the other?

 Reversible Isothermal Expansion of an Ideal Gas
• For ideal gas the internal energy is function of T only.

• So ∆U = 0 and q=w

• The work done by the gas during the expansion is

• The entropy change for the system is

• What will be the entropy change for the reservoir?

 Example 1
A heat engine is operating in a Carnot
cycle: all processes are reversible. For
each of the processes, obtain
expressions for the change in entropy
of the engine and the change in
entropy of the surroundings after one
cycle. Assume one mole of an ideal
monatomic gas.
 Example 1
1. For the reversible isothermal expansion process from A to B :

2. For the reversible adiabatic expansion process from B to C :

3. For the reversible isothermal compression process from C to D :

4. For the reversible adiabatic compression process from D to A :

 Example 2
The initial state of 1 mole of a monatomic ideal gas is P = 10 atm and T = 300 K.

Calculate the change in the entropy of the gas for

a. An isothermal decrease in the pressure to 5 atm

b. A reversible adiabatic expansion to a pressure of 5 atm

c. A constant-volume decrease in the pressure to 5 atm