Chap. 3.

The Second Law

Law of Spontaneity, world gets more random

Kelvin - No process can transform heat completely into work

Chap. 3. The Second Law
Law of Spontaneity, world gets more random

Kelvin - No process can transform heat completely into work

The entropy of an isolated system increases in the course of

a spontaneous change.

- Entropy, the degree of randomness

- State function, completely specified by thermodynamic variables
- Unit: Energy/temperature (K)
- Thermodynamic definition:
Chap. 3. The Second Law
Law of Spontaneity, world gets more random

Kelvin - No process can transform heat completely into work

The entropy of an isolated system increases in the course of

a spontaneous change.

- Entropy, the degree of randomness

- State function, completely specified by thermodynamic variables
- Unit: Energy/temperature (K)
- Thermodynamic definition:
For surroundings,

because

The above relation holds

even for finite amount of heat
For surroundings,

because

The above relation holds

even for finite amount of heat

For adiabatic process,

For surroundings,

because

The above relation holds

even for finite amount of heat

For adiabatic process,

Isothermal expansion of an ideal gas

 Carnot Cycle (Ideal Gas)
1
I - (VI ,T1) II - (VII ,T1)

Fig. 3.6 (with

4 2
different notations)
3
IV - (VIV ,T2) III - (VIII ,T2)

1,3 - Reversible and isothermal processes

2,4 - Reversible and adiabatic processes
 Carnot Cycle (Ideal Gas)
1
I - (VI ,T1) II - (VII ,T1)

Fig. 3.6 (with

4 2
different notations)
3
IV - (VIV ,T2) III - (VIII ,T2)

1,3 - Reversible and isothermal processes

2,4 - Reversible and adiabatic processes

and
 Carnot Cycle (Ideal Gas)
1
I - (VI ,T1) II - (VII ,T1)

Fig. 3.6 (with

4 2
different notations)
3
IV - (VIV ,T2) III - (VIII ,T2)

1,3 - Reversible and isothermal processes

2,4 - Reversible and adiabatic processes

and
 Carnot Cycle (Ideal Gas)
1
I - (VI ,Tup) II - (VII ,Tup)

Fig. 3.6 (with

4 2
different notations)
3
IV - (VIV ,Tlo) III - (VIII ,Tlo)
 Carnot Cycle (Ideal Gas)
1
I - (VI ,Tup) II - (VII ,Tup)

Fig. 3.6 (with

4 2
different notations)
3
IV - (VIV ,Tlo) III - (VIII ,Tlo)

and , where

See further information 2.1 (page 69)

 Carnot Cycle (Ideal Gas)
1
I - (VI ,Tup) II - (VII ,Tup)

Fig. 3.6 (with

4 2
different notations)
3
IV - (VIV ,Tlo) III - (VIII ,Tlo)

and , where

See further information 2.1 (page 69)

 Carnot Cycle (Ideal Gas)
1
I - (VI ,Tup) II - (VII ,Tup)

4 2

3
IV - (VIV ,Tlo) III - (VIII ,Tlo)
 Carnot Cycle (Ideal Gas)
1
I - (VI ,Tup) II - (VII ,Tup)

4 2

3
IV - (VIV ,Tlo) III - (VIII ,Tlo)
 Carnot Cycle (Ideal Gas)
1
I - (VI ,Tup) II - (VII ,Tup)

4 2

3
IV - (VIV ,Tlo) III - (VIII ,Tlo)

Efficiency:
 Carnot Cycle (General)
1
I - (VI ,Tup) II - (VII ,Tup)

4 2

3
IV - (VIV ,Tlo) III - (VIII ,Tlo)

(First law)

Efficiency:

S is not a state function

 Carnot cycle A with Carnot cycle B with
1 1’
I - (T
(Tup) II - (T
(Tup) I’ - (T
(Tup) II’
II’ - (T
(Tup)

4 2 4’ 2’
3 3’
IV - (T
(Tlo) III - (T
(Tlo) IV’
IV’ - (T
(Tlo) III’
III’ - (T
(Tlo)
 Carnot cycle A with Carnot cycle B with
1 1’
I - (T
(Tup) II - (T
(Tup) I’ - (T
(Tup) II’
II’ - (T
(Tup)

4 2 + 4’ 2’
3 3’
IV - (T
(Tlo) III - (T
(Tlo) IV’
IV’ - (T
(Tlo) III’
III’ - (T
(Tlo)

Combine A and reverse of B, and assume

Then,

This contradicts the second law by Kelvin!

 Carnot Cycle (General)
1
I - (VI ,Tup) II - (VII ,Tup)

4 2

3
IV - (VIV ,Tlo) III - (VIII ,Tlo)

Efficiency:

Any cycle can be considered as the sum

of infinitesimal Carnot cycles (Fig. 3.9)
Clausius Inequality:
 Clausius Inequality:

(i) System does maximum work

for reversible process.

(ii) Consider a change of system through a reversible process

(1)
The same change can happen through another process.
(2)
 Clausius Inequality:

(i) System does maximum work

for reversible process.

(ii) Consider a change of system through a reversible process

(1)
The same change can happen through another process.
(2)

(1)=(2)

(i)
For adiabatic process
Entropy change due to phase transition

Normal transition temperature: temperature at which

two phases are in equilibrium at 1 atm.

Heat transfer during phase

transition is reversible

Constant pressure
Entropy change due to heating

Constant pressure

If Cp is independent
of temperature
Entropy of a gas

(Debye extrapolation)

Nernst heat theorem

Third law of thermodynamics

Standard (third law) entropy

- the entropy in the standard state under the

assumption that S=0 at T=0.

Entropy of reaction for

Standard of entropies of ions are defined such that

 Determines the spontaneous
Helmholtz free energy (free) process at constant volume

(no non-expansion work)

Determines the spontaneous

Gibbs free energy (free) process at constant process

(no non-expansion work)

 Determines the spontaneous
Helmholtz free energy (free) process at constant volume

(no non-expansion work)

Maximum work system can do in isothermal situation

Determines the spontaneous

Gibbs free energy (free) process at constant process

(no non-expansion work)

Maximum non-expansion work system can do in

isothermal and isobaric situation
Standard Gibbs energy of reaction

Standard Gibbs energy of

formation

The standard Gibbs energy of formation for

ions are defined such that

zero standard Gibbs energy of

formation at all temperature
Fundamental equation
closed system, no non-expansion work, reversible change

valid even for irreversible change

Assume

and

Assume that and

 (2)

(3)

(4)

(2’
(2’)

(3’
(3’)

(4’
(4’)
 (2)

(3)

(4)

(2’
(2’)

(3’
(3’)

(4’
(4’)

(2’
(2’)

(3’
(3’)

(4’
(4’)
Gibbs-Helmholtz equation

Important equation for

understanding phase transition
 At constant temperature,

Molar Gibbs energy Molar volume

For liquids or solids, Vm is insensitive to pressure change

For an ideal gas,

When