Homework: Read Sample Problems page 540 and page 541

Sample Problem (p. 541)

Suppose 1.0 mol of nitrogen gas is confined to the left side of the
container of the figure below. You open the stopcock, and the volume
of the gas doubles. What is the entropy change of the gas for this
irreversible process? Treat the gas as ideal.
dQf
S  S f  Si  i
T

Vf Vf
Q  nRT ln  S rev  nR ln
Vi Vi
We have n= 1 mol, Vf/Vi=2:  S rev  1.0  8.31 ln 2  5.76 (J/K)
S irrev  S rev  5.76 (J/K)
Sample Problem:
The pericarp part of a popcorn kernel is a small container of liquid
water. When the popcorn is heated to ~1800C, the pericarp walls burst,
and the liquid vaporizes so rapidly that the vapor explodes the rest of
the kernel to many times its original volume. The explosion produces the
audible pop of the popcorn. If the water in a pericarp has a mass of
about 4 mg, what is the change in entropy of the water due to the
vaporization and expansion?

We calculate ΔS of the irreversible process (kernel => popped popcorn)

by calculating two reversible processes: (1) vaporization at 1800C;
(2) adiabatic expansion of the vapor (the process occurs so rapidly,
so it is adiabatic)
Process 1: Vaporization, T = constant

f dQ Q mLv
S1  i T
 
T T
Lv = 2256 kJ/kg: latent heat of vaporization of water

2256  103  4  10 6
S   1.99  10  2 (J/K )
453
Process 2: Adiabatic expansion, dQ = 0
S 2  0
Total change in entropy: S  S1  S 2  0.02(J/K)
Important Notes:
• Free expansion process (Q = 0, irreversible): dQ =0 but dS > 0,
the formula dS = dQ/T is not applicable.
• Adiabatic process (Q = 0, reversible): dQ =0, dS = 0
Entropy as a State Function
Key idea: To calculate the entropy change of a process, we need to
make that process reversible, which is done slowly in a series of
small steps with the gas in an equilibrium state at the end of each
step.
dEint  dQ  dW
nCV dT pdV
dQ  pdV  nCV dT
dQ dV dT
 nR  nCV
T V T
The entropy change: f dQ f dV f dT
S  i  i nR  i nCV
T V T
Vf Tf
S  nR ln  nCV ln
Vi Ti
the entropy change only depends on properties of the initial and
final states, therefore we say entropy is a state function.
 Chapter 4 Entropy and the Second Law of
Thermodynamics

4.1. Reversible, Irreversible Processes and Entropy

4.2. The Second Law of Thermodynamics

4.3. Entropy in the Real World: Engines
4.4. A Statistical View of Entropy
4.2. The Second Law of Thermodynamics
If a process occurs in a closed system, the entropy of the
system increases for irreversible processes and remains constant
for reversible processes. It never decreases.

• Irreversible processes (ex: free expansion):

Irreversible

Q
S gas   0 (gas received energy as heat)
T
• Reversible processes:

• (a) to (b): Q > 0,

• (b) to (a): Q < 0,

This energy is extracted from the gas and

transferred to the reservoir.

• We now consider a closed system gas + reservoir:

Q
S gas 
T S system  0 (closed system)
Q
S reservoir 
T
The second law of thermodynamics for a closed system:

S  0
4.3. Entropy in the Real World: Engines
• A heat engine is a device that extracts energy from its environment
in the form of heat and does useful work.

• A working substance is the heart of every engine, e.g., in a steam

engine the working substance is water (vapor and liquid).

• If an engine is to do work, the working substance must operate in a

closed cycle.
a. A Carnot Engine (an ideal engine):

What is an ideal engine?

•In an ideal engine, all processes are reversible and no wasteful energy
transfers occur due to, say, friction and turbulence.
The elements of a Carnot engine
•The Carnot cycle consists of two isothermal (ab and cd) and two
adiabatic processes (bc and da).

Adiabatic

Isothermal

•The working substance absorbs energy |QH| from a thermal reservoir

at a constant temperature TH and discharges |QL| to a second
reservoir at a constant lower temperature TL.
 The work in the Carnot cycle:

Eint  0
W  QH  QL
The entropy change of the working substance:
QH QL
S  S H  S L  
TH TL
For a closed cycle:

QH QL
S  0  
TH TL
energy we get W
The Efficiency of any engine:  
energy we pay for QH
•For a Carnot engine:
QH  QL QL TL
C   1  1
QH QH TH

•A perfect engine: QL=0, ε = 1

b. Stirling Engine:

The efficiency of a Stirling engine is lower than

that of a Carnot engine operating between the
same two temperatures.
http://ocw.mit.edu/
c. Entropy in the Real World: Refrigerators Element of a Refri.
•In an ideal refrigerator, all processes
are reversible and no wasteful energy
transfers occur due to, say, friction
and turbulence.
•The Efficiency of a refri. (coefficient
of performance):
QL
K
W
For a Carnot refri. (an ideal refri.):

W  QH  QL
QL
KC 
QH  QL
TL
KC 
TH  TL
 • A Perfect Refrigerator:
W  QH  QL  0
• We consider a closed system Refrigerator
+ two Reservoirs:
Q Q
S  
TH TL
TH  TL  S  0
this violates the 2nd law of thermodynamics
or a perfect refrigerator does not exist.
d. The efficiencies of Real Engines:
• Any real engine X whose efficiency must smaller than that of a
Carnot engine: εX < εC

Real engine Carnot engine

W W

Q 'H QH
•To prove the claim above, we couple engine X to a Carnot refrigerator:

We assume: εX > εC

W W
'

QH QH
W
is the efficiency of the
QH Carnot refri. when
operated as an engine

Q H  Q 'H
The 1st law:
QH  QC  Q 'H  QC'

Let Q  QH  Q  QC  Q  0
'
H
'
C

this coupling acts like a perfect

refrigerator! (ΔS<0)
4.4. A Statistical View of Entropy
•We consider 6 molecules in an insulated box.
•At any instant, a given molecule will be either
in the left or the right half of the box.

•Let n1 be the number of molecules in the left

and n2 be that in the right.
•A set (n1,n2) is called a configuration of the
six molecules.
For a given configuration, we can have different
arrangements of the molecules, which are called
microstates.
Example: for Configuration III (4,2), the
number of microstates or the multiplicity W:
6!
WIII   15 (6!: six factorial)
4!2!
In a general case: N!
W  15
n1!n2 !
Probability and Entropy:
L. Boltzmann derived a relationship between the entropy S of a
configuration of a gas and the multiplicity W of that configuration:

S  k ln W
Sample Problem (p. 553)
In Sample (p. 541), we already calculated the entropy change
for a free expansion:

Now, using the Boltzmann equation above to calculate ΔS!

Initial state, the configuration is (N,0):

Final state, the configuration is (N/2,N/2):

Initial entropy:

Final entropy:

Using Stirling’s approximation: ln N ! N (ln N )  N

The entropy change:

 The same result as the previous one (sample p.541)

Homework: 1, 2, 3, 5, 8 (page 556)
Final Exam: Chapter 18, 19, and 20 (not including “Engines”)

Assignment:
• a group of 5 people
• each group submits ONLY 1 report