Ch.

3 The Second and Third Laws

Entropy
The measurement of entropy
Concentrating on the system
Combining the first and second laws

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016

 • In nature, some things happen naturally but some things don’t.
ex) A gas expands to fill the available volume.
Hot body cools to the temperature of its surroundings.
A chemical reactions runs in one direction rather than
another.
• There is a spontaneous direction in a change.
• For the spontaneous change, no work is required to bring it
about.
• However, for the non-spontaneous change, work should be
done to bring it about.
ex) A gas can be confined to a smaller volume.
An object can be cooled by using a refrigerator.
Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-2
 • In thermodynamics, ‘spontaneous’ means a natural tendency
for a change.
• However, the spontaneous change may or may not be
realized in practice.  Thermodynamics is silent on the rate of
the change.
• The 2nd law of thermodynamics determines the spontaneous
direction in a change.

No process is possible in which the sole result is the

absorption of heat from a reservoir and its complete
conversion into work. Kelvin

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-3
 • This process shows a heat engine with a
efficiency of 100 %.
 The heat absorbed from a hot source is
completely changed into work in the
engine.

• The Kelvin’s statement means that such a process is

impossible, although the process is not conflict with the 1st law.

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-4
 • What determines the direction of spontaneous change?
 The energy of the system tends toward a minimum.
(Is this a correct answer? No.)
ex 1) A perfect gas expands spontaneously into a vacuum.
For the isothermal free expansion, U = 0 (w= 0 and q
=0).
ex 2) If the energy of a system decreases during a
spontaneous change, the energy of the surroundings
must increase by the same amount. (1st law)

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-5
 • In the 1st law, the internal energy (state function) was
introduced to identify permissible changes.
• For a permissible change, the internal energy of an isolated
system remains constant.

• In the 2nd law, the entropy (state function) is introduced to

identify spontaneous changes among those permissible
changes.
• For a spontaneous change, the entropy of an isolated system
increases in a course of a spontaneous change.

S tot  0
where Stot is the total entropy of the system and its surroundings.
Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-6
 • In thermodynamics, the definition of entropy concentrates on
the change in entropy (dS) which occurs as a result of a
physical or chemical change.
dqrev
• The thermodynamic definition of entropy is: dS 
T
• For a measurable change:
f dqrev
S  
i T

• To calculate S of a system, we should find a reversible

path !!!

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-7
 Calculate the entropy change of a sample of perfect gas when
the volume occupied by 1.00 mol of the perfect gas is doubled
at any constant T.
f dqrev 1 f q rev
For an isothermal expansion, S   i T

T 
i
dqrev 
T

U  wrev  q rev  0

 Vf  Vf Vf nRT Vf
q rev   wrev   
 
Vi
pex dV  
 Vi
pdV  
Vi V
dV  nRT ln
Vi

Vf
 S  nR ln
Vi
Vf
S  nR ln  1 mol  8.31 J/K  mol  ln2  5.76 J/K
Vi
Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-8
 • Now consider the change in entropy of the surroundings
(Ssur).
• The surroundings consist of a reservoir of constant volume.
• So the energy transferred to the surroundings as heat (dqsur)
can be identified with the change in their internal energy (dUsur).

• The dUsur is independent of whether the process is reversible

or irreversible.  The dqsur is also independent of the path.
dqsur ,rev dqsur
dS sur   dqv, sur  dU
Tsur Tsur
• For a measurable change:
1 qsur
 dS
dq
  sur S sur   dqsur   Tsur is constant.
sur
Tsur Tsur Tsur
Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-9
Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-10
 Surroundings
System
dqrev dqsur
dS  dS sur 
T Tsur
f dqrev
S   S sur 
qsur
i T Tsur

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-11
 • An atom or molecule can possess only certain energies, called
its energy levels.

Low T High T
• At T = 0, only the lowest energy state is
occupied by all molecules.
• Raising T excites some molecules into
higher energy states.
• At T = infinite, all energy states are equally
populated.

• These remarks are summarized quantitatively in the

Boltzmann distribution.
Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-12
 Ei

Ni e kT
• The Boltzmann distribution is:  Ei
N 
e
i
kT

where k  1.38110 23 J/K and Ni is the number of molecules

in a sample of N molecules that will be found in a state with an
energy Ei at a temperature T.

• Boltzmann also proposed that the entropy of a system is given

by
S  k ln W (called Statistical entropy)
where W is the number of microstates, the way in which
the molecules of a system can be arranged while keeping the
total energy constant.
Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-13
 S  k ln W

• If W=1, only one way of achieving a given energy, all

molecules in exactly the same state.  S = 0
• If W>1, S>1.
• For a given total energy, if more molecules can participate in
the distribution of energy, there are more microstates.
• Thus the entropy increases with the number of the
participating molecules.

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-14
 S  k ln W • At high T, molecules in a system can
occupy a large number of the available
energy levels.

High T • So, small additional transfer of heat will lead

to a relatively small change in the number of
accessible energy levels.
 Small increase of W (i.e. S)

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-15
 • At low T, molecules in a system can occupy
S  k ln W a small number of the available energy
levels.
• So the transfer of the same quantity of heat
Low T will increase the number of accessible energy
levels rather significantly.
 Large increase of W (i.e., S).
dqrev 1
dS  dS 
T T

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-16
 • Entropy is a state function.
• To prove this assertion, we need to prove that the integral of
dqrev/T around an arbitrary cycle is zero.
dqrev
 T 0
where the symbol  denotes integration around a closed
path.

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-17
 dqrev
• Now we prove the equation   0 in the following steps.
T

1. To show that the equation is true for a special cycle

(Carnot cycle) involving a perfect gas.
2. To show that the result is true whatever the working
substance.
3. To show that the result is true for any cycle.

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-18
 • The Carnot cycle consists of four reversible stages involving a
perfect gas.

AB: Reversible isothermal expansion

(at high T)
BC: Reversible adiabatic expansion
T falls from Th to Tc.
CD: Reversible isothermal compression
(at low T)
DA: Reversible adiabatic compression
T rises from Tc to Th.

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-19
 dqrev
Proof of step 1: To show that the equation is true for a
 T 0
special cycle (Carnot cycle) involving a perfect gas.

• Entropy change around the Carnot cycle:

qh qc q h qc
 dS  Th  0  Tc  0  Th  Tc  0
qh Th
since q
 
c Tc for a perfect gas
(see Justification 3.1).

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-20
 • Reading: 3A Entropy (p.118 ~ 124)

Prof. Yo-Sep Min Physical Chemistry I, Spring 2016 Lecture 11, Ch. 3-21