VIII.

Entropy
1. Macroscopic definition of entropy

dS

dQ
T

for a reversible process at constant T

dQ is path dependent
dS is path independent
S is additive function

S is function of state

2.The second law of thermodynamics

dQ
dS
T

for any process (including irreversible)

For closed, isolated system

(dQ = 0):

dS 0

any reversible cycle: S=0

any irreversible process in closed isolated system: S>0

Example 1: This P-V diagram represents a system consisting of a

fixed amount of ideal gas that undergoes three different processes in
going from state A to state B. Rank the change in entropy of the
system for each process.
P

State A

S1 = S2 = S3 = SB - SA

I
State B

The same as:

T1 = T2 = T3 = TB - TA
U1 = U2 = U3 = UB - UA

Example 2: Which of the following statements is false?

A. The change of entropy in a cyclic process is zero
B. The change of entropy for any adiabatic process is zero
C. The change of entropy for any isothermal process is zero
D. Entropy for a closed, isolated system is constant
E. Entropy of a system can decrease

Example 3: 50.0 kg of water is converted to ice at 0.0C.

What is the change in entropy of water?
m = 85.0

kg
T = 0.0C
L = 334*103 J/kg
S - ?

Q mL
S

T
T
50.0kg 334 103 J / kg
S
61kJ / K
273K

Example 4: The isolated system is 50.0 kg of ice at 0 C plus the

temperature reservoir at slightly above 0 C that is used to melt the ice.
What is the change in entropy of the system when the ice is melted ?
Solution:
The system is isolated:

Qice = -Qreservoir

The ice and the reservoir are at almost the same temperature: Tic = Treservoir=T
The system consists of both the ice and the temperature reservoir:

S system S ice S reservoir

Qice Qreservoir Qice Qice

0
T
T
T
T

S = 0. Therefore the process is reversible!

3. Entropy of ideal gas

dQ dU dW nCV dT nRTdV V
dT
dV
dS

nCV
nR
T
T
T
T
V
dU nCV dT
dW PdV nRTdV V

T2
S S 2 S1 nCV ln
T1

V2
nR ln

V1

3a. Free expansion of ideal gas

A given amount of an ideal gas undergo free expansion from volumeV1 to V2
Gas forms a closed and thermally isolated system. Because of that:

W=0, Q=0
U=0
T=0
T1 = T2
General equation for the entropy change of any ideal gas:

T2
S nCV ln
T1

V2
nR ln

V1

V2
S nR ln
V1

Closed and thermally isolated system with S>0: the process is irreversible!
Example: Two moles of an ideal gas undergo an adiabatic free expansion
from V1 = 1.00 L to V2 = e1.00 L = 2.72 L. (The gas is an isolated system).
The change in the entropy of the gas is __ J/K.

S 2.00mol 8.31J / mol K ln 2.72 16.6 J / K 0

The process is irreversible!

3b. Reversible isothermal expansion of ideal gas

Sgas nCV ln

Isolatedsystem =
gas+Treservoir(heatsource)
Theheatabsorbedbythegasis

ReversibleIsothermalExpansion(V2 V1 )
T2 T1 T , soln(T2 / T1 ) 0and

Qgas Wgas nRT ln

IdealGas :
T2
V2

nR
ln
V
T1
1

Sgas

V
nR ln 2
V1

ButSgas 0,sodoesn'tthismeanthat
theprocessisnotreversible?
Answer:No.Onemustconsideronly
isolatedsystemstoanswerthat.

V2
.
V1

Thechangeinentropyofthegasis
Sgas

Qgas
T

V2
,whichagrees

V
1

nR ln

withourpreviousresult.Theheat
absorbedbythereservoirisQreservoir Qgas .
Thechangeinentropyofthesystemis
Qgas Qgas
Ssystem Sgas Sreservoir

0.
T
T
Thustheprocessisreversible.

3c. Reversible Adiabatic Expansion of Ideal Gas

IdealGas :
Sgas

T
V
nCV ln 2 nR ln 2 (1)
T1
V1

ReversibleAdiabaticExpansion(V2 V1 )
Herethegasisanisolatedsystem(W Q 0).
ThereforeweexpectSgas 0.Adiabatic:
TV 1 constant=T1V1 1 T2V2 1 , so
T2 V1 1 V1

T1 V2 1 V2

T
V
ln 2 (1)ln 2
T1
V1

V
2
V1

1 1

and

V2
.

V
1

( 1)ln

SubstitutingthisexpressionintoEq.(1)gives
V2
.(2)
V1

Sgas n CV ( 1) R ln

Foranidealgas,
Cp CV R

.Therefore,
CV
CV
CV R
R
1
and
CV
CV
CV ( 1) R.(3)

SubstitutingEq.(3)into(2)gives
Sgas 0 .
Thustheprocessisindeedreversible.

4. Microscopic interpretation of entropy

2
S k B ln 2 k B ln 1 k B ln
1

S k B ln

number of possible microscopic states

Example 6: A thermally insulated box is divided by a partition into to compartments,

each having volume V. Initially one compartment contains n moles of an ideal gas at
temperature T, and other compartment is evacuated. We then break the partition, and
gas expands to fill both compartments. What is the entropy change in this freeexpansion process?

V2 2V1
n2 n1 n
S ?

V1

V2 2V1

N nN A

2 2N1

kB N A R

2
S k B ln k B ln 2 N k B N ln 2 nR ln 2
1