Thermodynamics

Module 7: Entropy
Bernard Gallois
George Meade Bond Professor of Engineering
Office: Burchard 410
Telephone: 201-216-5041
E-mail: bgallois@stevens.edu

The Clausius Inequality

We saw that an irreversible heat engine was less
efficient that a reversible heat engine operating between
the same heat reservoirs:
th ,rev
Irreversible heat engine

th th ,rev
Reversible heat engine

Impossible heat engine
th , rev

We recall that

QL
TL
th 1
and th ,rev 1
QH
TH

So that for an irreversible engine (equality for a

reversible engine) :

QL
TL
1
1
QH
TH

QL TL
or

1
QH TH

The Clausius Inequality

The previous equation can be re-written as

TL QH QL
TL
0 but since
0

QH TH TL
QH
QH QL
0

TH TL

This very important inequality is the Clausius inequality, which

has major consequences in thermodynamics. It is more
generally expressed as

T 0

The cyclic integral of Q/T is always less than or equal to zero.

3

The Clausius Inequality

Q

T 0
Here, Q is the net heat added to the system, Qnet...

The equality applies when there are

no irreversibilities within the system
as it executes the cycle.
The inequality applies when internal
irreversibilities are present.
4

Example 1(a): In a power plant, heat is added in

the amount of 3150kJ at 440oC and rejected in the
amount of 1950 kJ at 20oC. Is the Clausius inequality
satisfied and is the cycle reversible or irreversible?

T 0 or

Qnet
Q net
T in T

Qnet Q net
T T

in

3150

440 273

out

Qin

Tin

0
out

Q out

0
Tout

1950

2.237 kJ / K 0
20 273

The Clausius inequality is satisfied. The cycle has at least

one irreversible process and the cycle is irreversible.
5

Example 1(b):Calculate the net work, the cycle

efficiency and Carnot efficiency for this cycle.

Wnet Qin Qout 3150 1950 1200kJ

Wnet 1200
th

0.381 or 38.1%
Qin 3150

th ,Carnot

TL
20 273
1
1
0.589 or 58.9%
TH
440 273

Example 2(a): In a power plant, heat is added in

the amount of 3150kJ at 440oC and rejected in the
amount of 1294.46 kJ at 20oC. Is the Clausius inequality
satisfied and is the cycle reversible or irreversible?

T 0 or

Qnet
Q net
T in T

Qnet Q net
T T

in

3150

440 273

out

Qin

Tin

0
out

Q out

0
Tout

1294.46

0 kJ / K
20 273

The Clausius inequality is satisfied. The cycle is made of

reversible processes.
7

Example 2(b): What cycle could this be?

Calculate the net work and cycle efficiency.

Wnet Qin Qout 3150 1294.46 1855.4kJ

Wnet 1855.4
th

0.589 or 58.9%
Qin
3150
This is the Carnot efficiency

The Definition of Entropy

All processes A, B and C are
internally reversible.
Consider two cycles executed
by a closed system.

2
C

B
A

Cycle 1: A followed by C
Cycle 2: B followed by C

For the first and second

cycles
2
1

Q
1 T 2 T C 0 and 1 T 2 T
A
B
Subtracting one equation from the other yields:

Q
Q
1 T 1 T
A
2

0
C

The integral is the same for

processes A and B.

The Definition of Entropy

Since A and B are arbitrary, it follows that the integral has
the same value for any internally reversible process
between the two states.
The value of the integral depends only on the initial and
final states. The integral represents the change in some
property of the system. It is a state function.
Clausius called this function the entropy, S and its
change is given by:

Q
S2 S1
1 T int rev
2

Q
dS
(kJ/K)

T int rev

Entropy is an extensive property

Its units are J/K or kJ/K

These equations only

apply to internally
reversible processes.

10

Internally Reversible Isothermal Heat

Transfer

The entropy change during an internally reversible

isothermal heat transfer process is given by:

Q
1
Q
S

T int rev 1 T0 int rev T0

1
Q
S
T0
2

Q
1

int rev

This relation is particularly useful to determine the

entropy change of thermal energy reservoirs since
they operate at constant temperature.
Note that the entropy change can be positive or negative
depending on the direction of heat transfer.

11

Isentropic Processes
Recall:

Q
dS
(kJ/K)

T int rev

For a reversible process in which Q = 0,

we have dS = 0 and S2 = S1
The reversible adiabatic process is called
an isentropic process.

12

The Principle of Increase of Entropy

The cycle shown consists of
an internally reversible
process 2-1 and an arbitrary
cycle 1-2. From the
Clausius inequality:

Q
Q
1 T 2 T int,rev 0
The second integral is simply the change in entropy:
2

Q
1 T S1 S2 0 or:
2

Q
Q
S 2 S1
or dS
T
T
1
2

T absolute temperature
> Irreversible process
= Reversible process
13

The Principle of Increase of Entropy

The entropy change of a closed
system is always greater than
the entropy transfer.

Q
S2 S1
T

1
2

Entropy is created during an irreversible process, as a

result of the irreversibilities.
The entropy generation is denoted by Sgen:

Q
S 2 S1
Sgen
T
1
2

Ssys

The entropy generated is always a positive quantity (or

zero for a reversible process).
Its value depends on the process: it is not a property.
This equation has far reaching implications in
thermodynamics and other fields

14

Entropy Generation in Isolated Systems:

Increase of Entropy Principle
Note that the system
shown consists of several
sub-systems lumped
together into an isolated
system.
The entropy of an
isolated system during
a process always
increases, or in the case
of a reversible process,
remains constant.
A system and its
surroundings can be
viewed as the two subsystems of an isolated
system. See next slide.

but Q 0
T
1
2

Sisolated

Sisolated 0
15

Example: find the total entropy change, or

entropy generation, for the transfer of 1000kJ of
energy from a heat reservoir at 1000 K to a heat
reservoir at 500 K.

S gen Stotal STH STL

16

Entropy Generation in Isolated

Systems: Increase of Entropy Principle
The entropy change of the isolated
system: (system+surroundings) is
equal to the entropy generation:

Sgen S total Ssys Ssurr 0

The change in entropy of the surroundings results
from the occurrence of the process. Since no
actual process is reversible, some entropy is
generated during a process.
Since the universe can be considered to be an isolated
system, the entropy of the universe is continuously
increasing.
The more irreversible the process, the larger the
entropy generated during that process.
No entropy is generated during a reversible process.

17

Important Caveat
The increase of entropy principle does not imply
that the entropy of a process cannot decrease.
The entropy change of a system can be negative
during a process but entropy generation cannot.
The criteria to determine whether a process
occurs reversibly, irreversibly or does not occur
can be summarized:

Sgen 0
0

Irreversible Process
Reversible Process
Impossible Process
18

Example: analysis of a closed system

exchanging heat with the surroundings.

19

Example: analysis of a closed system

exchanging heat with the surroundings.

20

Further Remarks on Entropy

Processes can occur in certain directions only, not
in any direction, such that:
Sgen 0
Entropy is not a conserved property. There is
no conservation of entropy principle and the
entropy of the universe is constantly
increasing.
The performance of engineering systems is
degraded by the presence of irreversibilities.
Entropy generation is a measure of the magnitudes
of the irreversibilities present during a process.
21

Entropy Change of Pure Substances:

The T-s Diagram
Values of the entropy, with
respect to a suitable
reference state are tabulated
for many substances.
For the saturated mixture:

s s f xs fg

For the compressed liquid,

the entropy is approximated
by the entropy of the
saturated liquid:

s@T , P s f @T

(kJ/kg.K)

Values for the superheated

vapor are obtained directly
from the tables.

S ms m( s2 s1 ) (kJ/K)
22

Example: find the entropy and/or temperature of

water in the following states

Tsat = 263.99 oC
Not in table
Tsat = 207.15 oC
Tsat
Tsat = 75.87oC
sf =1.0259
sg = 7.6700
23

24

Example: determine the entropy change of

water contained in a closed system as it
changes phase from a saturated liquid to a
saturated vapor at a constant
pressure
System:
shownof 0.1
MPa. Why is the entropy change positive?
Property relations: steam tables
Process and diagram: constant
pressure in the saturation
region so T is constant (Tsat)
Conservation Principle
1

25

Example: Steam at 1 MPa and 600oC expands in

a turbine to 0.01 MPa. If the process is
isentropic, find the final temperature, the final
enthalpy of the steam and the turbine work.

System: see above

Property relations: steam tables
Process and diagram: isentropic so s1=s2=8.029 kJ/kg.K
Conservation principle: steady flow, neglect PE and KE, one entrance,
one exit
26

Example (cont.)
Recall mass balance and
energy balance from
previous chapter for
turbine

We get h1 and h2 from the

steam tables

At P2 = 0.01 MPa,
sf = 0.6491 and
sg = 8.151kJ/kg.K
sf < s2<sg
We are in the saturated region.
27

Example (cont.)
The work is now easily
determined since:

Since state 2 is in the

saturation region,
T2 = Tsat@0.01MPa=45.8oC

What does the process look

like on the T-s diagram?
28

Process Diagram
What does the area under the
curve represent?

Qint rev TdS

(kJ)

Qint rev TdS

(kJ)

The area under the process

curve under a T-s diagram
represents heat transfer during
an internally reversible process.
(Recall the P-V diagram, where
it represented the reversible
boundary work done).

On a unit mass basis:

2

qint,rev Tds
1

(kJ/kg)
29

T-S Diagram of the Carnot Cycle

What does this diagram
represent?
Two isentropic
processes: 4-1 and 2-3
Two isothermal
processes: 1-2 and 3-4
What does the area
within the rectangle
represent?

Wnet ,out QH QL

TH S1 2 QH
TL S3 4 QL
Area QH QL

30

The Tds Relations

Write the first law in differential form on a unit mass

basis:

Qint rev Wint rev,out dU

Qint rev TdS and Wint rev,out PdV

We obtain the first Tds relation:

TdS =dU PdV

Tds =du Pdv

(kJ)
(kJ/kg)
31

The Tds Relations

The second relation is obtained from the definition of h:

Tds dh vdP (kJ/kg)

TdS dH VdP
(kJ)
These relations are also used in the following manner:

du
Pdv
ds

T
T
dh
vdP
ds

T
T
These relations have many uses in thermodynamics and
serve as the starting point to determine changes in
entropy (or U or H) for processes.
32

Entropy Change of Liquids and Solids

Liquids and solids are almost always approximated as
incompressible substances in engineering.

du Pdv du
ds

T
T
T
since dv 0 during compression
C P Cv C for an incompressible substance:
dT
du CdT
and ds C
T
Liquids and solids
2

T2
dT
s2 s1 C (T )
Cav ln
T
T1
1

(kJ/kg.K)

Isentropic s2 s1 0 and T2 T1
33

Entropy Change of Ideal Gases

For an ideal gas

du Cv dT and P RT / v
Cv dT
dv
ds
R
T
v
The entropy change is obtained by integration:
2

Cv (T )dT
v2
s2 s1
R ln
T
v1
1
Using the enthalpy relation yields:

dh CP dT and v RT / P
2

CP (T )dT
P2
s2 s1
R ln
T
P1
1

34

Entropy Change of Ideal Gases

There are several ways to calculate the entropy
change of ideal gases:
1.Use a constant average value for the specific
heat
2.If a mathematical expression is available,
proceed by integration between the two states (we
will ignore this method)
3.Use the tabulated values of the entropy
2

Cv (T )dT
v2
s2 s1
R ln
T
v1
1

CP (T )dT
P2
s2 s1
R ln
T
P1
1
35

Constant Average Value of Cv or CP

On a mass basis, we obtain

T2
v2
s2 s1 Cv ,av ln R ln
T1
v1

kJ/kg.k

T2
P2
s2 s1 CP ,av ln R ln
T1
P1

kJ/kg.k

On a molar basis, after multiplying by the molar mass:

T2
v2
s2 s1 Cv ,av ln Ru ln
T1
v1

kJ/kmol.K

T2
P2
s2 s1 CP ,av ln Ru ln
T1
P1

kJ/kmol.K
36

Variable Specific Heat

CP (T )dT
The function s0 is defined as: s
0
(It is called the standard state entropy.)
It is only a function of temperature. Its value is zero at
absolute zero temperature. Its values are tabulated as a
function of temperature (Tables A-17 to A-25).
Now we can express s2-s1 as:
0

P2
s2 s1 s s R ln
P1
0
2

0
1

P2
s2 s1 s s Ru ln
P1
0
2

0
1

kJ/kg.K
kJ/kmol.K

Unlike the internal energy or the enthalpy, the entropy of

an ideal gas varies with specific volume or pressure as
well as temperature.

37

Isentropic Processes of Ideal Gases: s2 = s1

Constant Specific Heats
T2
v2
From slide 36, s2 s1 Cv,av ln R ln
T1
v1
T2
v2
Cv ln R ln
T1
v1

v1
T2
or ln ln
T1
v2

T2
v1


T1 s const . v2

R
Cv

k-1

(ideal gas)

since R CP Cv , k CP / Cv , and thus R / Cv k 1

38

Isentropic Processes of Ideal Gases: s2=s1

Constant Specific Heats

Two other relations can be derived by

using the same approach:
T2

T1 s const .

P2

P1

P2
v1


P1 s const . v2

(k-1)/k

(ideal gas)
k

(ideal gas)

Tv k 1 constant
In compact form:

TP

(1- k ) / k

constant

Pv constant
k

39

Example: air initially at 0.1 MPa, 27oC, is compressed

reversibly to a final state. Find the entropy change of
the air when the final state is
(a) 0.5 MPa, 227oC and (b) 0.5 MPa, 180oC
(c) find
the temperature
0.5 MPa that makes the
Assume
air is an idealatgas
entropy change zero.
(a) Second
law
(d) show
the processes
on a T-s diagram

40

Example
(b)

41

Example
Why are the pressure line not
horizontal as shown on the T-s
diagram for water?
It is a gas. The constant
pressure curve is horizontal
only in the saturation region.
As T increases at constant
pressure, S increases
Why do the entropy changes
have different signs?
While the pressure
contributions are the same,
the temperature contributions
are different. (Below 202.4oC
and above 202.4oC as shown
on the figure).
42

Example: nitrogen expands isentropically in a pistoncylinder device from a temperature of 500 K while its
volume doubles. What is the final temperature of the
nitrogen,
and
how much work
did the nitrogen do against
System: the
piston/cylinder
device
the piston, in kJ/kg?
Process: isentropic expansion
on T-s and P-v diagrams

43

Example
Isentropic Process

Why did the temperature

decrease?
The gas expands so that the
internal energy decreases and
thus T decreases
Now apply the first law to the
system:

Why is the net work positive?

It is an expansion. PdV>0 44

Example: a Carnot engine has 1 kg of air as the

working fluid. Heat is supplied to the air at 800K and
rejected by the air at 300 K. At the beginning of the heat
addition process, the pressure is 0.8MPa and during the
heat addition the volume triples.
(a) Calculate the net cycle work assuming air is an ideal gas
with constant specific heats.
(b) Calculate the amount of work done in the isentropic
expansion process.
(c) Calculate the entropy change during the heat rejection
process.
45

Example
System
Process
Property relations:
ideal gas, constant
properties
(a) The net cycle
work is:
Wnet = QH
But L
So that we need to
determine QH. How?
46

Example
(a) Apply the first law to process 1-2. Wnet,12 is the
work done during that process.

QH Wnet ,12 U12 mCv (T2 T1 ) 0

Wnet ,cycle thQH and th 1 TH / TL

2

QH Wnet ,12 Wb PdV mRT

1

dV
V2
mRT ln
V
V1

Note that now we can also determine QL. How?

47

Example
(b) Apply the first law,
closed system to the
isentropic expansion 2-3
(meaning Q23 = 0)

(c)

We know T3 = T4 = TL
We need to find P3 and P4
How do we proceed?
We know that during the
heat addition the volume
triples and the pressure is
equal to 0.8 MPa. The
temperature is 800 K. So..
We have a starting point to
determine P2, from which
we can determine P3 from
which we get P4.
48

Example

We get P2 from the

ideal gas law applied
to the isothermal
process 12.

We get P3 by
considering process 23

49

Example
Finally we get P4 by
considering process
41

50

Entropy and Molecular Disorder

As a substance goes from solid to liquid to
vapor, the degree of molecular disorder
increases and so does the entropy.
At a phase change, in particular, there is a
change in entropy: entropy of fusion and entropy
of vaporization, which is also an indication that
the degree of disorder of the substance has
increased.
In the same vein, mixing of two substances is
also accompanied by an entropy of mixing.
The molecular disorder of an isolated system
increases each time it undergoes a real process.
51

The Third Law of Thermodynamics

As the temperature of a gas is decreased, it will
transform into a liquid (at the melting point). The liquid
is less disordered than the gas. Upon further cooling
the liquid will crystallize, a more ordered state, as the
atoms form a regular three-dimensional array. As the
temperature is further reduced, the vibrational activity
of the atoms will continue to decrease. At absolute
zero, all vibrational activity will have essentially ceased
and the entropy of the substance will be zero.
The entropy of a pure crystalline substance is zero at
absolute zero temperature.
The third law provides an absolute reference point for
the determination of entropy. Absolute entropy is
determined with respect to this reference point and is
widely used in the analysis of chemical reactions.
The entropy of substances that do not crystallize is not
zero at absolute zero.
52

Entropy Balance

The entropy change of a system during a process is equal

to the sum of the net entropy transfer through the system
boundary and the entropy generated within the system.

Sin Sout S gen S system

53

Entropy Change of a System

The entropy change of a system is the result
of the process occurring within the system:
Entropy change = Entropy in final state Entropy in initial
state

S system S final Sinitial S 2 S1

54

Mechanisms of Entropy Transfer

Entropy can be transferred in or out of a system
by two mechanisms: heat transfer and mass
flow.
Entropy transfer is recognized at the system
boundary as it crosses the boundary, and it
represents the entropy gained or lost by a
system during a process.
The only form of entropy transfer for a closed
system is heat transfer.
The entropy transfer for an adiabatic system is
zero.
55

Entropy Transfer by Heat Transfer

The ratio of the heat transfer at a location to the
absolute temperature T at that location is called
the entropy flow or entropy transfer:

S heat

(T =constant)

Note that Q and S have the same sign.

When the temperature T is not constant, the
entropy transfer is determined by integration or
summation

S heat

Qk
Q

T
Tk

Where Qk is the heat transfer through the

boundary at temperature Tk at location k.

56

Entropy Transfer by Work

Entropy transfer by work, Swork = 0
Note the distinction between work and
heat:
An energy interaction that is accompanied by
entropy transfer is heat transfer
An energy interaction that is not accompanied
by entropy transfer is work

57

Entropy Transfer by Mass Flow

If the properties of the mass change during the process,

the entropy transfer is determined from:

S&mass s Vn dAc and Smass s m S&mass dt

Ac

Where Ac is the cross-sectional area of the flow and

Vn is the local velocity normal to area dAc
58

Entropy Generation
Entropy generation is a measure of the entropy
created by irreversibilities (friction, etc..).
For a reversible process, the entropy generation
is zero. The entropy change of the system is
equal to the entropy transfer.
The entropy balance (kJ/K) for any system
undergoing any process is expressed as:

Sin Sout S gen S system

14 2 43
{
123

Net entropy transfer

by heat and mass

Entropy
generation

Change in entropy

59

Rate of Entropy Generation

The rate of entropy generation (kW/K) is obtained
from the previous equation:

S&in S&out
14 2 43

Rate of net entropy transfer

by heat and mass

S&gen
{

Rate of entropy
generation

S&system
123

Rate of change
in entropy

&
Where S&heat Q&/ T and S&mass ms

On a unit mass basis (kJ/kg.K):

sin sout sgen ssystem

The term sgen represents the entropy generation within
the system boundary only and not the entropy
generation that could occur outside the system
boundary as result of external irreversibilities
60

Entropy Generation

sin sout sgen ssystem

The term Sgen is the

entropy generated
within the system
boundary only and does
not include the entropy
that may be generated
outside the system
boundary as a result of
external irreversibilities.
Note that Sgen = 0 for the
internally reversible
process.
61

Total Entropy Generated by a Process

The total entropy

generated during a
process is determined
by applying the
entropy balance to an
isolated system that
includes the system
and its surroundings.

62

Closed Systems
Closed system
Qk
T S gen Ssystem S2 S1
k
Where Qk is the heat transfer through the boundary at
temperature Tk at location k.

Adiabatic closed system (Q = 0)

S gen S adiabatic system

System + Surroundings

S gen S S system S surroundings

Where Ssystem = m(s2 - s1) and Ssurroundings = Qsurr/Tsurr

63

Control Volumes
The general entropy balance is given by:
Qk
T
{ k

Entropy transfer through

CV boundaries by heat transfer

mi si me se
1 4 42 4 43
Entropy transfer into CV
by mass flow

S gen
{

Entropy generation
within boundaries of CV

S 2 S1 CV
1 4 2 43
Entropy change
within CV

In rate form:

Q&k
& S& S&
&
&

m
s

m
s

S
T i i e e gen 2 1 CV (kW/K)
k

64

Steady-flow Process
Steadyflow control volumes experience no
change in entropy. The entropy balance becomes:

&
Q
&e se m
&i si k
S&gen m
Tk

For a single stream, it simplifies to:

&
Q
S&gen m& se si k
Tk

For a single stream, steady-flow, adiabatic device,

it becomes:

S&gen m& se si

If the flow is also reversible, then se = si

65

Example: an inventor claims to have developed a

water mixing device in which 10kg/s of water at 25oC
and 0.1 MPa and 0.5 kg/s of water at 100oC and 0.1
MPa are mixed to produce10.5 kg/s of water as a
saturated liquid at 0.1 MPa. If the surroundings to this
device are at 20oC, if this process possible? If not,
what temperature must the surroundings have for this
process to be possible?

System: shown here

Process: steady-flow mixing
Properties: steam tables
66

Example

How do we proceed? We must apply the second law

criterion that entropy generation is positive and calculate
the terms in the steady-flow entropy balance:

&
Q
&e se m
&i si k
S&gen m
Tk

(well simplify this expression later for the problem at hand)

How do we get the various terms? We can get the entropy
transfers due to mass flow in and out of the system readily
since the states of the water is fully specified. We need to
determine the entropy transfer due to heat transfer: from
the system to the surroundings.
How do we do this? By applying the first law to the system:
the steady-flow energy balance.
2
2

V
V
i
i
&
&
&
&
Q W me he
gze mi hi
gzi
2
2

1 4 4 4 2 4 4 4 3 1 4 4 4 2 4 4 43
67
For each exit
For each inlet

Example
We can neglect changes in PE and KE. There is no
work done. We have two inlet streams and one outlet
stream.

m&1 m&2 m&3

Q& m&1h1 m&2 h2 m&3h3

68

Example

Note that heat is transferred from the

surroundings to the system (>0).

&
Q
&e se m
&i si k
S&gen m
Tk
&
Q
&3 s3 m
&2 s2 m
&1s1 CV
S&gen m
Tsurr
S& 0.491 kJ/kg.s
gen

69

Example
Since sgen <0 , the process is impossible.
How do we determine the minimum value of the
temperature of the surroundings that would make
this process possible? This will occur when sgen = 0

70

Calculation of Ideal Work

For a completely reversible process

Q&
( Sm&) fs
0 or Q& T ( Sm&) fs
T

Substitute in the energy balance for a steady-flow device

1 2

&
&
( H u gz )m&

(
Sm
)

fs
s ( rev )

fs

The shaft work is for a completely reversible process, the ideal work

1 2

&
Wideal ( H u gz )m&
T ( Sm&) fs

fs

In most applications in ChE, PE and KE are negligible:

W&ideal Hm& fs T ( Sm&) fs

W&ideal m&(H T S ) Wideal H T S
71

Calculation of Ideal Work

The thermodynamic efficiency relates the actual
work in the process to the ideal work

W&ideal
t (work required) &
Ws
W&s
t (work produced) &
W

ideal

The lost work and power are defined by

Wlost Ws Wideal
W&lost W&s W&ideal

72

Lost Work
Lost work is the work that is lost as result of
irreversibilities in the system.

1 2
1 2

&
&
Wlost ( H u gz )m&
Q
( Hm& u gz
)

2
2

fs

W& T ( Sm&) Q&

lost

T ( Sm&) fs
fs

fs

And since

&
Q
S&G ( Sm&) fs
or T S&G T ( Sm&) fs Q&
T

We obtain the magnificent result:

W&lost T S&
G
73

Lost Work
We can also show that:

& S Q&
W&lost mT
&
Q
S&G m&S
T

Wlost T S Q
Q
SG S
T

Wlost T SG
Another magnificent result
74

Entropy and Molecular Disorder

As a substance goes from solid to liquid to
vapor, the degree of molecular disorder
increases and so does the entropy.
At a phase change, in particular, there is a
change in entropy: entropy of fusion and entropy
of vaporization, which is also an indication that
the degree of disorder of the substance has
increased.
In the same vein, mixing of two substances is
also accompanied by an entropy of mixing.
The molecular disorder of an isolated system
increases each time it undergoes a real process.
75

Entropy from the Microscopic

Viewpoint
What is the entropy
change that accompanies
going from the bags of
white and black atoms to
the mixture below?
Start from Boltzmann
relation

S = kln
k is Boltzmann
constant
76

Entropy from the Microscopic Viewpoint

The number of configuration, of the system is obtained
by calculating how many different (distinct) configurations
are possible. Assume we have a lattice of N points, n black
balls, N-n white balls. For the first ball I pick from the bag, I
have N choices to place it on the lattice, the second ball , N1 positions, the third ball , N-3the last ball, only one
choice so that I have N! of placing N balls on the lattice.
Assume now that I remove all the black balls. If I put back
the first one, I have n choices, the second one, n-1.. The
last one only one choice, so that the black balls have n!
indistinct configurations. The same is true if I remove all
the white balls , numbering N-n and I have (N-n)!
Undistinguishable configurations.
We conclude that
77

Entropy from the Microscopic Viewpoint

The math is tedious but easy:

N!

and since lnN ! N ln N N

( N n)! n !
ln ( N ln N N ) (( N n) ln( N n) ( N n)) ( n ln n n)
ln N ln N ( N n) ln( N n) n ln n
ln ( N n) ln N n ln N ( N n) ln( N n) n ln n
N n
n
ln ( N n) ln
n ln
N
N
Note that n/N and (N-n)/N are the mole fractions:

S mixing k ln R ( x1 ln1 x2 ln x2 )
The most magnificent equation yet!! Whenever you mix
two substances, you create entropy of mixing.

78