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- LINEAR EXPANSION
- Homi Bhabha - Class IX
- Mechanics. Kerson Huang
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We have seen in the previous chapter that systems can move from an initial equi-

librium state to a different final equilibrium state by exchanging heat and work

with their surroundings. A new state can also be generated when a constraint, such

as a barrier to mass or heat flow, is released. The concept of the directionality of

change, however, has not yet been addressed. Everyday experience suggests that

some kinds of processes, even though in full compliance with the First Law, never

occur spontaneously. Examples of spontaneous processes are given in the table be-

low; the reverse processes have never been observed in isolated systems.

Initial state

Final state

at different temperatures

at the same temperature

of a glass of pure water

the water

The
last
two
of
these
examples
(sugar
dissolving
in
water,
but
oil
separating

from
water)
illustrate
that
it
is
not
always
obvious
which
direction
(mixing
or
de-

mixing)
corresponds
to
spontaneous
change.
However,
once
the
spontaneous

change
direction
has
been
established,
it
is
impossible
to
convert
a
system
in
the

final
state
column
back
to
the
initial
state
without
the
action
of
an
external
agent.

For
example,
sugar
crystals
will
not
precipitate
out
of
solution
unless
the
water
is

evaporated.

Material
from
Essential
Thermodynamics,
Drios
Press
(2011),
A.Z.
Panagiotopoulos

36

3.1 Reversibility

37

3.1
Reversibility

Clearly,
all
processes
observed
naturally
are
spontaneous
and
thus
irreversi-

ble.
Spontaneous
changes
define
the
direction
of
the
arrow
of
time
and
are
rigor-

ously
analyzed
through
the
Second
Law
of
thermodynamics,
which
is
formally
in-

troduced
in
3.2.
By
eliminating
friction
and
all
gradients
of
temperature
or
pres-

sure,
and
by
performing
changes
at
an
infinitesimally
slow
rate,
one
can
approxi-

mate
an
idealized
reversible
process.
A
process
in
a
system
going
from
an
initial
to

a
final
state
is
formally
defined
as
reversible
if
the
system
can
be
brought
back
to

its
initial
state
from
the
final
state
with
no
change
to
any
part
of
the
universe.
Re-

versibility
is
an
idealized
abstraction
that
can
be
approximated
in
real
processes,
if

care
is
taken
to
avoid
friction,
internal
or
external
gradients
of
temperature,
pres-

sure,
or
composition,
as
well
as
any
conversion
of
mechanical
work
into
heat.
In

reversible
processes,
forces

across
any
boundary
exact-

ly
balance
at
all
times.
Pro-

cesses
take
an
infinitely

long
time
to
complete,
be-

cause
rates
of
heat
transfer,

macroscopic
flow
of
mate-

rial,
and
component
diffu-

sion
are,
respectively,
pro-

Figure
3.1
Rupture
of
a
partition
in
an
insulated
con-

portional
to
gradients
of

tainer.

temperature,
pressure,
and

chemical
potentials
(the

latter
defined
in
Chapter
5).

Consider
the
process
schematically
illustrated
in
Fig.
3.1.
A
thin
wall
separates

two
sides
of
an
insulated
container
in
the
initial
state
(A);
the
left-hand
side
con-

tains
a
gas
and
the
right-hand
side
is
evacuated.
The
wall
is
removed
and
the
gas

expands
to
fill
all
available
space.
After
some
time,
the
gas
reaches
a
new
equilibri-

um
state,
(B).
A
First
Law
balance
on
the
total
contents
of
the
container
gives
U
=

Q

/
+
W

/
=
0.
If
the
gas
is
ideal,
its
energy
depends
only
on
the
temperature,
and
T
=

0,
but
this
is
not
an
essential
characteristic
of
the
process;
for
real
gases,
the
tem-

perature
of
state
B
can
be

lower
or
higher
than
that

of
state
A.
We
can
return

the
gas
to
its
original
state

A
by
using
a
piston
to

compress
it
back
to
the

original
volume,
as
shown

in
Fig.
3.2.
For
this
reverse

process,
the
change
of
en-

Figure
3.2
Reversing
the
effect
of
expansion.

ergy
of
the
gas
is
the
same

38

as
previously,
U
=
0
=
Q
+
W

Q
=
W
;
since
we
clearly

need
to
provide
work
to

compress
the
gas,
the
re-

verse
process
is
only
pos-

sible
if
we
remove
heat

from
the
system.
If
some-

how
we
could
convert
all

Figure
3.3
Reversible
expansion.

of
the
heat
removed
into

work,
then
the
overall
pro-

cess
has
no
net
effect
on
the
environment
and
would
have
been
reversible
accord-

ing
to
the
definition
above.
However,
countless
experiments
have
shown
that

complete
conversion
of
heat
into
work
is
impossible;
we
thus
conclude
that
the

original
process
!A B
was
indeed
irreversible.

We
now
consider
a
different
process
(Fig.
3.3)
starting
from
the
same
initial

state
A
as
previously,
with
final
state
C
of
the
same
volume
as
B.
However,
we
now

perform
an
adiabatic
process
(!Q = 0 ),
using
a
well-lubricated,
frictionless
piston
to

obtain
work
from
the
expanding
gas.
The
amount
of
work
produced
by
the
gas
can

be
calculated
from:

V

WAC = C P dV

VA

!

Gases
generally
cool
as
they
expand
adiabatically,
so
that
the
final
tempera-

ture
will
be
TC
<
TA.
For
the
reverse
process
of
adiabatic
compression,
we
need
to

input
work,
which
in
the
absence
of
friction
will
be
equal
in
magnitude
and
oppo-

site
in
sign,
WCA
=
WA C.
Thus,
there
is
no
overall
net
effect
of
the
process

ACA
on
either
system
or
its
environment.
This
process
is
reversible.

The Second Law of thermodynamics places the concept of spontaneous changes on

a rigorous, quantitative basis. It allows for precise predictions about which trans-

formations can or cannot occur naturally in the absence of external driving

forces. It represents, in a highly compact fashion, the accumulated scientific

knowledge gained from countless experiments in carefully constructed systems.

While it cannot be proven from first principles and has to be postulated, it repre-

sents one of the most basic and well-established tenets of modern science.

This,
however,
is
not
true
for
all
substances.

3.1 Reversibility

39

The
Second
Law
can
be
stated
in
a
variety
of
equivalent
ways;
in
the
following,

we
use
a
traditional
approach
that
expresses
it
in
terms
of
heat
fluxes
around
heat

engines.
Heat
engines
are
devices
that
exchange
heat
and
work
with
their
envi-

ronment
in
processes
that
leave
no
net
effects
on
the
engines.
An
internal
combus-

tion
engine
undergoing
a
full
cycle
of
compression-ignition-expansion
is
a
classic

example
of
such
a
device.
However,
living
cells,
photovoltaic
arrays,
and
distilla-

tion
columns
can
also
be
considered
as
heat
engines,
provided
that
no
net
changes

accumulate
within
the
devices
over
the
period
of
interest.

Analysis
of
heat
engines
becomes
particularly
simple
if
they
exchange
heat

with
heat
reservoirs
large
enough
so
that
their
temperature
can
be
considered
con-

stant,
irrespective
of
the
amount
of
heat
exchanged
with
the
engines.
In
essence,

this
implies
that
the
amount
of
energy
exchanged
is
small
relative
to
the
total
heat

capacity
of
the
reservoirs.
Practical
approximations
of
heat
reservoirs
include
the

atmosphere,
rivers,
or
the
sea,
when
considered
over
short
enough
periods
of
time

so
that
their
temperature
does
not
vary
significantly.
Electrical
power
plants
are

usually
built
near
large
bodies
of
water
precisely
so
that
they
can
use
them
as
heat

reservoirs.
We
will
assume
that
heat
reservoirs
do
not
perform,
or
require,
any

work
in
the
process
of
interest.

The
Kelvin-Planck
postulate
(statement
of
the
Second
Law)
is
that:

It
is
not
possible
for
a
heat
engine
that
interacts
with
a
single
heat
reservoir
to

convert
all
the
heat
transferred
from
the
reservoir
into
work.

In
other
words,
heat
cannot
be
completely
converted
into
work.
However,
the
re-

verse
of
this
process,
converting
work
entirely
into
heat,
is
perfectly
possible.

Fig.
3.4
depicts
a
process
that
is
impossible
according

to
the
Kelvin-Planck
statement
of
the
Second
Law,
assum-

ing
that
the
signs
of
the
flows
of
heat
Q
and
work
W
are
as

indicated
by
the
arrows.
If
|Q|
=
|W|,
such
a
device
does
not

violate
the
First
Law,
as
a
trivial
balance
around
the
en-

gine
demonstrates.
No
such
device
has
ever
been
con- Figure
3.4
An
impossible

process.

structed,
despite
efforts
by
many
people
since
the
dawn

of
technological
civilization.
The
practical
value
of
being
able
to
extract
useful
en-

ergy
in
the
form
of
electricity
or
mechanical
work
by
cooling
the
sea
or
the
atmos-

phere
would
be
enormous;
fossil
fuel
use
could
then
be
reduced
to
zero
and
a
prac-

tically
inexhaustible
supply
of
energy
would
become
available
to
humanity.
Na-

ture,
however,
does
not
permit
such
a
device
ever
to
function.
Even
in
microscopic

systems,
where
spontaneous
fluctuations
occur
that
seem
to
result
in
mechanical

work
being
produced
at
the
expense
of
the
thermal
energy
of
a
reservoir
(e.g.

Brownian
motion
of
small
particles),
the
Second
Law
is
found
to
hold
when
the
av-

erage
behavior
of
a
system
is
determined
over
long
times.
Devices
that
violate
the

Kelvin-Planck

statement
of

the
Second

Law

40

First
or
Second
Laws
which
thus
can
never
be
constructed
are
called
perpetual

motion
machines
of
the
first
or
second
kind,
respectively.

The seemingly simple statement of

the impossibility of certain process-

es made by the Second Law has

enormous consequences on the be-

havior of natural and engineered

systems. To start analyzing its con-

sequences, consider the behavior of

heat engines operating between two

heat reservoirs of different thermo-

metric temperatures, H and C , as

shown in Fig. 3.5. We will assume Figure 3.5 Thermal engines operating between

that the top reservoir is at a higher two heat reservoirs. Left side (engine A) corre-

sponds to power production and right side

thermometric temperature, H > C.

(engine B) corresponds to refrigeration.

Thermometric temperature in phys-

ical systems is observed to increase as energy flows into them.

On the left side of Fig. 3.5, engine A removes heat from the hot reservoir and

dumps some of it to the cold reservoir, while producing some work. Engine B on

the right panel does the reverse, removing heat from the cold reservoir and dump-

ing it to the hot reservoir through the consumption (input) of work. Nothing in the

First or Second Laws of thermodynamics prohibits any of these processes; practi-

cal examples of such systems, in the form of thermal power generation systems

and refrigeration units are ubiquitous. Nevertheless, there must be some con-

straints in the magnitudes of the work and heat streams from these engines, be-

cause otherwise a combination of them could give rise to a perpetual motion ma-

chine. To see why this is the case, consider using the work output of a machine of

type A to provide the energy input to a machine of type B. Without loss of generali-

ty, we can assume that:

Q = QCB

! CA

This
is
the
case
since
we
can
always
adjust
the
size
of
the
heat
engine,
or
how

many
engine
cycles
are
performed
per
unit
of
time.
First
Law
balance
around
the

system
composed
of
the
engines
A+B
then
gives
the
net
work
input
as:

The
net
heat
input
is:

W = WB WA

!

41

Q = QHA QHB = W

!

If
W
<
0,
then

!

Net
work
is
being
produced
by
the
two
engines
by
removing
heat
from
the
hot
res-

ervoir.
This
is
equivalent
to
a
perpetual
motion
machine
of
the
second
kind,
violat-

ing
the
Kelvin-Plank
postulate,
so
it
is
an
impossibility.
Therefore,
we
must
have:

W 0 Q 0 QHA QHB

!

for
any
two
heat
engines
operating
between
two
specific
temperatures
H
and
C
.

The
arguments
of
the
previous
paragraph
also
apply
to
the
special
case
of
re-

versible
heat
engines,
known
as
Carnot
engines.
For
reversible
engines
we
can

simply
switch
the
role
of
A
and
B
at
will,
which
gives:

rev

rev

rev

rev

QHA

QHB

!!and!! QHB

QHA

rev

rev

QHA

= QHB

This
implies
that
for
any
reversible
heat
engine
that
operates
between
H
and
C

the
ratio
of
heat
fluxes
is
a
universal
function
of
the
two
temperatures:

QHrev

QCrev

= f (H ,C )

!

The
specific
form
of
the
function
in
Eq.

3.1
can
now
be
determined,
by
consider-

ing
a
cascade
of
heat
engines
operating
be-

tween
a
high
temperature
H,
an
interme-

diate
temperature
M
and
a
low
tempera-

ture
C,
as
shown
in
Fig.
3.6.
On
the
left

side,
two
Carnot
engines,
1
and
2,
are
used

between
H and
M
and
between
M
and

C
,
respectively.
On
the
right
side,
a
single

engine
3
operates
directly
between
H
and

C.
We
can
adjust
the
heat
flows
for
en-

gines
1
and
2
so
that
the
same
amount
of

heat
is
taken
and
removed
from
the
in-

termediate-temperature
reservoir
at
M,

and
we
can
also
adjust
engine
3
so
that
the

same
amount
of
heat
is
removed
from
the

hot
reservoir
as
for
engine
1.
Since
these

are
Carnot
(reversible)
engines,
we
must

have
that
|W1|
+
|W2|
=
|W3|.
Therefore,
the

(3.1)

Figure
3.6
Thermal
engines
operating

between
three
heat
reservoirs.

42

same
amount
of
heat
is
dumped
to
the
cold
reservoir
on
the
two
sides
of
the
cas-

cade:

QC = QC

QM / f (M ,C ) = QH / f (H ,C )

QH

QH

f (H ,M ) f (M ,C ) = f (H ,C )

f (M ,C ) f (H ,M ) f (H ,C )

!

Since
this
relationship
is
valid
for
any
temperatures
H,
M,
and
C,
the
func-

tional
form
of
f
must
be:

!

g(H )

f (H ,C ) =

g(C )

(3.2)

The
function
g()
is
universal
for
all
Carnot
engines.
Its
form
can
be
obtained

from
analysis
of
the
operation
of
any
reversible
heat
engine.
When
this
analysis
is

performed
for
engines
that
have
ideal
gases
as
working
fluids
(see
4.1),
we
ob-

tain
a
particularly
simple
relationship:
g()
=
T,
where
T
is
the
temperature
that

was
defined
through
the
ideal-gas
equation
of
state
in
2.4.
This
remarkable
prop-

erty
provides
a
connection
between
the
efficiency
of
reversible
engines
and
the

ideal-gas
temperature
scale.
The
absolute
temperature
scale
T
is
of
fundamental

importance
in
thermodynamics.

Given
that
f (H,C)
=
TH/TC,
we
can
now
show
that
reversible
heat
flows
occur-

ring
to
and
from
constant-temperature
reservoirs
are
linked
in
a
particularly
sim-

ple
way.
The
heat
flows
for
the
cold
and
hot
reservoirs
are
of
opposite
signs,
so
Eq.

3.1
can
be
expressed
as:

QHrev

QCrev

TH

TC

QHrev

TH

QCrev

TC

= 0

(3.3)

The
efficiency
of
a
Carnot
engine
that
draws
heat
from
a
hot
reservoir
and

produces
work
(left
side
of
Fig.
3.5)
is
defined
as
the
fraction
of
heat
removed
from

the
hot
reservoir
that
is
obtained
from
the
device
as
work.
From
a
First
Law
bal-

ance
around
a
reversible
engine,
we
have:

Carnot

Engine

efficiency

T

QHrev + QCrev +W = 0 QHrev C QHrev = W

TH

!

rev

!

W

QHrev

TH TC

TH

(3.4)

43

The
efficiency
is
between
0
and
1,
the
latter
value
being
a
theoretical
limit

that
can
only
be
asymptotically
approached
if
TC0
or
TH+.
Real
engines,
of

course,
operate
with
efficiencies
lower
than
those
of
reversible
engines,
since
oth-

erwise
an
irreversible
engine
could
be
combined
with
a
Carnot
engine
operating
in

reverse,
resulting
in
a
violation
of
the
Second
Law.
The
performance
of
real
en-

gines
operating
between
reservoirs
of
given
temperatures
is
not
the
same
for
all

irreversible
engines
it
varies
(sometimes
greatly),
depending
on
their
design
and

internal
losses.
The
reversible
engine
efficiency
provides
a
common
upper
limit
for

all
real
engines.

Example
3.1
Efficiency
of
geothermal
power
production

In
many
parts
of
the
world,
especially
near
edges
of
tectonic
plates,
relatively
high

temperatures
can
be
reached
by
drilling
to
moderate
depths.
Taking
advantage
of

these
high
temperatures
has
been
proposed
as
one
possible
technology
for
energy

generation
without
production
of
greenhouse
gases.
Assuming
that
heat
can
be

withdrawn
from
hot
rock
at
H
=
200
C
and
that
cooling
is
available
at
C
=
50
C,

what
is
the
maximum
possible
fraction
of
heat
removed
that
can
be
converted
to

electricity?

The
maximum
possible
fraction
of
heat
conversion
into
work
takes
place
using
a

reversible
Carnot
engine,
which
has
efficiency:

T T

200 50

rev = H C =

= 32%

TH

200 + 273

!

Note
that
only
absolute
temperatures
[in
K]
can
be
used
in
the
expression
for
;

however,
the
difference
between
two
temperatures
in
C
is
the
same
as
the
corre-

sponding
absolute
temperature
difference
in
K,
so
the
thermometric
temperature

values
can
be
used
in
the
numerator.

For
engines
operating
as
refrigeration
cycles
(right
side
of
Fig.
3.5,
p.
40),
with

heat
removed
from
the
cold
reservoir
through
the
net
input
of
work,
a
measure
of

performance
different
from
is
appropriate.
In
such
cases,
we
are
interested
in

the
amount
of
heat
removed
from
the
cold
side
(the
interior
of
the
refrigerator,
or

the
inside
of
a
building
in
the
case
of
air
conditioning)
per
unit
of
work
input.
The

coefficient
of
performance,
,
is:

! = !

!

QC

W

QC

QC QH

rev !=

QCrev

QCrev

T

+ H QCrev

TC

TC

TH TC

(3.5)

er temperatures inside a building in the winter, by withdrawing heat from the cold

44

outside
air.
In
this
case,
the
coefficient
of
performance
is
defined
as
the
ratio
of

heat
output
(into
the
building)
over
the
work
input:

!=!

QH

W

QH

QC QH

rev =

QHrev

T

C QHrev + QHrev

TH

TH

TH TC

(3.6)

The
two
coefficients
of
performance
defined
in
Eqs.
3.5
and
3.6
can
be
greater

than
1,
if
the
difference
between
hot
and
cold
temperatures
is
smaller
than
the
ab-

solute
value
of
the
cold
or
hot
temperature,
respectively.
Practical
power
and
re-

frigeration
cycles
are
discussed
in
Chapter
4.

Example
3.2
Air
conditioner
theoretical
efficiency

Calculate
the
maximum
possible
coefficient
of
performance
for
an
air
conditioning

unit
operating
between
an
indoor
temperature
of
68
F
and
outdoor
temperature

of
104
F.

We
first
need
to
convert
thermometric
to
absolute
temperatures:
C
=
68
F
C
=

293
K;
C
=
104
F
TH
=
313
K.
The
maximum
possible
coefficient
of
performance

is:

rev

!=!

QCrev

W

TC

TH TC

293

= 14.6

313 293

We showed in the previous section that reversible heat flows occurring to and

from constant-temperature reservoirs satisfy the condition QHrev /TH + QCrev /TC = 0 ;

!

this in turn suggests that a heat-related property can be defined that is conserved

for a system undergoing a reversible process that starts and ends at the same state

point. This new property is called the entropy S. For a reversible process in closed

systems for which all exchange of heat is done at a single temperature T, the en-

tropy change S is defined as:

Q rev

S

(3.7)

T

!

For
a
differential
change
of
state
during
a
reversible
process,
the
temperature

of
the
system
is
effectively
constant,
so
we
can
write:

Q rev

dS =

T

!

(3.8)

45

The
overall
entropy
change
for
a
general
process
that
involves
temperature

changes
along
its
path
is:

definition
of

entropy

rev

B Q

S = SB S A =

A T

!

(3.9)

states of a system, provided that external reservoirs are available to exchange heat

and work as needed. Thus, Eq. 3.9, along with a choice of a reference state for

which S = 0, in principle provides a way to generate values for the entropy of any

equilibrium state of a thermodynamic system. As will soon become apparent, Eq.

3.9 is not usually a practical approach to obtain actual entropy changes. Thermo-

dynamic relationships incorporating volumetric and heat capacity data, to be dis-

cussed later in the present section and in 7.3, are more commonly used for en-

tropy change calculations.

A key property of the entropy is that it always increases for spontaneous pro-

cesses in closed, isolated systems. This property is often used as an alternative

statement of the Second Law

here, we simply derive it from the

Kelvin-Planck postulate as follows.

Consider an irreversible, adiabatic

process taking place between ini-

tial state A and final state D, along

the dashed-line path of Fig. 3.7.

Curves AB and CD represent re-

versible adiabatic paths from the

initial and final state respectively,

and curve BC is an isothermal path

at temperature T. For the reversible

Figure 3.7 Pressure-volume relationship for ir-

process DCBA that brings the sys-

reversible process (dotted line) and adiabatic-

tem from state D back to the initial

isothermal-adiabatic path.

state A, all heat transfer takes place

along the isothermal step BC, so that:

rev

rev

rev

U UD = QDA

+WDA

= T(S A SD )+WDA

! A

For the irreversible process AD

irr

U U A = WAD

! D

Adding
these
two
expressions
we
obtain

rev

irr

T(S S )+WDA

+WAD

= 0

! A D

46

irr

rev

rev

+WDA

< 0 ,
then
T(S A SD ) = QDA

> 0 ;
the
overall
cycle
has
received

If
WAD

!

!

!

heat
input
from
a
single
reservoir
at
T
and
has
produced
net
work.
This
is
a
viola-

tion
of
the
Kelvin-Planck
postulate
and
therefore
impossible.
The
case

rev

W irr +WDA

= 0 implies
that
T(S A SD ) = Q rev = 0 and
the
final
state
could
be
re-

! AD

!

turned
to
the
initial
state
with
no
net
effect
on
the
environment;
this
contradicts

the
original
statement
that
the
process
AD
was
irreversible.
Therefore,
we
must

have,
for
any
irreversible
process
in
an
isolated
closed
system
from
state
AD,

T(S A SD ) < 0 ,
or
equivalently:

!D A

(3.10)

irr

rev

irr

rev

+WDA

> 0 WAD

> WDA

In
addition,
we
must
have
WAD

.
By
changing
the

!

direction
of
the
reversible
process
from
DA
to
AD
we
then
obtain:

rev

W irr > WAD

!!

! AD

(3.11)

Since
the
universe
can
be
considered
a
closed
isolated
system,
Eq.
3.10
is
the

mathematical
equivalent
of
the
Clausius
statement
of
the
Second
Law,
the
entropy

of
the
universe
tends
to
a
maximum.
Eq.
3.11
states
that
the
algebraic
work

amount
is
always
greater
for
an
irreversible
process.
If
the
reversible
process
re-

rev

!>!0! )
then
the
irreversible
process
requires
more
work
input;

quires
work
( WAD

!

rev

!<!0! ),
Eq.
3.11
suggests
that
the
ir-

if
the
reversible
process
produces
work
( WAD

!

reversible
process
will
produce
less
work
it
may
even
require
work
input!
Re-

versible
processes
are
the
best
of
all
possible
processes
in
achieving
a
given
task

with
the
least
expenditure
of
useful
work
and
in
extracting
the
maximum
possible

amount
of
useful
work
out
of
a
given
change
of
state.

Entropy
has
been
just
derived
from
analysis
of
heat
and
work
flows
in
reversi-

ble
heat
engines;
however,
once
it
has
been
established
that
entropy
is
a
proper

thermodynamic
function,
it
can
be
expressed
for
any
equilibrium
state
in
terms
of

any
convenient
thermodynamic
variables.
This
provides
the
starting
point
for
de-

velopment
of
thermodynamic
identities
through
the
formal
approach
described
in

Chapter
5.
Let
us
take
a
look
again
at
the
differential
form
of
the
First
Law
of
ther-

modynamics,
written
for
a
closed
system
undergoing
a
reversible
process:

rev

rev

!dU = Q + W

(3.12)

the system, so we can set Q rev = TdS . Since the pressure also remains constant

!

(within a differential amount), the work performed by the environment on the sys-

tem can be expressed as !W rev = PdV . Combining the expressions for Q rev and

!

rev

!W we get the fundamental equation of thermodynamics, which provides a syn-

thesis of the First and Second Laws:

47

(3.13)

Eq.
3.13
has
only
proper
thermodynamic
state
functions
on
both
sides,
contain-

ing
no
inexact
differentials
involving
heat
or
work
amounts.
Changes
in
state
func-

tions
are
independent
of
the
path,
so
the
equation
is
valid
for
all
processes,
re-

versible
or
irreversible.
In
irreversible
processes,
the
first
term
(TdS )
is
not
equal

to
the
amount
of
heat,
and
the
second
term,
(PdV )
does
not
equal
the
amount
of

work;
but
their
sum
still
gives
the
change
in
system
energy.

Example
3.3
Entropy
change
for
an
ideal
gas

10
mol
of
an
ideal
gas
with
CV
=
20.8
J/mol
at
T0
=
300
K
and
P0
=
0.3
MPa
occupy

the
left
half
of
an
insulated
vessel,
as
shown
in
Fig.
3.8.
The
other
half
is
evacuated.

At
time
t
=
0,
a
1
kW
electrical
heating
element
is
turned
on.
After
30
s,
the
parti-

tion
dividing
the
vessel
ruptures
and
the
heating
element
is
turned
off.
Calculate

(a)
the
final
temperature
Tf
and
pressure
Pf
of
the
gas
in
the
vessel
and
(b)
the
en-

tropy
change
of
the
gas
during
this
process.

The
final
temperature
of
the
gas
can
be
obtained
from
a
First
Law
balance
on
the

contents
of
the
vessel:

U = NCV T = Q + W Tf = T0 +

Q

NCV

30!s! !1000!J/s

Tf = 300!K! +

= 444!K

10!mol! 20.8!J/(mol!K)

!

Pf Vf

RTf

P0V0

RT0

Pf = P0

V0Tf

Vf T0

444!K

Pf = 0.3!MPa

= !0.222!MPa

2! !300!K

!

The
entropy
change
cannot
be
directly
obtained
from

the
definition
(Eq.
3.9),
as
this
is
not
a
reversible
pro-

cess.
Instead,
it
can
be
obtained
from
Eq.
3.13:

Figure
3.8
Schematic
of
pro-

cess
for
Example
3.3.

1

P

dU = TdS PdV dS = dU + dV

T

T

!

NCV

C

T

V

NR

S

R

dS =

dT +

dV

= V dT + dV = CV ln f + Rln f

T

V

N

T

V

T0

V0

!

Valid
for

any
process

in
a
closed

system

48

S

444

J

J

= 20.8ln

+ 8.314ln2 !

= (8.16 +5.76)!

N

300

mol!K

mol!K

J

J

S = 10!mol! 13.9

S = 139!

mol!K

K

!

!

The
entropy
change
is,
of
course,
greater
than
zero
during
this
irreversible
pro-

cess.

Using
the
same
approach
as
in
Example
3.3,
it
is
easy
to
prove
that
the
general

relationship
for
the
entropy
change
of
an
ideal
gas
with
temperature-independent

heat
capacities
during
a
process
that
takes
it
from
(T0 ,P0 ,V 0 ) (Tf ,Pf ,V f ) is:

Entropy

change
for

an
ideal
gas

S

!

IG

= CV ln

Tf

T0

+ Rln

Vf

V0

= C P ln

Tf

T0

Rln

Pf

P0

(3.14)

Eq.
3.14
is
of
general
applicability
to
changes
of
state
for
ideal
gases
the
pro-

cess
does
not
have
to
be
reversible,
at
constant
temperature
or
at
constant
pres-

sure.

Example
3.4
Forging

A
common
process
in
metallurgy
is
to
immerse
a
red-hot
item
(e.g.
a
blade
being

forged)
in
water
to
harden
it.
Let
us
consider
a
process
in
which
a
1
kg
steel
blade

at
1
=
800
C
is
immersed
in
a
large
vessel
filled
with
water
at
2
=
25
C
and
imme-

diately
quenched.
Assuming
that
steel
has
heat
capacity
CV
=
460
J/(kg
K),
inde-

pendent
of
temperature,
calculate
the
entropy
changes
during
this
process
of
(a)

the
steel
blade,
(b)
the
water,
and
(c)
the
universe.
Assume
that
there
is
enough

water
in
the
vessel
so
that
its
temperature
does
not
increase
appreciably
during

the
process
of
immersion.

The
entropy
change
of
the
steel
blade
in
this
irreversible
process
can
be
calculated

from
Eq.
3.13,
ignoring
the
small
volume
change
of
the
solid
as
it
cools
down:

dU = TdS PdV

!

NC dT

1

dS = dU = V

T

T

C

T

Sblade = N V dT = NCV ln f

T

T0

!

J

273+ 25

J

Sblade = 1!kg! !460!

!ln

= 589!

kg!K 273+ 800

K

!

49

Even
though
this
is
an
irreversible
process,
the
blades
entropy
goes
down
the

blade
is
not
an
isolated
system,
so
Eq.
3.10
does
not
apply.

For
the
water,
we
are
not
given
enough
information
to
calculate
its
temperature

change;
since
the
process
is
clearly
irreversible,
it
would
seem
that
we
cannot
use

the
definition
of
entropy
change
(Eq.
3.9)
however,
this
is
not
true!
Even
though

the
overall
process
is
irreversible
because
of
the
large
temperature
difference
be-

tween
the
blade
and
the
water,
we
can
devise
a
thought
experiment
in
which
the

heat
transfer
to
the
water
is
done
in
a
reversible
manner.
The
amount
of
heat

transferred
is:

J

Q = U blade = NCV T = 1!kg 460!

(25 800)!K!=!356!kJ

kg!K

!

The
entropy
change
for
the
water
in
a
reversible
process
with
the
same
Q
is:

Q rev

356!kJ

J

Swater =

=

= 1196!

T

(273+ 25)!K

K

!

The
entropy
change
of
the
universe
is:

J

J

Suniverse = Swater + Sblade = (589+1196) = +607

K

K

!

Once
again,
the
entropy
change
of
the
universe
is
positive,
as
it
should
be
for
an

overall
irreversible
process.

The entropy of an open system can change because of heat exchanged with the en-

vironment, because of flows into and out of the system and because of entropy

generation due to internal irreversibilities entropy is not a conserved quantity!

While entropy can be created, a process can never result in a net decrease in the

entropy of the universe; this would violate the Second Law of thermodynamics.

This condition translates into an inequality linking the entropy change of the sys-

tem Ssystem, the entropy change of the environment Senv, and the specific entro-

pies of entering and leaving streams:

!

leaving

streams

Nout S out

entering

streams

Nin S in 0 (3.15)

Why
are
the
terms
for
the
entering
and
leaving
streams
in
Eq.
3.15
of
opposite

sign
relative
to
Eqs.
2.16
or
2.19
(p.
18),
the
First
Law
balance
for
open
systems?

50

Eqs.
2.16
and
2.19
are
written
from
the
point
of
view
of
the
system,
which
gains

the
streams
that
enter
and
loses
the
streams
that
leave.
By
contrast,
Eq.
3.15
rep-

resents
a
balance
for
the
entropy
of
the
universe.
For
the
universe,
streams
enter-

ing
the
system
are
lost
and
streams
exiting
the
system
are
gained.
A
similar
re-

lationship
can
also
be
written
as
a
differential
(rate
of
change):

leaving

streams

N out S out

entering

streams

N in S in 0

(3.16)

For
reversible
processes,
Eqs.
3.15-3.16
become
equalities,
with
their
right-

hand
side
equal
to
zero.
For
other
special
cases,
specific
terms
can
be
set
to
zero,

significantly
simplifying
the
equations.
For
example,
the
term
Ssystem
is
zero
at

steady
state,
as
there
is
no
net
change
in
the
system.
Another
example
of
simplifi-

cation
is
for
an
adiabatic
process,
for
which
we
can
set
Senv =
0,
since
no
heat
flows

into
the
environment.

The
fact
that
entropy
generation
is
non-negative
for
all
feasible
processes
im-

poses
significant
constraints
on
the
amount
of
work
that
can
be
produced
from
(or

is
required
for)
specific
processes.
When
performing
a
thermodynamic
analysis,
a

typical
approach
is
to
apply
in
turn
a
First
Law
balance
followed
by
a
Second
Law

balance,
as
illustrated
in
the
examples
that
follow.

Example
3.5
Feasibility
of
a
process

An
inventor
is
proposing
a
black
box
device
for
producing
electrical
power
that

operates
on
a
stream
of
compressed
air
at
P1
=
4
bar,
T1
=
300
K.
The
input
stream
is

split
into
two
equal
flows
of
P2
=
P3
=
1
bar
at
T2
=
280
K
and
T3
=
260
K,
respectively.

The
claim
is
made
that
power
is
produced
at
a
steady-state
rate
of
W
=
3.4
kJ/mol

of
air
flowing
through
the
device.
Assuming
that
unlimited
heat
exchange
with
the

environment
at
Tenv
=
300
K
is
allowed,
you
are
asked
to
provide
an
analysis
of
the

thermodynamic
feasibility
of
such
a
device.
Assume
that
air
can
be
approximated

as
an
ideal
gas
with
CP
=
29.1
J
/(mol
K),
independent
of
temperature.

First,
we
apply
an
integral

First
Law
balance
on
this

open
system
over
the
pe-

riod
of
time
it
takes
for
1

mol
of
air
to
flow
through

the
device,
which
is
as-

sumed
to
be
at
steady

state.
The
flow
of
streams

2
and
3
is
half
the
flow
of

stream
1.
We
use
a
refer-

ence
state
for
the
enthalpy

51

such that H = C PT .

U

= 0 = Q +W + NH 1

!steady!state

T +T

N

N

H 2 H 3 Q = W NC P T1 2 3

2

2

2

J

260+ 280

Q = (3400)!J! 1!mol!

!

!29.1!

300

K != 2527!J

mol!K

2

!

Since
the
heat
calculated
from
the
systems
point
of
view
is
positive,
heat
flows

from
the
environment
to
the
system
during
this
process.
We
must
now
check

whether
the
entropy
generation
rate
for
the
universe
is
non-negative.
We
use
Eq.

3.14
(p.
48)
to
calculate
the
entropy
change
of
the
ideal
gas
streams
and
take
into

account
that
the
flow
of
heat
into
the
environment
is
the
opposite
of
the
value
cal-

culated
from
First
Law
balance
on
the
system:

Suniverse =

leaving!

entering!

steady!state

!

= !

streams

streams

Q N

N

Q N

+ S 2 + S 3 N S1 =

+ (S 2 S 1 + S 3 S 1 )

Tenv 2

2

Tenv 2

TT

PP

Q N

+ C P ln 2 3 Rln 2 3 =

Tenv 2

T12

P12

2527!J 1!mol

J

260 280

J

1

!+!

29.1!

ln

8.314

ln 2 =

2

300!K

2

mol!K

mol!K 4

300

J

J

!!!!!!!!!!!!!!!!!!!!!!!!!!! 8.42 3.09!+11.53 ! = +0.02!

K

K

!

The
entropy
change
of
the
universe
is
positive,
so
operation
of
the
device
is
possi-

ble
as
described.
However,
since
the
entropy
change
is
small
relative
to
the
terms

of
which
it
consists,
the
device
is
operating
near
the
thermodynamic
limit
for
re-

versible
processes.

Example
3.6
Solar
power
generation

Solar
collectors
are
used
to
heat,
continuously
and
at
steady
state,
a
molten
salt

stream
from
200
C
to
600
C
at
a
flow
rate
of
12
kg/s.
The
hot
stream
generates

electrical
power
by
a
complex
process
and
then
returns
to
the
solar
collectors.

What
is
the
maximum
amount
of
power
that
can
be
produced?
Assume
that
the

environment
is
at
20
C.
The
heat
capacity
of
the
molten
salt
at
constant
pressure
is

CP
=
0.8
kJ/(kg
K),
independent
of
temperature.

52

The
system
of
interest
is
the
power
plant
that

uses
the
salt
stream.
We
label
the

hot
stream
H
and
the
cold
one
C.
An
open-system
First
Law
balance
for
this
sys-

tem
gives:

dU

=0

dt

H HC )

= Q + W + N(H

steady!state

W = Q + NC P (TC TH )

!

The
maximum
amount
of
work
is
produced
in
a
reversible
process,
for
which

Suniverse = 0 =

leaving!

entering!

steady!state

streams

streams

T C

T

Q

ln C

+ N(S C SH ) Q = Tenv N C P dT = Tenv NC

P

T

Tenv

TH

H T

T

T ln H +T T

W = NC

P

env

C

H

TC

273+ 600

kg

kJ

W = 12 0.8

293!ln

+ 200 600 K!!= 2.12!MW

s

kg!K

273+ 200

!

The
power
is
negative
because
it
is
being
produced
by
the
power
plant.

A power plant operates with supercritical steam at T1 = 900 K and P1 = 8 MPa as in-

put to a turbine. The steam exits at T2 = 430 K. Assuming that the turbine operates

53

rate of 1 MW?

Figure 3.11 Schematic of process for Example 3.7.

For
reversible
operation
of
the
steam
turbine,
we
must
have:

reversible!process

steady!state

adiabatic

The
properties
of
steam
at
the
entrance
of
the
turbine
(T1
=
900
K
and
P1
=
8
MPa)

can
be
obtained
from
the
NIST
WebBook
as
follows:

kJ

kJ

H 1 = 3707! !!!!!S 1 = 7.095

kg

kg!K

!

We
now
need
to
find
the
pressure
for
which
S2
=
S1
=
7.095
kJ/(kg
K)
at
T2
=
430
K.

With
a
bit
of
trial-and-error
with
respect
to
the
pressure
range,
we
can
obtain
from

the
NIST
WebBook
P2
=
0.31
MPa,
H2
=
2775
kJ/kg.
A
First
Law
balance
on
the
tur-

bine
now
gives:

dU

= 0 = Q + W + N(H

1 H2 )

dT

!steady!state

W

103 !kJ/s

N =

=

H 2 H 1 (2775 3707)!!kJ/kg

!

Example
3.8
Work
for
evacuating
a
tank

kg

N = 1.073

s

!

P0. The environment is also air at T0 and P0. Obtain general expressions for the

minimum amount of work required to evacuate or compress the tank to a pressure

P1 = P0 (a) isothermally and (b) adiabatically. Perform illustrative calculations for

= 0.1 and 10, and obtain the work required for complete evacuation ( = 0). Air

can be considered an ideal gas with CV = 5R/2.

54

by transformation from an open to an equivalent

closed system. For the case of evacuation, we

would like to remove material from the tank of

volume V0 , initially at T0 and P0, to bring the pres-

sure down to P1. This process reduces the number

of moles in the tank from N0 to N1. Instead of ac-

complishing this by action of a pump, in the

Figure 3.12 Schematic of pro-

closed system process, a frictionless piston is set

cess for Example 3.8.

up as shown in Fig. 3.12, at a position within the

tank that contains an amount of material N1, has

volume V1, and is originally at T0 and P0. At the right-hand side of the piston there

is air at T0 and P0. We will pick V1 so that after the piston has moved from V1 to V0,

the final pressure within the tank is P1 = P0. This reversible process accomplishes

the same task as pumping the original tank (of volume V0) from P0 to P1. The mini-

mum work for evacuation is obtained as the work to move the piston rightward

from V1 to V0. A similar approach can give the minimum work required for com-

pression to a certain pressure, or the maximum work that can be obtained from a

cylinder of compressed air.

(a) Isothermal operation

For this case, from the ideal-gas equation-of-state, PV = NRT, the volume V1 is ob-

tained as:

V1

V

! 0

P1

P0

N1

N0

The
instantaneous
pressure
difference
across
the
piston
is
P
P0,
where
P
is
the

pressure
within
the
expanding
volume
on
the
left
side.
The
total
work
required
to

move
the
piston
to
the
right
is:

V

V0 N RT

1

V1

V1

W = 0 (P P0 )dV =

dV + P0(V0 V1 ) = N1RT ln

V1

V0

+ P0(V0 V1 )

V PV PV

P V

W N1

=

RT ln 1 + 0 0 0 1 = RT ln + RT 0 1 = RT ln + RT RT

N0 N0

V0 N0

N0

N1

W

W

=

= ln +1

RTN0 P0V0

Because ln0 as 0, the expression has a simple interpretation at the limit of

complete evacuation:

55

W

W

=

= 1 W = P0V0
for
complete
evacuation.

!

N0RT P0V0

!

In
other
words,
the
minimum
work
for
complete
evacuation
is
the
work
to
push

back
the
atmosphere
by
a
volume
equal
to
the
original
tank
volume.

n
the
case
of
pressurization,
a
more
meaningful
measure
than
the
work
per
mole

initially
in
the
tank
is
the
work
per
mole
of
compressed
air,
obtained
by
dividing

the
full
expression
above
by
=
N1/N0,

W

W

1

=

= ln + 1

RTN1 P1V0

For
=
10,
this
equation
gives
W/(RTN1)
=
1.403.
The
work
required
is
positive

(work
input
to
the
system)
for
both
lowering
and
increasing
the
tank
pressure
to
a

value
different
than
atmospheric.

(b)
Adiabatic
operation

Here,
we
will
use
the
expressions
obtained
in
2.4
for
adiabatic
compression
and

expansion
of
an
ideal
gas.
Even
though
we
did
not
state
so
at
the
time,
adiabatic

operation
(Q
=
0)
at
internal
equilibrium
implies
also
a
reversible
operation,
since

the
entropy
change
of
the
universe
for
such
a
process
is
zero.

As
previously,
we
find
V1
so
that
P1
=
P0
after
expansion.
From
Eq.
2.31,
with
ini-

tial
volume
and
pressure
V1
and
P0
and
final
values
V0
and
P1
:

V

== 0

P

V1

! 0

P1

V1

V0

= 1/ =

CV /C P

1

P

R/C

= 1 = P

T

P

! 0 0

The
work
performed
on
the
gas
during
the
expansion
is,
from
Eq.
2.32:

T1

T

R/C

Ugas = Q +Wgas Wgas = N1CV T = N1CV (T1 T0 ) = N1T1CV 1 0 = N1T1CV 1 P

T1

!

The
net
work
required
is
the
sum
of
the
work
performed
on
the
gas
and
the
work

to
push
back
the
atmosphere,

56

R/C P

) + P (V V )

0

N1T1CV

PV

PV

PV C

W

R/C P

=

1

+ 0 0 0 1 = 1 0 V

N0RT0

N0RT0

N0RT0 N0RT0

P0V0R

W

W

1/

=

=

+1 1/

RT0N0 P0V0

1

V

1 +1 1

V0

For
air,
=7/5=1.4,
so
that
for
=
0.1
we
obtain
W/(RTN0)
=
0.574.
A
little
less

work
is
required
for
adiabatic
evacuation
than
for
isothermal
one.
At
the
limit

0,
this
expression
also
gives
W
=
P0V0,
as
for
the
isothermal
case.

For
adiabatic
pressurization,
the
work
per
mole
of
compressed
air
is:

1/

W

W V0 W

W

11/ 1

1/

=

=

=

+11/

=

+ 1/ 1

RT N

1

RT N P V V1 RT0N0

1

! 0 1

! 0 1 1 0

For
=
10,
this
expression
gives
W
/
(RTN1)
=
1.520,
a
little
more
than
in
the
iso-

thermal
case.

By this point, we are familiar with the definition of entropy from a macroscopic

thermodynamic viewpoint as S = Qrev/T. But what is the origin of entropy in the

microscopic, molecular world? Qualitatively, we expect that irreversible processes

(which result in an increase in total entropy) also increase the degree of disorder

in a system. It turns out that a quantitative measure of disorder, specifically the

number of microscopic states available to a system at a given internal energy U

and for specified number of molecules (or moles) N and volume V, can be quantita-

tively linked to the entropy. A distinct microscopic state (microstate) is defined by

all microscopic degrees of freedom e.g. positions and velocities of molecules in a

gas. A set of microstates with specified common properties (e.g. number of parti-

cles N, volume V and energy U) defines an ensemble. The expression of S in terms of

microstates is provided by the famous 1872 entropy formula of Ludwig Boltz-

mann,

S = kB ln (N ,V ,U )

!

(3.17)

necting macroscopic and microscopic points of view. It allows calculations of mac-

roscopic thermodynamic properties by determining properties of microscopic

57

ideal-gas constant to Avogadros number, or equivalently the gas constant on a per

molecule basis: kB = R/NA =1.3806510-23 J/K.

To illustrate the concept of counting microstates, we will use the simple sys-

tem shown in Fig. 3.13. In the general case, it consists of N slots, each containing a

ball that can be at energy levels 0, +1, +2, +3, , measured in units of kBT0, where

T0 is a reference temperature. The specific case of N = 10 and 3 energy levels is

shown in the figure. The concept of discrete energy levels arises very naturally in

quantum mechanics. For this simple system, we can count states by using the

combinatorial formula giving the number of ways we can pick M specific distin-

guishable objects out of N total objects:

N

N!

N (N 1)(N M +1)

(3.18)

= M!(N M)! =

12M

M

!

There
is
only
1
state
with
internal
energy
U
=
0.
States
with
U
=
1
have
one
ball

at
level
+1
and
the
others
at
level
0,
so
for
N
=
10,
there
are
10
such
states.
States

with
energy
U
=
2
may
have
1
ball
at
+2
and
the
others
at
0,
or
2
balls
at
+1,
so
there

are:

10

+10 = 55

2

!

such
states.
We
can
similarly
obtain
(3 )= 220;
(4 )= 715,
(5 )= 2002,
and
so

on.
Note
that
the
number
of
microstates
increases
rapidly
with
the
total
energy
of

the
system.
This
is
generally
the
case
for
most
systems.

Now
we
are
in
a
position
to
show
that
S
defined
microscopically
from
Eq.
3.17

has
the
two
key
properties
associated
with
the
entropy
of
classical
thermodynam-

ics:

1.

! A+B B

The reason is that each microstate of system A can be combined with a

microstate of system B to give a microstate of the combined system. This is

clearly true for the simple system illustrated on the previous page. However,

when mixing two

gases or liquids, we

only get the above

expression if we

assume that the

particles in the

systems

are Figure 3.13 A system of 10 spheres with 3 energy levels.

indistinguishable. If

58

system resulting from the possibility of exchanging the labels of particles.

Although the indistinguishability of particles is really of quantum mechanical

origin, it was introduced ad hoc by Gibbs before the development of

quantum mechanics, in order to make entropy an extensive property.

2.

internal rigid walls or barriers to energy transfer), the number of possible

microstates is always smaller than the number of microstates after the

constraints are removed.

To demonstrate this second property, consider the box with particles of the

example above, and think of any constraint to the system at a given total

energy (say U=+2). An example of a "constraint" would be to have that the

first five slots have exactly 1 unit of energy. The number of microstates in

this case is (5x5=25), less than the 55 states available to the unconstrained

system.

tropy is that the former is physically meaningful only as a difference of entropy be-

tween specified states, while the latter appears to provide a measure of absolute

entropy. This apparent discrepancy results from the inability of classical physics to

define uniquely when two nearby states (e.g. positions of a particle in free space

differing by a fraction of a nm) are sufficiently different to justify distinguishing

them from each other. Quantum mechanical methods, on the other hand, provide

precise ways to count states.

At low temperatures, the number of microstates available to any physical sys-

tem decreases rapidly. At the limit of absolute zero temperature, T 0 , most sys-

tems adopt a unique ground state for which = 1 S = kBln = 0. This is the basis

of the Third Law of thermodynamics postulated by Nerst in the early 1900s. The

NIST Chemistry WebBook lists absolute entropies for pure components and chem-

ical elements in the thermochemistry data section. However, using entropy values

calculated with respect to an arbitrary reference state gives the same results as

absolute entropies for heat and work amounts.

Example 3.9 Entropy of a lattice chain

A common model for polymers is the Flory lattice model, which represents chains

as self-avoiding random walks on a lattice (grid). Self-avoiding means that two

beads cannot occupy the same position on the lattice. When two non-bonded

beads occupy adjacent positions, they have energy of interaction equal to kBT0,

where T0 is a reference temperature. Obtain the number of microstates for a

two-dimensional square-lattice chain of 5 beads, as a function of the energy U of

the chain.

59

Fig.
3.14
shows
the
number
of
configurations
for
a
square-lattice
chain
of
5
beads.

Without
loss
of
generality,
we
have
fixed
the
configuration
of
the
first
two
beads
of

the
chain
to
be
in
the
horizontal
direction,
with
the
second
bead
to
the
right
of
the

first.
This
reduces
the
total
number
of
configurations
by
a
factor
of
4;
such
a
multi-

plicative
factor
simply
shifts
the
value
of
S
obtained
from
Eq.
3.17
by
a
constant

factor,
akin
to
the
reference
state
for
the
entropy.
The
last
bond
is
shown
in
multi-

ple
configurations
(arrows),
along
with
their
number
and
energy:
!2(1)
for
the

top
left
image
means
there
are
2
configurations,
each
of
energy
1.

Overall,
counting
configurations
of
the
same
energy:

(U=0)
=
3+2+2+3+2+2+3=17
;
(U=1)
=
2+1+1+1+1+2=8

The
number
of
microscopic
configurations
and
energy
levels
increases
rapidly

with
chain
length.
Theoretical
and
Monte
Carlo
computer
simulation
techniques

are
used
for
determining
the
properties
of
models
of
this
type
for
longer
chains.

Figure
3.14
Configurations
for
a
two-dimensional
chain
of
5
beads

microstates when the overall constraints of a thermodynamic system are specified.

A basic postulate, comparable in importance to the postulate about the existence

of equilibrium states in classical thermodynamics discussed in 1.4 (p. 6), is that

all microstates of a system at a given U, N and V are equally probable. The conse-

quences of this postulate will be fully explored in Chapter 5.

60

The
basic
postulate
of
statistical
mechanics
implies
that
the
probability
of
any

microstate
,
P ,
is
the
same
as
that
of
any
other
microstate
in
the
constant
N ,V ,U

ensemble:

1

P =
at
constant
N,
V
and
U

(3.19)

!

From
this
postulate,
we
can
now
simply
derive
another
famous
expression,
the

Gibbs
entropy
formula,
by
substituting
Eq.
3.19
into
Eq.
3.17:

Gibbs

entropy

formula

S = kB

!

P lnP

(3.20)

all!micro+

states!

The
Gibbs
entropy
formula
can
be
shown
to
be
valid
even
for
systems
not
at

constant
energy
U,
volume
V,
and
number
of
particles
N.
This
is
in
contrast
to
Eq.

3.17,
which
is
only
valid
at
constant
for
microstates
at
constant
U
V
and
N.
For
ex-

ample,
in
5.6
we
prove
Eq.
3.20
for
systems
at
constant
N,
V,
and
T.

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