Lecture 6. Entropy of an Ideal Gas (Ch.

3)

Find O (U,V,N,...) the most challenging step
S (U,V,N,...) = k
B
ln O (U,V,N,...)

Solve for U = f (T,V,N,...)
1
,...) , , (

|
|
.
|

\
|
c
c

U
N V U S
T
Today we will achieve an important goal: well derive the equation(s) of state
for an ideal gas from the principles of statistical mechanics. We will follow the
path outlined in the previous lecture:
So far we have treated quantum systems whose states in the configuration
(phase) space may be enumerated. When dealing with classical systems with
translational degrees of freedom, we need to learn how to calculate the
multiplicity.
Multiplicity for a Single particle
- depends on three rather than two macro parameters (e.g., N, U, V).
Example: particle in a one-
dimensional box
-L
L
-L L x
p
x
Ap
x
-p
x
Ax
2
x x
x
L p L p
x p h
A A
=
A A
The number of microstates:
Q.M.
h p x
x
> A A
Quantum mechanics (the
uncertainty principle) helps
us to numerate all different
states in the configuration
(phase) space:
p space
O O = O
The total number of ways of filling up the cells in phase space is the
product of the number of ways the space cells can be filled times
the number of ways the momentum cells can be filled
Multiplicity of a Monatomic Ideal Gas (simplified)
For a molecule in a three-dimensional box: the state of the
molecule is a point in the 6D space - its position (x,y,z) and its
momentum (p
x
,p
y
,p
z
). The number of space microstates is:
There is some momentum distribution of molecules in an ideal
gas (Maxwell), with a long tail that goes all the way up to p =
(2mU)
1/2
(U is the total energy of the gas). However, the
momentum vector of an average molecule is confined within
a sphere of radius p ~ (2mU/N)
1/2
(U/N is the average energy
per molecule). Thus, for a single average molecule:
3
x
V
z y x
V
space
A
=
A A A
= O
z y x
p
p p p
p
A A A
O
3
3
4
t
The total number of microstates
for N molecules:
N
p
N
x
p space
h
V V
p x
p V
|
|
.
|

\
|

=
|
|
.
|

\
|
A A

~ O O = O
3 3
3
3
For N molecules:
N
space
x
V
|
.
|

\
|
A
= O
3
p
n
p
However, we have over-counted the multiplicity,
because we have assumed that the atoms are
distinguishable. For indistinguishable quantum
particles, the result should be divided by N! (the
number of ways of arranging N identical atoms in a
given set of boxes):
3
1
!
N
p
indistinguishable
V V
N h

| |
O ~
|
\ .
mU p p p
z y x
2
2 2 2
= + +
mU p p p p p p
z y x z y x
2
2
2
2
2
2
2
2
1
2
1
2
1
= + + + + +
1 particle -
2 particles -
The accessible momentum volume for N particles = the area of a 3N-dimensional hyper-
sphere Ap
1 3
2 / 3
! 1
2
3
2
area" "

|
.
|

\
|

=
N
N
r
N
t
( )
p
h
mU
N
V
N
N
N
N
A
|
.
|

\
|
~ O 2
2
! 2 / 3 !
1
2 / 3
2
t
Monatomic
ideal gas:
(3N degrees
of freedom)
N =1
( )
( ) | |
2 2
2 / 3
4 2 / ! 2 / 1
! 2 / 1
2
r r t t
t
= = =
f N- the total # of quadratic degrees of freedom
( )
2 / N f
U U O
The reason why m matters: for a
given U, a molecule with a larger
mass has a larger momentum, thus a
larger volume accessible in the
momentum space.
p
x
p
y
p
z
( ) p
N
U m
N
V
h
e
N V U
N
ishable indistingu
A
(
(

|
.
|

\
|
= O 2
3
4
, ,
2 / 3
3
2 / 5
t
Momentum constraints:
More Accurate Calculation of O
N
(I)
More Accurate Calculation of O
N
(II)
For a particle in a box (L)
3
: (Appendix A)
If p>>Ap, the total degeneracy (multiplicity)
of 1 particle with energy U is:
Plug in the area of the hyper-sphere:
p
x
p
y
p
z
( ) ( )
3/ 2
5/ 2
3
4
, , 2
3
N
indistinguishable
e V mU
U V N p
h N N
t
(
| |
O = A
(
|
\ .
(

( ) ( )
2 2 2
2
2 2 2
2
, ,
2 8
x y z
x y z x y z
p p p
h
E n n n n n n
m mL
+ +
= = + +
2
x
h
p
L
A =
( )
( )
( )
( ) ( )
3
3
1 3 3 3 3 3 3 3
2
1 1
2 2
p
p p
L
S p V
U S p S p
h h
p
A
O = = A = A
A
If p>>Ap, the total degeneracy (multiplicity) of N
indistinguishable particle with energy U is:
( )
( )
3
3
1
!
N
p
N N
N
V
U S p
N h
O = A
, , 0
x y z
n n n >
Entropy of an Ideal Gas
f 3 (monatomic), 5 (diatomic), 6 (polyatomic)
(Monatomic ideal gas)

+
(
(

|
.
|

\
|
=
2
5
3
4
ln ) , , (
2 / 3
2
N
U
h
m
N
V
k N U V N S
B
t
3/ 2
2
3 5 4 3
ln ln ln ln ( , )
2 3 3 2
B B B B
V U m V U
Nk Nk Nk Nk N m
N N h N N
t

(
(
| | | |
= + + = + +
(
| |
(
\ . \ .
(

The Sackur-Tetrode equation:
In general, for a gas of
polyatomic molecules:
) , ( ln
2
ln ) , , ( m N T k N
f
N
V
k N T V N S
B B
+ + =
( ) ( )
, , ln , ,
B
S U V N k U V N = O
( )
3/ 2
2
4 5
( , , ) ln ln 2
3 2
B B
V m U
S N V U Nk Nk p
N h N
t
(
| |
= + + A
(
|
\ .
(

an average volume
per molecule
an average energy
per molecule
Problem
Two cylinders (V = 1 liter each) are
connected by a valve. In one of the
cylinders Hydrogen (H
2
) at P = 10
5
Pa, T = 20
0
C , in another one
Helium (He) at P = 310
5
Pa,
T=100
0
C. Find the entropy change
after mixing and equilibrating.
i
f
B
i
f
B
T
T
k N
f
V
V
k N T V N S ln
2
ln ) , , ( + = A
H
2
:

( ) ( ) ( )
f total
T U T U T U = +
2 2 1 1
2
2
1
1
2 1
2 1
2 2 1 1
3 5
3 5
2
3
2
5
2
3
2
5
T
P
T
P
P P
k N k N
T k N T k N
T
B B
B B
f
+
+
=
+
+
=
1
ln
2
5
2 ln
2
T
T
k N k N S
f
B B H
+ = A He

:

2
2 2
ln
2
3
2 ln
T
T
k N k N S
f
B B He
+ = A
( )
(

+ + + = A + A = A
2
2
1
1 2 1
ln 3 ln 5
2
2 ln
2
T
T
N
T
T
N
k
k N N S S S
f f
B
B He H total
J/K 67 . 0
total
= AS
The temperature
after mixing:
f B B B B
T k N k N T k N T k N
|
.
|

\
|
+ = +
2 1 2 2 1 1
2
3
2
5
2
3
2
5
For each gas:
Entropy of Mixing
Consider two different ideal gases (N
1
,
N
2
) kept in two separate volumes (V
1
,V
2
)
at the same temperature. To calculate the
increase of entropy in the mixing process,
we can treat each gas as a separate
system. In the mixing process, U/N
remains the same (T will be the same
after mixing). The parameter that
changes is V/N:

+
(
(

|
.
|

\
|
=
2
5
3
4
ln ) , , (
2 / 3
2
N
U
h
m
N
V
k N U V N S
B
t
The total entropy of the system is greater after mixing thus,
mixing is irreversible.
|
|
.
|

\
|
+
|
|
.
|

\
|
=
A + A
=
A
2
2
1
1
ln ln
V
V
N
V
V
N
k
S S
k
S
B
B A
B
total
if N
1
=N
2
=1/2N , V
1
=V
2
=1/2V

2 ln
2 /
ln
2 2 /
ln
2
N
V
V N
V
V N
k
S
B
=
|
.
|

\
|
+
|
.
|

\
|
=
A
total
Gibbs Paradox
If two mixing gases are of the same kind (indistinguishable molecules):
( ) ( )
1 2 1 2
total 1 2 1 2
1 2 1 2
1 2 1 2
1 2
1 2 1 2
/ ln ln ln
ln ln 0 if
B total A B B
V V V V
S k S S S k N N N N
N N N N
V N V N N N N
N N
N V N V V V V
| | | | | | +
A = = +
| | |
+
\ . \ . \ .
| | | |
= + = = =
| |
\ . \ .
( )
N
N
N
N
N
mU
N h
V
N
3
2 / 3
3
2
!
2
3
2
!
1
|
.
|

\
|
= O
t
B B
k N
N
U
h
m
N
V
k N U V N S
2
5
3
4
ln ) , , (
2 / 3
2
+
(
(

|
.
|

\
|
=
t
Quantum-mechanical indistinguishability is important! (even though this equation
applies only in the low density limit, which is classical in the sense that the distinction
between fermions and bosons disappear.
AS
total
= 0 because U/N and V/N available for each molecule remain the same after mixing.
|
|
.
|

\
|
+
|
|
.
|

\
|
=
A + A
=
A
2
2
1
1
ln ln
V
V
N
V
V
N
k
S S
k
S
B
B A
B
total
- applies only if two gases are different !
Problem
Two identical perfect gases with the same pressure P and the same number of
particles N, but with different temperatures T
1
and T
2
, are confined in two vessels,
of volume V
1
and V
2
, which are then connected. find the change in entropy after
the system has reached equilibrium.
B B B B B
k N T k
h
m
N
V
k N k N
N
U
h
m
N
V
k N U V N S
2
5
2
3
3
4
ln
2
5
3
4
ln ) , , (
2 / 3
2
2 / 3
2
+
(
(

|
.
|

\
|
= +
(
(

|
.
|

\
|
=
t t
( )
( )
B f B f
k N T
N
V V
k N S 2
2
5
2
ln 2
2 / 3
2 1
+
(

+
= o
( )
( )
( ) ( )
( )
( )
( ) ( )
( )
( )
(

+
=
(

+
= + =
(

+
+
(

+
=
(
(

+
(

+
=
(
(

+
(
(

)
`

+
=
A
2 1
2
2 1 2 1
2 1
2 1
2
2 1
2 1
2
2 1
2 1
2
2 1
2
2 1
2 / 3
2
2 / 3
1
3
2 1
2
2
2 1
4
ln
2
5
2
2
4
ln
2
3
4
ln
ln
2
3
4
ln ln
2
ln
T T
T T T T
Nk V V P
T T
T T
V V
V V
T T
T
V V
V V
T T
T
V V
N
N
V V
k N
S
B
f f
B
o o
o
at T
1
=T
2
, AS=0, as it should be (Gibbs paradox)
( ) ( )
B B B B i
k N T
N
V
k N k N T
N
V
k N S S S
2
5
ln
2
5
ln
2 / 3
2
2
2 / 3
1
1
2 1
+
(

+ +
(

= + = o o
2
2 1
T T
T
f
+
=
- prove it!
An Ideal Gas: from S(N,V,U) - to U(N,V,T)
( ) ( )
2 /
, ,
N f N
U V N f N V U = O
Ideal gas:
(fN degrees of freedom)
( ) ) , ( ln ln
2
, , m N
N
V
Nk
N
U
Nk
f
N V U S
B B
+ + =
U
Nk f
U
S
T
B
2
1
=
c
c
=

T k N
f
T V N U
B
2
) , , ( =
The heat capacity for
a monatomic ideal gas:
B
N V
V
k N
f
T
U
C
2
,
=
|
.
|

\
|
c
c
=
- in agreement with the equipartition theorem, the total energy should be
k
B
T times the number of degrees of freedom.
- the energy
equation of state
Partial Derivatives of the Entropy
We have been considering the entropy changes in the processes where two
interacting systems exchanged the thermal energy but the volume and the number of
particles in these systems were fixed. In general, however, we need more than just
one parameter to specify a macrostate, e.g. for an ideal gas
Today we will explore what happens if we let the V
vary, and analyze the physical meaning of the
other two partial derivatives of the entropy:
N U
V
S
,
|
.
|

\
|
c
c
We are familiar with the physical meaning only
one partial derivative of entropy:
T U
S
N V
1
,
=
|
.
|

\
|
c
c
( ) ( ) N V U k N V U S S
B
, ln , , , O = =
When all macroscopic quantities S,V,N,U are allowed to vary:
N d
N
S
V d
V
S
U d
U
S
dS
V U U N V N , , ,
|
|
.
|

\
|
c
c
+
|
|
.
|

\
|
c
c
+
|
|
.
|

\
|
c
c
=
Mechanical Equilibrium
and Pressure
Lets fix U
A
,N
A
and U
B
,N
B
, but allow V to vary
(the membrane is insulating, impermeable for
gas molecules, but its position is not fixed).
Following the same logic, spontaneous
exchange of volume between sub-systems
will drive the system towards mechanical
equilibrium (the membrane at rest). The
equilibrium macropartition should have the
largest (by far) multiplicity O (U, V) and
entropy S (U, V).
U
A
, V
A
, N
A

U
B
, V
B
, N
B

0 =
c
c

c
c
=
c
c
+
c
c
=
c
c
B
B
A
A
A
B
A
A
A
AB
V
S
V
S
V
S
V
S
V
S
( )
B A
V V c = c
B
B
A
A
V
S
V
S
c
c
=
c
c
,
B
U N
k N S P
V V T
c
| |
= =
|
c
\ .
In mechanical equilibrium:
- the volume-per-molecule should be the same
for both sub-systems, or, if T is the same, P must
be the same on both sides of the membrane.
S
AB
V
A

V
A
eq
S
A
S
B
N V N U N U
U
S
V
S
V
S
T P
, , ,
/
|
|
.
|

\
|
c
c
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c

The stat. phys.

definition of pressure:
e.g. ideal gas
The Pressure Equation of State for an Ideal Gas
Ideal gas:
(fN degrees of freedom)
V
k N
T
V
S
T P
B
N U
=
|
.
|

\
|
c
c
=
,
T k N PV
B
=
U
k N
f
U
S
T
B
N V
1
2
1
,
=
|
.
|

\
|
c
c
=
The energy equation of state (U T):
T k N
f
U
B
2
=
The pressure equation of state (P T):
- we have finally derived the equation of state of an ideal gas from first principles!
) , ( ln
2
ln ) , , ( m N T k N
f
N
V
k N T V N S
B B
+ + =
Thermodynamic identity I
, , N V N U
S S
dS dU dV
U V
c c
| | | |
= +
| |
c c
\ . \ .
Lets assume N is fixed,
thermal equilibrium:
T U
S
N V
1
,
=
|
.
|

\
|
c
c
mechanical equilibrium:
, U N
S P
V T
c
| |
=
|
c
\ .
1 P
dS dU dV
T T
= +
dU TdS PdV =
i.e.
Quasi-Static Processes
const VT S
f
= = A
2 /
0
1
1
VT const

=
The quasi-static adiabatic process with an ideal gas :
const VT =
1
const PV =

- weve derived these equations from the 1

st

Law and PV=RT
On the other hand, from the Sackur-Tetrode equation for an isentropic process :
Quasistatic adiabatic (oQ = 0) processes:
0 = S d isentropic processes
(all processes)
dV P S d T U d =
W Q U d o o + =
(quasi-static processes with fixed N)
S d T Q = o Thus, for quasi-static processes :
T
Q
S d
o
=
T
Q
S d
o
=
- is an exact differential (S is a state function).
Thus, the factor 1/T converts oQ into an exact
differential for quasi-static processes.
Comment on State Functions :
P
V
0
0
= A
= A
Q
S
Problem:
(a) Calculate the entropy increase of an ideal gas in an isothermal process.
(b) Calculate the entropy increase of an ideal gas in an isochoric process.
( ) ( )
2 /
, ,
N f N
U V N f N V U = O
You should be able to do this using (a) Sackur-Tetrode eq. and (b)
T
Q
S d
o
=
|
.
|

\
|
+ = + = dV
V
T
dT
f
Nk PdV dU Q
B
2
o
|
.
|

\
|
+ = =
V
dV
T
dT f
Nk
T
Q
dS
B
2
o
( ) | |
2 /
ln
f
B
VT N g Nk S =
|
|
.
|

\
|
= A
=
i
f
B const T
V
V
Nk S ln
|
|
.
|

\
|
= A
=
i
f
B const V
T
T
Nk
f
S ln
2
(all the processes are quasi-static)
Lets verify that we get the same result with approaches a) and b) (e.g., for T=const):
Since AU = 0,
|
|
.
|

\
|
= = =
}
i
f
B
V
V
B
V
V
T k N dV
V
T k N
W Q
f
ln o o

T
Q
S
o
= A
(Pr. 2.34)
Problem:
A bacterias of mass M with heat capacity (per unit mass) C, initially at temperature
T
0
+AT, is brought into thermal contact with a heat bath at temperature T
0.
.

(a) Show that if AT<<T
0
, the increase AS in the entropy of the entire system (body+heat
bath) when equilibrium is reached is proportional to (AT)
2.
(b) Find AS if the body is a bacteria of mass 10
-15
kg with C=4 kJ/(kgK), T
0
=300K,
AT=0.03K.
(c) What is the probability of finding the bacteria at its initial T
0
+AT for At =10
-12
s over
the lifetime of the Universe (~10
18
s).
0 ln
0
0
0
0
0
0
<
|
|
.
|

\
|
A +
=
'
'
=
'
=
} }
A + A +
T T
T
C
T
T Cd
T
Q
S
T
T T
T
T T
body
o
(a)
0
0 0 0
0
0
>
A
=
'
= =
}
A +
T
T C
T
T Cd
T
Q
S
T
T T
bath heat
o
( ) 0
2
...
3 2
1 ln ln
2
0
3 2
0
0
0
>
|
|
.
|

\
|
A
=
(

+ = + ~
|
|
.
|

\
|
A +

A
= + =
T
T C
T
T T
C
T
T
C S S S
bath heat body total
o o
o o
(b)
K J
K J
T
T C
S
total
/ 10 2
300
03 . 0
2
/ 10 1 10 4
2
20
2
15 3
2
0

=
|
.
|

\
|

=
|
|
.
|

\
|
A
=
Problem (cont.)
(b) O for the (non-equilibrium) state with T
bacteria
= 300.03K is greater than O
in the equilibrium state with T
bacteria
= 300K by a factor of
630 1450
23
20
10
/ 10 38 . 1
/ 10 2
exp exp
0
0
~ ~
|
|
.
|

\
|

=
|
|
.
|

\
| A
=
O
O

A +
e
K J
K J
k
S
B
total
T T
T
The number of 1ps trials over the lifetime of the Universe:
30
12
18
10
10
10
=

Thus, the probability of the event happening in 10

30
trials:
( )( )
30 630
# events probability of occurrence of an event 10 10 0