February 05 Lecture 2 1

Lecture 2:
Lecture 2:
Intro. Statistical Mechanics
Intro. Statistical Mechanics
Statistical mechanics: concepts Statistical mechanics: concepts

Aims: Aims:
A microscopic view of entropy:
Joule expansion reviewed.
Boltzmanns postulate.
S = k ln g.
Methods:
Calculating arrangements;
Stirlings formula;
Fluctuations.
Assemblies of quantum oscillators.
N
N
ln(N!)
N!/10^6
N N N N ln ! ln
) log(g k S =
February 05 Lecture 2 2
Joule expansion
Joule expansion

Entropy and configuration: Entropy and configuration:

Review Joule expansion of ideal gas.

2 degenerate states per molecule: 2 degenerate states per molecule:

Take an ideal gas and double its volume:
For 1 mole: (contains N molecules)
S = R ln(2V/V) = R ln 2.

Boltzmann: Boltzmann: associated the increase in entropy

with the increased number of arrangements of the
molecules, g.
In the present example we have N molecules
The initial g arrangements become 2
N
g finally.
Entropy for final system (parts 1 and 2)
S = S
1
+ S
2
while the arrangements behave like
g = g
1
.g
2
.
Guess: S = k ln g. k = const.
February 05 Lecture 2 3
Proof of
Proof of
k
k
ln
ln
g
g
guess.
guess.
( ) ( ) [ ]
N R k
Nk
g g k S
N
=
=
=
2 ln
ln 2 ln
Boltzmanns constant
Boltzmanns constant
In the Joule expansion above,

Proof of Proof of ln ln g g guess: guess:

If, S = f(g)
S = S
1
+ S
2
g = g
1
.g
2
f(g) = f(g
1
.g
2
) = f(g
1
) + f(g
2
).
Differentiate w.r.t. g
1
,
g
2
f(g
1
. g
2
) = f(g
1
)
Differentiate w.r.t. g
2
,
f(g
1
g
2
) + g
1
.g
2
f(g
1
. g
2
) = 0
f(g) = -f(g)/g
f(g) = k/g
f(g) = k ln g + const.
February 05 Lecture 2 4
Calculating number of
Calculating number of
arrangements (Maths revision)
arrangements (Maths revision)
1 less to choose from, etc.
1 less to choose from, etc.
1st choice from N objects
1st choice from N objects
N
N
N!/10^6
ln(N!)

Factorials: Factorials:
Number of ways of selecting N distinguishable
objects:
N.(N-1).(N-2)1 = N!

Combinations: Combinations: (order unimportant)

E.g. distribute N distinguishable objects
between 2 boxes. n
1
in 1st box, and n
2
(=N-n
1
) in
second box.
Using earlier result.
February 05 Lecture 2 5
ways irrespective of order
ways irrespective of order
Combinations
Combinations
(Revision) (Revision)

The result from this argument,

N.(N-1)....(N-n
1
-1).(N-n
1
).(N-n
1
-1).1 = N!
depends on the order (as before)
If there are g arrangements independent of
order,
g(n
1
,n
2
) n
1
! n
2
! = N!
(Same as
n
C
r
= n!/r!(n-r)!, no. of ways of
selecting r from n irrespective of order)
Generalisation to N particles in r boxes
N.(N-1)..(N-n
1
+1)
N.(N-1)..(N-n
1
+1)
(N-n
1
).(N-n
1
-1)..1
(N-n
1
).(N-n
1
-1)..1
x
x
ways of arranging n
2
ways of arranging n
2
ways of arranging n
1
ways of arranging n
1
( )
( )! !
!
! !
!
,
1 1 2 1
2 1
n N n
N
n n
N
n n g

= =
( )

= =
i
r
n N
n n n
N
g ,
! ! !
!
2 1

A
A
February 05 Lecture 2 6
Stirlings approximation
Stirlings approximation
(Revision) (Revision)

Dealing with large factorials. Dealing with large factorials.

N!, when N is large:
For our purposes N~10
24
. It is an excellent
approximation.
[ ]
2 / 1
2 / 1
2 / 1
2 / 1
ln d ln
ln 2 ln 1 ln ! ln
+
+
=
+ + =
}
N
N
x x x x x
N N
N N N N ln ! ln
Stirlings approximation
Stirlings approximation
((n ln n - n)/n!)/10
-6
February 05 Lecture 2 7
N=6x10
23
Distribution function
Distribution function
between chambers
between chambers

How many molecules in each chamber? How many molecules in each chamber?
The numbers must fluctuate (while N is clearly
fixed). Let us calculate the deviation from ideal
partitioning, n.
Box 1 with (N/2+n); Box 2 with (N/2-n).
Using previous result, A, and Stirling:
Using ln(1+x) x-x
2
/2 +.. For small x.
A sharply-peaked
Gaussian.
( )
( ) ( )
( )
( ) ( )
( ) ( )
( ) ( )
( ) ( ) N n n N
N n n N N
n N n N n N
n N n N n N
N N N g
n N n N
N
n n g
/ 2 1 ln 2 /
/ 2 1 ln 2 / 2 ln
2 / 2 / ln 2 /
2 / 2 / ln 2 /
ln ln
! 2 / ! 2 /
!
,
2 1

+ + =
+
+ + + +

+
=
( )
( ) N n g
N n g
N
N
2
2
2 exp 2
2 2 ln ln


February 05 Lecture 2 8
2 non
2 non
-
-
degenerate states
degenerate states

What if the 2 chambers have different What if the 2 chambers have different
energies? energies?
For example molecules in the right chamber
have extra potential energy mgh.
The entropy comes from S = k ln g.
Free Energy F = U - TS is minimised at
equilibrium. (See also Q6, sheet 1.)
Boltzmann distribution (to be derived more
formally later).
( ) ( ) ( )
[ ] ) 1 ln( ) 1 ( ln
! ! 1
!
ln
f f f f Nk
Nf f N
N
k S
+
|
.
|

\
|

=
[ ]
( ) kT
f
f
f F
f f f f NkT Nf F
/ exp
1
0
) 1 ln( ) 1 ( ln

=
+ + =
February 05 Lecture 2 9
Quantum oscillators
Quantum oscillators

Commence a systematic presentation of Commence a systematic presentation of

statistical mechanics. statistical mechanics.

Counting microstates: Counting microstates: (easier in a quantised

system)
weakly interacting assembly of quantum
oscillators. I.e.
They interact to exchange energy, BUT
Energy levels of each oscillator unaffected by
the interaction.
For simplicity take energy levels equally
spaced =m, Separation E= .

Example: Example:
5 oscillators sharing 4 quanta.
N.B. Even with this small number a Boltzmann
distribution emerges. 0 quanta most likely.
Oscillator No 1 2 3 4 5 No. of states
4 0 0 0 0 5
3 1 0 0 0 20
2 2 0 0 0 10
2 1 1 0 0 30
1 1 1 1 0 5
Total no. of microstates 70
February 05 Lecture 2 10
Counting microstates
Counting microstates

Counting states: Counting states:

Represent quanta as x and divided into
oscillators by |. Eg last 2 lines of table;
|xx |x |x | | |
|x |x |x |x | |
Have N-1 boundaries separating the quanta
(Always have 2 boundaries on the outside).
Need to know No. of arrangements of N-1
boundaries and m quanta.
( = 8!/4!4! = 70, for N = 5, m = 4)

Distribution for one Distribution for one- -oscillator. oscillator.

( )
( ) ! ! 1
! 1
) , (
m N
m N
m N g

+
=
0 qu: {(4/5 x 5) + (3/5 x 20) + (3/5 x 10) + (2/5 x 30) + (1/5 x 5)}/70 = 0.5
1 qu: {(0/5 x 5) + (1/5 x 20) + (0/5 x 10) + (2/5 x 30) + (4/5 x 5)}/70 = 0.29
2 qu: {(0/5 x 5) + (0/5 x 20) + (2/5 x 10) + (1/5 x 30) + (0/5 x 5)}/70 = 0.14
3 qu: {(0/5 x 5) + (1/5 x 20) + (0/5 x 10) + (0/5 x 30) + (0/5 x 5)}/70 = 0.06
4 qu: {(1/5 x 5) + (0/5 x 20) + (0/5 x 10) + (0/5 x 30) + (0/5 x 5)}/70 = 0.01
Boltzmann distribution
Boltzmann distribution
February 05 Lecture 2 11
Concluding remarks
Concluding remarks
Direct calculation of the number of ways of
getting, for example, 2 quanta = no. of ways of
giving remaining 2 quanta (i.e. m-1 quanta) to
remaining 4 oscillators (i.e. N-1 osc.).
= (4-1+2)! / (4-1)! (2)! = 5! / 3! 2! = 10

General calculation General calculation

Number of ways an oscillator gets n quanta,
when m quanta are distributed between N
oscillators is:

Note on Q. 3(d), sheet 1 Note on Q. 3(d), sheet 1

Asks how energy is partitioned between two
systems (N
1
and N
2
oscillators respectively),
when the two are in thermal equilibrium.
Evidently, if they have m1 and m2 quanta, we
expect m
1
/ N
1
= m
2
/ N
2
.
Look at ln(g(m
1
) and maximise
Sharpness (curvature) of peak
( ) { }
( ) { } ( )
( )
)! ( )! 2 (
! 2
! ! 1 1
! 1 ) ( 1
n m N
m N
n m N
n m N

+
=

+
( ) 0 ln
1 1
= m m g
( )
peak
m m g
2
1 1
2
ln