Problem Set 4

Solutions
3.20 MIT
Dr. Anton Van Der Ven
Fall 2002

Problem 1-22

For this problem we need the formula given in class (McQuarie 1-33) for the energy states
of a particle in an three-dimensional infinite well, namely

 nxnynz  h 2 n 2  n 2  n 2  , n x , n y , n z  1, 2. . . .
x y z
8ma 2

Now we can make a table

n x n y n z n 2x  n 2y  n 2z Degeneracy
1 1 1 3 1
1 1 2 6
1 2 1 6 3
2 1 1 6
1 2 2 9
2 1 2 9 3
2 2 1 9
1 1 3 11
1 3 1 11 3
3 1 1 11

Problem 1-29
Start with the differential form for E

dE  TdS  pdV
E  T S p
V T V T

S
We can use a Maxwell relation on V T
from FT, V

S p

V T T V

So,

E p
T  p
V T T V

Problem 1-41

Show that x  x  2  x 2  x 2

x  x  2  x 2  2x x  x 2  x 2  2x x  x 2  x 2  2 x  x   x 2  x 2  x 2
 Problem 1-43

1 x x  2
Here we have to plot the Gaussian px  exp  2 2
for several values of 
 2
to see what happens as   0

As   0, the function becomes sharper and sharper (remember the area under the curve is
contrained to be 1, as we will see in problem 1-44a). Thus, the Gaussian approaches a delta
function.

Problem 1-44

Gaussian distribution is

2
px  1 exp  x  x 
 2 2 2


(a) show  pxdx  1


2

  1 exp  x  x  dx
 2 2 2

Let
 u  x  x , then du  dx
2 2

So we now have


  1 expu 2 du


And using standard integral tables or the math software, it can be show that this integral is
equal to 1.
(b) n th central moment for n  0, 1, 2, and 3

For n  0

x  x  0  1 see part a

For n  1

  x  x  x  x  2
x  x     x  x   pxdx    exp 
2 2
dx
 2

Let

u  x  x , then du  dx
2 2

Then
 0 
x  x   1

  u  expu 2 du  1

  u  expu 2 du  1

 0 u  expu 2 du
I II

For I let v  u and dv  du. Then

 
I 1

0 u  expu 2 du  1

 0 v  expv 2 dv  II

Thus,


1

  u  expu 2 du  0

For n  2

  x  x  2 x  x  2
x  x  2    x  x   pxdx    exp 
2 2
dx
 2

Let
 u  x  x , then du  dx
2 2
 
3
x  x   1   2 2 u 2 expu 2 du  2 2   u 2 expu 2 du
 

Now lets take a crack at this integral....


  u 2 expu 2 du

We have to do this by parts. Remembering how to do that....

yx   y  x  yx 
 
  y  x  yx     yx 

For our case, let

y   2u expu 2 du and x  u

2
y  expu 2  and x    1
2
 So,

  
  u 2 expu 2 du  u expu 2 
2 
   1
2
expu 2 

0  2

Which leaves us with,

x  x  2   2
For n  3

  x  x  3 x  x  2
x  x  
3
  x  x  3
 pxdx    exp 
2 2
dx
 2

As before, let

u  x  x , then du  dx
2 2

Then,


3 2
x  x   2    u 3 expu 2 
2
Since e u is a symmetric function around the origin and u 3 is an antisymmetric
function around the origin, the integral of the product of the
two functions is zero.

3
x  x   0

1 x x  2
(c) lim px  lim exp  2 2
 x  x , the delta function
0 0  2

The delta function is defined as

  
  x  a  xdx  a and   xdx  1

So lets see if this works for our case

2
lim 

1 exp  x  a  xdx
0   2 2 2

xa dx
Let u  and du 
 2  2


lim 1
0 
  expu 2     2 a

Since   0

 a 
1

  expu 2   a  
  expu 2  a


Problem 1-49

Maximize

WN 1 , N 2 , . . . . N m   N!
m
 j1 Nj!

under the contraints that  N j  N and  E j N j  .

Since the natural log is a monotonic function, we can maximize lnW.

M  ln WN 1 , N 2 , . . . . N m   ln N!
m
 j1 Nj!

Using Sterling approximation, this can be written as

 N ln N  N   N j ln N j   N j
j j

But the maximization must be constrained therefore we intoduce Lagrange multipliers

M  N ln N  N   N j ln N j  N j   Nj  N   EjNj  
j j

N

Remembering  N j  N and taking the derivative of M with respect to N j

M   ln N j  1    E j  0
N j
 ln N j  1    E j
ln N j     E j , with    1  

N j  exp   expE j 

Problem 1-50

We want to show that the maximum of

WN 1 , N 2 , . . . N m   N!
m
 Nj!
j1
N
occurs for N 1  N 2  N s     s

Maximize

M  ln W  N ln N  N   N j ln N j   N j

subject to the constraint  N j  N. So we must use Lagrange multipliers:

M  N ln N  N   N j ln N j   N j    Nj  N
 M   ln N  1    0
j
N j
ln N j  1    N j  exp1  

But now we must determine 

s s
 N j   exp1    S exp1    N  exp1    N
s
j1 j1

So
N
Nj  s
Problem 1-51

Here we use Lagrange multipliers again with the constraint  j P j  1.

N N
M    P j ln P j    Pj  1
j1 j1

Maximize

M   ln P j  1    0
P j
P j  exp1  

Determine 

N
 P j  N exp1    1
j1

exp1    1
N

Thus

1
Pj  N

Problem 2-1

From stat mech we get

E p
  p
V N,  N,V

And from thermo we have

 E p
T  p
V N,T T N,V

To show why   cont  T lets see what happens if we let   T where  is a constant

E p
 T  p
V N, T N,V

or

E p
T  p
V N,T T N,V

p S
but from a Maxwell relation we know T
 V N,T
and we can write
N,V

E  T S  p
V N,T V N,T

dE  TdS  PdV

This statement violates the second law of thermodynamics because it implies that
Q
Q  TdS  T  dS
 Problem 2-2

Given

n  n!
n!n  n 1 !

is n 1  n 1 ?

 n 1 is the value of n 1 that maximizes n. From problem 1-50, we know that
n 1  n2 .
 n 1 is given by

n
 n1 n!
n 1 !nn 1 !
n 1 0
n1  n 2-2-1
 n!
n 1 !nn 1 !
n 1 0

We also know that (given in the problem):

n
y  1  x n   xn 1 n!
n 1 !n  n 1 !
n 1 0

If we take the derivative of y with respect to x we get

n

y  n1  x n1
  n1xn 11 n!
n 1 !n  n 1 !
n 1 0

If we let x  1:

n
n2 n1
  n1 n!
n 1 !n  n 1 !
n 1 0

Furthermore,
 n
2n   n!
n 1 !n  n 1 !
n 1 0

So if we put this all together back in (2-2-1) we get

n
 n1 n!
n 1 !nn 1 ! n1
 n2 n  n  n 1
n 1 0
n1  n 2 2
 n!
n 1 !nn 1 !
n 1 0

n 1  n 1

Problem 2-5

Show that S  k  P j ln P j

We have the following three relations already

 ln Q
S  kT  k ln Q
T N,V
E j
exp kT
Pj 
Q
and
E j
Q  exp kT
j

Starting with S we can write

Q Ej E j
S  kT
Q T
 k ln Q  kT
Q
 kT 2
exp
kT
 k ln Q
j

Ej E j
S k
Q
 kT
exp
kT
 k ln Q
j

E j E j
S k
Q
 ln exp
kT
exp
kT
 k ln Q
j
 E j
E j exp
S  k  ln exp
kT
k ln Q
kT Q
j
P j

Since  P j  1

E j
S  k  P j  ln exp  k ln Q  Pj
j
kT j

E j
S  k  P j  ln exp  k  P j  ln 1
kT Q
j j
E j
exp
S  k  P j ln
kT
Q
j

S  k  j P j ln P j

Problem 2-8

Q

  E j expE j 
j

 E j expE j  
Q
j   ln Q
E   
Q Q 
 ln Q
E  

Problem 2-10

 ln Q
First derive E  kT 2 T
starting from the result of problem 2-8, namely
N,V

 ln Q
E 

 From the chain rule

 ln Q T
E 
T N,V 

1 T
We know   kT
so 
 kT 2 , thus

 ln Q
E  kT 2
T N,V

 ln Q
We can check this by taking kT 2 T
.
N,V

Q E
 ln Q

 exp  kTj
T N,V 2 T N,V
kT 2  kT 2  kT
T N,V Q Q
E E Ej

2 T
 exp  kTj  exp  kTj  kT 2
kT 
Q Q

The kT 2 cancels and we are left with

E
2  ln Q  E j exp  kTj
kT 
T N,V Q
definition of E

 ln Q
So we have shown again that indeed E  kT 2 T
.

Now for the relation involving p

E
Ej E j Ej

kT V  exp  kTj
 p j exp  kT
  V
exp  kT j N,T
p   
Q Q Q
Q
kT  ln Q
p  Q
V
 kT V N,T
 Problem 2-11

Starting with F  kT ln Q (Remember F  A

S   F
T V,N

 ln Q
S  kT T
 k ln Q Eqn. 2-33
V,N

p   F
V T,N

 ln Q
p  kT V
Eqn. 2-32
T,N

F  E  TS  E  F  TS
 ln Q
E  kT ln Q  T  kT  k ln Q
T V,N

 ln Q
E  kT 2 T
Eqn. 2-31
V,N

Problem 2-13

E
For a particle confined to a cube of length a we are asked to show p j  23 Vj . We can start
with the equation for the energy states of a particle in an three-dimensional infinite well,
namely

Ej  h 2 n 2  n 2  n 2  , n x , n y , n z  1, 2. . . .
x y z
8ma 2

1
Remembering that a 3  V or a  V 3 we can write E j in terms of V

2
2
E j  h V n 2x  n 2y  n 2z 
3

8m
5 2
E j 2 2
 2 h V n 2x  n 2y  n 2z   2  1  h V n 2x  n 2y  n 2z 
3 3
pj  
V 3 8m 3 V 8m
Ej

So we have
 2 Ej
pj  3 V

and taking the ensemble average gives us

p  2 E
3 V

Problem 2-14

3N

QN, V, T  1 2mkT 2
VN
N! h2

For p ,

 ln Q
p  kT
V T.N

ln Q  ln 1  3N ln 2mkT  N ln V
N! 2 h2
p  kTN
V

Now for E

2mk
2  ln Q 2 3N h2
E  kT  kT
T N,V 2 2mkT
h2

E  3N kT
2

Ideal gas equation of state is obtained when Q  fTV N  ln Q  ln fT  N ln V

 ln Q ln fT N ln V

p  kT  kT  kT
V T.N V T,N V
NkT
p  V
Problem 2-15

We are given Q as

h 3N
exp
Q 2kT
exp U o
1 exp h kT
kT

h
substituting in   k

3N
exp  
Q 2T
exp U o
1  exp 
 kT
T

To find c v we need to use the following two relations

 ln Q
E  kT 2
T N,V

cv  E
T

Using your favorite math package (Maple), we can get E as

Uo U o  k 2  kU o Uo U o  k 2  kU o
Uo
1
2
e  kT 3Nk e kT
 12Nk e kT
 9Nk e kT
 2U o e kT
 4U o e kT
 2U o e kT

E  2
1  e T

and c v as

cv  E 3 kN 2 e T
T  2
T 2 1  e T

Now we can take the lim c v and we find that

T
 

lim 3 k 2 e T N  3Nk
T  2
2
T 1  e T