Caulfield, Miller

PHYS 301-01

Computer Assignment 2
Part 1: An Isolated Solid

Q1: kT/ε is a representation of the temperature of the system in units of ε/k. In this Einstein solid,
it describes the entropy of the system, as well as the average kinetic energy of the molecules
that compose it. When the temperature is very low (kT << ε), the quantum number, ε, of each
oscillator must be low to compensate and maintain the ratio. In the equation ε = hf, f must be
low to keep ε low. That makes sense because f is the frequency of the oscillator, oscillators in
Einstein solids at low temperature oscillate slowly. When the temperature is very high (kT >>
ε), the quantum number, ε, of each oscillator must be high to compensate and maintain the
ratio. Oscillators in Einstein solids at high temperature oscillate quickly.
200

150
S/k

100

50

0
0 0.5 1 1.5 2 2.5
kT/ε

Graph 1
 Caulfield, Miller
PHYS 301-01

250

200

150
U/ε

100

50

0
0 0.5 1 1.5 2 2.5
kT/ε

Graph 2

Q2: As T approaches zero, the Graph 1 suggests that S approaches negative infinity. Graph 2
curves towards the origin when approaching zero from the right side and suggests that U goes
to 0 as T approaches zero. As for high temperatures, Graph 1 suggests that that entropy
increases logarithmically to infinity and energy increases approximately linearly to infinity. The
heat capacity of the Einstein solid is related to the temperature and entropy as described
below. A graph of heat capacity verses temperature is on the next page.

∆  ∆

∆
 
∆
 Caulfield, Miller
PHYS 301-01

0.8

0.6
C/Nk

0.4

0.2

0
0 0.5 1 1.5 2 2.5
kT/ε

Graph 3

Q3: Heat capacity is defined in the text in equation 1.44 as

∆ 
 
∆


and according to Graph 2, in the high temperature limit, kT is proportional to U with a

proportionality constant equal to N (in the case of the graph, N = 100). This gives the relation
   

 


Graph 3 confirms that, in the high temperature limit, C/Nk approaches 1, yielding C = Nk. To
obtain the molar heat capacity of the solid, one must take the heat capacity, C, and divide it by
the number of moles of particles in the solid. In this case, there are N/3 atoms, and N/(3 * NA)
moles, where NA is Avogadro’s number. This gives us
3 

 


 3

 3
 Caulfield, Miller
PHYS 301-01

as classical thermodynamics predicts. The experimental data in Figure 1.14 in the text shows
heat capacity above the predicted 3R limit. This discrepancy shows that classical and statistical
models are incomplete. The Einstein solid here provides a more accurate description for a
solid with 100 oscillators than the general theory because it makes no assumptions about the
relative sizes of q and N.
 Caulfield, Miller
PHYS 301-01

Part 2: Theory

Q4: According to equation 2.18 in the text,

  !
ln Ω  ln  
! !
    ln      ln    ln 

and the following

S     ln     ln    ln 




   
S     ln     ln   ln 

∂  1
ln    
∂U 
∂  1
ln 
∂U 

we plug in and continue deriving

∂S 1  1 1  N U1 1 
    ln       ln
∂U    
U
 1 1  1 
 %   ln   ln &


U  
   1  ln   ln

 
 ln   ln

1 
 ln 
 
 Caulfield, Miller
PHYS 301-01

and solving for U


 ln 1 
 
 (
 ' )*  1

 (
 ' )*  1


 (
' )*  1

Finally we solve for CV



 
 +,

( /0
   -' )*  1.
 ( ( /1
  - ' )* . -' )*  1.

 1 ( ( /1
 -' )* . -' )*  1.

1 (
- . -' )* .

  ( 1
-' )*  1.

Q5: Using the identity

lim ' 4  7  1
456

it is fair to conclude
1 (

- . -' )* .

 ( 1
-' )*  1.
1 ( 1
- . -' )* . - . -  1.
lim ( 1 

1
)58
-' )*  1. - .

1
  1
1
- .
 Caulfield, Miller
PHYS 301-01

and in the limit

1 01
lim  1  1
)58 1 1
- .


0.8

0.6
C/Nk

0.4

0.2

0
0 0.5 1 1.5 2 2.5
kT/ε

Graph 4
 Caulfield, Miller
PHYS 301-01

Part 3: Interacting Einstein Solids

Q6: (a) Graph below

(b) At thermal equilibrium, the ratio of q/N for each solid must be equal. In the case of this

: ;
system


: ;
: 120  : 

100 300
120 1 1 /0
:     30
300 100 300

which is right where Graph 4, below, peaks.

2.5E+119

2E+119
Total Multiplicity

1.5E+119

1E+119

5E+118

0
0 20 40 60 80 100 120
q of a

Graph 5

(c) According to the calculated multiplicities, the width of this graph at half of the maximum
multiplicity value is ∆qFWHM = 13.
(d) By summing the multiplicities from qa = 24 to qa = 36 and dividing this result by the sum of
the multiplicities from qa = 0 to qa = 120, I was able to obtain the probability of about 0.771.
Q7: (a) See graph below
 Caulfield, Miller
PHYS 301-01

Multiplicity

0 20 40 60 80 100 120
q of A

Graph 6

(b) On the graph above, the slope of the multiplicity is proportional to the temperature of the
solid in question. The top most line is the total multiplicity, the second one down is the
multiplicity of solid B, and the third down is the multiplicity of solid A. When the slope for the
total multiplicity is equal to zero, the slope for solid A added to the slope of solid B equals
zero. The two solids are at the same temperature and at thermal equilibrium. The slope for
the total multiplicity of the system is zero when qa is equal to 30.
 Caulfield, Miller
PHYS 301-01

Part 4: The Boltzmann Factor

Q8: The multiplicity for ΩA is 1 for every value of q. With only one oscillator to store energy, there
is only one way to store any amount of energy. Since the multiplicity of this system never
increases, the entropy never increases. Temperature as defined by the partial derivative of
entropy in terms of change of energy will always have a change in entropy of zero, making
temperature infinite. It does not make sense to define the temperature of this system in that
way.
Q9: The temperature of the reservoir changes, but not by much. By the time the reservoir has
given up 20 units of q, the temperature is about 83% of the original. This spreadsheet does a
reasonable job of modeling an unchangeable reservoir
Q10: The most probable value of qA is qA = 0. This is not a surprising result because system A has
very nearly no space to store energy when compared to the 10,000 oscillators of system B. It
might as well not even be part of the system.
Q11: The equation for the trend line is y(x) = -5.4328x + 574.1

700

600

y = -5.4328x + 574.1
500
ln[Ω total (q_A)]

400

300

200

100

0
0 10 20 30 40 50 60 70 80 90 100
q_A

Graph 7
ln=   5.43287  574.1  
=   ' /C.DE1F GH

The slope of the trend line on this graph is related to ε/kT. According to the spreadsheet, the
average value is 5.5609, which is very close to the slope of the line that we calculated.
 Caulfield, Miller
PHYS 301-01

To calculate an expression for the probability of the system being in a certain state given qA,
I GH
=   ' / JK
MH
 / I
I
=   ' JK
ε
M
=   '
/ H
JK

ε
substituting in the values for the problem:

 5.5609
kT
0.10
T
5.5609 8.617 R 10/C 
T  207 K
and
6.16
/
=0.20  ' F.T0UR06VW 16U

=0.20   1.350 R 10/C 

1.350 R 10/C 1 R 10T   13.50

which yields about 13 or 14 systems in 1,000,000.