NOTES AND SOLUTIONS TO THERMAL PHYSICS BY CHARLES KITTLE AND HERBERT KROEMER

ERNEST YEUNG - LOS ANGELES

A BSTRACT. These are notes and solutions to Kittle and Kroemers Thermal Physics. The solutions are (almost) complete: I will
continuously add to subsections, before the problems in each chapter, my notes that I write down as I read (and continuously reread).
I am attempting a manifold formulation of the equilibrium states in the style of Schutzs Geometrical Methods of Mathematical
Physics and will point out how it applies directly to Thermal Physics. Other useful references along this avenue of investigation is
provided at the very bottom in the references.
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S ECOND E DITION. Thermal Physics. Charles Kittel. Herbert Kroemer. W. H. Freeman and Company. New York.
QC311.5.K52 1980 536.7 ISBN 0-7167-1088-9

1. S TATES OF A M ODEL S YSTEM

2. E NTROPY AND T EMPERATURE
Thermal Equilibrium. EY : 20150821 Based on considering the physical setup of two systems that can only exchange
energy between each other, that are in thermal contact, this is a derivation of temperature.
U = U1 + U2 is constant total energy of 2 systems 1, 2 in thermal contact
multiplicity g(N, U ) of combined system is
X
g(N, U ) = g1 (N1 , U1 )g2 (N2 , U U1 )
U1 U

The differential of g(N, U ) is

   
g1 g2
dg = g2 dU + g1 dU2 = 0
U1 N1 U2 N2

EY : 20150821 This step can be made mathematically sensible by considering the exterior derivative d of g C (), where
is the manifold of states of the system, with local coordinates N, U , where U happens to be a global coordinate. Then,

consider a curve in s.t. it has no component in N , N 1
, and this curve is a null curve so that the vector field X X()
generated by this curve is s.t. dg(X) = 0.
With dU1 = dU2 ,
       
1 g1 1 g2 ln g1 ln g2
= = =
g1 U1 N1 g2 U2 N2 U1 N1 U2 N2
Define
(N, U ) := ln g(N, U )
Then
   
1 2
= =
U1 N1 U2 N2

Date: Fall 2008.

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1
Temperature. T1 = T2 - temperatures of 2 systems in thermal equilibrium are equal.



T must be a function of U N
[?].
 
1
= = kB
T U N
Experimentally, kB = 1.381 1023 J/K = 1.381 1016 ergs/K.
Now  
1
= = kB T
U N
Problems. Solution 1. Entropy and temperature.

(a) Recall that 1 U


N,V
and (N, U ) log g(N, U ). Given g(U ) = CU 3N/2 ,
3N
(N, U ) = log CU 3N/2 = log C + log U
2
3N 1 1 3N
= = = U =
U 2 U 2
 
2
(b) U 2 <0?
N
2
   
3N 1
= <0
U 2 N 2 U2
Solution 2. Paramagnetism.

U
U (s) = U1 (s1 ) + U2 (s2 ) = 2mB(s1 + s2 ) = 2mBs or s =
2mB
i.e. potential energy U (s) = 2s mB.
For |s|  N , then
U 2
 
2


g(N, s) ' g(N, 0) exp 2s /N = g(N, 0) exp
2(mB)2 N
U2 1
(N, U ) = ln g(N, U ) = 0 where 0 = ln g(N, 0)
2m2 B 2 N
 
1 U 1
= = 2 2
U N m B N
What is the thermal equilibrium value of this N -spin system of fractional magnetization? If U denotes hU i, thermal average
energy, we also get the thermal average spin excess.
hU i = h2mBsi = 2mBhsi
m2 B 2 N mBN
= = =
U 2hsi
Solution 3. Quantum harmonic oscillator.
(N +n1)!
(a) Result from Ch. 1: g(N, n) = n!(N 1)! .
Let N 1 N = g(N + 1, n) = (Nn!N
+n)!
! .

(N + n)!
(N + 1, n) ln g(N + 1, n) = ln
= ln (N + n)! ln (n!) ln (N !)
n!N !
(N + n) ln (N + n) N n n ln n + n N ln N + N = (N + n) ln (N + n) n ln n N ln N
(b) Let U denote total energy n~ of oscillators.
U
U = n~ or n = ~

U U U U
(N, U ) = (N + ) ln (N + ) ln N ln N

1


At , = U N .
 
1 1 U 1 U 1 N N
= ln (N + ) ln = ln + 1 or U =
U exp (/ ) 1
2
Solution 4. The meaning of never.
Suppose 1010 monkeys.
(a) Hamlet represents one specific ordering of 1015 with 44 possibilities for each character. The probability of hitting
1 100000

1
upon Hamlet from a given, random sequence is 44 = . Given that log10 44 = 1.64345, then
44100000
101.64345 = 44 or 101.64345 = 441 so then
 100000
1
= 10164345
44
(b)    
10 keys 10 keys
(age of universe) = 1018 s = 1019 keys
second second
 
1 hamlet
1019 keys 1010 monkeys = 1029 keys typed out 5
= 1024 possible Hamlets
10 characters
From part (a), the probability that a given, random sequence is Hamlet, 10164345
(1029 characters)(10164345 ) = 10164316
164345
Note, I think that the probability should be (1029 characters) 1015 Hamlet ) = 10164321


characters (10
5
Since we are considering the number of Hamlet, 10 character sequences.

3. B OLTZMANN D ISTRIBUTION AND H ELMHOLTZ F REE E NERGY

cf. Example: Energy and heat capacity of a two state system, pp. 62 of Kittel and Kroemer [1]. Kittel and Kroemer
introduces the heat capacity very early, specific to this example.
Definition 1. heat capacity CV at constant volume is defined as
 

(1) CV :=
V
Recall the thermodynamic identity (which is introduced many equations later):
dU = d pdV 1 ()
where is a manifold of states of all systems.

Consider local coordinates of , (, V ). Consider curve c : R s.t. c generates a vector field c =

i.e. no component
c( )
in the V direction. Notice the prescient choice of parameter .
Now for internal energy U C (), taking the exterior derivative d results in
U U
dU = d + dV
V

Then applying dU onto vector field ,
 
U
dU = =
+0

Now,        
U U
= =
V V V V
Hence,
   
U
(2) CV := =
V V
EY: 20150825 Why do we need differential geometry? Its because I always wondered why you could do this:
   
? U ?
CV := = with d = dU = = U
V V
and talk of differentials.
Definition: Reversible process. EY : 20150824 Mathematically, 1-forms are exact.
3
Pressure. Consider coordinates (, V ) of manifold of thermodynamic states .
Imagine a reversible compression of a cube system (so imagine dV < 0; cubes volume get smaller).
constant, i.e. d = 0 (on this curve in ) because as particles in cube gets squeezed, less positions particles could sit in,
but they get more kinetic energy, more energetic (more momentum squared).
Now U = U (,
V ) C ().

= dU = U U
V d + V dV
Again, imagine a curve c : R , connecting 1 state (, V ) to another state (, V + dV ) s.t. c = V V

.
 
U
= dU (c) = V
V

Introduce 1-form W 1 () of work done on the cube system from some external agent

W = pdV

so W > 0 when dV < 0.

Then
 
U
= pV = dU (c)
W (c) = V
V

 
U
(3) = p =
V

Consider another set of coordinates (U, V ) for manifold . Now entropy is a function of U, V , as = (U, V )
C (M ), so

that



d = U V
dU + V U
dV
Consider curve c = (U, V ) . Then c = U U
+ V V

. For this curve c, is constant, meaning d(c)
= 0 (its a null
curve of d
   

d(c)
=0= U+ V
U V V U
Now define

Definition 2.
 
1
(4) :=
U V

So then we have 1 U + V U V = 0. For the parameter of curve c, choose the parameter to be V , knowing that is constant

on this curve, or thermodynamic process. Thus

     
1 U p
= = = or
V V U V U

 

(5) p=
V U

Thermodynamic Let
= (U, V ) C (). Then

Identity.

d = U V dU + V U dV 1 ().
Now recall the quantities weve recently used: 1 := U

(this is a definition) and p = V




V U
(it comes from the physics,
of doing work on the system, by some external agent). Then the thermodynamic identity is obtained:

Theorem 1.

(6) d = dU + pdV

Ideal Gas: A First Look.

4
One atom in a box. one atom of mass M in cubical box of volume V = L3
~2 2
2M =  p = ~i
p2 = 
ny y

nx x
= (x) = A sin L sin L sin nzLz


~2 2


n = 2M L (n2x + n2y + n2z )
Then the partition function Z1 is
~2  2 2
   
X n X
Z1 = exp = exp (nx + n2y + n2z )
n
2M L
(nx ,ny ,nz )

Let
~2 2 ~
2 = 2
or =
2M L (2M )1/2 V 2/d
Then
Z Z Z Z 3  3  1/2 3  1/2 3
1
Z1 = dnx dny dnz exp [2 (n2x + n2y + n2z )] = dnx exp (2 n2x ) = =
0 0 0 0 2 2
 1/2
d

In general, Z1 = 2
Now
!d
1/2 V 1/d V nQ
Z1 = = = nQ V =
2 (2M~ 2~ d/2 n


)1/2 M

in terms of concentration n = 1/V .

M d/2


nQ := 2~ 2 is the quantum concentration. It is the concentration associated with one atom in a cube of side equal
to the thermal average de Broglie wavelength. (pp. 73, Ch. 3: Boltzmann Distribution and Helmholtz Free Energy, Section
Ideal Gas: A First Look of Kittel and Kroemer [1])
From Kittel and Kroemer (1980) [1], Example : N atoms in a box, Chapter 3: Boltzmann Distribution and Helmholtz Free
Energy,
state of energy  (1) +  (2) + +  (N ), , , . . . denote orbital indces of atoms in successive boxes.
each entry occurs N ! times in Z1N (EY: 20151022) N ! ways to fill , . . . orbitals with N distinguishable particles. Thus,
1 N 1
ZN = Z = (nQ V )N
N! 1 N!

Problems. Solution 1. Free energy of a two state system.

(a)
Z = 1 + e/
F = ln Z = ln (1 + e/ )
(b)
(F/ ) e/
U = 2 =
1 + e/
 /
F e
= = ln (1 + e/ ) + /
(1 + e )
Solution 2. Magnetic susceptibility
(a) Remember to calculate the multiplicity in the N -spin system (its not enough to sum up exp (s / ) factors).
M = 2sm Us = M B = 2smB N = N+ + N
2s = N+ N = N+ (N N+ ) = 2N+ N

N/2 N/2 N
X N  
2smB
 X N!

2mBs
 X N!

2mB

N

Z= exp = N

N
exp = exp s =
N+ 2 +s ! 2 s ! s=0
s!(N s)! 2
s=N/2 s=N/2
 
N mB 2mB mB
= e (1 + e )N = 2N coshN

5
 PN N


where it was crucial to use (1 + x)N = j=1 j xj . Note, in changing the sum index, since N is large, we can
neglect dropping the s = 0 term.
    
mB mB m
Z = 2N (N )(coshN 1 ) sinh
2
 
mB
M = 2 ln Z = N m tanh

2
 
M Nm mB
= = sech2
B
(b)      
mB N mB
F = ln Z = ln (2 cosh ) = N ln (2 cosh )

   
M 2 N
= tanh mB 2 4

2
For x nm . Now 1 tanh y = sech y. F = N ln 1x2
= 2 ln 1x 2 .
m2 N
mB
 1, cosh2 mB


(c) For 1. =

Solution 3. Free energy of a harmonic oscillator
(a)
 
X s~0 1
Z= exp = ~
= (1 e~0 / )1
1 e 0 /
s=0
 
~0 / ~0 ~0
F = ln Z = ln (1 e ) ' ln for 1 

(b)
 
F ~0 / ~0 / ~0 ~0 / ~0
= = {ln (1 e )+ ~ /
(e ) } = ~ / ln (1 e )
1e 0 e 0 1
Solution 4. Energy fluctuations.
X
Z= es
1 s
=
s es /
X P
Z = es U= s = ln Z
1 s Z
= = 2
2 Z =
X
2 es
s
s
! 2 !
(2 Z)Z ( Z)2 2 Z
   
U 2 2 Z Z
= U = = 2 = 2
=
Z Z2 Z Z
U
= 2 = h2 i hi2

Solution 5. Overhauser effect. System S in energy eigenstate En = n.
P (E) = (1)gR (E)
Note UR = ( 1). US = . dU dUR dUtot
d + d = 1 + ( 1) = = d in a specific energy eigenstate; gS (n) = 1
S

While gR (UR ) = multiplicity of reservoir R with UR energy.

Now
R 1
=
Es
and
gR (UR ) = exp (R (UR ))
dUR
If  d = ( 1) = UR small compared to UR .

dUR
UR (ES = (n + 1)) = UR (n) +  = UR (n) + ( 1)
d
1
R (UR ((n + 1))) ' R (UR (n)) + ( 1)

P (ES = (n + 1)) exp (R (UR (n)) + 1 ( 1))   
= = exp (1 )
P (ES = n) exp (R (UR (n)))
Solution 6. Rotation of diatomic molecules.
6
 (a) (j) = j(j + 1)0 . g(j) = 2j + 1
Remember that Z is a sum over all states, not over all levels.
  2
X
j(j+1)0 /
X d (j 2 +j)0 / X d  0 / j +j
Z= (2j + 1)e = (e ) = e
j=0 j=0
dj 0 0 j=0 dj
0
(b) For 1 
Z 2
d  0 / x +x  0 / x2 +x 
ZR ( ) = e dx = (e ) (e0 / )0 =
0 0 dx 0 0

(c) For 0 1
ZR ( ) = 1 + 3e20 /
(d)  
ln Z 0
U = 2 for 1  U = 2 ln =
0
60 e20 /
   
2 1 20 / 20
for  1, U = (3e ) =
0 1 + 3e20 / 2 1 + 3e20 /
 
U 0
CV = = 1 when 1 
V

2 / !
e20 / 2 20 / 20 / 20


20 /
 

0
2 (1 + 3e ) (3e ) 2 e 0 2e 1
CV = 60 = 120
(1 + 3e20 / )2 2 (1 + 3e20 / )2
 20 / 
e
For very small 0  1, CV 12
( /0 )2
(e) See sketch.
Solution 7. Zipper problem.
(a) N links. s = 0 closed,  open.
N
X 1 e(N +1)/
Z= exp (s/ ) =
s=0
1 e/

(b) 1  .
P N
Z= exp (sB)
s=0
PN
1 1 s=0 (s)es
ln Z = = hsi =
  Z
1 e/ e(N +1)/ ((N + 1))(1 e/ ) (e/ )()(1 e(N +1)// )
   
= =
1 e(N +1)/ (1 e/ )2
e/ (eN  (N + 1)(1 e ) (1 e(N +1)/ )) e/ (eN  (N + 1)(1 e ) 1)
= '
(1 e(N +1)/ )(1 e/ ) (1 e )
This still does not give the desired approximation. Consider the following:
1 e(N +1) e eN 
Z= =
1 e e 1
N 

((e + N e )(e 1) (e )(e eN  )) (e (e + N eN  e + eN  ) e N eN  )
Z = =
(e 1)2 (e 1)2
Z (e (N + 1)eN  e N eN  ) (e (N + 1)eN  e+ N eN  )
= ' =
Z (e 1)(e eN  ) e2
(N e(N 1) + e(N 1) e N eN  ) ((N + 1)e(N 1) (e + N eN  ))
= = =
 e2   
2
  e  N  
 
N
 (Ne+1)e
N  eNn e  (N +1)e
eN 
e  N e +eeNe

e 
N eN 

= = = = '
e2 e2 e2 eN  e
(eN  )
' = e
eN  e
7
 = hsi = e/
n y
p2
Solution 8. Quantum concentration. Now (x, y, z) = A sin nxLx sin yL sin nzLz . p = 1i , 1


2
2m = 2m .
Ground orbital: nx = ny = nz = 1.
3  2 3  2
T = h0 |0 i =
2m L 2m L
where h0 |0 i = 1, normalized. It was normalized in this way:

2nx x

 L  L
Z Z L 2nx x n sin


 n x  1 cos x
sin2
x L 2nx
 = L
L

dnx = dnx =
0 L 0 2 2 
 2
0
 3
L A2 L3 8
h|i = A2 = = 1 or A2 = 3
2 8 L
m 3/2


Recall that nQ = 2~ 2 .
Consider the condition that there will be a concentration for which the zero-point quantum kinetic energy is equal to the
temperature :
3/2
3 2

3 2 2/3 2/3 2m 2m
= = n = or n = or n =
2m L2 2m 3 2 ~2 3 2 ~2
   3/2
4 m 3/2 4
= n = ( ) = nQ
3 2~2 3
Solution 9. Partition function for two systems.
     
X E1+2 X E1 E2
Z(1 + 2) = g(E1+2 ) exp = g(E1 + E2 ) exp exp =

E1+2 E1 +E2 =E0
   
XX E1 E2
= g(E1 )g(E2 ) exp exp = Z(1)Z(2)

E1 E2

since systems are independent.

Solution 10. Elasticity of polymers.
2s+N
(a) Consider 2s = N+ N ; N = N+ + N , 2s = N+ (N N+ ) = 2N+ N . N+ = 2 .
For 2s, consider 2s = N+ (N N+ ) = 2N+ N . N+ = 2s+N
2 .
2N !
= g(N, s) + g(N, s) = N
+ s ! N2 s !



2

(b) |s|  N

    
l l 2(N !)
(l) = ln g N, + g N, = ln     =
2 2 N
+ l
! N
+ l
2 2 2 2 !
           
N L N l N l N l N l N l
= ln (2N !) = { + ln + + + ln }
2 2 2 2 2 2 2 2 2 2 2 2
where we used ln(x + x) ' ln x + x1 x.
          
N l N 1 l N N l N 1 l
(l) = ln (2N !) { + ln + + ln + }=
2 2 2 N/2 2 2 2 2 2 N/2 2
 2
l2
   
N N N N N N l N l 2 l l l N
= ln (2N !) { ln + ln + ln + + + ln + }
2 2 2 2 2 2 2 2 2 N 2 2 2 2 N 22
!
2N ! l2
(l) = ln N

N


2 ! 2 !
N 2
(c)
2l 2l
= = f =
l N 2 N 2
8
Solution 11. One-dimensional gas.
~2  2 2
n = n in one dimension
2m L
 2   Z
X ~ 2 2 2 2
Z1 = exp n / = dne n =
n=1
2m L 0 2
~2   2
2 =
2m L
where .
~/L
=
2m 1/2
Recall that = F


, F = U , so that
   
2 2~/L
F = ln Z = N ln = N ln = N ln =
2 2m 1/2
!
2~2
 
2~ 1
= N ln = N ln
mL 1/2 2 mL2
!
2~2 2~2
  
F 1 N 1
= N ln + 2~2
=
mL2 mL2 2


2 2 mL2

2~2 2~2
     
1 N N
= N ln + = ln 1
2 mL2 2 2 mL2

4. T HERMAL R ADIATION AND P LANCK D ISTRIBUTION

Problems. Solution 1. Number of thermal photons.
We consider a cavity of volume V , and of edge length L (so V L3 ). So then n = nc/L.
1
Now exp ~ is the thermal average number of photons in a single mode frequency . So then
( n )1
X X 1
hsn i = ~n


exp 1
Consider (nx , ny , nz ) on positive octant, and 2 independent polarization s of em field.
(2)
Z
n2 dn
Z
X 1 2 1

= 4n dn
=
=
n
exp ~nc
L 1 8 0 exp ~nc
L 1 0 exp ~nc
L 1
 3 Z  2 
L x dx V  3
= = N = (2.404)
~c 0 ex 1 2 ~c
where I used the substitutions
~cn
x=
L
L x
=n
~c
L
(dx) = dn
~c
Now ( ) = (4 2 V /45)( /~c)3 , so then
4 4
 
1
= ' 3.602
N 2.404 45
R 2
Now how was 0 dx exx 1 dx
evaluated?
Solution 2. Surface temperature of a Sun. Given the solar constant of the Earth, the total radiant energy flux density at
the Earth from the Sun normal to the incident rays, integrated over all emission wavelengths,
solar constant = 0.136 J s1 cm2 , (49)
(a)
2
102 cm

4(1.49 1011 m)2 0.136 J s1 cm2 = (4)(1.49)2 1022 0.136 104 = 3.8 1026 J s1
1m
Note that I had used 1.49 1011 m as the distance of the Earth from the Sun.
9
 (b) J = energy flux density or rate of energy emission per unit area.
2 k4
B = 60~3Bc2 = 5.670 108 W m2 K 4 .
Note that W = 1sJ . I will use R = 6.9599 1010 cm as the radius of the Sun.

4 1026 J s1
= J = B T 4
4(6.9599 1010 cm)2
 2
2 102 cm
26
4 10 J s 1 1 m 1m 4 4
k = T

10
4(6.9599 10 cm) 2 5.670 108 J/s

T ' 5830 K
Solution 3. Average temperature of the interior of the Sun.
(a)
R 4 R
3


G 3 r (4r2 dr) 16 2 2
Z Z
16 4
U = = 2 G2 r4 dr = GR5 ; M = R3
0 r 3 0 15 3
3GM 2
U=
5R
4
1 RG R
3


3 r 8 2 2 8 2 2
Z Z
U = (4r2 dr) = G r4 dr = GR5 =
2 0 r 3 0 15
2
3 GM 2

8 2 5 M
= GR 4 3
= = 1.14 1041 J
15 3 R
10 R
(b) Using the virial theorem of mechanics, note that
2
 
11 1 kg
1 3 GM 3 6.67 10
2 kg sm2 kg
m
2 2 10
33
g 103 g
U= = = 5.72 1040 J
7 1010 cm 1012mcm


2 20 R 20
1
Now hsi = exp (~/ )1 , is the Planck distribution function, giving the thermal average number of photons in a
single mode frequency .
thermal average energy hi = hsi~ = exp (~/
~
)1 for  ~, hi '
40
So then 5.72 10 J = N hi = N .

5.72 1040 J
= = 4.14 106 K
1 1057 (1.381 1023 J/K)
Solution 4. Age of the Sun.
(a) Consider 4H 42 He. Then 4(1.0078) 4.0026 = 0.0286 amu. Then
1.6726 1027 kg
 
(0.0286 amu) (3 108 m/s)2 = 4.27 1012 J
1.00727647 u
Given M = 2 103 3 g,
  
1 1.00727647 u
(2 1030 kg)(0.10) (4.27 1012 J) = 1.28 1044 J
4 (1.0078 amu) 1.6726 1027 kg

So 1.28 1044 J energy is available.

(b)
1.15 1045 J
   
1 hr 1 day 1 yr
= 1.02 1010 years
4 1026 J s1 3600 s 24 hr 365 days
4
Solution 5. Surface temperature of the Earth. JS = b T is the radiant power per unit area.
2
Total emitted radiation energy of the sun is JS 4R .
2
4R JS R2
2
4RES
= R2 JS = radiation energy hitting 1 cm2 of Earths surface in one second
ES
Since the Earth is considered a black-body, the rate of absorption must equal the rate of emission:
2
r
R 4 4 4 4 2 7 1010 cm
2 b T = b Te or Te = T R = Te = 5800 K = 396.2 K = 123 C
RES 1.5 1013 cm
Solution 6. Pressure of thermal radiation.
10
 (a) sj = number of photons in that mode. Suppose modes of j , j = 0, 1, 2, . . . .
j = sj ~j = total energy in jth mode, sj photons in jth mode.
X X U X j
U= j = sj ~j P = = sj ~
j j
V j
V

(b) j = jc/L, V = L3 . So then j = jcV 1/3 .

dj 1 1 j
= = jcV 4/3 =
dV 3 3 V
U
(c) p = 3V
(d) We want the Kinetic pressure at a concentration of (1 mol/cm3 ). Recalling P = N kVB T ,
3 
6.022 1023
   2 
1 mol 10 cm 23 J N
P = 1.381 10 (2 107 K) = 1.663 1014 2
cm3 1 mol 1m K m
Now for the thermal radiation pressure,
U 1 2 N
p= = 3 3
4 = 4.03 1013 2
3V 3 15~ c m
where t = 2 107 K.
For the pressures to be equal,
1 2 4 4 N kB 3 45(~c)3 N kB
k T = T or T = so that T = 3.2 107 K
3 15~3 c3 B V 4V
2 kB
Solution 7.Free energy of a photon gas
P
1
Consider Z = s=0 es~/ = 1e~/ 1
Q
(a) Z = n 1e~ n /
for a single mode.
~n / nc
P
(b) F = ln Z = n ln (1 e ) n = L .
Z 2 Z
X 4n dn
F = ln (1 e~n / ) = (2) ln (1 e~nc/ L ) = dnn2 ln (1 e~nc/ L ) =
n 0 8 0
  Z n3 e~nc/ L

~c

~ 2 c
Z
n3
= (n3 ln (1 e~nc/ L )) dn = dn =

0 0 1 e~nc/ L L L 0 e~n/ L 1
3 Z
x3 ( L)3 2

L
= =
~c 0 ex 1 (~2 c3 ) 45
~nc
where I used x = L .
Solution 8. Heat shields. For Ju = B (Tu4 Tl4 ), the thermal flux without the heat shield, in the middle region. Plane m
absorbs B Tu4 + B Tl4 and emits Jm = B (Tu4 + Tl4 ) = Tm4
.
Tm = (Tu + Tl ) . The key point is that, by symmetry, plane m emits J2m flux on each side.
4 4 1/4

 4
Tu + Tl4
 4
Tu Tl4
 
4 Ju
Jnet = B Tu (B ) = B =
2 2 2
Jnet is the same for the other side of the heat shield:
Tu4 + Tl4 Tu4 Tl4
   
Jnet = B Tl4 + B = B
2 2
n
Solution 9. Photon gas in one dimension. E = E0 sin (kx) cos (t) is the form of a solution with kL = n or k = L ,
since
n
v 2 Ex x = Et t v 2 k 2 = 2 or = v, n = v
k L

X 1
Zj = es~/ =
s=0
1 e~/
where Zj is the partition function for a particular mode frequency .
s~
P n      
s=0 se

1 d ~n 1 1 ~ 2 ~n
hsi = =Z (1 exp ) = Z (1 exp ) exp =
Z d(~n / )
exp (~n / )
=
1 exp (~n / )
11
So
~n X ~vn/L X
hsi~n = hn i =
U= hn i =


exp 1 ~n
n n
exp ~vn
L 1

2 2
X ~v 2 n2 exp ~vn
     ~v ~vn




U X ~vn/L ~vn ~vn X
L n exp L L L
=
2 exp = =
L 2



L (exp ~nv 1)2 L n 1)
(exp ~v 2


n exp ~vn
L 1 n L n
P R
Now n 0 dn for one-dimensional photon. Let = ~v L .
Letting x = n,
Z
 nv 2 Z n2 exp (n) x2 ex x2
Z
U 1 1 xdx
= dn n 2
= dx x 2
= { x
+ x
}
L (e 1) (e 1) (e 1) 0 e 1
R R (kx) (kx)3
Coefficient of k term of f (k) is j = 0 exx1 dx. Now f (k) = 0 sin ex 1 dx, sin (kx) = kx 3! + . . . , so that
Z
2 x
= x1
dx
6 0 e

L 2
 
U L
= = = CV
~v 6 6~v
Solution 10. Heat capacity of intergalactic space.
Given the density 1 atom m3 , considering thermal radiation at 2.9 K, then kB T = (1.381 1023 J/K)(2.9 K), ~c =
(1.05457 1034 J s)(3 108 m s ).
2
4 2
Recall for radiation, that the energy per unit volume: VU = 15~3 c3 4 so that U 3
= 15~3 c3 V .
3 dU 3
Assume hydrogen atoms modeled as ideal gas: U = 2 N , d = 2 N .
3
CVmatter 2N 45(~c)3 (N/V )
= 4 2
= = 2.8 1010
CVradiation 15~3 c3 3V 8 2 (kB T )3
~n ~vn vn
Solution 11. Heat capacity of solids in high temperature limit. = L ; n = L . For  ~n , 0 n nD .
   2    3
~n ~n ~n 1 1 ~n
exp 1'1+ + + + 1
2 6
By doing long division
~n ~n ~n (~n )2

'  = (~n )2
= + + + ...
exp ~n
1 ~n
1+ ~n
+ (~n ) 2
1+ ~n
+ 2 12
2 6 2 2 6 2

For np = (6N/)1/3
3 nD (~n )2 3 nD ~ vn ~2 2 v 2 n2
Z Z
2 ~n
U= dnn ( + )= dnn2 ( + )=
2 0 2 12 2 0 2 L 12 L2
4/3
~v n4D ~2 2 v 2 1 5 3 2 ~v 6N 3~2 3 v 2 (6N/)5/3

3 1 3 6N
= { nD + 2
n D } = +
2 3 2L 4 12 L 5 2 16L 120 L2
So 4/3
3 2 ~v 6N 3~2 3 V 2 (6N/)5/3

U = 3N +
16L 120 L2
  2 1/3
Now T = , = k~vB (6 L N)

So then
~v(6 2 N )1/3 3 2 ~v 61/3 N 4/3 6 15 (6 2 N )1/3 ~v
 
15
U = 3N = = N k B
L 16L 4/3 8 L 8
23
     
U 15 15 6.022 10 particles
= N kB = (1.381 1023 J/K) = 15.59
8 8 1 mol
which is very close to experimental values.
2 V 4 4 2 V 3
Solution 12. Heat capacity of photons and phonons. For a photon: U = 15~ 3 c3 U = 15~ 3 c3 .
4 4 4 3
3 N U 12 N
phonon: U ( ) = 5(k B )
3. = 5(kB )3
So then 3
12 4 1022

1
CV = = 2.3 1018
5 100
12
for a phonon.
For a photon,
4 2 (1.381 1023 J/K)3
3 = 220 /K 3 3
15 (1.05457 1034 J s(3 1010 cm/s))3
Temperature at which to photon contribution equals to phonon contribution:
(220/K 3 ) 3 = 2.3 1018 = = 2.2 105 K
Solution 13. Energy fluctuations in a solid at low temperatures.
 
U
2 = h( hi)2 i
V
Recall that
12 4 N 3 3 4 N 4
 
U
= 3
where U =
V 5 (kB ) 5(kB )3
!  3
h( hi)2 i 12 4 N 5
   
1 20 1 1 1 3 0.068
2
= 9 8 N 2 8
= (k B ) =
hi 5(kB )3 25(kB )6
3 4 N 3 N T
s  3
0.070 200
F= = 0.02
1015 102
Solution 14. Heat capacity of liquid 4 He at low temperatures.
(a) Given v = 2.383 104 cm s1 and accounting for only longitudinal waves (only longitudinal polarization), then the
Debye temperature is
1/3 1 He

!!1/3
18 2 N (1.05457 1034 J s)(2.383 104 cm/s) 18 2 0.145 g 1.00727647 u 4.0026u
 
~v
= = =
kB V 1.381 1023 J/K cm3 1.67262 1024 g
= 28.6 K
(b) Recall the derivation for U for phonons in a solid. Account for only longitudinal waves (only longitudinal polariza-
tion).
nD n2 ~n nD 2 ~ nv ~ 2 v nD n3
Z Z Z
L
U= dn = n dn = dn
2 0 exp (~n / ) 1 2 0 exp (x) 1 2L 0 exp (x) 1
With n = n L
~nv


L v, x = L or ~v x = n, then
 2   4 Z nD
~ v L x3
U= x
dx
2L ~v 0 e 1

18N
1/3 1/3 2/3 1/3
Dv
= 18 ~ n v to go to .


For low temperatures, small so take xD = ~n L = ~vL
2
  4

U 3
V
2(~v) 15
 2 
Recall that CV = U 2

3 4
V . Then CV /V = 15 (~v)3 . Recall B = kB T , and given v = 2.383 10 cm/s, then

kB (1.381 1023 J/K)

= = 5.495 106 (1/K cm)
~v (1.05457266 1034 J s)(2.383 104 cm/s)
So if we take CV /V and divide by the given density = 0.145 g/cm3 to get the heat capacity per gram, (and multiply
by kB , the Boltzmann constant to get the correct units; Kittel and Kroemer likes using dimensionless formulas ) then
 3
cm3
 
2 2 kB 3
(CV /V )/ = (kB ) T = 0.0208 T 3
15 ~v 0.145 g
Solution 15. Angular distribution of radiant energy flux.
(a) Recall
~ 3
u =
2 c2 exp ~


1
is the radiation energy per unit volume per unit frequency range.
cu = energy per unit time, per cross sectional area per unit frequency range.
em waves emitted spherically from pt. Q.
13
 Suppose em wave comes in at a funny angle other than directly inward.
Consider area da thats from the spherical wave from pt. Q. How much of that goes into solid angle d?
= cu cos dA
So cu cos is the energy per unit time, per cross-sectional area, per unit frequency range, that enters into some solid
angle d.

r2 d d
=
4r2 4
is the fraction of the spectral density that if arrives in solid angle d.

d
= cu cos
4
is the spectral density of radiant energy flux that arrives in solid angle d.
(b)
 /2  
1 1
Z Z
sin 2 cos 2 
cos sin dd = 2 d = = =
2 2 
0 2
cu
=
4
Solution 17. Entropy and occupancy.

X 1
Z= es~/ =
s=0
1 e~/
   
X s~ ~ ~
Z = es~/ 2
= (1 e ~/ 2
) (e ~/
) 2
= Z 2 hsi
s=0

Then
e~/ 1
hsi = ~/
hs + 1i =
1e 1 e~/
Z ~ ~
= ( ln Z) = ln Z + = ln hs + 1i + 2 hsi = ln hs + 1i + hsi
Z
Now (nyn)  
hs + 1i ~
hsi ln = Ze~/ ln e~/ = hsi
hsi
= = hs + 1i ln hs + 1i + hsi ln hsi
Solution 18. Isentropic expansion of photon gas.
1/3 1/3
(a) i Vi = f Vf or
 1/3
Vi f 2.9 K
= = = 103
Vf i 3000 K
r t
r = r(t) = t so that r = t or r = t

rf ri ri tf ti ti
=1 = =1
rf rf tf tf
ri ti
Knwowing that rf = 103 , then tf = 103 .
(b) Now
= V 1/3
 3
=V

For constant entropy expansion.
2 2
 4 
U 4 2 4
= 3 3
U = 3
V = 3
V 15~ c 15(~c) V 4/3 15(~c) V 1/3
2
   
U 1 4/3
= 4 V
V 15(~c)3 3
14
 ! !
4/3
2 2 4 2 Vi i4 2 Vi i3
Z Vf
4 1/3  1 1 1 f
W = pdV = (V ) = = = (i f )
15(~c)3 15(~c)3 1/3 1/3 15(~c)3 1/3 1/3 15(~c)3

Vi Vi Vf Vi i V i
Exercise 19. Reflective heat shield and Kirchhoffs law.
For a left plane sheet at u temperature, right plane sheet at l temperature
+Ju = b u4 Jl = b l4
reflection rJu = (1 a)b u4 reflection rJl = (1 a)b l4
absorb (left) aJu = ab u4 absorb (left) aJl = ab l4
total absorption: a(Ju + Jl ) = ab (u4 + l4 )
total emission: ab (u4 + l4 ). By symmetry, a(Ju2+Jl ) emitted to the left, and to right.
e emissivity, where emissivity is defined so radiation flux emitted by the object is e times the flux emitted by a blackbody at
the same temperature.
By Kirchhoff law, for equilibrium, a = e; object must emit at same rate as it absorbs.

a(Ju + Jl ) (1 r)(Ju + Jl ) (1 r)Ju (1 r)Jl (Ju Jl )

Jnet = rJu + Ju = + (1 r)Ju = = (1 r) =
2 2 2 2 2
b (u4 l4 )
 
a(Ju + Jl ) (1 r)(Ju Jl )
= (1 r) = + rJl Jl =
2 2 2

5. C HEMICAL P OTENTIAL AND G IBBS D ISTRIBUTION

Chemical Potential and Entropy. Let = (U, V, N ) (so now has 3 coordinates U, V, N ). Then
     

d = dU + dV + dN
U V,N V U,N N U,V

Consider curve c : R s.t. c = U U

+ N N

X() (i.e. dV (c)
= 0)
c(t)

Let = (U, V, N ) C ()
d 1 ()
Suppose d (c)
= 0 (i.e. c is a null curve of d or c is an isothermal curve, or i.e. overall temperature change d is 0)
       
d(c)
dU (c)
d(c)
= dU (c)
+ dN (c)
or = +
U N dN (c)
U dN (c) N
Now recall that originally, considering a system with only thermal contact to a huge heat reservoir/bath (it can be the universe),
then only N ,U mattered in describing this system, and so = (N, U ), so that 1 = U


N
.
Now
U
 
dU (c)
c(U
) U
= = =
dN (c)
c(N
) N N ,V
Similarly,
 
d(c)
c()

= =
dN (c)
N N ,V
So      
1 U
= +
N ,V N ,V N U,V
Consider F U . Now consider dF = dU d d. Apply dF onto c,
our vector field generated by our particular
isothermal, and constant volume curve in :
dF (c) d (c)
= dU (c) = U 0 d(c)
d(c)
The right hand side is
   
F F F
= U
dF (c) + N = U (1) + N
U N ,V N ,N
15
Left hand side is       !
1 U
U N N + U
N ,V N ,V U V,N

Subtract U from both sides. U was arbitrary (and so is N ), and so

       
F U
= or =
N ,V N ,V N ,V N U,V
Thermodynamic identity. Generalize thermodynamic identity for = (U, V, N )
     

d = dU + dV + dN =
U V,N V U,N N U,V
1 p
= dU + dV dN or dU = d pdV + dN

Solution 1. Centrifuge.
T = 12 mr 2 + 12 mr2 2 .
Consider ext = 12 M r2 2 (negative so for bigger r away from r = 0 axis, lower chemical potential , so to show
centrifugal force outwards.
tot = ln (n/nQ ) 12 M r2 2 .
tot (r) = tot (0) for diffusion equilibrium.
     
n 1 n(0) n(r) 1
ln M r2 2 = ln = ln = M r2 2
nQ 2 nQ n(0) 2

M r2 2 M r2 2
   
n(r)
= exp or n(r) = n(0) exp
n(0) 2 2
Solution 2. Molecules in the Earths atmosphere.
M 3/2


Recall that for ideal gas, F = [N ln Z1 ln N !]; Z1 = nQ V = 2~ 2 V.
   
F d n
= = [log Z1 ln N !] = ln
N ,V dN nQ
M 3/2


where nQ = 2~ 2  .
Now = log nnQ
R

2
GMe gRm GMe
ext = r = r since g = Re2 .
tot = ln (n/nQ ) + M gh
In equilibrium, this must be independent of r: tot (r) = tot (R).

gR2 M M gR2
ln (n(r)/nQ) = ln (n(R)/nQ )
 2 r  R
M g R2
    
n(r) R n(r)
ln = Mg R or exp R =
n(R) r r n(R)
M g R2
  
1
= n(r) = n(R) exp
r R
so that

M gR2
 
M gR
Z
N = 4n(R) exp r2 dr exp
R r
Solution 3. Potential energy of gas in gravitational field.
I looked at the solution from Ed Groth [?] for Problem 3, Homework No. 4, Physics 301 for a hint, which prompted me to
recall that diffusive equilibrium between 2 systems means their chemical potential i s are equal.
1

Problem 3 Potential energy of gas in gravitational field of Chapter 5: Chemical Potential and Gibbs Distribution from
Kittel and Kroemer (1980) [1]: Consider a column of atoms each of mass M at temperature in a uniform gravitational
field g.
1John D. Naud via Ed Groth, Problem 3, Homework No. 4, Physics 301, Fall 1999, http://grothserver.princeton.edu/ groth/

phys301f99/hw04sol.pdf
16
Consider an infinitesimal layer at height h and at height h + dh. At each height h, the layers of atoms are in diffusive and
thermal equilibrium, and so
(h + dh) = (h) =
(thermal equilibrium) and
(h + dh) = (h)
(diffusive equilibrium).
Now for chemical potential = (, V, N ),
3/2 !
2~2

= int + ext = ln n + M gh
M
Thus, to first order,  
1 dn(h) M gh
= M g or n(h) = n(0) exp
n(h) dh
The thermal average potential energy per atom is
 
h exp ( M gh
) exp ( M gh
) 
R
M g/

+
(M g/ )2 
dhM ghn(h)
hU i = 0 R = Mg   0
= Mg = = hU i
0
dhn(h) M gh
exp ( ) 
 Mg
M g/ 
0
From Ch.3, Eq. (64) of Kittel and Kroemer (1980) [1],
P
n exp [n / ] ln Z1 3
U= n = 2 =
Z1 2
So the total heat capacity per atom C is
E (hU i + U ) 3 5
C= = = ( + )= =C
2 2
 
Solution 4. = int + ext = ln nnQ + ext
 4   
10 n n
ext = ln ln = ln 104 = 300 K 0.0000861733 eV /K ln 104 = 0.24 eV
nQ nQ
Note that I checked this solution afterwards with the one by John D. Naud, via Ed Groths materials [?], for Problem 4,
Homework No. 4, Physics 301 2.
Solution 5. Magnetic concentration.
This problem pertains to Figure 5.6. Recall the example on pp. 127 of Kittel and Kroemer (1980) [1], Example: Chemical
potential of mobile magnetic particles in a magnetic field. Consider system of N identical particles with magnetic
moment m.
Now
2~2
   
n 3
tot () = ln mB = ln n + ln mB
nQ 2 M
2~2
 
3
tot ()(B = 0) = ln (n (B = 0)) + ln
2 M
2~2
 
3
tot ()(B = 20 kgauss) = ln (n (B = 20 kgauss)) + ln m(20 kgauss)
2 M

7 3
When n (B = 0) = 2 10 cm ,
9 3
n (B = 20 kgauss) = 2 10 cm
tot ()(B = 0) = tot ()(B = 20 kgauss)
so
2 109 cm3
 
ln = m(20 kgauss)
2 107 cm3

2John D. Naud via Ed Groth, Problem 4, Homework No. 4, Physics 301, Fall 1999, http://grothserver.princeton.edu/ groth/

phys301f99/hw04sol.pdf
17
Given = 300 K,
300 K kB ln (102 )
m= = 9.54 1018 erg/gauss = 103 Bohr magnetons
20 kgauss
where we take the Bohr magneton B e~/2mc to be 9.274 1021 erg/gauss.
Solution 6. Gibbs sum for a two level system. Recall that
X
X X 
Z(, ) = exp [(N s(N ) )/ ] = exp [(N s(N ) )/ ]; = exp

N =0 s(N ) ASN

 



(a) Z = 1 + + exp , 1 for N = 0; for N = 1, + exp . for  = 0.
0(1)+(1)(+ exp ( 
))
(b) hN i = Z = (1+expZ(/ ))
0(1)+(0)()+ exp (/ )
(c) hN ()i = Z = exp Z(/ )
(d) hi = hN ()i =  expZ(/ )
(e)
Z = 1 + + exp (/ ) + 2 exp (/ ) = (1 + )(1 + exp (/ )
where we considered the possibility the orbital at 0 and at  are

each occupied by one particle at the same time.
So that, for total energy being , exp [(2 )/ ] = (exp )2 e/ = 2 e/ .
Solution 7. States of positive and negative ionization.

Z = e 2 + e 2 + e 2 + 2 e 2

Z = 0 + e/2 + e 2 + 2e 2
(e/2 + e/2 + 2e/2 )
ln Z = =1
e 2 + e 2 + e 2 + 2 e 2
2 e/2 = e/2
e/2 + e/2 + 22 e/2 = e/2 = e/2 + e/2 + 2 e/2 =
2 = e/ or 2 ln = /

2 ln =
Solution 8. Carbon monoxide poisoning.
(a) Z = 1 + (O2 )eA /
(O2 )eA
 
A
P (O2 ) = = 0.9 or 0.9 = 0.1(O 2 ) exp
1 + (O2 )eA /
   
9 A (O2 )
= ln = ; or ln = A
(O2 ) 9
   5 
(O2 ) 5 eV 10
A = (kB T ) ln = (8.617 10 )(273 + 39) ln = 0.3686 eV
9 k 9
(b) Z = 1 + (O2 )eA / + (CO)eB /

(O2 )eA /
P (O2 ) = = 0.1 = 0.1 + 0.1(CO)eB / = 0.9(O2 )eA /
1 + (O2 )eA / + (CO)eB /

9(O2 )eA / 1
   
B (CO)
ln = or B = ln = 0.5511 eV
(CO) 9(O2 )eA / 1
Solution 9. Absorption of O2 in a magnetic field. Recall that 2j + 1 = total number of spin states.
2(1) + 1 = 3.
Now U = m B.
+B B A (A +B B)
Z = 1 + (O2 )e + (O2 )e + (O2 )e
=
 
B B
Z = 1 + (O2 )eA / (1 + 2 cosh )

18
  
B B
(O2 )eA / (1 + 2 cosh ) 
B B

0.91 =   or 0.91 = 0.09(O2 )eA / (1 + 2 cosh )
1 + (O2 )eA / (1 + 2 cosh B B )
      
1 91 1 B B 1 91 1
eA / 1 = cosh or B = arccosh eA / 1
2 9 (O2 ) B 2 9 (O2 )
The Gibbs sum in the limit of zero magnetic field will differ from that of Problem 8 because there the spin multiplicity of the
bound state was neglected.

Z = 1 + 3(O2 )eA /
3(O2 )eA /
P (O2 ) = = 0.9 or 0.9 = 0.3(O2 )eA /
1 + 3(O2 )eA /
 
3 (O2 )
ln = A / or A = ln = 0.6227
(O2 ) 3
for T = 300 K, so that = 0.049375 eV .
0.049375 0.59927
= B = 0.59927 = = 511.1 T
B 5.7884 1011 106 eV /T
Solution 10. Concentration fluctuations.
P P
(a) Recall that Z = N =0 s(N ) exp [(N s(N ) )/ ].
2Z X  N 2 2 2Z
2
= exp [(N s(N ) )/ ] hN i =
2 Z 2
ASN
(b)
 2  
Z 2Z
  ! 2
Z
,V ,V
hN i = = +

Z Z2 Z

,V

= hN i = hN 2 i hN i2 = h(N )2 i

Solution 11. Equivalent definition of chemical potential.
Recall that      

d = dU + dV + dN (31)
U V,N V U,N N U,V
 

= (35)
N U,V
Consider when d = dV = 0.  

= dN + dU = 0
U V,N
 
dU
=
U V,N dN
dU U


Note that dN = N ,V .

1 , so then


Using the definition, U N,V
 
U
=
N ,V
Now F = U , by definition. Consider the thermodynamic identity, dU = d pdV + dN .
dF = dU d d = d pdV + dN d d =
= pdV + dN d
 
F
= = (, V, N )
N ,V
U F



Likewise, = N ,V is equivalent to (, V, N ) = N ,V
through the thermodynamic identity as well.
dU = d pdV + dN
19
, V constant. d, dV = 0.  
U
= =
N ,V
Solution 12. Ascent of sap in trees. Given: relative humidity r = 0.9. T = 25 C

n0 = concentration in saturated air that stands immediately above pool of water of water vapor in air.
rn0 = actual concentration of water vapor in air at uppermost leaves is rn0 .

At pool, H2 O = vapor for diffusion equilibrium.

Same condition at uppermost leaves, otherwise theres evaporation:

sap = vapor (h).
sap = H2 O (no flow going on in water). Thus, vapor (h) = vapor (0) and treat water vapor as an ideal gas.
   
n(h) n(0)
ln + mgh = ln
nQ nQ
     
rn0 1 1
ln = mgh = ln = mgh or h = ln
n0 r mg r
2
(1.381 1023 K 1
)(298 K)(kg m 10


s2 ) ln 9
h=  27 kg
 = 147.1 m
(18 amu) 1.6710 1 amu (9.8 m/s2 )
Solution 13. Isentropic expansion.
(a)
M 3/2


(b) Recall that F = [N ln Z1 ln N !] where Z1 = nQ V = 2~ 2 V and
= F


V,W .
 3/2
F 1 M 3 1/2
= [N ln Z1 ln N !] [N 2
V]=
Z1 2~ 2
1 3 3
= [N ln Z1 ln N !] [N nQ V ] = [N ln Z1 ln N !] N
Z1 2 2
M

3/2 3/2
With N constant and Z1 = 2~ 2 V , then for an isentropic expansion, V 2/3 must remain constant.
Solution 14. Multiple binding of O2 .
(a) Be wary of the multiplicity, how you count, each of the energy states.
   
/ 4 2 2/ 4 3 3/
Z = 1 + 4e + e + e + 4 e4/ = (1 + e/ )4
2 3

4e/
P () =
(1 + e/ )4
(b)
4 e/ e/
P (4) = / 4
= 4
(1 + e ) 1
+e/

6. I DEAL G AS
Classical Limit. Recall, Ch. 6, Sec. Classical Limit of Kittel and Kroemer [1], an ideal gas is defined as a system of free
noninteracting particles in the classical regime.
f () average occupancy of an orbital at energy 
 energy of orbital occupied by 1 particle; not energy of system of N particles
1
Fermi-Dirac and Bose-Einstein distribution f () = exp [()/ ]1
In order for f ()  1 orbitals, exp [( )/ ]  1 .

= f () ' exp [( )/ ] = exp (/ ) exp

f (), average occupancy of orbital of energy , is classical distribution function.
M 3/2


In Ch. 3 of Kittel and Kroemer [1], Z1 = nQ V , nQ = 2~ 2 .
20
 = e/
N n
N = Z1 = nQ V = =
nQ V nQ
 n
= = exp =
nQ
Heat Capacity. Now
Q = Q(, p) = p dp + Cp d = dU + W = dU + pdV
Let c s.t. dp(c)
= 0 (constant pressure). And so
Q(c)
= 0 + Cp d (c)
= d(c)
= dU (c)
+ pdV (c)


for c = (, 0), c = T .
     
U V
= Cp = = +p
p p p
for heat capacity at constant pressure is larger than CV because additional heat must be added to perform the work needed to
expand volume of gas against constant pressure.
Now recall for enthalpy
H = U + pV
H = H(, p)
Then
dH = dU + pdV + V dp = Q + V dp
Thus, for c , dp(c)
= 0 (constant pressure). Hence
 
H
dH(c) = = Q(c)
+ 0 = Cp
p
Hence,    
H Q
Cp = =
p p
Now Z Z Z
dH = Hf Hi = Q= Cp d = Cp (f i )
c c c
(if Cp constant over desired temperature range)
Reversible Isothermal Expansion. Q = 0, insulated gas, no heat flow to or from the gas (adiabatic)
constant in system isolated from reservoir, if expansion reverisble (slowly)
What is the pressure after expansion? Remember
5
Cp 2N 5
= 3 = =
CV 2N
3
So let
1 3
=
1 2
1
(7) (, V ) = N (ln 1 + ln V + constant ) (61)

1 1
(8) ln 1 V = constant or 1 V constant (62)

1 1
(9) = 11 V1 = 21 V2 (63)
for ideal monoatomic gas.
Use pV = N

1 1
(10) = 1 = 2 (64)
p1 p2
1 1

or p11 V11 = p21 V21 or p1 V1 = p2 V2

I will recap Problem 10 and my solution.
21
Isentropic relations of ideal gas.
C
(a) = CVp . For isentropic process, pV = pi Vi .
Then, essentially and equivalently, take the exterior derivative:
dp dV
V dp + pV 1 dV = 0 = + =0
p V
For
V 1 = i Vi1
then taking d:
d 1
d V 1 + ( 1)V 2 dV = 0 = + dV = 0
V
For

1 p = i1 pi
then taking d:
21 dp d
dp 1 + 1 d p = 0 = + =0
1 p 1
(b) isentropic bulk moduli
pi Vi
 
p
B = V = = p
V V
pi Vi
since p = V

B = p
EY : 20150606 I think when one consider small, linear longitudinal perturbations of the gas system, with pressure
being the external restoring force, then sound waves propagate (correct me if Im wrong) and this is the way to derive
B .  
p
isothermal bulk moduli B = V V = n
V =p

 1/2  1/2
velocity of sound in gas is c = B = p
for ideal gas of molecules of mass M , pV = N
Manifold interpretation; Im using Chapter 5 Applications in Physics, Section A Thermodynamics of [2]. Consider a 2-
dimensional manifold of equilibrium states M, s.t. dimM = 2. Local coordinates are (U, V ) with U being a global
coordinate.
Now U = CV so use as a global coordinate, i.e. the local coordinates of M can be (, V ).

Consider a curve in M parametrized by : ( (), V ()). The corresponding tangent vector X = + V V

X(M) has

components in coordinate vector basis = ()

V = V ()
Recall
d 1
+ dV = 0
V
Consider applying this 1-form onto X:
 
d 1 1 d
dV (X) = + V = 0 = ( V 1 ) = 0
V V d
Then the equalities of the endpoints of this curve ( (), V ()) are the equalities above. The interpretation is that the isentropic
process draws out a curve in M and can be written as a curve or as a tangent vector field (specifically a section of T M).

(11) 1 V11 = 2 V21 (66)

1 1
(12) 1 P1 = 2 P2 (67)
(13) P1 V1 = P2 V2 (68)
22
for, indeed,    
pV =N N 1 N 2
p1 V1 = p2 V2 p1 = p2 so
p1 p2

p1
1 1 = p1
2 2 or p1 11 = p2 21
  1   1
1

1
p1 2 p2
= p1 1 = p2 2 or = =
p2 1 p1
T1 = 300 K , V1 /V2 = 12 ,
 2/3
1
(14) T2 = (300 K) = 189 K (69)
2
The gas is cooled in expansion process by
(15) T1 T2 = 300 K 189 K = 111 K (70)
Expansion at constant entropy is important e.g. methods of refridgeration.
What is the change in energy in the expansion?
1
U2 U1 = CV (2 1 ) = N (2 1 )
1
Problems. Solution 1. Derivative of Fermi-Dirac function. Recall f = 1
exp [()/ ]+1 = (e()/ + 1)1
 
1
 f = 1(e()/ + 1)2 (e()/ )

1
 f ( = ) =
4
Solution 2. Symmetry of filled and vacant orbitals.  = +
1 e/ 1
f () = f ( + ) = = = 1 + / = 1 f ( )
+1 1 + e/
e/ e +1
Solution 3. Distribution function for double occupancy statistics.
(a) = 1 + e/ + 2 e2/ where = e/ .
/ e/ + 22 e2/
hN i = ln = (e + 2e2/ ) =

(b) = 1 + 2e/ + 2 e2/
2e/ + 22 e2/ 2(e/ )(1 + e/ )
hN i = ln = =

P p/tau
Solution 4. Energy of gas of extreme relativistic particles. For p ' p, s e = Z.
With the factor 2 for the 2 possible polarizations,
4 2  Z
Z Z
Z = (2) p dpep/ = { p2 ep/ ( ) 2pep/ ( )} = 2 pep/ dp =

8 0 0 0 0
 Z
p/
== 2 { pe ( ) ep/ ( )dp} = 2 3

0 0
ln Z
U = 2 = 2 {ln (2 3 )} = 2 (3 ln ) = U = 3

Solution 5. Integration of the thermodynamic identity for an ideal gas. For constant N , recall
   
dU pdV 1 U 1 U pdV
d = + = d + dV +
V V
U


CV = V , and for an ideal gas pV = N .
Z Z  
1 U
d = = CV ln + N ln V + dV + 1

Now U = 23 for an ideal gas, so V
U



= 0.
= = CV ln + N ln V + 1
1 independent constant of and V .
23
Solution 6. Entropy of mixing.
Solution 7. Relation of pressure and energy density.
U


(a) Recall that U = U (, V, N ). p = V N , and
P s /
s s e
U= Z

       X  s   1 
U X s s / 1 s s /
X
= e + s e /Z es / s2 es / /Z 2
V s
V N V N s
V s 2

U


Now p = V N .
s


So if the system is in state s; then ps = V N .

s
es /
P

s V N
= hpi = p =
Z
2 2 2 2
n ~ n ~
(b) Now s = L2 2M = V 2/3 2M

n2 ~2
 
s 2 2
= V 5/3 = s
V N 3 2M 3V
(c)
P 2s s /  
s 3V e 2 1
p= = U
Z 3 V
Solution 8. Time for a large fluctuation.
nQ
5 M 3/2


 n + 2 ]. nQ =
(a) Recall = N [ln 2~2 .
n 2V
f = N [ln QA N + 52 ]
 
n V
i = N [ln QA N + 52 ]
Now     N
nQ N 5N 5N NQ
g e exp ln + =e 2
n 2 n
2 4
  2
(938 M eV /c )((0.8617 10 eV )/K)(300 K) 1 M eV 1c
nQ = 4 = 7.88 1030 /m3
2(6.582122 1022 M eV s)2 106 eV 3 108 m/s
Now P V = N . Then
 
1.013105 N/m2 kgm/s2
P N (1 atm)( 1 atm ) 1N
= = 23
= 2.445 1025 /m3
V 1.381 10 J/K(300 K)
Now 1 L = 103 m3 and so for 0.1 L,
1
(2.445 1025 )(104 m3 ) = 2.445 1021
m3
With
7.88 1030 /m3
 
= 3.22 105
2.445 1025 /m3
5 21 21
= g e 2 (2.44510 )
(3.22 105 )2.44510
(b)
(c)
Solution 9. Gas of atoms with internal degree of freedom.
For an ideal monatomic gas, assume noninteracting.
M 3/2


(a) int = . = exp (/ ) ideal gas. = ln (n/nQ ); nQ = 2~2 .

ext = exp (/ ) or 1
M 3/2


Z1 is the usual canonical partition function, Z1 = nQ V where nQ = 2~ 2
   
X s
Z1 = ( exp (s / )(1) + exp exp )Z1 = (1 + e/ )Z1
s

24
 (Z1 )N = ((1 + e/ )Z1 )N
(b)
(c)
Solution 10. Isentropic relations of ideal gas.
(a) Isentropic process, so pV = pi Vi .
dp
V dp + pV 1 dV = 0 = + dV = 0
p V
Dealing with an ideal gas, pV = N still applies.

V 1 = i Vi1
d V 1 + ( 1)V 2 dV = 0
d ( 1)
= + dV = 0
V
Using pV = N again, note that p1 = constant .
dp d
(1 )p dp + p1 1 d = 0 = + =0
p 1
pi Vi
(b) Using p = V ,
p pi Vi
=
V V +1
p pi Vi
= V = = p
V V
So that B = V (p/V ) = p, the isentropic bulk moduli.
 
P n
B = V = =p
V V
since
pV = n
n
p=
V
p n
=
V V2
7. F ERMI AND B OSE G ASES
Problems. Problem 1. Density of orbitals in one and two dimensions.
(a) Show that the density of orbitals of a free electron in one dimension is
(16) D1 () = (L/)(2m/~2 )1/2 ,
where L is the length of the line.
(b) Show that in two dimensions, for a square of area A,
(17) D2 () = Am/~2
independent of .
p2 ~2 2
Solution 1. Recall, for the free electron: H = 2m = 2m
2 2 2
~ 2 n2 2 ~2 (nx +ny )
= s = 2m L2 for 1 dim., s =
x
2m for 2-dim.
L2
If F = Fermi energy, energy of the highest filled orbital,
n2
1-dim: N = 2nF . 2-dim.: N = (2) 14 (n2F ) = 2F

2 factor for 2 possible spin states.

q
~2 N 2 2 1 ~N 2 1 1 ~m 2 2 2V 2






1-dim: F = 2m 2 L2 = 2m 2 V 2 = 2m 2 n N= 2mF ~
~2 2N


2 ~2 N 2 ~2 N ~2 mV F
2-dim: F = 2m L = m V = m V = m n N = ~2

25
 dN
q
2V 2 1

1/2 N L

 2m 2 1/2
1-dim.: D() = d = 2m ~ 2 (F ) = 2 = ~ 
2-dim.: N  = Am/~2
Problem 2. Energy of relativistic Fermi gas. For electrons with an energy   mc2 , where m is the rest mass of the
electron, the energy is given by  ' pc, where p is the momentum. For electrons in a cube of volume V = L3 the momentum
is of the form (~/L), multiplied by (n2x + n2y + n2z )1/2 , exactly as for the nonrelativistic limit.
(a) Show that in this extreme relativistic limit the Fermi energy of a gas of N electrons is given by
(18) F = ~c(3n/)1/3 ,
where n = N/V .
(b) Show that the total energy of the ground state of the gas is
3
(19) U 0 = N F .
4
The general problem is treated by F. Juttner, Zeitschrift fur Physik 47, 542 (1928).
Solution 2.
~nF
(a)  ' pc = ~n
L c, F = L c.
3N 1/3
= (2) 81 4 3

3



Recall, for 3-dim.: N 3 nF = 3 nF . nF = .

~ 3N 1/3 3n 1/3



F = L = ~c
(b)
nF
~ 2 c nF ~ 2 c 4
Z Z
X 1 ~nc
U0 = 2 n = 2 4 = dnn2 dnn3 = n =
0 8 L L 0 4L F
nnF
4
~ 2 c F L ~ 2 c 3N
   
F L 3
= = = N F
4L ~c 4L ~c 4
Problem 3. Pressure and entropy of degenerate Fermi gas.
(a) Show that a Fermi electron gas in the ground state exerts a pressure
 5/3
(3 2 )2/3 ~2 N
(20) p=
5 m V
In a uniform decrease of the volume of a cube every orbital has its energy raised: The energy of an orbital is
proportional to 1/L2 or to 1/V 2/3 .
(b) Find an expression for the entropy of a Fermi electron gas in the region  F . Notice that 0 as 0.
Solution 3.
2
(a) Recall U0 = 53 N 2m
~
(3 2 N )2/3 V 2/3
5/3
3 ~2 1 ~2
  
U 2 N
= N (3 2 N )2/3 V 5/3 = (3 2 )2/3
V 5 2m 3 5 m V
So then
 5/3
U0 1 ~2 2 2/3 N
p= = (3 )
V 5m V
 2 2/3
~2 3 N
(b) Recall that F F = 2m V and that the heat capacity of an electron gas is Cel = 12 2 N F = U
, which
helps directly with finding the entropy.
Z Z
1 11 2 2 N
( ) (0 ) = dU = N d =
0 0 2 F 2F
Let (0 = 0) = 0,
2 N
( ) =
2F
Problem 4. Chemical potential versus temperature. Explain graphically why the initial curvature of versus is upward
for a fermion gas in one dimension and downward in three dimensions (Figure 7.7). Hint: The D1 () and D3 () curves are
different, where D1 is given in Problem 1. It will be found useful to set up the integral for N , the number of particles, and to
consider from the graphs Rthe behavior of the integrand between zero temperature and a finite temperature.
F
Solution 4. Recall, N = 0 dD().
26
1-dim:
F F 1/2  
L (2m)1/2 F
Z  Z Z
L 2m
N= dD1 () = d = d1/2 =
0 0 ~2  ~ 0
 F
L (2m)1/2 1/2  L (2m)1/2 1/2
   
= (2 ) = 2F
~ ~ 0
3-dim:
Z F  3/2  3/2  F  3/2
V 2m 1/2 V 2m 2 3/2 V 2m 3/2
N= d 2  =   = F

0 2 ~2 2 2 ~2 3  3 2 ~2
0
Note the difference in the concavity of the N () curves.
Solution 5.
(a) For 3 He, given I = 1/2, density of liquid 0.081 g cm3 , we want to find vF , F , F .
 2
~
F = (3 2 n)2/3 =
2m
2/3
(6.582 1022 M eV s)2
    3
2 0.081 g 1 kg 1u 1 He
= 2 3 =
cm3 103 g 1.67 1027 kg 3u

1c
2 3 938 M eV /c2 31010 cm/s

= 4.24 1010 M eV = 4.24 104 eV

2F
Now suppose we have a nonrelativistic gas. Then 12 mvF2 or vF2 = m .
cm
vF = 1.675 104
sec

4.24 104 eV
TF = = 4.92 K
0.8619 104 eV /K
(b)
2 2 3N 2
D(F ) =
Cel = = N = 1.003kB T N
3 3 2F 2 F
Solution 6. Mass-radius relationship for white dwarfs.
(a)
G 4 r3 2 3GM 2
Z Z
M 4 1 M
U = (r)(r)r2 4dr = 4 3 r dr = 4 4 3 G R5 4 3 =
r 3 R
3 5 3 R
5R
(b)  2
~
F = (3 2 n)2/3
2m
is the Fermi energy.
With V = 34 R3 ,
2/3
h2 3 2 N (3 2 )2/3 ~2 N 5/3 (3 2 )2/3 ~2 N 5/3
  
1 2
Ttot = N mv = N F = N = = =
2 2m V 2 m V 2/3 2 m 4
2/3 R2
3
9 2/3 2 5/3


5/3
4 ~ N 2 (M/MH )
= ' ~
2 mR2 mR2
M
since N = MH since MH  m.
(c)
~2 M 5/3 GM 2 ~2 /G
5/3
= = M 1/3 R ' 5/3
mMH R2 R mMH
2
(6.582 1022 M eV s)(1.05457 1034 J s) 103 g m3 /s2 (3 108 m/s)2
  
 3  /(6.67 1011 )
0.511 M eV /c2 ((1.67 1027 kg) 10 g 5/3 1 kg kg 1 c2
1 kg )

Dealing with units and dimensions,

m2 N m2 m3 /s2 m3 /s2
J = kg ; = kg =
s2 kg 2 kg 2 kg
27
  2  2
m2 102 cm 103 g
(6.582 1022 M eV s)(1.05457 1034 kg s ) 1m 1 kg

(3 1010 cm/s)2

1020 g 1/3 cm
3 2
102 cm 3 1 c2
1011 mkg/s


(0.511 M eV /c2 )(1.67 1024 g)5/3 (6.67 1m )
(d)
M M M2 (2 1033 g)2 3 1066 g 2
= 4 = 3 = 4 = 4 =
3 R
3
3 10
60g cm3 60
3 10 g cm
3 1060 g cm3

4 1020 g 1/3 cm
3 M 1/3
g
106
cm3
(e)
~2 /G 1017 g 1/3 cm
M 1/3 R ' 5/3
1017 g 1/3 cm = R = = 7.937 km
mMH (2 1033 g)1/3
Solution 7. Photon condensation. Ne = 2.404V 3 / 2 ~3 c3 .
The condition is that N = Ne :
2.404V 3
N = Ne =
2 ~3 c3
 2 3 3 1/3
~ c N
=
2.404 V
With a concentration of 1020 cm3 , T = 1.7 106 K (the critical temperature in K below which Ne < N .
Solution 8. Energy, heat capacity, and entropy of degenerate boson gas.
Recall that the distribution function for bosons is
1
f (, ) =
exp [( )/ ] 1
Consider N noninteracting bosons of spin zero.
1
 = 0 for ground state. Thus, f (0, ) = exp . Recall that
( )1
Z Z  3/2
V 2M 1
N ( ) = dD()f (, ) = d 2 2
1/2 1 


1
0 0 4 ~ exp
Recall,
  Z Z  3/2
1   V 2M
U =0 + D()d = 1/2 d =
exp (/ ) 1 0 e()/ 1 0 e()/ 1 4 2 ~2
3/2 Z
3/2

V 2M
= 2 2 ()/
4 ~ 0 e 1
<  , so 1, for N0 to be sufficiently large.
3/2 Z
3/2

V 2M
= U =
4 2 ~2 0 e/ 1
x = /
Using
dx = d/
3/2
x3/2 dx
 Z
V 2M
= U = 5/2 = B0 5/2 C0
4 2 ~2 0 ex 1



Its true that (e/ ) = e/ 2
   3/2 Z 3/2
5 V 2M 3/2 x dx
CV =
2 4 2 ~2 0 ex 1
1


Now = U V .

V B0 25 3/2 C0 d
Z Z Z
1 5
(U ) (U0 ) = dU = = V B0 C0 1/2 d =
2

5 3/2
dU =V B0 C0 d 5 2
2= V B0 C0 3/2 

2 3 0
28
 5 5 U 3/5 5
(U ) = V B0 C0 3/2 = V B0 C0 3/5
= (V B0 C0 )2/5 U 3/5 =
3 3 (V B0 C0 ) 3
 3/2 Z 3/2 !2/5
V 2M x dx 5 3/5
= U
4 ~2 0 e x1 3
 3/5
where we had used U = V B0 5/2 C0 or V BU0 C0 = 3/2 .
Solution 9. Boson gas in one dimension.
In one-dim.,
~2 2 n 2 ~2 2 n 2 2mV 2
s = = or s = n2
2m L2 2m V 2 ~2 2
1/2 1/2
2mV 2 2mV 2
 
dn 1
= n = 1/2 = =
~2 2 d ~2 2 21/2
Note the difference with 3-dim.: For spinless bosons,
1/2
4n2 dn 2mL2 2mL2
 
1
D(n)dn = =  s d =
8 2 ~2 2 ~2 2 21/2
3/2
2mL2

= 1/2 d = D()d
4 ~2 2

1/2
2mV 2
Z Z 
1 1 
N ( ) = dD()f (, ) = d 1
exp 1=
0 0 ~2 2 1/2
2
 2
1/2 Z
1 2mV d 1 
= ( exp 1)
2 ~2 2 0 1/2
For  0, N ( ) which is not characteristic of a Boson.
Solution 10. Relativistic white dwarf stars.  ' pc = 2~/p.
Virial theorem:
2hT i = hU i 2hT i = khU i
 1/3
3GM 2 3GM 2
   
3 3 4/3 3 1
2 N F = N ~c = =
4 2 L 5R 5R
 1/3
3n
F = ~c

Approximating the sphere as a box,
4
L3 = R3 1/3
3

3
 1/3 L=R
4 4
L= 1/3 R
3

3/4 3/4
GM 2 GM 2 2GM 2 41/3
      
4/3 2L 2L
N = = N = =
5R ~ 2/3 c31/3 5R ~ 2/3 c31/3 5 ~32/3 1/3 c
Now M = N mH , where mH is the mass of hydrogen, so
3/4
2Gm2H 41/3
 
1= N 1/2
5 ~3 1/3 c
2/3

3/2 !3/2  3/2

5~(32/3 ) 1/3 c (1.05457 1034 J s)(3 108 m/s) 5(32/3 ) 1/3

= N = = m3
= 2.2 1058
41/3 (2Gm2H ) (6.67 1011 kgs2 )(1.67 10
27 kg)2 41/3 2
29
 8. H EAT AND W ORK
Energy and Entropy transfer: Definition of Heat and Work. Consider , a manifold consisting of points representing
thermodynamic states of a single system. For instance, for global coordinates (U, V ),
(U, V ) .
Consider W, Q 1 (), 1-forms on .
Now define Q as

Q d

with = (U, V ) C ()
= (U, V ) C ()
Recall energy conservation in this form:
dU = W + Q
Consider pure heat and, so, no work. Now Q = d

Heat Engines: Conversion of Heat into Work. Consider curve c : R s.t. c generates vector field c =
(U is suited
c(t)
for this).

Act on this vector field X() with Q, i.e.
 

Q =

This is whats meant when its said reversible heat transfer accompanying 1 unit of entropy is given by temperature [1].
Consider Figure 8.1 on page 229 of Kittel and Kroemer [1]. Roughly it looks like this:
= h dh = Qh /h Qh

= l dl = Ql /l Ql

But whats really going on?

Consider Qh = dU , the initial heat input at high temperature (Ill show that later) h .

Consider a curve c0 s.t. c0 = 0 . Then
 
U
Qh (c0 ) = dU (c0 ) = = 0 h 0
V
We can integrate the 1-form dU 1 () for 2 reasons: mathematically, it is an exact form. Physically, we are considering
a reversible process, passing through thermodynamic states of the system, starting with the system being in energy U0 and
ending up with energy U1 , and all the energy states ( R) in between.
Z 1
= U1 U0 = h d
0
R1
If this is conducted all at temperature h during the whole process, then U1 U0 = h 0
d = h (1 0 ). Its in this case
that d is an exact form and can be integrated over that curve c0 .
Legendre transforms revisited. Lets recall 2 of our favorite thermodynamic potentials, U , and Helmholtz free energy F .
They are related by Legendre transformations that transform 1 coordinate into its conjugate coordinate, somewhat like how
the Legendre transform transforms that Lagrangian in canonical coordinates into a Hamiltonian written with the conjugate
momentum. However, I do want to point out that, for Lagrangians and Hamiltonians, the Legendre transformation is a fiber
derivative between tangent bundle to the cotangent bundle on the manifold. In our current case, we want a mundane Legendre
transformation between convex function to another convex function, a coordinate transformation by a C function, not a
morphism between vector spaces.
Recall F . Its defined as such:
F U , so
dF = dU d d = d pdV
30
Consider curve c : R
c(t)
Consider 2 curves that generate vector fields:

c = or c = V
V
Now, in general, mathematically,
   
F F
dF = + d + dV
V V
Thus,
 
F
=
V
 
F
= p
V
Maxwell relations are easily derived:
2F 2F
   
p
= so =
V V V V

So-called natural coordinates for F are , V . So 3 (, V ) (i.e. after a Legendre transformation, the coordinates become
(, V ) for each thermodynamic state.
Recall U as a thermodynamic potential. Using energy conservation and how Q is defined,

dU = Q + W = d + pdV

Natural coordinates are , V for U . So 3 (, V ).

heat engine
ideal heat engine:
(1 , V0 )
1

Qh = h dh Ql = l dl W Qh = h dh Ql = l dl

0 2 (0 , V0 ) (2 , V1 )

W + Ql = Qh or W = Qh Ql
Qh Ql
h l l = h so =
W = Qh Ql Qh = C Qh h l
h
h l
Carnot efficiency C h is the ratio of the work generated to the heat added, in the reversible process.

Carnot cycle.
W23 W23
3 2 (H , l ) (H , h )

W34 W12 = Qh W34 W12 = Qh

4 1 (L , l ) (L , h )
W41 W41
H
The total work is as such: dU = 0 for 2 reasons: mathematically, the integration of an exact 1-form around a closed curve
is 0, and physically, we return the system back to its original state, as this is a reversible process.
I I I I I
dU = 0 = d pdV = W = d = [h (H L ) + 0 + l (L H ) + 0] = (h l )(H L )

31
 Example: Carnot cycle for an ideal gas.
W23 W23
3 2 (H , l , V3 ) (H , h , V2 )

W34 = Ql W12 = Qh W34 = Ql W12 = Qh

4 1 (L , l , V4 ) (L , h , V1 )
W41 W41
with

Z 2  
V2
isothermal expansion Qh = W12 = pdV = N h ln
1 V1  1
 1
Z 3 V3 h
adiabatic expansion W23 = dU = U (h ) U (l ) = CV (h l ) l V31 = h V21 or =
V2 l
2
Z 4
V3
isothermal compression Ql = W34 = pdV = N l ln V4 h 1
3 V4 = ( ) 1
V1 l
adiabatic compression W41 = CV (h l )
U


EY : 20150911 I dont have a good reason why CV which is defined for constant V , that CV V , can be used in the
isentropic (i.e. adiabatic) expansion from 2 3.
The total work done is  
V2
W = N (h l ) ln
V1
Energy Conversion and the Second Law of Thermodynamics.
W1 = 1 Qh Wout = 2 Qh 1 Qh
11 12

Qh Qh Qh
Ql1 = (1 1 )Qh Ql2

01 02
Q(in) = (2 1 )Qh

Ql2 = (1 2 )Qh

Ql2 waste heat

W1 Wout
11 12
Qh

01 02
Q(in)
Ql2

So with Q(in) heat in, Wout net work can be done. But thats a decrease in overall entropy. This violates the law of increasing
entropy.
32
Define H = U + pV . H C (), where is the manifold of equilibrium (and non-equilibrium) states of the system.
Path Dependence of Heat and Work. Mathematically, Q and W are not necessarily exact 1-forms. So they are path-dependent.
EY : 20150911 That Q, W are not necessarily exact 1-forms would imply that has some nontrivial, interesting topological
features.
Heat and Work at Constant Temperature or Constant Pressure.
isothermal work.
dU = W + Q = W + d
F = U
dF = dU d d = W d
If d = 0, on an isothermal curve,
dF = W , W becomes an exact 1-form, with potential function F , the Helmholtz free energy.
isobaric heat and work. e.g. boiling of liquid. When liquid boils under atmospheric pressure, vapor pressure displacing
atmospheric odes work against atmospheric pressure. isobaric process.
Consider this change of volume:
dx = dVA . Now
peq = vapor pressure.

F = peq A = patm A (force equilibrium)

(1 , V1 )

W = patm Adx = patm dV

(0 , V0 )

W = patm dV pdV = d(pV ) is part of total work done on system.

If d(pV ) > 0, work provided by environment and is free.

If d(pV ) < 0, work delivered to environment and not extractable from system for other purposes.

W + d(pV ) = dU Q + d(pV ) = dH Q
Recall that for enthalpy H = U + pV ,
dH = dU + V dp + pdV = dU W + V dp = d + V dp
, p are natural coordinates of H.

dH Q = W + d(pV )
An isobaric curve s.t. dp = 0,
dH = Q + W + d(pV )
so
Q + W is an exact 1-form of H pV = d(H pV ) = W + Q.
2 classes of constant pressure processes:
(a)
W + d(pV ) = 0
dH = Q
e.g. liquid evaporation from open vessel, because no effective work is done.
heat of evaporation is enthalpy difference between vapor phase and liquid phase
(b) constant temperature and constant pressure.
G = F + pV = U + pV
dG = dF + V dp + pdV = dU d d + V dp + pdV = V dp d
dG = W d + d(pV ) = W + d(pV ) d
with natural variables are p,
at constant temperature, W + d(pV ) is exact 1-form, dG
33
 F IGURE 1. Problem 8.1(c)

Problems. Solution 1. Heat pump.

(a) For a heat pump,
input: h = Qhh
output: l = Qll
Reversible condition: h = l = Qhh = Qll so that Qh = hl Ql .
Qh Ql = Qh hl Qh = hh
l
Qh net heat inputted to pump heat.
Thus,
W h l
= c =
Qh h
Qh Ql l
If heat pump is not reversible, h > l , so that h > l or h Qh > Ql ,
l
W Qh Ql Qh h Qh
= < = c, ideal
Qh Qh Qh
(b) Qh = electricity consumed by reversible heat pump.
Carnot engine: W = (hh l )(hh l ), with hh = Qhhhh
, and l = Qll
Condition that electricity consumed by reversible heat pump:
 
Qhh Ql
W = (hh l ) = Qh
hh l
Note we let l = Qll since both heat pump andCarnot engine are reversible.
   
Qhh Qh Qh Qhh 1 1 Qhh hh (h + hh l )
= = = = Qh + = =
hh h hh l hh hh l h Qh h (hh l )
For Thh = 600 K, Th = 300 K, Tl = 270 K,
Qhh 600(300 + 600 270)
= = 3.82
Qh 300(600 270)
(c) See Figure (1).
Solution 2. Absorption refrigerator.
(a) See Figure (2).
(b) Given hh > h ,
by energy conservation: Qhh + Ql Qh = 0
reversible refrigerator: hh + l h = 0,
Qhh Ql Qh
= + =0
hh l h
   
Qhh Ql Qhh + Ql 1 1 1 1
+ = or Qhh = Ql
hh l h hh h h l
          
Ql 1 1 1 1 h hh l h hh h l Ql
= / = / = =
Qhh hh h h l h hh h l h l hh Qhh
Note that Ql Qh = Ql (Qhh + Ql ) = Qhh ; weve removed Qhh heat from refrigerators inside.
34
 F IGURE 2. Problem 8.2(a)

i .
~
Solution 3. Photon Carnot engine. Recall, photons are relativistic:  = pc. Recall p = = s = pc = ~ks c =
ns


L ~c.
Recalling that there are 2 polarization states for a photon in 3-dim. space,
Z
2 ~c 3
   
~c
Z
1 2
 n  n
L ~c/
U = (2) (4) n dn ~c e = n dnexp n =
8 0 L L 0 L
 2     Z   
~c 3 ~c L  2 ~c L
= { n exp n  3n exp n dn} =
L L ~c 0 0 L ~c
 2    Z  
~c K ~c
= {(1) 3 n2 exp n dn} =
L ~c 0 L
 2       Z   
~c L ~c L ~c L
3{ n2 exp

= {(1) n  2nexp n dn =
L ~c L ~c 0 0 L ~c
 2   2 Z   
~c 2 L ~c L
= (1) 3(2) nexp n dn =
L ~c 0 L ~c
 2   3 Z    2   4   
~c L ~c ~c L ~c
(1)3 (1)3

= 3(2)(1) exp n dn = 3(2)1 exp n  =
L ~c 0 L L ~c L 0
 3
L V
=6 4 = 6 2 3 4 = U
2 ~c ( ~c)

= 1 , and using this is usually the most direct way to obtain entropy.


To get the entropy, recall, U V

8V 3
Z Z
dU 6V d 6V 1
= d = = 4 3 = 2 2 3 3 = ( ) = 2 2 3
( 2 ~2 c)3 ( ~ c) 3 ( ~ c)
Consider
Isothermal expansion: Helmholtz free energy F is needed.
6V 4 8V 3 2V 4
F = U = =
( 2 ~2 c)3 ( 2 ~2 c)3 ( 2 ~2 c)3
Then
2 4
 
F 8h3
p= = 12 = (V2 V1 )
V , N ( 2 ~2 c)3 ( 2 ~2 c)3
2h4 8 4
W12 = p(V2 V1 ) = (V2 V1 ) Q12 = = 2 2h 3 (V2 V1 )
( ~2 c)3
2 ( ~ c)
 3
h
Isentropic expansion: = V2 h3 = V3 l3 or V3 = V2 l .
So for this isentropic process, V2 h3 =V , 3

4/3
V2 h3 6(V2 h3 )4/3 1/3

6V
U= = V
( 2 ~2 c)3 V ( 2 ~2 c)3
35
 6(V2 h3 )4/3 2(V2 h3 )4/3 4/3
 
U 1 4/3
p= = V V =
V ( 2 ~2 c)3 ( 2 ~2 c)3 3
V3 !
2(V2 h3 )4/3 4/3 2(V2 h3 )4/3 6(V2 h3 )4/3
Z Z
1/3 
 1 1
W23 = pdV = V dV = (3V ) = =
( 2 ~2 c)3 ( 2 ~2 c)3 
V2 ( 2 ~2 c)3 1/3
V3
1/3
V2
6V2 4
 
l
= 2 2h 3 1
( ~ c) h
2l4 2h3 l
Isothermal compression: W34 = ( 2 ~2 c)3 (V4 V3 ) = ( 2 ~2 c)3 (V1 V2 ).
8l3 8h3
34 = ( 2 ~c)3 (V4 V3 ) = ( 2 ~c)3 (V1 V2 ).
 3
h
Isentropic compressiong: V4 l3 = V1 h3 or V4 = V1 l .
!
6(V4 l3 )4/3 6V1 h4
 
1 1 l
W41 = = 1
( 2 ~2 c)3 V4
1/3
V1
1/3 ( 2 ~2 c)3 h

2h4 6V2 4 2 3 l 6V1 4 8 4 (V2 V1 )

     
l l l
W = 2 2 3
(V2 V1 )+ 2 2 h 3 1 + 2 h2 3 (V1 V2 )+ 2 2 h3 1 = h 2 2 3 1
( ~ c) ( ~ c) h ( ~ c) ( ~ c) h ( ~ c) h

8h4 (V2 V1 ) W l
Qh = = =1
( 2 ~c)3 Qh h
Solution 4. Heat engine-refrigerator cascade. Consider the heat engine as a Carnot cycle.

W + Wr = (h l )h
where Wr = work consumed by refrigerator.
Qh Ql
= h =
= l
h l
This must be true for any heat engine undergoing Carnot cycle; furthermore, we can say its the most efficient heat engine
possible.
reversible refrigerator: QL + Wr = QH , (by E-consv.)
L = H = QLL = QHH , (by reversible condition)
Note, Ql is energy transfer from heat engine to l reservoir. QL is energy transfer from l reservoir to refrigerator. QL Ql ,
otherwise, no cooling, no thermal energy extracted from l resevoir to lower its temperature. QL = Ql at equilibrium; no
further cooling, r reached.
Note that l is given as the environmental temperature. Assume refrigerator throws out QH heat into the environment.
H = l . Since QL heat inputed into refrigerator from a l reservoir now lowered to r , l r .
 
l l
Wr = QL QL = 1 QL
r r
QL QH
since for a reversible refrigerator, L = H = L = H .
        
W r l QL r l r l
= = 1 1 = 1 1 = 1
Qh h r Qh h r h h
Combinations of reversible systems = reversible system.
Tl = 20 C
Solution 5. Thermal pollution. Given . Consider a Carnot cycle.
Th = 500 C
   
Ql h 500
W = (h l )l = (h l ) = 1 Ql = 1 1500 M W = 36000M W
l l 20
If improvements in hot-steam technology would permit raising Th by 100 C,
 
600
W = 1 1500 M W = (29)(1500 M W ) = 43500 M W
20
There was a 17.2 % increase in output.
Solution 6. Room air conditioner.
36
 (a)
 
Ql h
W = (h l ) = 1 Ql
l l
   
h dQl h P
P = 1 = 1 A(h l ) = l = (h l )(h l ) = h2 2h l + l2
l dt l A
P
= l2 2h l l + h2 = 0
A
r
P P 2
l = h + (h + ) h2
2A 2A
(b) For Tl = 17 C = 290 K, Th = 310 K,
P l (2 kW )(290 K) 580 103 W W
A= = = = 1450
(h l )2 (310 290)2 400 K K
Solution 7. Light bulb in a refrigerator
Carnot refrigerator draws 100 W. For any Carnot cycle,
   
Ql h l
W = (h l ) = 1 Ql = 1 Qh
l l h
Carnot refrigerator expels Qh thermal energy to hot h environment and inputs Ql thermal energy from l reservoir.
Ql + W = Qh
Work W must be drawn by Carnot refrigerator to do work. Suppose Carnot cycle part of the refrigerator must input in heat
from light bulb to cool down its inside, i.e. consider Carnot refrigerator in equilibrium with light bulb, now inputting in heat
from light bulb Qext , and drawing in work to expend out Qh thermal energy into the environment.
= Qext = Ql
= Q l in this case, so
W
   
h h
1 Ql Ql = 0 or 2 Ql = 0
l l
h 300 K
= l = = = 150 K
2 2
Solution 8. Geothermal energy.
Given Qh = M CdTh ,
Tl lower reservoir temperature stays constant. h decreasing, dh < 0.
 
Qh l dh
W = (h l ) = 1 (M C)
h h kB
      
MC MC i
= W = (h l ln h )|fi = l ln (i f )
kB kB f
For M = 1017 g, C = 1 J/g K, Tl = 20 C = 293 K, Ti = 600 C = 873 K, Tf = 110 C = 383 K
W = 2.486 1019 J
Note that 1014 kW h = 1017 Js h 3600 sec


1h = 3.6 1020 J.
U


Solution 9. Cooling of nonmetallic solid to T = 0. Recall that C = aT 3 = T V . Then dQl = aTl3 dTl . Now dl < 0
since l decreasing.
For the refrigerator: Ql + W = Qh .
     
Ql h 1 a h a
dW = (h l ) = 1 (al3 dl ) 4 = 4 1 l3 dl = 4 (h l2 l3 )dl
l l kB kB l kB
0
aTh3

a 1 1
W = 4 h l3 l4  =

=W
kB 3 4 h 12kB
37
 9. G IBBS F REE E NERGY AND C HEMICAL R EACTIONS
Solution 1. Thermal expansion near absolute zero
(a)   
G G
= =V
N, p p
   
V
 2   2    = =
G V p p
 
G
= =
p p p p p
   
G G
= =V
N p p
   
V
 2   2    = =
G V N p p N
 
G
= =
pN N p N N p p N p
 2     2       
G G
= = = =
N N N N N N N
 
1
(b) = V1 V


p = V p = 0 as 0 since constant as 0 by third law of thermodynamics.

Solution 2. Thermal ionization of hydrogen.
(a) Given e + H +  H, note that e + H + H = 0. Recall
[e][H + ] Y
= K( ) = nQjj exp [j Fj (int)/ ]
[H] j

M 3/2


where nQ = 2~ 2 V.
For dissocation of H into e + H + choose zero of internal energy of each composite particle (here H) to concide
with energy of dissociated particles (here H + , e ) at rest; place energy of ground state of composite particle H at
I, I is energy required in reaction to dissociate composite particle into its constituents and is taken to be positive,
i.e. the ionization energy.

K( ) = (ne )1 exp [Fint (e )/ ] (nH + )1 exp [Fint (H + )/ ](nH )1 exp ((1)(Fint (H)/ ))
Note that nH + ' nH . Let ne = nQ . Importantly, note
Fint (e ) + Fint (H + ) Fint (H) = I
Fint (H) is at a lower free energy than e and H + .
[e][H + ]
= K( ) = nQ eI/ = = nQ eI/
[H]
(b) By charge conservation, [e] = [H + ], so that
1/2
[e] = [H]1/2 nQ exp (I/2 )
Given [H] ' 1023 cm3 , me = 0.511 M eV /c2 , T = 5000 K, I = 13.6 eV ionization energy,
[e] = (1023 cm3 )1/2 (2.92 1010 1/cm3/2 )1/2 exp (13.6 eV /2kB 5000 K) = 1.3 1015 cm3
Note that H(exc) and H are just two different states of atomic hydrogen. Their concentrations must therefore be
proportional to the probability of occurrence of these states, and the ratio of probabilities is the ratio of the respective
Boltzmann
[H(exc)] p(H(exc))
=
[H] p(H)
If H(exc) is the internal energy of the first excited state and H is the internal energy of the ground state of atomic
hydrogen, we are given that H(exc) H = 34 I. We also need to take into account the fact that the first excited
electronic state of hydrogen is 4-fold degenerate i.e. one 2s-orbital and three 2p-orbitals.3 Therefore,
[H(exc)] p(H(exc)) 4eH(exc) /
= = = 4e3I/4
[H] p(H) eH /
[H(exc)] = 4[H]e3I/4 = 2.092 1013 cm3

3(from solutions to Homework 8, Ph12c, Caltech, June 6, 2008, by Prabha Mandayam, Heywood Tam)
38
 [e]
= 62
[H(exc)]
Solution 3. Ionization of donor impurities in semiconductors.
Consider a pentavalent impurity (donor), introduced in place of tetravalent silicon atom, acts like a hydrogen atom in free
space.
Then recall, from Problem 3, e + H +  H, and so
[e][H + ]
= nQ exp (I/ )
[H]
m 3/2


where nQ 2~ 2 refers to the electron.
By charge conservation, [e] = [H + ].
So
1/2
[e] = [H]1/2 nQ exp (I/2 )
Now given [H] = 1017 donors per cm3 , = 100 K,
 3/2  3/2
m 0.3 0.511 M eV /c2 100 K 0.00008617 eV /K
nQ = = = 1263. donors per cm3
2~2 2(4.136 1015 eV /s)2
q1 q2
Now F = r2 ,
 q q  q1 q2
Z Z
q1 q2 1 2 
W = F dr = 2
dr = +  =
r0 r r r0 r0
e2 1
and so I = r0 =  (13.6 eV ) where 13.6 eV is the ionization energy of an electron from a (real) hydrogen atom.
So
[e] = 2. 1018 donors per cm3
Solution 4. Biopolymer growth.
Recall that G(N, p, ) P
= N (p, ), since G was chosen to be an extensive quantity (it scales with size). For more than one
chemical species G = j Nj j .
dF = 0 for equilibrium, for constant P, .

j = chemical potential of species j, j = (G/Nj ),p .

P
Given i j Aj , e.g. H2 + Cl2 = 2HCl,
P
dG = ( j j j )dN where dNj = j dN
, dG = 0 P j j = 0.
j

Recall the mass action law derivation: assume constituents act as ideal gases; j = (ln nj ln cj ), nj concentration of
species j; cj nQj Zj (int).

X X X X Y
j ln nj = j ln cj = ln nj j = ln cj j = ln nj j = ln K( )
j j j j j

Y
nj j = K( ) mass action law
j

[ monomer][N mer] [1][N ]

(a) By mass action law, [(N +1)mer] = [N +1] = KN .

[1][1] [1]2 [1][2] [1]3

= K1 = = K1 K2
[2] [2] [3] [3]
j j+1 = [N + 1] = [1]N +1 /K1 K2 K3 . . . KN
[1]j+1 [1][j + 1] Y [1]j+2 Y
= Kl Kj+1 = = Kl
[j + 1] [j + 2] [j + 2]
l=1 l=1
Q
(b) Recall that K( ) = j nQjj exp [j Fj (int)/ ]
     
nQ (N )nQ (1) FN F1 FN +1 nQ (N )nQ (1) (FN + F1 FN +1 )
KN = exp exp = exp
nQ (N + 1) nQ (N + 1)

3/2
where nQ (N ) = M N
2~2 and MN is the mass of N mer molecules, FN is the free energy of one N mer molecule.
39
 (c) Assume N  1 so nQ (N ) ' nQ (N + 1). Assume [1] = 1020 cm3 . Assume F = FN +1 FN F1 = 0,
meaning zero free energy change in the basic reaction step. Were given the molecular weight of the monomer to be
200.
M1 3/2
We want [N[N+1]


] at room temperature. Now KN ' nQ (1) = 2~2 .
3/2 3/2
2~2
 
[1][N ] M1 [N + 1] [1]
= nQ (1) = or = = 1020 cm3
[N + 1] 2~2 [N ] nQ (1) M1
 2 3/2
2(6.5821022 M eV s)2

31010 cm/s
Note that 200(938M eV /c2 )(0.8617104 eV /K)(298 K) 1c = 0.3627 1027 cm.

[N + 1]
= = 3.627 108
[N ]
(d) We want the condition
 
[N + 1] [1] F nQ (1) F
1< = exp or ln <
[N ] nQ (1) [1]
[1]
= F < ln = 0.44 eV
nQ (1)

10. P HASE T RANSFORMATIONS

Vapor Pressure Equation.

Derivation of the Coexistence Curve p versus . Suppose g (p0 , 0 ) = l (p0 , 0 ) and g (p0 + dp, 0 + d ) = l (p0 +
dp, 0 + d )
       
g g l l
= g (p0 , 0 ) + dp + d + = l (p0 , 0 ) + dp + d + . . .
p p p p
   
l g

dp
= p  p
d g
p l


v V /N
s /N
   
1 G
=v=
N p N, p
   
1 G
= = s =
N N,p N p
sg sl related directly to quantity of heat that must be added to system to transfer 1 molecule reversibly from liquid to
gas, while temperature constant. (if heat isnt added to system from outside in the process, temperature will decrease when
molecule transferred to gas)
(21) L (sg sl )
latent heat of vaporization

(22) v = vg vl
change of volume when 1 molecule transferred from liquid to gas

dp L
(23) =
d v
is the Clausius-Clapeyron equation or vapor pressure equation.
Assumptions:
(a) if assume vg  vl , then v
= vg = Vg /Ng at p = 1 atm (at atmospheric pressure), vg /vl 103
(b) ideal gas law pVg = Ng = v = /p
40
 dp L d L
= 2 p or ln p = 2
d d
L latent heat per molecule
R dpheat L Rindependent
If latent
d
of temperature over temperature range of interest, L = L0
p = L0 2 whence ln p = L0 / + const or p( ) = p0 exp (L0 / )
L0
Consider , L0 , latent heat of vaporization of 1 molecule.
L0
Now compare it with RT ,
where R N0 kB gas constant.
1
N0 = 6.02205 1023 mol
23
kB = 1.38066 10 J/K (usual Boltzmann constant)
R = 8.31441 J/K mol
So for
L0 L0
=
RT N0 kB T
Then that implies
1 1 1
= 1
1 particle N0 1 particle mol
which implies that L0 now is the latent heat of vaporization of a mole (mol) of the gas.
Latent heat and enthalpy. crossing the coexistence curve,
d = dU + pdV (g l )dN
if liquid gas, l > g (or 0 > g l )
on coexistence curve, g = l
L = d()
= dU ()
+ pdV ()
= (dU + pdV )()
+ 0 = (dU + pdV )()
+ V dp() = Hg Hl
= dH()
where dp()
= 0 since is a path s.t. pressure p is constant.

Recall that H = U + pV .
dH = dU + pdV + V dp
Cp = = H



R p = (,R
p)()
= (dU (, p)() + pdV (, p)()) p
Then H = Cp d = Cp d
Example: Model system for gas-solid equilibrium (pp.285 Ch. 10 Phase transformations, Kittel and Kroemer (1980)
[1])
imagine solid of N atoms
each atom bound as harmonic oscillator of frequency
binding energy of each atom in ground state 0 , i.e. energy of atom in ground state is 0
energy of a single oscillator  = n~ 0 , n Z+
Zs partition function of a single oscillator in solid, 1/
X X e0
Zs = exp [(n~ 0 )] = 0 (e )n =
n n
1 e
Free energy Fs = Us s = ln Zs
Gibbs free energy in the solid, per atom
Gs = Us s + pvs = Fs + pVs = s
Supposing vs  vg (volume vs per atom in solid phase much smaller than volume vg per atom in gas phase)
s = Fs + pvs Fs
1
s := exp (s ) ' exp (Fs ) = exp ( ln Zs ) = = exp (0 )(1 exp ())
Zs
use ideal gas approximation to describe gas phase, and spin of atom to be 0. From Ch. 6,
3/2
p 2~2

n p
g = = =
nQ nQ M
gas in equilibrium with solid with g = s , or
 3/2
p M
= g = s = e0 (1 e ) = p = 5/2 exp (0 / )(1 exp (~/ ))
nQ 2~2
41
Van Der Waals Equation of State.
F (ideal gas) = N [ln (nQ /n) + 1]
N N
n := V = V N b (hardcore repulsion at short distances)
Mean Field Method. Let (r) := potential energy of interaction of 2 atoms separated by distance r.
average value of total interaction of all other atoms on atom at r = 0
Z Z
dV (r)n = n dV (r) = 2na (2 factor is convention)
0 b
excluded hardcore sphere of volume b from volume of integration.
assumed mean value of n, concentration n constant throughout volume accessible to gas molecules.
ignored increase of concentration in regions of strong attractive potential energy i.e.
mean field method meglects correlations between interacting molecules.
F ' U = 1 2 (2N na) = N a/V
2
1 1 2
where 2 N (N 1) ' 2 N (N large)

= F (vdW) = N (ln [nQ (V N b)/N ] + 1) N 2 a/V

N 2a N 2a
   
F N
p= = 2 or p + 2 (V N b) = N
V ,N V Nb V V
Critical Points for the Van der Waals Gas.
a
pc =
27b2
Vc = 3N b
8a
c =
27b
p
pb :=
pc
V
Vb :=
Vc

b :=
c
since
8 8 9
  
p 3 V 1 8
+ = = 8a =
pc (V /Vc )2 Vc 3 3c 3c 3 27b a/b
3a/27b2 N 2a 1 1 9
 
p 3 1 1
+ = (p + ) = (p + ) = a =
pc (V /Vc )2 pc V 2 /9N 2 b2 pc V2 pc Vc 27b 2 3N b a/b
 
V 1 1
= (V N b)
Vc 3 V0
   8
3 1 8 b 3
= pb + Vb = b or pb = 3 1
Vb 2 3 3 Vb 3 Vb 2
   2 
at pb = 1, Vb = 1, b = 1, b constant, Vbpb = 0, Vbpb2 =0
b b
Above c , no phase separation exists.
Gibbs Free Energy of the Van der Waals Gas. G = F + pV
NV 2N 2 a
G(, V, N ) = N (ln [nQ (V N b)/N ] + 1)
V Nb V
Recall dG = dN d + V dp
 
G
= = = (p, ) or G(N, p, ) = N (p, )
N ,p
cf. (9.13) of Kittel and Kroemer (1980) [1]
G(, p, N ) solved numerically.
on p-V diagram,
coexistence line: consider dG = d + V dp + dN
at constant , constant total Rnumber of particles, N ,
dG() = V dp() = Gg Gl = V dp
42
 R
if V dp = 0, Gp = Gl , Gg (, p) = Gl (, p), so g (, p) = l (, p) along horizontal coexistence line

Nucleation. Let = g l chemical potential difference between

vapor surrounding small liquid droplet and
liquid in bulk (infinitely large drop)
surface free energy of liquid drop is positive and tends to increase free energy of liquid
for small drop radii, surface can be dominant and drop can be unstable with respect to gas
nl concentration of molecules in liquid
 
4
G = Gl Gg = R3 nl + 4R2
3
where surface free energy per limit area.

dG 2
= 0 = 4R2 nl + 8R or Rc =
dR nl
Rc critical radius for nucleation
when R < Rc , G > 0, so drop will evaporate (to gas) spontaneously
when R > Rc , G < 0, drop will tend to grow spontaneously

16 3
(G)c = [ 2 ]
3 nl ()2
where (G)c = G(R = Rc )
assume vapor behaves like ideal gas:
 
p
= ln
peq
   
Eq. (12a), chemical potential of the ideal gas, = ln nnQ = ln ppeq
p vapor pressure in gas phase
peq equilibrium vapor pressure of bulk liquid (R )
erg 2 6
use = 72 cm 2 , p = 1.1peq , = 300 K (H2 O), Rc = n = 1 10 cm.
l

Problems. Problem 1. Entropy, energy, and enthalpy of van der Waals gas.
(a) Recall the generalized thermodynamic identity; starting with = (U, V, N ) C () = C ((U, V, N )), the
identity is dU = d pdV + dN .
By definition, F = U , so that
dF = dU d d = pdV + dN d
F


Then clearly, V,N
= .
Now
F (vdW) = N (ln [nQ (V N b)/N ] + 1) N 2 a/V
as was postulated about the hardcore repulsion inside a molecule, making V into V N b.
M 3/2


Remembering that quantum concentration does depend on : nQ 2~ 2

Consider
 3/2 !  3/2 ! !
M (V N b) 3 M (V N b)
3
ln ( ) + 1 = ln + ln + 1

2~2 N 2 2~2 N 2

Thus
         
F nQ (V N b) 3 nQ (V N b) 5
= =N
ln + 1 + N = N ln +

V,N N 2 N 2

(b) Recall that F := U or U = F + = F F 2 F

V,N = V,N

3 N 2a 3N N 2a
U = 2 (N ) + = + =U
2 V 2 V
43
 (c) Give to first order in the van der Waals correction terms a, b.

N N 2a N N 2a N Nb N 2a
p= 2 = 2 = (1 + ) 2
V Nb V V (1 N b/V ) V V V V
where N b  V .
Thus,
5 N 2 b 2N 2 a
H(, V ) := U + pV = N +
2 V V
Problem 2. Calculation of dT /dp for water
Using the Clausius-Clapeyron equation or vapor pressure equation,
dp L
=
d v
Vg
assume v := vg vl vg Ng (i.e. the volume of the gas is much bigger than the volume of the liquid), and pVg = Ng
Vg
or Ng = p (i.e. water vapor acts like an ideal gas)

L L
2
v p
Looking up fundamental constants and unit conversions manually appears, to me at least, in the 21st century, to be an obsolete
exercise (an exercise in insanity?). I would like to propose presenting the fundamental constants and unit conversions,
sourced from the NIST (National Institute of Standards and Technology) website, and using Python library pandas, as
panda dataframe objects, to make the data accessible and computable, and persisting them or databasing the values as panda
dataframe objects.
Open up thermo.py, which relies on the Physique repository (Ill put it up on my github, ernestyalumni).
N A = F u n d C o n s t [ F u n d C o n s t [ Q u a n t i t y ] . s t r . c o n t a i n s ( Avogadro ) ] . l o c [ 4 2 , : ]
k BOLTZ = F u n d C o n s t [ F u n d C o n s t [ Q u a n t i t y ] . s t r . c o n t a i n s ( B o l t z m a n n ) ] . l o c [ 4 9 , : ]
P frmATM = conv [ conv [ T o c o n v e r t f r o m ] . s t r . c o n t a i n s ( atm ) ] . l o c [ 1 5 , : ] # 1 atm t o P a s c a l c o n v e r s i o n f o r p r e s s u r e

...

## 2 . C a l c u l a t i o n o f $dT / dp$ f o r w a t e r

L = 2260 # J g{1}
b o i l i n g w a t e r t e m p K = KCconv . s u b s ( T C , 1 0 0 ) . r h s # room t e m p e r a t u r e i n K e l v i n
t a u b o i l i n g w a t e r = b o i l i n g w a t e r t e m p K k BOLTZ . V a l u e
P = 1 # atm

d p d t a u 1 0 0 2 = L 1 8 . 0 1 5 3 / f l o a t ( N A . V a l u e ) / ( t a u b o i l i n g w a t e r 2 )
dtaudp 1002 = 1 . / dpdtau 1002 # in J / Pascal
dTdp 1002 = d t a u d p 1 0 0 2 / ( k BOLTZ . V a l u e ) # 2 8 . 4 3 4 8 5 3 5 1 1 1 2 6 2 K / atm

dT
= 28.43K/atm
dp
Problem 3. Heat of vaporization of ice
Given
P (H2 O vapor)(T = 2 C) = 3.88 mm Hg
P (H2 O vapor)(T = 0 C) = 4.58 mm Hg
Use the Clausius-Clapeyron equation or vapor pressure equation (for coexistence equilibrium).

dp L L
= 2
d v /p
dp p p(2 ) p(1 )
with =
d 2 1
N
Now idealizing water vapor as a perfect ideal gas, p = V , so p linear in , i.e. p = p( ).
Note that while p is linear in , the given temperature values correspond to T , in K, and so one would need this form of
the slope equation y = mx + b, where m = N V times a bunch of conversion factors, and one must also include a nonzero b
constant, the result of choice of units (celsius versus energy units).
dp 2
Thus, L = d p , with L being the latent heat of vaporization per particle.
particles
Note, I treat Avogadros number as a units conversion, 1 = NA = 6.02205 1023 mol . So in the end, for the desired
J/mol, multiply L by NA , LNA .
44
L1003 = ( 4 . 5 8 3 . 8 8 ) / ( 0 ( 2.) ) ( ( KCconv . s u b s ( T C , 1 . ) . r h s ) 2 ) / ( ( 4 . 5 8 3 . 8 8 ) / ( 0 ( 2)) ( 1 . ) + 3 . 8 8 )
k BOLTZ . V a l u e N A . V a l u e # 5 1 7 0 5 . 6 7 5 7 6 4 0 4 8 5

L = 5.17 104 J/mol

Problem 4. Gas-solid equilibrium
(a) Lets review the quantum harmonic oscillator (qho).
Recall the Hamiltonian in d dimensions
2
b = pb + 1 m 2 x
H b2
2m 2

where pb = i x i ei .

Suppose for the Hilbert space H, that H = Hx1 Hx2 Hx3 ,

|i H = Hx1 Hx2 Hx3 = |i = |x1 i |x2 i |x3 i |x1 i|x2 i|x3 i
Now
d  2 !  2 !
X 1 1 1 1
H|i
b = + m 2 (b
xi )2 |i + m 2 (b
xi )2 |i
i=1
2m xi 2 2m xi 2

The ladder operators make it much more simpler and straightforward than directly solving the differential equation.
Let
r   r
m i 1
ai = bi +
x pbi x i
b = (ai + ai )
2 m 2m
r   r
m i m
ai = bi
x pbi pbi = i (ai ai )
2 m 2
Now let
m pi )2
(b 1
Ni = ai ai = xi )2 +
((b 2
)
2 (m) 2
where the uncertainty principle commutator relation was used:
bi pbi pbi x
x bi = [b
xi , pbi ] = i
Thus
b = (N1 + 1 ) + (N2 + 1 ) + (N3 + 1 )
H
2 2 2
1 1 1
H|i
b = ((nx + ) + (ny + ) + (nz + ))|i
2 2 2
Consider
  !d  d
X 1 1 1 X 1
Zs = exp ((nx + ) + (ny + ) + (nz + ) 0 ) = e0 (e )n =e 0

nx ,ny ,nz
2 2 2 n
1 e

The derivation of p = p( ) goes, as above (with Example: Model system for gas-solid equilibrium (pp.285 Ch.
10 Phase transformations, Kittel and Kroemer (1980) [1])); recall
n p
g = s , g = =
nQ nQ
and so for  ~ or 1  ,
 3/2  3/2
M 5/2 0 d M 1 5/2 0 d d
p= 2
e (1 e ) = e
2~ 2 ~3
For d = 3,
3/2
3 0

M
p= e
2 1/2
45
 (b) From above part (a),  
dp 1 1 1 1
= + (0 )
d p 2 2
Now using the approximation that v vg , and the ideal gas idealization,
dp 2
L= = 0
d p 2
My explanation: we must excite the atom by its (bounded) ground state energy, 0 . On the other hand, thermal energy
of gas, with increasing linear temperature, helps to remove atom from solid to gas.
Problem 5. Gas-solid equilibrium
(a) Now
Z Ns
Fs = ln s = (Ns ln Zs ln Ns !) ' (Ns ln Zs Ns ln Ns + Ns )
Ns !
where Stirlings approximation was used and (1/Ns !) factor is for indistinguishability (from quantum mechanics).
Recall
e0
Zs = so ln Zs = 0 d ln (1 e )
(1 e )d
from Example: Model system for gas-solid equilibrium (pp.285 Ch. 10 Phase transformations, Kittel and Kroemer
(1980) [1]).
Then
(24) Fs = Ns 0 + Ns d ln (1 e ) + Ns ln Ns Ns
Recall this useful relation (its easy to calculate from Helmholtz free energy F ):
 
F
=
V
and so
   
Fs 1 1
= Ns d ln (1 e/ ) + Ns ln Ns Ns + Ns d (e
)() =
1 e
(25)
e
= Ns d ln (1 e ) + Ns ln Ns Ns Ns d =
1 e
Suppose  or 1  . Then = Ns d ln (1 e ) + Ns ln Ns Ns (1 + d).
So take the (given) extreme assumption that the entropy of the solid maybe neglected over the temperature range
of interest. [1]
Then comparing from Eq. 25 and Fs from Eq. 24, then
Fs ' Ns 0

   
Ng
F = Fs + Fg = Ns 0 + N ln 1
V nQ
(b) Now      
Ng Ng
F = Ns 0 + Ng [ln 1] = 0 (N Ng ) + Ng ln 1
V nQ V nQ
Now, taking the partial derivative,
   
F Ng 1
= 0 + ln 1 + Ng
Ng V nQ Ng
Taking the minimum free energy with respect to Ng , i.e. set the partial derivative to 0,
   
F Ng 0
= 0 = 0 + ln or Ng = nQ V exp
Ng V nQ
(c) Idealize the gas with the ideal gas law.
   3/2  
0 M 5/2 0
pV = Ng = pg = nQ exp = exp = pg
2~2
46
 11. B INARY M IXTURES
12. C RYOGENICS
13. S EMICONDUCTOR S TATISTICS
14. K INETIC T HEORY
Kinetic Theory of the Ideal Gas Law. Consider molecule strike unit area of wall.
Let vz velocity component normal to plane of wall.
Suppose molecules, of mass M , reflected specularly (mirror-like) from wall,
pz = 2M |vz |
Let a(vz )dvz , number of molecules per unit volume with z-component of velocity between vz and vz + dvz .
Z
N
a(vz )dvz = =n
V
a(vz )vz dvz number of molecules in (vz , vz + dvz ) velocity range that strike unit area of wall in (per) unit time
Z Z
pressure p = 2M vz a(vz )vz dvz = M vz2 a(vz )dvz = M nhvz2 i
0
1 2 1
2 M hvz i = 2 by equipartition of energy (Ch.3)
N
p = nM hvz2 i = n =
V

Maxwell Distribution of Velocities. cf. Ch.6. distribution function of ideal gas f (n ) = exp  n

Recall, Ch. 6, Sec. Classical Limit of Kittel and Kroemer [1], an ideal gas is defined as a system of free noninteracting
particles in the classical regime.
f () average occupancy of an orbital at energy 
 energy of orbital occupied by 1 particle; not energy of system of N particles
1
Fermi-Dirac and Bose-Einstein distribution f () = exp [()/ ]1
In order for f ()  1 orbitals, exp [( )/ ]  1 .

= f () ' exp [( )/ ] = exp (/ ) exp

f (), average occupancy of orbital of energy , is classical distribution function.
n 2
1

1 1

2 1 2
particle in a box: n = 2M L (for, recall 2M i = 2M = E)
number of orbitals in range of quantum number (n, n + dn), probability such orbital is occupied

1 1
( n2 dn)f (n ) = n2 exp (n / )dn
2 2
1 1  n 2 (M L)2 2 M Lv
M v2 = or n2 = v or n =
2 2M L 2
Consider system of N particles in volume V .
Let N P (v)dv number of atoms with velocity magnitude in range dv at v
3
M v 2
  
1 dn 1 ML
N P (v)dv = n2 exp (n / ) dv = v 2 exp dv
2 dv 2 2
 2 3/2
cf. Ch. 6, = nnQ = LN3 2~
M

 3/2  3  3/2
1 N 2 ML N
= 4N
2 L3 M 2
3/2
M v 2
  
M 2
(26) = P (v) = 4 v exp
2 2
P (v) is Maxwell velocity distribution, P (v)dv is probability particle has speed in dv at v
47
Experimental verification. velocity distribution of atoms which exit from slit of oven.
exit beam weighted in favor of atoms of high velocity at expense of those at low velocity.
weight factor is velocity component v cos normal to plane of hole.
/2
2R3 cos 2 
Z Z Z 
1 2 3 sin 2d
(cos )drrdr sin d = ( (2)R3 ) cos sin d = ( R ) = =
3 3 2 3 4 
0
2R3 1 + 1 2R3 1
   
= =
3 4 3 2
Probability atom leaves hole will have velocity in (v, v + dv) : Pbeam (v)dv

M v 2
 
Pbeam (v) vPMaxwell v 3 exp
2
3/2
 2

M
v 2 exp M v


with, recall PMaxwell = 4 2 2
Pbeam distribution of transmission through a hole is Maxwell transmission distribution.

/2 3/2 Z   
M 2
Z Z
M 1
hvout i = v cos sin dPMaxwell (v)dv = 4 v 3 exp v dv =
0 2 2 0 2
3/2 3/2  2 
21/2  1/2
    
M 1 1 1 M 1 4
= 4 0 = 4 2
= 1/2
2 2 2 2 4 M M
for (doing the integration by hand)
2 2
(ev )0 = 2vev
2 2 2
(v 2 ev )0 = 2v 3 ev + 2vev
2
2 ev 0 2
(v 2 ev + ) = 2v 3 ev

Particle Diffusion. pp. 399 of Kittel and Kroemer [1]
Consider a system.
One end in diffusive contact with reservoir at chemical potential 1
Other end in diffusive contact with reservoir at chemical potential 2
Constant temperature .
If 1 > 2 , particle flow through system from reservoir 1 to reservoir 2; 1 2.
ni particle concentration in i
Take
(27) jn = Dgradn
which is Ficks law, and where D particle diffusion constant or diffusivity.
Mean free path l. Particles freely travel over l.
Assume in a collision at z, particles come into local equilibrium at local chemical potential (z), local concentration n(z).
1
At z, particle flux density in positive z direction 2 n(z lz )cz
particle flux density in negative z direction 12 n(z + lz )cz
Note n(z lz ) is particle concentration at z lz
1 dn
Jnz = [n(z lz ) n(z + lz )] cz = cz lz
2 dz

where cz = c cos
lz = l cos
R /2 R 2
cos2 dS
R
hemisphere 0
d 0 d cos2 sin d 1
hcz lz i = cl R = cl R /2 R 2 = cl
hemisphere
dS d sin 0 d 3
0
Comparing with Ficks law,
1 dn 1
Jnz = cl or JN = cln
3 dz 3
For diffusivity D is then D = 31 cl.
48
Now recall that l, the mean free path, was derived from kinetic theory:
1
l=
nd2
where d is the diameter of the particle.
The mean thermal velocity was derived from the Maxwell distribution:
 1/2
8
c=
M
Problems. Problem 1. Mean speeds in a Maxwellian distribution.
 
M 3/2 2 v2
v exp M


(a) P (v) = 4 2 2
Now
Z Z  0 Z
exp (v 2 ) 2
Z
4 2 3 2 exp (v ) 3 2
dvv exp (v ) = v = 0 3v = v exp (v 2 ) =
0 0 2 2 0 2
2
!0 " Z v2 #
ev
Z
3 3 e 3
= v = 0 =
2 2 2 2 42 2
So
Z  3/2
2 2 M 3 1 3 1 3
hv i = v P (v) = 4 = M =
M 2

q
0 2 4 2 M 2 2
2 M
2
so
 1/2
3
vrms =
M
Now  1/2
3
hv 2 i = 3hvx2 i = so hvx2 i1/2 =
M M
(b)
    r
P (v) 2P (v) M 2 M 2
= + P (v) v = P (v) v = 0 if vmp = 0 or vmp =
v v v M
where mp stands for most probable.
r r
2 3
vmp = < = vrms
M M
(c)
3/2 3/2 Z M v2
!0

M v 2 e 2
Z Z    
M 3 M 2
c= dvvP (v) =: hvi = dv4 v exp = 4 dvv M
=
0 0 2 2 2 0
3/2 " Z M v2
# 3/2 " M v2
! # 3/2 2
e 2 2 e 2
  
M M  M 2
= 4 0 dv2v M = 4 = 4 =

2 2 M M 
2 M2
0 
0
r r
1 8
= 3/2
8 =
(2) M M
Note
3 1/2 1/2


vrms M 3
= =
c 8 1/2 8


M
(d) |vz | = |v cos | = v| cos |. For for a fixed , v cos is 1 point on a sphere, whereas v| cos | could be 2 pts on a
sphere.
Now
Z Z /2 Z Z /2 Z
sin 2d sin 2d
| cos | sin d = cos sin d + cos sin d = + =
0 0 /2 0 2 /2 2
 /2  
cos 2d  cos 2  1 1+1
= + = + =1
4 
0 4 
/2 2 4
49
 P (v)dv is probability that particle has speed or velocity magnitude in (v, v + dv).
R /2
It counts the event of v cos and v cos ( ), so it counts v| cos | twice. P (v)dv = 0 d2P (v| cos |)
Z Z  1/2
P (v)dv 2
= cz = h|vz |i = h|v cos |i = hv| cos |i = v | cos |d =
0 0 2 M
15. P ROPAGATION
Heat Conduction Equation. nonrelativistic case:
Let manifold N = R M , with dimM = n.
Let J X(N ) = X(R M ) be a vector field in N .

Let C (N ) be a smooth function on N .
= (t, x) locally
Let J 1 (N ) be a 1-form on N that is isomorphic to J (Tangent-Cotangent isomorphism theorem), i.e.
J = J[
Ji = gij Jj
with gij being the metric on N (not just M !)
Note that as N = R M , g0j = 0j
The local form of J is the following:

J= + ji i i = 1...n
t x
So
J = Ji dxi = gij Jj dxi = dt + jk dxk k = 1...n
Thus
(28) J = dt + jk dxk k = 1...n
Now do the Hodge star operator, resulting in a n-form
J n (N )
and so
J = dt + jk dxk = voln + ij voln+1
as
g 0
dt =  dxi dxin i1 . . . in {1 . . . n}
n! i1 ...in 1
g
jk dxk = gkl j l k dxi1 dxin = ij voln+1
(n + 1)! i1 ...in
so thus
J = voln + ij voln+1
Hence
1 1
(29) dJ = ( g) voln+1 + ( gjk ) voln+1 = d(voln ) + dij voln+1
t g xk g

g
Special case: t =0
 
n+1 jk
dJ = vol + k
ln g jk voln+1 + voln+1 = 0
t x xk
 
jk
= + ln g jk + =0
t xk xk

Special case: if g constant, jk
t + xk = 0
i
Let j Dd (j is a closed form on M ) where d = xi dx i = 1 . . . n, D constant

d J = dvoln + Dd d = 0

For flat metric, g constant,
2
=D
t (xk )2
For relativistic case,
50
Consider manifold M , with dimension dimM = n + 1

J= + ji i
t x
Let J = J[ . J = g J
For special case of flat Minkowski space,
J = dt + ji dxi

J = dt + ji dxi

g g
0i1 ...in dxi1 dxin + ji i dx1 dxn
(n + 1)! (n + 1)! 1 ...n

( g) 1 (ji g) 1
dJ = voln+1 + voln+1 = 0
t g xi g

( g) (ji g)
= + =0
t xi

Fick law (14.19) for particle flux density, j = Dn dn where Dn particle diffusivity constant
n particle concentration
J = ndt + j
thermal conductivity; homogeneous medium C heat capacity per unit volume. ju = Kd
b
J = C
b dt + ju

(30) b + (ju )k = 0
C (5)
t xk

2
(31) = D D K/C
b (6)
t (xk )2

Propagation of Sound Waves in Gases. pressure associated with sound wave

(32) p = p0 exp [i(kx t)] (27)

Suppose ideal gas:
(33) pV = N or p = /M (28)
Consider solid ball or billiard ball particle (extended particle, not pt. particle, but no internal structure)
NM
=
V
Force on particle
Z Z Z
dP d M M u
F = = voln u = L +u u = + [u, u]
dt dt V t V t
Suppose [u, u] = 0 (certainly for flat spaces; what about for curved spaces? [u, u] 6= 0? Possibly? I dont know. EY:
20150317

(34) dU + pdV = d
define fractional deviations s,

= 0 (1 + s)
(35) (5)
= 0 (1 + )
where 0 , 0 are density and temperature in absence of sound wave.
assume u, s, have form of traveling exp [i(kx t)]
51
    
k k
(36) u s =0 (39)
M M
(37) s ku = 0 (40)
(38) bV ps = 0 or C
C bV ns = 0 (41)

 
k n
u = 1+ s
M C
bV
 
k n k
= 1+
M CV
b
So
 1/2
(39) = k (42)
M

C
bV + n Cbp
= =
C
bV CbV
 1/2

vs = =
k M

Problems. Problem 1. Fourier analysis of pulse

t=0

Z
1
(40) (x, 0) = (x) = dk exp (ikx) (58)
2

Z
1
(41) (x, t) = dk exp [i(kx t)] (59)
2

Given a dispersion relation at this form:

(42) Dk 2 = i (10)

Z
1
(43) (x, t) = dk exp [ikx Dk 2 t] (60)
2

and so, doing the Gaussian integral,

x2
 
1
(44) (x, t) = exp (14)
4Dt 4Dt
Problem Diffusion in two and three dimensions.
(a)
2 2 r 2 2
= +
t t 4 Dt2
2
2 1 2 1 2 1 2
= + (x2 + y 2 )
(xi )2 2 Dt 2 Dt 4 D2 t2

2 2 2
= =D
t (xi )2
(b)
(c)
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 R EFERENCES
[1] Charles Kittel, Herbert Kroemer, Thermal Physics, W. H. Freeman; Second Edition edition, 1980. ISBN-13: 978-0716710882
[2] Bernard F. Schutz, Geometrical Methods of Mathematical Physics, Cambridge University Press, 1980. ISBN-13: 978-0521298872
[3] Paul Bamberg and Shlomo Sternberg, A Course in Mathematics for students of physics: 2, Cambridge University Press, 1990.
[4] T. Frankel, The Geometry of Physics, Cambridge University Press, Second Edition, 2004.
[5] Ed Groth. Physics 301, Thermal Physics, Fall 1999, Fall 2002, Fall 2003, Fall 2004, Fall 2005, http://grothserver.princeton.edu/
groth/phys301f99/
There is a Third Edition of T. Frankels The Geometry of Physics [4], but I dont have the funds to purchase the book (about
$ 71 US dollars, with sales tax). It would be nice to have the hardcopy text to see new updates and to use for research, as the
second edition allowed me to formulate fluid mechanics and elasticity in a covariant manner. Please help me out and donate
at ernestyalumni.tilt.com.
E-mail address: ernestyalumni@gmail.com
URL: http://ernestyalumni.wordpress.com

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