Chapter 9 Problem Solutions

1. At what temperature would one in a thousand of the atoms in a gas of atomic hydrogen be
in the n=2 energy level?
【sol】
g(ε 2 ) = 8, g (ε1 ) = 2
n(ε 2 ) 1
Then, = = 4 e −(ε2 −ε1)/kT = 4 e 3ε1 /kT
n(ε1 ) 1000
 1  (3/ 4)(−ε 1 ) (3/ 4)(13. 6 eV )
T =  = −
= 1.43 × 10 4 K
 k  ln 4000 (8.62 × 10 eV/K )(ln 4000 )
5

where ε 2 = ε1 / 4, and ε1 = − 13.6 eV

3. The 3 2Pl/2 first excited sate in sodium is 2.093 eV above the 3 2S1/2 ground state. Find the ratio
between the numbers of atoms in each state in sodium vapor at l200 K. (see Example 7.6.)

【sol】
multiplicity of P-level : 2L+1=3, multiplicity of S-level : 1
The ratio of the numbers of atoms in the states is then,
 3  2.09 eV 
  exp  −  = 4.86 × 10 − 9
 1  (8.62 × 10 − 5 eV/K )(1200 K ) 
 

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 5. The moment of inertia of the H2 molecule is 4.64×10-48 kg·m2. (a) Find the relative popula-
tions of the J=0,1,2,3, and 4 rotational states at 300 K. (b) can the populations of the J=2 and
J=3 states ever be equal? If so, at what temperature does this occur?
【sol】
J (J + 1)h 2
(a) g (J ) = 2J + 1, εJ = ε J =0 = 0
2I J ( J +1)
N (J )  J (J + 1)h 2    2 
= (2J + 1) exp −  = ( 2J + 1) exp − h 
N (J = 0 )  2IkT  
 2IkT


 
J ( J +1)
  (1.06 × 10 −34 J ⋅ s)2 
= (2J + 1) exp − − 48 − 23


  2( 4 .64 × 10 kg ⋅ m 2
)(1 .38 × 10 J/K )( 300 K )  
= (2J + 1)[0. 749]J ( J +1)

Applying this expression to J=0, 1, 2, 3, and 4 gives, respectively, 1 exactly, 1.68, 0.880, 0.217,
and 0.0275.
(b) Introduce the dimensionless parameter . Then, for the populations of the J=2 and J=3 states
to be equal,
5 5
5x 6 = 7x 12 , x6 = and 6 ln x = ln
7 7
Using , ln x = − h 2 / 2IkT and ln ( 5/7 ) = - ln ( 7/5) and solving for T,

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 6h2
T =
2Ik ln(7 / 5)
6(1.05 × 10 − 34 J ⋅ s)2
= − 48 − 23
= 1.55 × 10 3 K
2( 4.64 × 10 kg ⋅ m )(1.38 × 10
2
J/K) ln(1.4)

7. Find v and vrms for an assembly of two molecules, one with a speed of 1.00 m/s and
the other with a speed of 3.00 m/s.
【sol】
v = 12 (1.00 + 3.00) = 2.00 (m/s)

vrms = 1 [1.00 2
2
+ 3.00 2 ] = 2 .24 (m/s)

9. At what temperature will the average molecular kinetic energy in gaseous hydrogen equal
the binding energy of a hydrogen atom?
【sol】
For a monatomic hydrogen, the kinetic energy is all translational and KE = 32 kT
solving for T with KE = − E1
2  E1  (2 / 3)(13.6 eV)
T = −  = = 1 .05 × 10 5
K
3  k  (8.62 × 10− 5 eV/K)

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 11. Find the width due to the Doppler effect of the 656.3-nm spectral line emitted by a gas of
atomic hydrogen at 500 K.
【sol】
For nonrelativistic atoms, the shift in wavelength will be between +λ(v/c) and -λ(v/c) and
the width of the Doppler-broadened line will be 2λ(v/c). Using the rms speed
from KE=(3/2)kT = (1/2)mv2, v = 3kT /m , and
3kT /m
∆λ = 2λ
c
−9 3(1.38 × 10−23 J/K)(500 K)/(1.67 × 10−27 kg)
= 2(656.3 × 10 m)
3.0 × 108 m/s
= 1.54 × 10−11 m = 15.4 pm
13. Verify that the average value of 1/v for an ideal-gas molecule is 2m /πkT .
∞ 2
[Note : ∫0 ve −av dv = 1/( 2a )]
【sol】 1 1 ∞1
N ∫0 v
= n (v )dv
The average value of 1/v is v
3/ 2
1  m  ∞ − mv 2 / 2kT
= 4πN   ∫ ve dv
N  2πkT  0

3/ 2
= 4π 
m   kT  = 2m 1
   =2
 2πkT  m  πkT <v >

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 17. How many independent standing waves with wavelengths between 95 and 10.5 mm can
occur in a cubical cavity 1 m on a side? How many with wavelengths between 99.5 and 100.5
mm? (Hint: First show that g(λ)dλ = 8πL3 dλ/λ4.)
【sol】
The number of standing waves in the cavity is
8πL3ν 2
g(ν )dν = dν
c3 2
8πL3  c  c 8πL3
g ( λ)dλ = g (ν)dν =   dλ = dλ
c 3  λ  λ2 λ4
Therefore the number of standing waves between 9.5mm and 10.5mm is
8π (1 m)3
g( λ )dλ = 4
(1.0 mm ) = 2.5 × 10 6
(10 mm )
Similarly, the number of waves between99.5mm and 100.5mm is 2.5x102, lower by a
factor of 104.

l9. A thermograph measures the rate at which each small portion of a persons skin emits
infrared radiation. To verify that a small difference in skin temperature means a significant
difference in radiation rate, find the percentage difference between the total radiation from skin
at 34o and at 35oC.

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 【sol】
By the Stefan-Boltzmann law, the total energy density is proportional to the fourth power of
the absolute temperature of the cavity walls, as
R = σT 4
The percentage difference is
4
σT14 − σT 24 T14 − T 24 T   307 K 
= = 1 −  2  = 1 −   = 0.013 = 1. 3%
σT14 T14 T
 1  308 K 
For temperature variations this small, the fractional variation may be approximated by
∆ R ∆(T 4 ) 3T 3∆T ∆T 1K
= = = 3 = 3 = 0.013
R T4 T4 T 308 K
21. At what rate would solar energy arrive at the earth if the solar surface had a temperature
10 percent lower than it is?
【sol】
Lowering the Kelvin temperature by a given fraction will lower the radiation by a factor
equal to the fourth power of the ratio of the temperatures. Using 1.4 kW/m2 as the rate at
which the sun’s energy arrives at the surface of the earth
(1.4 kW/m 2 )(0.90)4 = 0.92 kW/m 2 (= 66%)

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 23. An object is at a temperature of 400oC. At what temperature would it radiate energy twice as
fast?
【sol】
To radiate at twice the radiate, the fourth power of the Kelvin temperature would need to double.
Thus, 2[( 400 + 273) K]4 = T 4 T = 673 × 21/ 4 K = 800 K(527 o C)

25. At what rate does radiation escape from a hole l0 cm2 in area in the wall of a furnace
whose interior is at 700oC?
【sol】
The power radiated per unit area with unit emissivity in the wall is P=σT4. Then the
power radiated for the hole in the wall is
P ' = σT 4 A = (5.67 × 10−8 W/(m 2 ⋅ K 4 ))( 973 K )4 (10 × 10− 4 m 2 ) = 51 W

27. Find the surface area of a blackbody that radiates 100 kW when its temperature is 500oC. If
the blackbody is a sphere, what is its radius?
【sol】
The radiated power of the blackbody (assuming unit emissivity) is
P 100 × 103 W
P = Ae σT 4
A= =
eσT 4 (1)(5.67 × 10−8 W/(m 2 ⋅ K 4 ))((500 + 273)K )4
= 4. 94 × 10− 2 m 2 = 494 cm2

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 The radius of a sphere with this surface area is, then,
A = 4πr 2 r = A / 4π = 6.27 cm

31. The brightest part of the spectrum of the star Sirius is located at a wavelength of about 290
nm. What is the surface temperature of Sirius?
【sol】
From the Wien’s displacement law, the surface temperature of Sirius is
2.898 × 10− 3 m ⋅ K 2.898 × 10− 3 m ⋅ K
T = = −
= 1.0 × 104 K
λmax 290 × 10 m9

33. A gas cloud in our galaxy emits radiation at a rate of 1.0x1027 W. The radiation has its
maximum intensity at a wavelength of 10 µm. If the cloud is spherical and radiates like a
blackbody, find its surface temperature and its diameter.
【sol】
From the Wien’s displacement law, the surface temperature of cloud is
2.898 × 10 − 3 m ⋅ K
T = = 2 .9 × 10 2
K = 290 K = 17 o
C
10 × 10 m-6
P P
Assuming unit emissivity, the radiation rate is R = σT 4 = =
A πD 2
where D is the cloud’s diameter. Solving for D,
1 /2
P  1.0 × 10 27 W 
D= =  
4
= 8.9 × 1011 m
πσT 4
 π (5.67 × 10 -8
W/m 2
⋅ K 4
)( 290 K ) 

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 35. Find the specific heat at constant volume of 1.00 cm3 of radiation in thermal equilibrium at
1000 K.
【sol】
The total energy(U) is related to the energy density by U=Vu, where V is the volume.
In terms of temperature,
U = Vu = VaT 4 = V 4σ T 4
c
The specific heat at constant volume is then
∂U 16σ 3
cV = = T V
∂T c
16( 5.67 × 10 − 8 W/m 2 ⋅ K 4 ) −6 3
= (1000 K )3
(1 . 0 × 10 m )
2 .998 × 108 m/s
= 3 .03 × 10 −12 J/K
37. Show that the median energy in a free-electron gas at T=0 is equal to ε F/22/3 =0.630εF.
【sol】
At T=0, all states with energy less than the Fermi energy εF are occupied, and all states with
energy above the Fermi energy are empty. For 0≤ε≤εF, the electron energy distribution is
proportional to ε . The median energy is that energy for which there are many occupied
states below the median as there are above. The median energy εM is then the energy such that
εM 1 εF
∫0 ε dε = ∫
2 0
ε dε

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 Evaluating the integrals,
2 (ε )3/ 2 = 13 (ε F )3/ 2 , or ε M = ( 12 )3/ 2 ε F = 0.63 ε F
3 M

39. The Fermi energy in silver is 5.51 eV. (a)What is the average energy of the free electrons in
silver at O K? (b)What temperature is necessary for the average molecular energy in an ideal
gas to have this value? (c)What is the speed of an electron with this energy?
【sol】
(a) The average energy at T=0 K is ε 0 = 35 ε F = 3. 31 eV

(b) Setting (3/2)kT=(3/5)εF and solving for T,

2 εF 2 5.51 eV
T = = = 2.56 × 104 K
5 k 5 8.62 × 10 eV/K
- 5
(c) The speed in terms of the kinetic energy is
2KE 6ε F 6(5.51 eV )(1.602 × 10−19 J/eV )
v = = = − 31
= 1.08 × 10 6 m/s
m 5m 5(9.11 × 10 kg)

43. Show that, if the average occupancy of a state of energy εF+∆ε is fl at any temperature, then
the average occupancy of a state of energy εF-∆ε is f2=1-f1. (This is the reason for the symmetry
of the curves in Fig.9.10 about εF.)

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 【sol】
Using the Fermi-Dirac distribution function
1 1
f 1 = f FD (ε F + ∆ε ) = f 2 = f FD (ε F − ∆ε ) =
e ∆ε /kT + 1 e − ∆ε /kT + 1
1 1 1 e ∆ε /kT
f1 + f 2 = ∆ε /kT + − ∆ε /kT = ∆ε /kT + ∆ε /kT =1
e +1 e +1 e +1 e +1
45. The density of zinc is 7.l3 g/cm3 and its atomic mass is 65.4 u. The electronic structure of zinc
is given in Table 7.4, and the effective mass of an electron in zinc is 0.85 me. Calculate the Fermi
energy in zinc.
【sol】
Zinc in its ground state has two electrons in 4 s subshell and completely filled K, L, and M shells.
Thus, there are two free electrons per atom. The number of atoms per unit volume is the ratio of
the mass density ρZn to the mass per atom mZn . Then,
2 /3
h2  3( 2) ρ Zn 
εF =  
2m *  8π mZn 
2 /3
 (6.626 × 10 −34 J ⋅ s)2  3(2)(7.13 × 103 kg/m 3 ) 
=  



 2(0.85)(9. 11 × 10 kg)  8π (65.4u)(1.66 × 10 kg/u ) 
- 31 - 27

= 1.78 × 10−18 J = 11 eV

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47. Find the number of electron states per electronvolt at ε=εF/2 in a 1.00-g sample of copper at O K.
Are we justified in considering the electron energy distribution as continuous in a metal?
【sol】
3N
At T=0, the electron distribution n(ε) is n (ε ) = (ε F )− 3 /2 ε
2
At ε=εF/2, ( )
n ε2F =
3 N
8 εF
The number of atoms is the mass divided by the mass per atom,
(1.00 × 10− 3 kg)
N = = 9 . 48 × 10 21
( 63.55 u)(1.66 × 10− 27 kg/u )
with the atomic mass of copper from the front endpapers and εF =7.04 eV. The number of
states per electronvolt is
 εF  3 9.48 × 1021
n  = = 1.43 × 1021 states/eV
 2  8 7.04 eV
and the distribution may certainly be considered to be continuous.

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 49. The Bose-Einstein and Fermi-Dirac distribution functions both reduce to the Maxwell-
Boltzmann function when eαeε/kT>>1. For energies in the neighborhood of kT, this
approximation holds if eα>>1. Helium atoms have spin 0 and so obey Bose-Einstein statistics
verify that f(ε)=1/eαeε/kT≈Ae-ε/kT is valid for He at STP (20oC and atmospheric pressure, when
the volume of 1 kmol of any gas is=22.4 m3) by showing that of A<< l under these circumstances.
To do this, use Eq(9.55) for g(ε)dε with a coefficient of 4 instead of 8 since a He atom does not
have the two spin states of an electron, and employing the approximation, find A from the
norma1ization condition n(ε)dε=N, where N is the total number of atoms in the sample. (A
kilomole of He contains Avogadro’s number No atoms, the atomic mass of He is 4.00 u and
∞
∫0 x e −αx dx = π / a / 2a

【sol】
Using the approximation f(ε)=Ae-ε/kT, and a factor of 4 instead of 8 in Equation (9.55),
Equation (9.57) becomes
Vm 3/ 2 − ε /kT
n(ε )dε = g (ε ) f (ε )dε = A 4 2π ε e dε
h3
Integrating over all energies,

∞ Vm 3 / 2 ∞
N = ∫ n (ε )dε = A 4 2π ∫ ε e − ε /kT d ε
0
h3 0

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 .The integral is that given in the problem with x= ε and a=kT,
∞ −ε /kT π (kT )3
∫0
εe dε = , so that
2

Vm 3/2 π(kT )3 V 3/ 2
N = A4 2π = A ( 2πmkT )
h3 2 h3
Solving for A,
N 3
A= h ( 2πmkT )− 3/ 2
V
Using the given numerical values,
6.022 × 1026 kmol −1
A= (6.626 ×10− 34 J ⋅ s ) 3 × [ 2π( 4.00 u)(1.66 ×10 − 27 kg/u)(1.38 1× 10-23 J/K )( 293K )]− 3 / 2
22.4 kg/kmol
= 3.56 ×10 −6 ,

which is much less than one.

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 51. The Fermi-Dirac distribution function for the free electrons in a metal cannot be
approximated by the Maxwell-Boltzmann function at STP for energies in the neighborhood of
kT. Verify this by using the method of Exercise 49 to show that A>1 in copper if
f(ε)≈Aexp(ε/kT). As calculated in Sec. 9.9 N/V=8.48x1028 electrons/m3 for copper. Note that
Eq.(9.55) must be used unchanged here.
【sol】
Here, the original factor of 8 must be retained, with the result that
1N 3
A= h ( 2πm ekT ) − 3 / 2
2V
= 12 (8.48 × 1026 m −3 )( 6.63 ×10 −34 J ⋅ s ) 3 × [ 2π(9.11 ×10 −31 )(1.38 ×10 −23 J/K )( 293 K)]− 3 / 2
= 3.50 ×103 ,
Which is much greater than one, and so the Fermi-Dirac distribution cannot be approximated
by a Maxwell-Boltzmann distribution.

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