Chapter 0
Introduction and orientation
All the following material P.W. Atkins and R.S. Friedman.
Exercises
0.1 Use E h; h 6.626 1034 J s; 1/T [T: period]
(a) E (6.626 1034 J s)/(1.0 1015 s) 6.626 1019 J
(b) E h/(1.0 1014 s) 6.626 1020 J
(c) E h/(1.0 s) 6.626 1034 J
0.2 Use Wiens law: maxT const.; const. hc/5k [Problem 0.1] 2.878 mm K [End paper 1
of text]. Hence
T (2.878 mm K)/(480 109 m) 6 103 K
0.3 Use the Law of Dulong and Petit (Section 0.2):
molar heat capacity = 25 J K1 mole1 = specific heat capacity molar mass
The molar mass is therefore 25 J K1 mole1/0.91 J K1 g1 = 27 g mol1
and the metal is Al.
0.4 The energy of 1.00 mol of photons is given by
E = (hc/) 6.02214 1023 photons/mole
giving (a) 2.3 105 J, (b) 1.20 103 J, (c) 9.2 108 J.
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0.5
Use eqn 0.10: 2C sin 2 12
with C = 2.426 pm and = 600. Hence = 1.213 pm and the wavelength of the
scattered radiation is f = i + = 25.878 pm + 1.213 pm = 27.091 pm.
0.6
2.3 eV corresponds to 2.3 (1.602 1019 C) V 3.7 1019 J. Then use eqn 0.7 in the
form
v {(2/me)(h )}1/2
so long as h
(a) h hc/ 6.62 1019 J when 300 nm:
v {[2/(9.10938 1031 kg)] (2.9 1019 J)}1/2 8.0 105 m s1
(b) h 3.31 1019 J ; hence no electrons are emitted.
Exercise: Examine the case where the ejection speed is so great that it must be treated
relativistically.
0.7 Use eqn 0.11 for the Balmer series wavenumbers:
1
1
v~ RH 2 2
n
2
with RH = 1.097 10 cm .
The highest wavenumber corresponds to n = and is 2.743 104 cm1, corresponding
to a wavelength of 1/(2.743 104 cm1) = 3.646 105 cm = 364.6 nm.
The lowest wavenumber corresponds to n = 3 and is 1.524 104 cm1, corresponding to
a wavelength of 1/(1.524 104 cm1) = 6.563 105 cm = 656.3 nm.
0.8 The permitted energy levels of the electron in a hydrogen atom are given by eqn 0.13:
C00 p. 2
En
e 4
13.6 eV
1
2.18 10 18 J
2
2
2
8h 0 n
n
n2
The two lowest levels are therefore
n = 1: E1 = 2.18 1018 J = 13.6 eV
n = 2: E2 = 5.45 1019 J = 3.40 eV
0.9 The de Broglie wavelength is given by eqn 0.14:
Problems
0.1
hc / kT
8hc e
[eqn 0.5]
5
hc / kT
1 e
(8hc / 5 )
e hc / kT 1
d
40hc / 6 (8hc / 5 )(hc / 2 kT )e hc / kT
hc / kT
0
d
e
1
(e hc / kT 1) 2
That is, at the maximum
5
(hc / 2 kT )e hc / kT
(hc / 2 kT )
e hc / kT 1
1 e hc / kT
and hence
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hc
1 ehc/kT
5kT
At short wavelengths (hc/kT 1)
hc
1, which implies that T hc/5k
5kT
Exercise: Confirm that the extremum of is in fact a maximum.
0.4 The Boltzmann distribution is
pi
e i
i e i
[ 1/kT]
Hence
1 dq
pi i q d
i
In this case, i v (v
1
2
i
q e
)h, so
( v 12 ) h
12 h
v0
1 h
e 2
1 e h
(e h )v
v0
n
1
x (1 x)
n
Hence
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he h 1
h
2 h h
h
h
e 1
1 e
1
2
CV
Nd Nd d
N d
2
dT
d dT
kT d
e h
N ( h ) 2
Nk ( E / T ) 2 e h
(eh 1) 2
kT 2 (e h 1) 2
[E h/k]
There are three modes of oscillation for each atom in a solid, so
CV,m 3Rf
( E / T ) 2 e E / T
(1 e E / T ) 2
as in eqn 0.6a.
Exercise: Derive an expression for the heat capacity of a two-level system, and plot it
as a function of temperature.
0.7 For sodium D/T 0.50; for diamond D/T 6.20. If we use the Einstein formula (with
E D), then
Na(s): f 0.979; hence C V ,m / R 2.94
C(d): f 0.078; hence C V ,m / R 0.23
The Debye formula can be evaluated by numerical integration but it is also tabulated.
See the American Institute of Physics Handbook, D.E. Gray (ed.), McGraw-Hill (1972),
p.4.113. Then
Na(s): f (D/T 0.50) 0.988; hence C V ,m / R 2.96
C(d): f (D/T 6.20) 0.249; hence C V ,m / R 0.747
Exercise: Evaluate CV,m at 300 K for the Group 1 metals.
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0.10 Use the experimental data at 195 nm and eqn 0.7 to compute the work function of the
metal surface.
h EK (hc/)
1
2
mev2
(6.626 1034 J s)(3.00 108 m s1)/(195 109 m)
1
2
(9.10938 1031 kg)(1.23 106 m s1)2
3.303 1019 J
When light of wavelength 255 nm is used, the kinetic energy of the ejected electron is
EK (hc/)
(6.626 1034 J s)(3.00 108 m s1)/(255 109 m) 3.303 1019 J
4.492 1019 J
corresponding to a speed of
2E
v K
m
1/ 2
9.93 105 m s1
Exercise: For the above problem, what is the longest wavelength of light capable of
ejecting electrons from the metal surface?
0.13 From eqn 0.11, 1/ RH{(1/22) (1/n2)}, n 3, 4, . . .
Hence, plot 1/ against 1/n2, and find RH from the intercept at n (since then 1/
RH/4). The data extrapolate (linear regression) to
1/ 2.743 106 m1 2.743 104 cm1
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hence
RH 4 (2.743 104 cm1) 1.097 105 cm1
The ionization energy (I) is the energy required for the transition n2 n1 1;
hence I hcR H 2.179 1018 J. Because 1 eV 1.602 1019 J, I 13.6 eV.
0.16 The square of the fine structure constant is
from which it follows that (using the mass of the electron for the reduced mass in the
Rydberg constant):
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