Chapter 1: The Quantum Theory of The Submicroscopic World

CHAPTER 1: THE QUANTUM THEORY OF THE SUBMICROSCOPIC WORLD
194
CHAPTER 1
THE QUANTUM THEORY OF THE
SUBMICROSCOPIC WORLD
1.1
1.2
(a)
c
3.00 108 m s1
3.5 106 m 3.5 103 nm

13 1
8.6 10 s
(b)
c
3.00 108 m s1
5.30 1014 s1 5.30 1014 Hz

9
566 10 m
(a)
Strategy: We are given the wavelength of an electromagnetic wave and asked to calculate the frequency.
Rearranging Equation (1.2) of the text and replacing u with c (the speed of light) gives:
Solution: Because the speed of light is given in meters per second, it is convenient to first convert
wavelength to units of meters. Recall that 1 nm 1 10 9 m. We write:

456 nm
1 109 m
456 109 m 4.56 107 m
1 nm
Substituting in the wavelength and the speed of light ( 3.00 108 ms 1 ), the frequency is:
c
3.00 108 m s 1
6.58 1014 s 1 or 6.58 1014 Hz
4.56 107 m
Check: The answer shows that 6.58 1014 waves pass a fixed point every second. This very high
frequency is in accordance with the very high speed of light.
(b)
Strategy: We are given the frequency of an electromagnetic wave and asked to calculate the wavelength.
Solution: Substituting in the frequency and the speed of light ( 3.00 108 ms 1 ) into the above equation,
the wavelength is:
c
3.00 108 m s 1

0.122 m
2.45 109 s 1
The problem asks for the wavelength in units of nanometers. Recall that 1 nm 1 10 9 m.
195
0.122 m
1.3
1 nm
1 10
1.22 108 nm
c
3.00 108 m s 1
3.26 102 m 3.26 107 nm

1
9192631770 s
This radiation falls in the microwave region of the spectrum. (See Figure 1.6 of the text.)
1.4
The wavelength is:
1m
6.05780211 107 m
1,650,763.73 wavelengths
c
3.00 108 m s 1
=
4.95 1014 s 1 or 4.95 1014 Hz
7
6.05780211 10 m
hc
(6.63 1034 J s)(3.00 108 m s 1 )
3.19 1019 J
624 109 m
1.5
E h
1.6
(a)
Strategy: We are given the frequency of an electromagnetic wave and asked to calculate the wavelength.
Solution: Substituting in the frequency and the speed of light (3.00 108 m s-1) into the above equation,
the wavelength is:
3.00 108 m s 1

4.0 107 m 4.0 102 nm
7.5 1014 s 1
Check: The wavelength of 400 nm calculated is in the blue region of the visible spectrum as expected.
(b)
Strategy: We are given the frequency of an electromagnetic wave and asked to calculate its energy.
Equation (1.3) of the text relates the energy and frequency of an electromagnetic wave.
E h
Solution: Substituting in the frequency and Planck's constant (6.63 10
the energy of a single photon associated with this frequency is:
34
J s) into the above equation,
E h (6.63 1034 J s) 7.5 1014 s 1 5.0 1019 J

Check: We expect the energy of a single photon to be a very small energy as calculated above, 5.0 10
19
J.
1.7
(a)
196
c
3.00 108 m s 1
5.0 103 m 5.0 1012 nm
6.0 104 s 1
The radiation does not fall in the visible region; it is radio radiation. (See Figure 1.6 of the text.)
1.8
34
J s)(6.0 104 s-1) 4.0 10
(b)
E h (6.63 10
(c)
Converting to J mol-1: E
29
4.0 1029 J 6.022 1023 photons
2.4 105 J mol 1

1 photon
1 mol
The energy given in this problem is for 1 mole of photons. To apply E h, we must divide the energy by
Avogadros number. The energy of one photon is:
E
1.0 103 kJ
1 mol
1000 J
1.7 1018 J
23
1 mol
1 kJ
6.022 10 photons
The wavelength of this photon can be found using the relationship, E
(6.63 1034 J s) 3.00 108 m s 1

hc
E
1.7 1018 J
1.2 107 m
hc
.
1 nm
1 10
1.2 102 nm
The radiation is in the ultraviolet region (see Figure 1.6 of the text).
1.9
E h
1.10
(a)
hc
( 6.63 1034 J s )( 3.00 108 m s 1 )
1.29 1015 J
9
( 0.154 10 m )
c
3.00 108 m s 1
14 1
8.11 10 s
3.70 107 m 3.70 102 nm
(b)
to
Checking Figure 1.6 of the text, you should find that the visible region of the spectrum runs from 400
700 nm. 370 nm is in the ultraviolet region of the spectrum.
(c)
E h. Substitute the frequency () into this equation to solve for the energy of one quantum
associated with this frequency.
E h ( 6.63 1034 J s ) 8.11 1014 s 1 5.38 1019 J
1.11
First, we need to calculate the energy of one 600 nm photon. Then, we can determine how many photons
are needed to provide 4.0 10 17 J of energy.

The energy of one 600 nm photon is:
197
hc
(6.63 1034 J s)(3.00 108 m s 1 )
3.32 1019 J
600 109 m
The number of photons needed to produce 4.0 10

(4.0 1017 J)
1.12
1 photon
3.32 10
19
17
J of energy is:
1.2 102 photons
The heat needed to raise the temperature of 150 mL of water from 20C to 100C is:
heat (150 ml)(4.184 J ml -1 C-1)(100 20)C 5.0 104 J
The microwave will need to supply more energy than this because only 92.0% of microwave energy is
converted to thermal energy of water. The energy that needs to be supplied by the microwave is:
5.0 104 J
5.4 104 J
0.920
The energy supplied by one photon with a wavelength of 1.22 108 nm (0.122 m) is:
E
hc
(6.63 1034 J s)(3.00 108 m s 1 )
1.63 1024 J
(0.122 m)
The number of photons needed to supply 5.4 104 J of energy is:

(5.4 104 J)
1.13
1 photon
1.63 10
24
3.3 1028 photons
This problem must be worked to four significant figure accuracy. We use 6.6256 10
8
constant and 2.998 10 ms
hc
(6.6256 1034 J s)(2.998 108 m s1 )
3.372 1019 J
9
589.0 10 m
hc
(6.6256 1034 J s)(2.998 108 m s1 )
3.369 1019 J
9
589.6 10 m
For one photon the energy difference is:

19
Js for Plancks
for the speed of light. First calculate the energy of each of the photons.
E (3.372 10
34
J) (3.369 10
19
J) 3 10
22
For one mole of photons the energy difference is:

3 1022 J 6.022 1023 photons
2 102 J mol 1
1 photon
1 mol
1.14
The radiation emitted by the star is measured as a function of wavelength ( ). The wavelength
corresponding to the maximum intensity is then plugged in to Wiens law (Tmax = 1.44 10-2 K m) to
determine the surface temperature.
1.15
Wiens law: Tmax = 1.44 10-2 Km.

Solving for temperature (T) yields:
T
198
1.44 10 2 Km
100nm: ultraviolet
1.44 10 2 K m
1.44 10 5 K
100 10 9 m
300nm: ultraviolet
1.44 10 2 K m
4.80 10 4 K
300 10 9 m
500nm: visible (green)
1.44 10 2 K m
2.88 10 4 K
500 10 9 m
800nm: infrared
1.44 10 2 K m
1.80 10 4 K
800 10 9 m
Most night vision goggles work by converting low energy infrared radiation (which our eyes can not detect)
to higher energy visible radiation.
1.16
Because the same number of photons are being delivered by both lasers and because both lasers produce
photons with enough energy to eject electrons from the metal, each laser will eject the same number of
electrons. The electrons ejected by the blue laser will have higher kinetic energy because the photons from
the blue laser have higher energy.
1.17
In the photoelectric effect, light of sufficient energy shining on a metal surface causes electrons to be ejected
(photoelectrons). Since the electrons are charged particles, the metal surface becomes positively charged as
more electrons are lost. After a long enough period of time, the positive surface charge becomes large
enough to increase the amount of energy needed to eject electrons from the metal.
1.18
(a) The maximum wavelength is obtained by solving Equation 1.4 when the kinetic energy of the ejected
electrons is equal to zero. In this case, Equation 1.4, together with the relation c / , gives
E
(b)
34
8
1
hc 6.626 10 J s 3.00 10 m s
3.82 1019 J
520 10 9 m
h (kineticEnergy)
(kineticEnergy)
hc

199
(kinetic Energy)
6.626 10
34
J s 3.00 108 m s 1
450 109 m
3.8227 10 19 J 5.9 10 20 J
Please remember to carry extra significant figures during the calculation and then round at the
very end to the appropriate number of significant figures.
1.19 The minimum (threshold) frequency is obtained by solving Equation 1.4 when the kinetic energy of the ejected
electrons is equal to zero. In this case, Equation 1.4 gives
E h 6.626 10 34 J s 8.54 1014 s 1 5.66 1019 J
1.20
The emitted light could be analyzed by passing it through a prism.
1.21
Light emitted by fluorescent materials always has lower energy than the light striking the fluorescent
substance. Absorption of visible light could not give rise to emitted ultraviolet light because the latter has
higher energy.
The reverse process, ultraviolet light producing visible light by fluorescence, is very common. Certain
brands of laundry detergents contain materials called optical brighteners which, for example, can make a
white shirt look much whiter and brighter than a similar shirt washed in ordinary detergent.
1.22
Excited atoms of the chemical elements emit the same characteristic frequencies or lines in a terrestrial
laboratory, in the sun, or in a star many light-years distant from earth.
1.23
(a)
The energy difference between states E1 and E4 is:

E4 E1 (1.0 10
(b)
J) (15 10
19
J) 14 10
19
hc
(6.63 1034 J s)(3.00 108 m s 1 )
1.4 107 m 140 nm

E
14 1019 J
The energy difference between the states E2 and E3 is:

E3 E2 (5.0 10
(c)
19
19
J) (10.0 10
19
J) 5 10
19
19
The energy difference between the states E1 and E3 is:

E1 E3 (15 10
19
J) (5.0 10
19
J) 10 10
Ignoring the negative sign of E, the wavelength is found as in part (a).

1.24
hc
(6.63 1034 J s)(3.00 108 m s 1 )
2.0 107 m 200 nm

19
E
10 10 J
We use more accurate values of h and c for this problem.

E
hc
( 6.6256 1034 J s )( 2.998 108 m s1 )
=
3.027 1019 J
9
656.3 10 m
1.25
200
In this problem ni 3 and nf 5.
E RH
n
i
(2.18 1018 J)
nf
52
1.55 1019 J
The sign of E means that this is energy associated with an absorption process.
hc
(6.626 1034 J s)(2.998 108 m s1 )
1.28 106 m 1.28 103 nm

E
1.55 1019 J
Is the sign of the energy change consistent with the sign conventions for exo- and endothermic processes?
1.26
Strategy: We are given the initial and final states in the emission process. We can calculate the energy of
the emitted photon using Equation (1.5) of the text. Then, from this energy, we can solve for the frequency
of the photon, and from the frequency we can solve for the wavelength. The value of Rydberg's constant is
2.18 10 18 J.
Solution: From Equation (1.5) we write:
1
E RH
n2
i
nf2
1
E (2.18 1018 J)
E 4.09 10
19
22
The negative sign for E indicates that this is energy associated with an emission process. To calculate the
frequency, we will omit the minus sign for E because the frequency of the photon must be positive. We
know that
E h
Rearranging this equation and substituting in the known values,
E
4.09 1019 J
=
6.17 1014 s 1 or 6.17 1014 Hz
34
h
6.63 10 J s
We also know that
3.00 108 m s 1
14 1
6.17 10 s
c
. Substituting the frequency calculated above into this equation gives:
4.86 107 m 486 nm
Check: This wavelength is in the visible region of the electromagnetic region (see Figure 1.6 of the text).
This is consistent with the transition from ni 4 to nf 2 gives rise to a spectral line in the Balmer series
(see Figure 1.15 of the text).
1.27
The Balmer series corresponds to transitions to the n 2 level.
For He :
201
E R
He
n2
i
nf2
hc
(6.63 1034 J s)(3.00 108 m s 1 )
E
E
For the transition, n 6 2

1
E (8.72 1018 J)
62
1.99 10
25
1.94 10
Jm
18
1
2
1.94 1018 J
1.03 107 m 103 nm
For the transition, n 6 2, E 1.94 10
18
103 nm
18
109 nm
18
121 nm
18
164 nm
For H, the calculations are identical to those above, except the Rydberg constant for H is 2.18 10
19
411 nm
19
434 nm
19
487 nm
19
657 nm
18
J.
All the Balmer transitions for He are in the ultraviolet region; whereas, the transitions for H are all in the
visible region. Note the negative sign for energy indicating that a photon has been emitted.
1.28
Equation 1.14:
rn
0 h2n2
Z me e 2
for n = 2: r2
(8.8542 10 12 C 2 J 1 m 1 )(6.626 10 34 Js)2 2

2.117x10 10 m=211.7 pm
1 (9.109 10 31 kg)(1.602 10 19 C)2
for n = 3: r3
(8.8542 10 12 C2 J 1 m 1 )(6.626 10 34 Js)2 3

4.764x10 10 m=476.4 pm
1 (9.109 10 31 kg)(1.602 10 19 C)2
1.29
ni 236, nf 235
E (2.18 1018 J)
236
2352
3.34 1025 J
202
hc
(6.63 1034 J s)(3.00 108 m s 1 )
0.596 m
E
3.34 1025 J
This wavelength is in the microwave region. (See Figure 1.6 of the text.)
1.30
Z 2 RH
1
1.31
1
1
2
2
n1 n2
3.289832496 10
15
s 1
1 1
3.289832496x1015 s 1 3.289832496x1015 Hz
1
First convert the parameters to the appropriate units and then use the following equation:
(a)
1.50 10 8 cm
1.50 10 6 m
m
6
1
100cm
1.50 10 ms
s
s
(b)
h
mu
6.626 10 34 Js
4.85 10 10 m
(9.1094 10 31 kg)(1.50 10 6 ms 1 )
kg
60.0g
0.0600kg 6.00 10 2 kg
1 1000g
m
1500cm
15.00m
1
1
1

15.00ms 1.500 10 ms
s
100cm
s
6.626 10 34 J s
7.36 10 34 m
(6.00 10 2 kg)(1.500 101 m s 1 )
h
6.63 1034 J s
5.65 1010 m 0.565 nm

27
2
1
mu
(1.675 10
kg)(7.00 10 m s )
1.32
1.33
Strategy: We are given the mass and the speed of the proton and asked to calculate the wavelength. We
need the de Broglie equation, which is Equation 1.20 of the text. Note that because the units of Planck's
constant are J s, m must be in kg and u must be in m s1 (1 J 1 kg m2 s2).
Solution: Using Equation 1.20 we write:
h
mu
6.63 1034 kg m 2 s 1
h

1.37 1015 m
mu
(1.673 1027 kg)(2.90 108 m s 1 )
203
The problem asks to express the wavelength in nanometers.
(1.37 1015 m)
1.34
1 nm
1 10
1.37 106 nm
Converting the velocity to units of ms 1:

120 mi 1.61 km 1000 m
1 hr
53.7 m s1
1 hr
1 mi
1 km
3600 s
1.35
h
6.63 1034 J s
9.96 1034 m 9.96 1032 cm

1
mu
(0.0124 kg)(53.7 m s )
First, we convert mph to m s1.

35 mi 1.61 km 1000 m
1h
16 m s1
1h
1 mi
1 km
3600 s
6.63 1034 kg m 2 s 1
h

=
1.7 1032 m 1.7 1023 nm
3
1
mu
(2.5 10 kg)(16 m s )
1.36
From the Heisenberg uncertainty principle (Equation 1.22) we have

x p
h
2
For the minimum uncertainty we can change the greater than sign to an equal sign.
p
h
1.055 1034 J s
1 10 24 kg m s 1
2 x
2 (4 10 11m)
Because p = m u, the uncertainty in the velocity is given by

u
p 1 10 24 kgms 1
1 10 6 ms 1
m 9.1095 10 31 kg
The minimum uncertainty in the velocity is 1 106 m s1.

1.37
Below are the probability distributions for the first three energy levels for a one-dimensional particle in a
box, as shown in Figure 1.24. The average value for x for all of the states for a one-dimensional particle in
a box is L/2 (the middle of the box). This is true even for those states (like the second state) that have no
probability of being exactly in the middle of the box.
1.38
204
The difference between the energy levels n and (n + 1) for a one-dimensional particle in a box is given by
Equation 1.31:
Enn1
h2
(2n 1) .
8mL2
All we have to do is to plug the numbers into the equation remembering that 1 =10 -10 m.
Enn1
(6.626 10 34 Js)2 [2(2) 1]

1.20 10 18 J
8(9.109 10 31 kg)[5.00 10 10 m]2
Energy is equal to Plancks constant times frequency. We can rearrange this equation to solve for frequency.
1.39
E
1.20 10 18 J
1.81 1015 s 1 1.81 1015 Hz

h 6.626 10 34 Js
From Equation 1.15 we can derive an equation for the change in energy going from the n=1 to n=2 states for
a hydrogen atom:
E
3Z 2 e4 me
.
32h 2 02
From Equation 1.31 we can derive an equation for the change in energy going from the n=1 to n=2 states for
a particle in a box:
3h 2
.
8mL2
We can combine the two equations and solve for L.
3Z 2 e4 me
3h 2
32h 2 02
8mL2
L
4h 4 02
2h 2 0 2(6.626 10 34 Js)2 (8.8542 10 12 C 2 J 1 m 1 )
3.326 10 10 m
Z 2 e4 me2 Ze2 me
1(1.602 10 19 C)2 (9.109 10 31 kg)
The radius of the ground state of the hydrogen atom (the Bohr radius) is 5.29 10-11 m (see Example 1.4).
This leads to a diameter of 1.06 10-10 m, which is only a third the size of L that we calculated. So, it seems
like a crude estimate.
205
1.40
The average value for x will be greater than L/2. The larger the electric field, the larger the average value of
x.
1.41
(a) The number given in front of the designation of the subshell is the principal quantum number, so in
this case n 3. For s orbitals, l 0. ml can have integer values from l to l, therefore, ml 0. The
electron spin quantum number, ms, can be either 1/2 or 1/2.
Following the same reasoning as part (a)
(b)
4p: n 4; l 1; ml 1, 0, or 1; ms 1/2, 1/2
(c)
3d: n 3; l 2; ml 2, 1, 0, 1, or 2; ms 1/2, 1/2
An orbital in a subshell can have any of the allowed values of the magnetic quantum number for that
subshell. All the orbitals in a subshell have exactly the same energy.
1.42
(a)
(b)
(c)
2p: n 2, l 1, ml 1, 0, or 1
6s: n 6, l 0, ml 0 (only allowed value)
5d: n 5, l 2, ml 2, 1, 0, 1, or 2
An orbital in a subshell can have any of the allowed values of the magnetic quantum number for that
subshell. All the orbitals in a subshell have exactly the same energy.
1.43
The allowed values of l are 0, 1, 2, 3, and 4. These correspond to the 5s, 5p, 5d, 5f, and 5g subshells. These
subshells each have one, three, five, seven, and nine orbitals, respectively.
1.44
For n 6, the allowed values of l are 0, 1, 2, 3, 4, and 5 [l 0 to (n 1), integer values]. These l values
correspond to the 6s, 6p, 6d, 6f, 6g, and 6h subshells. These subshells each have 1, 3, 5, 7, 9, and 11
orbitals, respectively (number of orbitals 2l 1).
1.45
There can be a maximum of two electrons occupying one orbital.
(a)
two
(b)
six
(c)
ten
(d)
206
fourteen
What rule of nature demands a maximum of two electrons per orbital? Do they have the same energy? How
are they different? Would five 4d orbitals hold as many electrons as five 3d orbitals? In other words, does
the principal quantum number n affect the number of electrons in a given subshell?
1.46
A 2s orbital is larger than a 1s orbital. Both have the same spherical shape. The 1s orbital is lower in
energy than the 2s. The 1s orbital does not have a node while the 2s orbital does.
1.47
The two orbitals are very similar in shape, though the 3py is larger and has a higher energy. The 3py orbital
will have 1 radial node, in contrast to the 2px orbital, which has no radial nodes. The two orbitals also differ
in their orientation: 3py is oriented parallel to the y-axis and 2px is oriented parallel to the x-axis. Can you
assign a specific value of the magnetic quantum number to these orbitals? What are the allowed values of
the magnetic quantum number for the 2p subshell?
1.48
We can modify Equation 1.15 to determine the ionization energies of single electron atoms. Ionization is
the process of removing an electron (exciting it to a infinitely high energy state).
Z 2 e 4 me 1 1
Z 2 e4 me 1
8h 2 20 n12
8h 2 20 n12
Eionization
He+ has two protons in the nucleus and hence a +2 nuclear charge, making Z=2.
Z 2 e 4 me 1
2 (1.602 10 19 C)4 (9.109 10 31 kg)
8h 2 02 n12
8(6.626 10 34 Js)2 (8.8542 10 12 C 2 J 1 m 1 )2
1
8.715 10 18 J
2
1
Eionization
We need to convert our answer to kJ mol1.

8.715 10 18 J 1kJ 6.022 10 23
3
1
1000
5.248 10 kJmol
1
mol
Eionization
Li2+ has three protons in the nucleus and hence a +3 nuclear charge, making Z = 3.
Z 2 e 4 me 1
3 (1.602 10 19 C)4 (9.109 10 31 kg)
8h 2 02 n12
8(6.626 10 34 Js)2 (8.8542 10 12 C 2 J 1 m 1 )2
1
1.961 10 17 J
2
1
Eionization
We need to convert our answer to kJ mol1.

1.961 10 17 J 1kJ 6.022 10 23
4
1
1000
1.181 10 kJ mol
1
mol
Eionization
1.49
Equation 1.15 yields the energy of the photon absorbed for different transitions. For an emission, Equation
1.15 can be written:
Ephoton
Z 2 e 4 me
8h 2 02
1
1
n2 n2
final
initial
Energy equals Plancks constant times the speed of light divided by the wavelength: E
hc
.
207
We can use this relationship to modify the above equation.

hc Z 2 e4 me
8h 2 02
1
1
n2 n2
final
initial
We can now solve for one over ninitial.
1
ninitial
1
n
2
final
8h 3 02 c
Z 2 e 4 me
34
3
12 2
1
1 2
8
1
1 8(6.626 10 Js) (8.8542 10 C J m ) 3.0 10 ms
1
0.20
22
5
12 (1.602 10 19 C)4 (9.109 10 31 kg) 434 10 9 m
Hence, ninitial is 5.
1.50
1.51
(a)
False. n 2 is the first excited state.
(b)
False. In the n 4 state, the electron is (on average) further from the nucleus and hence easier to
remove.
(c)
True.
(d)
False. The n 4 to n 1 transition is a higher energy transition, which corresponds to a shorter

wavelength.
(e)
True.
The energy given in the problem is the energy of 1 mole of gamma rays. We need to convert this to the
energy of one gamma ray, and then we can calculate the wavelength and frequency of this gamma ray.
1.29 1011 J
1 mol
2.14 1013 J
23
1 mol
6.022 10 gamma rays
Now, we can calculate the wavelength and frequency from this energy.
E
hc
hc
(6.63 1034 J s)(3.00 108 m s1 )
9.29 1013 m 0.929 pm

13
E
2.14 10 J
and
E h
1.52
E
2.14 1013 J
3.23 1020 s 1 3.23 1020 Hz

34
h
6.63 10 J s
We first calculate the wavelength, then we find the color using Figure 1.6 of the text.
hc
(6.63 1034 J s)(3.00 108 m s1 )
4.63 107 m 463 nm, which is blue.

19
E
4.30 10 J
1.53
(a)
208
First, we can calculate the energy of a single photon with a wavelength of 633 nm.
E
hc
(6.63 1034 J s)(3.00 108 m s 1 )
3.14 1019 J
633 109 m
The number of photons produced in a 0.376 J pulse is:

1 photon
0.376 J
(b)
3.14 1019 J
1.20 1018 photons
Since a 1 W 1 J s-1, the power delivered per a 1.00 10 9 s pulse is:

0.376 J
1.00 10
3.76 108 J s1 3.76 108 W
Compare this with the power delivered by a 100-W light bulb!

1.54
The energy required to heat the water is:

mCsT (368 g)(4.184 J g-1 C-1)(5.00C) 7.70 103 J,
where m is the mass, Cs the specific heat of water, and T is the change in temperature.
The energy of a photon with a wavelength of 1.06 104 nm can be calculated as follows:
E h
hc
(6.63 1034 J s)(3.00 108 m s1 )
1.88 1020 J
1.06 105 m
The number of photons required is:

(7.70 103 J)
1.55
1 photon
1.88 10
20
4.10 1023 photons
First, lets find the energy needed to photodissociate one water molecule.
285.8 kJ
1 mol
4.746 1022 kJ 4.746 1019 J

23
1 mol
6.022 10 molecules
The maximum wavelength of a photon that would provide the above energy is:

hc
(6.63 1034 J s)(3.00 108 m s1 )
4.19 107 m 419 nm

19
E
4.746 10 J
This wavelength is in the visible region of the electromagnetic spectrum. Since water is continuously being
struck by visible radiation without decomposition, it seems unlikely that photodissociation of water by this
method is feasible.
1.56
For the Lyman series nf = 1. The longest wavelength emission corresponds to the smallest change in energy
(ni 2). By multiplying both sides of Equation 1.5 by Plancks constant the following equation is obtained:
209
E h hRH
n 2
i
22
(2.18 1018 J)
nf
1
2
1.64 1018 J
hc
(6.63 1034 J s)(3.00 108 m s 1 )
1.21 107 m 121 nm

18
E
1.64 10 J
For the Balmer series nf = 2, the shortest wavelength emission corresponds to the largest change in energy
(ni ).
E h hRH
n 2
i
1
1
5.45 1019 J
2
2
2
(2.18 1018 J)
nf
hc
(6.63 1034 J s)(3.00 108 m s 1 )
3.65 107 m 365 nm

E
5.45 1019 J
The longest wavelength emission for the Lyman series (121 nm) is shorter than the shortest wavelength
emission for the Balmer series (365 nm). Hence, the two series do not overlap.
1.57
Since 1 W 1 J s-1, the energy output of the 75-W light bulb in 1 second is 75 J. The actual energy
converted to visible light is 15 percent of this value (0.15 75 = 11 J).
First, we need to calculate the energy of one 550 nm photon. Then, we can determine how many photons
are needed to provide 11 J of energy.
The energy of one 550 nm photon is:
hc
(6.63 1034 J s)(3.00 108 m s 1 )
3.62 1019 J
9
550 10 m
The number of photons needed to produce 11 J of energy is:

11 J
1.58
1 photon
3.62 1019 J
3.0 1019 photons
The energy needed per photon for the process is:

248 103 J
1 mol
4.12 1019 J
1 mol
6.022 1023 photons

hc
(6.63 1034 J s)(3.00 108 m s1 )
4.83 107 m 483 nm

E
(4.12 1019 J)
Any wavelength shorter than 483 nm will also promote this reaction. Once a person goes indoors, the
reverse reaction Ag Cl AgCl takes place.
1.59
210
Starting with Equation 1.4,
1
m u2 ,
2 e
we can set the kinetic energy equal to eV,

h eV ,
divide both sides by h to yield:
e
V.
h h
To use the equation above to determine h and we plot as a function of V. The slope will be equal to e/h
and the y-intercept will be equal to /h. Before we can plot, we have to calculate from using v=c,
where c is the speed of light.
nm)
V (volt)
(x10 sec )
14
-1
405.0
435.5
480.0
520.0
577.7
650.0
1.475
1.268
1.027
0.886
0.667
0.381
7.402
6.884
6.245
5.765
5.189
4.612
7.5 1014
e
1.602 1019 J V 1
6.125x10-34 Js
slope 2.6153 1014 s 1 V 1
Y = M0 + M1*X
M0 3.5314e+14
M1 2.6153e+14
7 1014
2.163 10
1.60
-19
From Equation 1.17:
6.125 10
34
Js
0.99794
6.5 1014
1
3.5314 10 s
14
Frequency(sec )
y intercept 6.125 1034 Js
6 1014
5.5 1014
5 1014
4.5 1014
0.2
0.4
0.6
0.8
Voltage(V)
RH
e 4 me
(1.60218 1019 C) 4 (9.10939 1031 kg)
3.28986 1015 s 1 .
8h3 02 8(6.62608 1034 J s)3 (8.85419 10 12 C2 J 1 m 1 ) 2
For the hydrogen atom the mass of the nucleus is just equal to the mass of a proton.
9.10939 10 31 kg 1.67262 1027 kg
me mN
9.10443 10 31 kg
me mN 9.10939 1031 kg 1.67262 10 27 kg
RH'
e4
(1.60218 1019 C)4 (9.10443 1031 kg)
3.28806 1015 s 1
8h3 02 8(6.62608 1034 J s)3 (8.85419 10 12 C2 J 1 m 1 ) 2
1.2
1.4
1.6
211
Percentage change
RH RH'
3.28986 1015 s 1 3.28806 1015 s 1
100
100 0.0547%
RH
3.28986 1015 s 1
For the helium-4 isotope the mass of the nucleus is equal to 6.64610-27 kg.
9.10939 1031 kg 6.646 10-27 kg 9.10814 1031 kg

me mN
me mN 9.10939 10 31 kg 6.646 10-27 kg
RH'
e4
(1.60218 10 19 C)4 (9.10814 10 31 kg)
3.28940 1015 s 1
8h3 02 8(6.62608 1034 J s)3 (8.85419 10 12 C2 J 1 m 1 ) 2
Percentage change
RH RH'
3.28986 1015 s 1 3.28940 1015 s 1
100
100 0.014%
RH
3.28986 1015 s 1
That the percent change for a He+ is smaller illustrates that the bigger the difference in the two masses (the
mass of the electron and of the nucleus), the closer the reduced mass is to the lighter mass (the mass of the
electron).
1.61
(a)
For an s orbital, l is zero. Hence, the orbital angular momentum for an electron in an s orbital is
zero.
(b)
Bohrs model only allowed for orbits with angular momentum equal to an integer multiple of
h
h, where h is defined as Planks constant divided by two times pi h
1.62
The Fe14+ in the corona is presumed to be formed by the ionization of Fe 13+, which takes 3.5104 kJ mol-1 of
energy. The energy for the ionization comes from collisions. Hence, for there to be Fe 14+ in the corona, we
can assume that the average kinetic energy of the corona gases has to be atleast equal to the ionization
energy of Fe13+.
3RT
3.5 104 kJ mol-1
2
T
2 3.5 104 kJ mol-1

3R
2 3.5 10 4 kJ mol -1
3 8.31447 103 kJ K -1mol-1
2.8 106 K
The actual temperature can be, and most probably is, higher than this.
1.63
Since the energy corresponding to a photon of wavelength 1 equals the energy of photon of wavelength 2
plus the energy of photon of wavelength 3, then the equation must relate the wavelength to energy.
energy of photon 1 (energy of photon 2 energy of photon 3)
Since E
hc
, then:
212
hc
hc hc
1
2
3
Dividing by hc:
1.64
From the Heisenberg uncertainty principle (Equation 1.22) we have

x p
h
2
For the minimum uncertainty we can change the greater than sign to an equal sign. We can solve for the
uncertainty in momentum (p) by dividing both sides by the uncertainty in the position (x).
p
h
2 x
The uncertainty of the oxygen molecules position in any one direction is equal to the diameter of the alveoli
(5.0 x 10-5 m).
p
h
1.055 1034 J s
1.1 1030 kg m s 1
2 x 2 (5.0 10 5 m)
Momentum is equal to mass times velocity. If we assume that the there is no uncertainty in the mass, then
the uncertainty in the momentum is equal to mass times the uncertainty in the velocity (p = m u). By
dividing both sides by the mass, we see that the uncertainty in the velocity is equal to the uncertainty in
momentum divided by the mass.
u
p 1.1 10 30 kg m s 1
2.0 10 5 m s 1
m
5.3 10 26 kg
Because we had started by changing the greater than sign in Heisenbergs equation to an equal sign, the
minimum uncertainty in the velocity is 2.0 10-5 m s-1.
1.65
It takes:
(5.0 102 g ice)
334 J
1.67 105 J to melt 5.0 102 g of ice.
1 g ice
Energy of a photon with a wavelength of 660 nm:

E
hc
(6.63 1034 J s)(3.00 108 m s 1 )
3.01 1019 J
660 109 m
Number of photons needed to melt 5.0 102 g of ice:

(1.67 105 J )
1 photon
5.5 1023 photons
3.01 1019 J
213
The number of water molecules is:

1 mol H 2 O
6.022 1023 H 2 O molecules
(5.0 102 g H 2 O)

18.02 g H 2 O
1 mol H 2 O
The number of water molecules converted from ice to water by one photon is:
5.5 1023 photons
1.66
31 H 2 O molecules per photon
Energy of a photon at 360 nm:

E h
hc
(6.63 1034 J s)(3.00 108 m s 1 )
5.53 1019 J
360 109 m
Area of exposed body in cm2:

1 cm
0.45 m
1 102 m
2
4.5 103 cm 2
The number of photons absorbed by the body in 2 hours is:

0.5
2.0 1016 photons

7200 s
(4.5 103 cm 2 )
3.2 1023 photons
2 hr
cm 2 s
The factor of 0.5 is used above because only 50% of the radiation is absorbed.
3.2 1023 photons with a wavelength of 360 nm correspond to an energy of:
(3.2 1023 photons)
1.67
1.68
5.53 1019 J
1.8 105 J
1 photon
The anti-atom of hydrogen should show the same characteristics as a hydrogen atom. Should an anti-atom
of hydrogen collide with a hydrogen atom, they would be annihilated and energy would be given off.
h
Looking at the de Broglie equation
, the mass of an N2 molecule (in kg) and the velocity of an N2
mu
molecule (in m/s) is needed to calculate the de Broglie wavelength of N 2.

First, calculate the root-mean-square velocity of N2.
M(N2) 28.02 g mol1 0.02802 kg mol1
urms =
(3) 8.314 J mol1 K 1 300 K
0.02802 kg mol
516.8 m s 1
Second, calculate the mass of one N2 molecule in kilograms.
214
28.02 g N 2
1 mol N 2
1 kg
4.653 1026 kg
1 mol N 2
6.022 1023 N 2 molecules 1000 g
Now, substitute the mass of an N2 molecule and the root-mean-square velocity into the de Broglie equation
to solve for the de Broglie wavelength of an N2 molecule.
h
(6.63 1034 J s-1 )
2.76 1011 m
mu
(4.653 1026 kg)(516.8 m s 1 )
1.69
Based on the selection rule, which states that l 1, only (b) and (d) are allowed transitions.
1.70
The kinetic energy acquired by the electrons is equal to the voltage times the charge on the electron. After
calculating the kinetic energy, we can calculate the velocity of the electrons (KE 1/2mu2). Finally, we can
calculate the wavelength associated with the electrons using the de Broglie equation.
KE (5.00 103 V)
1.602 1019 J
8.01 1016 J
1V
We can now calculate the velocity of the electrons.

KE
1 2
mu
2
8.01 1016 J
1
(9.1094 1031 kg)u 2
2
u 4.19 107 m s-1

Finally, we can calculate the wavelength associated with the electrons using the de Broglie equation.
1.71
(a)
h
mu
(6.63 1034 J s)
1.74 1011 m 17.4 pm
(9.1094 1031 kg)(4.19 107 m s 1 )
We use the Heisenberg Uncertainty Principle to determine the uncertainty in knowing the position of the
electron.
xp
h
4
We use the equal sign in the uncertainty equation to calculate the minimum uncertainty values.
p mu, which gives:
x(mu)
x
h
4
h
6.63 1034 J s
1 109 m
4 mu
4 (9.1094 1031 kg)[(0.01)(5 106 m s 1 )]
215
Note that because of the unit Joule in Plancks constant, mass must be in kilograms and velocity must be
in m s-1.
The uncertainly in the position of the electron is much larger than that radius of the atom. Thus, we
have no idea where the electron is in the atom.
(b)
We again start with the Heisenberg Uncertainly Principle to calculate the uncertainty in the baseballs
position.
x
h
4p
6.63 1034 J s
7.9 109 m
7
1
4 (1.0 10 )(6.7 kg m s )
This uncertainty in position of the baseball is such a small number as to be of no consequence.
1.72
(a) The average kinetic energy of 1 mole of an ideal gas is 3/2RT. Converting to the average kinetic
energy per atom, we have:
3
1 mol
(8.314 J mol1 K 1 )(298 K)
6.171 1021 J atom 1
2
6.022 1023 atoms
(b)
To calculate the energy difference between the n 1 and n 2 levels in the hydrogen atom, we modify
Equation 1.5 of the text.
1
1
2
nf2
ni
1
1
2
2
1

(2.180 1018 J)
E RH
E 1.635 10
(c)
18
For a collision to excite an electron in a hydrogen atom from the n 1 to n 2 level,

KE E
3
RT
2
1.635 1018 J
NA
T
2 (1.635 1018 J)(6.022 1023 mol1 )

7.90 104 K
1
1
3
(8.314 J mol K )
This is an extremely high temperature. Other means of exciting H atoms must be used to be practical.
1.73
To calculate the energy to remove at electron from the n 1 state and the n 5 state in the Li 2 ion, we use
the following equation:
1
1
2 .
2
nf
ni
E RH Z 2
216
For ni 1, nf , and Z 3, we have:

1
1
2
2
1

E (2.18 1018 J)(3)2
1.96 1017 J
For ni 5, nf , and Z 3, we have:

1
1
2
2
5

E (2.18 1018 J)(3)2
7.85 1019 J
To calculate the wavelength of the emitted photon in the electronic transition from n 5 to n 1, we first
calculate E and then calculate the wavelength.
1
1
2
2
nf
ni
E RH Z 2
1
1
2
2
5
1
(2.18 1018 J)(3)2
1.88 1017 J
We ignore the minus sign for E in calculating .
hc
(6.63 1034 J s 1 )(3.00 108 m s 1 )
E
1.88 1017 J
1.06 108 m 10.6 nm
1.74
The minimum value of the uncertainty is found using xp

x(mu)
u
h
4
h
4 mx
For the electron with a mass of 9.109 10

u
h
and p mu. Solving for u:
4
31
kg and taking x as the radius of the nucleus, we find:
6.63 1034 J s
5.8 1010 m s 1
4 (9.109 1031 kg)(1.0 1015 m)
This value for the uncertainty is impossible, as it far exceeds the speed of light. Consequently, it is
impossible to confine an electron within a nucleus.
Repeating the calculation for the proton with a mass of 1.673 10
u
27
kg gives:
6.63 1034 J s
3.2 107 m s 1
4 (1.673 1027 kg)(1.0 1015 m)
While still a large value, the uncertainty is less than the speed of light, and the confinement of a proton to the
nucleus does not represent a physical impossibility. The large value does indicate the necessity of using
quantum mechanics to describe nucleons in the nucleus, just as quantum mechanics must be used for
electrons in atoms and molecules.
1.75
Below are the solutions for the particle in a one dimensional box (Equation 1.35).
217
2
L
1/2
n (x)
n x
L
n 1, 2,3,....
sin
The equation below yields the average value of x, for a particle in a one dimensional box.
2
2
n x
2
f x (x) dx x sin 2
dx
L
L

L
0
0
L
xsin
n x
L dx
We can use the following relation obtained from a table of integrals:
xsin ax dx
2
x 2 x sin(2ax) cos 2ax
4
4a
8a 2
2
f x (x) dx
L
0
L
n x
2 x2
0 xsin L dx L 4
2n x
2n x
cos
L
L
2
n
n
4
8
L
L
x sin
We now evaluate this for x equal to L and 0.
2 L2
1
f
L 4
n
2
1

2
L
8 n
L
L
2
The result above shows us that for all states for a particle in a box, the average value of x is L/2. This makes
sense, because the squared wavefunctions are all symmetric about x = L/2.
The equation below yields the average value of x2, for a particle in a one dimensional box.
2
2
n x
2
f x 2 (x) dx x 2 sin 2
dx
L
L
L
0
0
L
x sin
2
n x
L dx
We can use the following relation obtained from a table of integrals:
2 2
x 3 x cos(2ax) 2a x 1 sin 2ax
x sin ax dx 6 4a2
8a3
2
2
L
f x 2 (x) dx
0
n x
2 x3
dx
L 6
L
2
2
x sin
0
2n x
x cos
L
n
4
L
n
2
L
2n x
x 2 1 sin
L
n
8
L
218
We now evaluate this for x equal to L and 0.
1
2 1

L
2
3 2 n
2 L3
L
f
L 6
n
for n = 1 the average value of x2 is 0.283 L2

1.76
The average value of r using Equation 1.41: r rP r dr r 3 R(r) dr

0
3/2
Z
r r 3 R10 (r) dr r 3 2
a0
0
0
Zr
ao
dr 4 Z
a0
3
r e
2 Zr
ao
dr
From an integral table:
x e
n ax
dx
n!
a n1
To use the above integral to solve our problem, n = 3, x = r, and a

Z
r 4
a0
3
r e
2Zr
ao
Z
dr 4
a0
6ao4
4
16Z
2Z
,
ao
3ao 3
a .
2Z 2 o
Hence, the average value for r for a 1s orbital is
3
a . Remember that Z is the nuclear charge and is equal to
2 o
1 for a hydrogen atom.

To calculate the most probable value of r, we set the derivative of the radial probability function to zero and
solve for r.
P r r R r
Z
d
P r 4
dr
a0
Z
r 2
a0
r e
2Zr
ao
3/2
Z
4
a0
Zr
ao
Z
4
a0
2re
2Zr
ao
r 2e
2Zr
ao
2Zr
Z
2Z 2 ao
8
r e
ao
a0
2Zr
Z 2 a
r r e o
ao
219
ao
ao the derivative is zero, which corresponds to the most likely value of r. This is consistent
Z
with ao being the Bohr radius.
When r
For the 2s orbital
The average value of r: r rP r dr r 3 R(r) dr

0
3/2
Zr
2 Z
Zr 2ao
r r R10 (r) dr r
2
e
dr
ao
4 a0
0
0
3
Zr
Zr
Zr
2
1 Z
4Z
Z
ao
ao
ao
3
4
5
r
4
r
e
dr
r
e
dr
r
e
dr
2
8 a0
ao
ao
Using the same integral solution as above, we can solve for the three integrals in the square brackets
4 r e
3
Zr
ao
dr 4
6ao4
Z4
4Z
ao
Z2
ao2
4
r e
r e
5
Zr
ao
Zr
ao
dr
4Z
ao
Z2
ao2
dr
24ao4
Z4
24ao5
96ao4
5
Z
Z4
120ao6
Z 6
120ao4
Z4
When we plug in the results for the integrals into the above equation we get that the average distance from
the nucleus for a 2s orbital is six times the Bohr radius. Notice that this is four times the average distance
from the nucleus for a 1s orbital.
1 Z
r
8 a0
24ao4
96ao4
Z
120ao4
Z
1 Z

8 a0
48ao4
ao
6ao
Z
To calculate the most probable value of r, we can set the derivative of the radial probability function to zero
and solve for r.
P r r R r
2
1 Z
P r
8 a0
3/2
Zr
ao
2
Zr
ao
2 Z
r2
4 a0
4r e
4Zr 3
e
ao
Zr 2ao
2
ao
Zr
Z 2r 4
e
ao2
Zr
ao
1 Z

8 a0
Zr
4Zr Z 2 r 2 ao
r2 4
2 e
ao
ao

Zr
Zr
Zr
d 2 ao 4Zr 3 ao Z 2 r 4 ao
4r e
e 2 e
dr
ao
ao
d
1 Z
P r
dr
8 a0
d
1 Z
P r
dr
8 a0
d
1 Z
P r
dr
8 a0
d
1 Z
P r
dr
8 a0
220
Zr
Zr 2
4Z 2 Zr 3
Z2
Zr 4 ao
3
4
2r
3r
4r
ao
ao
ao
ao
ao2

Zr
8r
16Zr 2 8Z 2 r 3 Z 3r 4 ao
3 e
ao
ao2
ao
Zr
rZ 3 8ao3 16ao2 r ao r 2
a
3
o
r
e
3 3
Z
Z2
ao Z
The above polynomial can be solved computationally to determine three roots. The largest root, which
corresponds to the most probable value is r
3 5 a 3 5 a .
Z
o
1.77
2
0 L
1/2
n x
L
sin
2

L
1/2
m x
L
sin
n x
m x
2
sin
sin
dx
L 0
L
L
L
dx
Using a table of integrals, it can be shown that the last integral listed above is zero if n does not equal m,
and is L/2 if n equals m. Hence, the wavefunctions for a one-dimensional particle in a box are orthogonal.
1.78
The five lowest energy levels for a two-dimensional particle in a box correspond to the following sets of
quantum numbers: (nx=1, ny=1), (nx=1, ny=2), (nx=2, ny=1), (nx=2, ny=2), (nx=3, ny=1) , (nx=1, ny=3) , (nx=3,
ny=2) , (nx=2, ny=3). These wavefunctions are plotted below with the lowest energy wavefunction at the
bottom. Notice that the states (nx=1, ny=2) and (nx=2, ny=1) have the same energy as do the states (nx=1,
ny=3) and (nx=3, ny=1) and the states (nx=3, ny=2) and (nx=2, ny=3).
221

Chapter 1: The Quantum Theory of The Submicroscopic World

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Chapter 1: The Quantum Theory of The Submicroscopic World

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CHAPTER 1: THE QUANTUM THEORY OF THE SUBMICROSCOPIC WORLD

3.5 106 m 3.5 103 nm

5.30 1014 s1 5.30 1014 Hz

wavelength to units of meters. Recall that 1 nm 1 10 9 m. We write:

6.58 1014 s 1 or 6.58 1014 Hz