7 The Quantum‐

Mechanical Model
of the Atom
Problems by Topic
Electromagnetic Radiation
7.51 Given: distance to sun = 1.496  108 km Find: time for light to travel from sun to Earth
Conceptual Plan: distance km  distance m  time
1000 m distance
time 
km 3.00  10 8 m s 1
1000 m s
Solution: 1.496  10 8 km    499s
km 3.00  10 8 m
Check: The units of the answer, seconds, are correct. The magnitude of the answer is reasonable, since it
corresponds to about 8 min.

7.53 (i) By increasing wavelength the order is d) ultraviolet < c) infrared < b) microwaves < a) radio waves.
(ii) By increasing energy the order is a) radio waves < b) microwaves < c) infrared < d) ultraviolet.

7.55 (a) Given: λ  632.8 nm Find: frequency (ν )

Conceptual Plan: nm  m  ν
m c

10 9 nm λ
m 3.00  108 m 1
Solution: 632.8 nm   6.328  10 7 m    4.74  1014 s 1
109 nm s 6.328  10 7 m
Check: The units of the answer, s−1, are correct. The magnitude of the answer seems reasonable
since wavelength and frequency are inversely proportional.

(b) Given: λ  503 nm Find: frequency (ν )

Conceptual Plan: nm  m  ν
m c

10 9 nm λ
m 3.00  10 8 m 1
Solution: 503 nm   5.03  10 7 m    5.96  1014 s 1
109 nm s 5.03  10 7 m
Check: The units of the answer, s−1, are correct. The magnitude of the answer seems reasonable
since wavelength and frequency are inversely proportional.

(c) Given: λ  0.052 nm Find: frequency (ν )

Conceptual Plan: nm  m  ν
m c

10 9 nm λ

135
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136 Chapter 7 The Quantum‐Mechanical Model of the Atom

m 3.00  108 m 1
Solution: 0.052 nm   5.2  10 11 m    5.8  1018 s 1
10 nm 9
s 5.2  10 11 m
Check: The units of the answer, s−1, are correct. The magnitude of the answer seems reasonable
since wavelength and frequency are inversely proportional.

7.57 (a) Given: frequency (ν) from 5 a. = 4.74  1014 s−1 Find: energy
Conceptual Plan: ν  E
E = hν h = 6.626  10−34 J s
4.74  1014
Solution: 6.626  10 34 J s   3.14  10 19 J
s
Check: The units of the answer, J, are correct. The magnitude of the answer is reasonable since we
are talking about the energy of one photon.

(b) Given: frequency (ν ) from 5 b. = 5.96  1014 s−1 Find: energy

Conceptual Plan: ν  E
E = hν h = 6.626  10−34 J s
5.96  1014
Solution: 6.626  10 34 J s   3.95  10 19 J
s
Check: The units of the answer, J, are correct. The magnitude of the answer is reasonable since we
are talking about the energy of one photon.

(c) Given: frequency (ν ) from 5 c. = 5.8  1018 s−1 Find: energy

Conceptual Plan: ν  E
E = hν h = 6.626  10−34 J s
5.8  1018
Solution: 6.626  10 34 J s   3.8  10 15 J
s
Check: The units of the answer, J, are correct. The magnitude of the answer is reasonable since we
are talking about the energy of one photon.

7.59 Given: λ  532 nm and Epulse = 3.85 mJ Find: number of photons

Conceptual Plan: nm  m  Ephoton  number of photons
m hc Epulse
E ; h = 6.626  10−34 J s
10 9 nm λ Ephoton

3.00  10 8 m
6.626  10 34 J s 
m s
Solution: 532 nm   5.32  10 7 m E   3.7364  10 19 J photon 1
109 nm 5.32  10 7 m

J 1 photon
3.85 mJ    1.03  1016 photons
1000 mJ 3.7364  10 19 J
Check: The units of the answer, number of photons, are correct. The magnitude of the answer is reason‐
able for the amount of energy involved.

7.61 (a) Given: λ  1500 nm Find: E for 1 mol photons

Conceptual Plan: nm  m  Ephoton  E(J)mol  E(kJ)mol
m hc mol kJ
E ; h = 6.626  10−34 J s
10 9 nm λ 6.022  10 23 photons 1000 J

Solution:
3.00  108 m
6.626  1034 J s 
m s
1500 nm   1.500  106 m E  1.3252  1019 J photon1
109 nm 1.500  106 m

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Chapter 7 The Quantum‐Mechanical Model of the Atom 137

1.3252  10 19 J 6.022  10 23 photons kJ

   79.8 kJ mol 1
photon mol 1000 J
Check: The units of the answer, kJ mol−1, are correct. The magnitude of the answer is reasonable
for a wavelength in the infrared region.

(b) Given: λ  500 nm Find: E for 1 mol photons

Conceptual Plan: nm  m  Ephoton  Emol  E(kJ)mol
m hc mol kJ
E  ; h = 6.626  10−34 J s
10 9 nm λ 6.022  10 23 photons 1000 J

Solution:
3.00  10 8 m
6.626  10 34 J s 
m s
500 nm   5.00  10 7 m E  3.9756  10 19 J photon 1
109 nm 5.00  10 7 m
3.9756  10 19 J 6.022  10 23 photons kJ
   239 kJ mol 1
photon mol 1000 J
Check: The units of the answer, kJ mol−1, are correct. The magnitude of the answer is reasonable
for a wavelength in the visible region.

(c) Given: λ  150 nm Find: E for 1 mol photons

Conceptual Plan: nm  m  Ephoton  Emol  E(kJ)mol
m hc mol kJ
E ; h = 6.626  10−34 J s
10 9 nm λ 6.022  1023 photons 1000 J

Solution:
3.00  10 8 m
6.626  10 34 J s 
m s
150 nm   1.50  10 7 m E  1.3252  10 18 J photon 1
109 nm 1.50  10 7 m
1.3252  10 18 J 6.022  10 23 photons kJ
   798 kJ mol 1
photon mol 1000 J
Check: The units of the answer, kJ mol−1, are correct. The magnitude of the answer is reasonable
for a wavelength in the ultraviolet region. Note: The energy increases from the IR to the VIS to the
UV as expected.

Photoelectric Effect
7.63 Given: for aluminum   412 kJ mol 1 , Elight = 471 kJ mol−1, me = 9.11  10−31 kg Find: velocity of electrons
emitted
Conceptual Plan: Determine the energy of each photon and then calculate the difference between the
photon energy and the work function to find the kinetic energy of the electron.

6.022  10 23 photons 1000 J

KEelectron  Ephoton  
1 mol 1 kJ

Use the kinetic energy of the electron and the mass of the electron to find the velocity.

1
KE  mv 2
2
1 mol 471 kJ 1000 J
Solution: Ephoton     7.8213  10 19 J
6.022  10 23 photons 1 mol 1 kJ

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138 Chapter 7 The Quantum‐Mechanical Model of the Atom

1 mol 412 kJ 1000 J

    6.8416  10 19 J
6.022  10 23 electrons 1 mol 1 kJ
KEelectron  Ephoton    7.8213  10 19 J  6.8416  10 19 J  9.797  10 20 J

1 KE 9.797  10 20 J
KE  mv 2 v   4.637697  10 5 m s 1  4.64  10 5 m s 1
2 (0.5)( m) (0.5)(9.11  10 31 kg)

Check: The units (m s−1) are correct and the magnitude of the velocity (105) is reasonable for an electron.

Atomic Spectroscopy
7.65 When the atom emits the photon of energy that was needed to raise the electron to the n = 2 level, the
photon has the same energy as the energy absorbed to move the electron to the excited state. Therefore,
the electron has to be in n = 1 (the ground state) following the emission of the photon.

7.67 (a) Given: n = 2  n = 1 Find: λ

Conceptual Plan: n = 1, n = 2  ΔEatom  ΔEphoton  λ
hc
Eatom  E1  E2 Eatom  Ephoton E
λ
Solution:
E  E1  E2
1   1   1   1  
 2.18  10 18 J  2    2.18  10 18  2    2.18  10 18 J  2    2    1.635  10 18 J
1    2   1   2  
hc (6.626  1034 J  s)(3.00  108 m s 1 )
Ephoton  Eatom  1.635  1018 J λ   1.22  107 m or 122 nm
E 1.635  1018 J
This transition would produce a wavelength in the UV region.
Check: The units of the answer, m, are correct. The magnitude of the answer is reasonable since it
is in the region of UV radiation.

(b) Given: n = 3  n = 1 Find: λ

Conceptual Plan: n = 1, n = 3  ΔEatom  ΔEphoton  λ
hc
Eatom  E1  E3 Eatom  Ephoton E
λ
Solution:
E  E1  E3
1   1   1   1  
 2.18  10 18 J  2    2.18  10 18  2    2.18  10 18 J  2    2    1.938  10 18 J
1    3   1   3  
hc (6.626  10 34 J  s)(3.00  10 8 m s 1 )
Ephoton  Eatom  1.938  10 18 J λ   1.03  10 7 m or 103 nm
E 1.938  10 18 J
This transition would produce a wavelength in the UV region.
Check: The units of the answer, m, are correct. The magnitude of the answer is reasonable since it
is in the region of UV radiation.

(c) Given: n = 4  n = 2 Find: λ

Conceptual Plan: n = 2, n = 4  ΔEatom  ΔEphoton  λ
hc
Eatom  E2  E4 Eatom  Ephoton E
λ
Solution:
E  E2  E4
 1   1   1   1  
 2.18  10 18 J  2    2.18  10 18  2    2.18  10 18 J  2    2    4.087  10 19 J
2    4   2   4  

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Chapter 7 The Quantum‐Mechanical Model of the Atom 139

hc (6.626  10 34 J  s)(3.00  10 8 m s 1 )

Ephoton  Eatom  4.087  10 19 J λ   4.86  10 7 m or 486 nm
E 4.087  10 19 J
This transition would produce a wavelength in the visible region.
Check: The units of the answer, m, are correct. The magnitude of the answer is reasonable since it
is in the region of visible light.
(d) Given: n = 5  n = 2 Find: λ
Conceptual Plan: n = 2, n = 5  ΔEatom  ΔEphoton  λ
hc
Eatom  E2  E5 Eatom  Ephoton E
λ
Solution:
E  E2  E5
 1   1   1   1  
 2.18  10 18 J  2    2.18  10 18  2    2.18  10 18 J  2    2    4.578  10 19 J
  
2  
5  2   5  
hc (6.626  10 34 J  s)(3.00  10 8 m s 1 )
Ephoton  Eatom  4.578  10 19 J λ   4.34  10 7 m or 434 nm
E 4.578  10 19 J
This transition would produce a wavelength in the visible region.
Check: The units of the answer, m, are correct. The magnitude of the answer is reasonable since it
is in the region of visible light.

7.69 Given: n(initial) = 7 λ = 397 nm Find: n(final)

Conceptual Plan: λ  ΔEphoton  ΔEatom  n = x, n = 7
hc
E Ephoton  Eatom Eatom  Ex  E7
λ
hc (6.626  10 34 J  s)(3.00  108 m s 1 )
Solution: E    5.007  10 19 J
λ  m 
(397 nm )  9 
 10 nm 
Eatom  Ephoton  5.007  10 19 J
 1    1   1   1  
E  Ex  E7  5.007  10 19  2.18  10 18 J  2    2.18  10 18  2    2.18  10 18 J  2    2  
  
x  
7  x   7  
 1   1  1 
0.2297   2    2  0.25229   2  x 2  3.998 x=2
x  7  x 
Check: The answer is reasonable since it is an integer less than the initial value of 7.
7.71 (a) Given: electron in H atom; nf = 4, ni = 2 Find: ΔE in kJ mol−1
Conceptual Plan: nf , ni  ΔE and then J  kJ and ΔE, NA  ΔE in kJ mol−1
 1 1  1 kJ 6.022  10 23 electrons
ΔE  2.18  10 18 J  2  2 
 n f ni  1000 J 1 mol
 

 1 1  1 1
Solution: ΔE  2.18  10 18 J  2  2   2.18  10 18 J  2  2   2.18  10 18 J  0.1875   4.09  10 19 J.
 n f ni  4 2 
 
1 kJ 6.022  10 23 electrons
For one mole of electrons: ΔE = 4.09  10−19 J    246 kJ mol 1 of electrons.
1000 J 1 mol
Check: The units (kJ mol−1) are correct. The energy difference is positive since energy must be
absorbed in order to move the electron to a higher energy level.
(b) The energy change for the same transition in He+ would be greater because of the greater nuclear
charge (Z) on the nucleus of helium. For hydrogen‐like atoms, the equation for the energy difference

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140 Chapter 7 The Quantum‐Mechanical Model of the Atom

 Z2 Z2 
between energy levels is ΔE  2.18  10 18 J  2  2  . The presence of the Z2 term leads to greater
 n f ni 
 
energy differences.

The Wave Nature of Matter and the Uncertainty Principle

7.73 The interference pattern would be a series of light and dark lines.

7.75 Given: m = 9.109  10−31 kg, λ = 0.20 nm Find: v

Conceptual Plan: m, λ  v
h
v
mλ

kg  m 2
6.626  10 34 s
Solution: s2  3.6  10 6 m s 1
 1m 
(9.109  10 31 kg )(0.20 nm )  
 1  10 nm 
9

Check: The units of the answer, m s−1, are correct. The magnitude of the answer is large, as would be
expected for the speed of the electron.

7.77 Given: m = 9.109  10−31 kg; v = 1.35  105 m s−1 Find: λ

Conceptual Plan: m,v  λ
h
λ
mv

kg  m 2
6.626  10 34 s
s2
Solution:  5.39  10 9 m  5.39 nm
31  1.35  10 5 m 
(9.109  10 kg )  
 s 
Check: The units of the answer, m, are correct. The magnitude is reasonable since we are looking at an
electron.

7.79 Given: m = 143 g; v = 42 m s−1 Find: λ

Conceptual Plan: m,v  λ
h
λ
mv

kg  m 2
6.626  10 34 s
s2
Solution:  1.1  10 34 m
 kg   42 m 
(143 g)   
 1000 g   s 
 
The value of the wavelength, 1.1  10−34 m, is so small it will not have an effect on the trajectory of the
baseball.
Check: The units of the answer, m, are correct. The magnitude of the answer is very small, as would be
expected for the de Broglie wavelength of a baseball.

7.81 Given: Δx = 552 pm, m = 9.109  10−31 kg Find: Δv

Conceptual Plan: Δx, m  Δv

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Chapter 7 The Quantum‐Mechanical Model of the Atom 141
h
x  mv 
4π

kg  m 2
6.626  10 34 s
Solution: s2
 1.05  10 5 m s 1
 m 
4(3.141)(9.109  10 31 kg )(552 pm )  
 1  1012 pm 
 
Check: The units of the answer, m s , are correct. The magnitude is reasonable for the uncertainty in the
−1

speed of an electron.

Orbitals and Quantum Numbers

n2 h2
E , n  1,2,3,
8ma 2

7.83 (a) since the energy levels for a particle in a 1‐D box are reciprocally dependent on the size of the box, if
the box doubles in size the energy levels get four times closer together:

i.e., The spacing between energy levels between the first two energy levels, E1 and E2, for a box of size a
would be,

22 h 2 12 h 2 3h 2
E2  E1   =
8ma 2 8ma 2 8ma 2

The spacing between the same two energy levels for a particle in a box of size 2a would be

22 h 2 12 h 2 3h 2 3h2
E2  E1   = = which is four times less than above.
8m  2a  8m  2a 
2 2 2
8m4a 24ma 2

(b) the energy levels get 100 times closer together

22 h2 12 h 2 3h2 3h2
i.e., E2  E1   = =
8m 10a  8m 10a 
2 2
8m100a 2 800ma 2

7.85 (a) Quantum physics treats electrons as waves and restricts them to regions of space—for example in
atoms—due the attraction between oppositely charged electrons and the nucleus. This treatment results
in quantization of energy levels.
(b) An atomic orbital is a region of space where there is a high probability of finding an electron.
(c) The solutions to the Schrödinger equation are characterized by three quantum numbers: n, l, and ml.
The principal quantum number (n) determines the energy of the electron in the orbital and the size of the
orbital; the angular momentum quantum number (I) determines the shape of the orbital; and the magnetic
quantum number (ml) determines the orientation of the orbital.
(d) In a multielectron atom, the 2s orbital is lower in energy than the 2p orbital because the 2s orbital
penetrates closer to the nucleus, and therefore the 2s electrons are not fully shielded by the 1s electrons.

7.87 Given: proton in a one‐dimensional box; a = 1.0 nm Find: ground state energy
Conceptual Plan: h, n, m, a  E
1  10 9 m n2 h 2
h = 6.626  10−34 J s mproton = 1.673  10−27 kg E 1 J = 1 kg m2 s−2
1 nm 8 ma2
Solution: The ground state corresponds to n = 1. Substitute h, n, m, and a, with proper units, and solve for
energy.

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142 Chapter 7 The Quantum‐Mechanical Model of the Atom

 
2
12 6.626  10 34 J s
E=
  
2
8 1.673  10 27 kg 1.0  10 9 m

 
2
12 6.626  10 34 kg m 2 s 1
=
  
2
8 1.673  10 27 kg 1.0  10 9 m
kg 2 m 4 s 2
 3.28  10 23
kg m 2
 3.3  10 23 kg m 2 s 2 (or J)
Check: The units (kg m2 s−2) are correct, as they are equivalent to Joules.

7.89 Since the size of the orbital is determined by the n quantum, with the size increasing with increasing n,
an electron in a 2s orbital is closer, on average, to the nucleus than an electron in a 3s orbital.

7.91 The value of l is an integer that lies between 0 and n − 1.

(a) When n = 1, l can only be l = 0.
(b) When n = 2, l can be l = 0 or l = 1.
(c) When n = 3, l can be l = 0, l = 1, or l = 2.
(d) When n = 4, l can be l = 0, l = 1, l = 2, or l = 3.

7.93 Set c cannot occur together as a set of quantum numbers to specify an orbital. l must lie between 0 and
n − 1, so for n = 3, l can only be as high as 2.

7.95 The 2s orbital would be the same shape as the 1s orbital but would be larger in size and the 3p orbitals
would have the same shape as the 2p orbitals but would be larger in size. Also, the 2s and 3p orbitals
would have more nodes.

7.97 (a) The quantum numbers n = 3, l = 1, ml = 1 correspond to a particular orbital in the 3p subshell of an
atom. A single orbital can hold a maximum of two electrons and so an atom could only have two
electrons with these quantum numbers.
(b) The quantum numbers n = 3, l = 1 correspond to the 3p subshell of an atom. The 3p subshell can hold
a maximum of six electrons and so an atom could have six electrons with these quantum numbers.
(c) The quantum number n = 3 corresponds to the third principal shell of an atom which has s, p, and
d subshells. The s subshell can hold two electrons, the p subshell can hold six electrons, and the
d subshell can hold 10 electrons, for a total of 18 electrons. Therefore, an atom could have 18 elec‐
trons with n = 3.

7.99 (a) For a 3s orbital, n = 3 and l = 0. Total nodes = n − 1 = 3 − 1 = 2. Radial nodes = n − l − 1 = 3 − 0 − 1 = 2.

Angular nodes = total nodes − radial nodes = 2 − 2 = 0.
(b) For a 3p orbital, n = 3 and l = 1. Total nodes = n − 1 = 3 − 1 = 2. Radial nodes = n − l − 1 = 3 − 1 − 1 = 1.
Angular nodes = total nodes − radial nodes = 2 − 1 = 1.

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Chapter 7 The Quantum‐Mechanical Model of the Atom 143

(c) For a 3d orbital, n = 3 and l = 2. Total nodes = n − 1 = 3 − 1 = 2. Radial nodes = n − l − 1 = 3 − 2 − 1 = 0.

Angular nodes = total nodes − radial nodes = 2 − 0 = 2.

Electron Configurations of Atoms and Ions and Magnetic Properties

7.101 (a) Si Silicon has 14 electrons. Distribute two of these into the 1s orbital, two into the 2s orbital, six
into the 2p orbital, two into the 3s orbital, and two into the 3p orbital. 1s22s22p63s23p2

(b) O Oxygen has 8 electrons. Distribute two of these into the 1s orbital, two into the 2s orbital, and
four into the 2p orbital. 1s22s22p4

(c) K Potassium has 19 electrons. Distribute two of these into the 1s orbital, two into the 2s orbital, six
into the 2p orbital, two into the 3s orbital, six into the 3p orbital, and one into the 4s
orbital. 1s22s22p63s23p64s1

(d) Ne Neon has 10 electrons. Distribute two of these into the 1s orbital, two into the 2s orbital, and
six into the 2p orbital. 1s22s22p6

(e) F Fluorine has 9 electrons. Distribute two of these into the 1s orbital, two into the 2s orbital,
and 5 into the 2p orbital. 1s22s22p5

7.103 (a) N Nitrogen has 7 electrons and has the electron configuration 1s22s22p3. Draw a box for each
orbital, putting the lowest energy orbital (1s) on the far left and proceeding to orbitals
of higher energy to the right. Distribute the 7 electrons into the boxes representing the
orbitals, allowing a maximum of two electrons per orbital and remembering Hund’s rule.
You can see from the diagram that nitrogen has 3 unpaired electrons.

(b) As Arsenic has 33 electrons and has the same electron configuration as argon plus two electrons
in the 4s orbital, ten electrons in the 3d orbitals, and three electrons in the 4p orbitals. The con‐
densed electron configuration is [Ar] 4s23d104p3.
[Ar]

(c) As3+ The As3+ ion has 30 electrons and has the same electron configuration as argon plus two
electrons in the 4s orbital, and ten electrons in the 3d orbitals. The condensed electron
configuration is [Ar] 4s23d10.
[Ar]

(d) Sn4+ The Sn4+ ion has 46 electrons and has the same electron configuration as krypton plus ten
electrons in the 4d orbitals. When removing electrons, the electrons in the highest energy

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144 Chapter 7 The Quantum‐Mechanical Model of the Atom

(highest n‐value) orbitals are removed first. The configuration of Sn is [Kr] 5s24d105p2.
Electrons are removed from the 5p orbitals first and then the 5s orbital. The condensed elec‐
tron configuration of Sn4+ is [Kr] 4d10.
[Kr]

7.105 (a) O2− Begin by writing the electron configuration of the neutral atom.
O 1s22s22p4
Since this ion has a 2− charge, add two electrons to write the electron configuration of the ion.
O2− 1s22s22p6 This is isoelectronic with Ne.
(b) Br− Begin by writing the electron configuration of the neutral atom.
Br [Ar]4s23d104p5
Since this ion has a 1− charge, add one electron to write the electron configuration of the ion.
Br− [Ar]4s23d104p6 This is isoelectronic with Kr.
(c) Sr2+ Begin by writing the electron configuration of the neutral atom.
Sr [Kr]5s2
Since this ion has a 2+ charge, remove two electrons to write the electron configuration of
the ion.
Sr2+ [Kr]
(d) Co3+ Begin by writing the electron configuration of the neutral atom.
Co [Ar]4s23d7
Since this ion has a 3+ charge, remove three electrons to write the electron configuration of the
ion. Since it is a transition metal, remove the electrons from the 4s orbital before removing
electrons from the 3d orbitals.
Co3+ [Ar]4s03d6
(e) Cu2+ Begin by writing the electron configuration of the neutral atom. Remember, Cu is one of our
exceptions.
Cu [Ar]4s13d10
Since this ion has a 2+ charge, remove two electrons to write the electron configuration of the
ion. Since it is a transition metal, remove the electrons from the 4s orbital before removing
electrons from the 3d orbitals.
Cu2+ [Ar]4s03d9
7.107 Identify the noble gas that precedes the element and put it in square brackets.
Determine the outer principal quantum level for the s orbital. Subtract one to obtain the quantum level
for the d orbital. If the element is in the third or fourth transition series, include (n − 2)f electrons in the
configuration. Count across the row to see how many electrons are in the neutral atom.
For an ion, remove the required number of electrons, first from the s and then from the d orbitals.
(a) Ni; Ni2+
The noble gas that precedes Ni is Ar. Ni is in the fourth period so the orbitals we use are 4s and 3d
and Ni has ten more electrons than Ar.
Ni [Ar]4s23d8
Ni will lose electrons from the 4s and then from the 3d.
Ni2+ [Ar]4s03d8
(b) Mn; Mn4+
The noble gas that precedes Mn is Ar. Mn is in the fourth period so the orbitals we use are 4s and
3d and Mn has seven more electrons than Ar.
Mn [Ar]4s23d5
Mn will lose electrons from the 4s and then from the 3d.
Mn4+ [Ar]3d3
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Chapter 7 The Quantum‐Mechanical Model of the Atom 145

(c) Y; Y3+
The noble gas that precedes Y is Kr. Y is in the fifth period so the orbitals we use are 5s and 4d and
Y has three more electrons than Kr.
Y [Kr]5s24d1
Y will lose electrons from the 5s and then from the 4d.
Y3+ [Kr]
(d) Ta; Ta5+
The noble gas that precedes Ta is Xe. Ta is in the sixth period so the orbitals we use are 6s, 5d, and
4f and Ta has 19 more electrons than Xe.
Ta [Xe]6s24f14 5d3
Ta will lose electrons from the 6s and then from the 5d.
Ta5+ [Xe]4f 14

7.109 (a) V5+ Begin by writing the electron configuration of the neutral atom.
V [Ar]4s23d3
Since this ion has a 5+ charge, remove five electrons to write the electron configuration of the
ion. Since it is a transition metal, remove the electrons from the 4s orbital before removing
electrons from the 3d orbitals.
V5+

V5+ is diamagnetic.
(b) Cr3+ Begin by writing the electron configuration of the neutral atom. Remember, Cr is one of our
exceptions.
Cr [Ar]4s13d5
Since this ion has a 3+ charge, remove three electrons to write the electron configuration of
the ion. Since it is a transition metal, remove the electrons from the 4s orbital before remov‐
ing electrons from the 3d orbitals.
Cr3+

Cr3+ is paramagnetic.
(c) Ni2+ Begin by writing the electron configuration of the neutral atom.
Ni [Ar]4s23d8
Since this ion has a 2+ charge, remove two electrons to write the electron configuration of
the ion. Since it is a transition metal, remove the electrons from the 4s orbital before remov‐
ing electrons from the 3d orbitals.
Ni2+

Ni2+ is paramagnetic.
(d) Fe3+ Begin by writing the electron configuration of the neutral atom.
Fe [Ar]4s23d6
Since this ion has a 3+ charge, remove three electrons to write the electron configuration of
the ion. Since it is a transition metal, remove the electrons from the 4s orbital before remov‐
ing electrons from the 3d orbitals.
Fe3+

Fe3+ is paramagnetic.

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146 Chapter 7 The Quantum‐Mechanical Model of the Atom

Cumulative Problems
7.111 Given: 348 kJ mol−1 Find: λ
Conceptual Plan: kJ mol−1  kJ molec−1  J molec−1  λ
6.022  10 23 C  C bonds 1000 J hc
E
mol C  C bonds kJ λ

348 kJ mol C  C bonds 1000 J

Solution:    5.779  10 19 J
mol C  C bonds 6.022  10 C  C bonds
23
kJ
(6.626  10 34 J  s)(3.00  10 8 m s 1 )
λ  3.44  10 7 m  344 nm
5.779  10 19 J
Check: The units of the answer, m or nm, are correct. The magnitude of the answer is reasonable since
this wavelength is in the UV region.

7.113 Given: Epulse = 5.0 watts; d = 5.5 mm; hole = 1.2 mm; λ = 532 nm Find: photon s−1
Conceptual Plan: fraction of beam through hole  fraction of power and then Ephoton  number
photons s−1
area hole hc power s 1
fraction  power E
area beam λ Ephotun1

 (0.60 mm)2 J s1

Solution: A   r 2  0.0476 0.0476  5.0 watts   0.238 J s1
 (2.75 mm)2 watt
(6.626  10 34 J  s)(3.00  10 8 m s 1 )
Ephoton   3.736  10 19 J photon 1
 m 
(532 nm )  9 
 10 nm 
0.238 J s 1
 6.4  1017 photons s 1
3.736  10 19 J photon 1
Check: The units of the answer, number of photons s−1, are correct. The magnitude of the answer is
reasonable.

7.115 Given: KE = 506 eV Find: λ

Conceptual Plan: KEev  KEJ  v  λ
1.602  1019 J h
KE  1/2 mv 2 λ 
eV mv
Solution:
 kg  m 2 
 1.602  10 19
J   s2  1
506 eV      (9.11  10 31 kg) v 2
 eV   J  2

 
 kg  m 2 
 1.602  10  
19
J  s2 
506 eV  
 eV   J 
  2
v2     1.7796  1014 m
2
1 s
(9.11  10 31 kg )
2
kg  m 2
6.626  10 34 s
h s2
v  1.334  10 7 m s 1 λ   5.45  10 11 m  0.0545 nm
mv (9.11  10 31 kg )(1.334  107 m s 1 )
Check: The units of the answer, m or nm, are correct. The magnitude of the answer is reasonable
because a de Broglie wavelength is usually a very small number.

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Chapter 7 The Quantum‐Mechanical Model of the Atom 147

7.117 Given: n = 1  n = ∞ Find: E; λ

Conceptual Plan: n = ∞, n = 1  ΔEatom  ΔEphoton  λ
hc
Eatom  E  E1 Eatom  Ephoton E
λ
  1 
Solution: E  E  E1  0   2.18  10 18  2    2.18  10 18 J
  1 
Ephoton  Eatom  2.18  1018 J
hc (6.626  10 34 J  s)(3.00  10 8 m s 1 )
λ   9.12  10 8 m  91.2 nm
E 2.18  10 18 J
Check: The units of the answers, J for E and m or nm for part 1, are correct. The magnitude of the
answer is reasonable because it would require more energy to completely remove the electron than just
moving it to a higher n level. This results in a shorter wavelength.
7.119 (a) Given: n = 1 Find: number of orbitals if l = 0  n
Conceptual Plan: value n  values l  values ml  number of orbitals
l=0n ml = −l  + l total ml
Solution: n= 1
l= 0 1
ml = 0 −1, 0, +1
total 4 orbitals
Check: The total orbitals will be equal to the number of l sublevels2.
(b) Given: n = 2 Find: number of orbitals if l = 0  n
Conceptual Plan: value n  values l  values ml  number of orbitals
l=0n ml = −l  + l total ml
Solution: n= 2
l= 0 1 2
ml = 0 −1, 0, +1 −2, −1, 0, 1, 2
total 9 orbitals
Check: The total orbitals will be equal to the number of l sublevels2.
(c) Given: n = 3 Find: number of orbitals if l = 0  n
Conceptual Plan: value n  values l  values ml  number of orbitals
l=0n ml = −l  +l total ml
Solution: n= 3
l= 0 1 2 3
ml = 0 −1, 0, +1 −2, −1, 0, 1, 2 −3, −2, −1, 0, 1, 2, 3
total 16 orbitals
Check: The total orbitals will be equal to the number of l sublevels2.
7.121 Given: λ = 1875 nm; 1282 nm; 1093 nm Find: equivalent transitions
Conceptual Plan: λ  Ephoton  Eatom then Eatom, nf  ni
hc  1 1 
E Ephoton   Eatom E  2.18  10 18 J  2  2 
λ  nf ni 
Solution: Since the wavelength of the transitions are longer wavelengths than those obtained in the
visual region, the electron must relax to a higher n level. Therefore, we can assume that the electron
returns to the n = 3 level.
(6.626  10 34 J  s)(3.00  108 m s 1 )
For λ = 1875 nm: Ephoton   1.060  10 19 J; Eatom   Ephoton  1.060  10 19 J
 m 
1875 nm  9 
 10 nm 
 1 1 
1.060  10 19 J  2.18  10 18  2  2  ; n  4
 3 n 

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148 Chapter 7 The Quantum‐Mechanical Model of the Atom

(6.626  10 34 J  s)(3.00  108 m s 1 )

For λ = 1282 nm: Ephoton   1.551  10 19 J; Eatom   Ephoton  1.551  10 19 J
 m 
1282 nm  9 
 10 nm 
 1 1 
1.551  10 19  2.18  10 18  2  2  ; n  5
 3 n 
(6.626  10 34 J  s)(3.00  108 m s 1 )
For λ = 1093 nm: Ephoton   1.819  10 19 J; Eatom   Ephoton  1.819  10 19 J
 m 
1093 nm  9 
 10 nm 
 1 1 
1.819  10 19 J  2.18  10 18  2  2  ; n  6
 3 n 
Check: The values obtained are all integers, which is correct. The values of n: 4,5,6, are reasonable. The
values of n increase as the wavelength decreases because the two n levels involved are further apart and
more energy is released as the electron relaxes to the n = 3 level.

7.123 Given:  = 193 kJ mol−1 Find: threshold frequency (ν)

Conceptual Plan:  kJ mol−1   kJ atom−1   J atom−1  ν
6.022  10 23 atoms 1000 J
  h
mol kJ

 193 kJ  mol   1000 J 

    
  mol  6.022  10 atoms   kJ
23 
Solution:        4.84  1014 s 1
h 6.626  10 34 J  s
Check: The units of the answer, s−1, are correct. The magnitude of the answer puts the frequency in the
infrared range and is a reasonable answer.
7.125 Given: νlow = 30 s−1 νhi = 1.5  104 s−1; speed = 344 m s−1 Find: λlow − λhi
Conceptual Plan: νlow  λlow and νhi = λhi then λlow − λhi
λν = speed
speed 344 m s 1 344 m s 1
Solution: λ  λlow   11 m λhi   0.023 m 11 m  0.023 m  11 m
 30 s1 1.5  10 4 s 1
Check: The units of the answer, m, are correct. The magnitude is reasonable since the value is only
determined by the low frequency value because of significant figures.
7.127 Given: λ = 792 nm, V = 100.0 mL, P = 55.7 mtorr, T = 25°C Find: E to dissociate 15.0%
Conceptual Plan: λ  E molecule−1 and then P.V.T  n  molecules
hc PV 6.022  10 23 molecules
E n
λ RT mole

(6.626  10 34 J  s)(3.00  10 8 m s 1 )

Solution: E   2.51  10 19 J molecule 1
 m 
792 nm  9 
 10 nm 
 1 torr   1 bar   L   6.022  10 23 molecules 
(55.7 mtorr )     (100.0 mL )   
 1000 mtorr   750.1 torr   1000 mL   mol 
 1.80  1017 molecules
 0.08314 L bar 
  (298 K)
 mol K 
(1.80  1017 molecules)(0.15%) = 2.70  1016 molecules dissociated
1
(2.51  1019 J molecule )(2.70  1016 molecules ) = 6.777  10−3 J = 6.78  10−3 J
Check: The units of the answer, J, are correct. The magnitude is reasonable since it is for a part of a mole of
molecules.

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Chapter 7 The Quantum‐Mechanical Model of the Atom 149

7.129 Given: 20.0 mW, 1.00 hr., 2.29  1020 photons Find: λ
Conceptual Plan: mW  W  J  J photon−1  λ
W E hc
E  Wxs λ
1000 mW number of photons E

 J 
 1W  s  3600 s 
  19 1
Solution: (20.0 mW )    3.14  10 J photon
 1000 mW  W  2.29  10 20
photons 
 
 
 109 nm 
(6.626  10 34 J  s)(3.00  108 m s 1 )  
 m   632 nm
3.14  10 19 J
Check: The units of the answer, nm, are correct. The magnitude is reasonable because it is in the red range.

7.131 Write the electron configuration of vanadium.

V: [Ar]4s23d3
Since this ion has a 3+ charge, remove three electrons to write the electron configuration of the ion. Since it is
a transition metal, remove the electrons from the 4s orbital before removing electrons from the 3d orbitals.
V3+: [Ar]4s03d2
Both vanadium and the V3+ ion have unpaired electrons and are paramagnetic.

7.133 (a) Cr [Ar]4s13d5 (b) Cu [Ar]4s13d10

Cr+ [Ar]4s03d5 Cu+ [Ar]4s03d10
Cr2+ [Ar]4s03d4 Cu2+ [Ar]4s03d9
Cr3+ [Ar]4s03d3
7.135 (a)

 
v = 175.1 km h 1 1000

 m  1 h 

km   3600 s 
  48.64 m s
1

1 1
E  mv 2   0.1701 kg   48.64 m s 1   201.2 kg m 2 s 2 or 201.2 J
2

2 2

8  201.2 J  0.1701 kg 19.5 m   J kg m 2 J2 

2
n 2h 2 8 Ema 2
E  n   4.87  1035  2 2 or 2 
 J s J 
 6.626  10 J s 
2
8ma 2 h 2 34

An enormous value, 11 orders of magnitude larger than Avogadro’s number.
(b) As can be deduced from Figure 7.24, n/2 is the number of full waves in the box (between the blue
line and the goalie). Therefore,
distance 19.5 m
   8.01  1035 m
n2 4.87  1035 2
From deBroglie,
h 6.626  1034 kg m 2 s 1
   8.01  1035 m
mv  0.1701 kg   48.64 m s 1 
The deBroglie equation and the particle in a box give the same wavelength.

Challenge Problems
7.137 (a) Given: n = 1, n = 2, n = 3, L = 155 pm Find: E1, E2, E3
Conceptual Plan: n  E
n2 h 2
En 
8 m L2

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150 Chapter 7 The Quantum‐Mechanical Model of the Atom

Solution:
12 (6.626  10 34 J  s)2 1(6.626  10 34 )2 J 2 s 2
E1  
 
2
8(9.11  10 31kg)(155  10 12 )2 m 2
m
8(9.11  10 31kg)(155 pm )2  12 
 10 pm 
 
 kg  m 2 
1(6.626  10 34 )2   J s2
 s2 
    2.51  10 18 J
31 12 2
8(9.11  10 kg )(155  10 ) m 2
2 2 (6.626  10 34 J  s)2 4(6.626  10 34 )2 J 2 s 2
E2  
 
2
8(9.11  10 31kg)(155  10 12 )2 m 2
m
8(9.11  10 kg)(155 pm )  12
31 2

 10 pm 
 
 kg  m 2 
4(6.626  10 34 )2   J s2
 s2 
    1.00  10 17 J
31 12 2
8(9.11  10 kg )(155  10 ) m 2

32 (6.626  10 34 J  s)2 9(6.626  10 34 )2 J 2 s 2

E3  
 
2
8(9.11  10 31kg)(155  10 12 )2 m 2
m
8(9.11  10 31 kg)(155 pm )2  12 
 10 pm 
 
 kg  m 2 
9(6.626  10 34 )2   J s2
 s2 
    2.26  10 17 J
8(9.11  10 31 kg )(155  10 12 )2 m 2
Check: The units of the answers, J, are correct. The answers seem reasonable since the energy is
increasing with increasing n level.

(b) Given: n = 1  n = 2 and n = 2  n = 3 Find: λ

Conceptual Plan: n = 1, n = 2  ΔEatom  ΔEphoton  λ
hc
Eatom  E2  E1 Eatom   Ephoton E
λ
Solution: Using the energies calculated in part a
E2 − E1 = (1.00  10−17 J − 2.51  10−18 J) = 7.49  10−18 J
(6.626  1034 J  s)(3.00  108 m s 1 )
λ  2.65  108 m  26.5 nm
7.49  10 18 J
E3 − E2 = (2.26  10−17 J − 1.00  10−17 J) = 1.26  10−17 J
(6.626  10 34 J  s)(3.00  108 m s 1 )
λ  1.58  108 m  15.8 nm
1.26  1017 J
These wavelengths would lie in the UV region.
Check: The units of the answers, m, are correct. The magnitude of the answers is reasonable based on the
energies obtained for the levels.

7.139 For the 1s orbital in the Excel spreadsheet, call column A: r; and column B:  (1s). Make the values
for r column A: 0−200. In column B, put the equation for the wave function written as follows:
=(POWER(1/3.1415,1/2))*(1/POWER(53,3/2))*(EXP(‐A2/53)). Go to make chart, choose xy scatter.

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Chapter 7 The Quantum‐Mechanical Model of the Atom 151

e.g., sample values

r (1s)
0 7.000146224
1 7.000143491
2 7.000140809
3 7.000138177
4 7.000135594
5 7.00013306
6 7.000130573

For the 2s orbital in the same Excel spreadsheet, call column A: r; and column C:  (2s). Use the same
values for r in column A: 0−200. In column C, put the equation for the wave function written as follows:
=(POWER(1/((32)*(3.1415)),1/2))*(1/POWER(53,3/2))*(2‐(A2/53))*(EXP(‐A2/53)). Go to make chart, choose
xy scatter.
e.g., sample values
r (2s)
0 7.0000516979
1 7.000050253
2 7.0000488441
3 7.0000474702
4 7.0000461307
5 7.0000448247
6 7.0000435513

Note: The plot for the 2s orbital extends below the x‐axis. The x‐intercept represents the radial node of the
orbital.

7.141 Given: threshold frequency = 2.25  1014 s−1; λ = 5.00  10−7 m Find: v of electron
Conceptual Plan: v   and then λ  E and then  KE  v
hc
  h E KE  E   KE  1/2 mv 2
λ
Solution:
(6.626  10 34 J  s)(3.00  108 m s 1 )
  (6.626  1034 J  s)(2.25  1014 s1 )  1.491  1019 J E   3.976  10 19 J
5.00  10 7 m
kg  m 2
2.485  10 19
s2 m2
KE  3.976  1019 J  1.491  1019 J  2.485  1019 J v2   5.455  1011
1 s2
(9.11  10 31 kg )
2
v = 7.39  105 m s−1
Check: The units of the answer, m s−1, are correct. The magnitude of the answer is reasonable for the speed
of an electron.

7.143 Given: t = 5.0 fs, λlow = 722 nm Find: ΔE, and λhigh
Conceptual Plan: t  ΔE and then λlow  Ehigh  Elow  λhigh
h hc hc
t  E  E E  E λ
4 λ E
6.626  10 34 J  s
Solution:  1.055  10 20 J
 s 
4(3.141)(5.0 fs )  
 1  10 fs 
15

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152 Chapter 7 The Quantum‐Mechanical Model of the Atom

(6.626  10 34 J  s)(3.00  108 m s 1 )

E  2.75  10 19 J
 m 
722 nm  9 
 10 nm 
2.75  10−19 J − 1.06  10−20 J  2.64  1019 J
 109 nm 
(6.626  10 34 J  s)(3.00  10 8 m s 1 )  
 m  = 752.9 nm = 7.5  102 nm
(2.64  10 19 J)
Check: The units of the answer, nm, are correct. The magnitude of the answer is reasonable since it is a
longer wavelength but it is close to the original wavelength.
7.145 Given: r = 1.8 m Find: λ
Conceptual Plan: r  C
C  2 r
Solution: (2)(3.141)(1.8 m)  11.3 m  the circumference of the orbit. So the largest wavelength that would
fit the orbit would be 11 m.
Check: The units of the answer, m, are correct. The magnitude of the wave is about the circumference of
the orbit.
7.147 Given: r = 100.00 pm, qproton = 1.60218  10−19 C, qelectron = −1.60218  10−19 C
Find: IE in kJ mol−1 and λ of ionization
Conceptual Plan: r, qproton, qelectron,  Eatom  Emol and then Eatom  λ
1 qp qe 1000 J 6.022  0 23 atom hc
E λ
4 e0 r kJ mol E

1 (1.602  10 19 C)(  1.602  10 19 C)

Solution: E    2.308  10 18 J atom 1
 C 2
  1m 
(4)(3.141)  8.85  10 12  (100.00 pm )  
 J m   1  10 12
pm 
 
6.022  10 atom kJ
2.308  1018 J/ atom    1.39  10 3 kJ mol 1
mol (1000 J)
IE = 0 − (−1.39  103 kJ mol−1) = 1.39  103 kJ mol−1
 1  109 nm 
(6.626  10 34 J s)(3.00  108 m s 1 )  
 m   86.1 nm
λ
(2.308  10 18 J)
Check: The units of the answer (kJ mol−1) are correct. The magnitude of the answer is reasonable since the
value is positive and energy must be added to the atom to remove the electron. The units of the wave‐
length (nm) are correct and the magnitude is reasonable based on the ionization energy.
n2 h 2
7.149 Given: Schrödinger equation for particle in one‐dimensional box and n(x) Find: show that E 
8ma2
Conceptual Plan: Start with equation for particle in a one‐dimensional box and then substitute
wavefunction.
h2 d2 n
 n  x 
2
   E sin x
8 m dx 2
2
a a
Use trigonometric derivatives and chain rule to take second derivative of wavefunction and then simplify.
d
dx
 sin x   cos x d
dx
 cos x   sin x

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Chapter 7 The Quantum‐Mechanical Model of the Atom 153

Solution:
h2  d2 
     E
8 2 m  dx 2 
h2  d2 2 n   2 n 
  sin x  = E sin x
8 2 m  dx 2 A a  
  A a 

h 2  n d 2 n   2 n 
  cos x  = E sin x
8 2 m  a dx A a   
 A a 
h 2  n2 2 2 n   2 n 
  sin x   E sin x
8 2 m  a 2 A a   
 A a 
n2 h 2  2 n   2 n 
 sin x   E sin x
8 ma2  A a  
 A a 
2 2
nh
 = E
8 ma 2
n2 h 2
 E
8 ma2

Conceptual Problems
7.151 (a) Since the interference pattern is caused by single electrons interfering with themselves, the pattern
remains the same even when the rate of the electrons passing through the slits is one electron per
minute. It will simply take longer for the full pattern to develop.
(b) When a light is placed behind the slits, it flashes to indicate which hole the electron passed through,
but the interference pattern is now absent. With the laser on, the electrons hit positions directly
behind each slit, as if they were ordinary particles.
(c) Diffraction occurs when a wave encounters an obstacle of a slit that is comparable in size to its
wavelength. The wave bends around the slit. The diffraction of light through two slits separated
by a distance comparable to the wavelength of the light results in an interference pattern. Each slit
acts as a new wave source, and the two new waves interfere with each other, which results in a
pattern of bright and dark lines.

(d) Since the mass of the bullets and their particle size are not absolutely small, the bullets will not
produce an interference pattern when they pass through the slits. The de Broglie wavelength pro‐
duced by the bullets will not be large enough to interfere with the bullet trajectory and no
interference pattern will be observed.

7.153 According to the quantum‐mechanical model, the higher the n level the higher the energy. So, the transi‐
tion from 3p  1s would be a greater energy difference than a transition from 2p  1s. The lower
energy transition would have the longer wavelength. Therefore, the 2p  1s transition would produce a
longer wavelength.

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