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496 CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY

60. Quantum numbers give the allowed solutions to Schrödinger equation. Each solution is an
allowed energy level called a wave function or an orbital. Each wave function solution is
described by three quantum numbers, n, ℓ, and m

. The physical significance of the quantum
numbers are:

n: Gives the energy (it completely specifies the energy only for the H atom or ions with
one electron) and the relative size of the orbitals.

ℓ: Gives the type (shape) of orbital.

m

: Gives information about the direction in which the orbital is pointing.

The specific rules for assigning values to the quantum numbers n, ℓ, and m

are covered in
Section 12.9. In Section 12.10, the spin quantum number m
s
is discussed. Since we cannot
locate electrons, we cannot see if they are spinning. The spin is a convenient model. It refers
to the ability of the two electrons that can occupy any specific orbital to produce two
differently oriented magnetic moments.

61. The 2p orbitals differ from each other in the direction in which they point in space. The 2p
and 3p orbitals differ from each other in their size, energy, and number of nodes. A nodal
surface in an atomic orbital is a surface in which the probability of finding an electron is zero.

62.










63. For r = a
o
and θ = 0° (Z = 1 for H):

¢
2 / 3
11 2 / 1
p 2
10 29 . 5
1
) π 2 ( 4
1
z |
|
.
|

\
|
×
=
÷
(1) e
÷1/2
cos 0 = 1.57 ! 10
14
; ψ
2
= 2.46 ! 10
28


For r = a
o
and θ = 90°:
z
p 2
ψ = 0 because cos 90° = 0; ψ
2
= 0; the xy plane is a node for the
2p
z
atomic orbital.

64. A node occurs when ψ = 0. ψ
300
= 0 when 27 ÷ 18σ + 2σ
2
= 0.

Solving using the quadratic formula: σ =
4
) 27 )( 2 ( 4 ) 18 ( 18
2
÷ ±
=
4
108 18±

σ = 7.10 or σ = 1.90; because σ = r/a
o
, the nodes occur at r = (7.10)a
o
= 3.76 ! 10
÷10
m and at
r = (1.90)a
o
= 1.01 ! 10
÷10
m, where r is the distance from the nucleus.
r
2p
¢
2
r
3p
¢
2

496 CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY

60. Quantum numbers give the allowed solutions to Schrödinger equation. Each solution is an
allowed energy level called a wave function or an orbital. Each wave function solution is
described by three quantum numbers, n, ℓ, and m

. The physical significance of the quantum
numbers are:

n: Gives the energy (it completely specifies the energy only for the H atom or ions with
one electron) and the relative size of the orbitals.

ℓ: Gives the type (shape) of orbital.

m

: Gives information about the direction in which the orbital is pointing.

The specific rules for assigning values to the quantum numbers n, ℓ, and m

are covered in
Section 12.9. In Section 12.10, the spin quantum number m
s
is discussed. Since we cannot
locate electrons, we cannot see if they are spinning. The spin is a convenient model. It refers
to the ability of the two electrons that can occupy any specific orbital to produce two
differently oriented magnetic moments.

61. The 2p orbitals differ from each other in the direction in which they point in space. The 2p
and 3p orbitals differ from each other in their size, energy, and number of nodes. A nodal
surface in an atomic orbital is a surface in which the probability of finding an electron is zero.

62.










63. For r = a
o
and θ = 0° (Z = 1 for H):

¢
2 / 3
11 2 / 1
p 2
10 29 . 5
1
) π 2 ( 4
1
z |
|
.
|

\
|
×
=
÷
(1) e
÷1/2
cos 0 = 1.57 ! 10
14
; ψ
2
= 2.46 ! 10
28


For r = a
o
and θ = 90°:
z
p 2
ψ = 0 because cos 90° = 0; ψ
2
= 0; the xy plane is a node for the
2p
z
atomic orbital.

64. A node occurs when ψ = 0. ψ
300
= 0 when 27 ÷ 18σ + 2σ
2
= 0.

Solving using the quadratic formula: σ =
4
) 27 )( 2 ( 4 ) 18 ( 18
2
÷ ±
=
4
108 18±

σ = 7.10 or σ = 1.90; because σ = r/a
o
, the nodes occur at r = (7.10)a
o
= 3.76 ! 10
÷10
m and at
r = (1.90)a
o
= 1.01 ! 10
÷10
m, where r is the distance from the nucleus.
r
2p
¢
2
r
3p
¢
2
CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 497

65. a. For n = 3, ℓ = 3 is not possible.
d. m
s
cannot equal 1.
e. ℓ cannot be a negative number. f. For ℓ = 1, m

cannot equal 2.
The quantum numbers in parts b and c are allowed.

66. b. For ℓ = 3, m

can range from -3 to +3; thus +4 is not allowed.
c. n cannot equal zero. d. ℓ cannot be a negative number.
The quantum numbers in part a are allowed.

67. 1p, 0 electrons (ℓ ≠ 1 when n = 1);
2 2
y x
d 6

, 2 electrons (specifies one atomic orbital); 4f,
14 electrons (7 orbitals have 4f designation); 7p
y
, 2 electrons (specifies one atomic orbital);
2s, 2 electrons (specifies one atomic orbital); n = 3, 18 electrons (3s, 3p, and 3d orbitals are
possible; there are one 3s orbital, three 3p orbitals, and five 3d orbitals).

68. 5p: three orbitals
2
z
d 3 : one orbital 4d: five orbitals
n = 5: ℓ = 0 (1 orbital), ℓ = 1 (3 orbitals), ℓ = 2 (5 orbitals), ℓ = 3 (7 orbitals),
ℓ = 4 (9 orbitals); total for n = 5 is 25 orbitals.
n = 4: ℓ = 0 (1), ℓ = 1 (3), ℓ = 2 (5), ℓ = 3 (7); total for n = 4 is 16 orbitals.

69. 1p: n = 1, ℓ = 1 is not possible; 3f: n = 3, ℓ = 3 is not possible; 2d: n = 2, ℓ = 2 is not
possible; in all three incorrect cases, n = ℓ. The maximum value ℓ can have is n  1, not n.

70. ψ
2
gives the probability of finding the electron at that point.

Polyelectronic Atoms

71. Valence electrons are the electrons in the outermost principal quantum level of an atom
(those electrons in the highest n value orbitals). The electrons in the lower n value orbitals are
all inner core or just core electrons. The key is that the outermost electrons are the valence
electrons. When atoms interact with each other, it will be the outermost electrons that are
involved in these interactions. In addition, how tightly the nucleus holds these outermost
electrons determines atomic size, ionization energy, and other properties of atoms. Elements
in the same group have similar valence electron configurations and, as a result, have similar
chemical properties.

72. The widths of the various blocks in the periodic table are determined by the number of
electrons that can occupy the specific orbital(s). In the s block, we have one orbital (ℓ = 0, m


= 0) that can hold two electrons; the s block is two elements wide. For the f block, there are 7
degenerate f orbitals (ℓ = 3, m

= 3, 2, 1, 0, 1, 2, 3), so the f block is 14 elements wide.
The g block corresponds to ℓ = 4. The number of degenerate g orbitals is 9. This comes from
the 9 possible m

values when ℓ = 4 (m

= 4, 3, 2, 1, 0, 1, 2, 3, 4). With 9 orbitals, each
orbital holding two electrons, the g block would be 18 elements wide. The h block has ℓ = 5,
m

= 5, 4, 3, 2, 1, 0, 1, 2, 3, 4, 5. With 11 degenerate h orbitals, the h block would be
22 elements wide.
CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 497

65. a. For n = 3, ℓ = 3 is not possible.
d. m
s
cannot equal 1.
e. ℓ cannot be a negative number. f. For ℓ = 1, m

cannot equal 2.
The quantum numbers in parts b and c are allowed.

66. b. For ℓ = 3, m

can range from -3 to +3; thus +4 is not allowed.
c. n cannot equal zero. d. ℓ cannot be a negative number.
The quantum numbers in part a are allowed.

67. 1p, 0 electrons (ℓ ≠ 1 when n = 1);
2 2
y x
d 6

, 2 electrons (specifies one atomic orbital); 4f,
14 electrons (7 orbitals have 4f designation); 7p
y
, 2 electrons (specifies one atomic orbital);
2s, 2 electrons (specifies one atomic orbital); n = 3, 18 electrons (3s, 3p, and 3d orbitals are
possible; there are one 3s orbital, three 3p orbitals, and five 3d orbitals).

68. 5p: three orbitals
2
z
d 3 : one orbital 4d: five orbitals
n = 5: ℓ = 0 (1 orbital), ℓ = 1 (3 orbitals), ℓ = 2 (5 orbitals), ℓ = 3 (7 orbitals),
ℓ = 4 (9 orbitals); total for n = 5 is 25 orbitals.
n = 4: ℓ = 0 (1), ℓ = 1 (3), ℓ = 2 (5), ℓ = 3 (7); total for n = 4 is 16 orbitals.

69. 1p: n = 1, ℓ = 1 is not possible; 3f: n = 3, ℓ = 3 is not possible; 2d: n = 2, ℓ = 2 is not
possible; in all three incorrect cases, n = ℓ. The maximum value ℓ can have is n  1, not n.

70. ψ
2
gives the probability of finding the electron at that point.

Polyelectronic Atoms

71. Valence electrons are the electrons in the outermost principal quantum level of an atom
(those electrons in the highest n value orbitals). The electrons in the lower n value orbitals are
all inner core or just core electrons. The key is that the outermost electrons are the valence
electrons. When atoms interact with each other, it will be the outermost electrons that are
involved in these interactions. In addition, how tightly the nucleus holds these outermost
electrons determines atomic size, ionization energy, and other properties of atoms. Elements
in the same group have similar valence electron configurations and, as a result, have similar
chemical properties.

72. The widths of the various blocks in the periodic table are determined by the number of
electrons that can occupy the specific orbital(s). In the s block, we have one orbital (ℓ = 0, m


= 0) that can hold two electrons; the s block is two elements wide. For the f block, there are 7
degenerate f orbitals (ℓ = 3, m

= 3, 2, 1, 0, 1, 2, 3), so the f block is 14 elements wide.
The g block corresponds to ℓ = 4. The number of degenerate g orbitals is 9. This comes from
the 9 possible m

values when ℓ = 4 (m

= 4, 3, 2, 1, 0, 1, 2, 3, 4). With 9 orbitals, each
orbital holding two electrons, the g block would be 18 elements wide. The h block has ℓ = 5,
m

= 5, 4, 3, 2, 1, 0, 1, 2, 3, 4, 5. With 11 degenerate h orbitals, the h block would be
22 elements wide.






518 CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY

146. For hydrogen: ΔE = ÷2.178 ! 10
÷18
J |
.
|

\
|
÷
2 2
5
1
2
1
= ÷4.574 !
19
10
÷
J

For a similar blue light emission, He
+
will need about the same ΔE value.

For He
+
: E
n
= ÷2.178 !
18
10
÷
J (Z
2
/n
2
), where Z = 2:

ΔE = ÷4.574 !
19
10
÷
J = ÷2.178 ! 10
÷18
J
|
|
.
|

\
|
÷
2
2
2
f
2
4
2 2
n


0.2100 =
16
4 4
2
f
÷
n
, 0.4600 =
2
f
4
n
, n
f
= 2.949

The transition from n = 4 to n = 3 for He
+
should emit similar-colored blue light as the n = 5
to n = 2 hydrogen transition; both these transitions correspond to very nearly the same energy
change.

147. a. Assuming the Bohr model applies to the 1s electron, E
1s
= ÷R
H
Z
2
/n
2
= ÷R
H
Z
2
eff
, where
n = 1.

IE = E
·
÷ E
1s
= 0 – E
1s
= R
H
Z
2
eff


kJ
J 1000
10 0221 . 6
mol 1
mol
kJ 10 462 . 2
23
6
×
×
×
×
= 2.178 × 10
÷18
J (Z
eff
)
2
, Z
eff
= 43.33

b. Silver is element 47, so Z = 47 for silver. Our calculated Z
eff
value is slightly less than
47. Electrons in other orbitals can penetrate the 1s orbital. Thus a 1s electron can be
slightly shielded from the nucleus, giving a Z
eff
close to but less than Z.

148. a. L
x
= L
y
= L
z
; E
xyz
=
2
2
z
2
y
2
x
2
8mL
) ( h n n n + +


E
111
=
2
2
mL 8
h 3
; E
112
=
2
2
mL 8
h
(1
2
+ 1
2
+ 2
2
) =
2
2
mL 8
h 6


E
122
=
2
2
mL 8
h
(1
2
+ 2
2
+ 2
2
) =
2
2
mL 8
h 9


b. E
111
: only a single state; E
112
: triple degenerate, either n
x
, n
y
or n
z
can equal 2; E
122
:
triple degenerate, either n
x
, n
y
or n
z
can equal 1; E
222
: single state





CHAPTER 12 QUANTUM MECHANICS AND ATOMIC THEORY 519

Cubic Box Rectangular box

E
222
____


E
122
These are no longer degenerate.
_____
_____


E
112
These are no longer degenerate.
_____
_____

E
111
_____

149. E
xyz
=
2
2
z
2
y
2
x
2
mL 8
) ( h n n n  
, where L = L
x
= L
y
= L
z
.

The first four energy levels will be filled with the 8 electrons. The first four energy levels
are:
E
111
=
2
2 2 2 2
8mL
) 1 1 (1 h  
=
2
2
mL 8
h 3


E
211
= E
121
= E
112
=
2
2
mL 8
h 6
(These three energy levels are degenerate.)

The next energy levels correspond to the first excited state. The energy for these levels are:

E
221
= E
212
= E
122
=
2
2
mL 8
h 9
(These three energy levels are degenerate.)

The electronic transition in question is from one of the degenerate E
211
, E
121
, or E
112
levels to
one of the degenerate E
221
, E
212
, or E
122
levels.

ΔE =
2
2
2
2
2
2
mL 8
h 3
mL 8
h 6
mL 8
h 9
 

ΔE =
2 9 31
2 34
) m 10 50 . 1 )( kg 10 109 . 9 ( 8
) s J 10 626 . 6 ( 3
 

 

= 8.03 ! 10
20
J


J 10 03 . 8
) s / m 10 998 . 2 )( s J 10 626 . 6 (
E Δ
hc
λ
20
8 34



 
  = 2.47 ! 10
6
m = 2470 nm