CHAPTER 1

ATOMS: THE QUANTUM WORLD

1.1

(a)Radiation may pass through a metal foil.(b)All light

(electromagnetic radiation) travels at the same speed; the slower speed
supports the particle model.(c)This observation supports the radiation
model.(d)This observation supports the particle model;
electromagnetic radiation has no mass and no charge.

1.3

microwaves < visible light < ultraviolet light < x-rays < -rays

1.5

All of these can be determined using Eh and c . For example, in

the first entry frequency is given, so:

c
2.998108 m s -1

= 3.410-7 m = 340 nm ;
14 -1

8.710 s

-34
-14 -1
-19
and E h 6.62610 J s 8.710 s = 5.810 J

Frequency

Wavelength

Energy of photon

Event

(2 s.f.)
8.7 1014 Hz
5.0 1014 Hz
300 MHz
1.2 1017 Hz

(2 s.f.)
340 nm
600 nm
1m
2.5 nm

(2 s.f.)
5.8 10-19 J
3.3 10-19 J
2 10-25 J
7.9 10-17 J

Suntan
Reading
Microwave popcorn
Dental X-ray

SM-50

1.7

Wiens law states that T max constant 2.88 10 3 K m.

If T /K 1540C 273C 1813 K, then max

2.88 103 K m
1813 K

max 1.59 106 m, or 1590 nm

1.9

(a) From c n and E hn, we can write

E hc 1
(6.626 08 1034 J s) (2.997 92 108 ) (589 10 9 m) 1
3.37 1019 J
5.00 103 g Na
23
1
E
(6.022 10 atoms mol )
1
22.99 g mol Na

(b)

(3.37 1019 J atom 1 )

44.1 J

(c)

1.11

E (6.022 1023 atoms mol 1 )(3.37 10 19 J atom 1 )

2.03 105 J or 203 kJ

The energy is first converted from eV to joules:

E (140.511 103 eV) (1.6022 10 19 J eV 1 ) 2.2513 1014 J
From E hv and c v we can write
hc
E
(6.626 08 1034 J s) (2.997 92 108 m
s 1 )

2.2513 1014 J

8.8237 1012 m or 8.8237 pm

1.13

(a)false. The total intensity is proportional to T 4 . (Stefan-Boltzmann

Law)(b)true;(c)false. Photons of radio-frequency radiation are
lower in energy than photons of ultraviolet radiation.

SM-51

1.15

(a)Use the de Broglie relationship, hp 1 h(mv) 1 .

me (9.109 39 1028 g) (1 kg/1000 g) 9.109 39 1031 kg
(3.6 103 km s 1 ) (1000 m km 1 ) 3.6 106 m s1

h(mv ) 1

6.626 08 1034 J s
(9.109 39 1031 kg) (3.6 106 m s 1 )

2.0 1010 m
E h
(b)

(6.626 08 1034 J s) (2.50 1016 s 1 )

1.66 1017 J

(c)The photon needs to contain enough energy to eject the electron from
the surface as well as to cause it to move at 3.6 103 km s 1 . The energy
1
2
involved is the kinetic energy of the electron, which equals 2 mv .

1
mv 2
2
1
J (9.109 39 1031 kg) (3.6 106 m s 1 ) 2
2
J 5.9 1018 J

Ephoton 1.66 1017 J

1.66 1017
1.66 1017

2.25 1017 J
But we are asked for the wavelength of the photon, which we can get from
E hv and c v or E hc 1 .

2.25 1017 kg m 2 s 2 (6.62608 10

34 kg m2 s 1 )
(2.99792 108 m s 1 ) 1

8.8 109 m
8.8 nm
(d)8.6 nm is in the x-ray/gamma ray region.
1.17

To answer this question, we need to convert the quantities to a consistent

set of units, in this case, SI units.

SM-52

(5.15 ounce) (28.3 g ounce 1 ) (1 kg/1000 g) 0.146 kg

1 km
92 mi 1 h
1000 m
1
h 3600 s 0.6214 mi 1 km 41 m s

Use the de Broglie relationship.

hp 1 h(mv) 1
h(mv ) 1

6.626 08 1034 J s
(0.146 kg) (0.041 km s 1 )

6.626 08 1034 kg m 2 s 1

(0.146 kg) (41 m s 1 )

1.1 1034 m

1.19

From the de Broglie relationship, p h 1 or h mv , we can calculate

the velocity of the neutron:
v

h
m

(6.626 08 1034 kg m 2 s 1 )

(remember that 1 J 1 kg m 2 s 2 )
27
12
(1.674 93 10 kg) (100 10 m)
3.96 103 m s 1
1.21

Yes there are degenerate levels. The first three cases of degenerate levels
are:
n1 = 1, n2 = 2 is degenerate with n1 = 2 , n2 = 1

n1 1, n2 3 is degenerate with n1 3, n2 1
n1 2, n2 3 is degenerate with n1 3, n2 2

1.23

n2 n2 n2
x
y
z

2
L

h2
Given the expression for the cubic box is E xyz
8m

where E xyz represents the energy of a given level having n values

corresponding to x, y and z we can describe each new level by
incrementing each n by one; any levels with the same energy will be
SM-53

degenerate. The three lowest energy levels will therefore be E111 , E211 ,
and E221 . From this we can arrive at expressions for the energy of each
h2 12 12 12
3 h2

level: E111
. Similarly, the other two energy
8 m

L2
8 mL2
3 h2
9 h2
levels are determined to be E211
and E221
. The 211
4 mL2
8 mL2
and the 221 levels are degenerate; that is E211 E121 E112 and

1.25

221

212

122

(a) Refer to the plot below for parts (a) thru (d); nodes are where the
wavefunction is zero:
1.42

n=2

n=3

(x)/m-1/2
0.00

-1.42
0.00

0.333

0.500

0.667

1.00

x (m)

(b) for n = 2 there is one node at x = 0.500 m.

(c) for n = 3 there are two nodes, one at x = 0.333 and 0.667 m .
(d) the number of nodes is equal to n 1
Refer to the plot below for parts (e) and (f):

SM-54

n=2

n=3

(x)2/m-1/2

0.00

0.17 0.25

0.50

0.75 0.83

1.00

x (m)

(e) for n = 2 a particle is most likely to be found at x = 0.25 m and x = 0.75

m.
(f) for n = 3 a particle is most likely to be found at x = 0.17, 0.50 and 0.83
m.
1.27

(a) Integrate over the left half of the box or from 0 to L:

L
2

2 L2
n x
sin
dx

0
L
L

2 1
n x
n x x

cos
sin

L 2n
L
L
2

given n is an integer:

L
2

2 L / 2

L 2
2

(b) Integrate over the left third of the box or from 0 to 1/3 L:

L
2

2 L
n x
2 sin
dx
0
L
L
2

2 1
n x
n x x

cos
sin

L 2n
L
L
2

1
n
n 1

cos
sin

L n

3
3 3

L
3

SM-55

if n is a multiple of 3, the first term in this sum is zero and the

probability of finding an electron in the left third of the box is
1/ 3. Also, as n becomes large the probability of finding the
electron in the left third of the box approaches 1/3.

1.29

(a)The Rydberg equation gives when 3.29 1015 s 1 , from which

one can calculate from the relationship c .

1
1
2 2
n2
n1
and c 2.99792 108 m s 1
1
1
c 2 2
n2
n1

1
1

4 16

2.99792 108 m s 1 (3.29 1015 s 1 )

4.86 10 -7 m 486 nm

(b)Balmer series
(c)visible, blue
1.31

For hydrogen-like one-electron ions, we use the Z-dependent Rydberg

relation with the relationship c to determine the transition
wavelength. For He+, Z = 2.
1
1
1
1

2 2 3.29 1015 s 1 2 2 9.87 1015 Hz

2
2
1
2
n1 n2

Z 2

1.33

c 2.99792 108 m s1

3.04 10-8 m 30.4 nm

15 1

9.87 10 s

(a)This problem is the same as that solved in Example 1.5, but the
electron is moving between different energy levels. For movement
between energy levels separated by a difference of 1 in principal quantum
number, the expression is
E En 1 En

(n 1) 2 h 2 n 2 h 2 (2n 1)h 2

8mL2
8mL2
8mL2

SM-56

For n 2 and n 1 3, E
Then 3,2

5h 2
8mL2

hc 8mhcL2 8mcL2

E
5h
5h 2

For an electron in a 150-pm box, the expression becomes

3,2

8(9.109 39 10 31 kg) (2.997 92 108 m s 1 ) (150 10 12 m) 2

5(6.626 08 1034 J s)

1.5 10 8 m

1.48 10 8 m

(b)We need to remember that the equation for E was originally

determined for energy separations between successive energy levels, so
the expression needs to be altered to make it general for energy levels two
units apart:
(n 2) 2 h 2 n 2 h 2 (n 2 4n 4 n 2 )h 2 (4n 4)h 2

8mL2
8mL2
8mL2
8mL2
hc
hc(8mL2 )
8mcL2

E h 2 [4n 4] h 2 [4n 4]
E En 2 En

For n 2, the expression becomes

8mcL2
8mcL2

h[( 4 2) 4]
12h
8(9.10939 10 31 kg) ( 2.99792 10 8 m s 1 ) (150 10 12 m) 2
12(6.62608 10 34 kg m 2 s 1 )

6.18 10 9 m

1.35

In each of these series, the principal quantum number for the lower energy
level involved is the same for each absorption line. Thus, for the Lyman
series, the lower energy level is n 1; for the Balmer series, n 2; for
Paschen series, n 3; and for the Brackett series, n 4.

SM-57

1.37

(a) 1s

2p

3d

(b)A node is a region in space where the wavefunction passes through

0.(c)The simplest s -orbital has 0 nodes, the simplest p -orbital has 1
nodal plane, and the simplest d-orbital has 2 nodal planes.(d)Given the
increase in number of nodes, an f-orbital would be expected to have 3
nodal planes.

1.39

The px orbital will have its lobes oriented along the x axis, the py orbital
will have its lobes oriented along the y axis, and the pz orbital will have
its lobes oriented along the z axis.

1.41

The equation derived in Illustration 1.4 can be used:

e

2 ( r 0.55a0 , , )

2 (0, , )

1.43

2(0.55 a0 ) / a0

a03
1

3
a0

0.33

To show that three p orbitals taken together are spherically symmetric,

sum the three probability distributions (the wavefunctions squared) and
show that the magnitude of the sum is not a function of or .
px R( r )C sin cos
p y R (r )C sin sin
pz R (r )C cos
1

3 2

4
Squaring the three wavefunctions and summing them:
where C

SM-58

R (r ) 2 C 2 sin 2 cos 2 R(r ) 2 C 2 sin 2 sin 2 R( r ) 2 C 2 cos 2

R (r ) 2 C 2 sin 2 cos 2 sin 2 sin 2 cos 2

R (r ) 2 C 2 sin 2 cos 2 sin 2 cos 2

Using the identity cos 2 x sin 2 x 1 this becomes

R (r ) 2 C 2 sin 2 cos 2 R(r ) 2 C 2

With one electron in each p orbital, the electron distribution is

not a fuction of or and is, therefore, spherically symmetric.
1.45

(a) The probability (P) of finding an electron within a sphere of radius ao

may be determined by integrating the appropriate wavefunction squared
from 0 to ao :
2r
4 ao
P 2 r 2 exp dr
ao 0
ao
This integral is easier to evaluate if we allow the following
change of variables:
z

2r
ao

a
z 2 when r ao , z 0 when r 0, and dr o dz
2
2

1 2
1
P z 2 exp( z )dz ( z 2 2 z 2) exp( z )
0
2
2
0
1
(4 4 2) exp(2) 2
2
0.323 or 32.3%

(b) Following the answer developed in (a) changing the integration limits
to 0 to 2 ao:
a
z 4 when r 2ao , z 0 when r 0, and dr o dz
2
4

1 4
1
P z 2 exp( z )dz ( z 2 2 z 2) exp( z )
0
2
2
0
1
26 exp(4) 4
2
0.761 or 76.1%

SM-59

1.47

(a)1 orbital;(b)5 orbitals;(c)3 orbitals;(d)7 orbitals

1.49

(a)7 values: 0, 1, 2, 3, 4, 5, 6;(b)5 values; 2, 1, 0, 1, 2; (c)3

values: 1, 0, 1; (d)4 subshells: 4 s, 4 p, 4d , and 4 f

1.51

(a) n 6; l 1; (b) n 3; l 2; (c) n 2; l 1; (d) n 5; l 3

1.53

(a) 1, 0, 1; (b) 2, 1, 0, 1, 2; (c) 1, 0, 1;

(d) 3,2, 1, 0, 1, 2, 3.

1.55

(a)6 electrons; (b)10 electrons;(c)2 electrons;(d)14 electrons

1.57

(a) 5d , five;(b) 1s, one;(c) 6 f , seven;(d) 2 p, three

1.59

(a) six;(b)two;(c) eight;(d)two

1.61

(a)cannot exist;(b)exists;(c)cannot exist;(d)exists

1.63

(a)The total Coulomb potential energy V (r ) is the sum of the individual

coulombic attractions and repulsions. There will be one attraction between
the nucleus and each electron plus a repulsive term to represent the
interaction between each pair of electrons. For lithium, there are three
protons in the nucleus and three electrons. Each attractive Coulomb
potential will be equal to
(e)(3e) 3e 2

4 0 r
4 0 r
where e is the charge on the electron and 3e is the charge on the
nucleus, 0 is the vacuum permittivity, and r is the distance from the
electron to the nucleus. The total attractive potential will thus be

SM-60

 3e 2

4 0 r1

3e 2
3e 2
3e 2

4
4 0 r2
0 r3
4 0

1 1 1

r1 r2 r3

The repulsive terms will have the form

(e)(e)
e2

4 0 rab
4 0 rab
where rab represents the distance between two electrons a and b. The total
repulsive term will thus be
e2
e2
e2
e2

4 0 r12 4 0 r13 4 0 r23 4 0

1
1 1

r12 r13 r23

This gives
3e 2 1 1 1
e 2
1
1 1

4
4 0 r2 r2 r3
0 r12 r13 r23

V (r )

(b)The first term represents the coulombic attractions between the

nucleus and each electron, and the second term represents the coulombic
repulsions between each pair of electrons.

1.65

(a)false. Zeff is considerably affected by the total number of electrons

present in the atom because the electrons in the lower energy orbitals will
shield the electrons in the higher energy orbitals from the nucleus. This
effect arises because the e-e repulsions tend to offset the attraction of the
electron to the nucleus.(b)true;(c) false. The electrons are
increasingly less able to penetrate to the nucleus as l increases.(d)true.

1.67

Only (d) is the configuration expected for a ground-state atom; the others
all represent excited-state configurations.

1.69

(a)This configuration is possible.(b)This configuration is not possible

because l 0 here, so m1 must also equal 0.(c)This configuration is
not possible because the maximum value l can have is
n 1; n 4, so lmax 3.
SM-61

1.71

(a)silver

[Kr]4d 10 5s1

(b)beryllium

[He]2s 2

(c)antimony

[Kr]4d 10 5s 2 5 p 3

(d)gallium

[Ar]3d 10 4 s 2 4 p1

(e)tungsten

[Xe]4f 14 5d 4 6s 2

(f)iodine

[Kr]4d 10 5s 2 5 p 5

1.73

(a)tellurium;(b)vanadium;(c)carbon;(d)thorium

1.75

(a) 4 p; (b) 4 s; (c) 6 s; (d) 6s

1.77

(a)5;(b)11;(c)5;(d)20

1.79

(a)3;(b)2;(c)3;(d)2

1.81
Unpaired
Element
Ga

Electron Configuration
[Ar] 3d 10 4s 2 4 p1

electrons
1

Ge

[Ar] 3d 10 4s 2 4 p 2

As

[Ar] 3d 10 4s 2 4 p 3

Se

[Ar] 3d 10 4s 2 4 p 4

Br

[Ar] 3d 10 4s 2 4 p5

1.83

(a) ns1 ;(b) ns 2 np1 ; (c) (n 1)d 5 ns 2 ; (d) (n 1)d 10 ns1

1.85

(a)oxygen (1310 kJ mol1 ) > selenium (941 kJ mol1 ) > tellurium

(870 kJ mol 1 ); ionization energies generally decrease as one goes down
a group.(b)gold (890 kJ mol1 ) > osmium (840 kJ mol1 ) >

SM-62

tantalum (761 kJ mol 1 ); ionization energies generally decrease as one

goes from right to left in the periodic table.(c)lead (716 kJ mol1 ) >
barium (502 kJ mol1 ) > cesium (376 kJ mol1 ) ; ionization energies
generally decrease as one goes from right to left in the periodic table.
1.87

The atomic radii (in pm) are

Sc

161

Fe

124

Ti

145

Co

125

132

Ni

125

Cr

125

Cu

128

Mn

137

Zn

133

The major trend is for decreasing radius as the nuclear charge increases,
with the exception that Cu and Zn begin to show the effects of electronelectron repulsions and become larger as the d-subshell becomes filled.
Mn is also an exception as found for other properties; this may be
attributed to having the d-shell half-filled.
1.89

(a) Sb3+, Sb5+; (c) Tl+, Tl3+; (b) and (d) only form one positive ion each.

1.91

P3 S2 Cl

1.93

(a)fluorine;(b) carbon;(c)chlorine;(d)lithium.

1.95

(a) A diagonal relationship is a similarity in chemical properties between

an element in the periodic table and one lying one period lower and one
group to the right. (b) It is caused by the similarity in size of the ions. The
lower-right element in the pair would generally be larger because it lies in
a higher period, but it also will have a higher oxidation state, which will
cause the ion to be smaller. (c) For example, Al3 and Ge 4 compounds
show the diagonal relationship, as do Li and Mg 2 .
SM-63

1.97

Only (b)Li and Mg exhibit a diagonal relationship.

1.99

The ionization energies of the s -block metals are considerably lower, thus
making it easier for them to lose electrons in chemical reactions.

1.101 (a)metal;(b)nonmetal;(c)metal;(d)metalloid;(e)
metalloid;(f)metal

1.103 (a)

3600 cm 1
c

c(3600 cm 1 )
(2.997 92 108 m s 1 ) (3600 cm 1 )
(2.997 92 1010 cm s 1 ) (3600 cm 1 )
1.1 1014 s 1
(b) From E h : E (6.626 08 1034 J s)(1.079 1014 s 1 )
7.2 1020 J.
(c)1.00 mol of molecules 6.022 1023 molecules, so the energy
absorbed by 1.00 mol will be
(7.151 1020 J molecule 1 )(6.022 1023 molecules mol 1 )
4.3 104 J mol1 or 43 kJ mol 1 .
1.105 Cu = [Ar]3d104s1 and Cr = [Ar]3d54s1; In copper it is energetically
favorable for an electron to be promoted from the 4s orbital to a 3d orbital,
giving a completely filled 3d subshell. In the case of Cr, it is energetically
favorable for an electron to be promoted from the 4s orbital to a 3d orbital
to exactly fill the 3d subshell.
1.107 This trend is attributed to the inert-pair effect, which states that the s electrons are less available for bonding in the heavier elements. Thus,

SM-64

there is an increasing trend as we descend the periodic table for the

preferred oxidation number to be 2 units lower than the maximum one. As
one descends the periodic table, ionization energies tend to decrease. For
Tl, however, the values are slightly higher than those of its lighter
analogues.
1.109 (a)The relation is derived as follows: the energy of the photon entering,
Etotal , must be equal to the energy to eject the electron, Eejection , plus the
energy that ends up as kinetic energy, Ekinetic , in the movement of the
electron:
Etotal Eejection Ekinetic
1
2
But Etotal for the photon h and Ekinetic mv where m is the mass
2
of the object and v is its velocity. Eejection corresponds to the ionization
energy, I , so we arrive at the final relationship desired.
(b)

Etotal h hc 1
(6.62608 10 34 J s) (2.99792 10 8 m s 1 ) (58.4 10 9 m)1
3.401 10 18 J
Eejection Ekinetic

SM-65

 1 2
1
mv (9.10939 10 28 g) (2450 km s 1 )2
2

Ekinetic

1
(9.10939 10 31 kg) (2.450 10 6 m s1 )2
2

2.734 10 18 kg m 2 s2 2.734 10 18 J
3.401 10 18 J E ejection 2.734 10 18 J
E ejection 6.67 10 19 J

1.111 By the time we get to the lanthanides and actinides the two series of forbital filling elementsthe energy levels become very close together and
minor changes in environment cause the different types of orbitals to
switch in energy-level ordering. For the elements mentioned, the
electronic configurations are
La

[Xe] 6s 2 5d 1

Lu

[Xe] 6s 2 4f 14 5d 1

Ac

[Rn] 7s 2 6d 1

Lr

[Rn] 7 s 2 5 f 14 6d 1

As can be seen, all these elements have one electron in a d-orbital, so

placement in the third column of the periodic table could be considered
appropriate for either, depending on what aspects of the chemistry of these
elements we are comparing. The choice is not without argument, and it is
discussed by W. B. Jensen (1982), J . Chem. Ed . 59, 634.
1.113 (a)(c)We can use the hydrogen 2s wavefunction found in Table 1.2.
Remember that the probability of locating an electron at a small region in
space is proportional to 2 , not .
1

2s
2s

1
1 2
r 2 a0

2

e
4 2 a03
a0

3
32 a0

r
e a
2
a 0

r
0

SM-66

1
r
a
2

3
2
a0
2 s (r , , ) 32 a0

2
0
2 s (0, , )

1 2 a
2 e

3
32 a0

r
a
2 e
a0

Because r will be equal to some fraction x times a0 , the expression will

simplify further:

xa0

xa0
a
2

2
a0
2 s ( r , , )
(2 x) 2 e x

4
4
2 s 2 (0, , )
0

Carrying out this calculation for the other points, we obtain:

x

relative probability

0.1

0.82

0.2

0.66

0.3

0.54

0.4

0.43

0.5

0.34

0.6

0.27

0.7

0.21

0.8

0.16

0.9

0.12

0.092

1.1

0.067

1.2

0.048

1.3

0.033

1.4

0.022

1.5

0.014

1.6

0.0081

1.7

0.0041

SM-67

1.8

0.0017

1.9

0.0004

0.0000

2.1

0.00031

2.2

0.0011

2.3

0.0023

2.4

0.0036

2.5

0.0051

2.6

0.0067

2.7

0.0082

2.8

0.0097

2.9

0.011

0.012

This can be most easily carried out graphically by simply plotting the
(2 x) 2 e x
function f ( x )
from 0 to 3.
4
0.80

relative probability

0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0.0

0.5

1.0

1.5

2.0

2.5

3.0

The node occurs when x = 2, or when r 2a0 . This is exactly what is

obtained by setting the radial part of the equation equal to 0.

SM-68

1.115 The approach to showing that this is true involves integrating the
probability function over all space. The probability function is given by
the square of the wave function, so that for the particle in the box we have
1

2 2 n x
sin

L
L

and the probability function will be given by

2
n x
2 sin 2

L
L

Because x can range from 0 to L (the length of the box), we can write the
integration as
x

x 2
n x
dx sin 2
dx
0
L
L

for the entire box, we write

probability of finding the particle somewhere in the box =

2
2 n x
sin
dx
L
L

2
probability
L

n x
sin 2
dx
L

2 L2
n x

sin

dx
0

L 0
L
L
2 1
n x
n x x

cos
sin

L 2n
L
L
2 0
2 1
L

cos n sin n 0
L 2n
2

L
2

if n is an integer, sin n will always be zero and

probability

2 L
1
L 2

1.117 (a) 4.8 x 10-10 esu; (b) 14 electrons

SM-69

1.119 Given that the energy needed to break a C C bond is 248 kJmol-1,
348kJ
1molCCbonds
1000J

=5.78 10 19 J
23
molCCbonds
6.022 10 CCbonds
1kJ
Substituting this value into hc E , this energy corresponds to a
wavelength of 3.44 10-7 m or 344 nm. This is in the ultraviolet region of
the electromagnetic spectrum.
h
2.18 10 18 J
1.121 Given that E
and

n
n2
n2

final

:
initial

(a) for an electron to fall from the 4d to 1s level, the energy of the photon

18 J 1 1
-18
is E E1 E4 = 2.18 10
2
= 2.04 10 J (the
2
1
4
negative sign means that energy is released or emitted);
(b) Similarly, an electron moving from the 4d to 2p level will emit a
photon of 4.09 10-19 J;
(c) same as (b); an electron moving from the 4d to 2s emits the same
amount of energy as it would if it were moving to the 2p orbital; this is
due to the fact that all orbitals having the same principal quantum number
n are degenerate (i.e. they have the same energy).
(d) In a hydrogen atom, no photon would be emitted on moving between
orbitals possessing the same n (due to degeneracy of the 4d and the 4s
orbitals in hydrogen).
(e) Since potassium has both more electrons and protons than hydrogen,
the individual orbitals within a given shell will have different energies
(arising from the attractions and repulsions of electrons with the nucleus
and other electrons in the atom). As a result we would expect to see

SM-70

emission lines for all the transitions; thus potassium should show four
lines while hydrogen only shows two.
1.123 = 1064 nm = 1.064 10-6 m; The energy of a photon of this wavelength

6.626 10 34 J sec 2.998 10 8 m

hc
is E
1.867 10 19 J ;
6

1.064 10 m
the energy of the ejected electron is 0.137 eV (1.602 10-19 JeV-1) =
2.195 10-20 J. The difference between these two values is 1.65 10-19 J or
1.65 10-22 kJ per atom of thulium. Multiplication by Avogadros number
gives an electron affinity of 99.2 kJ per mol of thulium.
1.125 The radial distribution of a 3s orbital is given by curve (b), while curve (a)
shows the same for a 3p orbital; this can be determined by examining the
electron density near the origin (which is the nucleus); the plot with the
most electron density closest to (0, 0) arises from the s orbital.

1.127 (a) The electron configuration of atomic chlorine is [Ne]3s 2 3p5 ; it has
one unpaired electron. The electron configuration of a chloride ion is
[Ne]3s 2 3p 6 ; this configuration is identical to neutral argon.
(b) Assuming a one quantum level jump, an excited chlorine should have
an electron configuration of [Ne]3s 2 3p 4 4s1 .
(c) The energy of a given level n in a non-hydrogen atom can be estimated

2
Z eff
2.18 10 18 J
2
Z
h
by E eff
. For chlorine, Zeff is

n
2
2
n
n

approximately equal to 6 (Fig. 1.45). For an electron to jump from the n =

3 to n = 4 quantum level the energy needed is: E E4 E3 =

SM-71

1
1
3.82 10 18 J . This energy
4 2 32

6 2 2.18 10 18 J

corresponds to a wavelength of 52.0 nm (the X-ray region).

(d) This amount of energy corresponds to 2.30103 kJmol-1 or 23.8 eV per
chlorine atom
(e) If the proportion of

37

Cl in a sample of chlorine atoms is reduced to

37.89% (half of its typical value), the proportion of

35

Cl will be increased

to 62.11%. Based on this, the average mass of a chlorine atom will be:
37.89%
62.11%
6.139 10 23 g
5.807 10 23 g

100
100

Clavemass

Clavemass 5.933 10 23 g/atom 35.73g/mol

SM-72

(f) thru (h): refer to the table below:

Compound

Chlorine

ClO2
NaClO
KClO3
NaClO4

oxidation number
+4
+1
+5
+7

SM-73

Name
Chlorine dioxide
Sodium hypochlorite
Potassium chlorate
Sodium perchlorate