Almond, Spillman & Page: Workbooks in Chemitry: Inorganic Chemistry

Solutions to questions in the text

Chapter 1: Atomic structure

Solution 1.1

First we must calculate the energy required to dissociate a single O2 molecule by

dividing the molar bond enthalpy by the Avogadro constant:

495 kJ mol−1 495000 J mol−1

E= = = 8.22 × 10−19 J
6.022 × 1023 mol−1 6.022 × 1023 mol−1

We can now calculate the frequency of a photon that possesses this energy, using the
Planck relation:
𝐸 = ℎ𝜈
𝐸
𝜈=
ℎ

8.22 × 10−19 J
𝜈= = 1.24 × 1015 s−1
6.626 × 10−34 J s

Now that we have obtained the frequency of the photon, it is possible to calculate its
wavelength:
c
λ=
ν

2.998 × 108 m s −1
𝜆= = 2.42 × 10−7 m = 242 × 10−9 m = 242 nm
1.24 × 1015 s−1

Solution 1.2

In this question, we are told to assume that the ideal wavelength for the electrons is 282 Remember, 1 pm = 1 ×
pm. 10-12 m

Using the de Broglie equation, we can then calculate their momentum and hence their
speed.
ℎ
𝜆=
𝑝
The units of velocity must
ℎ be ms-1. Joules are a derived
𝑝 = 𝑚𝑒 × 𝑣𝑒 =
𝜆 unit in the S.I. system: 1J =
ℎ 6.626 × 10−34 J s 1 kg m2 s-2. It can be seen if
𝑣𝑒 = = = 2.58 × 106 m s−1 we substitute this into the
𝜆 × 𝑚𝑒 282 × 10−12 m × 9.109 × 10−31 kg above fraction that we
obtain ms-1 as our final
units:
As we can see from this equation, the velocity required is inversely proportional to the ℎ Js
𝑣𝑒 = =
𝜆 × 𝑚𝑒 m kg
kg m2 s −2 s
= = m s −1
m kg
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mass of the particle diffracting and so using neutrons for diffraction means that a much
lower velocity will be required. Substituting the value for the mass of a neutron into the
equation leads to the following result:

ℎ 6.626 × 10−34 J s
𝑣𝑛𝑒𝑢𝑡𝑟𝑜𝑛 = = = 1400 m s −1
𝜆 × 𝑚𝑛𝑒𝑢𝑡𝑟𝑜𝑛 282 × 10−12 m × 1.675 × 10−27 kg

Solution 1.3

First, we calculate the energy of the photons:

ℎ𝑐
𝐸 = ℎ𝜈 =
𝜆

6.626 × 10−34 J s × 2.998 × 108 m s−1

E= = 1.18 × 10−18 J
169 × 10−9 m

We also know the wavelength of the ejected electrons. We can use this to calculate
their velocity, and hence their kinetic energy:

ℎ
𝜆=
𝑝

ℎ
𝑝 = 𝑚𝑒 × 𝑣 =
𝜆

ℎ
𝑣=
𝜆 × 𝑚𝑒

Where v is the velocity of the electron and me is the mass of the electron.

6.626 × 10−34 J s
𝑣= = 1.001 × 106 m s −1
727 × 10−12 m × 9.109 × 10−31 kg

Note that it is possible to

It is now possible to calculate the kinetic energy of the ejected electrons, using the work directly from the
equation electron wavelength to its
1 kinetic energy using the
𝐸𝐾𝐸 = 𝑚𝑒 𝑣 2 following equation:
2
1 𝑝 2 𝑝2
𝟏 𝐸𝐾𝐸 = 𝑚 ( ) =
𝑬𝑲𝑬 = × 𝟗. 𝟏𝟎𝟗 × 𝟏𝟎−𝟑𝟏 𝐤𝐠 × (𝟏. 𝟎𝟎𝟏 × 𝟏𝟎𝟔 𝐦 𝐬 −𝟏 )𝟐 = 𝟒. 𝟓𝟔 × 𝟏𝟎−𝟏𝟗 𝐉 2 𝑚 2𝑚
𝟐 ℎ 2
( )
= λ
We now know how much energy the photon had, and how much kinetic energy the 2𝑚𝑒
ℎ2
=
2𝑚𝑒 𝜆2

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Solutions to questions in the text

ejected electron had, and hence we can calculate the work function as follows:

Φ = Ephoton − Eelectron = 1.18 × 10−18 J − 4.56 × 10−19 J = 7.24 × 10−19 J

Finally, we convert this to kJ mol-1 by multiplying by Avogadro’s number and dividing

by 1000:

7.24×10−19 J ×6.022×1023 mol−1

Φ= = 436 kJ mol−1
1000

Solution 1.4

(a) First, we need to convert the work-function and kinetic energies into non-molar
quantities (i.e. the energy required to liberate a single electron, and the kinetic
energy per electron).
(b)
𝛷kJ mol−1 × 1000 202.6 kJ mol−1 × 1000 J kJ −1
𝛷= = = 3.36 × 10−19 J
𝑁𝐴 6.022 × 1023 mol−1

𝐸𝐾𝐸,kJ mol−1 × 1000 30 kJ mol−1 × 1000 J kJ −1

𝐸𝐾𝐸 = = = 4.98 × 10−20 J
𝑁𝐴 6.022 × 1023 mol−1

Now we can make use of the equation 𝐸𝐾𝐸 = ℎ𝜈 − 𝛷 to determine the frequency of the
𝑐
photons. We can then convert this to the wavelength by using 𝜆 = 𝜈.

ℎ𝜈 = 𝐸𝐾𝐸 + 𝛷
−20
𝐸𝐾𝐸 + 𝛷 4.98 × 10 J + 3.36 × 10−19 J
𝜈= = = 5.82 × 1014 s −1
ℎ 6.626 × 10−34 J s

𝑐 2.998 × 108 m s −1
𝜆= = = 5.15 × 10−7 m = 515 nm
𝜈 5.82 × 1014 s −1

Photons with a wavelength of 515 nm sit in the visible part of the electromagnetic
spectrum (green light).

(b) Here, as before, we first calculate the kinetic energy of a single electron. We then
calculate its velocity before determining what percentage of the speed of light it is

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travelling at.

𝐸𝐾𝐸,𝑘𝐽 𝑚𝑜𝑙−1 × 1000 30 kJ mol−1 × 1000 J kJ −1

𝐸𝐾𝐸 = = = 4.98 × 10−20 J
𝑁𝐴 6.022 × 1023 mol−1

1
We know that 𝐸𝐾𝐸 = 2 𝑚𝑒 𝑣 2 and hence rearranging to find v, we obtain:

2𝐸𝐾𝐸 2 × 4.98 × 10−20 J

𝑣=√ = √ −31
= 3.31 × 105 ms −1
𝑚𝑒 9.109 × 10 kg

Finally, we determine the percentage of c these electrons are travelling at:

3.31 × 105 m s−1
100 × ( ) = 0.11 %
2.998 × 108 m s−1

Solution 1.5

(a) In this question, we are asked to calculate the frequencies of the first three lines in
the Paschen series, which feature the common final energy level, where n = 3. The first
three lines must therefore occur when the initial energy levels are n = 4, 5 and 6
respectively.

The Rydberg constant has been quoted to us in frequency units, and hence we do not
need to perform any conversion of units to obtain the requested answers.

𝟏 𝟏 Frequency / Hz
𝒏𝒊 𝟐
− 𝟐
𝟑 𝒏𝒊
1 1 7 1.60 × 1014
4 − =
9 16 144
1 1 16 2.34 × 1014
5 − =
9 25 225
1 1 1 2.74 × 1014
6 − =
9 36 12

(b) The Balmer series features a common final energy level of n = 2. As we go to

higher values of n, the difference in energy between adjacent energy levels decreases.
For example, the difference in energy between n = 3 and n = 2 is greater than the
difference in energy between n = 4 and n = 3. The difference in energy between two
levels is related to the frequency of the line observed by the Planck relation, Δ𝐸 = ℎ𝜈.
As can be seen, the energy and frequency of a photon are directly proportional, and
hence the frequencies of the first three lines in the Balmer series will be higher than the

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Solutions to questions in the text

frequencies of the first three lines in the Paschen series.

Solution 1.6

(a) The highest energy lines correspond to the largest energy difference between the
energy levels in the transition. The difference in energy between adjacent energy levels
decreases as we go to higher values of n, i.e. the difference in energy between n = 2 and
n = 1 is greater than the difference in energy between n = 3 and n = 2. Therefore, we
can conclude that the highest energy lines must correspond to transitions that end on
the energy level with the lowest value of n. The lowest value allowed is n = 1, and
hence all transitions that end with n = 1 belong to the Lyman series. A logical
extension to this is that the next highest energy lines must end in the energy level with
n = 2, and hence all transitions that end with n = 2 belong to the Balmer series.

From this, we can see that the transitions (i) and (v) belong to the Lyman series,
transitions (ii) and (iv) belong to the Balmer series, and transition (iii) belongs to
neither series, and in fact belongs to the next highest energy series, known as the
Paschen series, the lines of which end with energy level n = 3.

(b) We are told that these lines belong to the Balmer series, and hence the final energy
level is 2 in each case.

Note that we are given two wavelengths, whilst the Rydberg constant is quoted in
wavenumbers. Therefore, we will need to perform some unit conversion in order to
obtain our correct answer.

We could attempt to solve this question by trial and error, substituting alternative
values for ni into the Rydberg equation until we obtain an answer that matches the data
we have been given. However, this could potentially be time-consuming if we do not
guess correctly. Instead, we can rearrange the Rydberg equation to solve for ni and
thereby prove that these lines belong to the Balmer series if we obtain integer values.
First, we convert the wavelengths of the lines into wavenumbers so that their units
match those of the Rydberg constant.
1
𝜈̅ =
𝜆
1
ν̅1 = = 1.52 × 106 m−1
656 × 10−9 m
1
ν̅2 = = 2.06 × 106 m−1
486 × 10−9 m

Now we rearrange the Rydberg equation, then substitute in the wavelengths for the
lines.

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1 1
𝜈̅ = 𝑅𝐻 ( 2 − 2 )
𝑛𝑓 𝑛𝑖
𝜈̅ 1 1
= 2− 2
𝑅𝐻 𝑛𝑓 𝑛𝑖
1 1 𝜈̅
2 = 2−𝑅
𝑛𝑖 𝑛𝑓 𝐻
2
1 ̅ 𝑛𝑓
𝑅𝐻 −𝜈
=
𝑛𝑖2 2𝑅
𝑛𝑓 𝐻

𝑛𝑓2 𝑅𝐻
𝑛𝑖2 =
𝑅𝐻 − 𝜈̅ 𝑛𝑓2
𝑛𝑓2 𝑅𝐻
𝑛𝑖 = √
𝑅𝐻 − 𝜈̅ 𝑛𝑓2

Substituting values in for the wavenumbers of the lines, nf = 2 and the Rydberg
constant allows us to calculate the value of ni in each case.

The first line:

𝑛𝑓2 𝑅𝐻 22 × 1.097 × 107 m−1
𝑛𝑖 = √ = √ =3
𝑅𝐻 − 𝜈̅ 𝑛𝑓2 (1.097 × 107 m−1 ) − (1.52 × 106 m−1 × 22 )

For the second line:

𝑛𝑓2 𝑅𝐻 22 × 1.097 × 107 m−1
𝑛𝑖 = √ = √ =4
𝑅𝐻 − 𝜈̅ 𝑛𝑓2 (1.097 × 107 m−1 ) − (2.06 × 106 m−1 × 22 )

The integer values obtained prove that these lines are members of the Balmer series.

Solution 1.7

(a) The labels of the orbitals allow us to determine n and l. The number gives us the
value of n, whilst the letter gives us the value of l, according to:

Letter s p d f
Value of l 0 1 2 3

We must also make use of the fact that ml can take integer values from –l to +l. Using a
table to keep track of these quantities leads to the answer:

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Orbital n l ml
2s 2 0 0
2p 2 1 -1, 0, +1
3s 3 0 0
3p 3 1 -1, 0, +1
3d 3 2 -2, -1, 0, +1, +2

(b) The total number of nodes is given by n - 1, the number of angular nodes is given
by l and the number of radial nodes given by n - l - 1. We combine this with the
information we obtained in part (a), again using a table for clarity, and obtain the
answer:

Orbital n l Total nodes Angular nodes Radial nodes

2s 2 0 1 0 1
2p 2 1 1 1 0
3s 3 0 2 0 2
3p 3 1 2 1 1
3d 3 2 2 2 0

(c) In a hydrogen atom, the energy of an orbital depends only on n and increases with
increasing n. Therefore, we expect the 2s and 2p orbitals to be degenerate, and of lower
energy than the degenerate 3s, 3p, and 3d orbitals.

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Solution 1.8

We can determine the value of l by counting the number of angular nodes an orbital
has. The total number of nodes is given by n – 1, and we can determine n using:
n = radial nodes + angular nodes + 1

To name the orbitals, we use the number for n and the letter associated with the value
for l as given in this table:

Letter s p d f
Value of l 0 1 2 3

Radial nodes Angular nodes l n Orbital

(a) 0 0 0=s 0+0+1=1 1s
(b) 1 1 1=p 1+1+1=3 3p
(c) 2 2 2=d 2+2+1=5 5d
(d) 0 2 2=d 0+2+1=3 3d
(e) 1 3 3=f 1+3+1=5 5f

Solution 1.9

a) Neutral sodium has 11 electrons. Using the Aufbau principle, and knowing
how many electrons can be contained in s and p orbitals means that we can
easily determine the electron configuration.
Two electrons occupy the 1s orbital, then then there are two more in the 2s
orbital. Six electrons are accommodated in the 2p orbitals and finally the
last electron occupies the 3s orbital.
Na: 1s2 2s2 2p6 3s1
There is one unpaired electron.

b) Na+ has 10 electrons (one electron lost from sodium to form a singly-
charged cation). The highest energy electron is lost first and hence it has the
following electron configuration, with no unpaired electrons:
Na+: 1s2 2s2 2p6

c) Neutral chlorine has 17 electrons – six more than neutral sodium. We can
therefore use the electron configuration of sodium (part i) as our starting
point, and add in the additional six electrons. In sodium the 3s orbital
contains an electron, and can accommodate one additional electron.

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Therefore the five remaining electrons must occupy a higher energy orbital.
The next subshell above 3s is 3p, which can accommodate up to six
electrons. Therefore, Cl has the following electron configuration:
Cl: 1s2 2s2 2p6 3s2 3p5
It has one unpaired electron.

d) The chloride anion has a single negative charge, so we must add one
electron to the electron configuration of neutral chlorine. The highest energy
orbital in chlorine is the 3p subshell. In neutral chlorine, this contains five
electrons. Because this subshell can accommodate up to six electrons, we
can conclude that Cl- has the following electron configuration:
Cl-: 1s2 2s2 2p6 3s2 3p6
It does not have any unpaired electrons.

e) Aluminium has 13 electrons; four fewer than chlorine. Therefore we can

easily obtain its electron configuration by removing four electrons from the
highest energy orbitals in the electron configuration of chlorine.
This leads us to:
Al: 1s2 2s2 2p6 3s2 3p1
Aluminium therefore has one unpaired electron.

f) The nitride ion, N3- must have three more electrons than nitrogen to account
for the 3- charge. Therefore, it has 10 electrons to account for. This is the
same as was seen for Na+ and hence it has the same electron configuration
and no unpaired electrons:
N3-: 1s2 2s2 2p6

g) Neutral magnesium has 12 electrons. This is one more than neutral sodium.
Using the electron configuration of sodium as our starting point, and adding
one electron to fill the 3s orbital leads us to the electron configuration of
neutral magnesium:
Mg: 1s2 2s2 2p6 3s2
This atom does not have any unpaired electrons.

h) The final example, Mg2+ must have two fewer electrons than neutral
magnesium to account for the 2+ charge. Therefore, it has 10 electrons in
total, which is the same number seen for Na+ and N3-. As such, it has the
same electron configuration, and no unpaired electrons:

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Solutions to questions in the text

Mg2+: 1s2 2s2 2p6

Solution 1.10

We could approach this question the same way that was used in worked example 1.5A
or in question 1.9. However, there is a quicker method when using the noble gas
shorthand, which enables us to very quickly obtain the electron configuration without
having to necessarily work out the “full” electron configuration first.

a) Lithium has one more proton than helium and so necessarily contains one
more electron than helium. Therefore we can use the electron configuration
of helium as a starting point and add one additional electron for neutral
lithium. Lithium is in the second period of the table and hence its valence
electron is in the 2s orbital. We can therefore write its electron configuration
as:
[He] 2s1

b) S2- has two more electrons than neutral sulfur. This means it has 18
electrons - the same number of electrons as argon, and hence has the same
electron configuration as argon. We can therefore write the electron
configuration of S2- as:
[Ar]

c) Calcium has two more protons (and hence the neutral atom has two more
electrons) than argon. We can therefore use argon as our “shorthand” for the
inner core of electrons. Calcium sits in the fourth row of the periodic table,
and therefore the two additional electrons occupy the 4s orbital. This gives
the following electron configuration for calcium:
[Ar] 4s2

d) The iodide ion has one more electron than iodine to account for the negative
charge. Therefore it has the same number of electrons as xenon, and hence
the same electron configuration. We can therefore write the electron
configuration of I- as:
[Xe]

e) Silicon has four more electrons than neon. We can therefore use neon to
represent the closed shell of electrons and add the valence electrons to this.
Silicon is in the third row of the periodic table, and hence we first fill the 3s
orbital, which can hold two electrons. The remaining two electrons

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therefore enter the next energy level – 3p giving the following electron
configuration:
[Ne] 3s2 3p2

f) Potassium has one more electron than argon. It is in the fourth row of the
periodic table and hence additional electron enters the 4s orbital. This gives
the electron configuration:
[Ar] 4s1

g) Neutral barium has two more electrons than xenon, and hence the Ba2+ ion
must have the same electron configuration as xenon. We can therefore write
the electron configuration of the Ba2+ ion as:
[Xe]

h) The hydride anion has one more electron than hydrogen, i.e. the same
number of electrons as helium. We can therefore use the following
shorthand notation to represent its electron configuration:
[He]

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