Topic 2: Atomic theory

2.1. The nuclear atom

Subatomic particles

Electron: The first subatomic particle discovered by Thomson in 1897. Absolute (=actual) and relative
(=as compared to) properties of an electron. Negatively charged electrons are found in the space
outside the nucleus. Relative mass is relative to 1/12 of the mass of a C-12 isotope.

absolute mass 9.1 x 10-28 g (1/1840 mass of proton)

relative mass* 5 x 10-4
absolute charge -1.602 x 10-19 C
relative charge* -1 (relative to proton)
symbol e

Proton found in the nucleus.

absolute mass 1.67 x 10-24 g

relative mass* 1
absolute charge +1.602 x 10-19 C
relative charge* +1
symbol p

Neutron which is also found in the nucleus.

An electrically neutral subatomic particle found in the nucleus and discovered by Chadwick (in 1932 –
much later, why?) as a by-product of the -particle bombardment of Be. Neutrons explained the
experimental results obtained from mass spectrometry showing naturally occurring elements containing
atoms with different mass (isotopes).

absolute mass 1.67 x 10-24 g

relative mass* 1
relative charge* 0
symbol n

Dense nucleus and electrons

The extremely small nucleus contains virtually all the mass and all the positive charge, i.e. one or more
protons, and usually at least as many neutrons. The rest of the atom is mostly empty space within which
the negatively charged electrons move around the nucleus. The radius of this empty space is
approximately one hundred thousand times greater than the radius of the nucleus.
The nucleus has a very high density. This is because the protons, which all have ‘like’ charges are
drawn very close together by very powerful nuclear forces. These forces need to be powerful as they
need to overcome the repulsion between the protons and they act only over a very short distance.

Nuclear symbol

The nuclear symbol represents a particular nuclide (atomic specie) or isotope of an element with a
specific atomic/isotopic mass; it is not what is shown in the periodic table for each element. The nuclear
symbol does not have the relative atomic mass value.

• its mass number (A) = number of protons and neutrons in the nucleus of an atom
• atomic number (Z) = the number of protons in the nucleus of an atom

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 mass number, A 131
I nuclide symbol
atomic number, Z 53

The atomic number is specific to each element and can therefore be used to identify the element.
You should be able to identify the number subatomic particles in:

• any atom:
o number of protons and electrons is the same as atoms are electrically neutral
o number of neutrons = mass number – atomic number
• negative ion (=anion) (more electrons than protons)
o charge of ion = number of electrons - number of protons
o number of neutrons = mass number – atomic number
• positive ion (cation) (more protons than electrons)
o charge of ion = number of protons - number of electrons
o number of neutrons = mass number – atomic number

Using the nuclear symbols below complete the table

species protons neutrons electrons

+
K (cation)
Br- (anion)
C4- (carbide ion)
Zn2+ (cation)
56
Fe2+

Isotopes of an element

Isotopes of an element are atoms of the same element with the same number of protons but with
a different number of neutrons. As all isotopes of the same element only differ in their mass number,
we use the notation of isotopes as shown in the table below. (iso = same; topos = place (in Period
Table)).
Examples of common isotopes:

isotope protons electrons neutrons isotope protons electrons neutrons

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1H or H-1 C-12
H-2
C-13
H-3 Cl-35

Cl-37

!!!!! Isotopes may differ in physical properties like mass, velocity, density, rate of diffusion,
melting and boiling points but usually have the same chemical properties.

The proportion of each isotope in a sample is known as its relative abundance e.g. relative abundance of
Cl-35 is 75%. The relative atomic mass is always closer to the relative mass of the most abundant
isotope.

Radioisotopes

Some isotopes are radioactive and are called radioisotopes. Such isotopes are dangerous to living
things as radiation can change the structure of DNA within the genes of cells. However, despite their
dangers some radioisotopes are useful. Examples:

14
C
Carbon-dating = using the decay of the 14C isotope to date or find out how old a piece of rock is in the
crust.
The 14C in the atmosphere (mostly in CO2) is continuously being formed but is also continuously being
broken down. This breaking down is referred to as radioactive decay (i.e. it emits beta radiation from its
nucleus which causes it to become a different element).
6C →
14 14 0
7 N + -1e

14
Both the formation and decay occur at a constant rate. As a result the amount or % of C in CO2 in the
atmosphere remains the same.

When a living organism dies, some CO2 is trapped inside the tissue and no more 14C can enter the
tissue. However, the 14C that is in the tissue will still decay and it does this at a fixed rate that is called
the half life. The half-life of 14C is 5730 years.

Scientists measure the % of 14C in the CO2 in a fossil and compare it with the % of 14C in the CO2 in
similar material in the present time. They then calculate how many times the amount has halved and
multiply that by 5730 years.

60
Co
Cancer cells appear to be affected by radiation more than normal cells. The penetrating gamma
radiation emitted (it also emits beta radiation) from the 60Co isotope is able to kill cancer cells (= medical
radiotherapy) in particular those which are quite difficult to get to in the human body by any other
medical means. This isotope is also used sterilize medical supplies or a source of radiation treatment to
sterilize food. This isotope has a relative short half-life i.e. 5.27 years.

131 125
I and I
Both radioisotopes are used as medical tracers and they emit beta and gamma radiation. This often
involves adding the radioisotope to a chemical taken is taken up by the animal or plant. A scanner or
radiation sensitive machine can then be used to follow this chemical e.g. where it is stored or broken
down.
The thyroid gland plays an important part in our metabolism. The activity of the thyroid gland is measured
by using radioactive iodine-131 which has a short half life (8 days) so it does not remain active for too
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long in the human body.

• The patient drinks a liquid or takes a tablet containing a tiny amount of iodine-131 or iodine-125.
• A scanner is used to measure the amount of radioactivity in the thyroid gland.
• A hyperactive thyroid accumulates more than the normal amount of iodine and this can be
detected on a scanner.

A similar procedure is followed when detecting cancer tissue in the thyroid gland.

Radioisotopes that have short half-lives are preferred for use in these drugs to minimize the radiation
dose to the patient. In most cases, these short-lived radioisotopes decay to stable elements within
minutes, hours, or days, allowing patients to be released from the hospital in a relatively short time.

The mass spectrometer

Sketch a mass spectrometer in your class book and on it label the 5 important parts using the labels in
the table below.

part process how?

if substance is a solid or liquid it is heated to change it into a vapour so that each
A vaporization
atom is separate and free to move independently;
neutral atoms and molecules are converted into positive ions by bombarding them
with high-speed electrons from the electron gun; these electrons collide with
B ionization electrons in the particle knocking them out and leaving a positive ion:
X (g) + e- ⎯→ X+ (g) + 2 e-

the positive ions are accelerated by an electric field created by charged plates
C acceleration
with a high potential difference.
the fast moving positive ions are deflected into a curved path by the magnetic
D deflection field produced by an electromagnet; the positive ions are separated into different
paths according to their mass/charge ratio’
ions strike the detector screen which detects the ion according to its mass; the ion
E detection
striking the screen produces a current which is what is detected.

Inside the mass spectrometer very low pressure is maintained as other particles will interfere with the
measurements as a result of collisions between the positive ions and other particles.

The mass spectrometer provides us with the following information:

1. The number of isotopes of an element (from the number of peaks in the mass spectrum).
2. The relative isotopic mass (compared with 1/12th of a C-12) of each isotope (expressed in m/z).
3. The relative abundance of each isotope (judged from the height of the peak and, usually,
expressed in %).
4. Information 2 and 3 then allows us to calculate the relative atomic mass of the element.

2. 2 Electron arrangement

The electromagnetic spectrum

All electromagnetic radiation or electromagnetic waves:

• have a given wavelength () and a given frequency (v); wavelength is measured in metres and
frequency is measured in Hertz (Hz) or number of waves per second (s-1);
• have their own wavelength and frequency;
• but obey the following wave equation:

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 c=v c = speed of light (= 3.00 x 108 m s-1)

• can be reflected/refracted/diffracted.

All electromagnetic radiation transfers energy in fixed or discrete amounts that are called photons
(parcels of energy).
The frequency, v, of electromagnetic waves and the energy, E, of the photons are connected by an
equation introduced by Planck:

E = hv E = energy (of photon) (in joules)

h = Planck’s constant (6.63 x 10-34 J s)
v = frequency (in s-1)

This links the frequency of waves directly to the amount of energy transferred by them.
The lower the wavelength of the waves (higher the frequency), the greater is the energy of the light (the
more energy is transferred). For instance UV has a higher frequency (high energy) but lower wavelength
than IR which has a lower frequency (less energy) but higher wavelength.

In the visible light spectrum red has the highest wavelength but lowest frequency so red transfers the
least amount of energy in its photons. The photons with the greatest amount of energy in the visible light
spectrum are transferred in violet radiation.

Emission spectra provide evidence for discrete energy levels

‘discrete’ means ‘separate’

Most pure substances (including solids) when in a gaseous state and excited by sufficient energy (e.g. an
electrical current like in a discharge tube - this has a gas at low pressure in) or when heated strongly in a
Bunsen flame – flame tests!!) give out or emit electromagnetic radiation.

The electromagnetic radiation in the visible light part of the spectrum can be dispersed (split) by using a
prism so that a visible emission spectrum can be obtained. The radiation in the IR and UV region can
also be split.

Any emission spectrum is always a line emission spectrum as opposed to a continuous

spectrum.

line emission spectrum continuous spectrum

• pattern of thin discrete or separate vertical • consists of continuous range of successive
lines, each of a different colour (or frequency or frequencies/wavelengths and is produced when
wavelength) there is radiation at each frequency or
• most of the spectrum is black with a few wavelength;
coloured lines. • a continuous spectrum has all the colours.
• does not have all possible frequencies or
wavelengths

Each line in the line spectrum corresponds to one particular frequency and therefore, using E = hf, to a
particular amount of energy which is being emitted by the atoms or ions of the substance.

Line emission spectrum provides evidence for discrete energy levels

As stated earlier, each line in the spectrum corresponds to a wave with a particular wavelength and
frequency and therefore a particular amount of energy that is being emitted in the photons.
Each element has its own line emission spectrum because all atoms of the same element can only emit
certain discrete amounts or photons of energy. This is because energy in an atom can only take discrete
values. Energy is quantized (fixed/discrete amounts) rather than continuous (=any possible value).

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When an atom is excited (by a high electrical current or a Bunsen burner flame), its electrons jump (or
are promoted) onto higher energy levels (circling the nucleus at a greater distance).

These atoms then emit light when the excited but unstable electrons in the atom/ion/molecule release or
emit energy in the form of light (or other electromagnetic radiation) as they drop back down to lower
energy levels. The moving up and down energy levels of electrons is called electronic transition.

As there are only a certain number of lines of emission (fixed lines) in the spectrum of an element, an
electron in an atom of that element can only emit certain fixed amounts of energy. This can only be the
case if the amount of energy an electron has in the atom is also quantized by being on discrete energy
levels.

The above ideas were first proposed by Niels Bohr who studied the hydrogen line spectrum.

Summary of Bohr’s theory:

1. The electron moving in an orbit in a hydrogen atom is only allowed to exist in certain discrete energy
levels (not in an infinite number of values) (or the electron can only orbit at certain distance from the
nucleus).
2. Radiation of a particular energy is emitted when the electron changes down from a particular higher
level into a lower energy level (=closer to the nucleus).
3. The energy of the radiation is equal to the difference between the two energy levels, E.

E (radiation) = E (higher energy level) – E (lower energy level) = E

4. The frequency of the emitted or absorbed light is related to E by E = hf so f = E/f.

Hydrogen emission spectrum

Main characteristics of the hydrogen line emission spectrum:

• several series of lines …
• that converge towards higher frequency

How does this relate to energy levels and electron transitions in a hydrogen atom?

• The whole line emission spectrum shows six series (= sets of lines which show a particular pattern);
each series represents electron transitions down to a particular lower energy level; each line is
related to an energy difference;
• The Lyman series is in the UV region of the electromagnetic spectrum, the Balmer series in the
visible light spectrum and the remaining series are in the infra-red spectrum;
• The Lyman series is the high frequency series, corresponding to the greatest emissions of energy as
the lines are produced by transitions from a particular higher level (eg n = 2, n = 3, n= 4, n = 5) to the
lowest energy level (n=1);
• The Balmer series are the most important as it is in the visible light spectrum and involves transitions
down from a particular higher energy level to the second lowest energy level (n = 2);
• The Paschen series is observed in the IR region as it involves transitions to n=3;
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• The greater the distance between the lines in the spectrum, the greater the difference in energy
between the two energy levels;
• The greatest distance between two consecutive lines within the whole spectrum is caused by the
transition from n = 2 to n =1;
• In each series the lines converge towards the high energy end - they come together; this is because
the higher energy levels also come closer together as the difference in energy between them
decreases. Where they come together is called the limit of convergence.
The diagram of the hydrogen line
spectrum to the left shows possible
electron transitions that produce the
Lyman, Balmer and Paschen series. Note
again that the lines in each series
converge towards the high frequency end
because the higher energy levels
converge at higher energies.
The notation I.E. in the diagram refers to
ionization energy which is the amount of
energy needed to remove an electron
from an atom.

Electron configuration or electron

arrangement

We already know from the emission spectra, that in an atom, its electrons occupy discrete energy levels.
These discrete energy levels are identified by an integer, n.
The electronic configuration of an atom tells us how the electrons in an atom are arranged on these
discrete energy levels. All atoms of the same element have the same electron configuration.
The significance of the electronic structure is that it dictates the chemical behaviour of the elements and
their position in the Periodic Table.

Each main energy level, n, can only hold a maximum number of electrons that can be found by applying
2n2.

first energy level (n = 1) 2 electrons

second energy level (n = 2) 8 electrons
third energy level (n = 3) 18 electrons
fourth energy level (n=4) 32 electrons

The evidence for the maximum number of electrons on an energy level (and the existence of sub-levels)
are explained in the HL section.
The term valence electron is used to describe the electrons in the highest main energy level.
An energy level which is occupied by its maximum number of electrons is called a filled energy level.

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Electrons are arranged so that the lowest energy level shells are filled first – this is referred to as the
Aufbau principle. If in an atom all electrons are in the lowest energy levels possible than we say the
atom is in its ground state = state of lowest energy.

Sub-levels

Within main energy levels there are also sub-levels. The higher in energy a main energy level is the more
sub-levels it has. Within sublevels electrons are found in orbtials. Each sub-level contains a fixed number
of orbitals. Relative energies of sub-levels within a single main energy level:

relative energies: s  p  d  f

This makes sense as an s electron tends to be on average more closely to the nucleus than electrons on
any of the other sub-levels. Remember that the more closely to the nucleus the more strongly an
electron is attracted, the lower its energy!

Orbitals

The Heisenberg Uncertainty Principle states that it is impossible to pinpoint accurately both the position
and the momentum of a small particle like an electron.
In simpler language, this means we can never be certain of where exactly an electron is in an atom.
To deal with this new idea, the concept of atomic orbitals was introduced.
An atomic orbital refers to a region of space around the nucleus in which there is a high probability (90%)
(not an absolute certainty) of finding an electron of a given energy.
An orbital therefore is an area of high electron density; it is an electron charge cloud which can be
occupied by a maximum of two electrons. Atomic orbitals can have different shapes; the shape depends
on the electron distribution.
These orbitals are found in the sub-levels. Each sublevel has its own electron distribution both in terms
of shape of the orbital and the number of orbitals.
Each orbital is on a particular energy level; orbitals in the same sub-level are equivalent in energy and
are called degenerate orbitals. The actual energy values of these levels depend on the electronic
configuration.

Each orbital has a defined energy state for a given electronic configuration and chemical environment. A
2s orbital in a hydrogen atom is on a different energy level than a 2s orbital in an oxygen atom. The
energy state of an orbital is determined by the repulsion and attraction in its environment. Also the
energy state of a 2s orbital in a hydrogen atom in a water molecule is different to the energy state of a 2s
orbital in a hydrogen atom in a methane molecule again because of different repulsion and attracting
forces.

The orbital in the s-sub-level has a spherical symmetrical shape: probability of finding electron is the
same in all directions. The 3 orbitals in the p-sublevel have an hourglass shape; the three orbitals are
labeled px, py and pz.

Just like the main energy levels which have been given numbers; each orbital is also given a number
depending on the main energy level it is in and its shape g 1s, 2p, 3d, 4f and so on. The larger the
principal quantum number,n, the larger the orbital.

Sub-level (+ in maximum number total number of

main brackets number of of orbitals in sub- electrons in the
shape of orbital
energy level electrons it can hold) level main energy level

n=1 s (2) 1 spherical 2

s (2) 1 spherical
n=2 8
p (6) 3 dumbbell

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 n=3 s (2) 1 spherical
p (6) 3 dumbbell 18
d (10) 5 lobes

s (2) 1 spherical
p (6) 3 dumbbell
n=4
d (10) 5 lobes 32
f (14) 7 lobes

Filling up of orbitals: electronic configuration

Electrons spin on their own axis which can be clockwise or anticlockwise, relative to the orbital of the
electron. Whenever a charge spins it produces a magnetic field; as a result electrons have their own
magnetic fields and they acts as magnets. The direction of the magnetic field of an electron depends on
the direction of its spin. Depending on their spin, two electrons either attract (both have opposite spin) or
repel (have same spin) each other.
Any repulsion between its electrons always increases the potential energy of an atom.
The greater the potential energy, the more unstable an atom becomes so electrons in atoms always
adopt the lowest possible energy configuration which is referred to as the ground state.

To determine the electron arrangement which achieves the lowest possible energy we need to
apply 3 principles which are described below:

1. The Aufbau principle:

When filling sub-levels with electrons, we start with the lowest level, 1s. Each sub-
level is filled before starting to fill the sub-level of the next highest energy.

2. Pauli Exclusion principle:

Remember that two electrons can occupy the same atomic orbital but they can only
do so if they have opposite or paired spins as this reduces the repulsion between
them and therefore the total amount of potential energy in the atom.

The Pauli Exclusion Principle states that an atomic orbital can only hold two
electrons if they have an opposite spin (no repulsion caused by opposite magnetic
spin of each electron).

Evidence for Pauli Principle includes the study of the magnetic effect of atoms; for
instance consider the helium atom which could have two possible electronic
configurations:

•  in this case the magnetic effect of each electron is cancelled out; the atom is diamagnetic
and should only be slightly repelled by a magnet; or

•  in this case the magnetic fields of each electron reinforce each other making the atom
paramagnetic and which would cause it to be attracted by a magnet (strength of
paramagnetism indicates number of unpaired electrons);

The experimental evidence shows that a magnet has very little effect on the helium
atom suggesting that it is diamagnetic and that electrons cancel out each other’s
magnetic fields.

3. Hund’s rule

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When filling up a sub-level with 3 or more atomic orbitals, the favoured arrangement is where electrons
occupy different atomic orbitals and have the same spin (or “electrons prefer to have parallel spins which
is only possible - as a result of Pauli’s exclusion principle - if they go into a different orbital of the same
sub-level” ) (or “in a sub-level with more than one orbital the electrons are spread out over these
degenerate sub-levels with their spins in the same direction”).

Exercise

Draw ‘electron-in-the boxes’ and show the electron configuration for the following species: B, F, Al, K,
K+, Cl-, O2-, Al3+, H-, S2-, Mg2+.

The electron structure of atoms: Aufbau, Hund, Pauli

You need to be able to write an electron configuration for the first 56 elements.

1. Electrons always fill from the lowest energy level upwards so that their total energy is kept at a
minimum. Called the Aufbau principle.

2. When one energy level is full the electrons start filling up the next highest energy level.

3. Electrons fill up the orbital in pairs. Each electron in the pair spins in opposite direction to one
another (represented by ). In the p and d orbitals the electrons fill up singularly first and then
as pairs. Called Hund’s rule.

4. It is impossible for two electrons with the same spin to be in the same orbital and an orbital can
only hold a maximum of two electrons. Called the Pauli Exclusion principle.

5. The electron structure is written in order of increasing energy level

number of electrons

1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 etc

energy
level
orbital

A short hand version can be used for more than 20 electrons by using an argon, Ar core (18
electrons.

e.g. for titanium with 22 electrons the electron configuration is 1s2 2s2 2p6 3s2 3p6 4s2 3d2 or Ar
4s2 3d2

6. The 4s orbital is lower in energy than the 3d orbital and so the 4s orbital will be filled before the
3d.

7. One exception to the Aufbau principle is chromium, Cr (atomic number = 24)

You would expect its electron configuration to be Ar 4s2 3d4 (4s __ 3d __ __ __ __ __)

but its electrons configuration is actually Ar 4s1 3d5 (4s __ 3d __ __ __ __ __)

This is because the energy of the 4s and 3d orbital are very similar and they almost act as one
orbital. ½ filled orbitals or completely full orbitals are more stable than a mixture of partially filled
orbitals so the most stable configuration is Ar 4s1 3d5.
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 Another exception is copper, Cu (atomic number = 29)

You would expect its electron configuration to be Ar 4s2 3d9 (4s __ 3d __ __ __ __ __)

but its electrons configuration is actually Ar 4s1 3d10 (4s __ 3d __ __ __ __ __)

Here a full 3d orbital and a ½ filled 4s orbital is more stable than a partially filled 3d orbital.

The link between the Periodic Table and the electronic configuration:

• The period number indicates the number of the main energy level that is being filled
• The group number indicates the number of electrons in the outer main energy level.

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