Atomic Structure

a) Protons, neutrons and electrons

Atoms are made up of three fundamental particles: protons, neutrons and electrons.

Protons and neutrons are found in the nucleus and are collectively called nucleons.

Electrons orbit the nucleus in a similar way to that in which planets orbit a sun.

In between the electrons and nucleus there is nothing (empty space).

The nucleus is very small; if an atom were the size of a football pitch, the nucleus would be
the size of a drawing pin.

The basic properties of these three particles can be summarized in the following table:

Particle Charge Mass

Proton +1 unit Approx 1 unit

Neutron No charge Approx 1 unit
Electron -1 unit Approx 1/1840 units (very small)

1 unit of charge is 1.602 x 10-19 coulombs. A proton is given a charge of +1 and an electron a
charge of -1. All charges are measured in these units.

1 unit of mass is 1.661 x 10-27 kg. This is also not a convenient number, so we use “atomic
mass units”.
Since the mass of protons and neutrons varies slightly depending on the nucleus, then in order
to define an “atomic mass unit” we need to choose one nucleus as a standard. For this
purpose 126C , or “carbon-12”, was chosen because its mass per nucleon
(1.661 x 10 –27 kg) is around average, which means all the other nuclei have masses close to
whole numbers. An atomic mass unit is thus defined as 1/12th of the mass of one atom of
carbon-12. Everything else is measured relative to this quantity.

1
b) Protons, neutrons and electrons in electric field

In an electric field, the neutrons are undeflected because the neutrons have no charge.

Electrons are attracted to the positive side of the electric field because electrons are
negatively charged.

Protons are attracted to negative side of the electric field because protons are positively
charged.

Why is the angle of deflection for protons smaller than electrons?

Protons are heavier than electrons and hence deflected less.

𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒
𝐴𝑛𝑔𝑙𝑒 𝑜𝑓 𝑑𝑒𝑓𝑙𝑒𝑐𝑡𝑖𝑜𝑛 →
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒

2
Example Question

1. Beams of charged particles are deflected by an electric field. If the particles are all
travelling at the same speed, through an electric field of constant strength, the angle
of deflection is proportional to their charge/mass ratio. In a particular experimental set
up, protons are deflected through an angle of +15 o.

(a) Assuming an identical set of experimental conditions, by what angles will the
following particles be deflected? ( D is deuterium, 2𝐻 and T is tritium, 3𝐻)
 D- ion
 T+ ion
 He2+

(b) Under identical conditions, a beam of particles, R, each having 12 times the mass
of proton, was deflected by an angle of +5 o,

(i) Suggest the overall charge on a particle of R

(ii) Given that a particle of R contains 6 protons, deduce the number of

neutrons and electrons in a particle of R.

3
c) Atomic numbers, mass numbers and isotopes

An atom is named after the number of protons in its nucleus. If the nucleus of an atom has 1
proton, it is hydrogen; if it has two protons, it is helium; if it has 3, it is lithium etc.

The number of protons in the nucleus of an atom is called the atomic number. It has the
symbol Z.

The atomic number is the number of protons in the nucleus of an atom

Not all atoms of the same element have equal numbers of neutrons; this may vary slightly.
The sum of the number of protons and neutrons in the nucleus of an atom is called its mass
number. It is represented by the symbol A.

The mass number is the sum of the number of protons and neutrons in the nucleus of an
atom

The nucleus of an atom can thus be completely described by its mass number and its atomic
number. It is generally represented as follows:

𝑍
𝐴𝐸
Eg. 94Be, 12
6C,
24
12Mg

Atoms with the same atomic number but with different mass numbers (ie different numbers
of neutrons) are called isotopes.

Isotopes are atoms with the same atomic number but with different mass numbers

Eg magnesium (atomic number 12) has 3 naturally occurring isotopes:

24
12Mg: 12 protons, 12 neutrons
25
12Mg: 12 protons, 13 neutrons
26
12Mg: 12 protons, 14 neutrons

4
d) Use of mass spectrometer to find isotopes

The time of flight (TOF) mass spectrometer is an instrument used for measuring the masses
of atoms and molecules.

It can also be used to measure the relative abundance of different isotopes and to predict the
structure of more complex molecules.

𝐺𝑎𝑠 𝑜𝑓 𝑎 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 → 𝑚𝑎𝑠𝑠 𝑠𝑝𝑒𝑐𝑡𝑟𝑜𝑚𝑒𝑡𝑒𝑟 → 𝑚𝑎𝑠𝑠 𝑠𝑝𝑒𝑐𝑡𝑟𝑢𝑚

How does the mass spectrum look like?

The mass spectrum of chlorine is shown above. From the mass spectrum, there is 75% of Cl35
and there is 25% of Cl37 atom.

Average mass number of Cl =

5
 Mass spectrum of Krypton,Kr

Calculate the average mass number of Kr.

e) Atoms and ions

In a neutral atom, the number of protons and electrons are the same. However, many
elements do not exist as neutral atoms, but exist as ions.

Ions are species in which the proton and electron numbers are not the same, and hence
have an overall positive or negative charge. The number of electrons in a species can be
deduced from its charge:

Eg
24 2+
12Mg : 12p, 12n, 10e
24 +
12Mg : 12p, 12n, 11e
24
12Mg 12p, 12n, 12e
24 -
12Mg : 12p, 12n, 13e

Ions with a positive charge are called CATIONS

Ions with a negative charge are called ANIONS.

6
 ELECTRONIC STRUCTURE

a) Energy levels

Electrons do not orbit the nucleus randomly; they occupy certain fixed energy levels. Each
atom has its own unique set of energy levels, which are difficult to calculate but which
depend on the number of protons and electrons in the atom.

Energy levels in an atom can be numbered 1,2,3.

1 is the lowest energy level (closest to the nucleus)

n=6
n=5
n=4

n=3

n=2

n=1

b) Orbitals and sub-levels

Electrons do not in fact orbit the nucleus in an orderly way. In fact they occupy areas of
space known as orbitals. The exact position of an electron within an orbital is impossible to
imagine; an orbital is simply an area of space in which there is a high probability of finding
an electron.

Orbitals can have a number of different shapes, the most common of which are as follows:

s-orbitals: these are spherical.

Every energy level contains one s-orbital.

An s-orbital in the first energy level is a 1s orbital.
An s-orbital in the second energy level is a 2s orbital, etc

7
p-orbitals: these are shaped like a dumbbell. They exist in groups of three:

Every energy level except the first level contains three p-orbitals.

Each p-orbital in the same energy level has the same energy but different orientations: x, y
and z.

A p-orbital in the second energy level is a 2p orbital (2px, 2py, 2pz)

A p-orbital in the third energy level is a 3p orbital (3px, 3py, 3pz), etc

In addition, the third and subsequent energy levels each contain five d-orbitals.

The fourth and subsequent energy levels contain seven f-orbitals and so on. Each type of
orbital has its own characteristic shape.

S, p and d orbitals do not all have the same energy. In any given energy level, s-orbitals
have the lowest energy and the energy of the other orbitals increases in the order p < d
< f etc. Thus each energy level must be divided into a number of different sub-levels, each of
which has a slightly different energy.

8
The number and type of orbitals in each energy level can thus be summarised as follows:

Energy level Number and type of orbital

1st sub- 2nd sub- 3rd sub- 4th sub- 5th sub-
level level level level level
1 1 x 1s
2 1 x 2s 3 x 2p
3 1 x 3s 3 x 3p 5 x 3d
4 1 x 4s 3 x 4p 5 x 4d 7 x 4f
5 1 x 5s 3 x 5p 5 x 5d 7 x 5f 9 x 5g

n=4 4f
4d
4p
n=3 3d
4s
3p
E 3s
N
E 2p
n=2
R
2s
G
Y

n=1
1s

9
c) Electrons

Electrons repel each other. In a small space such as an orbital, it is impossible to put more
than two electrons.

Since electrons are charged particles, and moving charges create a magnetic field, it is
possible to create a small magnetic attraction between two electrons if they are spinning in
opposite directions in the same orbital. This is the reason two electrons, and not one, are
permitted in the same orbital.

It is thus possible to calculate the maximum possible number of electrons in each sub-level,
and thus in each energy level:

Shell Number of electrons in each sub-level Max. no of electrons

1 2 x 1s 2
2 2 x 2s, 6 x 2p 8
3 2 x 3s, 6 x 3p 8
4 2 x 4s, 10 x 3d, 6 x 4p 18

d) Electron arrangement in orbitals

There are three rules which determine the way in which electrons fill the orbitals

1. Aufbau/building principle: electrons always fill the lowest energy orbitals first.

4s orbital is filled in with electrons first followed by 3d orbital

18𝐴𝑟 : 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6

19𝐾 : 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 4𝑠1

20𝐶𝑎 :

21𝑆𝑐 :

10
2. Hund's rule: electrons never pair up in the same orbital until all orbitals of the same
energy are singly occupied, and all unpaired electrons have parallel spin.

3. Pauli exclusion principle: only two electrons may occupy the same orbital, and they must
do so with opposite spin.

The arrangement of electrons in an atom is known as its electronic configuration. It can be

represented in two ways:

The arrow and box method represents each orbital as a box and each electron as an arrow.
The direction of spin is shown by the orientation of the arrow.

1s 2s 2p 3s 3p
H ↑

He ↑↓

Li ↑↓ ↑

Be ↑↓ ↑↓

B ↑↓ ↑↓ ↑

C ↑↓ ↑↓ ↑ ↑

N ↑↓ ↑↓ ↑ ↑ ↑

11
O ↑↓ ↑↓ ↑↓ ↑ ↑

F ↑↓ ↑↓ ↑↓ ↑↓ ↑

Ne ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Na ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Mg ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Al ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Si ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

P ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

S ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

Cl ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Ar ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

A shorthand form is often used for both the above methods. Full shells are not written in full
but represented by the symbol of the element to which they correspond, written in square
brackets. This is the noble gas configuration.

Eg. 1s22s22p6 is represented as [Ne] and 1s22s22p63s23p6 is represented as [Ar].

The shorthand electronic configuration of the elements with atomic numbers 18 to 36 can be
written as follows:
4s 3d 4p
K [Ar] ↑

Ca [Ar] ↑↓

Sc [Ar] ↑↓ ↑

Ti [Ar] ↑↓ ↑ ↑

V [Ar] ↑↓ ↑ ↑ ↑

Cr [Ar] ↑ ↑ ↑ ↑ ↑ ↑

Mn [Ar] ↑↓ ↑ ↑ ↑ ↑ ↑

Fe [Ar] ↑↓ ↑↓ ↑ ↑ ↑ ↑

12
Co [Ar] ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

Ni [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

Cu [Ar] ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Zn [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Note the unusual structures of chromium and copper.

Cr has 24 electrons. Hence,

24𝐶𝑟 : 1𝑠 2 2𝑠 2 3𝑠 2 3𝑝6 4𝑠 2 3𝑑 4

Cr [Ar] ↑↓ ↑ ↑ ↑ ↑ More repulsion

Less repulsion
Cr [Ar] ↑ ↑ ↑ ↑ ↑ ↑

- The difference in energy between the 3d and 4s electrons is very small

- In chromium, there is reduced repulsion because the electrons are no longer paired in
the 4s13d5 structure. Thus the 4s13d5 structure in Cr is preferred.

- This is called the half-filled stability configuration

Cu has 29 electrons. Hence,

29𝐶𝑢 : 1𝑠 2 2𝑠 2 3𝑠 2 3𝑝6 4𝑠 2 3𝑑 9

Cu [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ Less symmetry

Cu [Ar] ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ More symmetry

- A fully filled 3d orbital (3d10) is very stable due to the symmetrical distribution of
charge around the nucleus

- This results in similar repulsion at each point in space

13
e) Removal of electrons

Rule : 4s electrons are removed first before 3d electrons

14
 IONISATION ENERGIES

a) First ionisation energy

The first ionisation energy of an element is the energy required to remove one
electron from each of a mole of free gaseous atoms of that element.

It can also be described as the energy change per mole for the process:
M(g)  M+(g) + e

To explain to the above graph, 4 factors must be considered.

Nuclear charge

- Energy is required to remove electrons from atoms in order to overcome their attraction to the
nucleus
- The greater the number of protons, the greater the attraction of the electrons to the nucleus
and the harder it is to remove the electrons

Shielding effect

- The effect of this nuclear charge, however, is cancelled out to some extent by the other
electrons in the atom
- Each inner shell and inner sub-shell electron effectively cancels out one unit of charge from
the nucleus

15
Effective nuclear charge

- The outermost electrons in the atom thus only feel the residual positive charge after all inner
shell and inner sub-shell electrons have cancelled out much of the nuclear charge
- This residual positive charge is known as the effective nuclear charge

E.g. 3𝐿𝑖 ∶ 1𝑠 2 2𝑠1

Nuclear charge (proton number) = +3

Effective nuclear charge ≈ +1.3

Repulsion

- Electrons repel each other, particularly when they are in the same orbital
- The more repulsion between electrons the easier to remove the electrons

b) (i) General energy trends in first ionisation energy

Across period

- Nuclear charge increase

- Shielding effect remain constant as they have the same number of inner shell
- Effective nuclear charge increase
- Valence electrons are more strongly attracted to the nucleus
- First ionisation energy increase

Down the group

- Nuclear charge increase

- Shielding effect increases as they have more inner shells
- Increase in shielding effect outweighs the increase in nuclear charge.
- Valence electrons are less strongly attracted to nucleus

16
(ii) Exceptions to the general trends

Between Group II and III

Mg : 1𝑠 2 2𝑠 2 2𝑝6 𝟑𝒔𝟐

Al : 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 𝟑𝒑𝟏

- The 3p electron in Al is further away from the nucleus than the 3s electron in Mg and is less
strongly attracted to the nucleus

- Therefore, less energy is required to remove the electron in Al

Between Group V and VI

P: 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 𝟑𝒑𝟑 O: 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 𝟑𝒑𝟒

- The paired 3p electron in O experience inter-electronic repulsion

- Hence, less energy is required to remove the paired 3p electron

c) Successive ionisation energies

The second ionisation energy of an atom is the energy required to remove one electron from
each of a mole of free gaseous unipositive ions.

M+(g)  M2+(g) + e

Other ionisation energies can be defined in the same way:

The third ionisation energy of an atom is the energy required to remove one electron from each
of a mole of bipositive ions.

M2+(g)  M3+(g) + e

The nth ionisation energy can be defined as the energy required for the process

M(n-1)+(g)  Mn+(g) + e

It always becomes progressively more difficult to remove successive electrons from an atom; the
second ionisation energy is always greater than the first, the third always greater than the second and
so on

As more electrons are removed from an atom, the number of electrons remaining in the atom
decreases. The repulsion between these electrons therefore decreases, while the number of protons

17
remains the same. The remaining electrons are thus more stable and increasingly difficult to
remove.

Example Question

From the graph, deduce group that the element belongs to.

18