Atomic Structure

THE STRUCTURE OF THE ATOM

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.

b) 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:
A
E
Z

Eg. 9
Be, 126C, 2412Mg
4

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

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
12 Mg2+: 12p, 12n, 10e
24
12 Mg+: 12p, 12n, 11e
24
12 Mg 12p, 12n, 12e
24
12 Mg-: 12p, 12n, 13e
c) Relative atomic mass

The mass of an atom is measured in atomic mass units, where one

unit is 12th of the mass of one atom of carbon-12.

The relative isotopic mass of an isotope is the ratio of the mass of

one atom of that isotope to 1/12th of the mass of one atom of
carbon-12.

It is usually very close to a whole number ratio:

Isotope Mass Relative isotopic mass

number
1
1H 1 1.006
4
2He 4 4.003
9
4Be 9 9.012
27
Al
13 27 26.919
59
Co
27 59 58.933

The masses of protons and neutrons vary slightly from isotope to

isotope, so the relative isotopic mass is not exactly a whole number.

The relative atomic mass of an atom is the ratio of the average

mass of one atom of that element to 1/12th of the mass of one atom
of carbon-12.

The RAM is the average mass of all the isotopes, and is often not
close to a whole number:

Element Common mass Relative atomic mass

numbers
Mg 24, 25, 26 24.32
Cl 35, 37 35.45
Br 79, 81 79.91
Ba 134, 135, 136, 137, 137.33
138

Some elements and compounds exist as molecules; these also have

a characteristic mass:

The relative molecular mass of a molecule is the ratio of the

average mass of that molecule to 1/12th of the mass of an atom of
carbon-12.

The relative molecular mass of a molecule is the sum of the relative

atomic masses of its constituent atoms.

Eg The relative molecular mass of CO2 is 12.0 + 16.0 + 16.0 = 44.0

 MASS SPECTROMETRY

The 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.

1. How the mass spectrometer works

The workings of the mass spectrometer can be summarized in five

stages:

1- Gaseous material released into ionization chamber

2- Particles bombarded with electrons and ionized, mostly to +1
ions (IONISATION)
A metal wire is heated until it starts emitting high energy
electrons. These electrons hit the particles, knocking more
electrons off. Most of the particles are ionized to +1 ions
3- Ions accelerated to uniform speed by electric field
(ACCELERATION)
The positive ions are attracted to the negative plate and
accelerate towards it
4- Ions deflected by magnetic field; deflection depends on m/e ratio
(DEFLECTION)
The heavier the particle, the less the deflection
5- Electric current measured as ions land on plate (DETECTION)
The greater the abundance of the isotope, the larger the current
The degree of deflection depends on the mass and the charge; the
greater the mass, the less the deflection, and the greater the
charge, the greater the deflection. It can be shown that the
deflection is inversely proportional to the m/e ratio.

In most cases, however, the charge is +1, so the deflection depends

essentially on the relative mass of the species in the mass
spectrometer. If the spectrometer is calibrated, the masses of all the
species can be directly measured.

The greater the number of particles landing at a single point on the

detector, the greater the electric current and the larger the peak.
Thus the relative abundance of different isotopes can be measured.

Since the position at which an ion appears on the detector depends

on its mass, different isotopes appear at different points on the
detector. The magnitude of the peak gives the relative abundance
of the isotope.

Thus the relative atomic mass of the element can be calculated

from its mass spectrum.

An example of a simple mass spectrum is shown below:

Mass spectrum of Ne

The peak at 20 is Ne+, and the peak at 22 is

20
Ne+
22
2. Calculating relative atomic masses

The relative atomic mass can be calculated by the formula:

Σ (perentage abundance of each isotope x mass of each isotope)
100

eg Using the mass spectrum of neon above:

ram = (90 x 20 + 10 x 22)/100 = 20.2

All relative atomic masses have been found in this way.

3. Deducing relative molecular masses

It is also possible to put molecules into the mass spectrometer.

Because the conditions inside a mass spectrometer are very
extreme, the molecules often break up into smaller pieces. This is
known as fragmentation.

The mass spectrum of a molecule can thus look quite complicated:

Mass spectrum of pentane (C5H12)

Many of these peaks result from fragmentation of the molecule, but

the peak with the largest m/e ratio comes from the unbroken
molecular ion, in this case C5H12+, and is called the molecular ion
peak. The m/e ratio of this peak (72) will be the relative molecular
mass of the molecule.

The relative molecular mass of a molecule is obtained by

looking at the peak in the spectrum with the largest m/e
ratio (ie the peak furthest to the right).
 ELECTRONIC STRUCTURE

i) 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,…. To infinity. 1 is

the lowest energy level (closest to the nucleus) and energy level
infinity corresponds to the energy of an electron which is not
attracted to the nucleus at all. The energy levels thus converge as
they approach infinity:

ii) 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

p-orbitals: these are shaped like a 3D figure of eight. 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 (2p x, 2py, 2pz)
A p-orbital in the third energy level is a 3p orbital (3p x, 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.

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
iii) Shells

Since the different sub-levels have different energies, and the

energies of the different levels get closer together with increasing
energy level number, the high energy sub-levels of some energy
levels soon overlap with the low energy sub-levels of higher energy
levels, resulting in a more complex energy level diagram:

Starting with the lowest energy, the orbitals can thus be arranged as
follows:

1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p
6s 4f 5d 6p 7s 5f 6d

Many of these sub-levels have similar energy, and can be grouped

together.
A collection of sub-levels of similar energy is called a shell.

1s│2s 2p│3s 3p │ 4s 3d 4p │5s 4d 5p│6s 4f 5d 6p

The arrangement of shells and the maximum number of electrons in

each can be summarised as follows:

Shell number Orbitals in shell

1 1 x1s
2 1 x 2s, 3 x 2p
3 1 x 3s, 3 x 3p
4 1 x 4s, 5 x 3d, 3 x 4p
5 1 x 5s, 5 x 4d, 3 x 5p
6 1 x 6s, 7 x 4f, 5 x 5d, 3 x
6p

iv) 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- Max. no of electrons

level
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
5 2 x 5s, 10 x 4d, 6 x 5p 18
6 2 x 6s, 14 x 4f, 10 x 5d, 6 x 6p 32

v) 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.

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.
The electronic configuration of the first 18 elements using the arrow
in box method is as follows:

1s 2s 2p 3s 3p
H ↑

He ↑
↓

Li ↑ ↑
↓

Be ↑ ↑
↓ ↓

B ↑ ↑ ↑
↓ ↓

C ↑ ↑ ↑ ↑
↓ ↓

N ↑ ↑ ↑ ↑ ↑
↓ ↓

O ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓

F ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓

Ne ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓

Na ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓

Mg ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓

Al ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓

Si ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓

P ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓
S ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓ ↓

Cl ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓

Ar ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓
The orbital method indicates the number of electrons in each
orbital with a superscript written immediately after the orbital.

The electronic configurations of the first eighteen elements can be

shown with the orbital method as follows:

H: 1s1
He: 1s2
Li: 1s22s1
Be: 1s22s2
B: 1s22s22p1
C: 1s22s22p2 or 1s22s22p63s23px13py1
N: 1s22s22p3 or 1s22s22p63s23px13py13pz1
O: 1s22s22p4 or 1s22s22p63s23p23px23py13pz1
F: 1s22s22p5
Ne: 1s22s22p6
Na: 1s22s22p63s1
Mg: 1s22s22p63s2
Al: 1s22s22p63s23p1
Si: 1s22s22p63s23p2 or 1s22s22p63s23px13py1
P: 1s22s22p63s23p3 or 1s22s22p63s23px13py13pz1
S: 1s22s22p63s23p4 or 1s22s22p63s23px23py13pz1
Cl: 1s22s22p63s23p5
Ar: 1s22s22p63s23p6

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.

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] ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓

Co [Ar] ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓

Ni [Ar] ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓

Cu [Ar] ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓

Zn [Ar] ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓

Ga [Ar] ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓

Ge [Ar] ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓

As [Ar] ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓

Se [Ar] ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓ ↓

Br [Ar] ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
 ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓

Kr [Ar] ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓
Note the unusual structures of chromium and copper.
The difference in energy between the 3d and 4s electrons is very
small, and in chromium the energy required to promote and
electron from 4s to 3d is recovered in the reduced repulsion which
results from the fact that they are no longer paired. Thus the 4s 13d5
structure in Cr is preferred.
In copper, the 3d orbitals are actually lower in energy than the 4s
orbital, so the 4s13d10 structure in Cu is preferred.

v) Electron arrangement in ions

The electronic configuration of ions can be deduced by simply

adding or removing the appropriate number of electrons. The order
in which electrons are to be removed can be deduced from the
following rules:

- remove outer shell electrons first

- remove p-electrons first, then s-electrons and then d-electrons
- remove paired electrons before unpaired electrons in the same
sub-level

vi) Effect of electronic configuration on chemical properties

The chemical properties of an atom depend on the strength of the

attraction between the outer electrons and the nucleus. These in
turn depend on the number of protons and on the electronic
configuration, and so it follows that these two factors are
instrumental in determining the chemical properties of an atom.

This is in contrast with the neutron number however, which has no

effect on the chemical properties of an atom. Neutrons have no
charge and hence exert no attractive force on the nucleus.

Isotopes, therefore, tend to have very similar chemical

properties since they have the same atomic number and the
same electronic configuration. They differ only in number of
neutrons, which do not directly influence the chemical
properties of an element.
 IONISATION ENERGIES

i) 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

The amount of energy required to remove an electron from an atom

depends on the number of protons in the nucleus of the atom and
on the electronic configuration of that atom.

The first ionisation energies of the first 20 elements in the periodic

table is shown below:

Variation of first ionisation energy with atomic

number for the first twenty elements

2500
first ionisation energy (kJ

2000
per mole)

1500

1000

500

0
0 5 10 15 20
atomic number

There are various trends in this graph which can be explained by

reference to the proton number and electronic configuration of the
various elements. A number of factors must be considered:

- 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. The number of protons
in the nucleus is known as the nuclear charge.

- 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. This is known as shielding.
- 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.

- Electrons repel each other, particularly when they are in the same
orbital. The degree of repulsion between the outermost electrons
affects the ease with which electrons can be moved.

When considering trends in ionisation energies, it is thus necessary

to consider 4 factors:

- nuclear charge

- shielding

- effective nuclear charge

- electron repulsion

The trends in first ionisation energies amongst elements in the

periodic table can be explained on the basis of variations in one of
the four above factors.

Trend across period 1

Compare the first ionisation energies of H and He. Neither have

inner shells, so there is no shielding. He has two protons in the
nucleus; H only has one. Therefore the helium electrons are more
strongly attracted to the nucleus and hence more difficult to
remove.

The first ionisation energy of He is thus higher than that of H.

Since H and He are the only atoms whose outer electrons are not
shielded from the nucleus, it follows that He has the highest first
ionisation energy of all the elements. All elements (except H) have
outer electrons which are shielded to some extent from the nucleus
and thus are easier to remove.
So Helium has the highest first ionisation energy of all the elements.

Trends across period 2

Compare now the first ionisation energies of He (1s 2) and Li (1s22s1).

Li has an extra proton in the nucleus (3) but two inner-shell
electrons. These inner-shell electrons cancel out the charge of two
of the protons, reducing the effective nuclear charge on the 2s
electron to +1. This is lower than the effective nuclear charge on
the He 1s electrons, +2, and so the electrons are less strongly held
and easier to remove.

The first ionisation energy of Li is thus lower than that of He.

Compare the first ionisation energies of Li (1s22s1) and Be (1s22s2).

Be has one more proton in the nucleus than Li, and no extra inner-
shell electrons, so the effective nuclear charge on Be is higher and
the Be electrons are more strongly attracted to the nucleus.

The first ionisation energy of Be is thus higher than that of Li.

In general, the first ionisation energy increases across a period
because the nuclear charge increases but the shielding remains the
same.

Compare the first ionisation energies of Be (1s22s2) and B

(1s22s22p1).B has one more proton in the nucleus than Be but there
are also 2 extra inner sub-shell electrons. These cancel out the
charge of two more of the protons, leaving an effective nuclear
charge of only +1. This is less than Be (+2) so the electrons are less
strongly attracted to the nucleus and thus less difficult to remove.

The first ionisation energy of B is thus lower than that of Be.

Ionisation energies decrease from group II to group III because in
group III the electrons are removed from a p-orbital, so it is shielded
by the s-electrons in the outer shell. Thus the effective nuclear
charge decreases.

From B (1s22s22p1) to N (1s22s22p3) the proton number increases,

but the number of electrons shielding the nuclear charge remains
the same at 4. Thus the effective nuclear charge increases from B to
N and the electrons become progressively harder to remove.

The first ionisation energy thus increases from B to N.

So far the concepts of effective nuclear charge and shielding have
been used to explain the trend in first ionisation energies for the
first 7 elements. They cannot, however, explain the fall between N
and O. The electronic configurations of N and O must be considered
more carefully:
1s 2s 2p
N ↑↓ ↑↓ ↑ ↑ ↑

O ↑↓ ↑↓ ↑↓ ↑ ↑

Note that in N the electron is removed from an unpaired orbital, but

in O it is removed from a paired orbital. In a paired orbital, the two
electrons share a confined space and so repel each other. They are
therefore less stable and easier to remove. This repulsion effect
outweighs the higher effective nuclear charge in O.

The first ionisation energy of O is thus lower than that of N.

First ionisation energies decrease from group V to group VI, since
the electron removed from the group VI atom is paired, so there is
more repulsion between the electrons and the electron is easier to
remove.

The first ionisation energies increase as expected from O to Ne, due

to the increase in effective nuclear charge.

------------------------

The trend in first ionisation energies across period 2 can thus be

summarised as follows:

1. There is a general increase across the period as the nuclear

charge increases and the shielding remains the same.

2. There is a drop from Be to B because in B a 2p electron is being

removed and the extra shielding from the 2s subshell actually
causes a fall in the effective nuclear charge.

3. There is also a drop from N to O because the electron in O is

being removed from a paired orbital. The repulsion of the
electrons in this orbital makes them less stable and easier to
remove.

The same trend can also be found in Period 3 (Na - Ar). There is a
general increase, but a drop between Mg and Al and also between P
and S.

------------------
Trend down a group

The above graph also shows a clear decrease in first ionisation

energy on descending a group. This can be explained in the
following way:

On descending a group, the effective nuclear charge stays the same

but the number of inner shells increases. The repulsion between
these inner shells and the outer electrons makes them less stable,
pushes them further from the nucleus and makes them easier to
remove.

ii) 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. There are two satisfactory explanations for this:

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

The difference in successive ionisation energies, however, varies

widely and depends on the electronic configuration of the atom in
question. The difference in successive ionisation energies of an
atom can be predicted qualitatively by consideration of the effective
nuclear charge on the electron to be removed and the shielding of
that electron by the inner shell and inner sub-shell electrons.
Consider the successive ionisation energies of aluminium,
1s22s22p63s23p1:

The 1st ionisation energy is fairly low because the 3p electron is

shielded by all the other electrons, and the effective nuclear charge
is only +1.

The 2nd and 3rd ionisation energies are significantly higher than the
1st because 3s electrons are being removed and the effective
nuclear charge on these electrons is +3.

1st: 578 kJmol-1, 2nd: 1817 kJmol-1, 3rd: 2745 kJmol-1

There is a huge jump to the 4th ionisation energy, since a 2p electron

is now being removed. The shielding has fallen and the effective
nuclear charge has risen to +9.
The 5th and 6th ionisation energies are also high.

4th: 11578 kJmol-1, 5th: 14831 kJmol-1, 6th: 18378 kJmol-1

There is another significant jump to the 7 th ionisation energy, since

an unpaired 2p electron is now being removed.

7th: 23296 kJmol-1, 8th: 27460 kJmol-1, 9th: 31862 kJmol-1

The next significant jump is between the 9 th and 10th ionisation

energies, since the 10th requires the removal of a 2s electron.

10th: 38458kJmol-1, 11th: 42655 kJmol-1

There is a huge jump to the12th ionisation energy, since a 1s

electron is now being removed.

12th: 201276kJmol-1, 13th: 222313kJmol-1.

These ionisation energies could be plotted on a graph as follows:

 Variation of ionisation energy with number of
ionisations for aluminium

1000000
ionisation energy

100000

10000

1000

100
1 2 3 4 5 6 7 8 9 10 11 12 13
number of ionisations

Note that the largest jumps by far occur between the 3rd and 4 th
ionisation energies, and between the 11th and 12th ionisation
energies. In practice only large jumps such as this are visible on
such a graph.
The relative values of successive ionisation energies are therefore a
direct indicator of the electronic configuration of the atom in
question.

The trends can be summarised as follows:

1. The successive ionisation energies of an atom always increase.

The more electrons that are removed, the fewer the number
electrons that remain. There is therefore less repulsion between
the electrons in the resulting ion. The electrons are therefore
more stable and harder to remove.

2. By far the largest jumps between successive ionisation energies

come when the electron is removed from an inner shell. This
causes a large drop in shielding, a large increase in effective
nuclear charge and a large increase in ionisation energy

By applying the above principles in reverse, it is also possible to

predict the electronic structure of a species by analysis of the
successive ionisation energy data:

Eg Si:
 Variation of ionisation energy with number of
ionisations in silicon

1000000
ionisation energy

100000

10000

1000

100
1 3 5 7 9 11 13
number of ionisations

Large jumps occur between 4th and 5th and between 12th and 13th.

Therefore there are three shells: The first contains 2 electrons, the
second 8 and the third 4.