ELECTRONIC STRUCTURES OF ATOMS

The electrons are in certain energy levels (shells) and each energy level can hold up to
a certain number of electrons. The maximum number of electrons in a given energy
level n is given by 2n2 as summarized below.

Energy level or shell Maximum number of

electrons (2n2)
lst or K shell (2x12) = 2
2nd or L shell (2x22) = 8
3rd or M shell (2x32) = 18
4th or N shell (2x42) = 32
5th or O shell (2x42) = 32

SUB SHELLS AND ATOMIC ORBITALS

Shells Sub shell Atomic orbitals electrons

1,2,3,4,5,6,7 S, p, d, f S=1
P= 3
d=5
f=7

The electron will be found within a region of Space is known as an orbital. Therefore, an
orbital is a region of Space where an electron is likely to be found around the nucleus.
Each orbital can hold two electrons.
The sub shells are divided into s, p, d and f types.
 Energy level (shells) No. of subshells Subshells
1,2,3.4,5,6,7 S, p, d, f (S2, p6, d10, f14)
1 1 1s
2 2 2s 2p
3 3 3s 3p 3d
4 4 4s 4p 4d 4f
5 4 5s 5p 5d 5f
6 4 6s 6p 6d 6f
7 4 7s 7p 7d 7f

subshell No. of Maximum Electrons filled in atomic orbitals

orbitals number
of
elections
S 1 s2

P 3 p6

d 5 d10

f 7 f14

Electrons fill low energy levels (closer to the nucleus) before they fill higher ones. For
orbitals at the same energy level they fill the orbitals singly as far as possible.
 S - Subshell has one orbital which can contain maximum of two electrons.
 P-subshell consists of three orbitals each holding two electrons and maximum of
six electrons by each P-subshell.
 The d-subshell is made up of five orbitals each can hold two electrons and the
total number of electrons in 10 for each d- subshell.
 The f-subshell consists of seven orbitals and so can accommodate a maximum of
14 electrons.

Stability of subshells

subshell stable unstable Very unstable

s S2 S1
p p6 p3 P1, p2, p4, p5
 d d10 d5 d1, d2, d3, d6, d7, d8 d4, d9
f f14 f7 f1,2,3,4,5,8,9,10,11,12 F6, f13

Orbital overlap

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

5B 1s2s2p1
6C ls22s22p2
7N ls22s22p3
8O ls22s22p4
9F ls22s22p5
10Ne ls22s22p6

The order of filling the orbitals is ls,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p,6s,4f,5d,6p,7s etc.

Summary
Including all the inner levels: ls2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2

Examples
12 Mg ls22s22p63s2
16 S 1s22s22p63s23p4
19 K ls22s22p63s23p64s1
20 Ca 1s22s22p63s23p64s2
Notice in what follows that all the 3-level orbitals are written together, even though the
3d electrons are added to the atom after the 4s.
Including all the inner levels: ls2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2
Sc 1 s22s22p63s23p6 4s2 3d1
Ti 1 s22s22p63 s23 p6 4s2 3d2
V ls22s22p63s23p6 4s2 3d3
Cr ls22s22p63s23p6 4s1 3d5 *** 4s23d4

Mn 1s22s22p63s23p6 4s23d5
Fe 1s22s22p63s23p6 4s2 3d6
Co 1s22s22p63s23p6 4s2 3d7
Ni 1s22s22p63s23p6 4s2 3d8
Cu 1s22s22p63s23p6 4s1 3d10 ***4s23d9
Zn 1s22s22p63s23p6 4s2 3d10

Electronic structures of Ions

Positive ions are formed by removing electrons from the atomic orbitals
Negative ions are formed by adding more electrons to the atomic orbitals
Summary of removing electrons
Including all the inner levels: ls22s22p63s23p63d104s24p64d10 4f14

The electronic structures of ions are written in the same way as those of neutral atoms
Example,
Na - 1s22s22p63s1
Na+ - 1s22s22p6
Negative ions are represented in the same way remembering that a negative ion has
more electrons than its parent atom.
Example
Cl - ls22s22p63s23p5
Cl- - ls22s22p63s23p6
Transition metals have more than one oxidation state and the 4s-electrons are always
the first to be lost followed by electrons from the 3d-orbitals.
Example
Fe 1s22s22p63s23p63d64s2
Fe2+ ls22s22p63s23d6
Fe3+ ls22s22p63s23d5
 PHYSICAL PROPERTIES OF ELEMENTS IN THE PERIODIC TABLE
A periodic property is any physical or chemical property which changes periodically with
increasing atomic number. These properties include: -
1. Atomic radius and ionic radius
2. Electro negativity
3. Electro positivity
4. Electron affinity
5. Ionization energy
6. Metallic character
7. Melting and boiling points

The way in which these properties change through the Periodic Table leads to the
concept of Periodicity.

Definitions
1. Atomic radius is a measure of the size of an atom and it's half the distance between
two nuclei of identical atoms which are in contact with one another. I.e.
The average distance from the Centre of the atom to the region of its outermost shell
occupied by electrons

2. Ionic radius is the average distance from the centre of the nucleus of an ion to the
region of its outermost shell occupied by electrons.

3. Electronegativity is a measure of the tendency of an atom to attract a bonding pair of

electrons to itself.

4. Electropositivity / metallic character is a measure of the tendency of an atom to lose

the outermost shell elections to form a positively charged ion

5. Electron affinity is the energy change that occurs when a gaseous atom or ion gains
an electron

6. Ionisation energy is the minimum amount of energy required to remove an electron

from a gaseous atom or ion.
Forces in an atom

Effective nuclear charge (attraction) =Nuclear charge – screening effect

ENQ = NQ - SE
Variation of the effective nuclear charge across the periods in a Periodic Table

Element Na Mg Al Si P S Cl
Atomic number = P 11 12 13 14 15 16 17
Atomic number = e 11 12 13 14 15 16 17
ENQ = NQ - SE
ENQ = p - e
General explaination
The protons in the nucleus increases as you go across the period, which leads to
the increase in the nuclear charge.
Electrons are added to the same outermost sub shell and hence the screening
effect is almost constant.
Increase in nuclear charge outweighs screening effect, hence effective nuclear
attraction (charge) increases across the period from the left to the right.
As the effective nuclear attraction (charge) increases across the period ……………….

(a) Trends in Atomic Radius across the Periodic Table

The atomic radii of Period 2 and Period 3 elements of the Periodic table as shown
below.
Period 2 Li Be B C N O F
Atomic radius/A º 1.23 1.06 0.88 0.77 0.70 0.66 0.64
Period 3 Na Mg Al Si P S Cl
Atomic radius/A º 1.56 1.36 1.25 1.17 1.10 1.10 0.99
Note 1A =1 x 10
º -10

Trend: atomic size decreases across the periods

ENQ = NQ - SE
 As the effective nuclear attraction (charge) increases across the period, the
electrons are attracted inwards closer to the nucleus resulting into the decrease of
atomic size across the periods

(b) Patterns of electro negativity in the Periodic Table

The values for electro negativities of the elements in Periods, 2 and 3 of the Periodic
Table

I II III IV V VI VII
Li =1.0 Be = 1.5 B =2.0 C= N =3.0 O =3.5 F = 4.0
2.5
Na =0.9 Mg = 1.2 Al =1.5 Si = P = 2.1 S = 2.5 Cl =3.0
1.8
Variation of Electronegativity across the periods
ENQ = NQ - SE

Trend: Across each period, there is an increase in electro negativity from left to right

As the effective nuclear attraction (charge) increases across the period, the
atoms keep on developing an increasing electron attracting power hence the increase in
electro negativity across the period

(c) Variation of electro positivity across a period

Trend: Electro positivity decreases across the period from the left to the right

The result is increased effective nuclear charge and the outer most shell
electrons become more strongly held by the nucleus and hence become more
increasingly difficult to remove the outer electrons.

(d) Trend in electron affinity across a Period

Trend: electron affinity increases across a period as shown by the electron affinity
values of the elements of third period.
Element Na Mg Al S! P S Cl
1st E.A(KJMol-1) -20 +67 -30 -135 -60 -200 -364

The effective nuclear charge increases across the period so that the nuclear
attraction for the incoming electron increases and the electron affinity increases.

(e) ionization energies in period 3 are all lower than those in period 2.

Period 2 Li Be B C N O F Ne
Atomic number 3 4 5 6 7 8 9 10
1st I.E/KJMor-1 520 900 800 1080 1403 1320 1640 2080
Period 3 Na Mg AI Si P S CI Ar
Atomic number 11 12 13 14 15 16 17 18
1st .E/KJMor-1 495 738 577 787 1060 1000 1255 1520

Trend: Generally, ionization energy increases across the periodic Table

ENQ = NQ - SE
ENQ = p - e

The effective nuclear charge increases across the period. That causes a greater
attraction between the nucleus and the electrons and so increases the ionization
energies. In fact the increasing nuclear charge also drags the outer electrons in closer to
the nucleus. That increases the ionization energies still more as you go across the
period.

(f) Variation of metallic character across a period

Na Mg AI Si P S C1 Ar
11 12 13 14 15 16 17 18

Trend: Metallic character decreases across the period from the left to the right

The result is increased effective nuclear charge and the outer most shell
electrons become more strongly held by the nucleus and hence become more
increasingly difficult to remove the electrons making the metallic character to increase.
Variation of physical properties down the groups of the periodic table
A periodic property is any physical or chemical property which changes periodically with
increasing atomic number. These properties include: -
8. Atomic radius and ionic radius
9. Electro negativity
10. Electro positivity
11. Electron affinity
12. Ionization energy
13. Metallic character
14. Melting and boiling points

The way in which these properties change through the Periodic Table leads to the
concept of Periodicity.

Definitions
1. Atomic radius is a measure of the size of an atom and it's half the distance between
two nuclei of identical atoms which are in contact with one another. I.e.
The average distance from the Centre of the atom to the region of its outermost shell
occupied by electrons

2. Ionic radius is the average distance from the centre of the nucleus of an ion to the
region of its outermost shell occupied by electrons.

3. Electronegativity is a measure of the tendency of an atom to attract a bonding pair of

electrons to itself.

4. Electropositivity / metallic character is a measure of the tendency of an atom to lose

the outermost shell elections to form a positively charged ion

5. Electron affinity is the energy change that occurs when a gaseous atom or ion gains
an electron

6. Ionisation energy is the minimum amount of energy required to remove an electron

from a gaseous atom or ion.

Forces in an atom
 Effective nuclear charge (attraction) =Nuclear charge – screening effect
ENQ = NQ - SE

Variation of effective nuclear charge down the groups

Element Protons in Electron in a given shell electrons
nucleus =2n2
H 1 Shell 1 2
Li 3 Shell 2 8
Na 11 Shell 3 18
K 19 Shell 4 32

ENQ = NQ - SE
ENQ = p - e
General explaination
Down the group the number of protons in the nucleus increases, leading to the
increase in nuclear charge.
A new fully filled stable shell of electrons is added from one element to the next
leading to the increase in screening effect.
The increasing nuclear charge is outweighed by the increased screening effect,
hence the effective nuclear charge decreases down the groups.
As the effective nuclear charge decreases down the groups, ……………………………….

(a) Trends in atomic radius down a group

Element Atomic radii Ion Ionic radii

(A°) (nm)
Li 1.23 Li+ 0.060
Na 1.57 Na+ 0.095
K 2.03 K+ 0.135
Rb 2.16 Rb+ 0.148
Cs 2.35 Cs+ 0.168
Trend (variation)
The atomic (and ionic) size increases as you move down the groups.

Explanation
As the effective nuclear charge decreases down the groups, the electrons move
further away from the nucleus making the atomic radius to increase down the group.

IONIC RADII (rc, ra)

Ionic radius may be defined as the mean or average distance between the Centre of the
nucleus of an ion to the region of its outermost shell occupied by electrons.

ra rc

ra = radius of anion
rc = radius of action

(a)Positive ions
Positive ions have a smaller radius than the corresponding atoms.
e.g. Na 1.57A°; Na+ 1.02Aº
2:8:1 2:8
The ionic size keeps on decreasing as more electrons are being removed
Fe > Fe+ > Fe2+ > Fe3+ > Fe4+ > Fe5+
Explanation
The cations are formed by removal of electron(s) from gaseous atoms. The
number of protons in the nucleus continuously exceeds the number of electrons in the
shells.
There is increasing nuclear attraction for the remaining electrons which are pulled
closer to the nucleus leading to reduction in size of the ion.

(b) Negative ions

Negative ions are bigger than the corresponding atoms.
e.g. Cl 0.99Aº Cl- 1.81A0
Chlorine is 2:8:7; Cl- is 2:8:8

Explanation
The negative ion is formed by addition of electron(s) to the outermost shell of an atom.
This increases the number of electrons but the nuclear charge is constant. The effective
nuclear attraction on the electrons reduces and the electrons move further away from
the nucleus making the ion to become bigger in size than the parent atom.

(b) Variation of Electronegativity down the groups

Trend
Electronegativity decreases down the groups

Explanation
As the effective nuclear charge decreases down the groups, the electrons attracting
power reduces leading to a decrease in electro negativity down the group

(c) Variation of electro positivity down a group

Trend
As you go down the group the electro positivity of the elements increases. I.e. Down the
group elements become more electropositive which makes it increasingly easier to
remove the electrons.

Explanation
As the effective nuclear charge decreases down the groups the atoms readily lose the
outermost shell electrons as a result of reduced effective nuclear attraction. The
elements readily form positive ions as less energy is required to remove the electrons
and electro positivity increases.

(d) Variation of Metallic character down a group

C
Si
Ge
Sn
Pb

Trend
As you go down the group the Metallic character of the elements increases.

Explanation
As the effective nuclear charge decreases down the groups the atoms readily lose the
outermost shell electrons as a result of reduced effective nuclear attraction. The
elements readily form positive ions as less energy is required to remove the electrons
and metallic character increases.

(e)Trend in electron Affinity down a group

The first electron affinities of the group VII elements are given below.
Element 1st E.A
F -328 KJMol-1
Cl -349KJMol-1
Br -324KJMOl-1
I -295KJM01-1
Trend: As you go down the group, first electron affinity decreases
Explanation:
The effective nuclear attraction reduces down the group and so there is increased
distance between the incoming electron and the nucleus as you go down the group. The
greater the distance the less the nuclear attraction and so less energy is released as
electron affinity.

Note: The first electron affinity of fluorine is less than expected

The incoming electron is going to be closer to the nucleus in fluorine atom than in any
other of these elements and a high value of electron affinity would be expected.
However, because fluorine is such a small atom, the new electron goes into a region of
space already crowded with electrons and there is significant amount of repulsion. This
repulsion reduces the attraction the incoming electron experiences and so reduces the
electron affinity.

Note: The first electron affinity of oxygen (-142KJMol-1) is less than that of sulphur (-200
KJMol-1) for exactly the same reason that oxygen is smaller than sulphur.

(e) Trends in ionization energy down a Group

Taking group I as an example

Element Li Na K Rb Cs
1s1 I.E(KJMol-1) 520 498 419 403 376

Trend
Within a group the first ionization energy decreases down the group.
Explanation
The effective nuclear attraction reduces down the group and so there is increased
distance between the electron to be removed and the nucleus as you go down the
group. The greater the distance the less the nuclear attraction and so less energy is
needed to remove the outer most loosely attached electron hence the decrease in
ionization energy down the groups.

Melting points, bonding and structure

What is meant by melting point?

The melting point is the temperature at which a pure solid is in equilibrium with its own
liquid at a given atmospheric pressure. The melting point of an element is a direct
measure of the strength of the forces between the particles that make up the solid.

A high melting point indicates strong metallic bonding or the presence of a giant
covalent structure and a lower melting point is associated with covalently bonded
molecules.

Factors Affecting the Melting points of elements

(1) Among the metals, the melting point depends on the number of electrons involved in
metallic bonding. The greater the number of electrons involved in bonding per atom, the
stronger the metallic bonding and so the higher the melting points.
(ii) Among the non-metals or molecular substances, the melting points depend on the
molecular size and structure of the molecules.

The trend of Melting points across Period 3 elements

Element Na Mg Al Si P S Cl Ar
Melting Point/°C 98 650 660 1410 44 119 -101 -189

The graph of Melting points (0C) against increasing atomic number shows a distinct
overall shape.

Trend shown by the graph:

The melting points increase through metals and metalloids and then decrease to very
low values through non-metals.

The metals Sodium, Magnesium and Aluminium

The three elements Sodium, magnesium and aluminium have metallic structures
consisting of a regular lattice of metal ions (Na+, Mg2+ and Al3+respectively). These ions
are surrounded by delocalized valence electrons and strong forces of attraction exist
between the cations.
Magnesium has a higher melting point than sodium because each magnesium
atom contributes two electrons for metallic bonding while each sodium atom contributes
only one electron. The greater the number of electrons contributed for metallic bonding
the stronger the metallic tending.
However, there is a slight increase in melting point from magnesium to
aluminium. This is because aluminium atoms may not easily contribute all the three
valence electrons for metallic bonding.

The metalloid Silicon

Silicon has a giant covalent structure with very many covalent bonds between atoms.

The non-metals phosphorus, sulphur and chlorine

-The melting point of sulphur is higher than that of phosphorus because the S 8
molecules are bigger than P4 molecules and the Vander Waals forces holding the S 8
molecules together are stronger than those holding the P 4 molecules together. As a
result, sulphur melts at a higher temperature than phosphorus.

- Chlorine exists as diatomic molecules, C12, held together by weak Vander Waals
forces that are even broken at room temperature and hence chlorine exists as gas.
- Argon has the lowest melting point because it exists as individual argon atoms held
together by very weak Vander Waals forces.
 Specific explanations

ATOMIC AND IONIC RADIUS

The size of an atom is usually given as atomic radius. In covalent bonding the distance
between the centres of nuclei of two atoms bonded together is called bond length or
inter-nuclear distance and may be considered as the radii of the two atoms.

Atomic radius = d/2

d
Definition: Atomic radius is a measure of the size of an atom and it's half the distance
between two nuclei of identical atoms which are in contact with one another. It is
measured in the units of length, but since its value is very small the subunit of
nanometer (nm) is often used.
Note: 1 nm = 1 x 10-9 M
1 A0 = 1 x 10-8 M

Variation of Atomic Radius

 The size of an atom depends on how strongly the protons in the nucleus attract the
outer shell electrons.
 The reduced attraction by the protons for the outermost electrons caused by the
Electrons in inner fully filled shells is known as screening effect.
 The net positive charge which the outermost electrons experience through attraction
is called the
effective nuclear charge (effective nuclear attraction)

Trends in Atomic Radius across the Periodic Table

The atomic radii of Period 2 and Period 3 elements of the Periodic table as shown
below.
Period 2 Li Be B C N O F
Atomic radius/Aº 1.23 1.06 0.88 0.77 0.70 0.66 0.64
Period 3 Na Mg Al Si P S Cl
Atomic radius/A º 1.56 1.36 1.25 1.17 1.10 1.10 0.99
Note 1A =1 x 10
º -10

Treads in atomic radius in Periods 2 and 3Trend (variation)

In Periods 2 and 3, the atomic radius decreases steadily across the period as atomic
number increases from group 1 to group VII.
Explanation
Electrons are added to the same outermost sub shell and hence the screening
effect is almost constant.
The protons in the nucleus increases as you go across the period, which leads to
the increase in the nuclear charge.
 Therefore, the effective nuclear attraction (charge) increases across the period
from the left to the right.
As the effective nuclear attraction (charge) increases across the period, the
electrons are attracted inwards closer to the nucleus resulting into the decrease of
atomic size across the periods

Trends in atomic radius down a group

Element Atomic radii Ion Ionic radii

(A°) (nm)
Li 1.23 Li+ 0.060
Na 1.57 Na+ 0.095
K 2.03 K+ 0.135
Rb 2.16 Rb+ 0.148
Cs 2.35 Cs+ 0.168

Trend (variation)
The atomic (and ionic) size increases as you move down the groups.

Explanation:
Down the group the number of protons in the nucleus increases, with increasing
atomic number leading to the increase in nuclear charge.
A new fully filled shell of electrons is added from one element to the next leading
to the increase in screening effect.
The increasing nuclear charge is outweighed by the increased screening effect
caused by the extra inner filled shells of electrons, and hence the effective nuclear
charge decreases down the groups.
As the effective nuclear charge decreases down the groups, the electrons move
further away from the nucleus making the atomic radius to increase down the group.

Note1: The ionic size varies in exactly the same way as the atomic size across the
periods and down the groups in the periodic table

Note2: Atomic size is determined by:

- The nuclear attraction for the electrons
- The screening or shielding effect of the inner filled shells on the outer electrons.

ELECTRONEGATIVITY
Definition: Electronegativity is a measure of the tendency of an atom to attract a bonding
pair of electrons to itself
An atom of a molecule which tends to attract more electrons to itself is described as a
more electronegative atom. In a covalent bond such as between two chlorine atoms, the
two atoms attract the pair of electrons in the bond equally. However, in hydrogen
fluoride, because fluorine is more electronegative than hydrogen, the pair of electrons is
attracted more by the fluorine than the hydrogen. This results in a slight separation of
charge.
 H +—F -
In bond formation, the difference in electro negativity between the two atoms will
determine whether the bonding is predominantly ionic or covalent. The greater the
electro negativity difference between two bonding atoms, the greater the ionic character
of the bond formed.

Patterns of electro negativity in the Periodic Table

The values for electro negativities of the elements in Periods, 2 and 3 of the Periodic
Table

I II III IV V VI VII
Li =1.0 Be = 1.5 B =2.0 C= N =3.0 O =3.5 F = 4.0
2.5
Na =0.9 Mg = 1.2 Al =1.5 Si = P = 2.1 S = 2.5 Cl =3.0
1.8
K = 0.8 Ca = 1.0 Br =2.8

The electro negativity of an element is just a numerical value but not energy and it has
no units- Neon and argon do not have an electro negativity value, because they do not
form bonds.

Note: The factors influencing electro negativities include: - Nuclear charge, Atomic
radius and screening effect by inner sub shells.

(a)Variation of Electronegativity across the periods

Across each period, there is an increase in electro negativity from left to right

Explanation;
Electrons are added to the same outermost sub shell and hence the screening
effect is almost constant.
The protons in the nucleus increases as you go across the period, which leads to the
increase in the nuclear charge.
Therefore, the effective nuclear attraction (charge) increases across the period
from the left to the right.
As the effective nuclear attraction (charge) increases across the period, the
atoms keep on developing an increasing electron attracting power hence the increase in
electro negativity across the period

(b)Variation of Electronegativity down the groups

Trend
Electronegativity decreases. Down the groups

Explanation
Down the group the number of protons in the nucleus increases, with increasing atomic
number leading to the increase in nuclear charge.
A new fully filled shell of electrons is added from one element to the next leading to the
increase in screening effect.
The increasing nuclear charge is outweighed by the increased screening effect caused
by the extra inner filled shells of electrons, and hence the effective nuclear charge
decreases down the groups.
As the effective nuclear charge decreases down the groups, the electrons attracting
power reduces down the group leading to a decrease in electro negativity down the
group

ELECTROPOSITIVITY
This is a measure of the tendency of an atom to lose the outermost shell elections to
form a positively charged ion. Thus the easier the tendency the higher the electro
positivity

(a)Variation of electro positivity across a period

Trend
Electro positivity decreases across the period from the left to the right

I.e. Across a period elements become less electropositive which makes it increasingly
more difficult to remove the electrons

Explanation
As you move from one element to the next across a period, one proton is added to the
nucleus making nuclear charge to increase and one electron is added to the same outer
shell and no extra shell is added hence screening effect is almost constant. The result is
increased effective nuclear charge and the outer most shell electrons become more
strongly held by the nucleus and hence become more increasingly difficult to remove the
outer electrons.

Variation of electro positivity down a group

Trend
As you go down the group the electro positivity of the elements increases. I.e. Down the
group elements become more electropositive which makes it increasingly easier to
remove the electrons.

Explanation
On descending down the group from one element to the next, the number of outer
electrons remain the same, but there is an extra fully filled shell being added making the
screening effect to increase, and there is an increase in the nuclear charge due to
increase in the number of protons in the nucleus.
However, the screening effect of the full extra shell being added outweighs the effect of
increasing nuclear charge and the result is a decrease in the effective nuclear charge
down the group. Thus down the group the atoms readily lose the outermost shell
electrons as a result of reduced effective nuclear attraction. The elements readily form
positive ions as less energy is required to remove the electrons and electro positivity
increases.

ELECTRON AFFINITY
Electron affinities are always concerned with the formation of negative ions. Their use is
almost confined to elements in groups VI and VII of the Periodic Table.

Definition: Electron affinity is the energy change that occurs when a gaseous atom or
ion gains an electron.

Defining first Electron Affinity

The first electron affinity is the energy released when 1 mole of gaseous atoms each
acquire an electron to form a mole of negatively charged ions. This is more easily
written in symbol terms:
X(g) + e- X-(g) ∆H = 1st E.A

It is the energy released (per mole of X) when this change happens. Non-metals readily
accept electrons to form negative ions. In these atoms there are greater nuclear charges
to attract electrons. First electron affinities have negative values as energy is released.
For example, the first electron affinity of sulphur atom
S(g) + e-  S-(g) ∆H = -200K JMol-1

By convention, the negative sign shows release of energy.

Second Electron Affinity

This is likely to be found with group VI elements, oxygen and Sulphur which form ions
with a double negative charge (-2).
S-(g) + e-  S2-(g) 2nd E.A ∆H= +648.5KJMOI-1

The positive sign shows that energy is absorbed to perform the change. This process is
endothermic because it involves strong repulsion of a negatively charged ion for the
incoming electron. This repulsion makes the process difficult and energy must be
absorbed to enforce the process of addition. There is no such repulsion in the first
process. Thus the second and subsequent electron affinities are all endothermic
because the process involves bringing together two negatively charged particles.
(a)Trend in electron affinity across a Period
The trend in electron affinity across a period as shown by the electron affinity values of
the elements of third period.
Element Na Mg Al S! P S Cl
1st E.A(KJMol-1) -20 +67 -30 -135 -60 -200 -364

Question: Plot a graph of Electron affinity against atomic number

The electron affinity is a measure of the attraction between the incoming electron and
the nucleus. The stronger the attraction, the more energy is released.
The factors which affect this attraction are nuclear charge, atomic size and screening
effect

General trend
Across the Period electron affinity generally increases with some irregularities for
magnesium and phosphorus.

Explanation:
Electrons are added to the same outermost sub shell and hence the screening effect is
almost constant.
The protons in the nucleus increases as you go across the period, which leads to the
increase in the nuclear charge.
The effective nuclear charge increases across the period so that the nuclear attraction
for the incoming electron increases and the electron affinity increases.

However, the electron affinity for magnesium is more positive than expected
because the electron is being added to a full 3S2 sub shell which is thermodynamically
stable and so resists the addition and energy must be absorbed to effect the addition.

Similarly phosphorus has a lower value for electron affinity than expected
because the electron is being added to a stable half-full 3P3 sub shell which resists the
addition and so less energy than expected is released.

(b) Trend in electron Affinity down a group

The first electron affinities of the group VII elements are given below.
Element 1st E.A
F -328 KJMol-1
Cl -349KJMol-1
Br -324KJMOl-1
I -295KJM01-1
Trend: As you go down the group, first electron affinity decreases

Explanation:
Down the group the increase in screening effect outweigh the increase in nuclear
charge. The effective nuclear attraction reduces down the group and so there is
increased distance between the incoming electron and the nucleus as you go down the
group. The greater the distance the less the nuclear attraction and so less energy is
released as electron affinity.

Note: The first electron affinity of fluorine is less than expected

The incoming electron is going to be closer to the nucleus in fluorine atom than in any
other of these elements and a high value of electron affinity would be expected.
However, because fluorine is such a small atom, the new electron goes into a region of
space already crowded with electrons and there is significant amount of repulsion. This
repulsion reduces the attraction the incoming electron experiences and so reduces the
electron affinity.
Note: The first electron affinity of oxygen (-142KJMol-1) is less than that of sulphur (-200
KJMol-1) for exactly the same reason that oxygen is smaller than sulphur.

IONISATION ENERGY (IONISATION POTENTIAL)

Definition
Ionisation energy is the minimum amount of energy required to remove an electron from
a gaseous atom or ion against the attractive forces of the nucleus. Energy is required to
remove an electron from any atom because there is an attractive force between the
nucleus and the electron being removed which has to be overcome.

Defining first ionization energy

The first ionization energy is the energy required to remove the most loosely held
electron from one mole of gaseous atoms to produce one mole of a univalently charged
gaseous positive ions. This is more easily seen in symbol terms: X(g)  X+(g) + e
It is the energy needed to carry out this change per mole of X in gaseous state.

Factors affecting the size of ionization energy

Ionization energy is a measure of the energy needed to pull a particular electron away
from the attraction of the nucleus. A high value of ionization energy shows a high
attraction between the electrons and the nucleus. The size of that attraction is governed
by the following factors:
 The charge on the nucleus
The more protons there are in the nucleus, the more positively charged the nucleus is,
and the more strongly the electrons are attracted by the nucleus, consequently
ionization energy increases.

 The distance of the electron from the nucleus

Attraction falls off rapidly with the distance between the electron and the nucleus. An
electron closer to fie nucleus will be much more strongly attracted than one further away
from the nucleus. Thus ionisation energy decreases as the distance the between the
electron and the nucleus increases.

 The shielding or screening effect produced by Inner filled shells.

This lessening of the pull of the nucleus by inner electrons is known AS screening or
shielding. Shielding or screening involves the repulsion between the inner filled shells
and the electron being removed from the outer shell. The outermost shell electrons are
repelled by all the other electrons in the atom besides being attracted by the nucleus.
 Whether the electron is on its own in an orbital or paired with another electron
Two electrons in the same orbital experience some repulsion from each other. This
offsets the attraction of the nucleus, so that paired electrons are removed rather more
easily than you might expect.
 Type of configuration- Full shells and half filled sub shells are associated with
extra stability and therefore require more energy than expected to extract
electrons.
 The penetration effects: For a given quantum shell, the penetrating power of the
valence electrons decreases in the order s > p > d > f, where electrons in the s-
sub shell are always nearer to the nucleus and are said to be more penetrating
 than the p, d and f electrons. Thus electrons in s-orbitals with high penetrating
power are nearer to the nucleus and shield the less penetrating electrons in other
orbitals. This reduces the effective nuclear charge for the distant electrons and
consequently reduces the value of ionization energy. However, the increase in
penetrating power of the valence electrons increases the nuclear attraction and
this increases the value of ionization energy.

The patterns in Periods 2 and 3

The patterns in the two periods are identical - the difference being that the ionization
energies in period 3 are all lower than those in period 2.

Period 2 Li Be B C N O F Ne
Atomic number 3 4 5 6 7 8 9 10
1st I.E/KJMor-1 520 900 800 1080 1403 1320 1640 2080

Period 3 Na Mg AI Si P S CI Ar
Atomic number 11 12 13 14 15 16 17 18
1st .E/KJMor-1 495 738 577 787 1060 1000 1255 1520

Plot graph of First ionization energy of period 3 against atomic number

General trend across Periods 2 and 3

Ionization energies generally increase across period from the left to the right.

Explaining the general trend across Periods 2 and 3

` The protons in the nucleus increases as you go across the period, which leads to
the increase in the nuclear charge.
Electrons are added to the same outermost sub shell and hence the screening
effect is almost constant.
The effective nuclear charge increases across the period. That causes a greater
attraction between the nucleus and the electrons and so increases the ionization
energies. In fact the increasing nuclear charge also drags the outer electrons in closer to
the nucleus. That increases the ionization energies still more as you go across the
period.

Note: The trend is exactly the same in both period 2 and 3.

Why the drop between groups II and III (Be to B and Mg to Al)
The ionisation energy of boron is unexpectedly lower than that of beryllium while that of
aluminium is unexpectedly lower than that of magnesium. The explanation lies with the
structures of beryllium and boron.
Be ls22s2 1st I.E = +900KJmol-1
B Is 2s 2p
2 2 1 1st I.E = +799 KJmor-1
The outer 2s sub shell for beryllium is full and therefore stable. The 2p orbital in boron
2

is screened not only by the Is2 electrons but, to some extent, by the 2s2 electrons as
well. That also reduces the pull from the nucleus and so lowers the ionization energy for
boron.

The explanation for the drop between Mg and Al is the same, except that everything is
happening at the third energy level rather than the 2-level.
Mg 1s22s22p63s2 1stI.E = +736KJMol-1
Al 1s22s22p63s23p1 lst l.E = +577 KJMol-1
The electron that is removed in Al is from the 3p sub shell, which is further from the
nucleus than the 3s electron that is removed from Mg. It therefore requires less energy
to remove this electron during ionization, The 3s2 sub shell is a closed shell which is
more stable and therefore require more energy to remove the electron.

Question: Explain why the first ionisation energy of Beryllium is greater than the first
ionisation energy of Boron yet the second ionisation energy of Beryllium is less than the
second ionisation energy of Boron

Why the drop between groups V and VI (N to O and P to S)?

The ionization energies of oxygen and Sulphur are lower than would be expected. This
is also explained by the electronic structures of the atoms.
N ls22s22p3 1st I.E = +1400KJMol-1
O ls22s22p4 1s1 1.E = +1310KJMol-1
The difference is that in the oxygen the electron being removed is one of the 2p2K pair.
The repulsion between the two electrons in the same orbital means that the electron is
easier to remove than would otherwise he, while the half filled 2p 3 sub shell for nitrogen
is more stable and require more to remove an electron. The drop in ionization energy at
sulphur from phosphorus is accounted for in the same way.
P ls2P63s23p3 1st I.E = +1060KJMol-1
S Is 2s 2p 3s 3p
2 2 6 2 4 1st I.E = +1000KJMol-1
The 3p electrons in phosphorus all occupy separate orbitals and give a stable half filled
electronic configuration. The fourth p-electron in sulphur must enter one of these orbital
resulting in increased repulsion and lower ionization energy than otherwise expected.

Trends in ionization energy down a Group

Taking group I as an example

Element Li Na K Rb Cs
1s1 I.E(KJMol-1) 520 498 419 403 376

Trend
Within a group the first ionization energy decreases down the group.
Explanation
Down the group the increase in screening effect outweigh the increase in nuclear
charge. The effective nuclear attraction reduces down the group and so there is
increased distance between the electron to be removed and the nucleus as you go
down the group. The greater the distance the less the nuclear attraction and so less
energy is needed to remove the outer most loosely attached electron hence the
decrease in ionization energy down the groups.

SUCCESSIVE IONISATION ENERGIES

Defining Second ionization energy

Second ionization energy is defined by the equation: X +(g)  X2+(g) + e-
In the same way that an atom can be ionized by losing an electron, the resulting ion can
be further ionized. The process could be continued until there are no more electrons left
surrounding the nucleus. There are as many successive ionization energies as there are
electrons in the original atom.
By definition, the second ionization energy of an element is the amount of energy
required to remove one mole of electrons from one mole of univalently charged gaseous
positive ions to form one mole of divalently charged gaseous positive ions.
And the third ionization energy is the amount of energy required to remove one mole of
electrons from a divalently charged gaseous positive ions to form one mole of trivalently
charged gaseous positive ions.
All other successive ionization energies can be defined. The first four ionization
energies of magnesium, for example, are given below.

Ionization Energies/KJMol-1
2nd 3rd 4th
1st
738 1450 7740 10,500

Why do successive ionization energies become larger?

The ionization energies for an element increase in magnitude as successive electrons
are removed. This trend arises because the positive nuclear charge that provides the
attractive force remains the same, whereas the number of electrons steadily decreases.
Therefore, the effective nuclear charge experienced by the remaining electrons
increases. The remaining electrons are strongly attracted are more energy is needed to
remove them hence the increase in ionization energy

Why the 3"1 ionization energy of Magnesium is so large?

There is a big jump in the ionization energy when the third electron is being removed.
The electronic structure of magnesium is Is22s22p63s2. The first 2 electrons to be
removed come from the 3s-orbital, the third electron is removed from the 2p-level much
closer to the nucleus and is a closed shell which is extremely stable to disrupt.

Using ionization energies to work out the group which an element belongs
This big jump between two successive ionization energies is typical of suddenly
breaking into an inner level. Magnesium (ls22s22p63s2) is in group (II) of the periodic
table and has 12 successive ionization energies. The graph below shows successive
values of the ionization energies for magnesium.
 1 2 3 4 5 6 7 8 9

Electron removed

N.B: The 11th I.E is over 100 times the Is1 I.E of Magnesium and a logarithmic plot on the
y-axis is conveniently used.
Here the largest rate of increase in ionization energies occurs after the 2 nd I.E. It means
that there are 2 electrons which are relatively easy to remove (the 3s2 electrons). To
remove the third electron is much more difficult and needs much greater energy
because this electron comes from an inner 2p sub shell closer to the nucleus and is a
closed shell which is extremely stable to disrupt.
There is a steady increase in energy required as electrons are removed from the 2p and
then 2s orbitals. The removal of the 11th and 12th electrons require much greater
amounts of energy, as these electrons are closest to the nucleus in the Is orbital in
addition to being a full closed shell. The largest rate of increase in ionization energies of
an element also provides evidence for existence of energy levels.

Another example
The first eight ionization energies of an element B are shown below.

1st 2nd 3rd 4th 5th 6th 7th 8th

786 1580 3230 4360 16000 20000 23600 29100

To which group in the Periodic Table does element B belong? Give a reason for your
answer.

Sample answer
This element is in group IV. There is largest rate of increase in ionization energy after
the four electrons have been removed. There are four electrons which are relatively
easy to remove and their ionization energies are similar but the fifth electron comes from
an inner filled shell which is near to the nucleus and more strongly attracted by the
nucleus and this will require much more energy to remove.

Importance of ionization energies in studying the chemistry of element

 Atomic number can be derived from the number of successive ionization energies
an element has.
 Electronic arrangement and distribution in energy levels can be derived by
plotting values of ionization energies for an element. A graph will show distinct
breaks according to the energy levels.
 The metallic or non-metallic character of an element can be determined. The first
ionization energies of metals are always nearly below 800KJMol-1.

 Across the period ionization energy increases, so the metallic character

decreases across the periods.
 Down a group, the ionization energy decreases, so the metallic character
increases down the group.

METALLIC AND NON-METALLIC CHARACTER

The elements gradually change from metals to non-metals from left to right across a
period.
Period 2
Li Be B C N O F
---------------------- Metals ----- // Metalloid // ------------- Non-metals

Period3

Na Mg Al Si P S Cl
---------------------- Metals ----- // Metalloid // ------------- Non-metals

(a)Variation of metallic character across a period

Trend
Metallic character decreases across the period from the left to the right

Explanation
As you move from one element to the next across a period, one proton is added to the
nucleus making nuclear charge to increase and one electron is added to the same outer
shell and no extra shell is added hence screening effect is almost constant. The result is
increased effective nuclear charge and the outer most shell electrons become more
strongly held by the nucleus and hence become more increasingly difficult to remove the
electrons making the metallic character to increase.

Variation of Metallic character down a group

Trend
As you go down the group the Metallic character of the elements increases.

Explanation
On descending down the group from one element to the next, the number of outer
electrons remain the same, but there is an extra fully filled shell being added making the
screening effect to increase, and there is an increase in the nuclear charge due to
increase in the number of protons in the nucleus.
However, the screening effect of the full extra shell being added outweighs the effect of
increasing nuclear charge and the result is a decrease in the effective nuclear charge
down the group. Thus down the group the atoms readily lose the outermost shell
electrons as a result of reduced effective nuclear attraction. The elements readily form
positive ions as less energy is required to remove the electrons and metallic character
increases.