TOPIC 1

ATOMIC STRUCTURE
The optimist sees the glass half full. The pessimist
sees the glass half empty. The chemist sees the glass
completely full, half with liquid and half with air.
 LEARNING OUTCOMES
1. Identify, describe protons, neutrons & electrons in terms of their relative
charges & masses
2. Deduce the behaviour of beams of protons, neutrons & electrons in electric
fields
3. Deduce the numbers of nucleons, protons, neutrons and electrons.
4. Distinguish between isotopes on the basis of different numbers of neutrons.
5. Describe the number & relative energies of the s, p and d orbitals for
principal quantum numbers 1-4.
6. Describe and sketch the shapes of s and p orbitals.
7. State electronic configuration of atoms, ions given the proton number.
8. Explain term ionisation energy and factors influencing the ionisation
energies.
9. Explain the trends in ionisation energies across a Period and down a group.
10. Deduce the electronic configurations of elements from successive ionisation
energy data & interpret in terms of the position within the Periodic Table.
1.1
 RELATIVE CHARGES & RELATIVE MASSES 1.1

• The 3 fundamental (or sub-atomic) particles of atom :

Proton, Neutron, Electron.
• The relative masses and charges of these 3 subatomic particles :

Relative Location within

Particle Symbol Relative mass
charge the atom

Proton p 1 a.m.u +1 Nucleus

Neutron n 1 a.m.u 0 Nucleus

Electron e 1/1836 a.m.u -1 Orbital

[ a.m.u = atomic mass unit; 1 a.m.u. = 1.66 x 10-27 kg]

 BEHAVIOUR IN ELECTRIC FIELDS 1.1

•Neutron (no charge) – unaffected

•Proton (+ve charge) – deflected towards -ve potential
•Electron (-ve charge) – deflected towards +ve potential
•Electrons (much smaller & lighter) deflected more
 PROTON NUMBER & NUCLEON NUMBER 1.1

• Proton Number ( or Atomic Number)

The number of proton present in an atom.

• Nucleon Number (or Mass Number)

The sum of the number of protons & neutrons in the nucleus of an atom.

• For neutral :
A
Z x A = nucleon number
Z = proton number

• The number of neutrons in an atom

= ( A –Z )

Y
A charge
• For ion :
Z
 PROTON NUMBER & NUCLEON NUMBER 1.1

• To deduce the no. of protons, neutrons and electrons.

Atom / ion No. of protons No. of neutrons No. of electrons

17 35 – 17 = 18 17 + 0 = 17

17 37 – 17 = 20 17 + 0 = 17

17 35 – 17 = 18 17 + 1 = 18

• Formation of ion : cation - loss of electrons

anion - gain of electrons
 ISOTOPES 1.2

Definition : Atom of the same element that have the same

proton number but different nucleon number.

e.g. 35Cl & 37Cl

• same chemical properties - same number of electrons

• different physical properties - properties depend on weight
 BOHR’S 1.3
MODEL

• any of the possible energies an electron may have in an atom

• classic planetary model in which electrons whirl around the small
but dense nucleus: like planets orbiting the Sun
• developed by the Danish physicist Niels Bohr in 1911
• each electron has a certain energy that is determined by its path
around the nucleus
• explains how atoms (lose) emit or (gain) absorb energy resulting
energy: energy level
 BOHR’S 1.3
MODEL

Electron Arrangements
•Electron travel in the region of space around the nucleus.
•Arrangement of electrons in the orbitals of an atom
•When all electrons at their lowest energies this is called
ground state.
•Electrons occupy the lowest energy levels first.
•Electrons in the outermost energy levels of an atoms are
called valence electron
 1.3
ATOMIC ORBITAL

• Orbital
A region of space round the nucleus in which the
probability of finding a particular electron is the
greatest.
• Electron can occupy 4 types of orbital :
s, p, d & f orbital
(different in shape & their orientation in space)
 1.3
PRINCIPLE QUANTUM NUMBER

Energy Level
• Electrons go in shells or energy levels.
• The energy levels are called principle energy levels, 1 to 4.
• The energy levels contain sub-levels also known as orbitals.
Principle energy Number of sub-
level levels/ orbital
1 1
These sub-levels are
2 2 assigned the letters,
3 3 s, p, d, f

4 4
 ENERGY LEVELS & SUB-LEVELS 1.3

SUB LEVELS
PRINCIPAL The energy gap between successive levels
ENERGY
LEVELS
got increasingly smaller as the levels got
4 further from the nucleus.
INCREASING ENERGY / DISTANCE FROM NUCLEUS

The main energy levels were split into sub

3 levels.
Level 1 was split into 1 sub level
Level 2 was split into 2 sub levels
2 Level 3 was split into 3 sub levels
Level 4 was split into 4 sub levels
1
 1.3
DEGENERATE ORBITALS

• Each type of orbital can hold a different maximum number of

electron.
• Degenerate orbitals are orbitals with same energy level.
- s has no degenerate orbital
- p has 3 degenerate orbitals : px, py, pz
- d has 5 degenerate orbitals Sub- Maximum number
- f has 7 degenerate orbitals level/Orbital of electrons
s 2
p 6
d 10
f 14
 3d 1.3
4s
3p

3s
1s

2s 2p
 SHAPES OF ORBITAL 2.6

S Orbitals

• Spherical
• 1s orbital vs 2s orbital : same shape but different size
 SHAPES OF ORBITAL 1.3

P Orbitals

• Dumb-bell shaped
• Can be arrange in different direction.
 SHAPES OF ORBITAL 1.3

D Orbitals

• Various shape
# A2 syllabus
 ELECTRONIC CONFIGURATION 1.3
• The electronic configuration of an element describes the
arrangement of the electrons in an atom.
• The orbitals are filled in order of increasing energy according to
the following rules :
(i) Aufbau Principle
The added electron will always occupy the orbital with the
lowest energy first.
(ii) Pauli Exclusion Principle
Each orbital can hold a maximum of two electrons of
opposite spins.
(iii) Hund’s Rule of Multiplicity
When filling a sub shell, each orbital must be occupied
singly before the are occupied in pairs.
 ELECTRONIC CONFIGURATION 1.3

• So how do you write it?

1s2

Number of
Energy level electrons
Sub-level

Example
For magnesium: 1s2, 2s2, 2p6, 3s2
 ORDER OF FILLING ORBITALS 1.3
PRINCIPAL SUB LEVELS PRINCIPAL SUB LEVELS
ENERGY LEVELS ENERGY LEVELS
4f 4f
4d 4d HOW TO REMEMBER
4 4
4p 4p ...

INCREASING ENERGY / DISTANCE FROM NUCLEUS

4s 3d
THE FILLING ORDER
4s
3d 3 3p 1s
3 3p 3s 2s 2p
3s
3s 3p 3d
2p
2 4s 4p 4d 4f
2p 2s
2 5s 5p 5d 5f
2s
6s 6p 6d
7s 7p

1 1s 1 1s

Orbitals are not filled in numerical order because the principal energy levels get
closer together as you get further from the nucleus. This results in overlap of
sub levels. The first example occurs when the 4s orbital is filled before the 3d
orbitals.
 ELECTRONIC CONFIGURATION 1.3
• The electronic structure follows a pattern – the order of filling the sub-
levels is 1s, 2s, 2p, 3s, 3p…
• After this there is a break in the pattern, as that the 4s fills before 3d.
• This is because the 4s sub-level is of lower energy than the 3d sub-
level.

At higher levels, with so

much overlap between
the energy levels that the
4f orbitals do not fill until
after the 6s
1.3
 1.3
4f
HYDROGEN
4d
4 1s1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Hydrogen atoms have one
3d electron. This goes into a
4s vacant orbital in the lowest
available energy level.
3 3p

3s
‘Aufbau’
Principle
2p
2
2s

1 1s
 1.3
4f
HELIUM
4d
4 1s2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Every orbital can contain 2
3d electrons, provided the
4s electrons are spinning in
opposite directions. This is
3 3p based on...
3s PAULI’S EXCLUSION
PRINCIPLE
The two electrons in a
2p helium atom can both go in
2 the 1s orbital.
2s

1 1s ‘Aufbau’
Principle
 1.3
4f
LITHIUM
4d
4 1s2 2s1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
1s orbitals can hold a
3d maximum of two electrons
4s so the third electron in a
lithium atom must go into
3 3p the next available orbital of
higher energy. This will be
3s
further from the nucleus in
the second principal
energy level.
2p
2 The second principal level
2s has two types of orbital (s
and p). An s orbital is
lower in energy than a p.

1 1s ‘Aufbau’
Principle
 4f
BORON
4d
4 1s2 2s2 2p1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
As the 2s sub level is now
3d full, the fifth electron goes
4s into one of the three p
orbitals in the 2p sub level.
3 3p The 2p orbitals are slightly
higher in energy than the
3s
2s orbital.

2p ‘Aufbau’
2
Principle
2s

1 1s
 1.3
4f
CARBON
4d
4 1s2 2s2 2p2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The next electron in
3d doesn’t pair up with the
4s one already there.

3 3p
When filling a sub shell,
3s each orbital must be
occupied singly (keeping
the electron spins the
2p same) before the are
2 occupied in pairs.
2s

HUND’S RULE
OF
1 1s
MAXIMUM MULTIPLICITY
 4f
OXYGEN
4d
4 1s2 2s2 2p4
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
With all three orbitals half-
3d filled, the eighth electron in
4s an oxygen atom must now
pair up with one of the
3 3p electrons already there.
3s
‘Aufbau’
Principle
2p
2
2s

1 1s
 1.3
4f
SCANDIUM
4d
4 1s2 2s2 2p6 3s2 3p6 4s2 3d1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
With the lower energy 4s
3d orbital filled, the next
4s electrons can now fill the
3d orbitals. There are five d
3 3p orbitals. They are filled
according to Hund’s Rule -
3s
BUT WATCH OUT FOR
TWO SPECIAL CASES.
2p
2
2s HUND’S RULE
OF
MAXIMUM MULTIPLICITY

1 1s
 1.3
4f
VANADIUM
4d
4 1s2 2s2 2p6 3s2 3p6 4s2 3d2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
In numerical terms one
3d would expect the 3d
4s orbitals to be filled next.

3 3p However, because the 4s

orbital is of a LOWER
3s ENERGY than the 3d
orbitals so gets filled first.

2p
2
2s ‘Aufbau’
Principle

1 1s
 ELECTRONIC CONFIGURATION 1.3

Exceptions :

- Configuration 4s13d5 is more stable than 4s23d4

(because half-filled 4s and 3d sub-shells are more stable)
e.g. Cr

- Configuration 4s13d10 is more stable than 4s23d9

(because a completely filled 3d sub-shell is more stable)
e.g. Cu
 1.3
4f
CHROMIUM
4d
4 1s2 2s2 2p6 3s2 3p6 4s1 3d5
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
One would expect the
3d configuration of chromium
4s atoms to end in 4s2 3d4.

3 3p To achieve a more stable

arrangement of lower
3s energy, one of the 4s
electrons is promoted into
the 3d to give six unpaired
2p electrons with lower
2 repulsion.
2s

HUND’S RULE
OF
1 1s MAXIMUM MULTIPLICITY
 1.3
4f
COPPER
4d
4 1s2 2s2 2p6 3s2 3p6 4s1 3d10
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
One would expect the
3d configuration of chromium
4s atoms to end in 4s2 3d9.

3 3p To achieve a more stable

arrangement of lower
3s energy, one of the 4s
electrons is promoted into
the 3d.
2p
2
2s

1 1s
Energy Levels
 ELECTRONIC CONFIGURATION OF IONS 1.3
• Positive ions (cations) are formed by removing electrons from atoms
• Negative ions (anions) are formed by adding electrons to atoms
• Electrons are removed first from the highest occupied orbitals

SODIUM
Na 1s2 2s2 2p6 3s 1 electron removed from 3s orbital
Na+ 1s2 2s2 2p6
CHLORINE
Cl 1s2 2s2 2p6 3s2 3p5 1 electron added to the 3p orbital
Cl 1s2 2s2 2p6 3s2 3p6
 ELECTRONIC CONFIGURATION OF IONS 1.3
Exception:

The 4s electrons are also removed first in the formation of positive ions.

Reason : once the 3d orbitals are occupied by electrons these repel the
4s orbital to a slightly higher energy level.

TITANIUM Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2

Ti+ 1s2 2s2 2p6 3s2 3p6 4s1 3d2

Ti2+ 1s2 2s2 2p6 3s2 3p6 3d2
Ti3+ 1s2 2s2 2p6 3s2 3p6 3d1
Ti4+ 1s2 2s2 2p6 3s2 3p6
 1.3
ISOELECTRONIC

Isoelectronic species are atoms or ions that have the same

number of electrons.

e.g. H2O & Na+ & Al3+ & F- are isoelectronic.

 IONISATION ENERGY 1.4
Ionisation Energy is a measure of the amount of energy needed
to remove electrons from atoms
FIRST IONISATION ENERGY
The amount of energy required to remove one electron from one
mole of gaseous atoms to produce one mole of gaseous cations.
Successive IE
In general, X (g) → X+ (g) + e ∆H1 = 1st IE
X+ (g) → X2+ (g) + e ∆H2 = 2nd IE
X2+ (g) → X3+ (g) + e ∆H3 = 3rd IE

 X (g) → X3+ (g) + 3e ∆H = ∆H1 + ∆H2 + ∆H3

 IONISATION ENERGY 1.4

• Endothermic reaction (Positive value)

Reason : Energy is absorbed in removing an electron.

• Increase with the removal of each electron.

Reason : The remaining electrons are attracted more strongly
by the constant +ve charge on the nucleus.

• The number of ionisation energies = its atomic number

 IONISATION ENERGY 1.4
The ionisation energy affected by :

(1) Size of atom / shielding effect:

I.E. decrease as the size of atom / ion increases or shielding
effect.
Reason : The attraction of the +ve nucleus for the –ve electron
decrease and less energy is required to remove an
electron.
(2) Nuclear charge : I.E increases, as the nuclear charge increases
Reason : The attraction for the outermost electrons increases
and more energy is required to remove an electron.
 IONISATION ENERGY 1.4
For cation: K vs K+
K+ is smaller than K. K has an extra shell that increases shielding
effect and decrease nuclear attraction.
K+ :1s2 2s2 2p6 3s2 3p6 K :1s2 2s2 3s2 2p6 3p6 4s1
IE for K+ is larger than K

For anion: Cl vs Cl-

Cl- is slightly larger than Cl because the third shell is retained, and
more electron added to it. Shielding effect increase and
nuclear attraction decrease.
Cl- :1s2 2s2 2p6 3s2 3p6 Cl :1s2 2s2 p6 3s2 3p5
IE for Cl is larger than Cl-
 IONISATION ENERGY 1.4
1st I.E DECREASE DOWN A GROUP

Reason : Increasing shielding (screening) effect

Outer electrons are further from the nucleus & are better
shielded by inner shells of electrons. They become less
strongly attracted by the positive nucleus & so less energy is
required to remove the electron. )
 Trends down a Group
1.4
• Ionisation energy decreases going down +
a Group.
• Going down a Group in the Periodic
Table, the electron removed during the +
first ionisation is from a higher energy

Down the Group

level and hence it is further from the
nucleus.
• The nuclear charge also increases, but +

the effect of the increased nuclear charge

is reduced by the inner electrons which
shield the outer electrons.
+
 Trends
TREND across
ACROSS Period
A PERIOD
1.4
1st I.E INCREASE ACROSS PERIOD

Reason : no of shell is the same so shielding effect is constant,

but proton number increases which increase the nuclear
charge. Thus, increase nuclear attraction towards valence
electrons
 Variation in 1st Ionisation Energy - PERIODS 1.4

1st Ionisation Energy shows a ‘general increase’ across a

given period
 1s
Variation in 1st Ionisation Energy 1.4
1s 2s 2p
1st IONISATION ENERGY / kJmol-1

1s 2s 2p

1s 2s 2p
1s
1s 2s 2p

1s 2s 2p

1s 2s
1s 2s 2p 3s
1s 2s 2p

1s 2s
1s 2s 2p 3s

ATOMIC NUMBER
12
 Exception in 1st Ionisation Energy 2.9

N has half filled p orbital which is

1st IONISATION ENERGY / kJmol-1

more stable.
O has paired electron that has spin
pair repulsion
1s 2s 2p

1s 2s 2p

1s 2s

1s 2s 2p Be has valence electron in 2s whereas B has

valence electron in 2p orbital. 2p orbital is
slightly further away from 2s. 2p experience
greater shielding effect.

ATOMIC NUMBER
12
 SUCCESSIVE I.E 1.4

Successive ionisation energies are always greater than the previous one
Reason :- the electron is being pulled away from a more positive species
 SUCCESSIVE I.E 1.4
K has a total of 19 electrons, which fall into four groups.
The first electron is relatively easy to remove
Suggested:
~ 2 electrons – very close to the nucleus ( in the 1st
quantum shell, which are most difficult to remove)
~ 8 electrons further out ( in the 2nd quantum shell)
~ Another 8 electrons even further out ( in the 3rd shell)
~ one further away still (in the 4th quantum shell)

• Hence, the electron arrangement in K is written

as 1s22s22p63s23p64s1
 INTERPRET SUCCESSIVE I.E DATA 1.4
The first seven I.E. of an element are as follows (in kJ mol-1) :

790, 1600, 3200, 4400, 16100, 19800 & 23800.

Q (a) Deduce the number of electrons in the outer shell of

the element and hence , the group in the Periodic
Table to which the element belongs.

(b) Write down the outer electronic configuration of the

element.
 INTERPRET SUCCESSIVE I.E DATA 1.4

Q The diagram shows the first eight I.E. of an element R.

(a) To which group in the Periodic Table does R belong?
(b) Write the electron arrangement in the outer shell of R.
(c) Can R be nitrogen? Explain.
(d) Explain why the I.E. increases as electrons are
removed.
 INTERPRET SUCCESSIVE I.E DATA 1.4
Answer