Raffles Institution

Year 5 H2 Chemistry 2017

Lecture Notes 2 - Atomic Structure
Lecturer: Mr. Wong Chee Choy
Mrs. Goh-Chua Juan Juan

Content

• The nucleus of the atom: neutrons and protons, isotopes, proton and nucleon numbers
• Electrons: electronic energy levels, ionisation energies, atomic orbitals, extranuclear
structure

Learning Outcomes

Candidates should be able to:

(a) identify and describe protons, neutrons and electrons in terms of their relative charges and
relative masses
(b) deduce the behaviour of beams of protons, neutrons and electrons in an electric field
(c) describe the distribution of mass and charges within an atom
(d} deduce the numbers of protons, neutrons and electrons present in bott1 atoms and ions
given proton and nucleon numbers (and charge)
(e) (i) describe the contribution of protons and neutror:is to atomic nuclei in terms of proton
number and nucleon number
(ii) distinguish between isotopes on the basis of different numbers of neutrons present
(f) describe the number and relative energies of the s, p and d orbitals for the principal
quantum numbers 1, 2 and 3 and also the 4s and 4p orbitals
(g) describe the shapes of s, p and d orbitals [knowledge of wave functions is not required]
(h) state the electronic configuration of atoms and ions given the proton number (and charge)
(i) explain the factors influencing the ionisation energies of elements (see the Data Booklet)
O} deduce the electronic configurations of elements from successive ionisation energy data
(k) interpret successive ionisation energy data of an element in terms of the position of that
element within the Periodic Table
(I) recognise variation in the electronic configurations across a Period and down a Group
(m)describe and explain qualitatively the trends and variations in atomic radius, ionic radius,
first ionisc!tion energy and electronegativity:
(i} across a Period in terms of shielding and nuclear charge
(ii) down a Group in terms of increasing number of electronic shells and nuclear charge

Lecture Outline References

1 Atomic structure 1 Chemistry for advanced level (by Peter Cann

2 The nucleus of the atom and Peter Hughes)
3 The electronic structure of the atom 2 Chemistry in Context (by Hill and Holman)
4 Electronic configurations 3 Cambridge International AS and A Level
5 Electrostatic effects Chemistry Coursebook (by Roger Norris, Lawrie
6 Atomic radius Ryan & David Acaster)
7 Ionic radius 4 Chemistry: The Molecular Nature of Matter and
8 Ionisation energies Change (by Martin S. Silberberg)
9 Electronegativity 5 Website: http://www.chemguide.co .uk

-1-
 1 ATOMIC STRUCTURE

1.1 The atom

• An atom is the smallest particle found in an element that can take part in a chemical
reaction.

Structure of an atom

Electron cloud
atom
• contains a small, dense nucleus
surrounded by electrons

I
nucleus
• contains protons and neutrons extra nuclear
(collectively known as nucleons} space Nucleus

• contains the bulk of the mass of an atom

• Atoms are very small. They have a
I
I I diameter of about 10-10 m.
protons neutrons electrons • The nucleus of an atom is even
smaller. It has a diameter of 10-15
• positively • uncharged • negatively charged to 10-14 m.
charged • concentrated in certain
~ The region around the nucleus
regions of space around
where electrons move is mostly
the nucleus called orbitals
empty space.

1.2 The subatomic particles

• Three important subatomic particles found in an atom are the proton, the neutron and the
electron .

Sub-atomic particle proton neutron electron

Ernest Rutherford James Chadwick Joseph John Thomson

Discovered by (1911} (1932) (1897)

bombardment of gold foil bombardment of beryllium with

Experiment with a. particles a. particles
cathode ray experiment

Location within
in the nucleus in the nucleus around the nucleus
the atom
Actual mass / kg 1.67 X 10-27 1.67 X 10-27 9.11 x10-31
1
Relative mass 1 1 - -
1840
Charge IC +1.60 X 10-19 0 -1 .60 X 10-19

Relative charge +1 0 -1

Symbol ½P
--re.l~fl'IC,
!(l()._'i,\;
--.1
,,o n -~ e
,

-2-
1.3 Behaviour of the subatomic particles in an electric field

• Consider the following beams of subatomic particles all travelling at the same speed:

o a beam of protons
o a beam of neutrons
o a beam of electrons

• When each of these beams is passed through an electric field, each beam is found to
behave differently in the following aspects:

o the direction of deflection and

o the angle of deflection.

Behaviour of the subatomic particles in an electric field

I 0

~I
protons
I
II
beam of
either
protons, I neutrons I
II
~
neutrons
or electrons

I I © electrons
I
Subatomic particle Direction of deflection Angle of deflection
proton (positively charged) towards the negatively charged plate Xo {xo < yo}

neutron (uncharged) not deflected oo

electron (negatively charged) towards the positively charged plate Yo (yo > xo}

• The direction of deflection is dependent on the charge on the subatomic particle.

• The angle of deflection is proportional to the magnitude of the charge

mass
ratio of the particle .

angle of deflection e< ql • The larger the charge q of the particle, the stronger is the
lm attraction towards the oppositely charged plate.
=> the greater the angle of deflection
where
q = charge on particle
m = mass of particle • The larger the mass m of the particle, the more difficult it is
to cause it to deviate towards the oppositely charged plate.
=> the smaller the angle of deflection

Note: In this case, protons and electrons have the same charge in terms of magnitude.
However, protons are heavier and hence the ang!e of deflection for the proton beam
iS Smaller, i.e. X 0 < y 0

-3-
tt· tfr"~ Worked Example 1
Beams of charged particlt:;s are deflected by an electric field . In a particular
experimental set-up, protons are deflected through an angle of 10°. Assuming an
;

identical set of experimental condition , by what angles will the beam of each of the
following particles (all travelling at the same speed) be deflected?

Particle
1:1 angle of deflection

1H+ 1 10°

(a) 2H+ 2.. 50

:).

(b) 18Q2- q
I
/. 11 °

,
9Se2+ .2.
(c)
----
"I
;J.. .).J,

2 THE NUCLEUS OF THE ATOM

2.1 Representation of a Nuclide

• A nuclide is any species of given mass number and atomic number.

The nuclide of an element is represented by

~
nucleon number
(or mass number) :-; A
proton number
(or atomic number)
~zX< symbol of the element

Nucleon number (Total no. of protons and neutrons) = A Nucleon number= 238
No. of protons= Z No. of protons = 92
No. of neutrons = A - Z No. of neutrons= 146
No. of electrons= No. of protons= Z No. of electrons= 92
rO\OY\ v'lUIYlber
Note: The a omic number determines the identity of an atom.
For example, every atom with an atomic number of 6 is a carbon atom; it contains 6
protons in its nucleus.

• The nuclide of an element is named by its elemental name followed by its mass number.

Examples:

~He
hydrogen-1 hydrogen-2 hydrogen-3 helium-4 carbon-12 carbon-13 carbon-14

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2.2 Isotopes

• Isotopes of an element are atoms that contain the same number of protons but different
number of neutrons in the nucleus.

E xamp e: Iso topes o f c hi onne

.
Nuclides No. of protons No. of electrons No. of neutrons
~~Cl 17 17 18

~~Cl 17 17 20

• Isotopes have the same number of electrons and therefore the same chemical
properties.

• Since isotopes have different number of neutrons, they have different masses and
hence different physical properties such as density, melting point, etc.

11
,!..
-
Worked Example 2
Complete the following table.

Nucleon number No. of p No. of n No. of e-

27 Al3+
13 2-l ,~ It (.2::t-1'1>) /CJ (12, -!i)
,~N3- l'l- 1 7 (14-t) 10 Ci'+~) I

Worked Example 3
With the aid of the Periodic Table, identify X and Y below.

(a) Some isotopes are unstable and decompose naturally. An example is

potassium-40 which undergoes decay by beta-particle emission as
represented by the following equation: 18K--+ X + -~r,
ruu-r1v-e VVl l.>\.Ss
. ~ Y~\O.t°WU.N\~r_ge
(b) In 1937, 0 Hahn became the first person to obtain energy from 'splitting the
atom'. He bombarded uranium.:...235 with neutrons. Each uranium-235 atom
split into two smaller atoms and two neutrons with the release of energy as
2
represented by the following equation : ~~U + Jn -~ Y + ~~Kr+ 2Jn.

Nucleon number of X = 40 Nucleon number of Y = 235 +1 - 90 - 2

= 144
Proton number of X = 19 - (-1)
= 20 Proton number of Y = 92 - 36 = 56

Hence X is 40
o.-0
G.-

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 3 THE ELECTRONIC STRUCTURE OF THE ATOM

3.1 Historical development of the atomic model

Dalton Thomson Rutherford Bohr Schrodinger

(1803) (1904) (1911) (1913) (1926)

0 ® O@
- hard &
indivisible
the "plum
pudding'
the
nuclear
the
planetary the quantum
- similar to model of model of model of mechanical
billiard the atom the atom the atom model of the
balls atom

1 The ancient Greeks (440 BC) 8 Max Planck (1900)

Leucippus originated the atom concept. • introduced the idea that matter absorbs and emits energy in discrete units called
He and his pupil, Democritus, refined quanta
and extended it in subsequent years. • each fixed quantity of energy emitted is called a quantum of energy
• .. . the first step towards quantum theory

2 John Dalton's Atomic Theory (1803) 9 Albert Einstein (1905)

• All matter consists of indivisible • worked on the photoelectric effect
particles called atoms. • proposed that light may behave as a particle as well as a wave
• Atoms of one element cannot be • extended the quantum concept to include light Botv"• modeloflhea-,,m
n=oo
converted into atoms of another • light consists of discrete units called photons
element. n=S
• Atoms of an element are identical and 10 Niels Bohr (1913) n=4
n=3
are different from the atoms of any • proposed the planetary model of the ,......-++--n=2
other element. hydrogen atom in which the electron moves in _,,._-,-rrr--n = 1
• Compounds result from chemical certain allowed circular orbits around the
combination of a specific ratio of atoms nucleus
from different elements. • used the idea of quantized electronic energy levels
• can explain the emission spectrum of the hydrogen atom but fails to explain the
3 G. J. Stoney (1874) spectra of atoms more complex than hydrogen
• suggested the name 'electron' for tiny • is built on the false assumption that the electron exists as a solid particle of
negative particles matter in an atom

4 Joseph John Thomson (1897) 11 Louis-Victor de Broglie (1923)

• discovered the electron while working • proposed that electrons may behave as waves as well as particles - the theory of
on cathode rays wave-particle duality

5 Joseph John Thomson (1904) 12 Werner Heisenburg (1927)

• proposed the 'plum pudding' model • proposed his uncertainty principle - it is impossible to know the position and
of the atom, of electrons embedded in momentum of the electron at the same instant in time
a sphere of positive charge • there are inevitable uncertainties introduced in measuring two variables such as
position and momentum of a particle at the same time

6 Ernest Rutherford (1911) 13 Erwin Schri:idinger (1926)

• discovered the nucleus while working • applied the idea of electron as a wave to work out a wave theory of the atom
on the gold foil experiment • developed the wave equation, popularly called the Schrodinger equation

7 Ernest Rutherford (1911) 14 Quantum Mechanical Model of the Atom

• described his nuclear model of the • a mathematical model described by the Schr6dinger equation
atom : an atom consists of a tiny dense, • solutions to the Schr6dinger equation define regions of space where there is a
positively charged central nucleus high probability of finding an electron of a given energy - atomic orbitals
surrounded by the negatively charged • no longer tells us where the electron is; it only tells us where it might be
electrons • introduces the idea of the probability of finding the electron in a certain volume:
the orbital

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3.2 The electron

What do we know about electrons?

• Electrons in an atom do not occupy fixed positions around

the nucleus. They do not move in orbits (or fixed
circular/elliptical paths) around the nucleus .
. : ...
__ _ _ ..... iI

• Electrons in an atom move in certain regions of space !

around the nucleus known as atomic orbitals. ·

• Each electron has energy that is quantised (i.e. each electron has energy
restricted to certain values). Each electron occupies a discrete energy level.

3.3 Arrangement of electrons in atoms

• The arrangement of electrons in an atom (or ion) is referred to its electronic structure.

The electronic structure provides us with the following information:

o the number of electrons in the atom or ion
o the distribution of electrons in the atom or ion
o the energies of the electrons

It is important because it determines how the atom will react with other atoms to form
ions or molecules.

Around principal contain contain

the quantum contain subshells orbitals electrons
~ / / ,
nucleus shells

Diagram showing the relationship between shell, subshells and orbitals

(using n = 2 as an example)
orbitals

subshells

3.4 Electronic shells

• Electrons in atoms are arranged in a series of shells or energy levels surrounding the
nucleus. Each shell is described by a number known as the principal quantum number,
n.

• The principal quantum number n is a positive integer i.e. n = 1, 2, 3, ... (numbered outward
from the nucleus).

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 The greater the value of n,
o the further the shell (or electron) is from the nucleus
o the higher the energy level of the shell (or electron)
o the weaker the electrostatic attraction between the nucleus and the electron
o the larger the size of the orbital (or the orbital becomes more diffuse)

Diagrams showing shells or energy levels corresponding to

the different principal quantum numbers

energy
= oo
=7
= ====~
- - - - - n=S
=6

- - - -- n=4

- - - -- n=3

- -- - -n= 2

- - - - - n=l

3.5 Subshells (sub-levels) and orbitals

• Each shell comprises of one or more subshells . Each subshell , in turn, comprises of one
or more orbitals.

• An orbital represents a region in space in which there is a high probability (> 95%) of
finding an electron.
o Each orbital can accommodate 2 electrons.
o Each orbital has a distinctive geometrical shape (see Section 3.6).
o The 'energy of an orbital' is the energy of the electron occupying the orbital.

RelationshiQ between QrinciQal guantum number and subshells

Principal quantum number, n Types of subshell
1 1s
2 2s,2p
3 3s, 3p, 3d
4 4s, 4p, 4d, 4f
Note: The shell with principal quantum number n contains n subshells .

RelationshiQ between subshells and orbitals

Subshell No. of orbitals Types of orbitals

sWf s 1 s

rvi""~ p 3 Px , Py , Pz
ol,~-1. d 5 dxz, dxy , dyz , d 2 2 , dx2-y2
~ J._ -1.1 f 7 (Read up on your own, if interested)

-8-
3.6 Shapes of the orbitals

Types of
. p orbitals d orbitals
s orbital
orbitals (Pu Py, Pz) (dxz, dxy, dyz, dxz-y2, d 22}
y z
z z

#.x
~

Shape of
orbital ~x
X
$·t· dxy d,•
spherical shape dumb-bell shape various shapes

(a) The s orbital

~~
z ~z
y

~ X X

1s 2s

• Shape of an s orbital: spherical shape

• s orbitals are non-directional as the electron density is not concentrated in any particular
direction.
• s orbitals of different shells have the same spherical shape but different sizes.
• As n increases, the s orbital
o increases in size, i.e. 1s < 2s < 3s < 4s
o becomes more diffuse

(b) The p orbitals

2 z

Px Py Pz

• Shape of a p orbital: dumbbell shape

• There are three p orbitals (i.e. Px, Py and p2 ) in a p subshell.

• p orbitals are directional as the electron density is concentrated in certain directions along
the x, y and z axes.
• The three p orbitals with the same principal quantum number n are degenerate (i.e. they
have the same energy).
• p orbitals of different shells have the same dumb-bell shape but different sizes.

• As n increases, the p orbital

o increases in size, i.e. 2p < 3p < 4p < Sp
o becomes more diffuse

-9-
(c) The d orbitals

• There are five d orbitals (i.e. d;z, dxy, dyz, dxz-yz and d 2 2) in ad subshell.
z z

y
y
z y *·. -
;.'\.._ z ,_·:
· Y * :._ Y

* *
?'' ~ -
. ~
X JC X r;_- X

......................................................................................·························
• These three orbitals have a similar 4-lobed • This orbital .... • This orbital
.
....
shape. also has a consists of a
4-lobed shape dumb-bell
• These orbitals have their lobes pointing but it has its ... surrounded by a
between the axes. lobes aligned
along the X
.
:
small doughnut
shaped ring at its
and y axes. ...: waist
..
... • This orbital is
aligned along the
..... zaxis .

3.7 Relative energies of the orbitals

Diagram showing the relative energy levels of the orbitals (not to scale)
in a multi-electron atom
Energy
.,.-- 4f - - - - - - - 4 f
n=4 ---- - 4d - - - -- --4d
---.e,=.: - - - ..4.P. - - - 4 p
', 13d]
n=3 --<=== t:4.~.-' -45 - - - -- --3d
~ - - - 3p - - - 3 p
.... 3s -3s

n=2 - 2p - - -2p
-------- 2s -2s

n =1 - - - - 1s -1s
Shell subshells orbitals

• For orbitals in the same shell (i.e. with the same value of n), their relative energies
increase in the following order: s < p < d < f
e.g. 4s < 4p < 4d < 4f

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Diagram showing the decrease in orbital energy with increasing atomic number

t
>
e
Q)
C
lll

25 50 75
Atomic number, Z

• As the nuclear charge increases, the energies of all the orbitals decrease, i.e. the
energies of the electrons occupying those orbitals decrease.

• Due to their proximity to the nucleus, the spherically symmetrical s orbitals are
affected to a greater degree than are the more angular p and d orbitals, and so their
energies decrease more rapidly than the other types of orbitals.

• By n = 4, there is, in fact an overlap between the 3 rd and 4 th shells. As seen from
the graph above, the energy of the 4s orbital has already become less than
that of the 3d orbital at Z = 18 (argon). ·

o Affects how electrons are filled (The Aufbau Principle) in section 4.1

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 3.8 Summary

Increasing distance from nucleus

Increasing energy level
(generally)

Principal
quantum n=1 n=2 n= 3 n=4
number j

one two three four

Subshells subshell subshells subshells subshells
(s, p, d, f)
1s 2s 2p 3s 3p 3d 4s 4p 4d 4f
one one three one three five one three five seven
1s 2s 2p 3s 3p 3d 4s 4p 4d 4f
orbital orbital orbitals orbital orbitals orbitals orbital orbitals orbitals orbitals
Orbitals 3dxz 4dxz
(s, p, d, f) Zpx 3px 3dxy, 4Px 4dxy, Read up
on your
ls 2s 2py 3s 3py 3dyz 4s 4py 4dyz own, ff
Zpz 3pz 3dz2 4pz 4dz2 interested

3dx' - y' 4dx'- y'

No. of
orbitals 1 1+3=4 1+3+5=9 1 + 3 + 5 + 7 = 16
pershell
Max. no.
of e-per 2 2 6 2 6 10 2 6 10 14
subshell
Max. no.
of e-per 2 8 18 32
shell

Note: Each orbital can accommodate a maximum of 2 electrons.

In the nth shell,

• number of subshells = n
• number of orbitals= n2 m/AY-.. Y\O. Q!?.
• maximum number of electrons that can be accommodated= 2n 2 ete.C:tron~

Example 1: In the 3rd shell,

• number of subshells = 3
• number of orbitals = 9
• maximum number of electrons that can be accommodated = (2)(32) = 18

Example 2: In the 4 th shell,

• number of subshells = 4
• number of orbitals = 16
• maximum number of electrons that can be accommodated = (2)(4 2) = 32

• A shell contains a group of orbitals with the same principal quantum number.
• A subshell is a group of orbitals with the same energy level but differ in their orientation in space.

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 4 ELECTRONIC CONFIGURATIONS

• The electronic configuration of an atom (or ion) refers to how its electrons are distributed
among the various atomic orbitals i.e. how its electrons are arranged in the shells,
subshells and orbitals.

• Different ways of writing electronic configurations

Using shells/energy levels

(i) Si: 2.8.4
notation
1s2 2s2 2p 6 3s 2 3p 2 or *[Ne] 3s 2 3p 2
(ii) Using the s, p, d, f notation Si: *[Ne] represents 1s2 2s2
2p6

(iii)
Using electrons-in-boxes
diagram
Si: [ill ffiJ I1~ 11~ 11~ I filJ 11 11 I I
1s 2s 2p 3s 3p

4.1 The basic rules to writing electronic configurations

• The principles that govern the distribution of electrons in the orbitals are:

1 The Aufbau • Electrons fill orbitals from the lowest energy orbital upwards.
(building-up) 1--__::.:.=.::.::..:=...:.:.:.:...::.:..::..:.=~========;::::::=======================.:.---1
Principle • Order of filling up of orbitals: _
1 s ~ 2s ~ 2p ~ 3s ~ 3p ~
4s -+ 3d ~ 4p -+ 5s -+ 4d
-+ ...

• Electrons occupy the 4s

orbital first before the 3d
because the 4s orbitals is at a
lower energy level than the
3d orbitals (see page 11 ).

2 The Pauli • Each orbital can hold a maximum of two electrons and they must
Exclusion be of opposite spins.
Principle

Note:
Paired electrons can only be stable when they spin in opposite directions
so that the magnetic attraction which results from their opposite spins
can counterbalance the electrical repulsion which results from their
identical charges.
3 Hund's Rule • Orbitals of a subshell (i.e. orbitals of the same energy) must be
occupied singly by electrons of parallel spins before pairing can
occur. This helps to minimise inter-electronic repulsion.

11 I1 I1 I ./ 11 I1 I ~ I 11~11 I X
2p 2p 2p

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4.2 Writing electronic configurations

principal quantum number~ ~ number of electrons in the orbital

1s 1
~ type of orbital

(a) The first twenty elements (Z = 1 to Z = 20)

'Electrons-in-boxes' Electronic
Element Element Electronic configuration
diagram configuration

1H
[]
1s
1s1 11Na 1s2 2s 2 2p 6 I 3s'
I
2He
ill] 1s2 12Mg 1s2 2s 2 2p6 35 2
1s

[] []
3Li
1s 2s
1s2 2s 1 13A/ 1s2 2s 2 2p 6 , 31'~r·
I
48e [ill [ill 1s2 2s 2 14Si 1s2 2s 2 2p6 3s 2 3p 2
1s 2s

sB [ill lliJ 11 I I I 1s2 2s 2 2p 1 1sP 1s2 2s2 2p6 13{'3( I

1s 2s 2p

sC lliJ
1s
uu2s 11~ I2p I I 1s2 2s 2 2p2 1sS 1s2 2s 2 2p 6 3s 2 3p 4

1N [ill ~ I 1i I 1 I I 1s2 2s2 2p 3 11CI 1s2 2s 2 2p6 13s'3r 1 I

1s 2s 2p

sO OlJ [ill Ii I 1~1 I 1s2 2s 2 2p 4 1sAr 1s2 2s2 2p 6 3s 2 3p 6

1s 2s 2p
..-··-. -:-:-

gF [ill uD !1i I1~11 I 1s2 2s 2 2p 5 19K

2
1s 2s 2p2 6
1ss· 3r' ~s 1

I
1s 2s 2p

10Ne ITO filJ I 1~I 1i11i I 1s2 2s 2 2p6 20Ca 1s2 2s 2 2p 6 35 2 3p6 4s 2
1s 2s 2p

Note: Electrons occupy the 4s orbital first before the 3d orbitals because the 4s orbital is at
a lower energy level than the 3d orbitals (see page 11 ).

-14-
 (b) The first row d-block elements (Z = 21 to Z = 30)

Using {Ar] to represent DI] [ill 11 ~ 11 ~ 11 ~ I [ill 11 ~ 11 ~ 11 ~ I

1s 2s 2p 3s 3p

Element 'Electrons-in-boxes' diagram Electronic configuration

3d 4s
21Sc {Ar] 11 I I I I ITO 1s2 2s 2 2p6 3s 2 3p6 3d 1 4s 2

{Ar] 11 11
22Ti I I I [ill 1s 2 2s2 2p6 3s 2 3p 6 3d 2 4s 2

23V [Ar] 11 11 11 I I ITO 1s2 2s2 2p6 3s2 3p6 3d 3 4s 2

24Cr * [Ar] 11 11 11 11 11 DJ 1s2 2s 2 2p 6 3s 2 3p6 3d 5 4s 1

2sMn [Ar] 11 11 11 11 11 I ITO 1s2 2s2 2p 6 3s2 3p6 3d 5 4s 2

,.,::,..·:
[Ar] 1~ 11 11 11 11
:,:
{.;·. ·:·
2sFe [ill 1s2 2s2 2p 6 3s2 3p 6 3d 6 4s 2

21Co [Ar] 1~11~11 11 11 [3I] 1s2 2s2 2p6 3s2 3p6 3d 7 4s 2

2sNi (Ar] 1~11~11~11 11 [TI] 1s2 2s2 2p6 3s 2 3p 6 3d 8 4s 2

2sCu * [Ar] 1~11 ~ 11 ~ 11 ~ 11 ~ 1s2 2s2 2p6 3s 2 3p6 3d 10 4s 1

!TI"
30Zn [Ar] 1~1 1~ 11 ~ 11 ~ 11 ~ [TI] ~ 2p 6
3s2 3p6 3d 10 4s 2

4.3 Anomalous electronic configurations of Cr and Cu j

• The electronic configuration of Cr is 1s 2 2s 2 2p 6 3s 2 3p6 3d 5 4s 1.

Expected electronic
configuration
[Ar] 11 11 11 11 I I [ill 1s2 2s 2 2p 6 3s2 3p6 3d 4 4s2
less stable
JC
3d 4s
24Cr
Actual electronic
configuration
[Ar] 11 11 11 11 11 I[[] 1s2 2s2 2p6 3s2 3p6 3d 5 4s 1
more stable
,/
3d 4s

Reason: . 3d and 4s orbitals are about equal in energy by the time Cr is reached.
By having one electron each in the 3d and 4s orbitals, inter-electronic repulsion
is minimised.

• The electronic configuration of Cu is 1s2 2s 2 2p 6 3s 2 3p6 3d 10 4s 1.

Expected electronic [Ar] 11~11~11~11~11 I IBJ 1s2 2s2 2p6 3s 2 3p6 3d 9 4s 2

X
configuration 3d 4s • less stable
29CU
Actual electronic [Ar] 11~11~11~11~11~1 DJ 1s2 2s2 2p6 3s2 3p 6 3d 10 4s 1 ,/
configuration 3d 4s • more stable
Reason: The fully filled 3d subshell is unusually stable due to the symmetrical charge
distribution around the metal centre.

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 ··············································································································.
Summary:
• Order of filling up electrons : 1s-+ 2s-+ 2p-+ 3s-+ 3p-+ 4s ~ 3d -+ 4p -+ 5s
(Electrons occupy the 4s orbital first before ttie 3d orbitals)
• Order or writing electronic configuration follows the order of the principal quantum shell
(i.e. 1s-+ 2s-+ 2p-+ 3s-+ 3p ~ 3d ~ 4s ~ 4p -+5s)
• Each orbital can fill up to 2 electrons
So. m Degenerate orbitals of a subshell must be occupied singly and with parallel spins
eneY9~. • Both Cr and Cu have anomalous electronic configuration . .•
•..•••••.........••....•...•..............•............................•.....•.............................•
4.4 Ground state and excited state

• An atom is in the ground state when the electrons are in the orbitals of lowest available
energy level. Most atoms are in their ground state at room temperature.

• The electronic configurations written so far on the earlier pages are all ground state
electronic configurations (i.e. the most stable electronic configurations).

• An atom is in the excited state when one or more electrons absorb energy and are
promoted to a higher energy level. Excited atoms are unstable and can emit energy to
return to the ground state.

sC (ground state) sC* (excited state) Other possible electronic

1s2 2s2 2p 2 1s2 2s 1 2p3 configurations of C in the
excited state: '\
energy energy
Q.3~
1s'2~
or 1s2 2 1 1 s1 3p 1
I1 I1 I I I1 I1 I1 I
'
[ill
2s
2p

[]
2s
:le e,
'\

*Note that the electrons in

the 1s orbital do not
usually get promoted

ill] [ill (energy gap between n=1

1s 1s and n=2 is too wide)

....· ...·. '

~

4.5 Electronic configurations of ions

• Ions are formed when atoms gain or lose electrons.

(a) Anions (negative iohs)

General rule: Electrons are added to the next available orbital (i.e. the next
energetically accessible orbital) in the atom during the formation of
an anion.
Example: 1sS
[ill [ill 11~11~11~1 [ill 11~11 11 I 1s2 2s2 2p6 3s 2 3p4
1s 2s 2p 3s 3p
16s 2-
[ill DI] 11~11~IHI [ill 11~11~11~1 1s2 2s 2 2p 6 3s2 3p6
1s 2s 2p 35 3p

-16- ·
(b) Cations (positive ions)

General rule: Electrons are first removed from the orbitals with the highest
I energy.
Example: Cations from the main groups (e.g. Al)
1s2 2s2 2p6 3s 2 3p 1
1~/
illJ [ill 11~ 11~ 11~ I IBJ 11 I I I
2p 3p
1s 2s 3s
1s2 2s2 2p6 3s2
1~r
[ill [ill 11~ 11~ 11~ I ITO
1s 2s 2p 3s
1~[3+
ill] [ill 11~11~11~1 1s2 2s2 2p 6
1s 2s 2p
Example: Cations from the d-block (e.g. Fe)
Note: 4s electrons are lost before the 3d electrons
(with reference to the first row transition elements)

Electrons occupy the 4s orbital first because the 4s orbital is at a lower

energy level than the 3d orbitals.

Once electrons occupy the inner 3d orbitals, they (i.e. the 3d electrons)
provide some shielding for the outermost 4s electrons. They repel the 4s
electrons to a slightly higher energy level.

Hence in the formation of cations, the 4s electrons are lost before the 3d
electrons.
1s2 2s 2 2p 6 3s 2 3p 6 3d 6 4s2
2sFe [Ar] 11 ~ 11 11 11 11 I [ill
3d 4s
2sFe2+
[Ar] 11~11 11 11 11 I 1s2 2s2 2p 6 3s2 3p6 3d 6 <p
3d I~
'li'

4.6 Electronic configurations and isoelectronic species

• lsoelectronic species are species with the same total number of electrons.
Examples of isoelectronic species:

Atoms or ion Electronic configuration Total number of electrons

N 3-, 0 2-, F-, Ne, Na+ 1s2 2s22p 6 10
Cr 1s 2s 2p 3s2 3p6 3d 5 4s 1
2 2 6
24
Mn+ 1s22s 22p6 3s 2 3p 6 3d 5 4s1 24
Fe + 2
1s22s2 2p 6 3s 2 3p 6 3d 6 24

-17-
 Worked Example 4 .
Write down the electronic configuration of each of the following species and draw an
energy level diagram to illustrate each electronic configuration.

(a) s2- (b) Ca 2 + (c) cu+

S: 1s2 2s2 2p6 3s 2 3p 4

Cu: 1~ '1J 1 .2-r' 3s' 3&1 Its'
10
Ca: 1s2 2s2 2p6 3s 2 3p 6 4s2
sz-: '\s')g1.2 p~3s 2 3~"' Ca 2 +: \ s.,2s 2 ~t 3s1.Jt
1
cu+: /{ 1 ls,2f 1 31'3ol
10

Energy Energy Energy

3p1L JL JL 3p..JL JL 1L
3s1L 3s1L 3d~ ~ JLlLJL
2pj!'._ jl_ J_!_ 2p -1L .Jl.. _J}_ 3pJL 1L 1L
2s.1L 2s1.L
3s JL
2pl Jf_ 1L_
2s_1_

1~ 1s1.L
1s-

! 1s~
!
I
:

-18-
 4.7 Electronic configurations and the Periodic Table

• Based on the electronic configurations of the elements, the elements in the Periodic
Table are grouped into four blocks, the s, p, d and f blocks, as shown below.

• The name of each block is determined by whether an s, p, d or f subshell is being filled in

successive elements of that block.

l<n-1)d' nsYI ns1 np' ------------- ns2 np6

Group
H 13 14 15 16 17 18
Peliod 1 He
Period2
Period 3 . 3 ~ 5 6 7 8 9 10 11 12
Period4
Period5
Period6
Period7

I
lantllar\iods
adiniods ...._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __,

Period
number
1 ~ r:;;
2 2s 2p
3 3s 3p
4 4s 3d 4p
5 5s 4d 5p
6 6s 5d 6p
7 7s 6d

4f
5f

• Horizontal rows in the Periodic Table are called periods. Elements in the same period
have the same number of electronic shells. The period number of an element is the number
{ of electronic shells occupied with electrons in an atom of that element.
( :.

• Vertical columns in the Periodic Table are called groups. Elements in the same group
have the same number of valence electrons and hence similar outer electron
configurations.

Group
Group number 1 2 13 14 15 16 17 18
alkali alkaline noble
Group name pnicogens chalcogens halogens
metals earth metals .gases
Electronic
configuration of ns 1 ns 2 ns2 np 1 ns2 np 2 ns2 np 3 ns2 np4 ns2 np 5 ns2 np6
valence shell

Example:

Chlorine is a Group 17 element => Electronic configuration of valence shell is ns2 np5
Chlorine is a Period 3 element => n = 3

Hence the electronic configuration of chlorine is 1s2 2s 2 2p6 3s 2 3p5

-19-
 5 ELECTROSTATIC EFFECTS

• Electrostatic effects - attraction of opposite charges and repulsion of like charges - play
a major role in determining the energy states of atoms and hence influence their atomic
properties, such as atomic size and ionisation energies.

• The main factors that affect the strength of the electrostatic attraction between the nucleus
and the electrons are: .

1. Number of electronic shells

If the number of shells increases,

o the principal quantum number, n, of the outermost (valence) shell increases
o distance between the nucleus and the valence electron increases
o electrostatic attraction between the nucleus and the valence electron
decreases

2. Nuclear charge, Z
2* Effective nuclear charge, (Zeff)
If the number of protons increases, The effective nuclear charge is the
o nuclear charge increases resultant positive charge experienced
o electrostatic attraction between by the valence electrons in a multi-
the nucleus and the valence electron atom taking into consideration
electron increases the shielding effect of the inner
electrons.
3. Shielding effect (or screening effect) by
inner electrons Zeff= 2- S
where Z = proton number
If the number of inner shell electrons
and S = shielding (constant)
increases
o shielding effect experienced by the
If effective nuclear charge increases,
valence electron increases
o electrostatic attraction between the
o electrostatic attraction between
nucleus and the valence electron
the nucleus and the valence
increases
electron decreases

Note: When discussing the trend of the atomic properties across a period, it is common
to consider factors 2 and 3 together and state their combined net effect using the
term, effective nuclear charge.

Note: We will be making use of these factors in explaining the trends and variations in:

o atomic radius and ionic radius

o first ionisation energies across a period
o first ionisation energies down a group
o successive ionisation energies of an element
o efectronegativity

-20-
 • What is meant by shielding?

Since all electrons are negatively charged, they repel

each other. The electrons in inner shells repel the 1s 2 2s 2 2p 6 3s 2 3p 3
electrons in outer shells and prevent them from '-y---1'----y--l
experiencing the full effect of the actual nuclear inner shell valence
charge. This is called shielding . electrons electrons

The greater the shielding of outer electrons by the inner shell electrons, the i
weaker the attractive forces between the nucleus and the outer electrons. '
;
Note: ;

Electrons in the same shell provide very poor shielding effect for one another. J

For a given shell n, shielding ability of electrons decreases in the following i

order: s > p > d > f !
i

d and f electrons usually provide poor shielding effect for outermost electrons
. ,. from the nuclear charge because the d and f orbitals are rather diffuse .
~ v e 0,c\ ~v-e.v
1
========================6=====A=T=O==M=IC==RA==D=l=U=S=====================o.:l'l ot=
a vci~fe~~-\ e~ .
6.1 Definitions

• Atomic radius is defined as half the shortest inter-nuclear distance found in the structure
of the element. This observed 'radius' of the atom depends upon how the atom bonds or
interacts with its neighbours.
The metallic radius of an atom is half the inter-nuclear
distance between two neighbouring atoms in the metal.

• Metallic radius is obviously restricted to those elements

that form metallic lattices.
Example: rM 9 = 0.160 nm
e-W I
I

' dmet
I
I

'
metallic .radius = 1dmet

1:·· .·\.
:~. _:i
.
: ·~--
The covalent radius of an atom is half the inter-nuclear
distance between two covalently bonded atoms.

• Covalent radius may be measured for most elements

Example: re,= 0.099 nm
w : dcov :

covalent radius = 1 dcov

The van der Waals' radius of an atom is half the inter-

nuclear distance between atoms which are not chemically
bonded.

• Van der Waal's radius is most easily determined for non-

metals, and is particularly useful for the lighter noble
G)G) I

: dldw
I

:
gases which do not form chemical bonds.
Example: rAr = 0.192 nm
van der Waals' radius= 1 dl.dw

-21-
6.2 Variation in atomic radii

Diagram showing the atomic radii of the elements

Period 4

0.2
E
-"'
C

::, *Note: the

=a
~ values of Ne,
e
(.)

0
0.1 Ar and Kr are
:i van der Waals'
radius

H
0.0 -+------r------r-----'"T-'___,.
0 10 20 30
Proton number (atomic number)

6.2.1 Trend in atomic radii across a Period

Group 1 2 13 14 15 16 17 18
Period 3 elements Na Mg Al Si p s Cl Ar
Atomic radius / nm 0.186 0.160 0.143 0.117 0.110 0.104 0.099 0.192

0 G
Note:
Data are obtained from
the Data Booklet. 0 0 0 0 @

Trend : Atomic radii decrease across a period . (with reference to Period 2 and 3.)
Explanation : Across a period,
• the number of shells remain the same .
• number of protons increases and hence nuclear charge increases .
• number of electrons also increases but these electrons are added to the
same outermost shell, and hence shielding effect remains
approximately constant.

• effective nuclear charge increases .

• electrostatic attraction between the nucleus and the valence electrons

increases, resulting in a decrease in the size of the electron cloud.

Hence atomic radii decrease across a period .

~ Ac.vo'3s \?e~.-,od. o.i orv., c. vo, cli1 : i

6.2.2 Trend in atomic radii down a Group l DowVI O. SnMP oct_
OI-YIIC vtA&(i : t
Group 17 elements F Cl Br I At
Atomic radius / nm 0.072 0.099 0.114 0.133 0.140
Trend : I Atomic radii increase down a group .

-22-
Explanation: Down a group,
• the number of electronic shells increases
• distance between the nucleus and the valence electrons increases

Despite the increasing nuclear charge,

• electrostatic attraction between the nucleus and the valence electrons
decreases, resulting in an increase in the size of the electron cloud .

Hence atomic radi i increase down a group.

7 IONIC RADIUS

The ionic rad ius of an ion can be defined as the radius of the sphericai ion in an ionic
compound.

Group 1 2 13 14 15 16 17 18
Period 3 elements Na Mg Al Si p s Cl Ar
Atomic radius / nm 0.186 0.160 0.143 0.117 0.110 0.104 0.099 0.192
Ion Na+ Mg2+ Af3+ Si4+ p3--- s 2- Cr -
Ionic radius / nm 0.095 0.065 0.050 0.041 0.212 0.184 0.181 --

G Gi) 0 0 0 0 @)

0Na• 0
Mg2•
0
AP•
0
Si' • 000
7.1 Cationic radius (rcation < ratom) ?OS\\1vt ·,ol'\S (10~-€-\ectYOl'\6)
Observation : The radius of a cation is always smaller than that of the parent atom.
Example: Mg: 1s2 2s2 2p6 3s2 Mg 2+: 1s2 2s2 2p6
rM 9 : 0.160 nm rM 92+ : 0.065 nm
Explanation : • Both the cation and its parent atom have the same number of protons
and hence have the same nuclear charge.
• However, the cation has one less electronic shell than its parent atom

Electrostatic attraction between the nucleus and the valence electrons

increases, resulting in a decrease in size of the electron cloud.

7.2 Anionic radius (ratom < raoion) Vl~~'\ye, \OY\'i. ( r{\\l'fe. e,J
Observation : The radius of an anion is always greater than that of the parent atom.
Example: S: 1s2 2s 2 2p6 3s 2 3p 4 s 2- : 1s2 2s2 2p6 3s 2 3p6
rs: 0.104 nm r5 2- : 0.184 nm
Explanation: • Both the anion and its parent atom have the same number of protons
and hence have the same nuclear charge.
• However, the anion has more electrons than its parent atom .
• With more electrons, electron-electron repulsion increases

• Electrostatic attraction between the nucleus and the valence electrons

decreases, resulting in an increase in the size of the electron cloud.

-23-
 S~YVW hO. ~i
7.3 Ionic radii of isoelectronic species

Graph of atomic and ionic radii against

atomic number of Period J elements (Na to Cl)

025
p ....
E . ·,
Q, 51-
-.
C 020
"o-g > anionic
~
:,
radius
'6
l! 0 15

Observation :
c"
.2
...0 0.10 I
~ atomic
radius
E" ~~
0
... .,_:---
< 0.05
- Al'·
---ti
cationic
radius
Si..
0.00
11 12 13 14 15 16 17
Atomic number

Ionic radii of isoelectronic ions decrease across a period .

Example: Na+> Mg 2 + > A/3 + p 3-> s2-> er
Trend

Ions Na+ Mg2+ AP+ p3- s2- Cf-

No. of p 11 12 13 15 16 17

No. of e- 10 10 10 18 18 1ff
Electronic
1s2 2s 2 2p 6 1s 2 2s2 2p6 3s 2 3p 6
configuration
Explanation: • Na+, Mg 2+ and AP+ are isoelectronic species and hence their valence
electrons experience the same shielding effect.
• However, nuclear charge increases from Na+ to AP+ .
• Effective nuclear charge increases from Na+ to A/3+

• Electrostatic attraction between the nucleus and the valence electrons

increases, resulting in the decrease in the size of the electron cloud.

Explanation for the trend observed from p3- to CJ- is the same as above.

• Additional point to note:

Observation : There is a sharp increase in ionic radius from AP+ to p3-_

Example: Af.3+: 1s 2 2s 2 2p6 P3-: 1s 2 2s2 2p6 3s 2 3p 6
Explanation:
• p 3 - has one more electronic shell than A{J+_
• Despite the increase in nuclear charge, the valence electrons of p3-
are less strongly attracted by the nucleus.
• Consequently the ionic radius of p 3- is bigger than that of Af.3+.

-24-
 )
8 IONISATION ENERGIES

8.1 Definitions

The first ionisation energy of an element M is the energy required to remove 1

mole of electrons from 1 mole of gaseous M atoms to form 1 mole of
first gaseous M· ions .
ionisation
energy Equation: M(g) -r M+(g) + e- .1.H = 1st ionisation energy
Example: Ca(g) -r ca+(g) + e- .1.H = +590 kJ mo1-1
The second ionisation energy of an element M is the energy required to
remove 1 mole of electrons from 1 mole of gaseous M· ions to form 1 mole
second of gaseous M2• ions.
ionisation
energy Equation: M+(g) -r M2· (g) + e- .1.H = 2nd ionisation energy
Example: ca+(g) -r Ca 2•(g) + e- .1.H = +1150 kJ mo1-1
. . . d ( !Ah~ e,l'\Q.VaY ) d . . t· - . ·t· I .
• Ionisation 1s an en ot ermtc process an 1onisa 10n energies are pos1 1ve va ues since
energy is absorbed during ionisation to overcome the attraction between the electron and
the nucleus.

• Ionisation energies affect the type of bond formed by the atom with other atoms. Elements
with low ionisation energ ies will find it easy to lose an electron to form a cation, resulting
in ionic bonds being formed .

Worked Example 5
(a) Write an equation to represent the reaction in which its enthalpy change is equal
to the third ionisation energy of sodium.
Nit-. ).4 ~) ~ N.__1-1 ½) -t <---

(b) Name the enthalpy change for the following reaction : O(g) -r 0 3 · (g) + 3e- .
Ir-+ -+ 2.. ~ + 3,.{ ~~ ·"' ,,# rrc~ J (..,\A_W\./) _

8.2 Trends in ionisation energies

,:;-: :';.
¼,::.i 8.2.1 Trend in first ionisation energies across a Period

Graph of first ionisation energy against atomic number of the first 30 elements
Period 2 Period 3 Period 4
(
- - ~ A - - ~\ (
- - ~ A . - - ~\ ~-~
2500
re
~ INE
..,.xE 2000 I

>-
I I ~r
...
Cl)
1 500 I I I

"'
C
-.. . . v
\ 1/ / \
Cl)

C
0 ,,V
~ 1000

c"'
-....,
.2
500
I
'r--i vi I

/ I'-, /
/
\ .1r' I
I. ./<

U::
I I K~ I i
I
0
l
Li

2 3 4 5
l

6 7 8
IN1 I I I I
9 10 11 12 13 14 15 16 17 18 19 2 0 21 22 23 24 25 26 2 7 28 29 30
1 1 ;

Atomic number

-25-
• 3 key points to take note when discussing the trend of first ionisation energies across a
period .

(i) general increment across a period (Period 2 & 3)

(ii) irregularity 1 - between Group 2 and Group 13 elements
(iii) irregularity 2 - between Group 15 and Group 16 elements

(i) General increment across a period

Trend: The first ionisation energies of the elements generally increase across
a period .
Explanation: Across a period,
• the number of shells remain the same .
• number of protons increases and hence nuclear charge increases .
• number of electrons also increases but these electrons are added to
the same outermost shell, and hence shielding effect remains
approximately constant.

• effective nuclear charge increases .

• electrostatic attraction between the nucleus and the valence

electrons increases, resulting in an increase in the energy required
to remove the valence electron from an atom.

Hence the first ionisation energies of the elements generally increase

across a period.

(ii) Irregularity 1 - Group 2 & Group 13

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

The first ionisation energy of Al is lower than that of Mg.
Explanation: · Mg: 1s2 2s 2 2p 6 3s 2 Al: 1s2 2s 2 2p 6 3s 2 3p 1

• The 3p electron to be removed from Al is at a higher energy level

than the 3s electron to be removed from Mg .
• Hence less energy is required to remove the 3p electron in A/
than the 3s electron in Mg.
• First ionisation energy of A/ is lower than that of Mg .

(iii) Irregularity 2 - Group 15 & Group 16

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

The first ionisation energy of S is lower than that of P.
Explanation: P: [Ne] S: [Ne]
[TI] 11 11 11 I [TI] 11 ~ 11 11 I
3s 3p 3s 3p

• The 3p electron to be removed from S is a paired electron while

that to be removed from Pis an unpaired electron.
• Due to inter-electronic repulsion between paired electrons in the
same orbital, less energy is required to remove the paired 3p
electron from S.
• Hence the first ionisation energy of S is lower than that of P .

-26-
 Graph of first (x) and second ionisation energies (o) against atomic number of the
first 20 elements
8000
~
I
7000 Note:
0
..,-"'E 6000 /' The maxima for
the two graphs
I occur at different
>-
OI
5000 atomic numbers.
C
L
(I)

4000
I) 2nd I.E.> 1st I.E.
>-¥'
(I)

, I' \
I
) ' because more
I'
C
.2 !'

.
"lii
c
3000
I J-¥1 I
.,I \
I
i
!
.J..~
; r"'
\I
energy is
required to
.2
2000

1000
I
\
45

v F-t ~ \
!
~
I
V
'y \ 11 remove an
electron from a
I r \ ..-4
0 Vil Ii T I ,
positive ion
-------------
I
;
1 2 3 4 5 6 7 8 9 W llll UM~~ DIB H m
H He Li Be B C N O F Ne Na Mg Al S1 P S Ci Ar K Ca

(a) Identify the similarities and differences between the variations of first ionisation
energies and that of second ionisation energies.
(b) Account for your observations in (a).

8.2.2 Trend in first ionisation energies down a Group

Group 1 1st I.E./ kJ mol-1 Group 17 1st I.E. / kJ mo1- 1

Li 519 F 1680
Na 494 CI 1260
K 418 Br 1140
Rb 403 I 1010
Cs 376 At 920

Trend: The first ionisation energies of.the elements generally decrease down a
group.
Explanation: Down a group,
• the number of electronic shells increases
• distance between the nucleus and the valence electron increases
Despite the increasing nuclear charge,
• electrostatic attraction between the nucleus and the valence electrons
decreases, resulting in a decrease in the energy required to remove
the valence electron from an atom.

Hence the first ionisation energies of the elements generally decrease

down a group.

-27-
 Worked Example 6
For each pair of species below, predict and explain which has a higher second
ionisation energy.

(a) A/ and Si (b) 0 and F

Ar: 1s2 2s 2 2p 6 3s2 o·: 1s2 2s 2 2p3

Si•: 1s2 2s 2 2p6 3s2 3p 1 P : 1s2 2s2 2p4
Note: ns 2 vs ns2 np 1 Note: ns2 np 3 vs ns2 np 4

• The 3p electron to be removed • Due to ~ - ~'- rt.f

wl.A'""'- -
from Si• is at a ~\.-v energy between paired electrons in the
level than the 3s ectron to be same 2p orbital, less energy is
removed from Ar. required to remove the 2p electron
• Hence less energy is required to from P.
remove the 3p electron in Si• than :. 0 has a higher 2nd I.E. than F.
the 3s electron in Ar.
:. Ar has a higher 2nd I.E. than Si.

8.2.3 Trend in successive ionisation energies of an element

1st 2nd 3rd 4th 5th 5th

Ionisation energies of K / kJ mo1-1 418 3070 4600 5860 7980 9650

Trend : Successive ionisation energies of an element increase.

Explanation: This is because once the first electron is removed from the neutral atom,
each successive electron is removed from an ion of increasing positive
charge which attracts the electrons more strongly.
Alternative K(g) ~ K•(g) ~ K2•(g) ~ K3 •(g) ~ K4 •(g) ~ K5 •(g) ~ K6 •(g)
explanation:
• number of protons remains the same and hence nuclear charge
remains the same
• number of electrons decreases
• electrostatic attraction between the nucleus and the remaining
electrons increases, resulting in an increase in energy required to
remove each subsequent electron .

8.2.4 Deducing group number from successive ionisation data

1st ionisation energy: K(g) -)- K·(g) + e- ~H1 =+418 kJ mo1-1

2nd ionisation energy: K·(g)-)- K2•(g) + e- LlH2 =+3070 kJ mo1-1

Observation: Large jump in the 1st and 2nd I.E. of K.

Explanation: K: 1s2 2s 2 2p6 3s2 3p 6 4s1 K·: 1s2 2s 2 2p 6 3s2 3p6

• K belongs to Group 1 and has 1 valence electron .

• Significantly more energy is required to remove the 2nd electron from
K as the 2nd electron is located in a different shell, one that is inner
and nearer to the nucleus, and hence experiences a stronger
electrostatic attraction to the nucleus.

-28-
 Worked Example 7
The first eight ionisation energies (in kJ mol-1) of an element E are as follows:
703 1610 2460 4350 5400 ' 8500 10300 12300
½-' ½-' \.....y-1 \.....y-1 ~ \.....y-1 \.....y-1
Difference: 907 850 1890 1050 3100 1800 2000
State the group of the Periodic Table to which Eis likely to belong. State your
reasoning clearly.

• A large jump in the and __r_ __e_

ionisation energies is observed.
• Significantly more energy is required to remove the 6th electron as it is located
in an inner shell.
.-. There are 5 electrons in the valence shell. =:> E is likely to be in Group JS_.
Worked Example 8
The graphs of the first six successive ionisation energies of an element X are
shown below.
C""-,
~:.<,..-·
- Deduce the group in the Periodic
Table Xis likely to belong to.
-
State your reasoning clearly.
-

t
I l

1 2 3 4 5 6 1 23 4 5 6
number of electron removed number of etectron removed

• A large jump in the 1st and 2nd ionisation energies is observed.

• Significantly more energy is required to remove the 2nd electron as it is
located in an inner shell.
.-.. There is 1 electron in the \lalence shell. =:> X is likely to be in Group _J_.

8.2.5 Deducing electronic configuration & other information from successive

ionisation data
Graph showing successive ionisation energies for an element X

_lg (ionisation energy)

n=4 n=3 n=2 n=1 Note:
6.0 I - I --------- ----------- ----,
I 11 I
It is common to have lg
I I I 11 I
I I I I I (ionisation energy)
I I 1
5.0 I :
I 1 1
11
I
I
instead of ionisation
.~ - ____) '-v':: : energy as the vertical
4.0 I ~

: six electrons
twOII

electrons : :
I

:
axis. This is to allow
: from the from the : : the large range of
3.0 : lhr~e 2 P_ 2s orbital : : ionisation energies to
, orbitals m . th ,,
I
I
'th2 m e2s , , be fitted conveniently
2.0 I I : su~s~ell subshell : : : on the vertical scale
L------------------ I l.-------------------' L--- - and also to make any
1.0 large difference
between successive
ionisation energies
0-+--,-,- 1- ,- ,- - - - - , - -,- - - . - - . - -....., ....................-
more apparent.
0 1 2 3 4 5 6 7 8 910111213141516171819
number of electron removed

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• Information which can be obtained from the above graph of successive ionisation
energies

(i) There are a total of 19 electrons present in an atom of the element.

The electronic configuration of the element X is 1s2 2s 2 2p6 3s 2 3p6 4s 1.

(ii) There are 4 electronic shells.

A large jump in ionisation energies is observed when an electron is removed from a

different shell, one that is inner and nearer to the nucleus, and hence
experiences a stronger electrostatic attraction to the nucleus.

The graph shows 3 such large increases in ionisation energies corresponding to the
removal of the 2nd, 10th and 18th electron
=> there are 4 different electronic shells.

(iii) There is 1 valence electron and hence the element belongs to Group 1 of the
Periodic Table.

A large jump between the 1st and 2nd ionisation energies is observed.
=> significantly more energy is required to remove the 2nd electron as it is located in
a different shell, one that is inner and nearer to the nucleus, and hence
experiences a stronger electrostatic attraction to the nucleus.
=> there is 1 valence electron
=> the element belongs to Group 1 of the Periodic Table

• Points to take note:

o Data of successive ionisation energies of an element provides evidence for the existence of electronic
shells of different principal quantum numbers (energy levels) and subshells (sub-levels) in an atom .
o Large jump observed in two successive ionisation energies
=:. removal of electrons from different shells
o Moderate difference (i.e. small jump) between two successive ionisation energies
=:. removal of electrons from different subshells

lg (ionisation energy)
• The small jump between 7th and
6.0 8 th ionisation energies is due to
2s electron
2p electron
the removal of electrons from
5.0 different subshells.

4.0 • The energy gap between

subshells is not as big as that
3.0 between shells and is sometimes
not discernible.~ not O~YVD, le
/v·1 (.\b\e .
2.0
For example, a small jump is
1.0 expected between the 15th and
16th ionisation energies (due to
04--,-,-,-,-,------.----, -~-.----..--........+ the removal of electrons from
different subshells) but this is not
0 2 3 4 5 6 7 9 10111213141516171819
observed in the graph.
number of electron removed

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 9 ELECTRONEGATIVITY

9.1 Definition
• The electronegativity of an atom in a molecule is a relative measure of its ability to attract
bonding electrons.

9.2 Variation in electronegativity

4.0
3.5 I /"F I I
~ 3.0
V Cl
:~
1u 2.5
/ V
[»
(I)
C: 2.0
l\ V /
.A .

e
0 1.5
V /(
V ./ ~ ea
(I)

t.-r-:-,;, iii 1.0 'T;

l Nn•~ ,......
K
0.5 I
iI I
0.0
0 5 10 15 20
Proton Number

9.2.1 Trend in electronegativity across a period

Trend: Electronegativity increases across a period.

Explanation: Across a period,
• the number of shells remain the same .
• number of protons increases and hence nuclear charge increases .
• number of electrons also increases but these electrons are added to the
same outermost shell, and hence shielding effect remains
approximately constant.

• effective nuclear charge increases .

• electrostatic attraction between the nucleus and the bonding electrons

increases

Hence electronegativity increases across a period.

9.2.2 Trend in electronegativity down a group

Trend: Electronegativity decreases down a group.

Explanation: Down a group,
• the number of shells increases .
• distance between the nucleus and the bonding electrons increases
Despite the increasing nuclear charge,
• electrostatic attraction between the nucleus and the bonding electrons
decreases

Hence electronegativity decreases down a group.

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9.2.3 Significance of Electronegativity {Refer to {f) of Chemical Bonding)

• When two atoms of similar electronegativity ar~ covalently bonded, a non- polar bond is
formed .

• If the difference between the electronegativities of the two bonding atoms increases, the
covalent bond becomes more polar.

• At the same time, the ionic character of the bond also increases. With sufficient difference
in electronegativity , the two atoms will form an ionic bond instead.

• In general, ,,
:--/

.1EN Bond type

t.EN < 0.5 Non polar covalent
0.5 <~EN< 1.6 Polar covalent
2.0 < t.EN Ionic

Note: Metals have low electronegativities, and tend to lose electrons, while non-metals have
high electronegativity, and tend to gain electrons. In fact, electronegativity can be
correlated to metal, metalloid, or non-metal, properties of an element.

\ QVt\ L ~~ OM. o_ 6~ J ~)'t,._1\ef\ ~ ¼

M ~ tx()S"<: ~ ch.,w vc-lC,N\,tl, !14,~ . _
L~ ½''J (C)tb·r-ttJ --';r ~,-+k'~\s ~ e- ~s ,6 ~
~s (U ~ - ~ ~"' ~ ~ Ji·~ ~W .

r
\.-/
t-

,-
--,.........______
,,,,.,----
'
J ~-
/
! !
i r. l

S \..tnl··
L'/f~V'-<7\ lf'\ o1,__

r,-,.,,_,,, (_,.1.,-t n--,J r L,·

: () ~ 1--1
V ,,

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