OCR AS Chemistry

Module 2 - Foundations in Chemistry

Part 2 – Electrons, bonding and
structure
2.2.2 Bonding and structure

Topic 18 – Electronegativity and bond

polarity
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Learning outcomes
electronegativity as the ability of an atom to attract the bonding electrons
in a covalent bond; interpretation of Pauling electronegativity values

explanation of:
(i) a polar bond and permanent dipole within molecules containing
covalently-bonded atoms with different electronegativities
(ii) a polar molecule and overall dipole in terms of permanent dipole(s)
and molecular shape

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 Starter
A covalent bond is the strong electrostatic attraction
between a shared pair of electrons and the nuclei of the
bonded atoms

+ e− +
nucleus
e −

electrostatic forces shared pair of electrons

of attraction
But what if the nuclei do not attract the shared electrons
equally?

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 Starter
Example: C−F covalent bond
core charge (a measure of the
attraction from the nucleus)

+4 e− +7
carbon fluorine
e −

shared pair of electrons

Which nucleus attracts the shared electron pair more strongly, carbon or fluorine?
Fluorine
What do you notice about the position of the shared electron pair?
The electron pair lies closer to the fluorine nucleus

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 Electronegativity
This leads to the concept of electronegativity,
which is a measure of the different pulling power
each atom has on the shared electrons in a
covalent bond.
Fluorine is said to be more electronegative than
carbon because the fluorine nucleus has a stronger
attraction for the shared electrons.

Key Definition
Electronegativity is the ability of an atom to attract the
bonding electrons in a covalent bond.

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 Atomic core
The attraction of an atom for electrons comes from its
positive atomic core i.e. the atom minus its outer electrons.
The core charge is the resultant of the positive charge on
the protons and the negative charge on the outer electrons.

Calculation of core charge for sodium

Nucleus = +11 charge from the protons
Electron shell configuration is 2.8.1
Inner electrons = 2 + 8 so charge = −10
Therefore the core charge is:
+11
−10
+1
core = nucleus + filled outer shell
inner shells of electrons of electrons

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 Factors affecting electronegativity
Electronegativity is increased by two factors:
Factor Example
Higher core charge Group 1 has a +1 core charge attracting
Core charge = nuclear charge minus the shared electrons.
number of inner electrons = group Group 2 will have a +2 charge attracting
number the shared electrons, and so on.
Smaller size of atom When fluorine shares electrons they are
With less shells of electrons the core closer to the nucleus than when chlorine
of the atom is closer to the shared shares electrons so fluorine pulls
electrons giving greater attraction bonding electrons more strongly and is
therefore more electronegative than
chlorine

As a result of these factors:

• Electronegativity increases from left to right across the
Periodic Table
• Electronegativity decreases down a group of elements
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Pauling scale of electronegativity

electronegativity increases
electronegativity increases

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 Electronegativity and bond polarity
Non-polar covalent bonds
Two atoms of the same electronegativity sharing electrons – the
electron pair are shared equally and the shared electrons are distributed
evenly between the two atoms.

+ e− +
e−

Examples


Why are these bonds described as non-polar?
H H Cl  Cl
× are shared equally and there is no ×separation of charge
Because the electrons
Explain in terms of electronegativity how a non-polar bond arises.
The two atoms sharing electrons have the same or very similar electronegativities

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 Electronegativity and bond polarity
Polar covalent bonds
Two atoms of different electronegativities sharing electrons – the
electron pair are shared unequally and the shared electrons are pulled
closer to the more electronegative atom.
A separation of charges called a dipole results.
δ+ δ−
+ e− +
e−

If this
The shared atom has
electrons arehigher
attracted
A permanent dipole is a small charge difference across a bond
electronegativity
more closely to its (or….
nucleus a
molecule)
What do thethat results
symbols δ+ from a mean?
and δ+ difference in the electronegativities of the
Examples
bonded
They show atoms.
small + and − charges (partial charges)
δ+how
(Dipole = 2 these
polessmall δ− arise.
= 2 charges) δ+ δ−
Explain
H  Cl charges
× atom
The more electronegative
A polar covalent bond C  F
× strongly so the
attracts the shared electrons more
has a permanent dipole.
shared electron pair lies closer to this atom, causing a separation of small charges.

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 Learning check
Polar covalent bonds are formed when atoms of different
electronegativities
_______________ share electrons. The electrons are then
unequally The more electronegative atom has a
shared _________.
shared/ bonding electrons and they are
stronger pull on the ______________
greater/bigger
pulled closer to this atom. This atom has a _____________
negatively
share of the electrons and so becomes slightly __________
charged (δ−). The less electronegative atom has a
smaller/lesser share of the electrons and becomes slightly
____________
positively charged (δ+). There is now a _______
_______ charge difference
dipole .
across the H-Cl bond. This is called a permanent ______

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 Electronegativity and bonding type
There is a gradual change from covalent to ionic bonding as the
difference in electronegativity of the bonding atoms increases.

Electronegativity difference increases

‘pure’ ionic ‘pure’ covalent

intermediate bonding
bonding bonding
δ+ δ−
Na Cl
+ −
H−Cl Cl−Cl

ionic bonding polar covalent bonding non-polar covalent

(full charges) (partial charges) bonding (no charges)

electrons shared unequally electrons

sometimesshared
called
electrons transferred (some ionic character) ‘pureequally
covalent’
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 Using difference in electronegativity to
predict bonding type
Bond type Electronegativity difference
non-polar (pure) covalent 0
polar covalent greater than 0 but less than 1.8
ionic greater than 1.8

Note that when the difference in electronegativity is small,

e.g. in C−H, the bond is usually regarded as non-polar

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Predict the type of bonding between the following pairs of
atoms:
H and F
electronegativity difference = 3.98−2.20 = 1.78
polar covalent bonding
K and F
electronegativity difference = 3.98−0.82 = 2.16
ionic bonding
C and Se
electronegativity difference = 2.55−2.55 = 0
non-polar (pure) covalent bonding
C and O
electronegativity difference = 3.44−2.55 = 0.89
polar covalent bonding

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 Exercise 18A

Complete exercise 18A on your

worksheet.

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 Polar molecules
A polar molecule has an overall dipole taking into account
any dipoles across the bonds (bond dipoles).
To have a permanent dipole:
• a molecule must have a difference in electronegativity
between the atoms in its bonds
and
• it must not be totally symmetrical
The dipoles across individual bonds are called bond dipoles

The dipole that can result from the addition of all the bond
dipoles in a molecule is called the overall dipole

Whether a molecule has an overall dipole depends on its shape

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 No overall dipole Overall dipole
• symmetrical molecule • not totally symmetrical molecule
• bond dipoles cancel out • bond dipoles reinforce each other
• molecule is non-polar • molecule has permanent dipole
• molecule is polar

Examples
δ− δ+ δ− δ+ non-linear
δ− δ−
linear
δ− tetrahedral with
different atoms
δ+ δ+ around central atom

δ− δ− δ− δ−

δ− tetrahedral δ−

Key
Bond dipoles are vectors – they have direction as well as
= bond dipole
size and can reinforce
= overall dipole each other or cancel out.
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 Learning check
δ−

δ+

δ− δ−

δ−

Why is CCl4 a non-polar molecule even though its bonds are polar?
Because the carbon atom is surrounded tetrahedrally (and therefore
symmetrically) by four chlorine atoms of identical electronegativity, so the
four bond dipoles cancel out.

A simple way of looking at this is that although there are small charges,
they are evenly spread around the molecule. So one end of the molecule
is not more negative than the other end.

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 Plenary
For each of the following molecules choose one category
from each list that applies.

1. SiF4 Shape Symmetry Polarity

2. PCl3
linear symmetrical overall dipole
3. BeCl2
non-linear not symmetrical no overall dipole

trigonal planar
tetrahedral
pyramidal

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 Plenary answers
For each of the following molecules choose one category
from each list that applies.

1. SiF4 Shape Symmetry Polarity

tetrahedral symmetrical no overall dipole

• no permanent dipole
• non-polar

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 Plenary answers
For each of the following molecules choose one category
from each list that applies.

2. PCl3 Shape Symmetry Polarity

pyramidal not symmetrical overall dipole

• permanent dipole
• polar molecule

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 Plenary answers
For each of the following molecules choose one category
from each list that applies.

3. BeCl2 Shape Symmetry Polarity

linear symmetrical no overall dipole

• no permanent dipole
• non-polar

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 Homework

• Finish exercises 18A-18B

• Revise shapes of molecules

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