Electronegativity and intermediate bonding

Definition F, O, N and Cl are the

most electronegative
Electronegativity is the relative tendency of an atom in a covalent bond atoms
in a molecule to attract electrons in a covalent bond to itself.

Electronegativity is measured
on the Pauling scale (ranges
from 0 to 4) F

The most electronegative N

4 H
element is fluorine and it C
Electronegativity
is given a value of 4.0 3.5 Cl
B
S
3 Be
P Br
Li Si
Se
Factors affecting 2.5 Al
Mg Ge As
electronegativity Ga I
2 Na
Electronegativity increases Sn Te
In Sb
across a period as the number 1.5 K Ca
of protons increases and the Sr
atomic radius decreases 1
Rb
because the electrons in the
0.5
same shell are pulled in more.
0
It decreases down a group 1 2 3
because the distance between 4 5
the nucleus and the outer 6 7
electrons increases and the
shielding of inner shell Group Number
electrons increases

INCREASING ELECTRONEGATIVITY

H
2.1
DECREASING ELECTRONEGATIVITY

Li Be B C N O F
1.0 1.5 2 2.5 3.0 3.5 4.0

Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.8 1.9 1.6 1.6 1.8 2.0 2.4 2.8

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I
0.7 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At
0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.8 1.9 2 2.2

Fr Ra Ac
0.7 0.9 1.1 N Goalby chemrevise.org 1
 Intermediate bonding

Ionic and covalent bonding are the extremes of a continuum of bonding type. Differences in
electronegativity between elements can determine where a compound lies on this scale

A compound containing elements of similar electronegativity and hence a small

electronegativity difference will be purely covalent

A compound containing elements of very different electronegativity and hence a

very large electronegativity difference (> 1.7) will be ionic

Non polar Covalent bond Polar Covalent bond Ionic bond

Electrons shared equally Electrons shared unequally Electrons are
transferred

Increasing ionic character

Difference in
electronegativity
0.4 1.7

Formation of a permanent dipole – (polar covalent) bond

A polar covalent bond forms when the elements in the bond have different electronegativities . (Of
around 0.3 to 1.7)

When a bond is a polar covalent bond, it has an unequal distribution of electrons in the bond and
produces a charge separation, (dipole) δ+ δ- ends.

δ indicates a slight deviation from being

neutral
δ–
d+

The element with the

larger electronegativity in
a polar compound will be
the δ- end
δ+ δ-
Covalent with ionic
character (polar covalent) H – Cl

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Polar and Non Polar molecules
Symmetric molecules

A symmetric molecule (all bonds identical and no lone pairs) will

not be polar even if individual bonds within the molecular are
polar.
CO2 is a symmetrical molecule and
The individual dipoles on the bonds ‘cancel out’ due to the
is a non-polar molecule
symmetrical shape of the molecule.
There is no net dipole moment: the molecule is non-polar

e.g. CCl4 will be non-polar whereas CH3Cl will be polar H

δ+
C δ-
H Cl
Non-symmetrical molecule
A non-symmetrical molecule (different bonds OR the
H
same bonds and having lone pairs) will be polar if
individual bond(s) are themselves polar

δ–

N O δ
H
δ+ -
H H
δ+ H
δ+ δ+
H δ+

Experiment effect of charged rod on polar/non-polar liquids

In this experiment, a charged rod (formed by rubbing a

plastic rod) is brought close to a jet of liquid flowing from a
burette.

If the liquid is polar, the jet of liquid will be attracted to the

electrostatic force of the rod. The dipoles in the polar molecules will
all align and the negative end δ- will be attracted to the positive rod ++++++++ +
(or vice versa). The stronger the dipole the more the deflection of the
jet.

Non-polar liquids will not be deflected and attracted to the charged rod.
Hexane will not be deflected by a charged rod.

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 Pure Ionic

+ - When 100 % ionic the ions are spherical.

Another point in the continuum between ionic and covalent is ionic with covalent character. It is possible to
explain this with difference in electronegativity but more commonly Fajan’s rules are used to explain the
change from purely ionic to ionic with covalent character.

Ionic with covalent character

-
+
When the negative ion becomes distorted and non spherical, it is
more covalent and is called polarised. The metal cation that causes
the polarisation is called more polarising if it polarises the negative
ion.

Fajan’s Rules
The extent of polarisation of the negative ion by the positive ion can be explained by Fajan’s rules.

There is a tendency towards covalent character when

• the positive ion is small
• the positive ion has multiple charges
• the negative ion is large
• the negative ion has multiple negative charges.

Example
AlCl3 shows quite large covalent character because Al has a +3 charge and is quite small, so is highly polarising.

Example
Consider the halides of magnesium
MgCl2 , MgBr2 , MgI2.
As the anions become larger they are more easily polarised, so they show more covalent character

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Van Arkel diagrams
Van Arkel diagrams illustrate on one diagram the type of bonding for all binary compounds. It
extends the continuum to include metallic bonding as well as ionic and covalent.
It shows their bonding type in terms of the difference in electronegativity (which is plotted on the y-
axis) and the average electronegativity of their constituent elements (which is plotted on the x-
axis).

Ionic (red)
CsF
3.6
LiF 3.4
x
3.2

Difference in Electronegativity
3.0
Li2O
x
2.8
x BeF2 2.6
MgO
x
2.4
x BF3 2.2
X NaCl 2.0
X Mg3N2 SiO2 1.8
x CF4
X MgCl2 X B2O3
x 1.6
X LiH X MgBr X AlN
2
1.4
X AlCl3 x NF3 1.2
x SiCl4
X CO2 1.0
X AlLi
0.8
X NO x OF2 0.6
CCl4
X GaAs
x 0.4
X
Al3Mg2
X GaSb 0.2
metallic 0
(blue) Cs Ba Ca Mg Be Ga Si B As H CS Br Cl N O F
K Li Ti Al Sn Sb P Covalent (yellow)
0.8 1.0 1.2 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2

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 Intermediate bonding Questions
1) Define electronegativity
2) Give 3 factors that affect electronegativity
Table of Electronegativities

H
2.1
Li Be B C N O F 4.0
1.0 1.5 2.0 2.5 3.0 3.5
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0

3) a) State and explain the trend in electronegativity down a group

b) State and explain the trend in electronegativity across a period
4) Draw diagrams to show the shape of the electron charge clouds in an ion, in a purely covalent molecule and a polar
covalent molecule. Explain using the ideas of electronegative difference how each case can occur.

5) Deduce using the ideas of electronegativity difference whether the following compounds have ionic bonding,
covalent bonding or intermediate polar covalent bonding. Predict for each one whether you would expect the melting
point to be high or low
a) sulfur dioxide
b) sodium oxide
c) lithium fluoride
d) nitrogen monoxide
e) hydrogen chloride
f) F2O
g) phosphine (PH3)
h) magnesium chloride
I) nitrogen trichloride
J) boron hydride

6) Explain why the chlorides NaCl, MgCl2, AlCl3 and SiCl4 have lower melting points as you move across the period
from Na to Si.

7) a) Describe what a polar covalent bond is and explain how one forms.
b) Find out and draw the displayed structures of the following compounds and draw on the relevant bonds the correct
dipoles
(i) H2O
(ii) NH3
(iii) HF
(iv) CH3Cl
(v) ethanol CH3CH2OH
(vi) SO2
(vii) CH3CH2Br
(viii) IF
δ+ δ-
8) The polarity of a carbon-hydrogen bond can be shown as C-H
(i) What does the symbol δ+, above the hydrogen atom, signify?
(ii) Why is there a charge separation on the C-H bond
(iii) Explain briefly, in terms of its shape, why a CH4 molecule has no overall polarity.

9) Find out and draw the displayed structures of the following compounds. Identify which of the following compounds
have no overall polarity and for the ones that are polar draw on the dipole
i) CH3Br
ii) CCl4
iii) BF3
iv) NF3
v) CO2
vi) BeCl2
vii) methanal
viii) Cl2O
ix) SO3 N Goalby chemrevise.org 6