Chapter 4 & 14:

Chemical Bonding
& Structure

Formal charges
& Bond polarity
 Formal charges & Bond polarity

Larger structures and more in-depth explanations of

bonding systems often require more sophisticated
concepts and theories of bonding.
1. Formal charge (FC) can be used to decide which Lewis (electron dot)
structure is preferred from several. The FC is the charge an atom would
have if all atoms in the molecule had the same electronegativity.
FC = (No. of valence e-)-½ (No. of bonding electrons) – (No. of non-
bonding electrons)

2. The Lewis (electron dot) structure with the atoms having FC values
closest to zero is preferred.

3. Deduction of the Lewis (electron dot) structures of molecules and ions

showing all valence electrons for up to six electron pairs on each atom.
 Formal charges & Bond polarity

4. Application of FC to ascertain which Lewis (electron dot) structure is

preferred from different Lewis (electron dot) structures.

5. The “octet rule” refers to the tendency of atoms to gain a valence

shell with a total of 8 electrons.

6. Some atoms, like Be and B, might form stable compounds with

incomplete octets of electrons.

7. Exceptions to the octet rule include some species having incomplete

octets and expanded octets.

8. Bond polarity results from the difference in electronegativities of the

bonded atoms.
 Molecules with more than
one Lewis Structures
• In previous topic, the idea of a Lewis structure was introduced as a
convenient way of showing how the valence electrons are
distributed in a covalent molecular species or a polyatomic ion.

• It is sometimes possible to follow the rules for drawing Lewis

(electron dot) structures, and come up with more than one possible
Lewis structures that seems to be acceptable.

• This happens especially with molecules that are able to form an

expanded octet. E.g. sulfur dioxide, SO2

or

• A useful approach in deciding which Lewis structure is the most

appropriate is to determine the formal charge (FC) of the atoms
present in the molecule or ion.
 What is “Formal Charge”?
• Formal Charge (FC) is the charge an atom would have
if all atoms in the molecule had the same
electronegativity.
• In order to calculate a formal charge, electrons are assigned to individual
atoms within the molecule based on two different rules:

➢ bonding electrons must be divided equally across the different

bonded atoms, and
➢ non-bonding electrons are considered part of the atom they are
located at.

• The calculation of FC for each atom can be considered as a process

involving electronic book-keeping; it is a hypothetical charge worked out
as follows:
FC = (No. of valence e-) – ½ (No. of bonding electrons)
– (No. of non-bonding electrons)
 Different interpretations of
“charge”

Ionic charge –
charge formed
when an atom
lose or gain Oxidation state – charge
electrons. an atom of an element
would have if it existed as
an ion in a compound.
Partial charge –
Formal charge – charge an
is created due to
atom would have if all atoms
the asymmetric
in the molecule had the same
distribution of
electronegativity.
electrons in a
chemical bond.
 Determining preferred Lewis
Structure using the FC (method 1)
• Let’s consider the example of the chlorate(V) ion, ClO3-.

• Below shows all possible Lewis structures for the chlorate ion.
This would represent the different ways that the valence
electrons in the ion can be distributed among the atoms.
Cl forms
single bonds
with 3 O
atoms

Cl forms 1 single bond with

Cl forms 3double bonds
1 O atom & 2 double
with 3 O atoms
bonds with 2 O atoms

• Which of the three Lewis structures would be preferred?

 Determining preferred Lewis
Structure using the FC (method 1)
• Let’s count the number of valence electrons each atom will have (using a
different colour to represent the electrons belonging to each atom).
Non-
bonding
electrons _ _ _
xx

Ox
xx
x Bonding
electrons O x
x
x
x
O x x
x xx x
x x xx xx
Use the formula to xx xx xx x xx xx x
calculate the FC for
x
x
x
O Cl O
x
x
x
x
x xO Cl O
xx
xx
xx
xx
xx
x
x
x
xx
xx
O Cl O
xx
xx
xx
xx
xx
x
x
xx xx xx
each atom in the
molecule.
Lewis structure 1: Lewis structure 2: Lewis structure 3:
FC = (No. of valence O (x) = 6 – ½ (2)- 6 = -1 O (x) = 6 – ½ (4) - 4 = 0 O (x) = 6 – ½ (4) - 4 = 0
e-) – ½ (No. of O (x) = 6 – ½ (2) - 6 = -1 O (x) = 6 – ½ (4) - 4 = 0 O (x) = 6 – ½ (4) - 4 = 0
bonding electrons) – O (x) = 6 – ½ (2) - 6 = -1 O (x) = 6 – ½ (2) - 6 = -1 O (x) = 6 – ½ (4) - 4 = 0
(No. of non-bonding Cl (x) = 7 – ½ (6) - 2 = +2 Cl (x) = 7 – ½ (10) - 2 = 0 Cl (x) = 7 – ½ (12) - 2 = -1
electrons)

• The Lewis structure with atoms having formal charges (closest to 0) would be
preferred (∆FC = FCmax – FCmin) → Lewis structures 2 and 3 are possible.
• However, O is more electronegative than Cl and therefore the -1 formal
charge would be preferred for O than for Cl. → Lewis structure 2 is the
preferred structure.
 Determining preferred Lewis
Structure using the FC (method 1)
• The Lewis (electron dot) structure with the atoms having
– FC values closest to zero or
– lowest overall FC value is preferred.

• The sum of the formal charges of all atoms in a molecule must be zero &
the sum of the formal charges in an ion should equal the charge of the ion.

• In the case where two Lewis structures have atoms with the same FC
values closest to zero,
– the one where the negative values are on the more electronegative
atoms is preferred.

• Having low formal charges mean that less charge transfer has taken place
in forming a structure from its atoms, and in general this represents the
most stable or preferred structure.
 Determining preferred Lewis
Structure using the FC (method 2)
• Formal charge treats covalent bonds as if they were purely
covalent with equal electron distribution – so for this, forget
about electronegativity differences between the atoms.

• The idea is to count how many electrons ‘belong’ to (are

assigned to) each atom in the Lewis structure and compare this
with the number of valence electrons in the non-bonded atom.

• The difference between these two is the formal charge.

 Determining preferred Lewis
Structure using the FC (method 2)
• Let’s count the number of valence electrons each atom will have :
(using a different colour to represent the electrons belonging to each atom).

_ _ _
Now let’s consider the xx x
xx
x O x x
difference between the Ox
x
x
x
xx xx xx
O x
xx
x
x xx x
xx
x xx xx
actual number of valence x
x
x
O Cl O
x
x
x
x
x
x
x
xx
xx
O Cl O
xx
xx
xx
xx
x
x xO Cl O
xx
xx
xx
xx
xx
x
x
electrons (in bold) of each xx xx xx xx

atom based on its

electronic configuration &
the assigned number of
electrons based on the
proposed Lewis structure.
Lewis structure 1: Lewis structure 2: Lewis structure 3:
O (x) = 6 – 7 = -1 O (x) = 6 – 6 = 0 O (x) = 6 – 6 = 0
O (x) = 6 – 7 = -1 O (x) = 6 – 6 = 0 O (x) = 6 – 6 = 0
O (x) = 6 – 7 = -1 O (x) = 6 – 7 = -1 O (x) = 6 – 6 = 0
Cl (x) = 7 – 5 = +2 Cl (x) = 7 – 7 = 0 Cl (x) = 7 – 8 = -1

• The Lewis structure with atoms having formal charges (closest to 0) would be preferred
→ Lewis structures 2 and 3 are possible.
• However, O is more electronegative than Cl and therefore the -1 formal charge would
be preferred for O than for Cl. → Lewis structure 2 is the preferred structure.
 Determining Formal Charge
of atoms in a molecule
• E.g.1: Draw the Lewis structure for NO3- and assign formal charges to
its atoms.

Calculate the
a a a
FC for each
atom in the
molecule. b c b c b c

Lewis structure 1: Lewis structure 2: Lewis structure 3:

Oa = 6 – ½ (4)- 4 = 0 Oa = 6 – ½ (2)- 6 = -1 Oa = 6 – ½ (2)- 6 = -1
Ob = 6 – ½ (2)- 6 = -1 Ob = 6 – ½ (2)- 6 = -1 Ob = 6 – ½ (4)- 4 = 0
Oc = 6 – ½ (2)- 6 = -1 Oc = 6 – ½ (4)- 4 = 0 Oc = 6 – ½ (2)- 6 = -1
N = 5 – ½ (8)- 0 = +1 N = 5 – ½ (8)- 0 = +1 N = 5 – ½ (8)- 0 = +1

Drawing Lewis Structure of NO3- Calculating NO3- Formal Charges:

https://www.youtube.com/watch https://www.youtube.com/watch
?v=OIkXw6d6sYw ?v=3qXiD-BI_uc
 Determining Formal Charge
of atoms in a molecule
• E.g.2: There are three possible Lewis structures for SO2 as shown
below. Determine which one of them is the preferred structure.

Step 1: Calculate
the FC for each
atom in the
molecule. Lewis structure 1: Lewis structure 2: Lewis structure 3:
O (LHS) = 6 – ½ (2)- 6 = -1 O (LHS) = 6 – ½ (4)- 4 = 0 O (LHS) = 6 – ½ (4)- 4 = 0
O (RHS) = 6 – ½ (4)- 4 = 0 O (RHS) = 6 – ½ (2)- 6 = -1 O (RHS) = 6 – ½ (4)- 4 = 0
S = 6 – ½ (6)- 2 = +1 S = 6 – ½ (6)- 2 = +1 S = 6 – ½ (8)- 2 = 0

• The preferred Lewis structure is the one where individual atoms have a formal
charge (FC) closest to 0.
➢ Thus it should be structure 3 →

https://www.youtube.com/watch?v=2iK5uAWJ628
 Determining Formal Charge
of atoms in a molecule
• E.g.3: Assign formal charges for the three Lewis (electron dot) structures
shown below for N2O and deduce which is the preferred structure.
Lewis structure 1: Lowest formal charges, but
N (LHS) = 5 – ½ (4)- 4 = -1 negative value is on N which is
N (centre) = 5 – ½ (8)- 0 = +1 of lower electronegativity than
O = 6 – ½ (4)- 4 = 0 O, thus not preferred.

Lewis structure 2: Lowest formal charges, and

N (LHS) = 5 – ½ (6)- 2 = 0 negative value is on O which is
N (centre) = 5 – ½ (8)- 0 = +1 of higher electronegativity
O = 6 – ½ (2)- 6 = -1 than N, thus preferred.

Lewis structure 3:
N (LHS) = 5 – ½ (2)- 6 = -2 Not preferred as the formal
N (centre) = 5 – ½ (8)- 0 = +1 charges are the largest.
O = 6 – ½ (6)- 2 = +1

• Lewis structure 2 is the one with lowest FC & negative value is on oxygen
(higher negativity).
 The Octet Rule
• When an atom forms a chemical bond by gaining, losing or sharing valency
electrons, its electronic configuration becomes the same as that of a noble gas.

• With the exception of helium, (that is, eight electrons) in the outer or noble
gases in group 18 have a stable octet valence shells of their atoms.
➢ The formation of chemical bonds to achieve a stable noble gas
configuration is known as the octet rule. It applies to both ionic and
covalent bonds,
➢ but there are a number of exceptions.
1. molecules in which a 2. molecules in which a 3. molecules with an
central atom has an central atom has an odd number of
incomplete octet expanded octet electrons.

Nitrogen
Phosphorus has 3 (odd)
Boron has has 10 (>8) electrons
only 6 (<8) electrons
electrons *Molecules and ions with an
unpaired electron are known
as free radicals.
 Exceptions to Octet Rule
1. Molecules in which a central atom has an incomplete octet:

• Central atom does not have a noble gas electronic configuration

(it has < 8 valence electrons). Usually Be, B & Al as central
atoms cannot achieve octet configuration even after sharing
electrons with other atoms.
• Molecules are electron deficient.
• Such molecules can act as reactive Lewis acids which are
defined as electron pair acceptors.
• E.g.

Be has 4 valence B has 6 valence Al has 6 valence

electrons electrons electrons
 Exceptions to Octet Rule
2. Molecules in which a central atom has an expanded octet:

• Central atom central has more than eight electrons.

• It is usually from Period 3 (P, S) → electrons can go into the d
sub-shells (can hold up to 18 electrons)
• E.g.

Xe has 12 valence P has 10 valence S has 12 valence

electrons electrons electrons
 Exceptions to Octet Rule
3. Molecules with odd number of electrons:

• In most stable molecules, the number of electrons is even

and complete pairing of electrons occurs.
• However, a small number of molecules and ions contain an
odd number of valence electrons. Usually the central atom is
from an odd-numbered group, such as N & Cl.
• Molecules and ions with an unpaired electron are known as
free radicals.
• E.g.

N has 7 valence Cl has 7 valence

electrons electrons
 Polarity of bonds & molecules
• Polarity is a separation of electric charge leading to a molecule
or its chemical groups having an electric dipole moment, with a
negatively charged end and a positively charged end.

➢ Dipole moment is a measure of the separation of positive &

negative electrical charges within a system.

• Polarity results from the uneven partial charge distribution

between various atoms in a molecule.

• Bond or the molecular polarities depend upon the

electronegativities of the atoms or the molecules.
 Bond polarity
• Diatomic molecules of elements, such as
hydrogen, oxygen, nitrogen & halogens,
consist of two identical atoms covalently
bonded together.
• The bonding electrons are symmetrically
arranged around the two nuclei and are
attracted equally to both nuclei.
• The two atoms have the same
electronegativity values.
• This type of bond is called a non-polar
bond.
• When two different atoms with
different electronegativity values
form a covalent bond, the shared pairs
of bonding electrons will be attracted
more strongly by the more
electronegative element.
• This results in an asymmetrical
distribution of the bonding electrons.
• This type of bond is called polar bond.
 Polar covalent bond
Atom A Big Atom B
https://www.youtube.com/w Weak pull electronegativity Strong pull
atch?v=09Vx5VHiMHA&t=12s difference

• A highly electronegative element will hold

strongly to its own electrons and also attract
those in atoms to which it is bonded.

• If the electron pair in a bond is not evenly

shared, a charge separation occurs.
Partial Partial
positive negative • The measure of the separation of charge is
charge charge
called a dipole moment and the overall
distortion of charge referred to as
Dipole moment polarisation.

• The bond is said to be polar.

 Polar covalent bond
https://www.youtube.com/ *Electronegativity values are given in Chemistry data booklet p8
watch?v=XwIv85gGDhM

(a) water molecule

Electronegativity of an element is a measure

of the ability of its atom to attract electrons in
(b) hydrogen chloride molecule a covalent bond.
 Deducing the polar nature
https://www.youtube.com
of a covalent bond
/watch?v=s1f7DzYF0jI
• The difference in electronegativity values
between two non-metallic atoms in a covalent
bond
➢ gives an approximate indication of the
polar nature of the covalent bond.

• The greater the difference in electronegativity,

the greater the polar nature of the covalent
bond.

• For example, the H–F bond is very polar since

the difference in the two electronegativity
values is 1.8.

• CO bond will be less polar because the

difference in electronegativity values is 1.0.
 Bonding continuum

Misconception:
• Compounds are either ionic (complete electron
https://www.youtube.com/
transfer) or completely covalent (sharing of
watch?v=PoQjsnQmxok electron pairs).
• Pure covalent bonding & ionic bonding can be considered as being at
opposite ends of a bonding continuum with polar covalent bonding
lying between these two extremes.
• Thus, there are 1) covalent bonds with ionic character
2) ionic bonds with covalent character
Ionic character in covalent
bonds
• Charge separation (polarity) in a covalent
molecule gives the molecule some ionic
character.

• E.g. compare the boiling points of water (100 oC)

and tetrachloromethane (77 oC).
➢ water molecules are polar while
tetrachloromethane molecules are non-
polar.
➢ The ionic character of the covalent bonds in
water molecule results in a higher than
expected boiling point.

The greater the polarity in a covalent

molecule (greater difference in
electronegativity of the atoms), the greater
the ionic character.
 Covalent character in ionic
bonds
• In an ionic compound, the positive ion may attract
the negative ion so strongly that it distorts
(polarises) its electron cloud.

➢ the electron density between the 2 ions is

increased.
➢ This strengthens the bond and gives it a degree
of covalent character.

• The polarizing power of the cation affects the

degree of covalent character.

➢ The greater the polarizing power of the cation,

the greater the covalent character.
 Covalent character in ionic
bonds
• The polarizing power of the cation is dependent on its charge
density:
➢ Small cation, high charge → highly polarizing

• The covalent character in an ionic bond can also be affected by the

charge density of the anion:
➢ Large anion, low charge → highly polarizable
 Polarization of electron
cloud of anion
Increasing in
polarization
https://www.youtube.com/
watch?v=b0AlDNvfR3w

Al3+ ion has

high charge
density

AlCl3 is a covalent compound

although Al is a metal bonded to Cl,
a non-metal.
→ Highly charged Al3+ ion polarized
the electron cloud of Cl- ion until it is
at the centre like a covalent bond.
Polarization of electron
cloud of anion
 Bonding continuum
https://www.youtube.com/
watch?v=Ur1IAHMB4Uw

The difference in electronegativity (ΔEN) of two elements can be used

to predict what kind of bond you expect.

If the difference in electronegativity between 2 atoms is

• > 2, the bonding is ionic
• Between 0 & 0.4, the bonding is covalent (equal sharing)
• Between 0.5 & 2, the bonding is polar covalent (unequal sharing)
Bonding continuum
 Summary

https://www.youtube.com/watch
?v=PVL24HAesnc&t=52s
 Deducing the polar nature
of a covalent molecule
• Are the following molecules polar in nature?

1. carbon dioxide (CO2) 2. trichloromethane (CHCl3)

polar

non-polar
https://www.youtube.com/
watch?v=VU0l_v1Ai-E

3. boron trifluoride (BF3) 4. tetrachloromethane (CCl4)

non-polar non-polar

https://www.youtube.com/
watch?v=gyRczfT-gFE
 Deducing the polar nature
of a covalent molecule
What are the factors for a molecule to be polar?
1. polar bonds
• the larger the difference in electronegativity,
the more polar the bond

2. a net dipole moment

• dipole moments do not cancel out due to the
geometry (shape) of the molecule.

symmetrical asymmetrical
molecule molecule
 Molecular shapes & Polarity
https://www.youtube.com/ • Polarity of a molecule containing >2 atoms
watch?v=K0BZT4U4vUE depends on
1. polarities of the bonds &
2. shape of the molecule
➢ net dipole moment

• A polar molecule has a partial positive end & partial

negative end →uneven distribution of electrons in
the molecule.

• Although both CO2 & HCN are linear in

shape, CO2 is non-polar but HCN is polar.
➢ CO2 – does not have a net dipole moment
➢ HCN – has a net dipole moment
 Polar bond vs Polar molecule
https://www.youtube.com
/watch?v=72CQe-_PJU4

• Not every molecule with a polar

bond is polar itself.

• If the polar bonds in the molecule

cancel out then the molecule is
terminal overall non-polar.
atoms are
different or • Polar molecule:
molecule ✓ contains polar bond(s)
has lone ✓ asymmetrical shape
pair(s) of ✓ has net dipole moment
electrons
• Non-polar molecule:
✓ may or may not contain
polar bonds
✓ symmetrical shape if
contain polar bonds
✓ no net dipole moment
Deducing the polar nature
of a covalent bond
Deducing the polar nature
of a covalent molecule