TOPIC 14: CHEMICAL

BONDING AND STRUCTURE

HL
HL Formal
Charge

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 Warm-Up
Pair Share
When we can draw more than one Lewis Dot structure for a compound, how do
we know which one is correct?

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 Sulfur Dioxide
• Let’s take a look at SO2, sulfur dioxide. Knowing that sulfur can sometimes
expand its octet, we can draw the Lewis Dot structure two ways:

Way 1

Way 2

Which one is correct?

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 Formal Charge
• Formal charge is used to help us determine which structure is most stable
• Formal charge treats each covalent bond as an equal electron distribution
with each atom “owning” 1 of the electrons in the bond.
• Each atom also “owns” every electron that is in a lone pair around it
• When calculating formal charge we count how many electrons each atom
“owns” and compare that to the original number of valence electrons it
started with; it is generally more favorable if those numbers are the same!

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 Calculating Formal Charge
• The number of valence electrons (V) is determined from the element’s group in
the Periodic Table.
• The number of electrons assigned to an atom in the Lewis (electron dot)
structure is calculated by assuming that:
o (a) each atom has an equal share of a bonding electron pair (one electron per atom), even if it is a coordinate
bond (1⁄2B);
o (b) an atom owns its lone pairs completely (L).

• This means that the number of electrons assigned = 1⁄2 number of electrons in
bonded pairs (1⁄2B) + number of electrons in lone pairs (L)
• So overall:
FC = V – (1⁄2B + L)

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Looking Back at SO2

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 SO2
• We can conclude that structure (ii) where all atoms have a formal charge of
zero is the most stable structure for SO2.

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 Let’s Practice
• Use the concept of formal charge to determine which of the following Lewis
(electron dot) structures for XeO3 is preferred?

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 Other Considerations
• In addition to formal charge, when looking at compounds
where multiple Lewis Dot structures can be drawn, we
should also look at electronegativity
• So, a useful guideline to follow is that the most stable of
several Lewis (electron dot) structures is the structure that
has:
• the lowest formal charges and
• negative values for formal charge on the more
electronegative atoms.
• Which is the correct structure here?

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 Let’s Practice
39 Use the concept of formal charge to explain why BF3 is an exception to the
octet rule.
40 Draw two different Lewis (electron dot) structures for SO42–, one of which
obeys the octet rule for all its atoms, the other which has an octet for S
expanded to 12 electrons. Use formal charges to determine which is the
preferred structure.

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Answers

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Sigma and Pi
Bonds

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 Molecular Orbitals
• When atoms covalently bond together, the s and p electron orbitals actually
change and hybridize in order to form molecular or bonding orbitals
• The molecular orbital is formed from one electron from each atom
overlapping and combining in an orbital with lower energy than the two
atomic orbitals where they started out

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 Sigma Bonds
• When two atomic orbitals overlap along the bond axis – an imaginary line
between the two nuclei – the bond is described as a sigma bond, denoted
using the Greek letter σ.
• This type of bond forms by the overlap of s orbitals, p orbitals, and hybrid
orbitals (to be described in the next section) in different combinations.
• It is always the bond that forms in a single covalent bond!!!

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Sigma Bond Picture

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Sigma Bonds
• s orbital
overlap

• p orbital
overlap

• s and p
overlap
 Sigma Bonds (σ) bond
• All single bonds are sigma
• In order to be a sigma bond, the bond must overlap
along the bond axis.
 Pi Bonds
• When two p orbitals overlap sideways, the electron density of the molecular
orbital is concentrated in two regions, above and below the plane of the
bond axis.
• This is known as a pi bond, denoted using the Greek letter π.
• This type of bond only forms by the overlap of p orbitals alongside the
formation of a sigma bond.
• In other words, pi bonds only form within a double bond or a triple bond.

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Pi Bond Picture

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 pi (π) bond
• Two p orbitals overlap sideways
• Electron density becomes concentrated in two regions. Where?
 pi (π) bond
• Pi bonds can only form alongside formation of a sigma bond.
• Pi bonds therefore only form within a double or triple bond.
▶ Linear combination of atomic orbitals.

Single Covalent Bond 1 sigma bond

Double Covalent Bond 1 sigma, 1 pi bond
Triple Covalent Bond 1 sigma, 2 pi bonds
 Pi Bonds vs. Sigma Bonds
• Pi bonds are weaker than sigma bonds, as their electron density is further from
the nucleus.
▶ Delocalization involves electrons that are shared by/between more than
pair in a molecule or ion as opposed to being localized between a pair o
atoms.
▶ A resonance structure is one of two or more
alternative Lewis (electron dot) structures for a
molecule or ion that cannot be described fully with
one Lewis (electron dot) structure alone.

▶ Delocalization makes species more stable by

spreading out the electron charge making it less
attractive to positive attackers (electrophiles)
▶ It is the stability of benzene that makes it such a serious
carcinogen
 = total number of bonding pairs
total number of resonance structures

3/2 =
1.5 bond order

4/3 =
1.33 bond order
▶ Ozone and oxygen play an important role in
protecting the surface of the Earth from damaging
effects of ultraviolet radiation
▶ UV radiation is absorbed by molecules or O2 or O3 as
they dissociate
▶ The highest energy UV radiation is absorbed by O2
14.2 Hybridization
 ▶ A hybrid orbital results from the mixing of different types of
atomic orbitals on the same atom.

▶ Hybridization in which s and p orbitals merge together to

create new atomic orbitals

▶ We need to know about three types of hybridization:

▶ sp3
▶ sp2
▶ sp
▶ One ‘s’ orbital combines with
three ‘p’ orbitals to create four
‘sp3’ orbitals

▶ The sp3 orbitals are arranged

tetrahedrally

▶ Most atoms with tetrahedral

geometry will be sp3
hybridized
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▶ One ‘s’ orbital combines with
two ‘p’ orbitals to create three
‘sp2’ orbitals, leaving one ‘p’
orbital untouched

▶ The sp2 orbitals have a trigonal

planar arrangement

▶ Most atoms with trigonal

planar geometry will be sp2
hybridized
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▶ One ‘s’ orbital combines with
one ‘p’ orbital to create two ‘sp’
orbitals and leaving two ‘p’
orbitals untouched

▶ The sp orbitals have a linear

arrangement

▶ Most atoms with linear

geometry will be sp hybridized
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 Let’s Practice
• Urea (see below) is present in solution in animal urine. What is the hybridization
of C and N in the molecule, and what are the approximate bond angles?

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