14.
1 Further aspects of covalent bonding
Higher level
and structure (PTO)
OBJECTIVES
• Covalent bonds result from the overlap of atomic orbitals. A sigma bond (σ) is
formed by the direct head-on/end-to-end overlap of atomic orbitals, resulting
in electron density concentrated between the nuclei of the bonding atoms. A pi
bond (π) is formed by the sideways overlap of atomic orbitals, resulting in
electron density above and below the plane of the nuclei of the bonding atoms.
• Formal charge (FC) can be used to decide which Lewis (electron dot) structure
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is preferred from several. The FC is the charge an atom would have if all atoms
in the molecule had the same electronegativity. FC = (Number of valence
electrons)-½(Number of bonding electrons)-(Number of non-bonding
electrons). The Lewis (electron dot) structure with the atoms having FC values
closest to zero is preferred.
• Exceptions to the octet rule include some species having incomplete octets
and expanded octets.
• Delocalization involves electrons that are shared by/between all atoms in a
molecule or ion as opposed to being localized between a pair of atoms.
14.1 Further aspects of covalent bonding
Higher level
and structure (cont...)
OBJECTIVES
• Resonance involves using two or more Lewis (electron dot) structures to
represent a particular molecule or ion. 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.
• Prediction whether sigma (σ) or pi (π) bonds are formed from the linear
combination of atomic orbitals.
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• Deduction of the Lewis (electron dot) structures of molecules and ions
showing all valence electrons for up to six electron pairs on each atom.
• Application of FC to ascertain which Lewis (electron dot) structure is preferred
from different Lewis (electron dot) structures.
• Deduction using VSEPR theory of the electron domain geometry and
molecular geometry with five and six electron domains and associated bond
angles.
• Explanation of the wavelength of light required to dissociate oxygen and
ozone.
• Description of the mechanism of the catalysis of ozone depletion when
catalysed by CFCs and NOx.
Higher level
Formal charge (FC)
Formal charge (FC) is:
FC = valence – ½ bonding – non-bonding
electrons electrons electrons
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To determine the most favoured Lewis structure we
chose:
1. The structure with a FC closest to zero
2. The structure with the negative FC on the most
electronegative atom
Problem 1: Determine the FC on the following
Higher level
compound:
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= valence electrons – ½ bonding electrons -
non-bonding electrons
FC(N) = 5 - ½ x 6 - 2 = 0
FC(C) = 4 - ½ x 8 - 0 = 0
FC(S) = 6 - ½ x 2 - 6 = -1
Higher level
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The electronegativity of N is 3.0 and S is 2.5, so
the negative FC is best suited to N.
Therefore the bottom structure is correct.
Higher level
Problem 2: Determine which is the preferred
structure.
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Higher level
FC(B) = 3 – 1/2x6 – 0 = 0 FC(B) = 3 – ½ x8 – 0 = -1
FC(F) FC(F single bond)
= 7 – ½ 2 x -6 = 0
=7–½x2–6=0
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= 7 – ½ 4 x -4 = +1
The first structure has the most atoms on zero
FC, so is the correct structure.
Higher level
VSEPR with expanded shells
Elements in the third period (Al to Ar) and below
can promote an electron to have more than 4
electron domains. This is called an expanded
octet.
eg. P = [Ne] 3s13p33d1 making PCl5
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5 electron domains: non-bonding electrons in the
equitorial positions of a trigonal bipyramidal
shape
6 electron domains: non-bonding electrons in the
axial positions of a octahedron or square
bipyramidal.
Higher level
Trigonal Bipyramidal Electron Domain
• There are two distinct
positions in this
geometry:
– Axial
– Equatorial
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Non-bonding electron pairs
fill the equatorial bonds
first because they are only
repelled by 2 bonds (axial).
Axial bonds are repelled
by 3 bonds (equatorial).
Higher level
Trigonal Bipyramidal Electron Domain
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Don’t forget non-bonding electron pairs distort
the angles!
Trigonal Bipyramidal Electron Domain
Higher level
There are four
distinct
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molecular
geometries in
this domain:
Trigonal
bipyramidal,
Seesaw, T-
shaped, Linear
Octahedral Electron Domain
Higher level
All positions are
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equivalent in the
octahedral domain.
There are three
molecular geometries:
Octahedral, Square
pyramidal, Square
planar
Overlapping orbitals (s and p)
Higher level
• s (sigma) bonds result from the axial overlap of
orbitals
• p (pi) bonds result from the sideways overlap of
parallel p orbitals
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• double bonds form by one s (sigma) and one p (pi)
bond
• triple bonds form by one s (sigma) and two p (pi)
bonds
σ bonds
Higher level
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• Sigma bonds (σ) are characterized by
– Head-to-head overlap.
– Cylindrical symmetry of electron density
about the internuclear axis.
π bonds
Higher level
• Pi bonds (π) are
characterized by
– Side-to-side
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overlap.
– Electron density
above and below
the internuclear
axis.
Single bonds are always s bonds, because s overlap
Higher level
is greater, resulting in a stronger bond and more
energy lowering.
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In a multiple bond one of the bonds is a s bond and
the rest are p bonds.
Higher level
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• Note the weakness of the extra bond –
the electron overlap is weaker, yet it is
still an extra bond so the energy required
to break them is still a bit stronger.
• Note the smaller bond lengths have
greater bond dissociation enthalpies.
Higher level
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CASE STUDY CONTINUED
OZONE
Resonance and bond order
Higher level
Bond order is the measurement of the number of
electrons involved in bonds between two atoms in a
molecule. If the bond order is 0 then there is no
bonding.
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Bond order =
Problem 1: Determine the bonding order of ozone.
Bond order = 3/2 = 1.5
Problem 2: Determine bond order
Higher level
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Bond order =
=
Importance of ozone
Higher level
Ozone at ground level reacts with chemicals to form smog, harms
respiratory systems and degrades materials (eg. rubber).
Ozone at atmospheric levels is
essential for life.
1. It absorbs harmful UV
radiation (which causes
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cancer and inhibition of
photosynthesis).
2. Exothermic reactions cause a
temperature inversion in the
stratosphere – this warm
layer prevent convection
keeping the layers of Earth’s
atmosphere stable.
Ozone formation review
Higher level
Review: O2 requires photons with more energy
as O3 only has the energy of a 1 ½ bond.
O2(g) + UV (λ<242nm) O•(g) + O•(g)
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O3(g) + UV (λ<330nm) O2(g) + O•(g)
Bond angle <120⁰
~ 117⁰
UV and O2/O3 bond calculations
Higher level
Equations:
Ephoton = hf
E = energy in one photon (J)
h = planks constant (6.63x10-34Js)
f = frequency (Hz)
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v = fλ
v = velocity = c = speed of light = (3.00 x 108 m/s)
λ = wavelength (nm)
Problem 1: The bond energy in ozone is 363kJ/mol.
Higher level
Calculated the wavelength of UV radiation needed to
break this bond.
Ephoton = 363 000J/mol / 6.02x1023photons/mol
= 6.03x10-19J per photon
Ephoton = hf so
f = Ephoton / h
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= 6.03x10-19J / 6.63x10-34Js
= 9.09 x 1014s
v = fλ so
λ = v/f = 3.00 x 108 m/s / 9.09 x 1014s
= 3.30 x 10-7m
= 330nm
Ozone formation
Higher level
UV light breaks the bonds in oxygen to create free
radicals (atoms/molecules with unpaired valence
electrons and so highly reactive): • is the symbol to
denote a radical.
O• actually has 6
O2(g) + UV (λ<242nm) O•(g) + O•(g) electrons in the
valence shell (not
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This then undergoes an exothermic reaction:
O•(g) + O2(g) O3(g)
Ozone depletion
Higher level
The reverse also occurs creating an O3 cycle.
Depletion is also exothermic.
O3(g) + UV (λ<330nm) O2(g) + O•(g)
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O3(g) + O•(g) 2O2(g)
Higher level
Ozone destroying chemicals
1. CFCs – chloroflourocarbons, catalyze the
breakdown of ozone
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2. NOx – also catalyze the breakdown of ozone
These compounds are free radicals (not complete
octets) and hence are highly reactive.
Catalytic ozone destruction
Higher level
The balance of the ozone cycle is disrupted by the
depletion of ozone from: Nitrogen monoxide free radical
(unpaired valence electrons)
1. nitrogen oxides:
NO•(g) + O3(g) NO2•(g) + O2(g) Nitrogen dioxide free radical
(unpaired valence electrons)
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NO2•(g) + O•(g) NO•(g) + O2(g)
Nitrogen oxides slowly diffuse their way from the
troposphere. Aircraft fly in the lower stratosphere causing
direct injection of NOx. NO can last from 22 to 111 years
before breaking down.
Catalytic ozone destruction
Higher level
2. chlorofluorocarbons (CFCs):
CCl2F2(g) CClF2•(g) + Cl•(g) by UV radiation
Cl•(g) + O3(g) O2(g) + ClO•(g)
ClO•(g) + O•(g) O2(g) + Cl•(g)
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ClO•(g) + O3 (g) 2O2(g) + Cl•(g)
As with NO, the Cl free radical catalyzes the decomposition
reaction thousands of times:
Summary: O3(g) + O•(g) 2O2(g)
14.2 Hybridization
Higher level
OBJECTIVES
• A hybrid orbital results from the mixing of different types of
atomic orbitals on the same atom.
• Explanation of the formation of sp3, sp2 and sp hybrid orbitals
in methane, ethene and ethyne.
• Identification and explanation of the relationships between
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Lewis (electron dot) structures, electron domains, molecular
geometries and types of hybridization.
14.2 Hybridization
Higher level
OBJECTIVES
• A hybrid orbital results from the mixing of different types of
atomic orbitals on the same atom.
• Explanation of the formation of sp3, sp2 and sp hybrid orbitals
in methane, ethene and ethyne.
• Identification and explanation of the relationships between
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Lewis (electron dot) structures, electron domains, molecular
geometries and types of hybridization.
Higher level
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It’s hard to imagine tetrahedral, trigonal bipyramidal,
and other geometries arising from the atomic orbitals
we recognize.
Orbital hybridization
Higher level
Hybridization is the mixing of different types of orbitals to
produce new types of orbitals. It is a mathematical
procedure.
The most common hybrid orbitals are combinations of s and
p orbitals that then form sigma bonds.
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(The number of orbitals mixed equals the number of hybrid
orbitals produced. Not all orbitals in a level are hybridized.
Count the number of sigma bonds to determine the number
of hybridized orbitals.)
Orbital hybridization
Higher level
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Two sp orbitals
Higher level
In triple bonds, as
in acetylene, two sp
orbitals form a s
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bond between the
carbons, and two
pairs of p orbitals
overlap to form the
two p bonds.
Three sp2 orbitals
Higher level
• In a molecule like
formaldehyde (shown
at left) an sp2 orbital
on carbon overlaps to
form a s bond with
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the corresponding
orbital on the oxygen.
• The unhybridized p
orbitals overlap in p
fashion.
Four sp3 orbitals
Higher level
• In a molecule like
methane (shown at
left) the sp3 orbitals
on carbon overlap to
form a s bond with
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the corresponding
orbitals on hydrogen.
Bonding in CO2
Higher level
• Pi bonds form from overlapping p orbitals
• C and O form hybrid orbitals to make the sigma bond
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BeF2 Hybridization – orbital diagrams
Higher level
• Consider beryllium:
– In its ground electronic
state, it would not be able
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to form bonds because it
has no singly-occupied
orbitals.
BeF2 Hybridization – orbital diagrams
Higher level
But if it absorbs the small
amount of energy
needed to promote an
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electron from the 2s to
the 2p orbital, it can
form two bonds.
σ bond π bond
BeF2 Hybridization
Higher level
• Mixing the s and p orbitals yields two degenerate
orbitals that are hybrids of the two orbitals.
– These sp hybrid orbitals have two lobes like a p orbital.
– One of the lobes is larger and more rounded as is the s
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orbital.
BeF2 Hybridization
Higher level
• These two degenerate orbitals would align themselves
180 from each other.
• This is consistent with the observed geometry of
beryllium compounds: linear.
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BeF2 Hybridization – orbital diagrams
Higher level
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bond
σ
bond
• With hybrid orbitals the orbital diagram for
beryllium would look like this.
• The sp orbitals are higher in energy than the
1s orbital but lower than the 2p.
BF3 Hybridization – orbital diagrams
Higher level
Using a similar model for boron leads to…
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σ σ σ
bond bond bond
BF3 Hybridization
Higher level
…three
degenerate
sp2 orbitals.
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CH4 Hybridization – orbital diagrams
Higher level
With carbon we get…
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σ σ σ σ
bond bond bond bond
CH4 Hybridization
Higher level
• …four degenerate
sp3 orbitals.
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Higher level
CHN Hybridization – animation
H C N
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C N
Higher level
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C N
Higher level
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C N
Higher level
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C N
Higher level
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H C N
Higher level
Hybridization of nitrogen in ammonia
Hybrid energy state
Lone 3σ
pair bonds
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•Number of electron
domains will tell you
what hybidization
there is.
•4 electron domains,
therefore 4 sp3
hybyridization
Higher level
Hybridization of oxygen in CO2
•Number of electron
domains will tell you
what hybidization
there is.
• Pi bonds form from
normal p orbitals
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π bond
Hybrid energy state
Lone Lone σ
pair pair bond
Problem 1: Analyse the SO42- molecule.
Higher level
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