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Topic 4 Bonding
Higher level
4.1 Ionic bonding and structure
OBJECTIVES
Loses 1
Na electron Na
Cl Gains 1 electron
(from sodium) Cl
nitrate NO3-
phosphate PO43-
hydroxide OH-
ammonium ion NH4+
sulfate SO42-
hydrogen carbonate HCO3-
carbonate CO32-
Describing the lattice structure
• Example: Small sodium chloride ionic lattice
Describing the lattice structure
• Endlessly repeating lattice of ions…depends on the
size of the crystal lattice...although arrangement of
ions stays the same
• The coordination number is (6,6) meaning each Na+
is surround by 6 Cl-, each Cl- is surrounded by 6 Na+.
4.2. Covalent bonding
OBJECTIVES
Bonding spectrum
A B A B +
A B
-
Increasing DEN
< <
Bonds strengths
A strong attraction between two nuclei for the electrons
creates a short bond length. Therefore short bond lengths
have high bond dissociation enthalpy.
Type of Ionic Covalent Metallic
bonding
Nature of Electrostatic attraction Electrostatic Electrostatic attraction
bonding between positive and attraction of a between lattice of positive
negative ions. shared pair of metal ions and delocalised
electrons between outer shell electrons.
atoms.
Strength of The smaller the ions The shorter the The smaller the metal ions, the
bonds and the greater the bond, the stronger greater the charge on the ions,
charge on the ions, the the bond (usually). and the more delocalised outer
stronger the attraction Double bonds are shell electrons there are, the
between the ions stronger than single stronger the attraction between
(usually). This is due to bonds, while triple the ions and electrons
a greater charge bonds are stronger (usually). This is due to a
density within the than double bonds. greater charge density within
structure. the structure.
4.3 Covalent structures
OBJECTIVES
• Lewis (electron dot) structures show all the valence electrons in a covalently bonded
species.
• The “octet rule” refers to the tendency of atoms to gain a valence shell with a total of 8
electrons.
• Some atoms, like Be and B, might form stable compounds with incomplete octets of
electrons.
• Resonance structures occur when there is more than one possible position for a
double bond in a molecule.
• Shapes of species are determined by the repulsion of electron pairs according to
VSEPR theory.
• Carbon and silicon form giant covalent/network covalent structures.
• Deduction of Lewis (electron dot) structure of molecules and ions showing all valence
electrons for up to four electron pairs on each atom.
• The use of VSEPR theory to predict the electron domain geometry and the molecular
geometry for species with two, three and four electron domains.
• Prediction of bond angles from molecular geometry and presence of non-bonding
pairs of electrons.
• Prediction of molecular polarity from bond polarity and molecular geometry.
• Deduction of resonance structures, examples include but are not limited to C6H6, CO32-
and O3 .
• Explanation of the properties of giant covalent
LEWIS STRUCTURES
Covalent Bonding – Lewis structures
• Lewis structures are representations of molecules
showing all electrons, bonding and nonbonding.
• Each bond contains 2 electrons.
• Elements pair up according to the octet rule – elements
gain or lose electrons in order to have the electron
configuration of a noble gas.
Cl2
How to draw Lewis structures
deductively
1. Draw out the atoms with the least occurring atom as
the central atom (if applicable).
Compounds that break the octet rule are often toxic and dangerous, ready to
react so the octet rule is obeyed!
O2 N2
CO2 HCN
O C O
C2H4 (ethene) C2H2 (ethyne)
CO NH4+
Draw this one now
or
BOND BOND
PAIRS SHAPE ANGLE(S) EXAMPLE
BOND PAIR - BOND PAIR < LONE PAIR - BOND PAIR < LONE PAIR - LONE PAIR
O O O
H C H
C H
Carbon - has four electrons to pair up Four covalent bonds are formed
Hydrogen - 1 electron to complete shell C and H now have complete shells
BOND PAIRS 4
H
LONE PAIRS 0
109.5°
C H
BOND ANGLE... 109.5°
H
H
SHAPE... TETRAHEDRAL
Ammonia NH3
H
BOND PAIRS 3
N H H N H LONE PAIRS 1
TOTAL PAIRS 4
• The shape is based on a tetrahedron but not all the repulsions are the same
• LP-BP REPULSIONS > BP-BP REPULSIONS
• The N-H bonds are pushed closer together
• Lone pairs are not included in the shape
N
H
107°
H
N N H
H H
H H ANGLE... 107°
H H
SHAPE... PYRAMIDAL
Ammonia NH3
H
BOND PAIRS 3
N H H N H LONE PAIRS 1
TOTAL PAIRS 4
Water H2O
H
BOND PAIRS 2
O H H O LONE PAIRS 2
TOTAL PAIRS 4
• The shape is based on a tetrahedron but not all the repulsions are the same
• LP-LP REPULSIONS > LP-BP REPULSIONS > BP-BP REPULSIONS
• The O-H bonds are pushed even closer together
• Lone pairs are not included in the shape
104.5°
H
O O H
H H ANGLE... 104.5°
H H
SHAPE... ANGULAR
Ammonium NH4+
NH4+
N+
BOND PAIRS 4
LONE PAIRS 0
TETRADHEDRAL H
H-N-H 109.5°
H N+ H
H
Hydronium ion H3O+
Bromine triflouride BrF3
F
F
BOND PAIRS 3
LONE PAIRS 2
F ’T’ SHAPED
Br F Br
ANGLE <90°
F F
Sulphur dioxide SO2
S has 2 bonded atoms , 1 lone pair (electron cloud),
120°, bent, V-shaped
.. .. ..
:O:: S:O: S
..
O O
Ethane C2H3, Ethene C2H4, Ethyne C2H2
Carbon dioxide CO2
The shape of a compound with a double bond is calculated in the same way.
A double bond repels other bonds as if it was single e.g. carbon dioxide
C O O C O
Carbon - needs four electrons to complete its shell The atoms share two electrons
Oxygen - needs two electron to complete its shell each to form two double bonds
RESONANCE STRUCTURES
Resonance
When a Lewis structure allows for the same arrangement of
atoms but a different but equally valid arrangement of
electrons, resonance occurs eg. Ozone, O3
The resonance hybrid is actually the dotted line below.
Properties:
– Electrical conductivity
– Stronger covalent bonds,
therefore stronger
materials
QUART
SILICON STRUCTURES
Silicon dioxide (SiO2)
• SiO2
repeating
unit as every
oxygen links
in with a
second Si
atom
• Structurally
think
tetrahedral,
SiO4
Difference between Si and C
(diamond)
• Si is larger than C so the Si-O bond length is
greater
• The greater the bond length, the lower the
bond enthalpy (energy) is
• This means it is easier to break
• Therefore Si is more reactive than C (diamond)
4.4 Intermolecular forces
OBJECTIVES
Hydrogen bond
DECREASING STRENGTH
Variation - - The more positive The more polar The more More
of the nucleus the the better polar the electrons
strength better better the better
within The more
group electrons the
better
Example Diamond NaCl Cu H2O SO2 O2
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
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.
• 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
Higher level
There are four
distinct
molecular
geometries in
this domain:
Trigonal
bipyramidal,
Seesaw, T-
shaped, Linear
Octahedral Electron Domain
Higher level
All positions are
equivalent in the
octahedral domain.
There are three
molecular geometries:
Octahedral, Square
pyramidal, Square
planar
Overlapping orbitals (s and )
Higher level
• s (sigma) bonds result from the axial overlap of
orbitals
Higher level
• 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
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.
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.
Higher level
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑝𝑎𝑖𝑟𝑠
Bond order =
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛𝑠
4
=
3
Importance of ozone
Higher level
Ozone at ground level reacts with chemicals to form smog, harms
respiratory systems and degrades materials (eg. rubber).
Higher level
Review: O2 requires photons with more energy
as O3 only has the energy of a 1 ½ bond.
Higher level
Equations:
Ephoton = hf
E = energy in one photon (J)
h = planks constant (6.63x10-34Js)
f = frequency (Hz)
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
= 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
one).
This then undergoes an exothermic reaction:
Higher level
The reverse also occurs creating an O3 cycle.
Depletion is also exothermic.
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:
Higher level
2. chlorofluorocarbons (CFCs):
Higher level
OBJECTIVES
Higher level
OBJECTIVES
Higher level
Hybridization is the mixing of different types of orbitals to
produce new types of orbitals. It is a mathematical
procedure.
Higher level
Two sp orbitals
Higher level
In triple bonds, as
in acetylene, two sp
orbitals form a s
bond between the
carbons, and two
pairs of p orbitals
overlap to form the
two 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
the corresponding
orbital on the oxygen.
• The unhybridized p
orbitals overlap in
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
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
Higher level
BeF2 Hybridization – orbital diagrams
• Consider beryllium:
– In its ground electronic
state, it would not be able
to form bonds because it
has no singly-occupied
orbitals.
Higher level
BeF2 Hybridization – orbital diagrams
σ bond π bond
Higher level
BeF2 Hybridization
σ σ
bond bond
σ σ σ
bond bond bond
Higher level
BF3 Hybridization
…three
degenerate
sp2 orbitals.
Higher level
CH4 Hybridization – orbital diagrams
With carbon we get…
σ σ σ σ
bond bond bond bond
CH4 Hybridization
Higher level
• …four degenerate
sp3 orbitals.
Higher level
CHN Hybridization – animation
H C N
C N
C
N
Higher level
C
N
Higher level
C
N
Higher level
H
C
N
Higher level
Higher level
Hybridization of nitrogen in ammonia
Lone 3σ
pair bonds
•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
π bond
Hybrid energy state
Lone Lone σ
pair pair bond
Problem 1: Analyse the SO42- molecule.
Higher level