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5 Chemical

bonding and
molecular
structure
5.1 Fundamentals of
bonding
• There are three types of interactions within a
molecule:
– Electrons and nuclei attract one another
– Electrons repel each other
– Nuclei repel each other A
• In any molecule, these three interactions are
balanced to give the molecule its greatest
possible stability
5.1 Fundamentals of
bonding
• This balance is achieved when the
electron density is situated between
the nuclei of bonded atoms
• This shared electron density is called
a covalent bond
• The attractive energy between nuclei
and electrons exceeds the repulsive
energy arising from nuclei-nuclei and
electron-electron interactions
5.1 Fundamentals of
bonding
• The hydrogen molecule
– These concepts are demonstrated below for
the simplest stable neutral molecule,
molecular hydrogen
5.1 Fundamentals of
bonding
• Bond length and bond energy
5.1 Fundamentals of
bonding
– Bond length is the separation distance at
which the molecule has the maximum
energetic advantage over the separated
atoms
– Bond energy is the energy required to
break the bond (kJ mol-1)
– Bond energy is always positive
– Each different chemical bond has a
characteristic bond length and energy
5.1 Fundamentals of
bonding
• Other diatomic molecule: F2
– Even when the atoms within a molecule contain
many electrons, bond formation is still
considered as the sharing of only two electrons
– The resulting bond is a sigma bond
5.1 Fundamentals of
bonding
• Unequal electron sharing
– In a chemical bond between any two
identical atoms, the nuclei share the
bonding electrons equally
– When it is two different atoms, unequal
attractive forces lead to an
unsymmetrical distribution of the bonding
electrons
– This results in a polar covalent bond
5.1 Fundamentals of
bonding
– Electronegativity gives a numerical value of
how strongly an atom attracts the electrons in
a chemical bond
5.2 Ionic bonding

• Compounds formed between elements


of very different electronegativities are
ionic in character
• Most ionic compounds are solids with
high melting points
• Ionic compounds are held together in
3D arrangements by the attractive
forces between oppositely charged ions
5.2 Ionic bonding
5.2 Ionic bonding

• The lattice energy of a compound is


dependent on the charges of the ions
5.3 Lewis structures

• The conventions
– Each atom is represented by its
elemental symbol
– Only the valence electrons appear in a
Lewis structure
– A line represents one pair of electrons
that is shared between two atoms
– Dots represent the nonbonding electrons
on that atom
5.3 Lewis structures
5.3 Lewis structures
– Procedure for drawing Lewis structures:
• Count the valence electrons
• Assemble the bonding framework using
single bonds
• Place three nonbonding pairs of electrons on
each outer atom except H
• Assign the remaining valence electrons to
inner atoms
• Minimise formal charges on all atoms
5.3 Lewis structures

• Building Lewis structures


– Lewis structures by themselves do not
imply any particular geometry for a
molecule or ion
– A set of four electrons associated with an
atom is often called an octet
– Larger atoms can accommodate more
than eight electrons, eg sulfur atom
– The nonbonding pairs are called lone
pairs
5.3 Lewis structures

• Resonance structures
– Are composites of equivalent Lewis structures
– They are connected by double-headed arrows
to emphasise that a complete depiction
requires all of them
5.3 Lewis structures
– Resonance structures differ only in the
position of the electrons, not atoms
– Resonance structures are not always
equivalent
– Resonance structures that are not
equivalent occur when electrons are
shifted between atoms of different
elements
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
• The VSEPR theory considers that
molecular shape is determined
primarily by the repulsions between
pairs of electrons in the molecule
• To minimise these repulsions,
electron pairs around an inner atom
within a molecule will be situated as
far apart as possible
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
• The procedure:
– Draw the Lewis structure of the molecule
– Count the number of sets of bonding pairs
and lone pairs of electrons
– Use the following table:
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
• Two sets of electron pairs: linear geometry
– Example: CO2
• Have two sets of electron pairs that need to be situated
as far away from each other as possible
• This is satisfied by placing the two sets in a linear
arrangement and results in a linear shape
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
• Three sets of electron pairs: trigonal
planar geometry
– Example: BF3
• Have three sets of electron pairs around an inner
atom
• In trigonal planar, the sets are oriented at 120° to
each other and are coplanar
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
• Four sets of electron pairs: tetrahedral
geometry
– Example: CH4
• Four sets of equivalent electron pairs
• The optimal geometry is tetrahedral, with H atoms
situated at the four vertices of a tetrahedron
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
– Example: NH3
• Total of four sets of electron pairs, three bonding
and one lone pair
• The single lone pair on the N atom takes up more
space than each of the three bonding pairs
• Adopts a trigonal pyramidal shape
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
– Example: H2O
• Four sets of electron pairs, two bonding and two
lone pairs
• The idealised tetrahedral geometry is significantly
distorted
• Water adopts a bent shape
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
• Five sets of electron pairs: trigonal
bipyramidal geometry
– Example: PCl5
• Five sets of equivalent electron pairs
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
• Six sets of electron pairs: octahedral
geometry
– Example: SF6
• Six sets of electron pairs around the S atom
• An octahedral geometry of the six sets places them
as far apart as possible
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
• All six positions around an octahedron are
equivalent
5.4 Valence shell electron
pair repulsion (VSEPR)
theory
5.5 Properties of
covalent bonds
• Dipole moments
– A molecule with asymmetrical distribution of
electron density is said to have a dipole
moment (μ)
5.5 Properties of
covalent bonds
– Dipole moments depend on bond polarities

– They also depend on molecular shape


5.5 Properties of
covalent bonds
• Bond length
– Bond length of a covalent bond is the nuclear
separation distance at which the molecule is
most stable
– At this distance, attractive interactions are
maximised relative to repulsive interactions
5.5
Properti
es of
covalent
bonds
5.5 Properties of
covalent bonds
5.5 Properties of covalent
bonds
• The following factors influence bond
length:
– The smaller the atoms, the shorter the
bond
– The more electrons in a bond, the
shorter the bond
– The larger the electronegativity
difference between the bonded atoms,
the shorter the bond
5.5 Properties of covalent
bonds
• Bond energy
– The amount of energy that must be
supplied to break a chemical bond
– Three consistent trends:
• Bond energies increase as more electrons are
shared between the atoms
• Bond energies increase at the electronegativity
difference between bonded atoms increases
• Bond energies decrease as bonds become
larger
Summary of
molecular
shapes
5.6 Valence bond theory
• Two ways to think about bonding:
– Valence bond theory
• Assumes that electrons are either localised
in bonds between two atoms or localised on
a single atom, usually in pairs
• Considers two types of orbitals
– Molecular orbital theory
• Uses delocalised bonds
• Requires a more complicated analysis, but
explains chemical properties that localised
bonds cannot
5.6 Valence bond theory

• Orbital overlap
– Bonding orbitals are created by
combining atomic orbitals
– Insert Figure 5.20, p178
5.6 Valence bond theory
– Orbital overlap occurs when two orbitals of the
same phase are superimposed and result in a
new orbital
5.6 Valence bond theory
• Conventions of the orbital overlap
model
– Each electron in a molecule is assigned
to a specific orbital
– No two electrons in a molecule have
identical descriptions
– The electrons in molecules obey the
aufbau principle
– Only the valence orbitals are needed to
describe bonding
5.6 Valence bond theory

• Hybridisation of atomic orbitals


– Hybrid orbitals are combinations of atomic
orbitals
– The process by which we combine them is
called hybridisation
– Example: methane
5.6 Valence bond theory
– Methane: sp3 hybrid orbitals
• The valence orbitals of interest are the one 2s and
three 2p orbitals
• These four atomic orbitals are ‘mixed’ to form four
new hybrid orbitals
5.6 Valence bond theory

• The total energy of the four atomic orbitals must equal the total
energy of the four hybrid orbitals
• The four sp3 orbitals position themselves so that their electrons
undergo the minimum repulsion
5.6 Valence bond theory

• sp3 hybridisation is not limited to C atoms. An atom


which exhibits a tetrahedral arrangement of
electron pairs can be considered to be sp3
hybridised
5.6 Valence bond theory
– sp2 hybrid orbitals
• Mixture of the 2s orbital and two 2p orbitals
5.6 Valence bond theory
• The three sp2 orbitals are coplanar
5.6 Valence bond theory
– sp hybrid orbitals
• Hybridisation of a 2s orbital with a 2p orbital
5.6 Valence bond theory
5.6 Valence bond theory

• Multiple bonds
– Bonding in ethene
• Charges can be minimised by forming a double
bond between the carbon atoms, leaving both
carbons with an octet of electrons
• The carbon atoms are sp2 hybridised
• Trigonal planar geometry
5.6 Valence bond theory
5.6 Valence bond theory

• The valence bond description of any


double bond can be constructed using
the following procedure:
– Determine the Lewis structure
– Use the Lewis structure to determine the
type of hybridisation
– Construct the σ bond framework
– Add the π bonds
5.6 Valence bond theory
– Bonding in ethyne
• The carbon atoms are joined by a triple bond
• sp hybrid orbitals describe the bonding
5.6 Valence bond theory

• Each triple bond has one C-C σ bond and two


C-C π bonds, which is always the case in any
alkyne
5.7 Molecular orbital theory:
diatomic molecules
• Molecular orbital theory can predict
and explain molecular properties
• Differs fundamentally from valence
bond theory
• Electrons within a molecule are not
localised, instead they occupy
molecular orbitals (MOs)
5.7 Molecular orbital theory:
diatomic molecules
• Molecular orbitals of H2 and He2
– The overlap of N atomic orbitals will
always lead to the formation of N
molecular orbitals
• In-phase overlap is constructive and results
in the formation of a molecular orbital with a
large amplitude
• Out-of-phase overlap is destructive and
gives a molecular orbital with zero amplitude
• The region of zero amplitude is called a node
5.7 Molecular orbital
theory: diatomic
molecules
5.7 Molecular orbital theory:
diatomic molecules
– Constructive overlap gives a bonding
molecular orbital
• Electron density is maximised between the
two nuclei
– Destructive overlap gives an antibonding
molecular orbital
• Electron density is minimised between the
two nuclei and is zero at the node
– Molecular orbital diagrams show the
relative energies of atomic and molecular
orbitals
5.7 Molecular orbital
theory: diatomic
molecules
• The bonding
orbital is of lower
energy than the
orbitals from which
it was formed
• The antibonding
orbital is of higher
energy
5.7 Molecular orbital theory:
diatomic molecules
– Electrons of the molecule are assigned
to orbitals of successively higher energy
according to the aufbau principle and
Hund’s rule
• Electrons occupy the lowest energy orbitals
first.
• Atoms are most stable with the highest
number of unpaired electrons
5.7 Molecular orbital
theory: diatomic
molecules
– Bond order represents the net amount of
bonding between two atoms
1
BO = ( # electrons in bonding MOs − # electrons in antibonding MOs )
2

– A bond order of 1 corresponds to a single


bond
Molecular orbitals of O2
5.7 Molecular orbital theory:
diatomic molecules
– Rules:
• The bonding and antibonding σs orbitals are
of lower energy than any of the six molecular
orbitals derived from the 2p orbitals
• The two π bonding orbitals are degenerate,
because the corresponding atomic p orbitals
from which they are derived are degenerate
• The antibonding orbitals formed from the
atomic 2p orbitals are highest in energy, with
the σ*p orbital higher than the π*
5.7
Molecular
orbital
theory:
diatomic
molecules
5.7 Molecular orbital theory:
diatomic molecules
• Homonuclear diatomic molecules
– A more refined treatment of the MO
theory considers interactions between
the 2s and 2p orbitals
– Orbital mixing causes the σs and σp
molecular orbitals to move further apart
in energy
– The amount of mixing depends on the
difference in energy between orbitals
5.7 Molecular
orbital
theory:
diatomic
molecules
Summary
• Covalent bonds are formed as a
result of the sharing of electrons
between nuclei in a way that balances
attractive and repulsive forces
• Unequal sharing of electrons gives a
polar covalent bond
• Electronegativities generally increase
across a period and decrease down a
group
Summary

• Ionic compounds are formed between


elements with very different
electronegativities
• Lattice energy is the total energy that
must be supplied to break the crystal
lattice into its gaseous ions
• Lewis structures show the distribution
of valence electrons within a molecule
Summary

• Lewis structures may be drawn using


a five-step procedure
• VSEPR theory states that a molecule
will adopt a shape in which electron
pair repulsions are minimised
• A molecule with an overall
asymmetric distribution of electrons
has a dipole moment
Summary
• Bond lengths in molecules are
dependent on the atomic radii of the
bonded atoms
• Valence bond theory describes
bonding in molecules using localised
bonds formed from orbital overlap of
hybrid orbitals
• MO theory considers all possible
overlaps between atomic orbitals in
terms of delocalised bonds