Covalent Bonding: Orbitals & Hybridization

Bond overlap in covalent bonds

 A single covalent bond is formed when two nonmetals combine

 Each atom that combines has an atomic orbital containing a single unpaired
electron
 When a covalent bond is formed, the atomic orbitals overlap to form
a combined orbital containing two electrons
o This new orbital is called the molecular orbital
 The greater the atomic orbital overlap, the stronger the bond
 Sigma (σ) bonds are formed by direct overlap of orbitals between the bonding
atoms
 Pi (π) bonds are formed by the sideways overlap of adjacent above and
below the σ bond

σ bonds

 Sigma (σ) bonds are formed from the end-on overlap of atomic orbitals

 S orbitals overlap this way as well as p orbitals

Sigma orbitals can be formed from the end-on overlap of s orbitals

 The electron density in a σ bond is symmetrical about a line joining the nuclei of
the atoms forming the bond
 The pair of electrons is found between the nuclei of the two atoms
 The electrostatic attraction between the electrons and nuclei bonds the atoms to
each other

π bonds

 Pi (π) bonds are formed from the sideways overlap of adjacent p orbitals

 The two lobes that make up the π bond lie above and below the plane of the σ
bond
  This maximises overlap of the p orbitals
 A single π bond is drawn as two electron clouds one arising from each lobe of
the p orbitals
 The two clouds of electrons in a π bond represent one bond containing two
electrons

π orbitals can be formed from the end-on overlap of p orbitals

Examples of sigma & pi bonds

 Hydrogen
o The hydrogen atom has only one s orbital
o The s orbitals of the two hydrogen atoms will overlap to form a σ bond

Direct overlap of the 1s orbitals of the hydrogen atoms results in the formation of
a σ bond

 Ethene
o Each carbon atom uses three of its four electrons to form σ bonds
o Two σ bonds are formed with the hydrogen atoms
o One σ bond is formed with the other carbon atom
 o The fourth electron from each carbon atom occupies a p orbital which
overlaps sideways with another p orbital on the other carbon atom to form
a π bond
o This means that the C-C is a double bond: one σ and one π bond

Overlap of the p orbitals results in the forming of a π bond in ethene

 Each carbon atom in ethene forms two sigma bonds with hydrogen atoms and
one σ bond with another carbon atom. The fourth electron is used to form a
π bond between the two carbon atoms

 Ethyne
o This molecule contains a triple bond formed from two π bonds (at right
angles to each other) and one σ bond
o Each carbon atom uses two of its four electrons to form σ bonds
o One σ bond is formed with the hydrogen atom
o One σ bond is formed with the other carbon atom
o Two electrons are used to form two π bonds with the other carbon atom

Ethyne has a triple bond formed from two π bonds and one σ bond between the
two carbon atoms

 Hydrogen cyanide
o Hydrogen cyanide contains a triple bond
o One σ bond is formed between the H and C atom (overlap of an sp C
hybridised orbital with the 1s H orbital)
o A second σ bond is formed between the C and N atom (overlap of an sp
C hybridised orbital with a p orbital of N)
o The remaining two sets of p orbitals of nitrogen and carbon will overlap
to form two π bonds at right angles to each other
 

Hydrogen cyanide has a triple bond formed from the overlap of two sets of p
orbitals of nitrogen and carbon and the overlap of an sp hybridised carbon orbital
and a p orbital on the nitrogen

 Nitrogen
o Nitrogen too contains a triple bond
o The triple bond is formed from the overlap of the s orbitals on each N to
form a σ bond and the overlap of two sets of p orbitals on the nitrogen
atoms to form two π bonds
o These π bonds are at right angles to each other

 
 The triple bond is formed from two π bonds and one σ bond

Hybridisation

 The p atomic orbitals can also overlap end-on to form σ bonds

 In order for them to do this, they first need to become modified in order to gain s
orbital character
 The orbitals are therefore slightly changed in shape to make one of the p
orbital lobes bigger
 This mixing of atomic orbitals to form covalent bonds is called hybridisation
o Mixing one s orbital with three p orbitals is called sp3 hybridisation (each
orbital has ¼ s character and ¾ p character)
o Mixing one s orbital with two p orbitals is called sp2 hybridisation
o Mixing one s orbital with one p orbital forms sp hybridised orbitals

 
π orbitals can be formed from the end-on overlap of p orbitals
The mixing of s orbitals with p orbitals to form molecular bonds is called
hybridisation
1.3.10 Bond Energy & Length
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Covalent Bonding: Bond Energy & Length

Bond energy

 The bond energy is the energy required to break one mole of a particular covalent bond
in the gaseous states
o Bond energy has units of kJ mol-1
 The larger the bond energy, the stronger the covalent bond is

Bond length

 The bond length is internuclear distance of two covalently bonded atoms

o It is the distance from the nucleus of one atom to another atom which forms the
covalent bond
 The greater the forces of attraction between electrons and nuclei, the more the atoms
are pulled closer to each other
 This decreases the bond length of a molecule and increases the strength of the
covalent bond
 Triple bonds are the shortest and strongest covalent bonds due to the large electron
density between the nuclei of the two atoms
 This increase the forces of attraction between the electrons and nuclei of the atoms
 As a result of this, the atoms are pulled closer together causing a shorter bond length
 The increased forces of attraction also means that the covalent bond is stronger

Triple bonds are the shortest covalent bonds and therefore the strongest ones

Reactivity of covalent molecules

 The reactivity of a covalent bond is greatly influenced by:

o The bond polarity
o The bond strength
 o The bond type (σ/π)

Worked example: Bond lengths & bond energies

Answer

Answer 1: Going down the halogen group, the atoms are bigger; the attractive force
between the bonding electrons and the nucleus get smaller so less energy is needed to
break the atom

Answer 2: Going down the group the increase in bond length is approximately 0.14-
0.20 nm

Fluorine is smaller than HCl, so a value between 0.09 and 0.11 nm is acceptable for the
bond length

Answer 3: The hydrogen halide with the longest bond length and therefore smallest
bond energy is the most reactive as it takes the least energy to break apart the
hydrogen and halide atoms apart

Therefore, HI is the most reactive hydrogen halide

 VSEPR: Theory & Predictions
 The valence shell electron pair repulsion theory (VSEPR) predicts the shape
and bond angles of molecules
 Electrons are negatively charged and will repel other electrons when close to
each other
 In a molecule, the bonding pair of electrons will repel other electrons around
the central atom forcing the molecule to adopt a shape in which these repulsive
forces are minimised
 When determining the shape and bond angles of a molecule, the following
VSEPR rules should be considered:
o Valence shell electrons are those electrons that are found in the outer
shell
o Electron pairs repel each other as they have similar charges
o Lone pair electrons repel each other more than bonded pairs
o Repulsion between multiple and single bonds is treated the same as for
repulsion between single bonds
o Repulsion between pairs of double bonds are greater
o The most stable shape is adopted to minimize the repulsion forces
 Different types of electron pairs have different repulsive forces
o Lone pairs of electrons have a more concentrated electron charge cloud
than bonding pairs of electrons
o The cloud charges are wider and closer to the central atom’s nucleus
o The order of repulsion is therefore: lone pair – lone pair > lone pair – bond
pair > bond pair – bond pair
 Different types of electron pairs have different repulsive forces

 Molecules can adapt the following shapes and bond angles:

Molecules of different shapes can adapt with their corresponding bond angles

Examples
 Examples of molecules with different shapes and bond angles

Worked example: VSEPR & shapes of molecules

Answer 1
Answer 2
Answer 3
 Hydrogen Bonding
Hydrogen bonding

 Hydrogen bonding is the strongest form of intermolecular bonding

o Intermolecular bonds are bonds between molecules
o Hydrogen bonding is a type of permanent dipole – permanent
dipole bonding
 For hydrogen bonding to take place the following is needed:
o A species which has an O or N (very electronegative) atom with an
available lone pair of electrons
o A species with an -OH or -NH group
 When hydrogen is covalently bonded to an electronegative atom, such
as O or N, the bond becomes very highly polarised
  The H becomes so δ+ charged that it can form a bond with the lone pair of
an O or N atom in another molecule

The electronegative atoms O or N have a stronger pull on the electrons in the

covalent bond with hydrogen, causing the bond to become polarised

 For hydrogen bonding to take place, the angle between the -OH/-NH and

the hydrogen bond is 180o
 The number of hydrogen bonds depends on:
o The number of hydrogen atoms attached to O or N in the molecule
o The number of lone pairs on the O or N

Ammonia can form a maximum of one hydrogen bond per molecule

 
 Water can form a maximum of two hydrogen bonds per molecule

Properties of water

 Hydrogen bonding in water, causes it to have anomalous properties such as

high melting and boiling points, high surface tension and anomalous density of
ice compared to water

High melting & boiling points

 Water has high melting and boiling points which is caused by the strong

intermolecular forces of hydrogen bonding between the molecules
 In ice (solid H2O) and water (liquid H2O) the molecules are tightly held together
by hydrogen bonds
 A lot of energy is therefore required to break the water molecules apart and melt
or boil them

Hydrogen bonds are strong intermolecular forces which are difficult to break
causing water to have high melting and boiling points
  The graph below compares the enthalpy of vaporisation (energy required to
boil a substance) of different hydrides
 The enthalpy changes increase going from H2S to H2Te due to the increased
number of electrons in the Group 16 elements
 This causes an increased instantaneous dipole - induced dipole forces as
the molecules become larger
 Based on this, H2O would have a much lower enthalpy change (around 17 kJ mol -
1
)
 However, the enthalpy change of vaporisation is almost 3 times larger which is
caused by the hydrogen bonds present in water but not in the other hydrides

The high enthalpy change of evaporation of water suggests that instantaneous

dipole-induced dipole forces are not the only forces present in the molecule –
there are also those of the strong hydrogen bonds, which cause the high boiling
points

High surface tension

 Water has a high surface tension

 Surface tension is the ability of a liquid surface to resist any external
forces (i.e. to stay unaffected by forces acting on the surface)
 The water molecules at the surface of liquid are bonded to other water
molecules through hydrogen bonds
  These molecules pull downwards on the surface molecules causing the
surface them to become compressed and more tightly together at the surface
 This increases water’s surface tension

The surface molecules are pulled downwards due to the hydrogen bonds with
other molecules, whereas the inner water molecules are pulled in all directions

Density

 Solids are denser than their liquids as the particles in solids are more closely

packed together than in their liquid state
 In ice however, the water molecules are packed in a 3D hydrogen-
bonded network in a rigid lattice
 Each oxygen atom is surrounded by hydrogen atoms
 This way of packing the molecules in a solid and the relatively long bond
lengths of the hydrogen bonds means that the water molecules are slightly
further apart than in the liquid form
 Therefore, ice has a lower density than liquid water
 The ‘more open’ structure of molecules in ice causes it to have a lower density
than liquid water

Exam Tip

Ice floats on water because of ice's lower density.

Polarity & Dipole Moments

 Electronegativity is the ability of an atom to draw a pair of electrons towards
itself in a covalent bond
 Electronegativity increases across a Period and decreases going down a Group

Polarity

 When two atoms in a covalent bond have the same electronegativity the

covalent bond is nonpolar
The two chlorine atoms have similar electronegativities so the bonding electrons
are shared equally between the two atoms

 When two atoms in a covalent bond have different electronegativities the

covalent bond is polar and the electrons will be drawn towards the more
electronegative atom
 As a result of this:
o The negative charge centre and positive charge centre do
not coincide with each other
o This means that the electron distribution is asymmetric
o The less electronegative atom gets a partial charge of δ+
(delta positive)
o The more electronegative atom gets a partial charge of δ-
(delta negative)
 The greater the difference in electronegativity the more polar the bond
becomes

Cl has a greater electronegativity than H causing the electrons to be more

attracted towards the Cl atom which becomes delta negative and the H delta
positive

Dipole moment
  The dipole moment is a measure of how polar a bond is
 The direction of the dipole moment is shown by the following sign in which
the arrow points to the partially negatively charged end of the dipole:

The sign shows the direction of the dipole moment and the arrow points to the
delta negative end of the dipole

Assigning polarity to molecules

 To determine whether a molecule with more than two atoms is polar, the

following things have to be taken into consideration:
o The polarity of each bond
o How the bonds are arranged in the molecule
 Some molecules have polar bonds but are overall not polar because the polar
bonds in the molecule are arranged in such way that the individual dipole
moments cancel each other out
There are four polar covalent bonds in CH3Cl which do not cancel each other out
causing CH3Cl to be a polar molecule; the overall dipole is towards the
electronegative chlorine atom
Though CCl4 has four polar covalent bonds, the individual dipole moments
cancel each other out causing CCl4 to be a nonpolar molecule

van der Waals' Forces & Dipoles

 Covalent bonds are strong intramolecular forces
  Molecules also contain weaker intermolecular forces which are
forces between molecules
 These intermolecular forces are called van der Waals’ forces
 There are two types of van der Waals’ forces:
o Instantaneous (temporary) dipole – induced dipole forces also called London
dispersion forces
o Permanent dipole – permanent dipole forces

The polar covalent bonds between O and H atoms are intramolecular forces and the
permanent dipole – permanent dipole forces between the molecules are intermolecular forces
as they are a type of van der Waals’ force

Instantaneous dipole - induced dipole (id - id)

 Instantaneous dipole - induced dipole forces or London dispersion forces exist

between all atoms or molecules
 The electron charge cloud in non-polar molecules or atoms are constantly moving
 During this movement, the electron charge cloud can be more on one side of the atom or
molecule than the other
 This causes a temporary dipole to arise
 This temporary dipole can induce a dipole on neighbouring molecules
 When this happens, the δ+ end of the dipole in one molecule and the δ- end of the
dipole in a neighbouring molecule are attracted towards each other
 Because the electron clouds are moving constantly, the dipoles are only temporary
 Id-id (London dispersion) forces between two non-polar molecules

 Id - id forces increase with:

o Increasing number of electrons (and atomic number) in the molecule
o Increasing the places where the molecules come close together
 

Going down the Group, the id-id forces increase due to the increased number of electrons in
the atoms

The increased number of contact points in petane means that it has more id-id forces and
therefore a higher boiling point

Permanent dipole - permanent dipole (pd - pd)

 Polar molecules have permanent dipoles

 The molecule will always have a negatively and positively charged end
  Forces between two molecules that have permanent dipoles are called permanent dipole
- permanent dipole forces
 The δ+ end of the dipole in one molecule and the δ- end of the dipole in a neighbouring
molecule are attracted towards each other

The delta negative end of one polar molecule will be attracted onwards the delta positive end
of a neighbouring polar molecule

 For small molecules with the same number of electrons, pd - pd forces

are stronger than id - id
o Butane and propanone have the same number of electrons
o Butane is a nonpolar molecule and will have id - id forces
o Propanone is a polar molecule and will have pd - pd forces
o Therefore, more energy is required to break the intermolecular forces between
propanone molecules than between butane molecules
o So, propanone has a higher boiling point than butane

Pd-pd forces are stronger than id-id forces in smaller molecules with an equal number of
electrons
Exam Tip

Remember this difference: intramolecular forces are forces within a molecule, whereas

intermolecular forces are forces between a molecule.
Hydrogen Bonding as a Permanent Dipole
 Hydrogen bonding is an intermolecular force between molecules with an -OH/-NH
group and molecules with an N/O atom
 Hydrogen bonding is a special case of a permanent dipole - dipole force between
molecules
o Hydrogen bonds are stronger forces than pd - pd forces
 The hydrogen is bonded to an O/N atom which is so electronegative, that almost all the
electron density from the covalent bond is drawn towards the O/N atom
 This leaves the H with a large delta positive and the O/N with a large delta negative
charging resulting in the formation of a permanent dipole in the molecule
 A delta positive H in one molecule is electrostatically attracted to the delta
negative O/N in a neighbouring molecule

Hydrogen bonds in water molecules