Cambridge AS & A Level Chemistry 9701

Notes
4 Chemical Bonding
Cambridge AS & A Level Chemistry

Types of Chemical Bonding

Types of chemical bonding

• Ionic bonding: the electrostatic attraction between positive and negative ions in
an ionic crystal lattice.
• Covalent bonds: formed when the outer electrons of two atoms are shared.
• The ionic or covalent bonds formed are usually very strong – it takes a lot of energy
to break them.
• Metallic bonding: a form strong bonding.
• Intermolecular forces: usually called van der Waals’ forces, is when the atoms
within molecules are kept together by strong covalent bonds, the forces between
molecules are weak.
Types of van der Waals’ forces:
- dipole (instantaneous dipole–induced dipole (id–id) forces, also called London
dispersion forces
- permanent dipole–permanent dipole (pd–pd) forces
- hydrogen bonding, which is a stronger form of permanent dipole–permanent
dipole force
• This information helps to explain the structure and physical properties of elements
and compounds.

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Ionic Bonding

How are ions formed?

• Positive ions formed when an atom loses one or more electrons. Metal atoms
usually lose electrons and form positive ions.
• Negative ions formed when an atom gains one or more electrons. Non-metal
atoms usually gain electrons and form negative ions.
• The strong force of attraction between the positive ions and negative ions in the
ionic crystal lattice results in an ionic (electrocovalent) bond.
• The charge on the ion depends on the number of electrons lost or gained.
• When metals combine with non-metals, the electrons in the outer shell of the metal
atoms are transferred to the non-metal atoms (they have an electronic
configuration of a noble gas).

Example of the formation of a sodium ion and chloride ion by electron transfer

Dot-and-cross diagrams

To keep track of where the electrons Use a ‘dot’ for electrons from one of the atoms and a ‘cross’ for the
have come from. electrons from the other atom and draw the outer electrons in pairs,
to emphasize the number of bond and lone pairs.
A dot-and-cross diagram shows:
Example: dot-and-cross diagram of magnesium oxide
• the outer electron shells only
• that the charge of the ion is
spread evenly, by using square
brackets
• the charge on each ion, written at
the top right-hand corner of the
square brackets.

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Covalent Bonding

Covalent bonding
Single Multiple Co-ordinate (dative)
• Formed when one atom
• When two non-metal atoms provides both the electrons
combine, they share one, or more, • Double covalent bond is when
needed for a covalent bond.
pairs of electrons. two pairs of electrons are
• The requirements are: one
• .A shared pair of electrons is called shared.
atom having a lone pair of
a single covalent bond, or a bond • A double line between the
electrons and a second atom
pair. atoms represents a double
having an unfilled orbital to
• A single line between the atoms covalent bond.
accept the lone pair
represents a single covalent bond. • Atoms can also bond together
(electron-deficient
• The pairs of outer-shell electrons by sharing three pairs of
compound).
electrons, which is called a
not used in bonding are called lone • Example: formation of a co-
pairs. triple covalent bond.
ordinate bond in ammonium
• Example: atoms of chlorine • Example: carbon dioxide
ion

Bond length and bond energy

• Double bonds are shorter than single bonds because double bonds have a greater quantity of negative
charge between the two atomic nuclei.
• The greater force of attraction between the electrons and the nuclei pulls the atoms closer together,
results in a stronger bond.
• The strength of a bond can be measured by its bond energy, the energy needed to break one mole of a
given bond in a gaseous molecule.
• Bond strength and bond polarity can influence the reactivity of a compound.
• A reaction only happens between molecules when a collision occurs with enough energy to break bonds
in either or both molecules.

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Shapes of Molecules

Valence shell electron pair repulsion theory (VSEPR)

VSEPR

• The valence shell electrons are the electrons in the main outer shell.
• Pairs of electrons repel each other because they have the same charge.
• A lone pair of electrons repel each other more than a bonded pair of electrons.
• Repulsion between multiple and single bonds is treated the same as for repulsion
between single bonds.
• Repulsions between pairs of double bonds are greater.
• The shape of a molecule can be deduced using this theory, with the most stable
shape being that which minimizes the forces of repulsion.

✓ The shape and bond angles of a covalently bonded molecule depend on the number of
pairs of electrons around each atom.
✓ Lone pairs of electrons have a more concentrated electron charge cloud than bond pairs
of electrons because their cloud charges are wider and slightly closer to the nucleus of
the central atom.
✓ The order of repulsion:
lone pair–lone pair (most repulsion) > lone pair–bond pair > bond pair–bond pair (least
repulsion).

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Shapes of Molecules

Working out the shapes of molecules

The differences in electron-pair repulsion determine the shape and bond angles in a
molecule.

Methane Ammonia

• has three bonding pairs of electrons and one

• has four bonding pairs of electrons surrounding lone pair
the central carbon atom • bonding pairs of electrons are pushed closer
• equal repulsive forces of each bonding pair of together
electrons • H─N─H bond angle is about 107°
• all H─C─H bond angles 109.5° • pyramidal shape or pyramidal structure.
• tetrahedral structure

Water

• has two bonding pairs of electrons and two

lone pairs
• greatest force between the two lone pairs
• bonds being pushed even closer together
• H─O─H bond angle is 104.5°
• non-linear V shape

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More Molecular Shapes

More molecular shapes

Boron trifluoride (trigonal planar) Carbon dioxide (linear)

Phosporus pentafluoride (trigonal bipyramidal) Sulfur hexafluoride (octahedral)

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σ Bonds and π Bonds

σ bonds and π bonds

• Covalent bonds are formed when atomic orbitals overlap.

• The combined orbital is called a molecular orbital.
• The greater the amount of overlap of the atomic orbitals, the stronger the bond.
• The mixing of atomic orbitals is called hybridisation.
• Mixing an s with three, two or one p-type orbitals forms sp3, sp2 and sp hybrid
orbitals.
• Sigma bonds (σ bonds) are formed from end-on overlap of atomic orbitals.
• Pi bonds (π bonds) are formed from sideways overlap of atomic orbitals

Formation of σ bonds

Formation of π bonds

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σ Bonds and π Bonds

‘

The shape of some organic molecules

The shapes of molecules can be explained in terms of electron density patterns found in
σ bonds and π bonds.

Ethane

Ethene

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Metallic Bonding

What is a metallic bond?

• In a metal, the atoms are packed closely together in a regular arrangement called
a lattice, where the atoms tend to lose their outer shell electrons and become
positive ions.
• Delocalised (mobile) electrons: electrons that are not associated with any one
particular atom or bond.
• Metallic bonding is strong because the ions are held together by the strong
electrostatic attraction between their positive charges and the negative charges of
the delocalised electrons.
• The strength of metallic bonding increases with:
- increasing positive charge on the ions in the metal lattice
- decreasing size of metal ions in the lattice
- increasing number of mobile electrons per atom

Properties of metals

• Most have high melting points and high boiling points

• Conduct electricity
ConducKey Point

• t heat

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Intermolecular Forces

Intermolecular forces

• The weaker forces between molecules.

• There are two types of van der Waals’ forces (intermolecular force):
- instantaneous (temporary) dipole–induced dipole forces (id–id) forces, also
called London dispersion forces
- permanent dipole–permanent dipole (pd–pd) forces (including hydrogen
bonding)

Electronegativity • The ability of a particular atom, which is covalently bonded to another atom, to attract the
bond pair of electrons towards itself.
• The greater the value of the electronegativity, the greater the power of an atom to attract
the electrons in a covalent bond towards itself.
• Electronegativity increases across a period from Group 1 to Group 17.
• Electronegativity increases up each group.
• Fluorine is the most electronegative element. For the most electronegative elements, the
order of electronegativity is:
Br < Cl < N < O < F
• Carbon and hydrogen have lower electronegativities than most of non-metallic elements.
Polarity in • Non-polar covalent bond is when the electronegativity values of the two atoms forming the
molecules bond are the same, the pair of electrons is equally shared.
• When there is a different electronegativity values:
- the more electronegative atom attracts the pair of electrons in the bond towards it,
- the center of positive charge does not coincide with the center of negative charge
- he electron distribution is asymmetric
- the two atoms are partially charged
- the less electronegative atom with the partial charge δ+ (‘delta positive’)
- the more electronegative atom with the partial charge δ– (‘delta negative’)
- the bond is polar (or that it has a dipole).

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Polarity and • Bond polarity influences chemical reactivity.

chemical • For example, both nitrogen and carbon monoxide have triple bonds requiring a similar
reactivity amount of energy to break them.
• Reagents such as OH– ions can attack the delta-positive carbon atom of the polarized C -
Cl bond.
Instantaneous • It is a weak forces of attraction between atoms that keep the atoms together in the liquid
dipole-induced state, which exist between all atoms or molecules.
dipole (id-id) • How it arises:
forces - The electron charge clouds in a non-polar molecule (or atom) are constantly moving.
- A temporary dipole is set up, which can induce a dipole on neighboring molecules.
- Because of this, there are forces of attraction between the δ+ end of the dipole in one
molecule and the δ– end of the dipole in a neighboring molecule.
- These dipoles are always temporary because the electrons clouds are always moving.
• It increases with:
- increasing number of electrons (and protons) in the molecule
- increasing the number of contact points between the molecules – contact points are
places where the molecules come close together.
• Differences in the size of the instantaneous dipole-induced dipole (id-id) forces can be used
to explain the trend in the enthalpy change of vaporization and boiling points of the noble
gases.
Permanent • Molecules with a permanent dipole are called polar molecules.
dipole-dipole • The forces between two molecules having permanent dipoles are called permanent dipole–
(pd-pd) forces dipole forces.
• The attractive force between the δ+ charge on one molecule and the δ– charge on a
neighboring molecule causes a weak attractive force between the molecules.
• For small molecules with the same number of electrons, permanent dipole–dipole forces
are often stronger than van der Waals’ forces.

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Hydrogen Bonding

Hydrogen bonding

• It is the strongest type of intermolecular force.

• For hydrogen bonding to occur between two molecules:
- one molecule must have a hydrogen atom covalently bonded to F, O or N (the
three most electronegative atoms)
- a second molecule having a F, O or N atom with an available lone pair of
electrons.
• For hydrogen bonding to happen the molecules must have:
- a H atom covalently bonded to a highly electronegative atom, e.g. N, O or F
- another highly electronegative atom with a lone pair of electrons
• When a hydrogen atom is covalently bonded to a very electronegative atom, the
bond is very highly polarised.
• The δ+ charge on the hydrogen atom is high enough for a bond to be formed with
a lone pair of electrons on the F, O or N atom of a neighboring molecule
• The force of attraction is about one-tenth of the strength of a normal covalent bond.
• For maximum bond strength, the angle between the covalent bond to the hydrogen
atom and the hydrogen bond is usually 180°.
• The average number of hydrogen bonds formed per molecule depends on:
- the number of hydrogen atoms attached to F, O or N in the molecule
- the number of lone pairs present on the F, O or N.

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Hydrogen Bonding

How does hydrogen bonding affect boiling point?

Based on the boiling points of the hydrogen halides graph above:

• The rise in boiling point from HCl to HI is due to the increasing number of electrons
in the halogen atoms as we go down the group.
• This leads to increased van der Waals’ forces as the molecules get bigger.
• The boiling point of hydrogen fluoride is 20 °C, which is much higher, due to the
stronger intermolecular forces of hydrogen bonding between the HF molecules.

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Hydrogen Bonding

The peculiar properties of water

Enthalpy change of vaporization and boiling point Ice is less dense than water

Water has a much higher enthalpy change of • Most solids are denser than their liquids.
vaporization and boiling point than expected due • But this is not true of water because in ice, a
to its extensive hydrogen bonding. three-dimensional hydrogen-bonded network
of water molecules produces a rigid lattice in
which each oxygen atom is surrounded by a
tetrahedron of hydrogen atoms.
• This ‘more open’ arrangement, due to the
relatively long hydrogen bonds, allows the
water molecules to be slightly further apart
than in the liquid.
• Therefore, the density of ice is less than that
of liquid water.

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Bonding and Physical Properties

Physical state at room remperature and pressure

Ionic compounds Metals Covalent compounds
• Solids. • Apart from mercury, are • Substances with a simple
• Strong electrostatic forces solids. molecular structure, like
(ionic bonds) • Most have high melting water and ammonia, are
• The ions are regularly points, boiling points, and usually liquids or gases.
arranged in a lattice enthalpy changes of • The forces between the
• High melting points, vaporization. molecules are weak.
boiling points and • Takes a lot of energy to • Does not take much
enthalpy changes of overcome the strong energy to overcome these
vaporization. attractive forces between intermolecular forces
• Takes a lot of energy to the positive ions and the • Have low melting points,
overcome the strong ‘sea’ of delocalised boiling points, and
electrostatic attractive electrons enthalpy changes of
forces vaporization
• Some substances may be
solids, like iodine and poly
(ethene).

Solubility Electrical Conductivity

Ionic compounds: Most are soluble in water because Ionic compounds: Do not conduct
water molecules are polar and they are attracted to the ions electricity when in the solid state because
on the surface of the ionic solid (ion–dipole attractions). the ions are fixed in the lattice and can
only vibrate around a fixed point. When
Metals: Do not dissolve in water. However, some metals,
molten, an ionic compound conducts
for example sodium and calcium, react with water.
electricity because the ions are mobile.
Covalent compounds: Covalently bonded substances with
Metals: Conduct electricity both when
a simple molecular structure fall into two groups. Those that
solid and when molten, because the
are insoluble in water, which molecules are non-polar
delocalised electrons are mobile.
(example is iodine). Those that are soluble in water, which
molecules can form hydrogen bonds with water (example is Covalent compounds: Do not conduct
ethanol, C2H5OH). Some substances react with water electricity because they have neither ions
rather than dissolving in it (hydrolysis reaction). nor electrons that are mobile.

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