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Chem Dept. (0773 495 379)

CHEMICAL BONDING
- The electrostatic force of attraction holding particles together is called a chemical bond.

Ionic bonding
- An ionic bond is the strong electrostatic force of attraction between oppositely charged
ions in a compound.
Examples
 In sodium chloride, NaCl.
There is a complete transfer of electrons from a sodium atom to a chlorine atom.
Na+ and Cl- ions are formed. Electrostatic forces of attraction will hold these ions
in a crystalline lattice structure of the ionic compound Na +Cl-. Ionic compounds
form crystals.
Electrons are transferred from a metal to a non-metal until the outer electron
shells of the resulting ions are identical to those of a noble gas.

Na+: 2.8 Cl-: 2.8.8

 In magnesium oxide, MgO.

 There is transfer of 2 valence electrons of Mg to the valence shell of O.
 Mg2+ and O2- ions are formed and these will be held together by strong forces of
attraction in a crystalline lattice structure.
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2.8 2.8

NB: Ionic compounds form a regular pattern or lattice of alternating positive and
negative ions. The ions are held together by strong ionic bonds. See example
below.

Factors influencing the formation of ions

a) Cations – ionization energy: in general, cations form easiest when

the resulting charge is small, and the radius of the atom is large.
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b) Anions – electron affinity: in general, anions form easiest when the

resulting charge is small, and the radius of the atom is small.

c) Lattice energies

- The conversion Na(s) → Na+(g) + e- is endothermic.

- This means Na+(g) is less stable than Na(s). However, the Na +(g) is stabilized when it
comes into contact with Cl- ions forming solid NaCl.

Na+(g) + Cl-(g) → NaCl(s) is highly exothermic, ∆H = -781kJmol-1

The heat change for this reaction is known as the lattice energy for NaCl.

The more exothermic the lattice energy the more stable the ionic compound.

Questions

1. Draw similar ‘dot and cross’ diagrams to represent the electron transfers which take
place in the formation of magnesium sulphide, aluminium chloride and potassium
oxide.

2. Element X has two electrons in its outer shell. What is the formula of the most likely
compound formed from X and Y?

Covalent bonding

- Is an electrostatic force of attraction between the nuclei of the bonded atoms and the
shared pair of electrons.

- A single covalent bond is formed when atoms share two electrons.

- Two atoms have to get sufficiently closer to each other for the atomic orbitals to overlap.

- The non-bonding (unshared pair(s)) electrons are known as ‘lone pair(s)’ of electrons.

Examples

a) Chlorine, Cl2
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Or Cl – Cl

b) Oxygen, O2

c) Nitrogen, N2

d) Hydrogen chloride, HCl

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e) Water, H2O

f) Carbon dioxide, CO2

Try the following: methane, CH4; ammonia, NH3; ethene, C2H4.

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NB: Elements and compounds consisting of small molecules have simple

molecular structures. Atoms within the molecules are held together by strong
covalent bonds. The discrete molecules are held together by weak forces of
attraction called intermolecular forces.

Co-ordinate (dative covalent) bonding

- Involves the sharing of a pair of electrons between 2 atoms, both electrons in the bond
being donated by one atom.

- One atom is a donor, the other is the acceptor. The atom which donates electrons has a
lone pair of electrons in the outermost shell, while the acceptor has an unfilled outermost
shell (vacant orbital).

- Once a dative bond has formed, it is indistinguishable from a covalent bond.

Examples

1. Ammonium ion, NH4+

- The lone pair of electrons of the N atom overlaps with the empty 1s orbital of H+ ion.

- The H+ ion will attain the noble structure of helium and the N atom a noble gas structure
in its outermost shell.

2. Aluminium chloride dimer, Al2Cl6

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- When gaseous aluminium chloride is cooled, AlCl3 molecules dimerise to form

molecules of Al2Cl6. Monomers of AlCl3 are held together in the Al 2Cl6 dimer by dative
covalent bonds.

monomer

dimer

3. Nitric acid, HNO3

4. Ammonia, NH3 and boron trifluoride, BF3

5. Carbon monoxide, CO
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Metallic bonding

example

- The metallic bond is the attraction between metal ions and free electrons (mobile or
delocalised electrons).
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Chem Dept. (0773 495 379)

- The metallic bond is usually described as a lattice of positive ions embedded in a ‘sea’ of
delocalised electrons.

- Each positive ion is attracted to the ‘sea’ of mobile electrons.

- It is the valence electrons that are delocalised to form positive ions e.g. 1 for Na to form
Na+ ions; 3 electrons for Al to form Al3+ ions.

- The ions sit in a lattice, held together by their strong attraction to the free electrons. And
because the ions are in a regular pattern, metals are crystalline.

- The strength of the metallic bonding increases with:

a) Increasing positive charge on the ions in the metal lattice

b) Decreasing size of metal ions in the lattice

c) Increasing number of mobile electrons per atom.

Physical properties of metals

 High melting points – a lot of heat energy is required to break up the lattice, with
its strong metallic bonds.

 Metals are malleable and ductile. Malleable – can be bent and pressed into
different shapes. Ductile – can be drawn out into wires. This is because the layers
can slide over each other. The layers can slide without breaking the metallic bond,
because the electrons are free to move too. The mobile electrons continue to hold
the lattice together.

 Good thermal conductors – the free electrons take in heat energy, which makes
them move faster. They quickly transfer the heat through the metal lattice
structure as they are mobile. As electrons move faster, they also collide with
neighbouring electrons thus heat is transferred in these collisions.

 Good electrical conductors – the delocalised electrons can move through the
lattice carrying charge, when a voltage is applied across the metal.

*** Ag is the best conductor of all metals followed by Cu. Cu is cheaper than Ag
and hence much more used.

Bonds of intermediate character

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e.g. Aluminium chloride (AlCl3) sublimes at quite low temperatures – a property more typical of
covalent compounds.

Similarly, there are covalent compounds that dissolve readily in water to produce ionic solutions
e.g. HCl (g) or NH3(g).

Compounds that are purely ionic or covalent are best regarded as extremes.

Polarization of ions

Ionic compounds that show some properties more characteristic of covalent compounds contain
anions that have become polarized. This means that the cation distorts the electron charge cloud
on the anion. Polarization brings more electron charge between the ionic nuclei, and thus
produces a significant degree of covalent bonding between the ions. Anions with a greater charge
or a larger radius are more easily polarized than those with a smaller charge or smaller radius.

Cations with a smaller radius or a greater charge will have a greater charge density. Such cations
will exert a greater degree of polarization on an anion than will cations with a larger radius or
lower charge.

3+ - Extensive polarization results with a smaller but highly charged cation

+ - ions of similar charge and radii, little or no polarization occurs. Purely ionic

Bonding.

Hybridization

- Is a theory that mixes orbitals in such a way that they match the observed shapes of
molecules e.g. the tetrahedral shape of CH4 is matched by mixing the single 2s orbital and
the three 2p orbitals on carbon to give a set of four sp 3hybrid orbitals (bonding orbitals).
One of the 2s electrons is promoted to the empty 2p orbital. There will be 4 unpaired
electrons able to make 4 bonds. One 2s and three 2p orbitals overlap and interfere with
one another in such a way that 4 new sp3 hybrid orbitals appear.

Activity
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Use energy level diagrams to show arrangement of electrons in the ground state of
carbon and the excited state of carbon.

Ground state electronic arrangement of carbon

*Show the excited state electronic arrangement in a similar way.

Examples of hybrid orbitals

Hybrid No. of hybrid Shape of molecule Example

orbitals
sp 2 Linear BeCl2
sp2 3 Triangular planar BCl3
sp3 4 Tetrahedral CH4
dsp2 4 Square planar XeF4
dsp3 5 Trigonal PCl5
bipyramidal
d2sp3 6 Octahedral SF6
d3s 4 Tetrahedral MnO4-

Sigma (σ) and pi (π) bonds

 Sigma (σ) bond: is a bond situated symmetrically between 2 atoms, formed by

the overlap of 2 orbitals (s and p). it is formed when orbitals overlap head-on or
end-on in a covalent bond. It is a result of the overlap of orbitals along the line
joining the two bonded atoms (p orbitals).
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 Pi (π) bond: is formed when two p orbitals overlap sideways.

Because each p orbital has two lobes, this bond has two regions, one above and
one below the plane of the molecule. The orbitals are parallel and overlap
sideways – important in double bonds. (see diagram above).

NB: sigma bonds are stronger than pi bonds because in a sigma bond the electrons
are between the nuclei whereas a pi bond has the electrons far from the nuclei
(above and below the nuclei). Nevertheless, the pi and sigma bonds together are
stronger than the single sigma bond that links the C atoms in ethane.
Consequently, the C = C bond in ethene is stronger and shorter than the C – C
bond in ethane.

Shapes of molecules

The bonds in molecules spread out so as to be as far apart as possible. The shape
of a simple molecule or ion is dictated by the number of regions of negative
charge around the central atom. Covalent bonds are directional and as a result a
molecule has a definite shape.
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The Valence Shell Electron Pair Repulsion Theory (VSEPR Theory)

States that: Molecules take up the shape that minimizes the repulsions between
the bonding and lone pairs of electrons.

The isoelectronic rule: Molecules or ions that are isoelectronic (having same
number of valence electrons) will have similar shapes.

A lone pair of electrons exerts a greater repelling effect than a bonded pair.

Order of repulsion strength

Lone pair – lone pair > lone pair – bond pair > bond pair – bond pair repulsion.

Multiple bonds are treated as a single region of negative charge.

Repulsion increases with an increase in electronegativity of the central atom e.g.

bond angle in NH3 is greater than the bond angle in PH 3. This is because N is
more electronegative than P hence bond pairs are closer to N than to P, resulting
in more repulsion in NH3.

1. 2 pairs of electrons

Both bonded, giving the molecule a linear shape with a bond angle of 180º.

Examples
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The electron pairs in a multiple bond are assumed to occupy the position of one
electron pair.

2. 3 pairs of electrons

If the central atom is surrounded by 3 bond pairs, the molecule will have a
trigonal planar shape. The 3 atoms bonded to the central atom will be at the
corners of a triangle and will be in the same plane. Bond angle is 120º.

Examples

3. 4 pairs of electrons

a. All bonded
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Four atoms lie at the apices of a tetrahedron. The shape is tetrahedral

with a bond angle of 109.5º.

Examples

methane, CH4

ammonium ion, NH4+

b. 3 bonded + 1 lone pair

Lone pair – bond pair repulsion > bond pair – bond pair repulsion

Shape is trigonal pyramidal with a bond angle of 107.3º.

Examples

NH3 and H3O+ both have a trigoanal pyramidal shape.

c. 2 bonded + 2 lone pairs

e.g. water, H2O. There are 2 bond pairs together with 2 lone pairs on
the oxygen atom. The effect of the two lone pairs is to squeeze the 2
bond pairs even further together than they are in NH 3. The H – O – H
angle is 104.5º.

lone pair – lone pair > lone pair – bond pair > bond pair – bond pair
repulsion.
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Shape is non-linear or v-shaped or bent shape.

4. 5 pairs of electrons (Expansion of the octet)

If all are bonded, the molecule has a trigonal bipyramidal shape. The bond
angles are 90º and 120º. Some atoms will have more than 8 electrons in the
valence shell. This is called expansion of the octet e.g. PCl 5in which 2 Cl
atoms occupy the axial position (90º) and 3 occupy the equatorial positions
(120º).

Take note that P – Cl bonds in the axial position are longer and weaker than
those in the equatorial positions.

5. 6 pairs of electrons

a. All bonded as in SF6

Molecule has an octahedral shape with a bond angle of 90º.

4 atoms are arranged in a square around the S atom and the other two F
atoms are above and below the square.

b. 4 bonded + 2 lone pairs e.g. in XeF4

The molecule has a shape of square planar with a bond angle of 90º. The
2 lone pairs are 1 below and the other above the planar.
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Chem Dept. (0773 495 379)

Activity

Use the VSEPR theory to predict the shapes of:

i. Ethane molecule, C2H6

ii. Ethene molecule, C2H4

iii. Benzene molecule, C6H6, around each carbon atom.

The Benzene molecule, C6H6

X-ray diffraction studies show that:

a. Benzene has a hexagonal planar shape with a bond angle of 120º.

b. All the C – C bonds in benzene are the same length (0.139nm, being in
between C – C single bond in cyclohexane, 0.154nm and C = C double
bond in cyclohexene, 0.133nm).

c. Enthalpy change of formation (theoretical) of gaseous benzene based

on Kekule structure is +252 kJmol -1. Experimental value is +82 kJmol -
1

The overlap of a p orbital on each of the 6 carbon atoms in benzene,

C6H6, leads to π molecular orbitals, one of which spreads over all of
the C atoms, i.e. the π electrons in benzene are delocalised. The pi
bond that is formed stretches in a ring around the molecule. The
carbon atoms in the ring are bonded to one another and to their
hydrogen atoms by sigma bonds. This leaves one unused p orbital on
each carbon, each containing a single electron. These p orbitals are
perpendicular to the plane of the ring, with one lobe above and one
below this plane. Each p orbital overlaps sideways with two
neighbouring orbitals to form a single pi bond that extends as a ring of
charge above and below the plane of the molecule.

The electrons in the pi bond cannot be said to belong to any particular

carbon atom. Each electron is free to move throughout the entire pi
system, so the electrons are said to be delocalised. It is this
delocalization that gives benzene its extra stability. The benzene
molecule is hexagonal planar, symmetrical and non-polar with a bond
angle of approximately 120º.
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Bond energy

- Is the amount of energy required to break one mole of bonds, in kJmol-1.

- It is absorbed when the bond is broken and evolved when the bond is formed.

- Uses of bond energies:

a. Comparing the strengths of bonds e.g. stability of HX bond in hydrogen

halides.

b. Understanding structure and bonding e.g. structure of benzene

c. Estimating the enthalpy changes in reactions

d. Understanding the mechanisms of chemical reactions.

Bond length

- Is the distance between the nuclei of two bonded atoms. The shorter the bond length, the
stronger the bond. It is measured in nanometers (nm).

- The lengths of double bonds are less than the lengths of single bonds between the same
two atoms, and triple bonds are even shorter than double bonds.
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Electronegativity

- Of an atom is the power of that atom in a molecule to attract electrons towards itself.

- Non-metals with a strong desire to gain electrons have the highest values of
electronegativity. Metals, being electropositive, have low values. It increases across a
period due to increasing nuclear charge, and decreases down a group due to increasing
atomic radii hence screening or shielding effect.

- Fluorine and the Group VI and VII elements near it are the most electronegative, and
Caesium and the other alkali metals close to it are the most electropositive.

Bond polarity

- Occurs when the electrons in a covalent bond are not shared equally between the atoms,
resulting in a partial positive charge (ẟ+) on one atom and a partial negative charge ( ẟ-)
on the other.

- As a result of differing electronegativities, there is a distortion of the equal sharing

expected in a pure covalent bond.

- As the polarity of the molecule increases, so does the extent of its ionic character.

- Most covalent bonds have some ionic character and all ionic bonds have some covalent
character e.g., X – Y, if X is more electronegative than Y, it gains a small negative
charge, ẟ-, leaving a small positive charge on Y, ẟ+, X ẟ- - Yẟ+. The molecule is said to be
polar and has a dipole moment.

- Polar bonds are chemically reactive than non-polar as they can attract electrophiles or
nucleophiles. The extent of polarity is the extent of reactivity.

- A molecule is said to be polarised if:

i. The bonds are polarised/have a dipole

ii. It is non-symmetrical

Examples

Polar Non-polar

Hẟ+ - Clẟ- Cl – Cl

H2O 1,4-dichlorobenzene

Nitrobenzene CCl4
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CHCl3 cyclohexane

Cyclohexene benzene

Symmetrical molecules are non-polar as their centre of +ve charge coincides exactly with
their centre of negative charge (are at the same point). This is not the case with non-
symmetrical molecules which are polar.

Intermolecular forces

1. Permanent dipole – permanent dipole attractions

e.g., in trichloromethane, CHCl3

CHCl3 molecules are polar as a result of the non-symmetrical distribution of

charge within each molecule (permanent dipole)

The interactions between permanent dipoles explain the attractions between

neighbouring CHCl3 molecules. They are intermolecular forces that hold together
polar molecules.

…………ẟ+CHCl3ẟ-…………. ẟ+CHCl3ẟ-………… ẟ+CHCl3ẟ-………….

The forces/attractions are much weaker than covalent/ionic bonds.

2. Van der Waals’ forces e.g., in Br2 (l) and liquid noble gases.

Are weak, short -range forces of attraction between molecules.

Involve attractions between induced dipole moments. Molecules that show the
strongest van der Waals’ forces are highly polarizable, i.e., their electron clouds
are easily distorted. They are usually large, heavy atoms or molecules.

How do van der Waals’ forces arise?

- Electrons in a molecule are in continual motion. On average the negative charge of non-
polar molecules is spread evenly around their nuclei. However, over very short periods of
time, the electron charge cloud around the molecule will not be perfectly symmetrical.
There is more -ve charge on one side of the molecule than on the other. It possesses an
instantaneous electric dipole.

- This dipole will induce dipoles in neighbouring molecules.

- Weak induced dipole – induced dipole attractions exist between molecules. As the size
of a molecule increases, the number of constituent electrons increases. The induced
dipole – induced dipole attractions become stronger.
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Influence of van der Waals’ forces

 the increase in b.p.s for the elements in Group VII (F 2, Cl2, Br2 and I2) is due to
the increase in strength of VDW’s forces as number of constituent electrons
increases with increase in molecular size.

 The increase in b.p.s for the homologous series of alkanes result from the stronger
VDW’s forces of attraction with increasing molecular size.

 VDW’s forces also account for the properties of graphite. Crystals of graphite are
composed of parallel layers of hexagonally arranged C atoms. Within each layer,
C atoms are linked by strong covalent bonds. The parallel layers are held together
by VDW’s forces. The VDW’s bonding between the layers is strong enough to
hold the layers together, but weak enough to allow them to slide over each other.
Because of this, graphite is soft and acts as a solid lubricant.

3. Hydrogen bonding

- Is a dipole-dipole attraction which occurs between a hydrogen atom attached to a strongly

electronegative atom and a second strongly electronegative atom with a lone pair of
electrons.

Essential requirements for a Hydrogen bond.

1. A hydrogen atom attached to a highly electronegative atom e.g., N, O, F with lone

pairs of electrons.

2. An unshared pair of