CHEMICAL BONDING – SUMMARY

Type of substance

Substance Metal Ionic compound Simple covalent Giant covalent

compound / discrete compound / giant
molecule molecule
Examples Fe, Al, Cu NaCl, MgO, Fe2O3 H2O, CO2, HCl diamond, graphite,
SiO2
Structure regular lattice of giant regular lattice discrete molecules giant molecule
positively charged of oppositely where there are where there are
cations surrounded charged ions strong covalent strong and extensive
by sea of delocalized bonds between covalent bonds
electrons atoms within the between atoms held
molecules in a giant lattice
Bonding Metallic bond: Ionic bond: electrostatic forces electrostatic forces of
electrostatic electrostatic of attraction attraction between the
attraction between attraction between between the 2 nuclei 2 nuclei and the
positively charged oppositely charged and the shared pair shared pair of
cations in a giant ions in a giant of electrons between electrons between
regular lattice and regular lattice them them
the delocalized
electrons from the Ionic bonds are non- Covalent bonds are
valence shells of the directional (in all directional
metal atoms. directions)
Attractive strong metallic strong ionic bonds weak intermolecular strong and extensive
forces to bonds forces of attraction covalent bonds
overcome (id-id interaction, pd-
during pd interaction or H-
melting bonding)
Remarks Melting point α Melting point α
valency. Larger strength of ionic bond
valency, greater α lattice energy α
charge of metal cation |(q+q-)/(r+ + r-)|
and more delocalized q – charge of ion
e-, hence stronger r – radius of ion
metallic bond, higher (only accurate for
mp. highly ionic
compounds)

Diamond Graphite Silicon Dioxide

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Exercise 1
Explain the melting point trends of the following sets of substances
a. Na – 97.7 0C Mg – 650 0C Al – 660 0C
b. NaF – 993 0C NaCl – 801 0C NaBr – 747 0C
c. Na2O – 1132 0C MgO – 2852 0C Al2O3 – 2072 0C

Physical Properties of substances

Substance Metal Ionic Simple covalent Giant covalent

Melting point High due to strong High due to strong Low due to weak High due to
/ boiling metallic bonds ionic bonds intermolecular strong and
point forces of attraction extensive
between molecules covalent bonds
Electrical Good due to free Good in molten or Non-conductors as Non-conductors
conductivity mobile electrons aqueous state due no charge carriers (except graphite
as charge carriers to mobile ions as where
Metals are good charge carriers delocalised
heat conductors electrons can act
due to mobile as charge
electrons also carriers within
layers)
Solubility in Insoluble due to Soluble as strong Insoluble due to Insoluble due to
polar solvent strong metallic ion-dipole poor interaction with strong and
(water) bonds interactions formed water hence energy extensive
between ions and released insufficient covalent bonds
water release to overcome
sufficient energy to hydrogen bonds
overcome ionic between water
bonds molecules
Solubility in Insoluble due to Insoluble as weak Soluble due to good Insoluble due to
non-polar strong metallic interaction between interaction with non- strong and
solvent bonds ions and non-polar polar solvent via id- extensive
solvent, hence id interactions covalent bonds
energy released
insufficient to
overcome ionic
bonds
Others heat conductors, Hard, brittle Hard (diamond)
ductile,malleable,
shiny

A Closer look at solubility in water (eg NaCl & C 6H12)

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Relationship between Ionic and Covalent Bonds and Everything in between

Type of cpd Ionic compound Covalent compound

Nature of Highly Ionic Ionic with Covalent with Polar (Covalent Non-polar
bond covalent ionic character with ionic (Highly
character character) covalent)
Example NaF, Na2O NaBr, MgCl2 AlCl3, AlBr3 HCl, NH3 H2, F2, O2
Diagram

Factors Polarising power of cation Difference in electronegativity

- depends on charge density (charge-size ratio) - greater difference in
- higher charge density, higher polarizing power, electronegativity, greater dipole
greater distortion of anion electron cloud, more moment, more polar bond
covalent character
- compare Na+, Mg2+, Al3+

Polarisability of anion
- depends on size of anion
- larger size of anion, more polarisable, greater
distortion of electron cloud, more covalent
character
- compare F-, Cl-, Br-, I-

Explanation - No distortion - cation high - cation high - big difference - little / no

of electron charge density charge density in electro- difference in
cloud and high (small size, high negativity electro-
- ions spherical polarizing charge) and - electron pair negativity
- hence highly power high polarizing pulled towards - electron pair
ionic - anion electron power more equally shared
cloud large and - anion electron electronegative - non-polar
polarisable cloud large and atom
- distortion of polarisable - polar bond
electron cloud - great
but no overlap distortion of
of orbital electron cloud
- hence ionic such that
with covalent orbital overlap
character - hence
- more covalent
properties of - compare
covalent cpds, MgCl2 vs AlCl3
eg lower mp - compare AlF3,
AlCl3, AlBr3
Trends
Ionic / cov

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σ (sigma) bond vs π (pi) bond
• σ (sigma) bond when orbital overlap is head-on
and directly along the axis joining the 2 nuclei.
Rotation of the bond about the axis does not affect
the overlapping and the stability of the bond, hence σ
bond can be rotated.

• π (pi) bond when orbital overlap is side-way and

above and below the axis joining the 2 nuclei.
Rotation of the bond about the axis affects the
overlapping and breaks the bond, hence π bond
cannot be rotated.

• σ is always formed first as σ bond has a better orbital overlap hence is stronger than π bond
• there can only be 1 σ bond but multiple π bonds between 2 atoms

C–C C=C CΞC

Bond energy, length, polarity and reactivity

• bond energy of a covalent bond is the energy required to break one mole of that bond (kJ mol-1)
• higher the bond energy, stronger the covalent bond, and less reactive the bond
• In general,
◦ shorter the bond length, stronger the bond
◦ triple bond stronger than double bond stronger than single bond
◦ polar bond stronger than non-polar bond due to additional electrostatic attraction from ionic
character (eg CO 1079 kJ mol-1 , N2 994 kJ mol-1)

Dative / Co-ordinate Bond

• covalent bond in which a pair of electrons is shared between 2
atoms but only one of them provides both electrons that make
up the bond
• Donor atom has lone pair of electrons for sharing
• Acceptor atom has an empty orbital to accept the lone pair
• Strength of dative bond and normal covalent bond are the
same

Exercise 2
Aluminium chloride in gaseous state exists as dimer Al2Cl6. Dative bonds hold monomers of aluminium
chloride together. Draw the structure of this dimer.

Drawing Dot-and-cross Diagram

• Central atom is usually
◦ atom that needs the greatest number of electrons to gain noble gas configuration.
◦ atoms that need less electrons to gain stable configuration but can expand octet hence can
form more bonds, eg XeF4, IO4-
• Not all molecules have a central atom. Eg H 2O2
• In general, atoms that need 1 electron to gain noble gas configuration will share 1 electron to form 1
bond (eg H, F, Cl, Br); atoms that need 2 electrons will form 2 bonds (eg O, S); atoms that need 3
electrons will form 3 bonds (eg N); atoms that need 4 electrons will form 4 bonds (eg C, Si).

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 • Expansion of Octet (for central atom)
◦ An atom from Period 3 and below can use its energetically accessible d-subshell for
bonding and hence can have more than eight electrons
◦ Only elements from Period 2 (B, C, N, O and F) cannot expand octet as they do not have d-
subshells
• Electron deficient atoms have less than 8 electrons and are unstable eg BeCl2, NO, NO2
• For anions, the additional electrons are added to the more electronegative atom
• For cations, the electrons are removed from the less electronegative atom
• For oxoacids such as HNO3, H2SO4, H3PO4, the hydrogen atoms are bonded to oxygen instead of
the central atom

Exercise 3 – Draw the dot-and-cross diagrams and lewis structures for the following molecules:
(a) BeCl2, PCl5, H2O2, NH4+ (b) NO, NO2, NO2+, NO2-, N2O, NO3- (c) SO42-, H2SO4, H3PO4
(d) ClO-, ClO3-, IO4-, PCl4- (e) CO, XeF4 , O3, I3-, N3-

Shapes of Molecules
• Shapes of simple covalent molecules and ions are determined by Valence Shell Electron Pair
Repulsion (VSEPR) Theory
• Postulate 1: Electron pairs (bonding or non-bonding) in the valence shell repel each other and
orientate themselves in space as far apart as possible so as to minimise the repulsion between them
◦ gives rise to the basic shape of the molecules or ions and is determined by the total number of
electron pairs (bonding and non-bonding) around the central atom
◦ electrons in a multiple bond (double or triple bonds) are regarded as one region of electron
cloud or one electron pair
Total no. of electron
pairs = bond pairs + Basic Shape Diagram Bond angle
lone pairs

• Postulate 2: Repulsion between electron pairs decrease in the following order:

lone pair-lone pair > lone pair-bond pair >bond pair-bond pair

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Exercise 4

Compound CH4 NH3 H2O

Dot-and-cross diagram

No. of electron pairs

Basic shape

No. of bond pairs

No. of lone pairs

Shape of molecule

Bond angle

Diagram

• Postulate 3: Repulsion between bond pairs of electrons increases with an increase in the
electronegativity of the central atom
◦ more electronegative atom has a stronger attraction for the bonded electron pairs and
results in a higher electron density around it causing stronger repulsion between the bond pairs
of electrons. This leads to an increase in bond angle.
Exercise 5
Explain why the bond angle in NH3 is slightly larger than that in PH3.

• Postulate 1 determines the basic shape of molecule or ion, Postulate 2 determines the actual shape
and bond angle, while Postulate 3 determines the slight deviations in the bond angles of two
molecules with same actual shape.
• General Steps in determining shape of molecules or ions
1. Draw dot-and-cross diagram / Lewis structure
2. Determine total number of electron pairs and hence basic shape (Postulate 1)
3. From number of bond pairs and lone pairs, determine the actual shape and bond angle
(Postulate 2)
4. If comparing 2 molecules with same actual shape, differentiate bond angles by electronegativity
of the central atom (Postulate 3)

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Exercise 6
e
pairs Shape of Bond
bp lp Diagram Examples
molecules angle

BeCl2, CO2,
2 2 0
HCN

BCl3, BH3,
3 0
SO3
3

2 1 SO2, SnCl2

4 0 CH4, NH4+

4 NH3, PF3,
3 1
H3O+

2 2 H2O, SCl2

5 0 PCl5

4 1 SCl4, TeCl4

3 2 ClF3

2 3 XeF2

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 6 0 SF6

5 1 BrF5, TeF5

6 4 2 XeF4, ICl4-

3 3 XeF3-

2 4 XeF22-

Exercise 7
Species SO3 SCl2 XeF2 BrF5
Dot-and-cross

E pairs
Basic shape
bp + lp
Shape

Bond angle