PHYSICAL CHEMISTRY

CHEMICAL BONDING
AND STRUCTURES

1
Overview
◼ Dot and cross diagrams
◼ Types of chemical Bonding
◼ Ionic bonding
◼ Covalent bonding
◼ Metallic bonding
◼ Dative bonding
◼ VSEPR and shapes of molecules and ions
◼ Hybridisation of atomic orbitals
◼ Electronegativity and type of bond
◼ Polarising power of cations
◼ Polar molecules and dipole-dipole bonds
◼ Intermolecular forces of attraction
◼ Permanent dipole-dipole interaction
◼ Temporary dipole-induced dipole (London Dispersion forces)
◼ Hydrogen bonds 2
Dot and Cross Diagrams
◼ Very few elements around us exist as free elements.
Elements tend to combine with each other to form
compounds which are naturally more stable than the free
elements.

◼ Chemical bonds are formed which bind the different

elements together.

◼ During the formation of chemical bond, each of the

combining atoms will change its electron arrangement to
achieve a duplet / octet electron arrangement.

3
Dot and Cross Diagrams
◼ Represent the electrons in the outer
shell of an atom or ion.
◼ Show where electrons come from.
◼ Each dot (•) or cross (x) represent 1
electron from different atom

4
Ionic bonding
◼ Electrovalent bonding
◼ Ionic bonding is formed by the transfer of
valence electrons from atom of element to
the outer orbital of another atom
◼ Atoms with low ionisation energy (usually
metals) will lose electrons to form positive
ions (cations).
◼ Non-metal atoms will gain electrons to form
negative ions ( anions).
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 Ionic bonding
◼ Both the cation and anion achieve stable electronic
configuration as that of the noble gas.
◼ Ionic bond is the strong electrostatic force of
attraction between the 2 oppositely charged ions.
◼ Strength of ionic bond is
(a) proportional to the charge on the ions
(b) inversely proportional to the distance between the
ions.
◼ The higher the charge on the ions / smaller the ionic
radius, the stronger is the attractive force between the
ions, stronger ionic bond.
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Ionic bonding

7
Covalent bonding
◼ Atoms of non-metal combine among each other or
with the atoms of another non-metal.
◼ Sharing of electrons between non-metal atoms.
◼ Attraction occurs between the pair of electrons and
the nucleus:-

8
Covalent bonding
◼ In the formation of a covalent bond:
(a) each atom has an orbital in the
outer shell containing single electron
(b) Overlapping of the 2 orbitals so that
electron pair is produced, that shared
by both atoms.

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Covalent bonding

◼ When the orbital has 2 electrons in we call them

bonds:
Single covalent bond: sigma bond (𝝈 bond)
Double covalent bond: sigma bond (𝝈 bond) and a pi bond (𝝅 bond)
Triple covalent bond: sigma bond (𝝈 bond) and 2 pi bond (𝝅 bond)

◼ Each bond is represented by a line: single bond

double bond
triple bond

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 Covalent bonding
Sigma(σ) bond :
◼ This type of covalent bond is formed by the end
to end (head-on) overlap of bonding orbitals
along the internuclear axis.
◼ This is called as head on overlap or axial
overlap. This can be formed by any one of the
3 types of combinations of atomic orbitals.

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Covalent bonding

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Covalent bonding
pi(𝝅 ) bond :
◼ In the formation of 𝝅 bond the atomic
orbitals overlap in such a way that their axes
remain parallel to each other and
perpendicular to the internuclear axis.
◼ The orbitals formed due to sidewise
overlapping consists of two saucer type
charged clouds above and below the plane of
the participating atoms.
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Covalent bonding

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Bond energy and bond
length
◼ The strength of covalent bond is measured by bond
energy.
◼ The covalent bond energy : amount of heat (in
kJmol-1) required to break a covalent bond, per mole
of bonds.
◼ The higher the bond energy, the stronger the
covalent bond.
A-B (g) A(g) + B (g) ΔH = positive

15
Bond energy and bond
length
◼ The covalent bond length is the
distance between 2 adjacent nuclei of
two atoms

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Bond energy and bond
length
◼ Generally, the longer the bond length, the weaker
the covalent bond.
◼ Multiple bonds are stronger than single bonds.

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 Chemical Bonds

Bond Type Single Double Triple

# of e’s 2 4 6
Notation — = 
Bond order 1 2 3
Bond
Increases from Single to Triple
strength
Bond length Decreases from Single to Triple
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 Placing electrons around atoms
Compound 4) Octet for
peripheral
atoms

1) Skeletal 5) Remaining
Structure e–s on center
atom

2) Count 6) Create
electrons multiple
bonds?

3) Electron Final structure

pairs in bonds

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Covalent bonding
Dots and Cross Diagrams & Lewis structure of molecules:
◼ Chlorine (Cl2)

◼ water (H2O)

◼ Ammonia (NH3)

◼ Phosphorus trichloride (PCl3)

◼ Methane (CH4)

◼ Hydrazine (N2H4)

◼ Oxygen (O2)

◼ Carbon dioxide (CO2)

◼ Ethene (C2H4)

◼ Nitrogen (N2)

◼ Hydrogen cyanide (HCN)

◼ Ethyne, (C2H2)
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Covalent bonding
◼ The surrounding atoms attain octet (or duplex for H) configuration
◼ There are some covalent molecules / species which do not obey the
octet rule (Exceptions to the octet rule)
1. Compounds with less than 8 electrons in outermost shell per atom
Beryllium chloride, BeCl2 (Be is surrounded by 4 e-)

Boron trihydride, BH3 (B is surrounded by 6 e-)

Aluminium chloride, AlCl3 (Al is surrounded by 6 e-)

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 Covalent bonding
2. Compound with more than 8 electrons in the outermost shell per
atom.
Phosphorus (V) chloride, PCl5 (P is surrounded by 10 e-)

Sulphur (VI) fluoride, SF6 (S is surrounded by 12e-)

Bromine (V) fluoride, BrF5 (Br is surrounded by 12e-)

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 Covalent bonding
3. Odd electron molecules
Nitrogen monoxide, NO (N is surrounded by 7 e-)

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Covalent bonding
◼ NF3 exist, but NF5 does not. Suggest
why?

◼ IF7 exists, but ClF7 does not. Suggest a

reason for this.

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 Metallic bonding
◼ In metal, the atoms are closely packed together.
◼ Metals are malleable and ductile
- Malleable: can be knocked into shapes
- Ductile: Can be drawn into wires.
◼ Good conductors of heat and electricity in the solid state.
◼ Metal atoms
- low electronegativities
- lose electron easily to become ions
◼ Electron occupy the space between the metal ions
- free to move
- delocalised.

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Metallic bonding
◼ Metallic bonds: forces of attraction between the positive
metal ions and negative delocalized electrons.
◼ To form metallic bonds, element must have
- big atoms
- a relatively low ionization energy
◼ Cations are immersed in the “sea of delocalised electrons”.

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 Metallic bonding
Factors affecting the strength of metallic bonding:
◼ Charge density of cation
- cation with smaller size and highly charge has stronger metallic bonding.
◼ Number of electrons per atom (outermost electrons / bonding electrons) and
charge on cations.
- more valence electrons per atom, strength of metallic bonding increases.
- exp: melting point of Na< Mg< Al
◼ Arrangement of atoms in solid lattice

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Dative bonding
(Co-ordinate bonding)
◼ In normal covalent bond, each atom provides one electron to
the pair of electrons that are shared between them.
A B A-B
+

◼ In dative bond, one atom provides two electrons which are

shared with another atom.
- Donor: must have a lone pair of electrons.
- Acceptor: must have an empty orbital to accommodate the 2
electrons.
A B A B
+
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Dative bonds (Co-ordinate
bonds)
◼ Aluminium Chloride Dimer (Al2Cl6)
AlCl3 is covalent compound
Al: relative small atomic size; high I.E.’s
required to become a cation of +3 charge.

(a dimer of AlCl3) 29
Dative bonding
(Co-ordinate bonding)
Draw the dot and cross diagram & Lewis structure for the
following species:
1. Ammonium ion (NH4+)
2. Hydroxonium ion (H3O+)
3. Carbon monoxide (CO)
4. Ozone (O3)
5. AlCl4-
6. BF4-
7. PF6-
8. NO2 (odd number electron on N atom)

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VSEPR and shapes of
molecules and ions
◼ The valence shell electron pair repulsion theory

◼ Lewis concept is unable to explain the shapes of

molecules. This theory provides a simple procedure
to predict the shapes of covalent molecules.

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VSEPR and shapes of
molecules and ions
• The shape of a molecule depends upon the number of
valence shell electron pairs (bonded or non-bonded)
around the central atom.

• Pairs of electrons in the valence shell repel one

another (equal repulsion) since their electron clouds
are negatively charged.

• These pairs of electrons tend to occupy such positions

in space that minimize repulsion and thus maximize
distance between them.
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VSEPR and shapes of
molecules and ions
• The valence shell is taken as a sphere with the
electron pairs localizing on the spherical surface at
maximum distance from one another.

• A multiple bond is treated as if it is a “single

electron pair”
- two or three electron pairs of a multiple bond are
treated as a single super pair.

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VSEPR and shapes of
molecules and ions
The repulsive interaction of electron pairs
decrease in the order:
Lone pair (lp) – Lone pair (lp) > Lone pair
(lp) – Bond pair (bp) > Bond pair (bp) –
Bond pair (bp)

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 VSEPR Model

To determine the electron pair geometry:

• draw the Lewis structure,
• count the total number of electron pairs around the central atom,
• arrange the electron pairs in one of the above geometries to
minimize e--e- repulsion, and count multiple bonds as one
bonding pair.

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VSEPR and shapes of
molecules and ions

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◼ Theoretically, the shape should have been trigonal planar
◼ But actually it is found to be bent or v-shaped.
◼ The lone pair bond pair repulsion is much more as
compared to the bond pair-bond pair repulsion.
◼ So the angle is reduced to 119.5° from 120°.

42
◼ If bp in place of lp, the shape would have been
tetrahedral
◼ but one lone pair is present and due to the repulsion
between lp-bp , which is more than bp-bp repulsion.
◼ the angle between bond pairs is reduced to 107° from
109.5°.
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◼ The shape should have been tetrahedral if there were all
bp
◼ two lp are present so the shape is distorted tetrahedral
or angular.
◼ The reason is lp-lp repulsion is more than lp-bp
repulsion which is more than bp-bp repulsion.
◼ Thus, the angle is reduced to 104.5° from 109.5°.
44
◼ In (a) the lp is present at axial position so there are three
lp-bp repulsions at 90°.
◼ In(b) the lp is in an equatorial position, and there are two
lp-bp repulsions.
◼ Hence, arrangement (b) is more stable. The shape shown
in (b) is described as a distorted tetrahedron, a folded
square or a see-saw.
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◼ In (a) the lp are at equatorial position so there are less lp-
bp repulsions as compared to others in which the lp are at
axial positions.
◼ So structure (a) is most stable. (T-shaped).
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 Describing the shape of
molecules / polyatomic ions
◼ _________electron pairs around center atom.

◼ _______bond pair(s), __________lone pair(s)

or _____single bond (s), _____double bond(s), ____triple bond.

◼ All electron pairs repel each other

◼ Lp-lp repulsion > lp-bp repulsion> bp-bp repulsion.

◼ Shape, Bond angle(s)

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Summary of VSEPR Molecular Shapes
e-pairs Notation Name of VSEPR shape Examples
2 AX2 Linear CS2 , CO2
3 AX3 Trigonal planar BF3 , GaI3
AX2E Non-linear (Bent) SO2 , SnCl2
4 AX4 Tetrahedral CCl4 , CH4 , BF4-
AX3E (Trigonal) Pyramidal NH3 , PH3
AX2E2 Non-Linear (Bent) H2O , OF2
5 AX5 Trigonal bipyramidal PCl5 , PF5
AX4E Distorted tetrahedral TeCl4 , SF4
(see-sawed)
AX3E2 T-Shaped ClF3 , BrF3
AX2E3 Linear I3- , ICl2-
6 AX6 Octahedral SF6 , PF6-
AX5E Square Pyramidal IF5 , BrF5
AX4E2 Square Planar ICl4- , BrF4-
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 Hybridisation of atomic
orbitals
◼ In the formation of covalent bonds, each combining atom contributes
one unpaired electron to the bonding pairs.
◼ According to the molecular orbital theory, we can expect the number
of bonds which an element can form to be equal to the number of
unpaired electrons in the valance shell.
◼ However, a problem is posed by elements like carbon, boron,
beryllium etc, where the number of unpaired electrons does not
represent the number of bonds formed.
◼ Sometimes, the number of covalent bonds that can be formed by a
particular atom exceeds the number of unpaired electrons in its
valence shell.
◼ Hybridisation: mixing of 2 or more orbitals to form a set of new
orbitals of identical shape and energy.
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Hybridisation of atomic
orbitals

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 Hybridisation of atomic
orbitals
◼ Carbon:
◼ When bonds are formed, energy is
released and the system becomes more
stable.
◼ There is only a small energy gap between
the 2s and 2p orbitals, and so it pays the
carbon to provide a small amount of
energy to promote an electron from the
2s to the empty 2p to give 4 unpaired
electrons.
◼ The carbon atom is now said to be in an
excited state. 51
 Hybridisation of atomic
orbitals
◼ sp3 hybridisation

52
Hybridisation of atomic
orbitals
◼ sp3 hybridization
- 4 hybrid orbitals arranged in tetrahedral
geometry
- Bond angle = 109.5o

53
Hybridisation of atomic
orbitals
◼ Example: CH4, C2H6

CH4 C2H6 54
Hybridisation of atomic
orbitals
◼ sp2 hybridization

55
Hybridisation of atomic
orbitals
◼ sp2 hybridization
- 3 hybrid orbitals arranged in trigonal
planar geometry.
- bond angle = 120o

56
Hybridisation of atomic
orbitals
◼ Example: C2H4

C2H4
57
Hybridisation of atomic
orbitals
◼ sp hybridization

58
Hybridisation of atomic
orbitals
◼ sp hybridization
- 2 hybrid orbitals arranged in linear
geometry.
- bond angle = 180o

59
Hybridisation of atomic
orbitals
◼ Example: C2H2

C2H2
60
Hybridisation of atomic
orbitals

61
Hybridisation of atomic
orbitals

Benzene has two resonance forms

◼ The six carbon - carbon bonds are of equal length,
intermediate between a single bond and double
bond
◼ The molecule is planar (sp2 hybridization)

◼ The bond angle around each carbon is

approximately 120°
62
Hybridisation of atomic
orbitals

◼ sp2 hybridization.
◼ 2 σ bonds with 2 adjacent C atoms and one σ bond with H
atom.
◼ Unbound pz orbital on each carbon atom perpendicular to the
plane of hexagonal planar ring.
◼ The 6 unhybridized p orbital will overlap sideways to form 2
rings of electron cloud (𝜋 electrons system).
◼ The 6 electrons in the 2𝜋electron cloud are free to move around
the benzene ring (delocalised electrons)
63
Electronegativity and
types of bonds
◼ Electronegativity is a measure of the tendency of
an atom in a covalent bond to attract a
bonding pair of electrons.

◼ The Pauling scale is the most commonly used.

Fluorine (the most electronegative element) is
assigned a value of 4.0, and values range down to
caesium and francium which are the least
electronegative at 0.7.

◼ The higher the electronegativity, the stronger the

attraction for the bonding electrons
64
Electronegativity and
types of bonds

65
Variation of Electronegativity with Atomic Number

66
 Electronegativity and
types of bonds
Electronegativity Nature of bond
difference
> 1.7 Ionic : Xm+ Yn-
0.4 - 1.7 Polar covalent: δ+ δ-

X-Y
0 Non-polar covalent: X-X

Increasing difference in electronegativity

Covalent Polar Covalent Ionic

share e- partial transfer of e- transfer e-

67
 Electronegativity and
types of bonds
◼ Relationship between the type of bond and difference
in electronegativity between two bonded atoms

Bond Difference in electronegativity Type of bond

between the two bonded
atoms
Cl-Cl 3.0 - 3.0 = 0 Covalent
Cl-C 3.0 - 2.5 = 0.5 Polar covalent
Cl-H 3.0 - 2.1 = 0.9 Polar covalent
F-Li 4.0 - 1.0 = 3.0 Ionic

68
Polarising power of
cations
Polarising power and the ionic bond
◼ Polarization can also occur in an ionic bond.
◼ A cation and anion is usually visualized as spherical
particles with uniform distribution of charge in the
ion.
◼ As cation approaches an anion, the positive electric
field on the cation tends to pull the electron cloud of
the anion towards it, causing distortion if the electron
cloud of the anion.

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Polarising power of
cations
◼ Such distortion produces a certain amount of
covalent character in the ionic bond.

70
Polarising power of
cations
◼ The percentage of covalent character in an ionic
bond depends on the extend to which the electron
cloud of the anion is being distorted.
◼ The polarising power of cationα
(Charge density)
◼ Polarising ability increases as the positive ion gets
smaller and the number of charges gets larger.
◼ Also depend on the polarisibility of the anion. The
larger the size of anion, the weaker the attraction
between nucleus and electrons.
◼ The electron cloud is easier to be polarised by
cations. 71
Polar molecules and
dipole- dipole bonds
If two atoms of equal electronegativity bond together:
◼ both have the same tendency to attract the bonding pair
of electrons, and so it will be found on average half way
between the two atoms.
◼ A and B would usually have to be the same atom.

◼ electrons are shared evenly between the two atoms.

◼ Example, H2 or Cl2 molecules.

a pure
covalent
bond
72
Polar molecules and
dipole- dipole bonds
if B is slightly more electronegative than A:
◼ B will attract the electron pair rather more than A does.

◼ the B end of the bond has more than its fair share of

electron density and so becomes slightly negative.

◼ the A end becomes slightly positive.

◼ The covalent bond is said to be polarised and gives rise

to a certain amount of ionic character in the covalent
bond.
◼ Example: HF, NH3, H2O
a polar
covalent
bond
73
Polar molecules and
dipole- dipole bonds
◼ In a molecule like HF, which has a small positive
charge on one end and a small negative charge on
the other end, is called polar molecule.
◼ The molecule is said to have dipole moment.
◼ Example: HF, NH3, H2O, CHCl3

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Dipole Moments and Polar Molecules

electron rich
electron poor
region
region

H F

d+ d-

m=Qxr
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C m 75
 Behavior of Polar Molecules

field off field on

76
Bond moments and resultant dipole moments in NH3 and NF3.

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78
Polar molecules and
dipole- dipole bonds
◼ There are molecules that do not have dipole
moment even though the bonds are polarised.
◼ Example: CO2, CH4, CCl4, AlCl3
◼ As the molecule is symmetrical, the dipole exactly
cancels out one another (no dipole moment).
◼ Thus, the molecule is non-polar.

79
Polar molecules and
dipole- dipole bonds
◼ A covalent molecule is polar if:-
(i) The covalent bond in the molecule is
polarised.

(ii) The dipole do not cancel out one

another (has dipole moment).

80
 Intermolecular forces of
attraction
◼ Polarity of Molecules : Very weak when compare with
covalent bond between atoms in molecule.

Intermolecular forces

Temporary dipole-
induced dipole
hydrogen Permanent dipole-
interaction (London bonding dipole interaction
dispersion forces)

electrostatic attraction between dipoles, i.e. the

attraction between the +ve end of one molecule and
the -ve end of another molecule 81
 Permanent dipole-dipole
interaction

A permanent dipole exists in all polar molecules as a result

of the difference in the electronegativity of bonded atoms.
82
 Permanent dipole-dipole
interaction
◼ Permanent dipole-dipole interaction

Polar molecules have permanent dipole moments.

They tend to orient themselves in such a way that the
attractive forces between molecules are maximized
while repulsive forces are minimized.
83
 Temporary dipole-induced dipole
interaction (London Dispersion
forces)

A temporary dipole exists as a result of fluctuation in the

electron cloud.
84
 Temporary dipole-induced dipole
interaction (London Dispersion
forces)
◼ Temporary dipole-induced dipole interaction

The instantaneous dipole will induce a dipole

moment in the neighbouring atom by
attracting opposite charges. If the +ve end
of the dipole is pointing towards a
neighbouring atom, the induced dipole will
then have its -ve end pointing towards the
+ve pole of that dipole.

85
Strength of intermolecular
forces

Type of interaction Magnitude (kJ mol-1)

Permanent dipole-dipole interaction 5-25

Temporary dipole-induced dipole 0.05-50

interaction

86
Strength of intermolecular
forces
Strength of the dispersion forces is
proportional to
(1) the size of the molecule or the
number of electrons in molecule.

87
 Strength of intermolecular
forces
Molecule Boiling point (oC) The greater the no. of e-s in a
molecule
Helium -269
Neon -246
Argon -186
Fluorine -188 The more weakly they are held
Chlorine -34.7 by the nucleus
Bromine 58.8
Methane -162
Ethane -88.6
The easier the instantaneous
Propane -42.2
dipole can be set up (greater
intermolecular forces)
88
Strength of intermolecular
forces
(2) total surface area of the molecule.
◼ The linear isomer has a higher boiling
point than the branched isomers.
◼ This is because branched isomers are

more spherical in shape and this

decrease their total surface area

89
Strength of intermolecular
forces

90
 Hydrogen bonding
◼ Strongest of the intermolecular forces

◼ Requisite for a hydrogen bond:-

1) Within a molecule, the hydrogen must be highly
polarised (very positive). Bond polarity is due to the effect
of unequal sharing of electrons.

2) Within a molecule, the atom joined to the hydrogen must

be very electronegative. Electronegativity is the measure
of the tendecy to attract a bonding electrons. For
examples, O, N, F

3) Within a molecule, the atom joined to the hydrogen must

also have a lone pair of electrons. O,N and F have a lone
pair. 91
Hydrogen bonding

NH3 H2O HF
92
Hydrogen bonding
Boiling points of hydrides of Group 14
◼ Boiling point increases with the increase in the proton
number of Group 14 element.
◼ Intermolecular forces holding the molecule together are
the Van der Waals forces, whose strength increases with
the size and the total number of electrons in the molecule.

93
Hydrogen bonding
◼ Boiling points of hydrides of Group 15, 16 and
17

94
 Hydrogen bonding
◼ NH3, H2O and HF have abnormally high boiling points
(although their size is the smallest in their respective
groups) because of the presence of strong hydrogen
bonds between the molecules.

◼ H2O has higher boiling point than NH3

- Oxygen has 2 lone pair of electrons. Each H2O
molecule can form 2 intermolecular hydrogen bonding
- NH3 has only 1 lone pair of electrons. Each NH3
molecule can form 1 intermolecular hydrogen bonding

95
Hydrogen bonding
◼ Although fluorine atom in HF has 3 lone pair of
electrons, each HF molecule can form only 1
hydrogen bond.
◼ Boiling point is lower than H2O but higher than NH3.
◼ Fluorine is more electronegative than nitrogen atom,
causing hydrogen bonding between HF molecules to
be stronger.

96
Hydrogen bonding

HF

NH3
H2O
97
Hydrogen bonding
Solubility of covalent compound in water
◼ A covalent compound like ethanol is soluble in water.

- Ethanol can displace the water molecule in the

aggregates through hydrogen bonding.
◼ Substances like haloalkanes, RX (X = Cl, Br, I) which

cannot form hydrogen bonding with water are

insoluble in water.
◼ Other organic compounds which soluble in water are
amines, carboxylic acids, amides and sugar

98
 Questions
The boiling points and solubilities in water of the three
gases ammonia, hydrogen chloride and carbon dioxide are
given in the table

gas formula Mr B pt/0 C Solubility in water/ mol dm-

3

ammonia NH3 17 -33 18

Hydrogen HCl 36.5 -85 23
chloride
Carbon dioxide CO2 44 -78 0.033

Describe both intramolecular (polarity of the bond, no. of single and

double bonds and overlapping of orbitals) and intermolecular
bonding(hydrogen bonding, permanent dipole-permanent
dipole,instantaneous dipole-induced dipole) in each of the compounds,
relating the bonding to the boiling point where appropriate. 99
Questions
◼ Ethene,C2H4 and hydrazine N2H4, are hydrides of elements
which are adjacent in the Periodic table. The melting
ponts of hydrazine is + 2 0C and the ethene is -169 0C.
Suggest reasons for these differences in terms of the
intermolecular forces each compound possesses.

◼ The molecular formulae of each of these three elements

Phosphorus (P), sulphur (S) and chlorine (Cl) are P4, S8
and Cl2.
(i) Place the elements in the order of their melting points
with the highest first. Suggest an explanation for the
order you have given in (i).
100