Physical Chemistry

Lewis Structure
• When atoms reacts to form chemical bonds, only the
valence electron is involved in the bond formation.
Practice:
Draw the Lewis diagrams for the following elements:
a) F
b) O
c) N
d) C
e) B
Electrovalent Bonding
1. The tendency for atoms in compounds to achieve noble gas
configuration with eight electrons is called octet rule.
2. The ionic bond in LiF is formed by the transfer of an
electron from a Li atom to a fluorine atom.
3. The electrovalent bond (ionic bond) is the electrostatic
attraction between two oppositely charged ions.
4. 1s2 2s2 2p6

1s2 2s2 2p6 3s23p6

Factor influencing the Formation of ions
1. Formation of cation: the lower the ionization energy of an
atom or ion, the easier it lose an electron to form cation.
2. Formation of anion: the more negative electron affinity, the
greater the atom to accept an electron and the more stable
is the anion formed.
3. Formation of ionic compound
Lattice energy: energy liberated when one mole of a solid
ionic compound is formed from its component ions in the
gaseous state.
Na+(g) + Cl-(g)  NaCl (s) Lattice energy: -788 kJ/mol
4. Lattice energy is exothermic. When elements is combined,
the content of energy is decreased.
Na(s) + ½ Cl2
(g)
∆H = -411.5kJ/mol
NaCl (s)
y gr e ne
1. The process of changing a chlorine gas into Cl- in the
gaseous state is exothermic process.
½ Cl2 (g) + e  Cl- (g) ∆H = -226.6 kJ/mol
2. The process of changing a sodium atom into Na+ in the
gaseous state is endothermic process.
Na(s)  Na+(g) + e ∆H = +603.1 kJ/mol
3. Gaseous sodium ion is less stable. Its can only be stabilized
by combining:
Na+ (g) + Cl-(g) -> NaCl (s) ∆H = -788 kJ/mol
(Lattice energy)
4. The net energy change when one mole of sodium chloride is
formed from its elements.
Na(s) + ½ Cl2 (g)  NaCl (s) ∆H = -411.5 kJ/mol
A very stable ionic compound is formed
when:

a) An element with low ionization energy

combines with an element with a high
electron affinity.

b) The lattice energy of the compound formed is

very high.
Covalent bonding: Sharing of Electrons
• When two non metallic atoms come together, electrostatic
interactions begin to develop between them.
• Attraction and repulsion between the electrons and the
nuclei of the atoms happen.
• The forces just balance when the nuclei are at a particular
distance apart called bond length
• A diatomic molecule consists of two identical atoms joined
together by a covalent.

• A pair of electrons in a covalent bond: bond pair.

Electron pairs in the valence shell that are not involved in
bonding : lone pairs.
Exception To the Octet Rule

F
F F
Cl Be Cl
S
F F
F
Multiple Covalent Bonds

Formula Lewis Structure Bond diagram

CO2

N2
Sulphate
ion
Carbonate
ions
Nitrate ion

Cyanide ion
Resonance Structures

1. O3
2. SO2
3. NO2
4. SO3
5. [NO3]-
6. [CO3]2-
7. [SO4]2-
Writing Dot-and Cross Formulae For Molecule
with Multiples Bonds

1. Calculate the total number of valence electrons from all

the atoms in the molecule or ion given.
2. Arrange all the atoms surrounding the central atom by
using a pair of electrons per bond. The central atom is
most often the atom which is least electronegative.
3. Assign the remaining electrons to the terminal atoms so
that each terminal atom has eight electrons.
4. Place any electrons left over on the central atom. Some
atoms such as sulphur and phosphorus, the central atom
may have more than eight electrons.
5. Form multiple bonds if there are not enough electrons to
give the central atom an octet of electrons.
Practice: C2H4, C2H2, ClO3-, CS2, N2H2, N2H2, [CuCl2]2-,
NO2 -
Covalent Bonds: Overlapping of Orbitals
Valence bonds theory
• When two atoms gets close together to form a covalent
bond, the orbitals of the outer shell of one atom overlap
with the orbitals of the other atom.
• The overlapping of atomic orbitals give molecular
orbitals.
• The pair of electrons in the covalent bond is shared
between two atoms in the area where the orbitals
overlaps.
• The strength of the covalent bond is proportional to the
area where the atomic orbitals overlap.
• The larger of the area of overlap, the stronger the
covalent bond.
Covalent Bonds: Overlapping of Orbitals
1s 1s

+ + + + + +

H H H2

F(2p)
H F

H(1s)
Hybrid atomic Orbitals

1. The process of mixing together two or more atomic

orbitals that have similar energies is called
hybridization.
2. Types of hybrid orbitals:
a) sp3 (tetrahedral shape)
b) sp2 (trigonal planar shape)
c) sp (linear shape)
Methane, CH4
The simple view of the bonding in methane

Electronic structure of carbon, 1s22s22px12py1.

You can see this more readily using the electrons-in-boxes notation.
Only the 2-level electrons are shown.
The 1s2 electrons are too deep inside the atom to be involved in bonding.
The only electrons directly available for sharing are the 2p electrons. Why
then isn't methane CH2?
Promotion of an electron

When bonds are formed,

energy is released and the system becomes more stable.
If carbon forms 4 bonds rather than 2,
twice as much energy is released and
so the resulting molecule becomes even 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 extra energy released when the bonds form
more than compensates for the initial input.
Hybridisation

The electrons rearrange themselves again

in a process called hybridisation.
This reorganises the electrons into
four identical hybrid orbitals called sp3 hybrids
(because they are made from one s orbital and three p orbitals).
You should read "sp3" as "s p three" - not as "s p cubed".
Ethane, C2H6

The hydrogens bond with the two carbons

to produce molecular orbitals just as they did with methane.
The two carbon atoms bond by merging their remaining
sp3 hybrid orbitals end-to-end to make a new molecular orbital.
The bond formed by this end-to-end overlap is called
a sigma bond. The bonds between the carbons
and hydrogens are also sigma bonds.
Sp2 Hybridization Orbitals

Sp2

Ground State Excited State

BF3, C2H4, C6H6

Sp Hybridization Orbitals
The simple view of the bonding in ethyne
Ethyne has a triple bond between the two carbon atoms.
In the diagram each line represents one pair of shared electrons.

sp
Sp Hybridization Orbitals
The Coordinate Bond
1. In some molecules or ions, both electrons in the covalent
bond are supplied by one of the bonded atoms,
(Coordinate bond).
H Cl

H N Al Cl Dimers

H Cl

H Cl

H N B Cl

H Cl
Complex Ions and Coordination Compounds
1. One of the most important chemical properties of the d-
block elements is their ability to form coordination.
2. A coordination compound is a compound in which a central
metal ion is linked to a group of surrounding molecules or
ions by coordinate dative bonds.
3. The ions or small molecules that surround the metal ion in
a coordination compound are called ligands.
Electronegativities and Polar Molecules

1. Different elements have different abilities to attract

electrons.
2. The ability of an atom that is covalently to another atom
to attract a pair of electrons to itself is called the
electronegativities.

Non-Polar Covalent Bonds

1. Two identical atoms having the same electronegativites
bonded covalently.
2. CO2, CCl4,BF3, C6H6, C6H12 are no polar molecules
because the molecule are symmetrical.
Polar Covalent Bonds
1. The bonding electrons will be attracted more strongly by
the more electronegative element and this results in an
asymmetrical distribution of the bonding electrons.
H Cl
2. The separation of charge in a polar covalent bond like H-Cl
is called polarization.
3. When two electrical charges of opposite sing are separated
by a small distance, a dipole is established.
4. The size dipole is measured by its dipole moment (µ).
µ = charge x distance = Q x r ,
Unit (D)
Hydrogen Halide Dipole moment
HF 1.91
HCl 1.05
HBr 0.80
HI 0.42
 Polar and Non Polar Molecules

Molecules Dipole Moment Polar @ Non Polar Molecule

HCl 1.05 Polar molecules

SO2 1.63 Polar molecules

CO2 0 Non-Polar molecules

C 6H 6 0 Non-Polar molecules
BF3 0 Non-polar molecules

C6H5Cl 1.67 Polar molecules

H 2O 1.84 Polar molecules

Electronegativity and type of Chemical Bonds
Ionic Character in a Covalent Bond
• The bonds between elements with a very large difference
in electronegativity is ionic.
Covalent bond C-I C-H C-Cl C-F

Ionic Character 0 4 6 40

• The bond between elements with similar electronegativity

may be polar or non polar covalent.

• The presence of dipoles gives ionic character to polar

covalent molecules. When the polarity of the covalent
molecules increases, the ionic character also increases.
Covalent Character and Ionic Bonds
1. An ionic bond is formed if:
b) The cation has a large ionic radius
c) The anion has a small ionic radius
d) The cation or anion carries a low electrical charge

2. The distortion of the charge cloud of the negative ion by a

neighboring positive ion is called polarization and the
negative ion is said to be polarized by the positive ion.

3. The polarizing Power A Cation depends on two

factors its charge and its size.
a) The larger the positive charge on the cation, the greater is
its attraction for the valence electrons of the neighboring
anion and the greater its polarizing.
b) The smaller the size of the positive ion, the larger its
polarizing power.
Covalent Character and Ionic Bonds

1. These two factors combine to make up the charge

density on the positive ion.
2. The charge density is the ratio of the charge on the
positive ion to the ionic radius of the ion.
3. Charge = (Charge/Ionic radius)
4. The greater the charge density on the positive ion, the
greater its polarizing power and the greater the covalent
character of the bond it forms with a given negative ion.
Covalent Character and Ionic Bonds