CHAPTER 4

CHEMICAL
Why chemical bonds form?
• It’s a well stablished fact that noble gases do not
undergo chemical combinations.
• He, Ne, Ar, Kr, Xe, Rn
• They exist as monoatomic gases and do not make
chemical bonds.
• The reason why they do so, is that, they have complete
valance shell with 8 electrons. (octet)
• It’s the need of remaining all elements to acquire inert
gas configuration & hence they form chemical bonds.
How chemical bonds form?
• Elements except noble gases have unstable atoms.
• In order to have stable atoms, they need to complete
their valance shells.
• This is achieved by two means;
• i) By gaining or loosing the electrons. (Ionic Bonds)
• ii) By sharing the unpaired electrons. (Covalent Bonds)
• When atoms transfer or share electrons, electrostatic
forces are produced which keep them bonded.
What are chemical bonds?
• The electrostatic force of attraction that holds the
atoms together in a compound is known as a chemical
bond.
• The bonded atoms possess lesser energy and higher
stability as compared to the unbonded atoms.
• This energy is actually associated with the electrons in
the energy levels.
• Hence bond formation is process that lowers the
energy.
IONIC BOND OR ELECTROVALENT BOND

• Chemical bond formed between two atoms

due to transfer of electron(s) from one atom
to the other atom is called "Ionic bond" or
"electrovalent bond".
• In ionic bond formation one atom looses electron(s) and
the other picks it up.
• The atom that looses the electron acquires positive
charge and the other atom which gains the electron
becomes a negatively charged particle.
• Due to opposite charge an electrostatic force of
attraction is setup between them.
• This force hold these atoms together in a unit.
• This force of attraction is referred to as IONIC BOND
FORMATION OF IONIC BOND BETWEEN Na & Cl
• Electronic arrangement of Na (Z=11) is K = 2 , L = 8, M = 1
• Electronic configuration of Na is 1s2, 2s2, 2p6, 3s1
• It has one valence electron.
• The loss of the valence electron from Na-atom 495 KJ/mole
energy is needed.
• Due to low ionization potential value, Na-atom loses its valence
electron
• Electronic arrangement after losing an electron is K = 2, L = 8 , M
=0
• Electronic configuration after losing an electron is 1s2, 2s2, 2p6
.This shows that its octet is complete.
• Due to loss of one electron Na becomes Na+ -ion.
• Electronic arrangement of Cl (Z=17) is K = 2, L = 8, M = 7
• Electronic configuration of Cl is 1s2, 2s2, 2p6, 3s2 3p5.
• Cl-atom needs one electron to complete its octet.
• The gain of one electron by chlorine atom releases 348 KJ/mole
energy.
• Electron lost by Na atom picks up by Cl atom.
• Electronic arrangement after acquiring an electron: K = 2, L = 8,
M=8
• Electronic configuration of Cl is 1s2, 2s2, 2p6, 3s2, 3p6 . This shows
that its octet is also complete.
• Cl + e- → Cl- : ∆H = −348 KJ/mole
• We know that positive and negative ions attract each
other, therefore an electrostatic force of attraction is set
up between Na+ & Cl- ions.
• This force unites these ions in a unit.
• In this way ionic bond is formed between Na and Cl atoms
which results in the formation of sodium chloride.
• In the above two steps we clearly observe that there is a
difference of energy i.e.
• This shows formation of one mole of NaCl increases the
energy of system by 147 KJ /mole.
• There arises a question "How this difference of energy is
compensated?"
• The answer to this question is that when oppositely
charged ions i.e. Na+ ions & Cl- ions attract each other
and arrange themselves to form crystal lattice of NaCl
which consists of very closely packed positive & negative
ions.
• In NaCl crystal each Na+ ion surrounded by six Cl- ions.
• Similarly each Cl- ion is surrounded by six Na+ ions.
• The force of attraction between these ions in the crystal lattice
decreases the energy of the system and making it stable
• Na+(g) + Cl-(g) → Na+Cl- (s) ∆H = -788 KJ/mole
• From above description, we conclude that for the formation of
ionic bond the sum of energies released in step-2 and step-3
must be larger than the required in step-1.
• CONCLUSION: - To form a stable ionic compound, there must be
a decrease in net energy.
COVALENT BOND
• Chemical bond formed between two atoms by the mutual
sharing of electrons is known as Covalent bond.
• In covalent bond formation each atom provides equal
number of electrons for sharing but no transfer of
electrons takes place.
• Each electron pair is attracted by both the nucleus.
• Chemical bond formed between two similar atoms is
always a covalent bond.
• Shared electrons spend much of the time between the
nuclei, resulting in the attractive forces between
negative charge of electron and positive charge of
nuclei.
• In actual practice shared electrons form an electronic
cloud which spreads over bonding atoms and fulfills the
requirements of each atom (octet or doublet).
POLAR & NON-POLAR COVALENT
BONDS
• A covalent bond formed between two different atoms is
known as Polar covalent bond.
• For example when a Covalent bond is formed between H
and Cl , it is polar in nature because Cl is more electro
negative than H atom .
• Therefore, electron cloud is shifted towards Cl atom.
• Due to this reason a partial -ve charge appeared on Cl
atom and an equal +ve charge on H atom
• A covalent bond formed between two like atoms is known
as Non-polar bond.
• Since difference of electro negativity is zero therefore,
both atoms attract electron pair equally and no charge
appears on any atom and the whole molecule becomes
neutral.
• Examples: H – H, Cl – Cl, F – F etc
IONIC CHARACTER OF COVALENT BOND
• When two atoms of different elements are linked by a covalent
bond, the shared electrons are not attracted equally by the two
nuclei of bonding atoms.
• Due to unequal distribution of electron cloud, one end of the
molecule acquires partial positive charge and the other end
acquires equal partial negative charge.
• The polarity of bond gives partial ionic character.
• The percentage of partial ionic character depends upon the
difference of E.N. of two atoms join with each other through a
covalent bond
• HCl molecule: -
• E.N. of H = 2.1 & E.N of Cl = 3.0
• Due to difference of E.N., the ability Cl-atom to attract shared pair of
electron is greater than that of H-atom.
• Therefore, covalent bond in HCl has ionic character. In HCl, covalent
bond is 17% to 18% ionic.
• HF molecule: -
• E.N. of H = 2.1 & E.N. of F = 4.0
• In this example difference of E.N. is greater as compare to HCl.
• Therefore, ionic character of HF is 64%.
• Ionic character of covalent compound affects properties of
these compounds.
• For example viscosity, M.P., B.P. of compounds having
ionic character are higher than that of non-polar
compounds.
• In addition to that, polarity or ionic character shortens the
bonds lengths and increases the bond energies.
• HF is much shorter than its expected bond length.
DIPOLE MOMENT
• The degree of polarity of a molecule is expressed in
terms of dipole moment.
• The product of magnitude of charge on a molecule and
the distance between
• two charges of equal magnitude with opposite sign is
equal to dipole moment.
• Dipole moment=charge x distance
•µ=exd
• Its unit is debye. (D)
• Dipole moment depends on three factors:
• 1. Polarity of molecule
• 2. Magnitude of charge &
• 3. Geometry of molecule
• 1. Homo-nuclear diatomic molecules have zero dipole moment due to
absence of charge.
• For example:
• H−H, O=O, Cl−Cl Have zero dipole moment.
• 2. Diatomic molecules of two different atoms have specific values of
dipole moment. Greater the difference of electronegativity, greater will
be the dipole moment.
• For example: H−F, μ =1.9 debye, H−Cl, μ =1.03 debye
• 3. Polyatomic molecules of linear structure have zero dipole
moment.
• For example: CO2, μ=0 debye & CS2, μ=0 debye
• 4. Molecules having angular or bent structure have certain
values of dipole moment.
• For example: H2O, μ =1.84 debye & NH3, μ = 1.46 debye
• 5. If molecular structure of a poly atomic molecule is
symmetrical than the dipole moment of molecule will be
zero.
• For example: CH4 = 0 debye, C6H6 = 0 debye & CCl4 = 0
debye
VBT & MOT
• Lewis dot cross model of covalent bonding failed to
explain molecular geometries and magnetic properties
of the molecules.
• In 1927, Walter Hietler & Fitz London proposed Valence
Bond Theory (VBT).
• Later in 1930’s Freidrich Hund, Robert Mullikan & Erich
Huckle proposed Molecular Orbital Theory (MOT).
• Both VBT & MOT support LCAO.
• Linear Combination of Atomic Orbitals.
• Essentially VBT and MOT are identical theories as they
both refer to the overlapping or fusion of atomic
orbitals for bond making and reject the electron pair
concept.

LCAO
+ + + + + VBT
LC
AO

Atomic Orbitals
+ + MOT
• VBT
• Atomic orbitals remain atomic
orbital after overlap.
• Electrons in atomic orbitals
are attracted & oriented by
single nucleus.
• They are mono centric.
• There is only one set of
overlapping.
• MOT
• AO’s lose their identity and
become Molecular Orbitals
MO’s which belong to the
molecule as whole.
• Electrons in MO’s are
oriented along both or all
bonding nuclei.
• They are polycentric.
• There are two sets of MO’s
• A) Bonding MO’s
• B) Antibonding MO’s
Bonding MO’s Antibonding MO’s
• An overlap that results in • An overlap that results in
lowering of energy and raising energy and
raising the stability lowering the stability
results in Bonding MO’s. results in Antibonding
• More electron density. MO’s.
• High Stability. • Low electron density.
• Very Low Energy. • Low Stability.
•
• There is essentially a Very High Energy.
strong bond. • There is essentially a no
bond.
Principle of Maximum Overlap.
• The greater the overlap the stronger will be the bond.
• p orbitals have longer lobes hence overlapping the involves
p orbitals in LCAO shall result in stronger bonds as compared
to s orbitals.
• Relative Strength.
• s – s 1.0
• s – p 1.7
• p – p 3.0
SIGMA BOND
• Sigma bond is formed by the linear or head to head or end on
overlapping of orbitals.
• Sigma bonds are the strong bonds due to maximum
overlapping of orbitals.
• Electron density is maximum around the bond axis.
• Compounds having sigma bonds are stable and hence less
reactive.
• First bond formed between two atoms is always a sigma bond.
• s-s overlap, s-p overlap and p-p overlap give rise to sigma bond.
s-s overlap in H2 molecule
• Hydrogen molecule consists of two H-atoms.
• Each atom contains one electron in 1s-orbital.
• E.C = 1s1
• According to molecular orbital theory two 1s 1 orbitals of two
H-atoms overlap linearly to produce two types of molecular
orbitals.
• 1. Bonding molecular orbital (σ-orbital)
• 2. Anti-bonding molecular orbital (σ *-orbital)
• This type of overlap is called s – s sigma.
s-p overlap in HF molecule
• s-p type overlap occurs in HF molecule.
• When one 1s-orbital of hydrogen atom overlaps 2p z -orbital of
fluorine to form two types of molecular orbitals.
• 1. Bonding molecular orbital (σ -orbital)
• 2. Anti-bonding molecular orbital (σ *-orbital)
• This type of overlap is called s – p sigma.
p-p overlap in F2 molecule
• p-p type overlap occurs in F2 molecule when one 2pz-
orbital of one fluorine atom overlaps 2pz-orbital of other
fluorine atom form two types of molecular orbitals.
• 1. Bonding molecular orbital (σ -orbital)
• 2. Anti-bonding molecular orbital (σ *-orbital)
• This type of overlap is called p – p sigma.
PI BOND
• A Pi bond is formed by the lateral or sideways or parallel
overlapping of P-orbital of the atoms which are already
bonded by a sigma bond and their axes are coplanar.
• This type of overlap generates two types of molecular
orbitals:
• (a) Pi-bonding molecular orbital (π-orbital)
• (b) Pi-antibonding molecular orbital (π*-orbital)
• A pi-bonding orbital has two regions of electron density below
and above the nodal plane.
• The electron contained in it are called pi-bonding electrons
which form the pi bond. It is not linearly symmetrical with
respect to the bond axis, rather it has a nodal plane.
• Pi-bonds are weaker than sigma bonds.
• In Pi-bonds, electron density lies in the regions above and
below the nuclei.
• Compounds having pi bonds are more reactive.
• Pi bond is formed when two atoms already bonded by a sigma
bond.
HYBRIDIZATION
• The phenomenon of mixing up of different atomic orbitals
of same energy level of an atom to produce equal number
of hybrid-orbitals of same energy and identical properties
is known as hybridization.
• Lets look at E.C of carbon: 1s22s22p2

1s 2s 2px 2py 2pz

↑↓ ↑ ↑ ↑ ↑
• Carbon makes four sigma bonds with four 1s hydrogen
atoms.
• According to MOT, carbon should give a weaker s – s
and three stronger s – p sigma bonds in methane CH4.
• It also suggests that bonds angles must be 90o.
• Fact is, all four bonds are alike and are at 109o.
• To explain this anomalies, Linus Pauling introduced
the idea of Hybridization.
• A hybrid orbital contains maximum two electrons with
opposite spin.
• In hybridization, only those orbital take part that has very
little difference of energy.
• Hybridization takes place in the orbitals of a single atom.
• Two different atoms cannot produce hybrid orbitals by
overlapping their orbitals.
Types of Hybridization
sp - hybridization
3
sp - hybridization
2
sp - hybridization