CHEMISTRY- PAPER II

Structure and Bonding

Dr. Manojkumar M. Jadhao

Assistant Professor
Institute of Chemical Technology Mumbai, Marathwada Campus, Jalna
 What is organic chemistry?
Organic Chemistry = chemistry of carbon containing (organic) molecules

convert visible light into brain cells are being bridged

nerve impulses by simple organic molecules
(neurotransmitter

• sugars to give you the energy you needed

Organic Chemist Periodic Table
Most Familiar compounds are “organic”
1) Cotton in clothing 4) Plastics
2) Gasoline 5) Drugs
3) Food 6) Dyes

Natural Products vs. Synthetic Organic compounds

Natural Products are compounds we find in the environment

May need to be refined or isolated from the source
Are starting materials for synthetic compounds
Synthetic Organic compounds do not occur naturally and must be
synthesized from simpler compounds
O CH3
Caffeine: an important organic molecule CH3 N
N

O N N

CH3
II. How will we study Organic Chemistry
a) Relationship of a molecule’s Structure with its Reactivity

b) Functional Group = a group of atoms that controls a molecule’s

reactivity
Method of classifying organic molecules
Similar reactivity for compounds having the same functional group

O
CH3CH2CH2CH2CH3 CH3CH2CH2CH2OH
CH3CH2CH2CH2COCH3
Alkane Alcohol Ester
c) Nomenclature = systematic naming of organic compounds

d) Reactivity
How to synthesize a functional group
The reactions a functional group can undergo
Mechanism = detailed intermediate steps in a reaction
 Text: Reactions are like Words Need Both to
Mechanisms are like Grammar “Speak” Organic
Chemistry

E. Stereochemistry = exact arrangement in space of the atoms in a

molecule
H H
C C
I Cl F
F Cl
I

F. Synthesis = making molecules from simpler starting materials

O O
CH3CH2CH2CH2COH + HOCH3 CH3CH2CH2CH2COCH3
 Nucleus is a Tiny Fraction of
the Volume of an Atom

Proton = 1.6726230 x 10-24 grms

Neutron = 1.674929 x 10-24 grms
Electron = 9.109390 x 10-28 grms
Electron Configurations
Orbitals are Probabilities
2s Orbital Has a Node
Bonding in H2
Sigma (s) Bond
The p Orbital
px, py, pz
Orbitals
Electron Configuration of Carbon
Filling up orbital in atom
Aufbau Principle
Pauli’s exclusion principle
Hund's Rule of Maximum multiplicity
The attractive force which holds various constituents (atoms, ions, etc.)
together in different chemical species is called a chemical bond.

Why do some atoms combine and certain don’t?

Why do molecule possess definite shape?

Theories and concepts

1) Kossel-Lewis approach (1916)
2) Valence Bond Theory (VBT) (1927)
3) Valence share electron pair repulsion theory (VSEPR) (1940)
4) Molecular Orbital Theory (MOT) (1932)
1) Kossel-Lewis approach (1916)
• First to provide some logical explanation of valence which was based on
the inertness of noble gases.
• Octate theory : atoms can combine either by transfer of valence
electrons from one atom to another (gaining or losing) or by sharing of
valence electrons in order to have an octet in their valence shells.
• Lewis postulated that atoms achieve the stable octet when they are
linked by chemical bonds.
• NaCl, Cl2, F2, Br2, Cl2

• Lewis Symbols: In the formation of a molecule, only the

outer shell electrons take part in chemical combination and
they are known as valence electrons.
• Langmuir introduce covalent binding

• Thus, when two atoms share ( electron pair they are said to be joined a
single covalent bond.
• Sharing of more than one electrons between two atoms form multiple
bond.
Simple Bonding
III. Coulomb Forces as a Simple Bonding Model
• Chemical Bond = energetically favorable interaction of 2 atoms which holds
them together at a defined distance from each other
• Energy (heat) is released as 2 atoms come together to form a bond (energy input is
required to break a chemical bond)
• Opposite charges attract
• Electrons spread out to fill a defined space

Covalent Bond =
shared electrons

Ionic Bond =
transferred electrons
B. Coulomb’s Law is a basis for chemical bonding

 [  ]  [ ] 
F  c 2 
“ The force between two charges
d
 is proportional
 to the amount of charge on both charges
and inversely proportional to the square of the distance between them”
Bond Length = distance between nuclei at minimum energy
The Octet Rule
• Periodic Table Review

• Atomic Number = # of protons = # of electrons in neutral atom

• Electron Shells: 2, 8, 18, …
• Valence Shell = outermost shell
• Filled electron shells are energetically desirable so atoms react accordingly
• Noble gases (He, Ne, Ar, Kr, Xe) have filled shells, are unreactive
• Duet important for H, He
• Octet important for C, N, O, …
 B. Pure Ionic Bonds
• Transfer of valence electrons from one neutral atom to another creates a cation and and anion
and forms an ionic bond

• Ionization Potential = energy input to remove an electron

Na Na+ + e- DE = 119 kcal/mol

3)Electron Affinity = energy released upon binding an electron

Cl + e- Cl- DE = -83 kcal/mol

4)Formation of an Ionic Bond

Na + Cl Na+Cl- Ionization Potential = +119 kcal/mol

Electron Affinity = -83 kcal/mol
Coulomb Attraction = -120 kcal/mol
Total DE = -84 kcal/mol

• Obviously ionic bonds will be formed more easily between elements

with comparatively low ionization enthalpies and elements with
comparatively high negative value of electron gain enthalpy.
C. Electron Dot Notation
• Core Configuration: Atomic symbol = nucleus + inner shell electrons
• Valence Electrons: represented by dots around the core

Na + Cl Na Cl
• Types of Hydrogen
• Hydrogen atom H
• Proton H
• Hydride
H
D. Covalent Bonds
• Sharing Electrons to reach octet configuration forms a bond
• Why aren’t all bonds ionic?

2H H H E = +300 kcal/mol

2 C C4+ C 4-
E = Very Large
 3) Sharing reduces charge and maximizes e- exchange

2H H H = H H

H + Cl H Cl = H Cl
= = single bond
H H
H H = = double bond
3H + N NH HNH = H N H
H H H = = triple bond
H H H H
2 HC C C = C C
H H H H

4)Unequal Sharing gives Polar Covalent Bonds

a) Electropositive = electron donating atoms (Na, K, left side of P.T.)
b) Electronegative = electron accepting atoms (Cl, N, O, right side P.T.)

H 2.2

Li 1.0 Be 1.6 B 2.0 C 2.6 N 3.0 O 3.4 F 4.0

Na 0.9 Mg 1.3 Al 1.6 Si 1.9 P 2.2 S 2.6 Cl 3.2

K 0.8 Br 3.0
 c) Ionic Bonds form between extremes

Na + Cl Na Cl
d)Covalent Bonds form between like electronegativities

2H HH = H H
e)A Polar Covalent Bond is one between unequal electronegativities

H + Cl H Cl = H Cl

f) Symmetry can cancel out the dipole moment for the whole molecule even if the
individual bonds are polar -
Cl
- +
- +  -  -
Cl C Cl 
O C O
Cl-


-
+ -  +
 H F H2N CH3
 Limitations of the Octet Rule
The incomplete octet of the central atom

In some compounds, the number of electrons surrounding the

central atom is less than eight.

Li, Be and B have 1,2 and 3 valence

electrons
only.
AlCl3 and BF3.
Odd-electron molecules
In molecules with an odd number of electrons like nitric
oxide, NO and nitrogen dioxide, NO2, the octet rule is
not satisfied for all the
atoms
Limitations of the Octet Rule

The expanded octet

the third period of the periodic table 3d orbitals also

available for bonding
 Limitations of the Octet Rule

Other drawbacks of the octet theory

• It is clear that octet rule is based upon the chemical
inertness of noble gases.
some noble gases also combine with oxygen and Fluorine
Ex XeF , KrF , XeOF etc.,
2 2 2

• This theory does not account for the shape of molecules.

• It does not explain the relative stability of the molecules

being totally silent about the energy of a molecule.
• Bond Length

Bond length is defined as the equilibrium distance between the nuclei of two bonded
atoms in a molecule.
Measured by X-ray diffraction and electron-diffraction techniques

• The covalent radius

The covalent radius is measured approximately as the radius of an atom’s core
which is in contact with the core of an adjacent atom in a bonded situation.
The covalent radius is half of the distance between two similar atoms joined by a
covalent bond in the same molecule.

The bond length in a covalent

molecule AB.
R=r
A + rB (R is the bond length and rA and rB

are the covalent radii of atoms A and B

respectively)
Bond Angle
It is defined as the angle between the orbitals
containing bonding electron pairs around the
central atom in a molecule/complex ion.

It gives some idea regarding the

distribution of orbitals around the central
atom in a molecule/complex ion and hence it
helps us in determining its shape.

Bond Enthalpy

• It is defined as the amount of energy required to break one mole of bonds

of a particular type between two atoms in a gaseous state.
The unit of bond enthalpy is kJ mol-1.
• larger the bond dissociation enthalpy, stronger will be the bond in the
molecule.
• Bond Order
In the Lewis description of covalent bond, the Bond Order is given by the
number of bonds between the two atoms in a molecule
• The bond order, H2 = single shared electron pair, BO is 1
O2 = two shared electron pairs, BO is 2
N2 = three shared electron pairs, BO is 3

• Isoelectronic molecules and ions have identical bond orders; for example,
F2 and O22– have bond order 1.
N2, CO and NO+ have bond order 3.

• with increase in bond order, bond enthalpy increases and bond

length decreases.

• Resonance Structures
whenever a single Lewis structure cannot
describe a molecule accurately, a number of
structures with similar energy, positions of
nuclei, bonding and non-bonding pairs of
electrons are taken as the canonical structures of
the hybrid which describes the molecule
accurately. Resonance in the O3 molecule
• Polar Covalent Bond
A bond in which electrons are shared between elements having a
difference of electronegativity of between 0.5 & 2.0.

• Dipole Moment (Greek letter 'µ'. )

Dipole moment is defined as the product of the magnitude of charge on anyone
of the atoms and the distance between them.
Expressed mathematically, as: µ = e × d
Where, e = charge on anyone of the atoms, d = distance between the atoms.
Its unit in CGS system is debye (D). 1 D = 3.33564 × 10–30 C m
• Further dipole moment is a vector quantity
• dipole moment is represented by the crossed arrow
• arrow symbolizes the direction of the shift of electron density in the molecule
• In polyatomic species
 Valence Shell Electron Pair Repulsion Theory(VSEPR)
by Sidgwick and Powell in 1940 • The valence shell is taken as a sphere
with the electron pairs localising on the
postulates of VSEPR theory spherical surface at maximum distance
from one another.
• The shape of a molecule depends
upon the number of valence shell • A multiple bond is treated as if it is a
electron pairs (bonded or nonbonded) single electron pair and the two or three
around the central atom. electron pairs of a multiple bond are
treated as a single super pair.
• Pairs of electrons in the valence shell
repel one another since their electron • Where two or more resonance structures
clouds are negatively charged. can represent a molecule, the VSEPR
model is applicable to any such structure.
• These pairs of electrons tend to The repulsive interaction of electron pairs
occupy such positions in space that decrease in the order:
minimize repulsion and thus Lone pair (lp) – Lone pair (lp) > Lone pair
maximise distancebetween them. (lp)– Bond pair (bp) > Bond pair (bp) –
Bond pair (bp)
 COMPOUNDS
AB2, AB3, AB4 AB5 and AB6
1) Central atom with Zero LP 2) Central atom with one or more LP

1) Central atom with Zero LP

The shapes of molecules in which

central atom has no lone pair
2) Central atom with one or more LP
Simple Molecules/Ions
 Bond Pair and Lone Pair

AB2E

AB3E

AB2E2
AB4E

• In (a) lp is present at axial position so there are three lp—bp repulsions

at 90°

• In (b) lp is in an equatorial position, and there are two lp—bp

repulsions
• Second geometry is more stable = Seesaw
AB3E2
VALENCE BOND THEORY & MOLECULAR ORBITAL THEORY

• VSEPR theory gives the geometry of simple molecules but

theoretically, it does not explain them and also it has limited
applications.

• New theory on Quantum Mechanical Principle : valence bond

(VB) theory and molecular orbital (MO) theory

• VBT : introduced by :Heitler and London (1927) & developed

further by Pauling and group

• VBT based on : atomic orbitals, electronic configurations of

elements, the overlap criteria of atomic orbitals, the
hybridization of atomic orbitals and the principles of variation
and superposition.
Valence Bond theory……..

VBT assumes that electrons that the electrons of one atom are
attracted to the nucleus of another atom.

This attraction increases as the atoms approach one another until the
atoms reach a minimum distance where the electron density begins to
cause repulsion between the two atoms.

This electron density at the minimum distance between the two atoms
with the lowest potential energy form chemical bond.
Valence Bond theory…….. Postulates

• The atoms which unite to form a molecule completely retain their

identities in the resulting molecule.
• The formation of a covalent bond is due to overlap of atomic
orbitals
• If the two atoms, each having on unpaired electron, come together,
the AO’s accommodating these unpaired electrons overlap (i.e,
electron waves interact) and the spins of the two electrons get
mutually neutralized, resulting in the formation of covalent bond
which is localized between the two atoms.
• If the electrons present in the AO’s have parallel spins, no bond
formation will occur, and no molecule will be formed.
Valence Bond theory…….. Postulates

• If the AO’s possess more than one unpaired electrons, more than
one bond can be formed.
• Thus, in N2 molecule there are three bonds, since N atom has
three unpaired electrons. N = 2s2 , 2px1 , 2py1 , 2pz1
• The strength of the covalent bond is related to the extent of
overlapping of the atomic orbitals.

Thus, greater the overlap of the atomic orbitals, the greater

will be the strength of the resulting covalent bond.
 Valence Bond theory…….. Types of Overlap
Sigma bond: A covalent bond resulting from the formation of a molecular orbital by
the end-to-end overlap of atomic orbitals along the internuclear axis. , denoted by
the symbol σ.

Overlap of two half filled s-

orbitals along

Overlap occurs between half

filled s-orbitals of one atom
and half filled p-orbitals of
others

Overlap between half filled

p-orbitals of the two
approaching atoms
Valence Bond theory…….. Types of Overlap

Pi bond: A covalent bond resulting from the formation of a molecular orbital by side
to side overlap of atomic orbitals along a plane perpendicular to a internuclear axis
the nuclei of the atoms, denoted by the symbol π.
HYBRIDISATION
Pauling introduced the concept of hybridisation.

The process of intermixing of the orbitals of slightly different energies

so as to redistribute their energies, resulting in the formation of new
set of orbitals of equivalent energies and shape.
Salient features of hybridisation

1. The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridised.

2. The hybridised orbitals are always equivalent in energy and shape.

3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.

4. These hybrid orbitals are directed in space in some preferred direction to have minimum
repulsion between electron pairs and thus a stable arrangement.

Therefore, the type of hybridization indicates the geometry of the molecules.

 HYBRIDIZATION RULES
1. Only orbitals of similar energies belonging to the same atom or
ion can hybridize together.
2. Number of hybrid orbitals produced is equal to the number of
orbitals undergoing hybridization. Hybrid bonds are stronger than
the single- non- hybridized bonds of comparable energy.
3. Most of the hybrid orbitals are similar but they are not necessarily
identical in shape. They differ from one another in their
orientation in space.
4. For equivalent hybrids the orientation in space is determined by:
the number of orbitals mixed and consequently the number of
hybrids obtained and which of x, y and z axis are preferred by the
orbitals when pure.
5. From the type of hybridization one can predict the geometry and
bond angles of a molecule.
6. An orbital which has been used to build up a hybrid orbital is no
longer available to hold electron in its pure form
 MOLECULAR ORBITAL THEORY
by F. Hund and R.S. Mulliken in 1932.

• The electrons in a molecule are present in the various molecular

orbitals as the electrons of atoms are present in the various atomic
orbitals.
• The atomic orbitals of comparable energies and proper symmetry
combine to form molecular orbitals.
• While an electron in an atomic orbital is influenced by one
nucleus, in a molecular orbital it is influenced by two or more
nuclei depending upon the number of atoms in the molecule.
• Thus, an atomic orbital is monocentric while a molecular orbital is
polycentric.
• The number of molecular orbital formed is equal to the number of
combining atomic orbitals. When two atomic orbitals combine, two
molecular orbitals are formed. One is known as bonding molecular
orbital while the other is called antibonding molecular orbital.
• The bonding molecular orbital has lower energy and hence greater
stability than the corresponding antibonding molecular orbital.
• Just as the electron probability distribution around a nucleus in an
atom is given by an atomic orbital, the electron probability
distribution around a group of nuclei in a molecule is given by a
molecular orbital.
• The molecular orbitals like atomic orbitals are filled in accordance
with the Aufbau principle obeying the Pauli’s exclusion principle and
the Hund’s rule.
Bonding molecular orbitals
-have electron density between the atom
-are lower in energy than the original atomic orbitals
-when these orbitals are occupied by electrons, it holds the atoms together,
forming a bond

Nonbonding molecular orbitals

-may occur when three or more atomic orbitals are combined
-have the same energy as the original atomic orbitals
-electrons occupying these orbitals do not stabilize or destabilize the
molecule

Antibonding molecular orbitals

-have electron density which is not between the atoms (there is a node
between the atoms)
-are higher in energy than the original atomic orbitals
-if these orbitals are occupied by electrons, it pulls the atoms away from
each other and weakens or prevents bonding.
 σ1s < σ*1s < σ2s < σ*2s
< (π 2px = π 2py) <σ2pz <
(π *2px= π *2py) < σ*2pz

Energy order of various Molecular Orbitals

The increasing order of energies of various molecular orbitals for O2
and F2 is
given below :
σ1s < σ*1s < σ2s < σ*2s <σ2pz<(π 2px = π 2py) < (π *2px= π *2py)<σ*2pz
• Wave functions (y ’s) which represent the amplitude of the electron waves,
which are obtained from the solution of Schrödinger wave equation.
• Difficult to obtain solution of Schrödinger wave equation for molecular
orbitals containing more than one electrons

• To overcome this problem, an approximate method known as linear

combination of atomic orbitals (LCAO) has been adopted
• LCAO can take place by addition and by subtraction of wave functions of
individual atomic orbitals

yMO = yA + yB
Therefore, the two molecular orbitals
s and s* are formed as :
s  yA + yB
s* = yA – yB
Order of Energy Levels for Boron, Carbon, Nitrogen etc.