XCELLENT CLASSES ROSHITA G PILLAI

CHEMICAL BONDING AND MOLECULAR STRUCTURE

CHEMICAL BOND:- The attractive forces which hold together the constituent particles(atoms, ions &molecules) in
a chemical species

Why do atoms combine?

In 1916 Kossel & Lewis succeeded independently in giving first successful explanation about the cause of
combination between atoms based upon understanding of electronic configuration of noble gases.
1. Tendency to acquire noble gas configuration or octet rule
2. Tendency to acquire minimum energy and stability

MODES OF CHEMICAL COMPOSITION:-

This can occur in two ways:
1. By complete transference of one or more electrons from one atom to another. This process is referred to as
electrovalency and the chemical bond formed is termed as electrovalent bond or ionic bond.
2. By sharing of electrons. This can occur in two ways as follows :
(a) When the shared electrons are contributed by the two combining atoms equally, the bond formed is
called covalent bond.
(b) When these electrons are contributed entirely by one of the atoms but shared by both, the bond
formed is known as a coordinate bond, also called dative bond.

LEWIS SYMBOL:- the symbol of element represents the whole atom except the valence electrons. The valence
electrons are represented by (.) or (x) around the symbol.

SIGNIFICANCE OF LEWIS SYMBOL:-

1. It indicate the no. of electrons in the outermost or valence shell
2. These helps to predict the common or group valence of element
3. Common valence valence of electron is either equal to no. of dots in lewis symbol or it is equal to 8 minus no.
of dots

OCTET RULE:- The principle of attaining maximum of 8 electrons in the valence shell of atoms is called octet rule

Limitations of the Octet Rule:-

1. Incomplete octet of the central atom in some compounds:
The number of electrons surrounding the central atom is less than eight. This is especially the case with elements with
less than four valence electrons. Examples: LiCl, BeH2, BCl3
2. Odd-electrons molecule:
In molecules with an odd number of electrons such as nitric oxide (NO) and nitrogen dioxide (NO2), the octet rule is
not satisfied for all the atoms.
3. Expanded octet:
Elements belonging to groups 15, 16 and 17 have more than four electrons in their valence (outermost) shell. The
elements of these groups form stable compounds in which there are more than eight electrons around the central atom.
Examples: PF5, PCl5, IF6, SF6

Drawbacks of the Octet Theory:-

1. It is clear that the octet rule is based on the chemical inertness of noble gases. However, some noble gases
(e.g. xenon and krypton) also combine with oxygen and fluorine to form compounds such as XeF2, KrF2 and
XeOF2.
2. This theory does not account for the shape of molecules.
3. It does not explain the relative stability of the molecules being totally silent about the energy of a molecule.

IONIC BOND (ELECTROVALENT BOND) :-

When a bond is formed by complete transference of electrons from one atom to another so as to complete their
outermost orbits by acquiring 8 electrons (i.e., octet) or 2 electrons (i.e., duplet) in case of hydrogen, lithium etc. and
hence acquire the stable nearest noble gas configuration, the bond formed is called ionic bond or electrovalent bond.

Explanation of Ionic Bond:-

1
XCELLENT CLASSES ROSHITA G PILLAI

1. Atoms are electrically neutral. Therefore, they possess equal number of protons and electrons.
2. On losing an electron, an atom becomes positively charged since now the number of protons exceeds the
number of electrons.
A A+ + e-
3. On the other hand, in case of atom, gaining the electron, the number of electrons exceeds the number of
protons and thus the atom becomes negatively charged.
B + e- B-
4. The oppositely charged particles formed above attract each other by electrostatic forces of attraction. The
bond thus formed is known as electrovalent or ionic bond.

ELECTROVALENCY: - The number of electrons lost or gained during the formation of an electrovalent linkage is
termed as the electrovalency of the element.
For example, sodium and calcium lost 1 and 2 electrons respectively and so their valencies are 1 and 2.
Similarly, chlorine and oxygen gain 1 and 2 electrons respectively, so they possess an electrovalency of 1 and 2.
In other words, valency is equal to the charge on the ion.

FORMATION OF IONIC BOND:-

1. The ease of formation of +ve and –ve ions from respective neutral atoms
2. The arrangement of +ve and –ve ions in solid . this is also called lattice of crystalline compound

FACTORS GOVERNING THE FORMATION OF IONIC BONDS:-

1. Ionisation Enthalpy (Ionization Energy) :-Ionisation enthaly of any element is the amount of energy
required to remove an electron from the outermost shell of an isolated atom in gaseous phase so as to convert
it into a gaseous positive ion.
It is clear that lesser the ionisation enthalpy, easier will be the removal of an electron, i.e., formation of a positive ion
and hence greater the chances of formation of an ionic bond.
Ionisation enthalpy (I.E.) of alkali metals (i.e., group I elements) is low, hence they have more tendency to form
positive ions.
2. Electron Gain Enthalpy (Electron Affinity):- Electron affinity or Electron gain enthalpy of an element is
the enthalpy change that takes place when an extra electron is added to an isolated atom in the gaseous phase
to form a gaseous negative ion.
Higher is the electron affinity, more is the energy released and stable will be the negative ion produced.
Halogens possess high electron affinity. So the formation of their negative ions is very common, e.g., in case of
chlorine, electron affinity is +348 kJ/mole,
i.e., Cl + e- Cl- + 348 kJ/mole
3. Lattice Enthalpy (Lattice Energy):- In the formation of ionic compounds, the positively charged ions
combine with negatively charged ions to form the compound.
A+ + B- AB
The energy released when the requisite number of gaseous positive and negative ions combines to form one mole of
the ionic compound is called lattice enthalpy.

NOTE: - For stable ionic compound-

 IE should be low
 EGE should be high
 LE should be high

Factors affecting lattice enthalpy:-

1. Size of ion- Smaller the size ----lesser is inter nuclear distance ----inter ionic attraction will be high----le will
be high
2. Charge on ions- larger the charge on ion ----greater will force of attraction between ions----LE will be high

CHARACTERISTICS OF IONIC COMPOUNDS:-

1. Physical State --These compounds usually exist in the solid state.
2. Crystal Structure --They exist as ions and not as molecules. These ions are arranged in a regular pattern in the
three dimensional space to form a lattice.
For example, in case of sodium chloride, each sodium ion is surrounded by six chloride ions and each
chloride by six sodium ions, thus giving rise to a three dimensional octahedral crystal structure (figure). The
formula of an ionic compound merely indicates the relative number of ions present.

2
XCELLENT CLASSES ROSHITA G PILLAI

3. High melting and boiling points --Ionic compounds possess high melting and boiling points. This is because
ions are tightly held together by strong electrostatic forces of attraction and hence a huge amount of energy is
required to break the crystal lattice.
4. Solubility-- Ionic solids are soluble in polar solvents and insoluble in non-polar solvents.
5. Electrical conductivity-- Ionic compounds are good conductors of electricity in solution or in the molten
state. In solution or molten state, their ions are free to move. As the ions are charged, they are attracted
towards electrodes and thus act as carriers of electric current.
6. Ionic Reactions-- The reactions of the ionic compounds are, in fact, the reactions between the ions produced
in solution. As the oppositely charged ions combine quickly, these reactions are, therefore, quite fast.
Na+ Cl- + Ag +NO3- AgCl + NaNO3

COVALENT BOND :-The bond formed between the two atoms by mutual sharing of electrons between them so as to
complete their octets or duplets in case of elements having only one shell is called covalent bond and the number of
electrons contributed by each atom is known as covalency

FORMAL CHARGE:- The formal charge on an atom in a molecule or ion is defined as the difference between the
number of valence electrons of that atom in the free state and the number of electrons assigned to that atom in the
Lewis structure

Formal charge (F.C.) on an atom in a Lewis structure = total number of valence electrons in the free atom — total
number of non bonding (lone pair) electrons — (1/2) total number of bonding(shared) electrons
V = total number of valence electrons in the free atom
L = total number of non bonding (lone pair) electrons
S = total number of bonding(shared) electrons
FC = V – L – ½ S

NOTE:- The Lewis dot structures can be written for molecules also, in which the combining atoms may be identical
or different. The important conditions being that:-

1. Each bond is formed as a result of sharing of an electron pair between the atoms.
2. Each combining atom contributes at least one electron to the shared pair.
3. The combining atoms attain the outershell noble gas configurations as a result of the sharing of electrons.

3
XCELLENT CLASSES ROSHITA G PILLAI

WRITING LEWIS STRUCTURE:-

1. The total number of electrons required for writing the structures are obtained by adding the valence electrons
of the combining atoms.
2. For anions, each negative charge would mean addition of one electron. For cations, each positive charge
would result in subtraction of one electron from the total number of valence electrons
3. Knowing the chemical symbols of the combining atoms and having knowledge of the skeletal structure of the
compound (known or guessed intelligently), it is easy to distribute the total number of electrons as bonding
shared pairs between the atoms in proportion to the total bonds.
4. In general the least electronegative atom occupies the central position in the molecule/ion. For example in the
NF3 and CO3 2–, nitrogen and carbon are the central atoms whereas fluorine and oxygen occupy the terminal
positions.
5. After accounting for the shared pairs of electrons for single bonds, the remaining electron pairs are either
utilized for multiple bonding or remain as the lone pairs.

LIMITATIONS OF LEWIS-LANGMUIR CONCEPT OF COVALENT BOND :-

1. It could not explain how the atoms are held together in the molecules like H2 , Cl2 etc. in which there are no
ions and hence there are no electrostatic forces of attraction, i.e., it could not explain the formation of a
covalent bond.
2. It could not explain the shapes of molecules containing covalent bonds.
3. It could not explain the release of energy during the formation of a covalent bond.

PROPERTIES OF COVALENT BOND:-

1. They doesnot exist as ions but they exist as molecules
2. Low melting and boling point
3. They are generally insoluble in water and other polar solvents but coluble in non-polar sovents like C6H6 ,
CCL4 etc..
4. Poor conductors of electricity
5. Reactions between covalent compound occur between their molecules

CO-ORDINATE COVALENT BOND:- The bond formed due to unequal sharing of electrons is called as co-
ordinate bond.
Co-ordinate compounds exhibit characteristics similar to covalent compounds.

4
XCELLENT CLASSES ROSHITA G PILLAI

 They do not ionize in water and are poor conductors of electricity.

 They are very sparingly soluble in water but dissolve in organic solvents.
 Since a co-ordinate linkage is semipolar, the co-ordinate compounds possess melting and boiling points which
are higher than those of purely covalent compounds but lower than the ionic compounds.
 The co-ordinate linkage is also rigid and directional and therefore ,such compounds can also exhibit space
isomerism.
 The co-ordinate linkage is easily broken when the donor and acceptor are molecules which are capable of
independent existence.

DONOR ACCEPTOR

BOND PARAMETERS:-
1. Bond length --The equilibrium distance between the centres of the nuclei of the two bonded atoms is called
its bond length.
Factors affecting bond length
 Size of the atoms : The bond length increases with increase in the size of the atoms. HI > HBr > HCl > HF
 Multiplicity of bond : The bond length decreases with the multiplicity of the bond. C = C < C = C < C – C
 Type of hybridisation :As s-orbital is smaller in size, greater the s-character, shorter is the hybrid orbital and
hence shorter is the bond length. sp3 C–H > sp2 C–H > sp C–H

2. Bond energy-- The amount of energy required to break one mole of bonds of a particular type so as to
separate them into gaseous atoms is called bond dissociation enthalpy or simply bond enthalpy
Factors affecting Bond energy
 Size of the atoms : Greater the size of the atoms, greater is the bond length and less is the bond dissociation
enthalpy, i.e., less is the bond strength.
 Multiplicity of bonds : For the bond between the same two atoms, greater is the multiplicity of the bond,
greater is the bond dissociation enthalpy. H–H < O = O < N= N
 Number of lone pairs of electrons present : Greater the number of lone pairs of electrons present on the
bonded atoms greater is the repulsion between the atoms and hence less is the bond dissociation enthalpy.

3. Bond angle-- The angle between the lines representing the directions of the bonds, i.e., the orbitals containing
the bonding electrons is called the bond angle.

4. Bond order --The number of bonds present between two atoms is called bond order.
H-H BO-1
O=O BO-2
N=N BO-3
POLARITY OF BONDS :- The existence of a hundred percent ionic or covalent bond represents an ideal situation.
In reality no bond or a compound is either completely covalent or ionic. Even in case of covalent bond between two
hydrogen atoms, there is some ionic character.
When covalent bond is formed between two similar atoms, for example in H2 , O2 , Cl2 , N2 or F2 , the shared
pair of electrons is equally attracted by the two atoms. As a result electron pair is situated exactly between the two
identical nuclei. The bond so formed is called nonpolar covalent bond.
Contrary to this in case of a heteronuclear molecule like HF, the shared electron pair between the two atoms
gets displaced more towards fluorine since the electronegativity of fluorine is far greater than that of hydrogen. The
resultant covalent bond is a polar covalent bond.

5
XCELLENT CLASSES ROSHITA G PILLAI

DIPOLE MOMENT:- It is defined as the product of the magnitude of the charge and the distance between the
centres of positive and negative charge.
It is usually designated by a Greek letter ‘µ’.
Mathematically, it is expressed as follows : Dipole moment (µ) = charge (Q) × distance of separation (r)
Dipole moment is usually expressed in Debye units (D).
The conversion factor is 1 D = 3.33564 × 10–30 C m where C is coulomb and m is meter
Dipole moment is represented by the crossed arrow ( ) put on Lewis structure of the molecule. The cross is
on positive end and arrow head is on negative end. For example the dipole moment of HF may be represented as :
H F
APPLICATIONS OF DIPOLE MOMENT:-
1. The dipole moment helps to predict whether a molecule is polar or non-polar. As µ = q X d, greater is the
magnitude of dipole moment, higher will be the polarity of the bond. For non-polar molecules, the dipole
moment is zero.
For example:
(i). Molecules such as H2, N2, O2, Cl2 etc. have non-polar bonds and zero value of dipole moment.
(ii). Molecules such as CO2, BF3, CH4, etc., have polar bonds but zero value of dipole moment.
(iii). Molecules such as HF, HCl, NH3, H2O, have polar bonds and their dipole moment is greater than zero. In other
words, they are polar molecules.
2. The percentage of ionic character can be calculated as
Percentage of ionic character = µobserved/ µionic x 100
For example, let us calculate the percentage of ionic character in HCl molecule. Experiments have shown that the
dipole moment of HCl is 1.03 D and its bond length is 1.275Å. Now for 100% ionic character the charge developed on
H and Cl atoms would be 4.8 ´ 10–10 e. s. u. Therefore, dipole moment in case of 100% ionic character is given as:
µ = 4.8 × 10–10 × 1.275 × 10–8 e. s. u.-cm
= 6.12 × 10–18 e. s. u.-cm = 6.12 D
The observed dipole moment µ = 1.03 D
Therefore, Percentage Ionic character = 1.03/6.12 × 100 = 16.83%
In general, larger the value of dipole moment is, more will be the ionic character.
3. Symmetrical molecules have zero dipole moment although they have two or more polar bonds.
4. It helps to distinguish between cis- and trans-isomers. Usually cis-isomer has higher dipole moment than
trans- isomer.
5. It helps to distinguish between ortho, meta and para-isomers. Dipole moment of para- isomer is zero. Dipole
moment of ortho- isomer is greater than that of meta-isomer

POLARISATION:- When a cation approaches an anion. Electron cloud of anion is attracted towards a cation and
hence get distorted. The effect is called polarisation of anion.
The power of cation to polarise anion is called polarising power.
Tendency of anion to get polarised is called polarisability

FAJAN’S RULE:-
1. The smaller the size of the cation and the larger the size of the anion, the greater the covalent character of an
ionic bond.
2. The greater the charge on the cation, the greater the covalent character of the ionic bond.
3. For cations of the same size and charge, the one, with electronic configuration (n-1)d nnso , typical of
transition metals, is more polarising than the one with a noble gas configuration, ns2 np6 , typical of alkali and
alkaline earth metal cations. The cation polarises the anion, pulling the electronic charge toward itself and
thereby increasing the electronic charge between the two. This is precisely what happens in a covalent bond,
i.e., buildup of electron charge density between the nuclei. The polarising power of the cation, the
polarisability of the anion and the extent of distortion (polarisation) of anion are the factors, which determine
the per cent covalent character of the ionic bond.

VSEPR THEORY(VALENCE SHELL ELECTRON PAIR REPULSION) :-

The theory was first presented by Sidgwick and Powell in 1940.
The Valence Shell Electron Pair Repulsion Theory abbreviated as VSEPR theory is based on the premise
that there is a repulsion between the pairs of valence electrons in all atoms, and the atoms will always tend to arrange
themselves in a manner in which this electron pair repulsion is minimalized. This arrangement of the atom determines
the geometry of the resulting molecule.

6
XCELLENT CLASSES ROSHITA G PILLAI

POSTULATES OF VSEPR THEORY:

The postulates of the VSEPR theory are listed below:-
 In polyatomic molecules (i.e. molecules made up of three or more atoms), one of the constituent atoms is
identified as the central atom to which all other atoms belonging to the molecule are linked.
 The total number of valence shell electron pairs decides the shape of the molecule.
 The electron pairs have a tendency to orient themselves in a way that minimizes the electron-electron
repulsion between them and maximizes the distance between them.
 The valence shell can be thought of as a sphere wherein the electron pairs are localized on the surface in such
a way that the distance between them is maximized.
 Should the central atom of the molecule be surrounded by bond pairs of electrons, then, the asymmetrically
shaped molecule can be expected.
 Should the central atom be surrounded by both lone pairs and bond pairs of electrons, the molecule would
tend to have a distorted shape.
 The VSEPR theory can be applied to each resonance structure of a molecule.
 The strength of the repulsion is strongest in two lone pairs and weakest in two bond pairs.
Lp-lp > lp-bp > bp-bp
 If electron pairs around the central atom are closer to each other, they will repel each other. This results in an
increase in the energy of the molecules.
 If the electron pairs lie far from each other, the repulsions between them will be less and eventually,
the energy of the molecule will be low.

LIMITATIONS OF VSEPR THEORY:

Some significant limitations of the VSEPR theory include:
 This theory fails to explain isoelectronic species (i.e. elements having the same number of electrons). The
species may vary in shapes despite having the same number of electrons.
 The VSEPR theory does not shed any light on the compounds of transition metals. The structure of several
such compounds cannot be correctly described by this theory. This is because the VSEPR theory does not take
into account the associated sizes of the substituent groups and the lone pairs that are inactive.
 Another limitation of VSEPR theory is that it predicts that halides of group 2 elements will have a linear
structure, whereas their actual structure is a bent one.

PREDICTING THE SHAPES OF MOLECULES:

The following steps must be followed in order to decide the shape of a molecule.
 The least electronegative atom must be selected as the central atom (since this atom has the highest ability to
share its electrons with the other atoms belonging to the molecule).
 The total number of electrons belonging to the outermost shell of the central atom must be counted.
 The total number of electrons belonging to other atoms and used in bonds with the central atom must be
counted.
 These two values must be added in order to obtain the valence shell electron pair number or the VSEP
number.

The VSEP number describes the shape of the molecule, as described in the table provided below.
VSEPR Number Shape of the Molecule
2 Linear
3 Trigonal Planar
4 Tetrahedral
5 Trigonal Bipyramidal
6 Octahedral
7 Pentagonal Bipyramidal

CALCULATION OF TOTAL NO. OF ELECTRON PAIR, LONE PAIR AND BOND PAIR:-
1. Total number of electron pairs around the central atom = ½ (number of valence electrons of central atom +
number of atoms linked to central atom by single bonds)
 For negative ions, add the number of electrons equal to the units of negative charge on the ions to the valence
electrons of the central atom.
 For positive ions, subtract the number of electrons equal to the units of positive charge on the ion from the
valence electrons of the central atom.
2. The number of Bond pair = Total number of atoms linked to central atom by single bonds.
3. Number of lone pairs = Total number of electron – No of shared pair

7
XCELLENT CLASSES ROSHITA G PILLAI

8
XCELLENT CLASSES ROSHITA G PILLAI

VALENCE BOND THEORY

Introduced by Heitler and London (1927) and developed further by Pauling and others.

ASSUMPTIONS OF VBT:-
1. Atoms do not lose their identity even after formation of molecules
2. Bond is formed due to interaction of only the valence electrons as the 2 atoms come closer to each other. The
inner electrons do not participate in bond formation
3. During bond formation, only valence electron from each bonded atom lose their identity . The other electrons
remain unaffected
4. The stability of bond is accounted by the fact that formation of bond is accompanied by release of energy.
5. The molecule has minimum energy at a certain distance knoe as internuclear distance. Larger the decrease in
energy, stronger will be bond formation

VBT OF H2 MOLECULE:-
Consider two hydrogen atoms A and B approaching each other having nuclei HA and HB and electrons present in them
are represented by eA and eB . When the two atoms are at large distance from each other, there is no interaction
between them. As these two atoms approach each other, new attractive and repulsive forces begin to operate.
1. Attractive forces arise between:
 Nucleus of one atom and its own electron that is HA – eA and HB – eB
 Nucleus of one atom and electron of other atom i.e., HA – eB , HB – eA .
2. Repulsive forces arise between:
 Electrons of two atoms like eA – eB ,
 Nuclei of two atoms NA – NB

Experimentally it has been found that the magnitude of new attractive force is more than the new repulsive forces.
As a result, two atoms approach each other and potential energy decreases. Ultimately a stage is reached where the net
force of attraction balances the force of repulsion and system acquires minimum energy. At this stage two hydrogen
atoms are said to be bonded together to form a stable molecule having the bond length of 74 pm. Since the energy gets
released when the bond is formed between two hydrogen atoms, the hydrogen molecule is more stable than that of
isolated hydrogen atoms. The energy so released is called as bond enthalpy, which is corresponding to minimum in the
curve. Conversely, 435.8 kJ of energy is required to dissociate one mole of H2 molecule.
H2 (g) + 435.8 kJ mol–1 → H(g) + H(g)

9
XCELLENT CLASSES ROSHITA G PILLAI

Why a helium molecule does not form He2?

This can be easily understood by calculating the attractive and repulsive forces, when two helium atoms come closer
to each other. Each helium atom has two electrons in its 1s-orbital. There are two attractive forces between the nucleus
and the electrons of each atom. It has been found that when two helium atoms comes close to each other four new
attractive force and five new repulsive force come into play. Therefore, repulsive force predominate and the potential
energy of the system increases resulting in instability. Thus, He2 represents unstable state and a chemical bond is not
formed between helium atoms.

ORBITAL OVERLAPPING OF COVALENT BOND

When two atoms comes closer to each other, and when two bonding orbital merges, it is known as overlapping of the
orbitals.
The overlapping orbitals results in the pairing of electrons. The strength of a covalent bond depends upon
the amount of overlapping taking place. Greater overlapping results in stronger bond formation between the atoms.
According to orbital theory, the formation of a covalent bond between two atoms is because of the pairing
of electrons with opposite spins belonging to valence shells of the pairing atoms.

TYPES OF COVALENT BOND

Depending upon the type of overlapping, the covalent bonds may be divided into following types
(a) Sigma (σ) bond
(b) Pi (π) bond

SIGMA BOND (σ BOND)

The bond formed because of overlapping of two half-filled atomic orbitals along their axis is called as sigma (σ) bond.
σ bond is a strong bond because overlapping is large as compared to pi bond. The hybrid orbitals always form σ-bond.
 S-S Overlapping: Overlapping of two half-filled s-orbitals taking place along the inter-nuclear axis results in
S-S overlapping.
 S-P overlapping: Overlapping of half-filled s orbital of one atom with half-filled p orbital of another atom
along the inter-nuclear axis to form bonds results in S-P overlapping.
 P-P overlapping: In this type, overlapping of one half-filled p orbital from each bonding atom undergoes
head-on overlapping along the inter-nuclear axis.

Pi BOND (π bond)
Lateral overlapping of half-filled atomic orbitals results in the formation of pi bond. The sidewise overlapping is quite
less as compared to sigma bond. Therefore, a pi bond formed is a weak bond. π bond overlapping takes place only at
the sides of two lobes. A π bond is formed only when a s bond already exists between combining atom.

10
XCELLENT CLASSES ROSHITA G PILLAI

STRENGTH OF SIGMA AND PI- BONDS

The strength of a covalent bond depends upon the amount of overlapping taking place in atomic orbitals at the time of
bond formation. During the formation of a sigma bond the overlapping of orbitals takes place to a larger extent, but
quite less at the time of formation of a pi-bond.Therefore the sigma bond is stronger than a pi-bond.

DIFFERENCE BETWEEN SIGMA AND PI-BOND

Sigma Bond Pi Bond

Formed by end to end filled atomic orbitals along the Formed by sidewise overlap of two half-filled p-orbitals.
intermolecular axis. The overlapping takes place between
two s-orbitals, one s and p orbitals.
Overlapping takes place to a greater extent, thereby Overlapping takes place to lesser extent, thereby forming
forming a stronger bond. a weaker bond.
The molecular orbital is symmetrical about inter nuclear Molecular orbital are discontinuous.
axis.
Atoms can freely rotate around sigma bond. Because of overlapping of electron cloud above and
below the plane of atoms, they cannot rotate freely.
Bond may be present between two atoms either alone or The bond is always present only when there is a sigma
along with sigma bond. bond. They cannot exist alone.
S orbital participates in the formation of sigma bond. S orbitals cannot participate in the formation of pi bond

HYBRIDIZATION
The concept of hybridization was introduced by Pauling and Slater.
It is defined as the intermixing of dissimilar orbitals of the same atom but having slightly different energies to form
same number of new orbitals of equal energies and identical shapes. The new orbitals so formed are known as hybrid
orbitals
OR
Defined as 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

CHARACTERISTICS OF HYBRIDIZATION
(1) Only orbitals of almost similar energies and belonging to the same atom or ion undergoes hybridization.
(2) Hybridization takes place only in orbitals, electrons are not involved in it.
(3) The number of hybrid orbitals produced is equal to the number of pure orbitals, mixed during hybridization.
(4) In the excited state, the number of unpaired electrons must correspond to the oxidation state of the central atom in
the molecule.
(5) Both half-filled orbitals or fully filled orbitals of equivalent energy can involve in hybridization.
(6) Hybrid orbitals form only sigma bonds.
(7) Orbitals involved in p bond formation do not participate in hybridization.
(8) Hybridization never takes place in an isolated atom but it occurs only at the time of bond formation.

HOW TO DETERMINE TYPE OF HYBRIDIZATION: The structure of any molecule can be predicted on the
basis of hybridization which in turn can be known by the following general formulation,
H = (1/2) (V+M+A)
Where; H = Number of orbitals involved in hybridization viz. 2, 3, 4, 5, 6 and 7, hence nature of hybridization will be
sp, sp2, sp3, sp3d, sp3d2, sp3d3 respectively.
V = Number electrons in valence shell of the central atom,
M = Number of monovalent atom
C = Charge on cation,
A = Charge on anion

IMPORTANT CONDITIONS FOR HYBRIDISATION

1. The orbitals present in the valence shell of the atom are hybridised.
2. The orbitals undergoing hybridisation should have almost equal energy
3. Promotion of electron is not essential condition prior to hybridisation.
4. It is not necessary that only half filled orbitals participate in hybridisation. In some cases, even filled orbitals
of valence shell take part in hybridisation
11
XCELLENT CLASSES ROSHITA G PILLAI

TYPES OF HYBRIDISATION
1. sp hybridisation: This type of hybridisation involves the mixing of one s and one p orbital resulting in the
formation of two equivalent sp hybrid orbitals. The suitable orbitals for sp hybridisation are s and pz , if the
hybrid orbitals are to lie along the z-axis. Each sp hybrid orbitals has 50% s-character and 50% p-character.
Such a molecule in which the central atom is sp-hybridised and linked directly to two other central atoms
possesses linear geometry. This type of hybridisation is also known as diagonal hybridisation
The two sp hybrids point in the opposite direction along the z-axis with projecting positive lobes
and very small negative lobes, which provides more effective overlapping resulting in the formation of
stronger bonds.

BeCl2 : The ground state electronic configuration of Be is 1s22s2 . In the exited state one of the 2s-electrons is
promoted to vacant 2p orbital to account for its bivalency. One 2s and one 2p-orbital gets hybridised to form
two sp hybridised orbitals. These two sp hybrid orbitals are oriented in opposite direction forming an angle of
180°. Each of the sp hybridised orbital overlaps with the 2p-orbital of chlorine axially and form two Be-Cl
sigma bonds.

2. sp2 hybridisation : In this hybridisation there is involvement of one s and two p-orbitals in order to form three
equivalent sp2 hybridised orbitals. For example, in BCl3 molecule, the ground state electronic configuration of
central boron atom is 1s22s22p1 . In the excited state, one of the 2s electrons is promoted to vacant 2p orbital
as a result boron has three unpaired electrons. These three orbitals (one 2s and two 2p) hybridise to form three
sp2 hybrid orbitals. The three hybrid orbitals so formed are oriented in a trigonal planar arrangement and
overlap with 2p orbitals of chlorine to form three B-Cl bonds. Therefore, in BCl3 the geometry is trigonal
planar with Cl-B-Cl bond angle of 120°

3. sp3 hybridisation: This type of hybridisation can be explained by taking the example of CH4 molecule in
which there is mixing of one s-orbital and three p-orbitals of the valence shell to form four sp3 hybrid orbital

12
XCELLENT CLASSES ROSHITA G PILLAI

of equivalent energies and shape. There is 25% s-character and 75% p-character in each sp3 hybrid orbital.
The four sp3 hybrid orbitals so formed are directed towards the four corners of the tetrahedron. The angle
between sp3 hybrid orbital is 109.5°

MOLECULAR ORBITAL THEORY

Molecular orbital (MO) theory was developed by F. Hund and R.S. Mulliken in 1932.

THE SALIENT FEATURES OF THIS THEORY :

1. The electrons in a molecule are present in the various molecular orbitals as the electrons of atoms are present
in the various atomic orbitals.
2. The atomic orbitals of comparable energies and proper symmetry combine to form molecular orbitals.
3. 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.

13
XCELLENT CLASSES ROSHITA G PILLAI

4. 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
5. The bonding molecular orbital has lower energy and hence greater stability than the corresponding
antibonding molecular orbital.
6. 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.
7. 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

14