Chemical Bonding

Chemical Bond : The attractive force which holds various constituents such as atoms, ions etc.,

together in different chemical species is called a chemical bond.

To explain nature of chemical bond, different theories are given

(i) Octet rule
(ii) Valence bond theory
(iii) Valence shell electron pair repulsion theory
(iv) Molecular orbital theory.

Octet rule :
“Tendency of atoms to have eight electrons in their outermost shell is known as Lewis octet rule". To
achieve inert gas configuration atoms lose, gain or share electrons.
(i) It has been observed that atoms of noble gases have little or no tendency to combine with each other
or with atoms of other elements.
(ii) It means that these atoms must have a stable electronic configuration.
(iii) These elements (noble gases) have 8 electrons (ns 2 np6) except helium which has 2 electrons (1s 2)
in their outer most shell.

Element Ne Ar Kr Xe Rn
Outer most shell
configuration 2s22p6 3s23p6 4s24p6 5s25p6 6s26p6
(iv) It is therefore concluded that ns np configuration in the outer energy level constitues a structure of
2 6

maximum stability or minimum energy.

The Octet rule can be understood by considering the formation of the chlorine molecule, Cl 2. The Cl
atom with electronic configuration, [Ne]10 3s2 3p5, is one electron short of the argon configuration. The
formation of the Cl2 molecule can be understood in terms of the sharing of a pair of electrons between
the two chlorine atoms, each chlorine atom contributing one electron to the shared pair. In the process
both

Cl + Cl Cl Cl

– –
8e 8e
or Cl – Cl
Covalent bond between two Cl atoms
Figure
chlorine atoms attain the outer shell octet of the nearest noble gas (i.e., argon). The dots represent
electrons. Such structures are referred to as Lewis dot structures.

CLASSIFICATION OF CHEMICAL BONDS :

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On the basis of electronic valency theory and structure, chemical bonds can be classified as follows.

Coordinate
bond

Bond Bond Energy per mole

Ionic, Covalent & Co–ordinate –––––––––– 200 kJ

Hydrogen bonding –––––––––– 10 – 40 kJ

Vander–waal’s –––––––––– 2 – 10 kJ

ELECTROVALENT OR IONIC BOND :

The chemical bond formed between two or more atoms as a result of complete transfer of one or more
electrons from one atom to another is called ionic or electrovalent bond.
Electrovalent bond is not possible between similar atoms. This type of bonding requires two atoms of
different nature. One atom should have the tendancy to loose electrons i.e. electropositive in nature and
the other atom should have the tendency to accept electrons i.e. electronegative in nature.
Electropositive atom looses electrons (group IA to IIIA)
Electronegative atom gains electron (group IVA to VII A)
Example : IA and VII A group elements form strong ionic compound.
+ –
Na + Cl ⎯→ Na + Cl
2, 8, 1 2, 8, 7 2, 8 2, 8, 8
(Ne configuration) (Ar configuration)
More the distance between two elements in the periodic table more will be the ionic character of the
bond.
Total number of electrons lost or gained is called electrovalency.
Example :

(1) Mg + O ⎯→ MgO

electrovalency of Mg = 2
electrovalency of O = 2

(2) Ca + 2Cl ⎯→ CaCl2

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+2
Ca Ca Cl Cl
2, 8, 8 2, 8, 8, 2 2, 8, 7 2, 8, 8
One e
Cl Cl
2, 8, 7 2, 8, 8
One e
electrovalency of Ca = 2
electrovalency of Cl = 1

(3) Ca + O ⎯→ CaO

electrovalency of Ca = 2
electrovalency of O = 2

• Electrostatic force of attraction between cation and anion is called ionic bond or electrovalent bond.
Force of attraction is equal in all direction so ionic bond is non–directional.
• A definite three dimensional structure called crystal lattice is formed .
Energy released during the formation of one mole crystal lattice is called lattice energy.
23 + 23 – 23
e.g. (6.023 × 10 )Na + (6.023 × 10 ) Cl ⎯→ (6.23 × 10 ) NaCl + 94.5 K.cal (Lattice energy).
• Ionic compounds do not have a molecular formula, they only have empirical formula.

e.g. NaCl is the empirical formula of sodium chloride.

Factors favouring formation of Ionic bonds :

Formation of ionic bond depends upon three factors :

(A) Ionisation energy (IE) :

Amount of energy required to remove an electron from the outermost orbit of an isolated gaseous atom
to form positve ion or cation is called ionzation energy [energy is absorbed so it is an endothermic
process]
+ –
M + I.E. ⎯⎯→ M + e
Less Ionisation energy  Greater tendency to form cation.

Example :
(B) Electron affinity :
Amount of energy released when an electron is added to an isotated gaseous atom to form negative ion
or anion is called electron affinity [energy is released so it is an exothermic process]
– –
X + e ⎯→ X + EA
High electron affinity  Greater tendency to form anions

Cl > F > Br > I

Anion formation tendency
2 3
F > O > N

LATTICE ENTHALPY :

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The Lattice Enthalpy of an ionic solid is defined as the energy required to completely separate one mole
of a solid ionic compound into gaseous constituent ions. For example, the lattice enthalpy of NaCI is
788 kJ mol-1. This means that 788 kJ of energy is required to separate one mole of solid NaCI into one
mole of Na+1 (g) and one mole of Cl–(g) to an infinite distance.
This process involves both the attractive forces between Ions of opposite charges and the repulsive
forces between ions of like charge. The solid crystal being three- dimensional; it is not possible to
calculate lattice enthalpy directly from the interaction of forces of attraction and repulsion only.
Factors associated with the crystal geometry have to be included.
Na+(g) + Cl–(g) —→ NaCl(s) H = Hlattice  –ve (always)
Mg2+(g) + 2Cl– (g) —→ MgCl2 (s)

Factors affecting L.E.

1
(i) Lattice energy (L.E.)  r = r+ + r–
r
= interionic distance
(ii) L.E.  Z+, Z–
Z+  charge on cation in terms electronic charge
Z–  charge on anion in terms electronic charge

(iii) Charge density of cation  L.E. 

(a) NaCl > KCl (size)
(b) NaCl < MgO (size, charge)
(c) NaCl < MgCl2 (size, charge)

In size and charge, charge will dominate

Na2O > NaF
NaCl < Na2S

(d) Al2O3 Na2O MgO

Al2O3 > MgO > Na2O

Characteristics of ionic compounds :

(i) Physical state
(a) Electrovalent compounds are generally crystalline, hard & brittle in nature.
(b) These compounds are generally made from ions which are arranged in a regular way as a lattice
structure.
(c) Thus electrovalent compounds exist as three dimensional solid aggregates.
(d) Normally each ion is surrounded by a number of oppositively charged ions and this number is
called co-ordination number

(ii) Boiling point and melting point :

High boiling point and melting points are due to strong electrostatic force of attraction.

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(iii) Electrical conductivity :

It depends on ionic mobility. In solid state there are no free ions so they are bad conductors of
electricity In fused state or aqueous solution free ions are present so they are good conductors of
electricity (Conductivity order) Solid state < Fused state < Aqueous solution
(iv) Ionic reactions :
 Ionic compounds show ionic reactions & covalent compounds show molecular reactions.
Ionic reactions are fast reactions.
Example : When NaCl is added to AgNO3 solution, white ppt of AgCl is formed at once.
+ – + + –
Ag NO3 + Na Cl Na NO3 + AgCl 
white ppt.
(v) Solubility – Ionic compounds are soluble in polar solvent like H2O, HF etc.
To explain solubility of ionic compound consider an example of NaCl in water.

H2O is polar solvent it can represent as

 +
The Na ions gets associated with partially negatively charged 'O' of water
–
 And Cl ions gets associated with partially positively charged 'H' of water.

+ –
Thus charge on Na and Cl decreases and electrostatic force also decreases which leads to free ion.


 Energy released due to interaction between polar solvent molecule and ions of solute is called
solva tion energy. If water used as solvent it is called hydration energy.
 Condition of the solubility of ionic compound in water is (Hydration energy > Lattice energy)

Solvation or Hydration :

Whenever any compound generally ionic or polar covalent is dissolved in an polar solvent or in water
then., different ions of the compound will get separated and will get surrounded by polar solvent
molecules. This process is known as solvation or hydration. Energy released in this process is known
as solvation energy or hydration energy
The ionic compound will be soluble only if solvation energy (H.E.) is more than the lattice energy
Applications of Hydration energy :
(a) Size of the hydrated ions: Greater the hydration of the ion greater will be its hydrated radii
Li+(aq) > Na+(aq)

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1
(b) Mobility of the ion: more is the hydration smaller will be the mobility of the ions 
Hydrated radii
Li+(aq) < Na+(aq) < K+(aq) < Rb+(aq) < Cs+(aq).
(c) Electrical conductance : is related to mobility so follows the same order

COVALENT BOND :
 A chemical bond formed by sharing of electrons between two elements is called as covalent bond.
A⎯A (Single bond) : When 2 electrons are shared between the two combining elements.
(Double bond) : When 4 electrons are shared between the two combining elements.
(Triple bond) : When 6 electrons are shared between the two combining elements.

•
H H

• • •
• • •
•
•

•
•
•
•
•

•
•
• •• •
• O ••
O
• N N

H2 molecule O2 N2
H H O=O NN
Covalency :
(i) It is defined as the number of electrons contributed by an atom of the element for sharing with
other atom so as to achieve noble gas configuration.
(ii) It can also be defined as the number of covalent bonds formed by the atom of the element with
other atoms.
(iii) The usual covalency of an element except hydrogen is equal to 8 minus the number of group
to which the element belongs.
Lewis structure and covalent bond :
(i) Structures in which valency electrons are represented by dots are called Lewis structures.
(ii) All atoms in the formulae will have eight electrons in it’s valence shell.H atom is an exception
for it can form large number of bonds with the atom present at the center of any crystal
structure. Other atoms surround it to complete their octet.
(iii) Lewis dot formulae shows only the number of valency electrons, the number and kinds of
bonds, but does not depict the three dimensional shapes of molecules and polyatomic ions.
(iv) Lewis formulae are based on the fact that the representative elements achieve a noble gas
configuration in most of their compounds i.e. 8 electrons in their outermost shell (except for H 2,
+ 2+
Li and Be ions which have only 2 electrons)
Lewis Dot Structures :
The Lewis dot structures can be written for other molecules also, in which the combining atoms may be
identical or different.
To write the Lewis dot structure following steps are to be followed :
(i) The total number of electrons are obtained by adding the valence electrons of combining atoms.
(ii) For Anions, we need to add one electron for each negative chanrge.
(iii) For cations, we need to subtract one electron for each positive charge.
(iv) After then the central atom is decided.

To decide, Central atom, following steps are followed :

(i) In general the least electronegative atom occupies the central position in the molecule/ion. For
example in the NF3 and CO32–, nitrogen and carbon are the central atoms whereas fluorine and oxygen
occupy the terminal positions.
(ii) Generally the atom which is/are less in number acts as central atom.
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(iii) Generally central atom is the atom which can form maximum number of bonds( which is generally equal
to the number of electrons present in the valence shell of the atom).
(iv) Atom of highest atomic number or largest atom generally acts as central atom.
Hence fluorine and hydrogen can never act as central atoms.
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. The basic requirement being that each
bonded atom gets an octet of electrons.
Lewis representations of a few molecules/ions are given in the following Table

Table-1

Molecule/ion H2 O2 O3 NF3 CO32 – HNO3 CH4 HCHO

2–
+ O
:

H
: :
:
: :
O :F – N – F : :O: +

: :

: :
:
:

Lewis Representation H – H : O= O: : O O = N – O –H H–C–H H–C–H

: :

: :
O:–

: :
:F : :O – C – O:
:

: : O:– H

:
Each H-atom attains the configuration of helium (a duplet of electrons)

Characteristics of covalent compounds :

(i) Physical state :
(a) Under normal temperature and pressure, they exist as gases or liquids of low boiling points.
(b) This is due to the fact that very weak forces of attraction (Vander waal’s forces) exist between
the molecules due to which molecules are far from each other.
(c) If their molecular masses are high they exist as soft solids ex. Sulphur, phosphorus and iodine
(ii) Crystal structures :
Various types of structures that are present in a covalent compound are as follows.
(a) Covalent solid – In this type of structure every atom is bonded to four other atoms by single
covalent bonds resulting in the formation of a giant structure e.g. SiC, AIN and diamond these
crystals are very hard and possess high melting point.
3
Diamond is sp hybridized carbon atom and it forms a tetrahedral structure.
2
Graphite is sp hybridized carbon atomsand it forms hexagonal layers which can slide over
each other due to weak Vander waal’s forces of attraction.Distance between C–C atom is 1.42
Å distance between layers is 3.6 Å. Graphite is more stable than diamond due to high
value of change in enthalpy.
(b) Molecular solids : They are formed when one atom combines with another by a covalent
bond and then the molecule combines with another similar molecule with the help of Vander
waal’s force of attraction or hydrogen bond

Example : CH4(Solid), dry ice, ice

(iii) Melting and boiling points :

(a) With the exception of a few which have giant three dimensional structures such as diamond,
carborundum (SiC), Silica (SiO2), Boron steel (B4C), others have relatively low melting and
boiling points.
(b) This is due to the presence of weak attractive forces between the molecules.

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(iv) Electrical conductivity :

(a) In general covalent substances are bad conductors of electricity. Since they do not contain
charged particles or free electrons.
(b) Substances which have polar character like HCl in a solution, can conduct electricity.
(c) Graphite can conduct electricity since electrons can pass from one layer to other.
(d) Some show conductivity due to self ionisation. example Liq NH3
+ –
NH3 + NH3 ⎯→ NH4 + NH2 (Amide ion)
+ –
H2O + H2O ⎯→ H3O + OH

(v) Chemical reactions :

Covalent substances give molecular reactions. Reaction rate is usually low because it involves
two steps (i) breaking of covalent bonds of the reactants (ii) establishing new bonds. While in
ionic reactions there is only regrouping of ions.
(vi) Solubility :
(a) Non polar compounds are soluble in non polar solvents. Non polar solvents are CCl 4, Benzene,
CS2 etc.
(b) Polar compounds are soluble in polar solvents (i.e. EN 0.9 to 1.8). Polar solvents are H 2O,
CHCl3, Alcohol etc.

(vii) Isomerism :
Covalent bonds are rigid and directional. On account of this there is a possibility of different
arrangement of atoms in space. Covalent compounds can thus shows isomerism (structural
and spatial)

Formal Charge :
The formal charge of an atom in a molecule or ion is defined as the difference between the number of
valence electrons of that atom in an isolated or free state and the number of electrons assigned to that
atom in the lewis structure.

Let us consider the ozone molecule (O3 ). The Lewis structure of O3, may be drawn as :

The atoms have been numbered as 1. 2 and 3. The formal charge on :

1
The central O atom marked 1 = 6 –2 – (6) = + 1
2
1
The terminal O atom marked 2 = 6 – 4 – (4) = 0
2
1
The terminal O atom marked 3 = 6 – 6 – (2) = – 1
2
Hence, we represent O3 along with the formal charges as follows :

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It should be kept in mind that formal charges do not indicate real charge separation within the molecule.
Indicating the charges on the atoms in the Lewis structure only helps in keeping track of the valence
electrons in the molecule. Formal charges help in the selection of the lowest energy structure
from a number of possible Lewis structures for a given species. Generally the lowest energy
structure is the one with the smallest formal charges on the atoms.
Note : The formal charge Is a factor based on a pure covalent view of bonding in which electron pairs
are shared equally by neighbouring atoms.

Limitations of the Octet Rule :

The octet rule, though useful, is not universal. It is quite useful for understanding .the structures of most
of the organic compounds and it applies mainly to the second period elements of the periodic table.
There are three types of exceptions to the octet rule.
1. The 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 having less than four valence electrons. Examples are LiCl, BeH 2 and
BCl3. BeF2 , BF3 , AlCl3

2. Odd-electron molecules
In molecules with an odd number of electrons like nitric oxide, NO and nitrogen dioxide. NO 2, the octet
rule is not satisfied for all the atoms.
e.g. NO, ClO2 , ClO3

3. The expanded octet, Super octet or Hypervalent molecules

Elements in and beyond the third period of the periodic table have, apart from 3s and 3p orbitals, 3d
orbitals also available for bonding. In a number of compounds of these elements there are more than
eight valence electrons around the central atom. This is termed as the expanded octet. Obviously the
octet rule does not apply in such cases.
Some of the examples of such compounds are: PF5, SF6, PCl5, HNO3, SO3, SO2, H2SO4 and a number
of coordination compounds.

 Interestingly, sulphur also forms many compounds in which the octet rule is obeyed. In sulphur
dichloride, the S atom has an octet of electrons around it.

4. Other drawbacks of the octet theory

(i) It is clear that octet rule is based upon the chemical inertness of noble gases. However, some noble
gases (for example xenon and krypton) also combine with oxygen and fluorine to form a number of
compounds like XeF2 , KrF2 , XeOF2 etc.,
(ii) This theory does not account for the shape of molecules.

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(iii) It does not explain the relative stability of the molecules being totally silent about the energy of a
molecule

Resonance :
It is often observed that a single Lewis structure is inadequate for the representation of a molecule in
conformity with its experimentally determined parameters. For example, the ozone, O 3 molecule can be
equally represented by the structures I and II shown below :

Resonance in the O3 molecule

Structures I and II represent the two canonical forms.
The structure III is the resonance hybrid
In both structures we have a O – O single bond and a O = O double bond. The normal O – O and O =
O bond lengths are 148 pm and 121 pm respectively.
Experimentally determined oxygen-oxygen bond lengths in the O3 molecule are same (128 pm). Thus
the oxygen-oxygen bonds in the O3 molecule are intermediate between a double and a single bond.
Obviously, this cannot be represented by either of the two Lewis structures shown above.
According to the concept of resonance, 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.
Thus for O3 the two structures shown above constitute the canonical structures or resonance structures
and their hybrid i.e., the III structure represents the structure of O 3, more accurately. This is also called
resonance hybrid. Resonance is represented by a double headed arrow.

Definition : Resonance may be defined as the phenomenon in which two or more structures involving
in identical position of atom, can be written for a particular compound

Resonance Hybrid : It is the actual structure of all different possible structures that can be written for
the molecule without violating the rules of covalence maxima for the atoms.

 
Resonance hybrid

Example :

(i) 

(ii) 

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(iii) 

(iv) 

 Resonance energy = Actual bond energy – Energy of most stable resonating structure.
 Stability of molecule  resonance energy.
 More is the number of covalent bonds in molecule more will be its resonance energy.
 Resonance energy  number of resonating structures.

Bond order in oxoanions and corresponding acids :

Let’s starts with example of HSO4–

Total No. of bonds formed between two atoms in all structures 2 + 2 +1

 Bond order = = = 5/3
Total No. of resonating structures 3
Consider another example of SO4– – :

Total No. of bonds formed between two atoms in all structures

 Bond order =
Total No. of resonating structures
2 + 2 + 1+ 2 + 1+ 1
= = 1.5
6
Consider another example of PO4– – – :

Total No. of bonds formed between two atoms in all structures

 Bond order =
Total No. of resonating structures
1+ 2 + 1+ 1
= = 5/4
4
MODERN CONCEPT OF COVALENT BOND (VBT) :
As we know that Lewis approach helps in writing the structure of molecules but it fails to explain the
formation of chemical bond. It also does not give any reason for the difference in bond dissociation
enthalpies and bond lengths in molecules like H 2 (435.8 kJ mol –, 74 pm) and F2 (150.6 kJ mol– , 42 pm);
although in both the cases a single covalent bond is formed by the sharing of an electron pair between
the respective atoms. It also gives no idea about the shapes of polyatomic molecules. Similarly the
VSEPR theory gives the geometry of simple molecules but theoretically, it does not explain them and
also it has limited applications. To overcome these limitations the two Important theories based on

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quantum mechanical principles are introduced. These are valence bond (VB) theory and molecular
orbital (MO) theory.
Valence bond theory was introduced by Heitler and London (1927) and developed further by Pauling
and others. A discussion of the valence bond theory is based on the knowledge of atomic orbitals,
electronic configurations of elements, the overlap criteria of atomic orbitals, the hybridization of atomic
orbitals and the principles of variation and superposition. Consider two hydrogen atoms A and B
approaching each other having nuclei NA and NB and electrons present in them are represented by e A
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.
Attractive forces arise between :
(i) nucleus of one atom and its own electron that is NA – eA and NB – eB.
(ii) nucleus of one atom and electron of other atom i.e., NA – eB. NB– eA.

Similarly repulsive forces arise between :

(i) electrons of two atoms like eA – eB , (ii) nuclei of two atoms NA – NB.

Attractive forces tend to bring the two atoms close to each other whereas repulsive forces tend to push
them apart (Fig.).

Fig- Forces of attraction and repulsion during the formation of H2 molecule.

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 depicted in Fig. Conversely. 435.8 kJ of
energy is required to dissociate one mole of H2 molecule.
H2(g) + 435.8 kJ mol – → H(g) + H(g)

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Fig. The potential energy curve for the formation of H2 molecule as a function of internuclear distance of
the H atoms. The minimum in the curve corresponds to the most stable state of H 2 .

Orbital Overlap Concept

In the formation of hydrogen molecule, there is a minimum energy state when two hydrogen atoms are
so near that their atomic orbltals undergo partial interpenetration. This partial merging of atomic orbitals
is called overlapping of atomic orbitals which results in the pairing of electrons. The extent of overlap
decides the strength of a covalent bond. In general, greater the overlap the stronger is the bond formed
between two atoms. Therefore, according to orbital overlap concept, the formation of a covalent bond
between two atoms results by pairing of electrons present In the valence shell having opposite spins.

Main points of valency bond theory :

(i) A covalent bond is formed by partial overlapping of two atomic orbitals

(ii) More is the extent of overlapping between the two atomic orbital, stronger will be bond.

< < [Principal Quantum no. same, n = 2]

() () ()
 s orbital are spherical in nature so they are least diffused hence it will provide less area for
overlapping.
(iii) Orbitals which are undergoing overlapping must be such that
(a) Each orbital should have one electron with opposite spin (for formation of covalent bond)
(b) One orbital have pair of electron and the other orbital have no electron (for formation of co-ordinate
bond)
(iv) If the overlapping is along the molecular axis then bond will be sigma () & in the perpendicular
direction, it will be pi() bond.

 Examples of overlapping of pure atomic orbitals.

(i) H2 (s–s) H= H=

(ii) HCl gas molecule (s-p)

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(iii) F2, Cl2, Br2, 2 (p-p)

F2 Cl2 Br2 2
2p-2p 3p-3p 4p-4p 5p-5p (Type of overlapped orbitals)
Overlapping of Atomic Orbitals
When two atoms come close to each other there is overlapping of atomic orbitals. This overlap may be
positive, negative or zero depending upon the properties of overlapping of atomic orbitals. The various
arrangements of s and p orbitals resulting in positive, negative and zero overlap are depicted in the
following figure.
The criterion of overlap, as the main factor for the formation of covalent bonds applies uniformly to the
homonuclear/heteronuclear diatomic molecules and polyatomic molecules.
Positive overlap Negative overlap

Zero overlap

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Figure : Positive, negative and zero overlaps of s and p atomic orbitals

Types of Overlapping and Nature of Covalent Bonds :
The covalent bond may be classified into two types depending upon the types of overlapping :
(i) Sigma () bond, and (ii) pi () bond
(i) Slgma () bond : This type of covalent bond is formed by the end to end (hand-on) overlap of
bonding orbitals along the intemuclear axis. This is called as head on overlap or axial overlap. This can
be formed by any one of the following types of combinations of atomic orbitals.
⚫ s-s overlapping : In this case, there is overlap of two half filled s-orbitals along the intemuclear axis as
shown below :

⚫ s-p overlapping: This type of overlap occurs between half filled s-orbitals of one atom and half filled
p-orbitals of another atom.

⚫ p-p overlapping : This type of overlap takes place between half filled p-orbitals of the two
approaching atoms.

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

Strength of Sigma and pi Bonds :

Basically the strength of a bond depends upon the extent of overlapping- In case of sigma bond, the
overlaping of orbitals takes place to a larger extent. Hence, it is stronger as compared to the pi bond
where the extent of overlapping occurs to a smaller extent. Further, it is important to note that pi bond .
between two atoms is formed in addition to a sigma bond. It is always present in the molecules
containing multiple bond (double or triple bonds)
Diffenence in  and  bonds :
Sigma () bond Pi () bond

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

1. It results from the end to end overlapping It result from the sidewise (lateral)
of two s orbitals or two p–orbitals or overlapping of two p orbitals.
one s and one p–orbital.

2. Its bonded orbital consists of a single Its bonded orbital consists of two electron
electron cloud symmetrical about clouds one above and the other below
internuclear Axis the plane of symimetry

3. Strong Weak

4. Bond energy 80 Kcals 65 Kcals

5. More stable Less Stable
6. Less reactive More reactive
7. Can independently axis Always exists alongwith a  bond
8. Hybridization depends upon  bond doesn't depend on  bond
9. The groups or atoms can undergo Due to resistance to rotation around
bond rotation about single sigma () the  bond the groups attached to it
bonds are not free to rotate.

10. The  electrons are referred as in  bond the electrons are held less
localised firmly bond thus can be easily
dissociated or polarised by an external
–
charge and hence the  e are referred
as mobile electrons.

11. Shape of the molecule is determined  bonding does not affect the shape
by the  bonds present in the molecule of the molecule

Valence shell electron pair repulsion (VSEPR) theory :

Lewis concept is unable to explain the shapes of molecules. This theory provides a simple procedure to
predict the shapes of covalent molecules. Sidgwick and Powell in 1940, proposed a simple theory
based on the repulsive interactions of the electron pairs in the valence shell of the atoms. It was further
developed and redefined by Nyholm and Gillespie (1957).
The main postulates of VSEPR theory are as follows:
(i) The shape of a molecule depends upon the number of valence shell electron pairs [bonded or
nonbonded) around the central atom.
(ii) Pairs of electrons in the valence shell repel one another since their electron clouds are
negatively charged.
(iii) These pairs of electrons tend to occupy such positions in space that minimise repulsion and
thus maximise distance between them.
(iv) The valence shell is taken as a sphere with the electron pairs localising on the spherical
surface at maximum distance from one another.
(v) A multiple bond is treated as if it is a single electron pair and the two or three electron pairs of a
multiple bond are treated as a single super pair.
(vi) Where two or more resonance structures can represent a molecule, the VSEPR model is
applicable to any such structure.
The repulsive interaction of electron pairs decreases in the order :

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

lone pair (p) - lone pair (p) > lone pair (p) - bond pair (bp) > bond pair (bp) -bond pair (bp)

Shape (molecular geometry) of Some Simple Molecules / ions with central atom / ion having no
Lone Pairs of Electrons (E).

Shape (molecular geometry) of Some Simple Molecules/Ions with central atom / ions having One
or More Lone Pairs of Electrons (E).

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Molecule No.of No.of Arrangement of Shape Examples

type bonding lone electron pairs
pairs pairs

:
AB2E 2 1 A Bent SO2 ,O3
B B

:
3 1 A Trigonal NH3
AB3E
B B pyramidal
B

:
AB2E2 2 2
A Bent H2O
B

:
B
B
4 1 B
AB4E :– A See saw SF4
B
B
B
: T–shape CIF3
AB3E2 3 2
B– A
:

B
B
: – –
AB2E3 2 3 –A Linear I3 ,ICl2 ,XeF2
:

B
B
AB5E B B Square BrF5
5 1 A pyramidal
B B
:
:

B B Square
AB4E2 4 2 XeF4
A planar
B B
:

Shapes of Molecules containing Bond Pair and Lone Pair

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Molecule No.of bonding No.of lone Shape Reason for the

type pairs pairs shape acquired
4

:
AB2E 1 It is found to be bent or v-shaped.

:
S Bent
:O =
=
0 O: The reason being the lone pair-
119.5 S

:
bond pair repulsion is much more

:
O=
=
O as compared to the bond pair-bond
pair repulsion. So the angle is reduced
0 0
to 119.5 from 120 .

:
N
H Trigonal It is found to be trigonal pyramidal
H 0
pyramidal
AB3E 3 1 107 due to the repulsion between lp-bp
H (which is more than bp–bp repulsion)
the angle between bond pairs is
reduced to 1070 to 109.50 .

:
N
H H
H
:
:

O Bent The shape is distored tetrahedral or

AB2E2 2 2 0 angular. The reason is lp-lp repulsion is
H 104.5 H
more than lp-bp repulsion. Thus , the
0 0
angle is reduced to 104.5 from 109.5 .
:

:
O
H H
:

F See- In (i) the lp is present at axial position 0

AB4E 4 1 (i) S saw so there are three lp-bp repulsion at 90 .
F In (ii) the lp is an equatorial position, and
F there are two lp-bp repulsions. Hence ,
F arrangement (ii) is more stable. The shape
shown in (ii) is called as a distorted
F tetrahedron, a folded square or a see-saw.
F
(ii) S (More stable)
F
F

AB3E2 3 2 F T–shape In (i) the lone pairs are at

: equatorial position (120º) so
Cl F there are less lp–bp
(i) : repulsions as compared
to others in which the lp
F are at axial positions.So
structure (i) is most
F stable. (T – shaped).
F
:

:
(ii) Cl F F Cl
(iii)
F F
:

I –
:
AB2E3 2 3 : –I Linear I3– ,ICl2– ,XeF2
:

 The VSEPR Theory is able to predict geometry of a large number of molecules, especially the
compounds of p-block elements accurately. It is also quite successful in determining the geometry
quite-accurately even when the energy difference between possible structures is very small.

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Chemical Bonding

Ex.2 Use the VSEPR model to predict the geometry of the following :
(a) XeF2 (b) ClO3–
Sol. Species Structure

(a) XeF2 lone pairs occupy the equatorial positions to have

minimum repulsion. Thus it is linear.

(b) ClO3– To minimize the repulsion between lone pair and double bond,

species acquires trigonal pyramidal.

Hybridisation :
– Hypothetical concept Introduced by pauling and slater.
– Atomic orbitals combine to form new set of equivalent orbitals know as hybrid orbitals.
– This phenomenon is known hybridization.
– Process of Intermixing of the atomic orbitals of equal or slightly different energies in the formation of
new set of orbitals of equivalent energies and shape is known as hybridization.

Salient features of hybridisation : The main features of hybridisation are as under :

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 is obtained. Therefore, the type of hybridisation
indicates the geometry of the molecules.

Important conditions for hybridisation :

(i) The orbitals present in the valence shell of the atom are hybridised.
(ii) The orbitals undergoing hybridisation should have almost equal energy.
(iii) Promotion of electron is not essential condition prior to hybridisation.
(iv) It is the orbital that undergo hybridization and not the electrons. For example, for orbitals of nitrogen
atom (2s2 2p1x 2p1y 2p1z ) belonging to valency shell when hybridize to form four hybrid orbitals , one

of which has two electrons (as before) and other three have one electron each. 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.

Determination of hybridisation of an atom in a molecule or ion:

Steric number rule (given by Gillespie) :

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Steric No. of an atom = number of atom bonded with that atom + number of lone pair(s) left on that
atom.
Note : This rule is not applicable to molecules/ions which have odd e – (ClO2, NO, NO2 ), free radicals
and compounds like B2H6 which involve 3 centre 2e– bond (banana bond).

For example : O=C=O S.No. = 2 + 0 = 2

S.No. = 2 + 1 = 3

S.No. = 3 + 0 = 3

S.No. = 3 + 1 = 4

Table-4
Steric number Types of Hybridisation Geometry Involving orbitals
2 sp Linear ns, npx / pz / py
3 sp2 Trigonal planar ns, npx , pz / py ,pz/px , py
3
4 sp Tetrahedral ns, npx , pz , py
3
5 sp d Trigonal bipyramidal ns, npx , pz , py dz2
3 2
6 sp d Octahedral ns, npx , pz , py dz2 dx2 − y 2

7 sp3 d3 Pentagonal bipyramidal ns, npx , pz , py dz2 dx2 − y 2 dxy

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.
 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 bigger positive
lobes and very small negative lobes, which provides more effective overlapping resulting in the
formation of stronger bonds.
Example of a molecule having sp hybridisation
BeCl2 : The ground state electronic configuration of Be is 1s 2 2s2. In the excited state one of the 2s-
electrons is promoted to vacant 2p orbital to account for its divalency. One 2s and one 2p-orbitals get
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.

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Figure : (A) Formation of sp hybrids from s and p orbitals ; (B) Formation of the linear BeCl 2 molecule.
Examples of sp hybridisation.
Species Important characteristic
H–C  N Linear, highly posionous, weak acid
H–C  C–H Linear,  bond planes are perpendicular
O=C=O Linear, both  bond are perpendicular to each other
H2C = C = CH2 Non planar both hydrogen are perpendicular to each other
N3– (azide ion) Iso electronic with CO2 and linear in shape. Both N–N bonds are similar

HgCl2
NO2+ (nitronium ion),
N2 O
Azide ion
sp2 hybridisation :
(i) Mixing of one s and two p orbitals to form 3 equivalent sp2 hybridized orbitals.
For example, in BCl3 molecule , the ground state electronic configuration of central boron atom is 1s 2
2s2 2p1. 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 sp 2 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 CI-B-Cl bond angle of 120°.

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Figure : Formation of sp2 hybrids and the BCl3 molecule

Steric No. = 3 Geometry = Trigonal planar Ideal bond angle = 120°

Table-5

Molecule Structure Statements

SO3 All three S–O bonds are equivalent. out of 3p bond

one p-p other to are p-d.

O3 V shaped molecule. Both O–O bond length are equal.

CO3– –

NO2– Bond order of N–O bond is 1.5, planar molecule.

sp3 hybridisation :
 mixing of one s and three p orbitals to form 4 equivalent sp3 hybridized orbitals.
 4 sp3 orbitals are directed towards four corner of tetrahedron.
 This type of hybridisation can be explained by taking the example of CH 4 molecule in which there is
mixing of one s-orbital and three p-orbitals of the valence shell to form four sp3 hybrid orbital 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° as shown in figure.

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Figure

Ammonia

Water

Steric No. = 4 Geometry = tetrahedral Ideal bond angle = 109° 28

Table-6

Some other Examples of sp3 hybridisation

Cl Cl Cl Cl

(a)  BeCl2 (s) , Be Be Be

Cl Cl Cl Cl

(b)  BF4– ;

(c)  Diamond, CCl4 , , all alkane ;

(d)  SiCl4, Silicates etc.

Structure of SiO2

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

SiO2 is a covalent network solid like diamond

(e)  NH2– (amide ion)

V-shape

 NH2–NH2 (hydrazine)

 NH2OH (hydroxylamine) lp-lp repulsion increases the N–O bond

length.

(f)  P4 (White phosphorus)

 P4O6

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

 P4O10

 Structures of cyclic silicates : [Si3O9]6–

= Silicon ; O = Oxygen

 H2 O 2 H2O2(g)

 SOCl2 (Thionyl chloride) Trigonal pyramidal

 XeO4

⚫ sp3 d hybridisation :
Steric number = 5 Geometry = trigonal bipyramidal
Table-7

Important points regarding sp3d -

(i) According to VSEPR theory lone pair will occupy equatorial positions but not axial.
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Mo.No. – 9950347993, 9166825993
Chemical Bonding

(ii) More electronegative atoms will prefer to occupy axial positions.

(iii) Since, double bonds occupy more space. Therefore, they will also prefer equatorial positions.

PCl5 (g)

PF5 (g)

PBr5 (g) PBr5 exist as (PBr4)+Br– in solid state.

PCl3 F2

PCl2 F3

SF4 SF4 molecule have See-saw shape/structure.

XeO2 F2 Both F atoms will be at equatorial position.

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Cl F3 shape/structure of ClF3 is T-shape

I3–

XeF2

sp3d2 hybridization :
Steric number = 6 Geometry = octahedral

Table-8

Important : Since, octahedral is a symmetrical figure hence

(a) positions of a lone pair can be any where
(b) but if there are two lone pairs (max.) then these must be in the trans position.

SF6

[XeO6]4–

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

XeOF4 Molecule has square pyramidal geometry.

XeF4 Molecule has square plannar geometry.

sp3 d3 Hybridization :
Steric number = 7 Geometry = Pentagonal bi-pyramidal
Table-9

Type AB7 AB6L AB5L2

Shape Pentagonal bi-pyramidal Distorted octahedral Pentagonal planar

Example IF7 XeF6 XeF5

F7 Bond angle = 72° & 90°

XeF6 (g)

or

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

 XeF6(s)

 [XeF5] –

 I2Cl6

Note : The liquid has an appreciable electrical conductance due to self ionization.
2Cl6 [Cl2]+ (bent) + [Cl4]– (square planar)
BOND LENGTH AND BOND ANGLE COMPARISION
Bond Length
(i) Size of atom (see along the group)  bond length
HF < HCl < HBr < HI
F – F < Cl – Cl < Br – Br <  – 
CH4 < SiH4 < GeH4 < SnH4

(ii) Multiplicity of bond (nearly same period element)

single bond > double bond > triple bond
C—C > C=C > CC
F—F > O=O > NN
(iii)
Electronegativity difference (See along the period)
H—C > H—N > H—O > H—F
HOW TO COMPARE BOND ANGLES
Bond angle depends on the following factor
I. Hybridisaition
II. No. of lone pair
III. Size or electronegativity of central atom
IV. Size or electronegativity of terminal atom
1. Hybridisaition :
sp > sp2 > sp3 > sp3d2
180° 120° 109°28’ 90°
2. Number of lone pair : If hybridisation of the central atom is same but number of lone pair is
different then more is the number of lone pair less is the bond angle.
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Chemical Bonding

e.g. CH4 NH3 H2 O

hybridisaition sp 3
sp 3
sp3
lone pair .P. = 0 .P. = 1 .P. = 2
B.A. 109°28’ 107° 104.5°
3. Size or electronegativity of central atom : When hybridisation is same and no. of lone pair is
same but central atom is different then see the electronegativity of central atom. More is the
electronegativity more is the bond angle.
e.g. NH3 PH3 AsH3 SbH3
hybridisaition sp 3
no no no
lone pair .P. = 1 .P. = 1 .P. = 1 .P. = 1
B.A. 107° 93° 92° 91°
4. Size or electronegativity of terminal atom :
Hybridisation same, lone pair same, central atom same but terminal atom is different then greater is the
size of the terminal atom greater will be the bond angle. Only in case of flourine the electronegativity
factor is considered, due to greater electronegativity of the flourine atom the bond angle for it comes out
to be smallest( due to smaller bond bond pair repulsions)
e.g. PF3 PCl3 PBr3 PI3
hybridisaition sp 3
sp3
sp 3
sp3
lone pair .P. = 1 .P. = 1 .P. = 1 .P. = 1
B.A. 98° 100° 101° 102°
Reasion : As the E.N. of x , b.p.–b.p. repulsion will less but l.p. compression will work as usual
Drago rule :
Element of 3rd period (p-Block) and lower than 3rd period does not allow hybridisation in
molecule when they form compound with less electronegative elements such as hydrogen
eg : PH3, SiH4, AsH3, H2S not have hybridisation
Bent rule :
According to Bent’s rule, more electronegative atoms prefer hybrid orbitals having less S character and
more electropositive atoms prefer hybrid orbitals having more S character.
eg : In CH2F2, F–C–F bond angle less than 109.5° indicating less than 25% S character.
H–C–H bond angle more than 109.5° indicating more than 25% S character.

Ex.3 Which is linear PH4+ , H3S+ or NO2+ ?

(A) Phosphonium ion (PH4+) (B) Sulphonium (H3S+)
(C) Nitronium ion (NO2 ) .
+
(D) None of these
Sol. Phosphonium ion (PH4 ) is tetrahedral, sulphonium (H3S+) is pyramidal, but nitronium ion (NO2+) is linear
+

; (sp hybridisation). Ans. (C)

Ex.4 The triodide ion (I3–) in which the I atoms are arranged in a straight line is stable, but the corresponding
F3– ion does not exist.
Sol. F3– and I3– are of same group. Iodine can expand its octet but F cannot and thus, in I3– octet rule is not
violated, but in F3– octet rule is violated.

Electron deficient bonding:

There are many compounds in which some electron deficient bonds are present apart from normal
covalent bonds or coordinate bonds which are 2c-2e bonds( two centre two electron bonds). These

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Chemical Bonding

electron deficient bonds have less number of electrons than the expected such as three centre-two
electron bonds(3c-2e) present in diborane B2H6, Al2(CH3)6, BeH2(s), bridging metal carbonyls.
B2H6 (diborane)  It is having (3centre – 2electron) bond / (banana bond) / (electron deficient bond)
–
3C – 2e bond

H x y H H
B2H6 2 B 1 B
Ht Hb H
–
3C – 2e bond

Cl Cl Cl
Al2Cl6 Al Al Only covalent bond, no electron deficient bond is present.
Cl Cl Cl
Back Bonding :
Back bonding generally takes place when out of two bonded atoms one of the atom has vacant orbitals
(generally this atom is from second or third period) and the other bonded atom is having some non-
bonded electron pair(generally this atom is from the second period). Back bonding increases the bond
strength and decreases the bond length. For example, in BF 3 the boron atom completes its octet by
accepting two 2p-electrons of fluorine into 2p empty orbital.

 Decrease in B – F bond length is due to delocalised p–p bonding between filled p-orbital of F atom
and vacant p-orbital of B atom.
The extent of back bonding is much larger if the orbitals involved in the back bonding are of same size,
for example the extent of back bonding in boron trihalides is as follows :
BF3 > BCl3 > BBr3
There is p-p back bonding in boron trihalide. The extent of back bonding decreases from BF 3 to BI3
because of increasing size of p-orbitals participating in back bonding that is from 2p(in F) to 4p(in Br).
 The extent of back bonding decreases if the atom having vacant orbitals is also having some non-
bonded electron pairs on it. So among the atoms of third period the extent of back bonding follows the
order :
Si > P > S > Cl
1
 The extent of p-p overlapping 
Lewis acid character

MOLECULAR ORBITAL THEORY (MOT) :

The molecular orbital theory was developed by F. Hund and R.S. Mulliken in 1932. The salient features are:
(i) Just as elctrons of any atom are present in various atomic orbitals, electrons of the molecule are
present in various molecular orbitals.
(ii) Molecular orbitals are formed by the combination of atomic orbitals of comparable energies and
proper symmetry.
(iii) An electron in an atomic orbital is influenced by one nucleus, while in a molecular orbital it is
influenced by two or more nuclei depending upon the number of the atoms in the molecule. Thus an
atomic orbital is monocentric while a molecular orbital is polycentric.

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Chemical Bonding

(iv) The number of molecular orbitals formed is equal to the number of combining atomic orbitals.
When two atomic orbitals combine, two molecular orbitals called bonding molecular orbital and anti-
bonding molecular orbital are formed.
(v) The bonding molecular orbital has lower energy and hence greater stability than the corresponding
antibonding molecular orbital.
(vi) Just as the electron probability distribution around a nuclues in an atom is given by an atomic
orbital , the electron probability distribution around a group of nuclei in a molecule is given by molecular
orbital.
(vii) The molecular orbitals like the atomic orbitals are filled in accordance with the Aufbau principle
obeying the Pauli Exclusion principle and the Hund’s Rule of Maximum Multiplicity. But the filling
order of these molecular orbitals is always experimentally decided, there is no rule like (n + l) rule in
case of atomic orbitals.
Formation of Molecular Orbitals : Linear Combination of Atomic Orbitals(LCAO)

Figure 1. The formation of molecular orbitals for H2.(a) A and B for individuals (b) A + B = m (c) Probability
function for the bonding orbital, (m)2. (d) A – B = *m. (e) Probability function for the antibonding
orbital, (m)2.

Figure 2. Another representation of the formation of molecular orbitals for H2. The  and *
orbitals
Conditions for the combination of atomic orbitals :
The linear combination of atomic orbitals to form molecular orbitals takes place only if the following
conditions are satisfied :

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1. The combining atomic orbitals must have the same or nearly the same energy. This means
that 1s orbital can combine with another 1s orbital but not with 2s orbital because the energy of 2s
orbital is appreciably higher than that of 1s orbital. It, therefore, means that only a limited number of
combinations of atomic orbitals are possible.

2. The combining atomic orbitals must have the same symmetry about the molecular axis. By
convention z-axis is taken as the molecular axis. It is important to note that atomic orbitals having
same or nearly the same energy will not combine if they do not have the same symmetry. For example,
2pz orbital of one atom can combine with 2pz orbital of the other atom but not with the 2px or 2py orbitals
because of their different symmetries.
3. The combining atomic orbitals must overlap to the maximum extent. Greater the extent of
overlap, the greater will be the electron-density between the nuclei of a molecular orbital.

TYPES OF MOLECULAR ORBITALS :

Molecular orbitals of diatomic molecules are designated as (sigma), (pie), (delta) etc.
In this nomenclature, the sigma () moleuclar orbitals are symmetrical around the bond-axis while
pi () molecular orbitals are not symmetrical. For example, the linear combination of 1s orbitals
centered on two nuclei produces two molecular orbitals which are symmetrical around the bond-axis.
Such molecular orbital’s are of the  type and are designated as  1s and *1s [Fig.(a)]. If internuclear
axis is taken to be in the direction, it can be seen that a linear combination of 2pz - orbitals of two atoms
also produces two sigma molecular orbitals designated as 2pz and * 2pz. [Fig. (b)] Molecular orbitals
obtained from 2px and 2py orbitals are not symmetrical around the bond axis because of the presence of
positive lobes plane. Such molecular orbitals, are labelled as  and * [Fig. (c)]. A  bonding MO has
large electron density above and below the inter nuclear axis. The * antibonding MO has a node
between the nuclei.
-type of molecular orbitals are obtained by involvement of d-orbitals into bonding.

Difference between  molecular orbitals and the  orbitals.

(1) For  overlap the lobes of the atomic orbitals are perpendicular to the line joining the nuclei, whilst
for  overlap the lobes point along the line joining the two nuclei.
(2) For  molecular orbitals,  is zero along the internuclear line and consequently the electron density
2 is also zero. This is in contrast to  orbitals.
(3) The symmetry of  molecular orbitals is different from that shown by  orbitals. If the bonding  MO
is rotated about the inter nuclear line a change in the sign of lobe occurs. The  bonding orbitals are
therefore ungerade, where as all  bonding MO’s are gerade. Conversely the antibonding  MO’s are
gerade while all  antibonding MO’s are ungerade.

ENERGY LEVEL DIAGRAM FOR MOLECULAR ORBITALS :

The energy levels of molecular orbitals have been determined experimentally from spectroscopic data
for homonuclear diatomic molecules of second row elements of the periodic table. The increasing order
of energies of various molecular orbitals for O2 and F2 is given below :
1s < *1s < 2s < *2s < 2pz < (2px = 2py) < (*2px = *2pz) < *2pz.

The increasing order of energies of various molecular orbitals for Be2, B2, C2, N2 etc., is :
 1s < * 1s < 2s < *2s < (2px = 2py) < 2pz < (*2px = *2py) < *2pz

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Chemical Bonding

The important characteristic feature of this order is that the energy of 2pz molecular orbital is higher
than that of 2px and 2py molecular orbitals.

Molecular Antibonding sigma

orbitals molecular orbital

Atomic Atomic – + – + – – + – +
orbital orbital
*2pz 2pz 2pz *1s
Energy

Bonding sigma
molecular orbital
2pz 2Pz
– + + + – – + –
→ →

2pz 2pz 2pz 2pz

(b)

Fig. Bonding and antibonding molecular orbitals formed through combinations of (a) 1s atomic orbitals;
(b) 2pz atomic orbitals and (c) 2px atomic orbitals.

Electronic configuration and molecular behaviour :

Bond order
Bond order (b.o.) is defined as one half the difference between the number of electrons present
in the bonding and the antibonding orbitals i.e., Bond order (b.o.) = ½ (Nb – Na)
A positive bond order (i.e., Nb > Na) means a stable molecule while a negative (i.e., Nb < Na) or zero
(i.e., Nb = Na) bond order means an unstable molecule.
Nature of the bond
Integral bond order values of 1, 2 or 3 correspond to single, double or triple bonds respectively.
Bond-length
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The bond order between two atoms in a molecule may be taken as an approximate measure of the
bond length. The bond length decreases as bond order increases.
Magnetic nature
If all the molecular orbitals in a molecule are doubly occupied, the substance is diamagnetic (repelled
by magnetic field) e.g., N2 molecule. However if one or more molecular orbitals are singly occupied it is
paramagnetic (attracted by magnetic field), e.g., O2 molecule.
Bonding in some Homonuclear diatomic molecules
1. Hydrogen molecule (H2) : H2 : (1s)2
Nb − Na 2 − 0
Bond order = = = 1 , it is diamagnetic.
2 2

 *1s

1s 1s
(Atomic orbital) (Atomic orbital)
H 1s H2 H
Molecular orbital
2. Helium molecule (He2) : He2 : (1s)2 (*1s)2
Bond order of He2 is ½(2 – 2) = 0, bond order of zero - in other words, no bond

 *1s

1s 1s

He21s
3. Lithium molecule (Li2) : (1s)2 (*1s)2 (2s)2
Its bond order, therefore, is 1/2(4 – 2) = 1. It means that Li2 molecule is stable and since it has
no unpaired electrons it should be diamagnetic.
4. Beryllium (Be2) : (1s)2 (*1s)2 (2s)2 (*2s)2
Be2 has the same number of antibonding and bonding electrons and consequently a bond order
of zero. Hence, like He2, Be2 is not a stable chemical species.

5. Boron (B2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p1x = 2p1y) (pz)0 The bond order of B2 is 1/2(6
– 4) = 1. B2 is paramagnetic. B2 is found only in the gas phase; solid boron is found in several
very hard forms with complex bonding, primarily involving B12 icosahedra.
B2 is also a good example of the energy level shift caused by the mixing of s and p orbitals.

6. Carbon molecule (C2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y) or KK (2s)2 (*2s)2
(2p2x = 2p2y )
The bond order of C2 is 1/2 (8–4) = 2 and C2 should be diamagnetic.

7. Nitrogen molecule (N2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y ) (2pz)2

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Chemical Bonding

*2pz

*2px = *2py
2p 2p
2pz

2px = 2py

s

2s 2s
N(AO) N(AO)

2s
N2(MO)
M.O. Energy level diagram for N2 molecule

N2 has a triple bond according to both the Lewis and the molecular orbital models.
The bond order of N2 is 1/2(10 – 4) = 3. It contains one sigma and two  bonds.

8. Oxygen molecule (O2) : O2 : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2p1y)

*2pz

2px 2py

2p x =  2py

2pz

2s

O(AO) O(AO)

2s
O2(MO)
M.O. Energy level diagram for O2molecule
1 1
O2 is paramagnetic. The bond order of O2 is Nb − Na  = [10 − 6] = 2 . So in oxygen molecule, atoms
2 2
are held by a double bond. Moreover, it may be noted that it contains two unpaired electrons in *2px
and *2py molecular orbitals, therefore, O2 molecule should be paramagnetic, a prediction that
corresponds to experimental observation. Several ionic forms of diatomic oxygen are known,
including O2+, and O22–. The internuclear O – O distance can be conveniently correlated with the bond
order predicated by the molecular orbital model, as shown in the following table.

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Chemical Bonding

9. Fluorine molecule (F2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px2 = *2p2y)

The molecular orbital picture of F2 shows a diamagnetic molecule having a single fluorine-fluorine bond,
in agreement with experimental data on this very reactive molecule.

10. Neon molecule (Ne2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px2 = *2p2y) (*2pz)2
All the molecular orbitals are filled, there are equal numbers of bonding and antibonding electrons and
the bond order is therefore zero. The Ne2 molecule is a transient species, if it exists at all.
Note : HOMO : Highest Occupied Molecular Orbital.
LUMO : Lowest Unoccupied Molecular Orbital

Ex.5 Though O2 molecule is paramagnetic yet it is a colourless gas. Why ?

Sol. It is because the energy gap between HOMO and LUMO levels in O 2 molecule is so large that
radiations of visible light cannot excite a e– from HOMO to LUMO. In fact O2 gas shows absorption in
UV zone. So it is colourless.

Ex.6 Correct order of bond energy is:

(A) N2 > N2+ >N2– >N22– (B) N2+ >N2– >N22– >N2 (C) N2 >N2¯ = N2+ >N22– (D) N2– >N2 = N2+ >N22–
Sol. (A) Bond order is directly proportional to the bond energy.
Bond order of N2 = 3 , N2+ , N2– = 2.5 N22– = 2
But N2– has more electrons in antibonding MO’s and thus N 2+ is more stable than N2–. So correct order
of bond energy will be N2 > N2+ >N2– >N22–

Ex.7 Which of the following species have a bond order of 3 ?

(A) CO (B) CN– (C) NO+ (D) O2+
Sol. (A,B,C) Species CO, CN–, NO+ are isoelectronic with 14 electrons to N2 which has bond order of 3 (i.e.
10 − 4
= 3), so their bond order will be equal to three.
3
Ex.8 Which of the following are diamagnetic ?
(A) C2 (B) O22– (C) Li2 (D) N2+
Sol. (A,B,C) Species C2, O22–, Li2 have all the electrons paired but N2+ has one unpaired electron in bonding
molecular orbital so it is paramagnetic.

COVALENT CHARACTER IN IONIC COMPOUNDS (FAJAN’S RULE) :

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When anion and cation approach each other, the valence shell of anion is pulled towards cation
nucleus and thus shape of anion is deformed. This phenomenon of deformation of anion by a cation is
known as polarisation and the ability of cation to polarize a near by anion is called as polarizing power
of cation.

Fajan’s pointed out that greater is the polarization of anion in a molecule, more is covalent character in
it.
More distortion of anion, more will be polarisation then covalent character increases.
Fajan’s gives some rules which govern the covalent character in the ionic compounds, which are as
follows:

(i) Size of cation : Size of cation  1/polarisation.

e.g. BeCl2 MgCl2 CaCl2 SrCl2 BaCl2

Size of cation increases Polarisation decreases Covalent character decreases

(ii) Size of anion : Size of anion  polarisation
e.g., LiF LiCl LiBr Lil

(iii) Charge on cation : Charge on cation  polarisation.

e.g., NaCl MgCl2 AlCl3
Na +
Mg2+ Al3+

(iv) Charge on anion : Charge on anion  polarisation.

e.g., AlF3 Al2O3 AlN
F– , O2– , N3–

(v) Pseudo inert gas configuration of cation : Cation having pseudo inert gas
configuration has more polarizing power than the cation that has inert gas configuration. Thus
NaCl having inert gas configuration will be more ionic whereas CuCl having pseudo inert gas
configuration will be more covalent in nature.
Cu+ = [Ne] 3s2 p6 d10 Na+ = 1s2 2s2 p6
–
18e 8e–
Pseudo inert gas configuration Inert gas configuration
(poor shielding of d-electrons) (more shielding of s and p electrons)

Application & Exceptions of Fajan’s Rules :

(i) Ag2S is less soluble than Ag2O in H2O because Ag2 S is more covalent due to bigger S2– ion.

(ii) Fe(OH)3 is less soluble than Fe(OH)2 in water because Fe3+ is smaller than Fe2+ and thus
charge is more. Therefore, Fe(OH)3 is more covalent than Fe(OH)2 .

(iii) The colour of some compounds can be explained on the basis of polarisation of their bigger
negative ions.
For example :

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AgCl is white AgBr, Ag, Ag2CO3 are yellow. Similarly, SnCl2 is white but Sn2 is black. PbCl2 is white but
Pb2 is yellow.
The bigger anions are more polarised and hence their electrons get excited by partial absorption of
visible light.
(iv) Variation of melting point [melting point of covalent compound < melting point of ionic
compound]
BeCl2 , MgCl2 , CaCl2, SrCl2, BaCl2
––––––––––––––>–––––––––––––––––––––>–
Ionic charater increases, melting point increases ; since size of cation increases & size of anions is
constant.
CaF2, CaCl2, CaBr2, Ca2
–––––––––––––––>–––––––––––––––––––––>–
Covalent character increase, melting point decrease ; since size of cations constant & size of anions is
increases.
Ex. AgCl is colourless whereas AgI is yellow, because of :
(A) Ag+ have 18 electron shell to screen the nuclear charge.
(B) Ag+ shows pseudo inert gas configuration.
(C) distortion of I– is more pronounced than Cl– ion.
(D) existence of d – d transition.
Sol. (C) the bigger anions are more polarised and hence their electrons get excited by partial absorption of
visible light.

POLARITY OF BONDS :
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 a covalent bond is formed between two similar atoms, for example in H 2, O2, Cl2, N2 or F2 the
shared pair of electrons is equally attracted by the 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.
As a result of polarisation, the molecule possesses the dipole moment which can be defined as the
product of magnitude of the partial charge (+ or –) developed on any of the covalently bonded atoms
and the distance between two atoms.
Dipole moment (µ) = Magnitude of charge (q) × distance of separation (d)
Dipole moment is usually expressed in Debye units (D). The conversion factors are
 1 D = 3.33564 × 10–30 Cm, where C is coulomb and m is meter.
 1 Debye = 1 × 10–18 e.s.u. cm.
Further dipole moment is a vector quantity and is depicted by a small arrow with tail on the positive
centre and head pointing towards the negative centre. For example the dipole moment of HF may be
represented as

The shift in electron density is represented by crossed arrow ( ) above the Lewis structure to
indicate the direction of the shift.
In case of polyatomic molecules the dipole moment not only depend upon the individual dipole
moments of bonds known as bond dipoles but also on the spatial arrangement of various bonds in the
molecule. In such case, the dipole moment of a molecule is the vector sum of the dipole moments of

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various bonds. i.e. a molecule will have a dipole moment if the summation of all of the individual
moment vector is non-zero.

R = P2 + Q2 + 2PQ cos  , where R is resultant dipole moment.

For example of H2O molecule, which has a bent structure, the two O—H bonds are oriented at an angle
of 104.5º. Net dipole moment of 6.17 × 10–30 Cm (1D = 3.33564 × 10–30 Cm) is the resultant of the dipole
moments of two O—H bonds.

Net Dipole moment,  = 1.85 D = 1.85 × 3.33564 × 10–30 Cm = 6.17 × 10–30 Cm.
(A) Diatomic molecules :
(i) Dipole moment is a vector quantity i.e., it has magnitude as well as direction. It is often represented
by an arrow with its tail at the positive centre and head pointing towards the negative end
(+ → –)
(ii) As a polar diatomic molecule posses only one polar bond, the dipole moment of that molecule is
equal to the dipole moment of the polar bond e.g. in case of HCl, the molecular dipole moment is equal
to the dipole moment of H–Cl bond i.e. 1.03 D. Thus.
+ –
H Cl  = 1.03 D
(B) Polyatomic molecules :
(i) As a polyatomic molecule has more than one polar bond, the dipole moment is equal to the resultant
dipole moment of all the individual bonds.
(ii) For example dipole moment of H 2O is 1.84 D which is equal to the resultant dipole moment of two
O–H bonds.
−
O

+ H H +
 = 1.84D
(iii) Think about CO2 molecule though C = O bond is polar due to electronegativity difference but the
resultant dipole moment of molecule is zero as the individual dipole moments are of equal moment and
opposite sign. This shows that CO2 is a linear molecule.

O C O
(iv) Again in case of symmetrical molecules such as BF 3, CH4 and CCl4 the molecular dipole moment
is found to be zero. This is due to the fact that individual dipole moments cancels out on account of
symmetry of the molecule.
+ −
H Cl
−
F − +
− C C
F B
+
− H + H Cl − Cl
−
H +
F
Cl −

 Following compounds have zero dipole moment :

BF3 ,CO2 , SO3 , CF4 , PF5 (g) , SF6 , XeF2 , CS2 , CCl4 , PCl5 (g) , XeF4

 Some important orders

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HF > HCl > HBr > H

1.92 D 1.08 0.78 0.38
CH3Cl > CH2Cl2 > CHCl3 > CCl4

1.86 1.6 1.0 0

 Usually for disubstituted Benzene order is o > m > p
But it all depends on the substituents

Note : For geometrical isomers usually the dipole moment of cis is more than trans but again there
can be exceptions.

For example :
cis - form (low dipole moment) trans - form (high dipole moment)
 The presence of a centre of symmetry, i, requires that the dipole moment be zero, since any
charge on one side of the molecule is canceled by an equal charge on the other side of the
molecule.
Thus [CoF6]3– , trans – N2F2 and the staggered conformer of ferrocene do not have dipole
moments.

Some important points about dipole moment :

 A polyatomic molecule having polar covalent bonds but zero dipole moment indicates the symmetrical
structure of the molecule. e.g. B–F bonds are polar in BF3 but BF3 has  = 0 due to its symmetrical
geometry.
 If molecule have  = 0, then it should be linear or having symmetrical geometry.
e.g. linear – CO2, CS2, BeCl2 (g) ; symmetrical geometry – BF3 , CH4 , PCl5 , SF6 , IF7 , XeF4.
 If molecule has   0 then it should be angular or having unsymmetrical geometry.
SnCl2 , PbCl2 , SO2 , angular molecular geometry.
NH3, H2O, NF3, SF4, H2S, unsymmetrical molecular geometry.
µExperimental (Observed)
 % Ionic character =  100 =  100
µTheoretical (100% Ionic compound)

Ex.9 What should be the percentage ionic character in CsF when electronegativity difference is 3.3
(1) 90.9% (2) 0.09% (3) 93.3% (4) 95.7%
Ans. (1)

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Ex.10 What is the increasing order of ionic character in H2Se, H2S, H2O
(1) H2Se < H2S < H2O (2) H2Se > H2S > H2O (3) H2Se < H2S > H2O (4) None of these
Ans. (1)
Ex.11 Which of the following molecules should not have  = 0 :–
(1) H2 (2) CO2 (3) Cl2 (4) SO2
Ans. (4)

Ex.12 Which of the following compounds should have higher dipole moment than the remaining three :–
(1) HF (2) H2O (3) NH3 (4) NF3
Ans. (2)

HYDROGEN BOND :
Nitrogen, oxygen and fluorine are the highly electronegative elements. When they are tied to a
hydrogen atom to form covalent bond , the electrons of the covalent bond are shifted towards the more
electronegative atom. This partially positively charged hydrogen atom forms a bond with the other more
electronegative atom. This bond is called as hydrogen bond and is weaker than covalent bond. For
example, in HF molecule, the hydrogen bond exists between hydrogen atom of one molecule and
fluorine atom of another molecule as given below : – – – H+ – F – – – – H+ – F– – – – H+ – F –
Here, hydrogen bond acts as a bridge between atoms which holds one atom by covalent bond and the
other by hydrogen bond. Hydrogen bond is represented by a dotted line (– – –) while a solid line
represents the covalent bond. Thus, hydrogen bond can be defined as the attractive force which binds
hydrogen atom of one molecule with the electronegative atom (F, O or N) of another molecule.

 Hydrogen bonding is said to be formed when slightly acidic hydrogen attached to a strongly
electronegative atom such as F, N and O is held with weak electrostatic forces by the lone pair of
electrons of the electronegative atom i.e. the strongly positive H and the strongly electronegative lone
pairs tend to line up and hold the molecules together. Other atoms with high electronegativity, such as
Cl ; can also form hydrogen bonds in strongly polar molecules such as chloroform, CHCl 3.

Conditions required for H-bond :

(i) Molecule should have more electronegative atom (F, O, N) linked to H-atom.
(ii) Size of electronegative atom should be smaller.
(iii) A lone pair should be present on electronegative atom.
Strength of H-bond :
The strength of H-bond is usually very low (5 - 10 kJ/mol) but in some cases this value may be as high
as 50 kJ/mol. The strongest H-bonds are formed by F atoms. Deuterium is more electropositive than H,
therefore it also form stronger bonds. The strength of the H-bond can be compared by the relative bond
energies and the geometry of the various compounds as given below.
F– + HF—→ [FHF]– ; H = – 161 ± 8 kJ mol–1
(CH3)2 CO + HF —→ (CH3)2 CO ...... HF ; H = – 46 kJ mol–1
H2O + HOH —→H2O ...... HOH (ice) ; H = – 25 kJ mol–1
HCN + HCN —→ HCN ...... HCN ; H = – 12 kJ mol–1
The magnitude of H-bonding depends on the physical state of the compounds. H-bonding is maximum
in the solid state and minimum in the gaseous state. Thus hydrogen bonds have strong influence on the
structure and properties of the compounds.
 Order of H-bond strength

> O H - - - - - - :O > N H - - - - - - :N > N H - - - - - - :O

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Types of Hydrogen Bonds :

(A) Intramolecular H-Bonding :
This type of H-bonding occurs when polar H and electronegative atom are present in the same
molecule i.e., it is formed when hydrogen atom is present in between the two highly electronegative (F,
O, N) atoms within the same molecule.

(a)

It has lower boiling point (i.e. more volatile) than its para-derivative (where association of molecules
takes place using intermolecular H-bonding) because it exists as discrete molecules.

(b)

It has lower boiling point (i.e. more volatile) than its para-derivative (where association of molecules
takes place using intermolecular H-bonding) because it exists as discrete molecules.

(c) Nickel dimethyl glyoximate (a chelate)

Extra stability of the complex is because of intramolecular hydrogen bonding in addition to the chelating
effect.

(d) Chloral hydrate

Chloral hydrate is stable only on account of intramolecular hydrogen bonding.

(e) Persulphate ion (HSO5–)

K1 of peroxomono sulphuric acid (i.e., caros acid) is greater than K 2. After the loss of one hydrogen, the
persulphate ion gets stabilised due to intramolecular hydrogen bonding and thus the removal of second
hydrogen becomes difficult.

(f)  Aceto acetic ester (enolic form)

The intramolecular hydrogen bonding attributes the stability of enolic form of aceto acetic ester.

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Necessary conditions for the formation of intramolecular hydrogen-bonding :

(a) the ring formed as a result of hydrogen bonding should be planar.
(b) a 5- or 6- membered ring should be formed.
(c) interacting atoms should be placed in such a way that there is minimum strain during the ring
closure.
(B) Intermolecular H-Bonding :
Exists between the negative and positive ends of different molecules of the same or different
substances i.e., it is formed between two different molecules of the same or different
compounds.
(a) In water molecules
Due to polar nature of H2O there is association of water molecules giving a liquid state of
abnormally high boiling point.

 When ice is formed from liquid water, some air gap is formed (in tetrahedral packing of water
molecules). The tetrahedral structure around each oxygen atom with two regular bonds to
hydrogen and two hydrogen bonds to other molecules requires a very open structure with large
spaces between ice molecules. Due to this volume of ice is greater than liquid water and thus
ice is lighter than water. We can say that density decreases when ice is formed. Reversely
when ice melts, density increases but only upto 4 oC, after this intermolecular H-bonding
between water molecules breaks hence, volume increases and hence density decreases. Thus,
water has maximum density at 4oC.
(b) The hydrogen bonds in HF link the F atom of one molecule with the H-atom of another
molecule, thus forming a zig-zag chain (HF)n in both the solid and also in the liquid.

Some hydrogen bonding also occurs in the gas, which consists of a mixture of cyclic (HF) 6
polymers, dimeric (HF)2, and monomeric HF.
Very strong hydrogen bonding occurs in the alkali metal hydrogen fluorides of formula M[HF 2];
in KHF2, for example, an X-ray diffraction study together with a neutrons diffraction study shows
that there is a liner symmetrical anion having an over all, F–H–F distance of 2.26 Å, which may
be compared with the H–F bond length of 0.92Å in hydrogen fluoride monomer.
(c) There is also similar H-bonding in alcohol (R—OH) ammonia (NH3) and phenol (C6H5OH)
molecules.

(d) Carboxylic acid dimerises in gaseous state due to H-bonding

(e) Alcohol is said to be highly soluble in water due to crossed intermolecular H-bonding (between
H2O and R—OH molecules).

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However isomeric ether is less soluble in water due to less polar nature of ether.

(f) HCO3– ions exist as dimer in KHCO3

O H O
O=C C=O
O¯ H O
In Na+HCO3–, the HCO3– ions are linked in to an infinite chain through intermolecular H-bonding.

Ex.13 C2H2 is not soluble in H2O but it is highly soluble in acetone.

Sol.

In hybridisation as %S character increase electronegativity increase hence C2H2 forms H–bonds with
O–atom of acetone and get dissolved. But H2O molecules are so much associated that it is not possible
for C2H2 molecules to break that association, hence C 2 H2 is not soluble in H2O.

Ex.14 Why SnCl2.2H2O readily loses one molecule of water at 80ºC ?

Sol. One water molecule is coordinated to lone pair of electrons on SnCl 2 and the other is hydrogen bonded
to coordinated water molecules .

Ex.15 Why crystalline sodium peroxide is highly hygroscopic in nature.

Sol. Na2O2 forms stable hydrates on account of H-bonding.
− − − O22− − − − (H2O)8 − − − O22− − − − (H2O)8 − − −

Ex.16 Explain that tetramethyl ammonium hydroxide is a stronger base than that of trimethyl ammonium
hydroxide.
+
CH3  CH3 
|  |  –
Sol. CH3 − N → H    O − H CH3 − N → CH3  O H
|  | 
 
CH3  CH3 
In the trimethyl compound the O–H group is hydrogen bonded to Me3NH group and this makes it more
difficult for the OH group to ionize and hence it is a weak base.
In the tetramethyl compound, hydrogen bonding can not occur, so the OH – group ionizes easily and
thus it is a much stronger base.

Intermolecular forces (Van der Waal’s Forces) :

Intermolecular attractions hold two or more molecules together. These are weakest chemical forces and
can be of following types.
(a) Dipole-dipole attraction :
(b) Ion-induced dipole attraction :
(c) Dipole-induced dipole attraction :
(d) Instantaneous dipole- Instantaneous induced dipole attraction : (Dispersion force or London forces)
strength of van der Waal’s forces a > b > c > d
(a) Dipole-dipole attraction :
This is electrostatic attractions between the oppositively charged ends of permanent dipoles.
Exists between polar molecules and due to this force gas can be liquified.
  
+ – +
–
H Cl H Cl

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(b) Ion-induced dipole attraction :

Exists between ion and non-polar molecules (e.g., an atom of a noble gas such as Xenon).
(c) Dipole-induced dipole attraction :
Exists between polar and non-polar molecules.

Head to tail arrangement of dipoles Antiparallel arrangement of dipoles

+ –  +  –
H Cl Cl Cl
(polar) (non-polar)
(d) Instantaneous dipole- Instantaneous induced dipole attraction :
Exists among the non-polar molecules like H2, O2, Cl2 etc. in solid or liquid states. Even in
atoms in molecules which have no permanent dipole, instantaneous dipoles will arise as a
result of momentary inbalances in electron distribution.
London forces are extremely short range in action and the weakest of all attractive forces. The
London forces increase rapidly with molecular weight, or more properly, with the molecular
volume and the number of polarizable electrons.

   

– + – +

e.g., Cl Cl Cl Cl
Special Point : attractive forces between an ion and a dipole are known as ion-dipole forces and these
are not vander waal forces.
• Ion- dipole forces are stronger then all vander waal forces because the charge of any ion is
much greater than the charge of a dipole.
• Ion dipole bonding is also stronger then hydrogen bonding.
Ion-dipole attraction :
Exists between an ion and a polar molecule. Its strength depends on (i) size of ion (ii) charge
on the ion (iii) dipole moment of the polar molecule. It is thought to be directional. Ion -dipole
forces are important in solutions of ionic compounds in polar solvents where solvated species
such as Na(OH2)x+ and F(H2O)y– (for solution of NaF in H2O) are found. Hence this force is
responsible for hydration.
+
+ 
H
–

Na O +
H
Note : Fluoro carbon have usually low boiling points because tightly held electrons in the
fluorine atoms have a small polarizability.
 Strength of vander waal force  molecular mass.

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 van der Waal’s force  boiling point.

Intermolecular forces
There are certain forces that condense matter. These forces can be both bonding forces and non-
bonding forces which are called intramolecular forces and intermolecular forces respectively.
(i) Intramolecular forces : (Bonds that exist within molecules) :
Example : Ionic bond, Covalent bond
(ii) Intermolecular forces (forces that exist between molecules) : Intermolecular forces are the
physical forces or just the interactions which act between the neighbouring bonded molecules. The
intermolecular forces are weaker than the intramolecular forces.
van der Waals (1837 – 1923), a Dutch scientist explained that the attractive forces present between the
molecules lead to the deviation of real gases from the ideal gas behaviour which we will study later in
this chapter. So, to honor the scientist, intermolecular forces are also known as vander Waals forces.
These forces of attraction exist between polar as well as non-polar molecules. These are the
electrostatic forces of attraction that exist between an area of negative charge on one molecule and an
area of positive charge on a second molecule. There are three types of van der Waals forces or
interactions.
(i) Dispersion forces or london forces
(ii) Dipole-Dipole forces
(iii) Dipole-Induced Dipole forces
Fourth type is a particularly strong type of dipole-dipole interactions called hydrogen bonding.
(i) Dispersion forces or london forces : (Associated with NON POLAR structures) These forces are
present in non-polar molecules like H2, O2 and N2 and also in nonpolar monoatomic molecules such as
noble gases like He, Ne, Ar etc., which exist with intermolecular forces and no bonding at all.
London forces are attractive in nature and the interaction energy is inversely proportional to the sixth
power of the distance between the two interacting particles.
1
Interaction energy  6 where r is the intermuclear distance between two interacting particles.
r
Larger the polariesability, stronger are the london forces.
(ii) Dipole-Dipole Forces : (Associated with POLAR structures) : Polar molecules have a partially
positive side and a partially negative side or a dipole. dipole-dipole forces operate between the
molecules which are through neutral but possess permanent dipole. The separation of partial charges
depends upon the electronegativity of the bonded atoms in a molecule. The partial charges are
indicated by the Greek letter delta () In these type of forces the partial positive end of the one
molecules is attracted towards the negative end of the other molecule.
Example : Dipole-dipole forces are present between the two HCl molecules. Chlorine being more
electronegative pulls the shared pair of electrons towards itself. So, it has a partial negative charge (–)
on it and hydrogen atom has a partial positive charge (+).
Polar Polar
Molecule Molecule
+ – + –

H—Cl H—Cl

Dipole-dipole
force (interactions)

The interaction energy is dependent upon the distance between the polar molecules.
(a) Stationary polar molecules : Dipole-dipole interaction energy is inversely proportional to the third
power of the distance between stationary polar molecules (in solids)
1
Interaction energy  3
r

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(b) Rotating polar molecules : Dipole-dipole interaction energy is inversely proportional to the sixth
power of the distance between the rotating polar molecules (like water)
1
Interaction energy  6
r
Dipole-dipole forces are stronger than the london forces because permanent dipoles are involved but
weaker than the ion-ion interaction because partial charges present in the polar molecules are always
less than the unit electronic charge (1.6×10–19) present on the ions.
(iii) Dipole-Induced Dipole Forces : (Between a polar and a non-polar molecule) This type of forces
operate between a polar molecule which has a permanent dipole and a non-polar molecule whose
electron density is symmetrical. A polar molecule may sometimes polarise a non-polar molecule.

Ex.17 Give the order of boiling point of following

Cl2 , HCl

Sol. Cl2 – Cl2 < HCl – HCl (boiling point)

dispersion force dipole-dipole attraction
As dipole-dipole attraction is stronger than dispersion force.

Ex.18 Arrange the inert gases, according to their increasing order of boiling points
Sol. He < Ne < Ar < Kr < Xe (boiling point)
Because strength of van der Waal’s force increases down the group with increase in molecular mass.

METALLIC BOND :
Most metals crystallise in close-packed structures. The ability of metals to conduct electricity and heat
must result from strong electrons interactions among 8 to 12 nearest neighbours (which is also called
coordination number). Bonding in metals is called metallic bonding. It results from the electrical
attractions among positively charged metal ions and mobile, delocalised electrons belonging to the
crystal as a whole.
Two models are considered to explain metallic bonding:
(A) Band model (B) Electron-sea model

(A) Band Model

The interaction of two atomic orbitals, say the 3s-orbitals of two sodium atoms, produces two molecular
orbitals, one bonding orbital and one antibonding orbital. If N atomic orbitals interact, N molecular
orbitals are formed. Atoms interact more strongly with nearby atoms than with those farther away . The
energy that separates bonding and antibonding molecular orbitals decreases as the interaction
(overlap) between the atomic orbitals decreases. When we consider all the possible interactions among
one mole of Na atoms, there is formation of series of very closely spaced molecular orbitals (3s and
3*s). This consists of a nearly continuous band of orbitals belonging to the crystal as a whole. One
mole of Na atoms contributes one mole (6.02 × 1023) of valence electrons thus, 6.02 × 1023 orbitals in
the band are half-filled.

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Fig. The band of orbitals resulting from interaction of the 3s - orbitals in a crystal of sodium
The empty 3 p atomic orbitals of Na atoms also interact to form a wide band of 3 × 6.07 × 10 23 orbitals.
The 3s and 3p atomic orbitals are quite close in energy , so that these bands of molecular orbitals
overlap. The two overlapping bands contain 4 × 6.02 ×1023 orbitals. Because each orbital can hold two
electrons, the resulting combination of bands is only one-eighth full.

Fig. Overlapping of a half–filled “3s” band with an empty “3p” band of NaN crystal

According to band theory, the highest-energy electrons of metallic crystals occupy either a partially filled
band or a filled band that overlaps an empty band. A band within which (or into which ) electrons must
move to allow electrical conduction is called a conduction band. The electrical conductivity of a metal
decreases as temperature increases. The increase in temperature causes thermal agitation of the metal
ions. This impedes the flow of electrons when an electric field is applied.
Crystalline non-metals, such as diamond and phosphorus, are insulators, they do not conduct
electricity. It is due to the fact that their highest-energy electrons occupy filled bands of molecular
orbitals that are separated from the lowest empty bond (conduction band) by an energy difference
called the band gap. In an insulator, this band gap is an energy difference that is too large for electrons
to jump to get to the conduction band.

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Fig. Distinction among metals, insulators and semiconductors. In each case an unshaded area
represents a conduction band.
Elements that are semiconductors have filled bands that are only slightly below, but do not overlap with
empty bands. They do not conduct electricity at low temperatures, but a small increase in temperature
is sufficient to excite some of the highest-energy electrons into the empty conduction band.
(B) Electron-Sea Model
Metals have ability to conduct electricity, ability to conduct heat, ease of deformation [that is, the ability
to be flattened into sheets (malleability) and to be drawn into wires (ductility)] and lustrous appearance.
One over simplified model that can account for some of these properties is the electron-sea model. The
metal is pictured as a network of positive ions immersed in a “sea of electrons” . In lithium the ions
would be Li+ and one electron per atom would be contributed to the sea. These free electrons account
for the characteristic metallic properties. If the ends of a bar of metal are connected to a source of
electric current, electrons from the external source enter the bar at one end. Free electrons pass
through the metal and leave the other end at the same rate.
In thermal conductivity no electrons leave or enter the metal but those in the region being heated gain
kinetic energy and transfer this to other electrons.
According to the electron-sea model, the case of deformation of metals can be thought of in this way :
If one layer of metal ions is forced across another, perhaps by hammering, the internal structure
remains unchanged as the sea of electrons rapidly adjusts to the new situation.

Fig. Effect of Distortion (by hammering) on Metal Sheet (assuming Electron Sea Model)
MISCELLANEOUS SOLVED PROBLEMS (MSPS)
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1. Classify the following bonds as ionic, polar covalent or covalent and give your reasons :
(a) SiSi bond in Cl3SiSiCl3 (b) SiCl bond in Cl3SiSiCl3
(c) CaF bond in CaF2 (d) NH bond in NH3
Sol. (a) Covalent, due to identical electronegativity.
(b) Covalent, due to less electronegativity difference.
(c) Ionic, due to more electronegativity difference.
(d) Covalent, due to nearly similar electronegativity.

2. (a) Which one has highest and lowest melting point and why?
NaCl KCl RbCl CsCl
(b) Why melting points of cesium halide (CsX) decrease in the order given below ?
CsF > CsCl > CsBr > CsI.
Sol. (a) NaCl will have highest lattice energy on account of the smaller Na + while CsCl has lowest lattice
energy on account of the larger Cs+. Hence NaCl has highest melting point and CsCl has lowest melting
point .
(b) As size of anions increase their polarisability increases thus their covalent character increases and
melting point decrease.

3. Which of the compounds MgCO3 and ZnCO3 is thermally more stable ? Explain.
Sol. Mg+2 has less polarising power due to inert gas configuration while Zn +2 has higher polarising power due
to pseudo inert gas configuration. A cation i.e. Zn 2+ with a greater, polarising power exercise a strong
pull on the electron cloud of the neighbouring O-atom of the CO32– ion and as such the metal carbonate
(ZnCO3) gets readily decomposed into CO2 and the oxide of the metal, ZnO. Thus ZnCO 3 is less stable
than MgCO3.

4. Why is anhydrous HCl predominantly covalent in the gaseous state but is ionic in aqueous solution?
Sol. It exists as HCl (bond formed by equal sharing of electrons) but in aqueous solution ionises as H + (or
H3O+) and Cl– due to polarity of HCl.

5. Which type of hybridisation is found in H3O+ ?

Sol. According to steric no. rule
Steric number = Number of bond pair(s) + number of lone pair(s) at central atom

So, steric number = 3 + 1 = 4.

Thus the hybridisation of oxygen in H3O+ is sp3.

6. Which of the following will be strongest Lewis base ?

(A) CH3 CN (B) CH3 NH2 (C) N2 (D) None of these
Sol. (B) In CH3 NH2, hybridisation of N is sp while in CH3 CN hybridisation of N is sp. N2 is also sp
3

hybridised.
We know that in hybridisation, as s-character increases the electronegativity of atom also increases.
Due to this tendency the release of lone pair of electrons becomes some what difficult. In methyl amine
the nitrogen is in sp3 hybridisation and therefore the donation of the lone pair of electron will be quite
easier; so it is strongest Lewis base.

7. Which is incorrect statement ?

(A) In CF2 = C = CF2 molecule all the four fluorine atoms are not in the same plane.

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(B) Ka2 of fumaric acid is more than Ka2 of maleic acid due to intra molecular hydrogen bonding in
maleic acid.
(C) The O – O bond length in O2[AsF4] is longer than KO2.
(D) The bond angle order in halogen – S – halogen is OSF2 < OSCl2 < OSBr2
Ans. (C)

Sol. (A)

As both carbon atoms are in different planes, all the four fluorine atoms are not in the same plane.
(B) maleic acid fumaric acid
O
O
H C
– C H
C O –
C
O
H
C C O H
O
H
C H C
O O
Due to intramolecular hydrogen bonding the maleate ion gets stabilized and thus removal of second
hydrogen becomes quite difficult.
(C) O2[AsF4] = O2+ B.O = 2.5
KO2 = O2– B.O = 1.5
1
Bond order  ; so O2+ has smaller bond length than O2–
bond length
(D) Greater the size of the halogen atoms greater will be the steric repulsions and thus larger will
be the bond angles.

8. Why BeF2 has zero dipole moment whereas H2O has some dipole moment ?
Sol. BeF2 has linear molecule and H2O has bent molecule.

=0

0

9. Why crystals of hydrated calcium sulphate are soft and easily cleaved where as anhydrous calcium
sulphate are very hard and very difficult to cleave ?
Sol. With in the Ca2+ / SO42– layer the ions are held together by strong electrovalent bonds but these
separated Ca2+ / SO42– layers are linked by relative weak H–bond. The weak H-bonds link SO42– ion in
the intermediate region.

10. Super oxides are coloured and paramagnetic why ?

Sol. Super oxides contain one unpaired electron in anti bonding molecular orbital and are coloured due to
transition of HOMO orbital electron within visible region.

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11. Of the species O2+ ,O2− , O2 and O22− which would have the maximum bond strength ?
Sol. O2+ has higher bond order i.e. 2.5 than O 2(2) and O2– (1.5) and bond strength is directly proportional to
bond order.

12. A diatomic molecule has a dipole moment of 1.2 D. If its bond distance is equal to 1.0Å then the fraction
of an electronic charge on each atom is :
(A) 25% (B) 37% (C) 52% (D) 42%
Ans. (A)
Sol. Assuming complete charge transfer then dipole moment = (4.8 × 10–10 esu) (10–8 cm) = 4.8 D
1.2
so % ionic character = × 100 % = 25%
4.8

13. The dipole moment of KCl is 3.336 × 10–29 Coulomb meter. The interionic distance in KCl is 2.6Å. Find
the % ionic character in KCl.
Sol. The theoretical dipole moment in KCl = e × d = 1.602 × 10–19 × 2.6 × 10–10 = 4.1652 × 10–29 C meter
exp erimental dipole moment
% ionic character = × 100 = (3.336 × 10–29/4.1652 × 10–29) × 100
theoretical dipole moment

14. The gaseous potassium chloride molecule has a measured dipole moment of 10.0 D, which indicates
that it is a very polar molecule. The separation between the nuclei in this molecule is 2.67 × 10 –8 cm.
Calculate the percentage ionic character in KCl molecule.
Sol. Dipole moment of compound would have been completely ionic
= (4.8 × 10–10 esu) (2.67 × 10–8 cm) = 12.8 D
10.0
so % ionic character = × 100% = 78.125 % ~ 78% Ans.
12.8

15. CO forms weak bonds to Lewis acid such as BF3. In contrast CO forms strong bonds to transition
metals. Why explain ?

Sol. CO ⎯⎯→ BF3

Transition metal CO
This is called synergic interaction and because of it the bond between CO and transition metal is
stronger.

16. SnCl4 has melting point - 15ºC where as SnCl2 has melting point 535ºC. Why?
Sol. According to Fajan's rule, as charge on cation increases its polarising power increases resulting in to
the greater polarisation of anion. Thus covalent character increases and melting point decreases.

17. Inorganic benzene is more reactive than organic benzene. Why?

Sol. Inorganic benzene (N3B3H6) contains polar covalent B – N bonds while benzene (C6H6) contains non-
polar covalent C–C bonds.

18. Which compound has the smallest bond angle in each series ?
(a) SbCl3 SbBr3 SbI3
(b) PI3 AsI3 SbI3

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Sol. (a)

97.1º 98.2º 99º

Cl, the most electronegative of the halogens in this series, pulls shared electrons the most strongly
away from Sb, reducing electron density near Sb. The consequence is that the lone pair exerts the
strongest influence on shape in SbCl3.

(b)

102º 100º 99º

Phosphorus is the most electronegative of the central atoms. Consequently, it exerts the strongest pull
on shared electrons, concentrating these electrons near P and increasing bonding pair-bonding pair
repulsions–hence, the largest angle in PI3. Sb, the least electronegative central atoms, has the
opposite effect : Shared electrons are attracted away from Sb, reducing repulsions between the Sb–I
bonds. The consequence is that the effect of the lone pair is greatest in SbI 3, which has the smallest
angle.
Atomic size arguments can also be used for these species. Larger outer atoms result in larger angles ;
larger central atoms result in smallest angles.
19. Why NO2+ and I3– are linear species ?
+
Sol. In NO2+ the N has sp hybridisation ; so it is linear O = N = O
In I3– there are 5 electron pairs around central iodine atom (3 lone pairs and 2 bond pairs). The
hybridisation of iodine is thus sp3d. To have minimum repulsions between lp-lp and lp-bp it acquires
linear shape as shown below.

20. Draw an electron dot structure for Br3– . Deduce an approximate value of the bond angle.
Sol. In Br3– there are 5 electron pairs around central bromine atom (3 lone pairs and 2 bond pairs). The
hybridisation of bromine is thus sp3d. To have minimum repulsions between lp-lp and lp-bp it acquires
linear shape as shown below.

linear

21. PCl5 has the shape of a trigonal bipyramidal where as IF5 has the shape of square pyramidal. Explain.
Sol. In PCl5 there are 5 electron pairs around central phosphorus atom and all are bond
pairs. The hybridisation of phosphorus is thus sp 3d. To have minimum repulsions between bp-bp it
acquires trigonal bipyramidal shape as shown below.

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Mo.No. – 9950347993, 9166825993
Chemical Bonding

Cl
Cl

P Cl
Cl
Cl
In IF5 there are 6 electron pairs around central iodine atom. The hybridisation of iodine is thus sp 3d.
6 electron pairs contain 5 bond pairs and one lone pair so it will be square pyramidal to have minimum
repulsions between lp-bp and bp-bp.
..
F F

F F

22. Why axial bonds of PCl5 are longer than equatorial bonds ?
Sol. This is due to greater repulsion on the axial bond pairs by the equatorial bond pairs of electrons.

23. (b) NCl5 is not possible but PCl5 is possible. Why ?

(c) F3– does not exist but I3– , Br3– exist. Why ?
(d) SCl6 does not exist but SF6 exists. Why ?
Sol. (b) This is because of the absence of d-orbitals in nitrogen for sp3d2 hybridisation.
(c) Because of the absence of d-orbitals in fluorine it can not expand its covalency.
(d) Bigger size of chlorine can not be accommodated around sulphur atom because of steric crowding.

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Mo.No. – 9950347993, 9166825993