Chemical Bonding

CHEMICAL BONDING
IIT-JEE-Syllabus
Lewis structure; orbital overlap and covalent bond; hybridisation involving s, p & d orbitals
only; coordinate covalent bond; ionic bond; orbital energy diagrams for diatomic species;
polarity in molecules, dipole moment (qualitative aspects only); VSEPR model and shapes
of molecules (linear, angular, planar, pyramidal, tetrahedral, octahedral and square planar.
INTRODUCTION
A molecule is formed if it is more stable and has lower energy than the individual atoms. Normally
only electrons in the outermost shell of an atom are involved in bond formation and in this
process each atom attains a stable electronic configuration of inert gas. Atoms may attain stable
electronic configuration in three different ways by loosing electrons, by gaining or by sharing
electrons. Elements may be divided into three classes.
 Electropositive elements, whose atoms give up one or more electrons easily, they have
low ionization potentials.
 Electronegative elements, which can gain electrons. They have higher value of
electronegativity.
 Elements which have little tendency to loose or gain electrons.
Three different types of bond may be formed depending on electropositive or
electronegative character of atoms involved.
Electropositive element + Electronegative element = Ionic bond (electrovalent bond)
Electronegative element + Electronegative element = Covalent bond
Electropositive + Electropositive element = Metallic bond.
ELECTROVALENCY
This type of valency involves transfer of electrons from one atom to another, whereby each atom
may attain octet in their outermost shell. The resulting ions that are formed by gain or loss of
electrons are held together by electrostatic force of attraction due to opposite nature of their
charges. The reaction between potassium and chlorine to form potassium chloride is an example
of this type of valency.
K  
Cl 

K+ Cl– (Ionic bond)

Here potassium has one electron excess of it’s octet and chlorine has one deficit of octet. So
potassium donates it’s electron to chlorine forming a ionic bond.
x O
Ca
x
Ca++ O2– (Ionic bond)

Here the oxygen accepts two electrons from calcium atom. It may be noted that ionic bond is not
a true bond as there is no proper overlap of orbitals.
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Criteria for Ionic Bond:
One of the species must have electrons in excess of octet while the other should be deficit of
octet. Does this mean that all substance having surplus electron and species having deficient
electron would form ionic bond? The answer is obviously no. Now you should ask why? The
reasoning is that in an ionic bond one of the species is cation and the other is anion. To form a
cation from a neutral atom energy must be supplied to remove the electron and that energy is
called ionisation energy. Now it is obvious that lower the ionisation energy of the element the
easier it is to remove the electron. To form the anion, an electron adds up to a neutral atom and
in this process energy is released. This process is called electron affinity.
So for an ionic bond one of the species must have low ionisation energy and the other
should have high electron affinity. Low ionisation energy is mainly exhibited by the alkali and
alkaline earth metals and high electron affinity by the halogen and chalcogens. Therefore this
group of elements are predominant in the field of ionic bonding.
COVALENCY
This type of valency involves sharing of electrons between the concerned atoms to attain the
octet configuration with the sharing pair being contributed by both species equally. The atoms are
then held by this common pair of electrons acting as a bond, known as covalent bond. If two
atoms share more than one pair then multiple bonds are formed. Some examples of covalent
bonds are
  xx
 
 Cl  Cl Cl – Cl x xx x
x N x x Nx NN
 
Sigma and Pi Bonding:

When two hydrogen atoms form a bond, their atomic orbitals overlap to produce a greater density
of electron cloud along the line connecting the two nuclei. In the simplified representations of the
formation of H2O and NH3 molecules, the O—H and N—H bonds are also formed in a similar
manner, the bonding electron cloud having its maximum density on the lines connecting the two
nuclei. Such bonds are called sigma bonds (-bond).
A covalent bond established between two atoms having the maximum density of the
electron cloud the line connecting the centre of the bonded atoms is called a -bond. A -
bond is thus said to possess a cylindrical symmetry along the internuclear axis.
Let us now consider the combination of two nitrogen atoms. Of the three singly occupied p-
orbitals in each, only one p-orbital from each nitrogen (say, the p x may undergo “head –on”
overlap to form a -bond. The other two p-orbitals on each can no longer enter into a direct
overlap. But each p-orbital may undergo lateral overlap with the corresponding p-orbital on the
neighbour atom. Thus we have two additional overlaps, one by the two p y orbitals, and the other
by the two pz orbitals. These overlaps are different from the type of overlap in a -bond. For each
set of p-orbitals, the overlap results in accumulation of charge cloud on two sides of the
internuclear axis. The bonding electron cloud does no more posses an axial symmetry as with the
-bond; instead, it possess a plane of symmetry. For the overlap of the p z atomic orbital, the xy
plane provides this plane of symmetry; for the overlap of the py atomic orbitals, the zx plane
serves the purpose. Bonds arising out of such orientation of the bonding electron cloud are
designated as -bonds. The bond formed by lateral overlap of two atomic orbitals having
maximum overlapping on both sides of the line connecting the centres of the atoms is
called a -bond. A -bond possess a plane of symmetry, often referred to as the nodal plane.
+ + +  + +
s s s-s  bond
+ + + -  + + -
s px s-px  bond
- + + + -  - + + -
px px px–px  - bond
+ + + +
+ 
- - - -
p - p bond
GENERAL PROPERTIES OF IONIC AND COVALENT BONDS
The different between ionic and covalent binding gives rise to difference in physical and chemical
properties. An ionic compound is composed of positive and negative ions –– the ion pairs of
opposite charges being held together by electrostatic attraction; the ions arrange themselves in a
regular geometrical pattern in the crystal of an ionic compound. X-ray analysis, for example,
reveals that the structure of sodium chloride crystal consists of two interlocking face centred cubic
lattices, one of sodium ions and the other of chloride ions –– each sodium unit in the crystal is
surrounded by six chlorine units, and each chlorine by six sodium units.
An ionic compound does not exist as a definite entity as molecules. There is no evidence,
for example, of molecules of sodium chloride as structural units in the lattice of sodium chloride.
All truly ionic compounds, e.g., common salt, posses ionic lattice. Owing to the restrictive
force in the crystal the ions are not free to move under the influence of an applied electric field.
But when an ionic compound is dissolved in water (or a suitable polar solvent which diminishes
the attraction between the ions) or melted, the ions acquire mobility and can move in opposite
directions in an electric field, i.e., ionic compound is polar and can conduct electricity in the
fused state or in solution in a suitable in a suitable solvent.
A purely covalent compound is a non-polar substance and does not conduct an electric
current. Anhydrous hydrogen chloride is a non-conductor, but its aqueous solution conducts
electricity as a result of chemical reaction which leads to the formation of ions:
HCl + H2O Cl + H3O+ (oxonium ion)
The ion-pairs tend to adhere to one another in electrovalent compounds and very powerful forces
hold the crystals together. Considerable energy is necessary to break the crystal lattice and
separate the ions. The electrovalent compounds are, therefore, solid that are not easily
vaporised. They have high melting points and high boiling points. Unlike the electrovalent
compounds covalent compounds exist as single molecules which have relatively little
attraction to one another –– the only force between them being the weak van der Waals forces;
the covalent compounds are therefore either gases, liquids or solids that are easily vaporised.
Since the force of attraction between the molecules is not large, covalent compounds melt and
boil at comparatively low temperature.
A covalent bond is rigid and directional (i.e., directed in space), and a covalent compound has
its atoms held in definite relative positions so that the different arrangements of the atoms are not
easily changed, i.e., a covalent compound may exhibit isomerism. Butane and isobutane for
example, are two distinct isomeric compounds. The ionic bond, on the other hand, is non-rigid
and non-directional, i.e., the charged particles are free to arrange and pack themselves in
chosen ionic lattices.
A polar liquid (with a high dielectric constant) such as water, alcohol and liquid ammonia
diminishes the force of attraction between the ions of an ionic compound; it will, therefore,
generally be a good solvent for ionic compounds. But a non-polar liquid (with a low dielectric
constant), e.g. organic solvents such as hydrocarbons and carbon tetrachlorde, is not good
enough to overcome the inter-ionic attraction, and therefore will be a very poor solvent for ionic
compounds.
CO - ORDINATE COVALENCY
A covalent bond results from the sharing of pair of electrons between two atoms where each
atom contributes one electron to the bond. It is also possible to have an electron pair bond where
both electrons originate from one atom and none from the other. Such bonds are called
coordinate bond or dative bonds. Since in coordinate bonds two electrons are shared by two
atoms, they differ from normal covalent-bond only in the way they are formed and once formed
they are identical to normal covalent –bond.
If is represented as 
Atom/ion/molecule donating electron pair is called Donor or Lewis base. Atom / ion / molecule
accepting electron pair is called Acceptor or Lewis acid [] points donor to acceptor
NH4+: NH3 has three (N – H) bond & one lone pair on N – atom. In NH4+ formation this lone pair is
donated to H+ (having no election)
NH3 + H+  NH4+
Lewis base Lewis acid
H H
H N
+ or H N H
H
H H
O
SO3
O S O
Cl
Cl
PCl 6 Cl P Cl
Cl
Cl
F
F
F Sb F
SbF6
F
F
Properties of the coordinate compounds are intermediates of ionic and covalent compounds.
Comparison of ionic, covalent & coordinate compounds
Ionic Covalent Coordinate

1. binding force between ions strong Between molecules in between
(coulombic) smaller (Vander
Waal’s)
2. mp/bp High less than ionic in between
3. condition conductor of electricity in bad conductor Greater than
fused state & covalent
in aqueous solution
4. solubility in polar High Less in between

solvent (H2O)
5. Solubility in non Low High in between
polar solvent (ether)
6. Physical state Generally solid liquid & gaseous solid, liquid
gas
Illustration 1. Classify the following bonds as ionic, polar covalent or covalent and give your
answer
a) Si - Si bond in Cl3 SiSiCl3
b) Si - Cl bond in Cl3SiSiCl3
c) Ca - F bond in CaF2
d) N - H bond in NH3
Solution: a) Covalent due to identical electronegativity
b) One electron pair is shared between Si & Cl and thus, covalent bond is
expected but electron negativity of Cl is greater than that of Si & some
polarity develops giving polar – covalent nature
c) Ionic since Ca completes its octet by transfer of two outershell electrons thus,
completing their octets
Ca [Ar]4s2, F[He)2s22p5
d) Polar covalent, explanation as in (b)
HYBRIDIZATION
We can explain the formation of four covalent bonds by an atom of carbon by considering
promotion of a 2s electron to a 2p orbital. Let us now consider the formation of a molecule of
methane, CH4, by such an excited carbon atom. There will be three C—H bonds formed by
overlap of the three 2p-orbitals of carbon with the 1s orbitals of three hydrogen atoms. The sp
bonds will be mutually perpendicular to one another. The fourth C—H bond would be formed by
overlap of the 2s orbital of carbon with an 1s orbital of hydrogen atom. Since the 2s orbital is
spherically symmetrical, the direction of the hydrogen atom held by this bond cannot be directly
ascertained. At the same time, one should expect this s—s bond to be of lower strength than the
other three s—p bonds. But it is contrary to our experience. We know that all four C—H bonds in
methane are all alike and they are arranged symmetrically around the central carbon atom
directed along the four corners of a tetrahedron. This necessitates a concept of mixing the s-
orbital of carbon with its three p-orbitals before overlap. The resulting equivalent orbitals, each
having one-fourth s-character and three –fourth p-character, may now undergo overlap with four
hydrogen atoms to form four equivalent C—H bonds. We may reasonably extend this concept to
interpret the equivalence of the two bonds in BeF 2 or the three bonds in BCl3. This procedure of
prior mixing of the orbitals has been given rigorous mathematical formulation.
Hybridization is a concept of mixing different atomic orbitals of comparable energy resulting in an
equal number of orbitals with mixed character. The resulting hybrid orbitals undergo better
overlap and form stronger bonds than the pure orbitals in conformity with the most stable
geometry for a molecule. The formation of four equivalent C—H bonds by carbon in forming
methane may then be conceived of in terms of the following successive steps:
  
C (ground state: only valence shell) 
2s 2p
C (excited state)    
2s 2p
3   
C (sp hybridised) 
3
sp hybrid orbitals
   
C (in CH4) X X X X
X Electrons from H-atoms
At first, a 2s electron of the carbon atom gets unpaired and promoted to a 2p orbital. The 2s and
the three 2p orbitals are now hybridized to give four equivalent orbitals, each possessing one part
s character to three parts p character in their wave function, directed to the corners of a regular
tetrahedron. These sp3 hybrid orbitals now form four equivalent C—H bonds in the methane
molecule; the bonds are distributed tetrahedrally around the carbon atom.
Shape Hybridisation
Linear sp
Trigonal planar sp2
Tetrahedral sp3
Trigonal bipyramidal sp3d
Octahedral sp3d2
Pentagonal bipyramidal sp3d3
VSEPR THEORY (VALENCE SHELL ELECTRON PAIR REPULSION THEORY)
This theory starts from the general principle that valence shell electrons occupy essentially
localised orbitals. Mutual interaction among the electrons orient the orbitals in space to an
equilibrium position where repulsion becomes minimum. The extent of repulsive interaction then
follows the order.
Lone pair – lone pair > lone pair – bond pair> bond pair – bond pair:
A lone pair is concentrated around the central atom while a bond pair is pulled out between two
bonded atoms. As such repulsion becomes greater when a lone pair is involved. Let’s take an
example to illustrate this theory. CH4 contains no lone pairs. The bond pair – bond pair
interactions brings about the most stable equilibrium bond angle of 109°28, the angle predicted
from sp3 hybridisation.
Illustration 2. Why the bond angle of H – C – H in methane (CH4) is 109° 28’ while H – N – H
bond angle in NH3 is 107° though both carbon and nitrogen are sp3 hybridized.
Solution: In CH4 there are 4 bond pair of electrons while in NH 3 are 3 bond pair of
electrons and 1 lone pair of electrons. Since bond pair bond pair repulsion is less
than lone pair bond pair repulsion, in NH 3 bond angle is reduced from 109°28’ to
107°.
Illustration 3. Why bond angle in NH3 is 107° while in H2O it is 104.5°. Though the central atom
in both the molecules is sp3 hybridized.
Solution: In NH3, central nitrogen atom bears only one lone pair of electrons whereas in
H2O central oxygen atom bears two lone pair of electrons.
Since the repulsion between lone pair – lone pair and lone pair – bond pair is
more than that between bond pair – bond pair, the repulsion in H2O is much
greater than that in NH3 which results in contraction of bond angle from 109°28”
to 104.5° in water while in NH3 contraction is less i.e. from 109°28” to 107°.
“If the electronegativity of the peripheral atoms is more, then the bond angle will be less”.
For example - if we consider NH3 and NF3, F – N – F bond angle will be lower than H – N – H
bond angle. This is because in NF3 the bond pair is displaced more towards F and in NH 3 it is
displaced more towards N. So accordingly the b.p. – b.p. interaction is less in NF3 and more in
NH3.
Illustration 4. The bond angle of H2O is 104° while that that of F2O is 102°.
Solution: Both H2O and F2O have a lone pair of electrons. But fluorine being highly
electronegative, the bond pair electrons are drawn more towards F in F2O,
whereas in H2O it is drawn towards O. So in F2O the bond pairs being displaced
away from the central atom has very little tendency to open up the angle. But in
H2O this opening up is more as the bond pair electrons are closer to each other.
So bond  of F2O is less than H2O.
O O
repulsion more
H H F F
Repulsion less
Exercise 1.
Among PCl3 & PF3 which is having greater bond angle and why?
“If the electronegativity of central atom is more then bond angle will be more”.
For example in NH3 and PH3, the H – N – H bond angle is more then H – P – H bond
angle. The reason for it can be explained in the same way as above.
Illustration 5. Out of H2O and H2S which is having greater bond angle and why?
Solution : H2O is having greater bond angle than H 2S since oxygen is more electronegative
than S and draws the shared pair of electrons toward itself more than S.
Therefore the bond pair interaction is more in case of H2O.
RULE FOR DETERMINATION OF TOTAL NUMBER OF HYBRID ORBITALS
 Detect the central atom along with the peripheral atoms.

 Count the valence electron of the central atom and the peripheral atoms.
 Divide the above value by 8. Then the quotient gives the number of  bonds and the
remainder gives the non-bonded electrons. So number of lone pair
non bonded electrons
= .
2
 The number of  bonds and the lone pair gives the total number of hybrid orbitals.
An example will make this method clear
SF4 Central atom S
Peripheral atom F
 Total number of valence electrons = 6+ (4 7) = 34
Now 8) 34 (4
32
 Number of hybrid orbital = 4 bonds + 1 lone pair
2
So 5 hybrid orbitals are necessary and hybridisation mode is sp 3d and it is trigonal bipyramidal
(TBP).
Both the structures are TBP. But the lone pair is placed in different position. In B it is placed in
equatorial position and in A it is in axial.
Now when a lone pair is in equatorial position the repulsion are minimized. So structure (B) is
correct.
Note: Whenever there are lone pairs in TBP geometry they should be placed in equatorial
position so that repulsion is minimum.
F
F
F
S S
F
F
F
F
F
(A) (B)
1. NCl3 Total valence electrons = 26

Requirement = 3  bonds + 1 lone pair N
Hybridsation = sp3
Cl Cl
Shape = pyramidal Cl
2. BBr3 Total valence electron = 24 Br
Requirement = 3 bonds
B
Hybridisation = sp2
Shape = planar trigonal Br Br
3. SiCl4 Total valence electrons = 32 Cl
Requirement = 4 bonds
Si
Hybridisation = sp3
Shape = Tetrahedral Cl Cl Cl
4. CI4 Total valence electron = 32 l
Requirements = 4  bonds
C
Hybridisation = sp3
Shape = Tetrahedral l l l
5. SF6 Total valence electrons = 48 F
Requirement = 6  bonds F F
hybridisation = sp3d2 S
shape = octahedral / square F F
bipyramidal
F
6. BeF2 Total valence electrons : 16
Requirement : 2  bonds
F – Be – F
Hybridisation : sp
Shape : Linear
7. ClF3 Total valence electrons : 28 F
Requirement : 3  bonds + 2 lone pairs
Hybridisation : sp3d Cl F
Shape : T – shaped
F
We have already discussed that whenever there are lone pairs they should be placed in
equatorial positions. Now a question that may come to your mind that though the hybridisation is
sp3d, so the shape should be T.B.P. But when all the bonds are present the actual shape is TBP.
But when instead of bond there are lone pairs in TBP the actual geometry is determined by the
bonds not by the lone pairs. Here in ClF3 the bond present (2 in axial and 1 in equatorial) gives
the impression of T shape.
8. PF5 Total valence electrons : 40
F
Requirement : 5  bonds F
Hybridisation : sp3d F
P
Shape : Trigonal bipyramidal (TBP)
F F
9. XeF4 Total valence electrons : 36
Requirement:4 bonds+ 2 lone pairs
Hybridisation : sp3d
Shape : Square planar
F F
F F F F
Xe Xe Xe
F F
F F
F F
(A) (B) (C)
Now three arrangements are possible out of which A and B are same. A and B can be inter
converted by simple rotation of molecule. The basic difference of (B) and (C) is that in (B) the
lone pair is present in the anti positions which minimize the repulsion which is not possible in
structure (C) where the lone pairs are adjacent. So in a octahedral structure the lone pairs must
be placed at the anti positions to minimize repulsion. So both structure (A) and (B) are correct.
10. XeF2 Total valence electrons : 22 F
Requirements : 2 bonds + 3 lone pairs
Hybridisation : sp3d
Xe
Shape : Linear
F
[ l.p. are present in equatorial position and ultimate shape is due to the bonds that are formed]
Br F
11. PF2Br3 Total valence electrons : 40
Requirements : 5  bonds
Hybridisation : sp3d P Br
Shape : trigonal bipyramidal

F
Br
Here we see that fluorine is placed in axial position whereas bromine is placed in equatorial
position. It is the more electronegative element that is placed in axial position and less
electronegative element is placed in equatorial position. Fluorine, being more electronegative
pulls away bonded electron towards itself more than that is done by bromine atom which results
in decrease in bp – bp repulsion and hence it is placed in axial position.
In this context it can also be noted that in T.B.P. shape the bond lengths are not same. The
equatorial bonds are smaller than axial bonds. But in square bipyramidal shape, all bond lengths
are same.
12. PO3- O O– O
4
etc.
Total valence electrons : 32 P P P
Requirement : 4  bonds O O O
O O O O O O
Hybridisation : sp3
Shape : tetrahedral
Here all the structures drawn are resonating structures with O – resonating with double bonded
oxygen.
13. NO2– Total valence electron: 18
Requirement : 2 bonds + 1 lone pair
N
Hybridisation: sp2
Shape: angular O O
14. CO32– Total valence electrons : 24
Requirement = 3  bonds
Hybrdisation = sp2
Shape: planar trigonal
But C has 4 valence electrons of these 3 form  bonds  the rest will form a  bond.
– –
O O O
C C C
O O O O O O
In the structure one bond is a double bond and the other 2 are single. The position of the double
bonds keeps changing in the figure. Since peripheral atoms are isovalent, so contribution of the
resonant structures are equal. Thus it is seen that none of the bonds are actually single or
double. The actual state is
–2/3
O
Bond order = 3/2 = 1.5

C
–2/3 –2/3
O O
15. CO2 Total valence electrons : 16 O=C=O
Requirement: 2 bonds
Hybridisation: sp
Shape: linear
16. BF4- Total valence electrons = 32 F
–
Requirement= 4  bonds
B
Hybridisation: sp3
F F
Shape: Tetrahedral F
17. ClO3- Total valence electron = 26
Requirement = 3  bond + 1 lone
Cl Cl Cl
pair
-
-
Hybridisation: sp3 O
O
O O
O
- O O
O
O
Shape: pyramidal
O
18. XeO2F2 Total valence electrons : 34 F
Requirement: 4  bonds +1 lone pairs

Hybridisation : sp3d Xe
Shape: Distorted TBP (sea-saw geometry) O
F
19. XeO3 Total valence electrons : 26

Requirement: 3  bonds + 1 lone pair Xe
Hybridisation: sp3 O O O
Shape: Pyramidal
20. XeOF4 Total valence electrons : 42 O
F F
Requirement: 5  bonds + 1 lone pair Xe
Hybridisation: sp3d2 F F
Shape: square pyramidal.
Exercise 2.
Draw the structure the following indicating the hybridisation of the central atom.
i) SOF2, ii) SO2, (iii) POCl3, (iv) I3–
Maximum Covalency:
3s 3p 3d
Elements which have vacant d-orbital can
expand their octet by transferring In ground state ↿⇂ ↿⇂ ↿ ↿
electrons, which arise after unpairing, to
In excited state ↿ ↿ ↿ ↿ ↿ ↿
these vacant d-orbital e.g. in sulphur.
In excited state sulphur has six unpaired electrons and shows a valency of six e.g. in SF 6. Thus
an element can show a maximum covalency equal to its group number e.g. chlorine shows
maximum covalency of seven.
RESONANCE
There may be many molecules and ions for which it is not possible to draw a single Lewis
structure. For example we can write two electronic structures of O3.
O O
O O O O
(A) (B)
In (A) the oxygen  oxygen bond on the left is a double bond and the oxygenoxygen bond on the
right is a single bond. In B the situation is just opposite. Experiment shows however, that the two
bonds are identical. Therefore neither structure A nor B can be correct.
One of the bonding pairs in ozone is spread over the region of all the three atom rather than
associated with particular oxygenoxygen bond. This delocalised bonding a type of bonding in
which bonding pair of electrons is spread over a number of atoms rather than localised between
two.
O
O O
(C)
Structures (A) and (B) are called resonating or canonical structures and C is the resonance
hybrid. This phenomenon is called resonance a situation in which more than one plausible
structure can be written for a species and in which the true structure cannot be written at all.
Some other examples
 CO32– ion
2-
O O O
O
O O O O O O
O O
 Carbonoxygen bond lengths in carboxylate ion are equal due to resonance.

-
O O O
R R R
-
O O O
 Benzene
 Vinyl Chloride
H2C H2C
+
Cl Cl
Difference in the energies of the canonical forms and resonance hybrid is called resonance
stabilization energy and provides stability to species.
RULES FOR WRITING RESONATING STRUCTURES
 Only electrons (not atoms) may be shifted and they may be shifted only to adjacent atoms
or bond positions.
 The number of unpaired electrons should be same in all the canonical form.
 The positive charge should reside as far as possible on less electronegative atom and
positive charge on more electronegative atom.
 Like charge should not reside on adjacent atom
 The larger the number of the resonating structures greater the stability of species.
 Greater number of covalent add to the stability of the molecule.
Illustration 6. Why C2  C3 bond length in 1, 3 butadiene is shorter than C – C bond length in
n – butane.
Solution:
C C C C
1 2 3 4
C C C C
Due to resonance in 1,3 butadiene, there is some sort of double bond character
present in C2  C3 single bond, which decreases the bond length.
Exercise 3.
The most unlikely representation of resonance structure of p – nitrophenoxide
ion is:
O O O O
(A) N
+ (B) N
+
O
O
O O O O
(C) N
+ (D) N
O O
DEVIATION FROM IDEAL BEHAVIOUR
Still now we have discussed all about those compounds which are either 100 percent ionic or
covalent from the Lewis theory i.e. the formation of the compound from the respective elements
takes place either by mutual sharing or by complete transfer of electrons resulting either covalent
species or ionic species.
Now we know that NaBr is an ionic crystal. Similarly AlBr3 is also an ionic crystal as its formation
takes place by complete transfer of electrons. So as both are ionic compounds and as it is a well
known fact that ionic compounds have high melting points, so we should expect a high melting
point for both. But contrary to our expectations the melting point of NaBr is 775°C and that of
AlBr3 is 97.5°C. Similarly CaF2 has got a melting point of 1400°C while that of CaI2 is 575°C. This
fact indicates that all those compounds which are ionic from the concept of transfer of electrons
are not 100% ionic but have some percent of covalent character induced in it. So it is better to
say a compound to be more of ionic rather than totally ionic.
Transition from Ionic to Covalent Character:
In an ideal ionic lattice, the ions are supposed to be hard inelastic spheres just touching each
other at equilibrium. But properties of most ionic solids deviate from ideal ionic character because
lattice may undergo some distortion. Cations are usually smaller than anions and have higher
effective nuclear charge than the latter. The outer electron cloud in a cation is more firmly held
than in an anion. Electron cloud in an anion is rather loosely held and may be attracted by the
neighbouring cation in the lattice. Hence the anion may not retain its spherical symmetry and may
be distorted. Such a phenomenon is known as polarisability of the anion and the capacity of the
cation to distort the electron cloud of anion is known as polarization power of the cation. As the
anion shift’s slightly its electrons towards cation, the positive charge over cation decreases and
negative charge over anion also decreases imparting partial ionic character to the bond. In other
words a completely ionic bond becomes partial ionic bond and shifting of electrons towards cation
imparts covalent nature to the bond i.e. bond starts behaving like polar covalent bond.
S+ S-
The polarising power of a cation is expressed by an index,  defined as
Cationic charge
 where  is called ionic potential.
Cationic radius
Again the extent to which an anion is polarised is given by its polarisability. This is governed by
the charge and size of the anion.
FACTORS GOVERNING POLARIZATION AND POLARISABILITY (FAJAN’S RULE)
Cation Size:
Smaller is the cation more is the value of  and hence more its polarising power. As a result more
covalent character will develop. Let us take the example of the chlorides of the alkaline earth
metals. As we go down from Be to Ba the cation size increases and the value of  decreases
which indicates that BaCl2 is less covalent i.e. more ionic. This is well reflected in their melting
points. Melting points of BeCl2 = 405°C and BaCl2 = 960°C.
Cationic Charge:
More is the charge on the cation, the higher is the value of  and higher is the polarising power.
This can be well illustrated by the example already given, NaBr and AlBr3. Here the charge on Na
is +1 while that of Al is +3, hence polarising power of Al is higher which in turn means a higher
degree of covalency resulting in a lowering of melting point of AlBr3 as compared to NaBr.
Noble Gas vs Pseudo Noble Gas Cation:
A Pseudo noble gas cation consists of a noble gas core surrounded by electron cloud due to
filled d-subshell. Since d-electrons provide inadequate shielding from the nuclei charge due to
relatively less penetration of orbitals into the inner electron core, the effective nuclear charge
(ENC) is relatively larger than that of a noble gas cation of the same period. NaCl has got a
melting point of 800°C while CuCl has got melting point of 425°C. The configuration of Cu + = [Ar]
3d10 while that Na+ = [Ne]. Due to presence of d electrons ENC is more and therefore Cl – is more
polarised in CuCl leading to a higher degree of covalency and lower melting point.
Anion Size:
Larger is the anion, more is the polarisability and hence more covalent character is expected. An
e.g. of this is CaF2 and CaI2, the former has meltingpoint of 1400°C and latter has 575°C. The
larger size of I– ion compared to F– causes more polarization of the molecule leading to a
lowering of covalency and increasing in melting point.
Anionic Charge:
Larger is the anionic charge, the more is the polarisability. A well illustrated example is the much
higher degree of covalency in magnesium nitride (3Mg++ N3–) compared to magnesium fluoride
(Mg++ 2F—). This is due to higher charge of nitride compare to fluoride.
These five factors are collectively known as Fajan’s Rule.
ROLE OF  (IONIC POTENTIAL)
1. Prediction of degree of covalency in an ionic compound.

2. Tendency of a cation to form complexes can be estimated.
3. Tendency of cations towards solvation.
Li+ Na+ K+ Rb+ Cs+
 increasing polarising power increases
Increased tendency to hydrate
Eq. Conductance or ion conductance
+
oil + +
E.g.: [Li(H2O)6] , [Na(H2O)4] , [Cs(H2O)]
4. Nature of oxides: Emperically for an oxide of the type Mn2 On
 Mn  2.2 basic
  lying between 2.2 – 3.2 amphoteric
   3.2 acidic
i.e. higher is the value of  greater is acidic nature of oxide.
Illustration 7. The melting point of KCl is higher than that of AgCl though the crystal radii of Ag +
and K+ ions are almost same.
Solution: Now whenever any comparison is asked about the melting point of the
compounds which are fully ionic from the electron transfer concept it means that
the compound having lower melting point has got lesser amount of ionic
character than the other one. To analyse such a question first find out the
difference between the 2 given compounds. Here in both the compounds the
anion is the same. So the deciding factor would be the cation. Now if the cation is
different, then the answer should be from the variation of the cation. Now in the
above example, the difference of the cation is their electronic configuration. K + =
[Ar]; Ag+ = [Kr] 4d10. This is now a comparison between a noble gas core and
pseudo noble gas core, the analysis of which we have already done.
Exercise 4.
Na2CO3 does not decompose on heating whereas CaCO 3 decomposes, why?
Illustration 8. The solubility of the hydroxides of the alkaline earth metals increases i.e.
Ba(OH)2 has got a higher solubility in water compared to Mg(OH) 2
Solution: Here both the cations Ba2+ and Mg2+ have the same charge, but as the radius of
Ba2+ is more therefore  of Ba2+ is less which implies that Ba(OH)2 having higher
degree of ionic character is more soluble in polar solvents like water.
But now if I ask to predict the solubility of MgSO 4 & BaSO4. The answer seems
to be quite similar to the earlier one and BaSO4 turns out to be the one having
higher solubility. But contrary to our expectation the trend is reversed here.
BaSO4 is sparingly soluble in water. The question comes why? In case of
hydroxide it is something. In case of sulfate it’s the other way around. Is there
any way by which we can a predict the solubility trend? The answer is yes.
When a lattice is dissolved in water, the ions are solvated and the solvated ions
are more stable than a free ion and due to this stability energy is released. This
energy released is called solvation energy and if this overcomes the lattice
energy then it is soluble. The lattice energy of NaCl is 778 kJ mol –1 and the
heats of hydration of Na+ and Cl– is –787 kJ mol–1. As it is more than the lattice
energy of NaCl therefore it is soluble.
Now we should focus our attention to the solubility trend in a given series. For a
comparison of the solubility both the lattice energy and hydration energy factors
have to be taken into account. If in a series the decrease of lattice energy is more
compared to the decrease in hydration energy then the substance becomes
soluble.
Now the hydration enthalpy of a salt is given by
k k
Hhydration  1  2 where k1 and k2 = constant
r r
k3
& lattice energy U  k3 = constant
r  r
Case I:
When r+ << r– the contribution of the anion to the hydration enthalpy is small so the total Hhydration
would be dominated by the cation alone. In a series of salts of a large anion, the hydrational
enthalpy will decrease in magnitude with increasing cation size. Now how does the lattice energy
respond to this changing cation radius? The lattice energy is inversely proportional to (r + + r–).
Since r– >> r+, the sum will not change significantly as r + increases. Consequently the lattice
energy will not decrease as fast as the hydration energy with increasing cationic size. The more
quickly diminishing hydration energy results in a decrease in solubility.
E.g. Solubility of LiI > NaI > KI…
MgSO4 > CaSO4 > SrSO4 > BaSO4
Case II:
r+  r–
Here the lattice energy decreases with increasing cationic size more rapidly than the hydration
energy which therefore results in an enhanced solubility in a series.
E.g. Solubility of LiF < NaF < KF
Mg(OH)2 < Ca(OH)2 < Ba(OH)2
Deviation from Covalent to Ionic Character:
In the previous section we discussed about those compounds which deviate from fully ionic to
some degree of covalency. A similar trend can also be observed with pure covalent molecules
which can change to a partially ionic bond.
This happens when the electronegativities of the two atoms which form the covalent bond are not
the same. The atom having higher electronegativity will draw the bonded electron pair more
towards itself resulting in a partial charge separation. The distribution of the electron cloud in the
bond does not remain uniform and shifts towards the more eletronegative one. Such bonds are
called polar covalent bonds. For example the bond formed between hydrogen and chlorine or
between hydrogen and oxygen in water is of this type.
 
H  Cl
  
H O  H
Molecules like HCl, H2O, NH3 i.e. molecules of the type H – X having two polar ends (positive and
negative) are known as polar molecules. The extent of polar character or the degree of polarity in
a compound is given by it’s dipole moment which is defined as the product of the net positive or
negative charge and the distance of separation of the charges i.e. the bond length. The symbol of
dipole moment is 
 = electronic charge (e)  distance
The unit of dipole moment is Debye (D)
1D = 3.33  10–30 Cm = 10–18 esu cm
Dipole moment is indicated by an arrow having a symbol ( ) pointing towards the negative end.
Dipole moment has both magnitude and direction and therefore it is a vector quantity.
To calculate the dipole moment of a molecule we should calculate the net dipole due to all bonds
and for lone pair if any. Diatomic molecules like HCl, HF have the dipole moment of the bond
(called bond dipole) equal to the molecular dipole as the structure has one bond only. But for poly
atomic molecules the net dipole is the resultant of the individual bond dipoles. A compound
having a zero dipole moment indicates that the compound is a symmetrical one.
Illustration 9. CO2 has got dipole moment of zero why?
Solutions: The structure of CO2 is O = C = O . This is a highly symmetrical structure with a

plane of symmetry passing through the carbon. The bond dipole of C–O is
directed towards oxygen as it is the negative end. Here two equal dipoles acting
in opposite direction cancel each other and therefore the dipole moment is zero.
Illustration 10. Dipole moment of CCl4 is zero while that of CHCl3 is non zero.
Solution: Both CCl4 & CHCl3 have tetrahedral structure but CCl4 is symmetrical while
CHCl3 is non-symmetrical.
Cl H
C C
Cl Cl Cl Cl
Cl Cl
Non-Symmetrical
Symmetrical
Due to the symmetrical structure of CCl4 the resultant of bond dipoles comes out
to be zero. But in case of CHCl3 it is not possible as the presence of hydrogen
introduces some dissymmetry.
Illustration 11. Compare the dipole moment of H2O and F2O.
Solution: Let’s draw the structure of both two compounds and then analyse it.
O O
H H F
F
In both H2O and F2O the structure is quite the same. In H2O as O is more
electronegative than hydrogen so the resultant bond dipole is towards O, which
means both the lone pair and bond pair dipole are acting in the same direction
and dipole moment of H2O is high. In case of F2O the bond dipole is acting
towards fluorine, so in F2O the lone pair and bond pair dipole are acting in
opposition resulting in a low dipole.
In C-H, carbon being more electronegative the dipole is projected towards C.
Now the question comes whether hybridization has anything to do with the dipole
moment. The answer is obviously yes. If yes, why? Depending on the
hybridization state the electronegativity of carbon changes and therefore the
dipole moment of C-H bond will change. As the s character in the hybridized
state increases, the electronegativity of C increases due to which C attracts the
electron pair of C-H bond more towards itself resulting in a high bond dipoles.
Now as we have said about carbon hydrogen bonds, the question that is coming
to your mind is whether we would be dealing with organic compounds or not. Yes
we would be dealing with the organic compounds.
For instance but -2- ene. It exists in two forms Cis and Trans.
H CH3 H CH3
C C
C
C
CH3 H
H CH3 Trans
Cis
The trans isomer is symmetrical with the 2 methyl groups in anti position. So the
bond dipoles the two Me– C bonds acting in opposition cancel each other result
in a zero dipole. Whereas in cis isomer the dipoles do not cancel each other
resulting in a net dipole.
Illustration 12. Compare the dipole moment of Cis 1,2 dichloroethylene and trans 1,2
dichloroethylene.
Solution: Cl Cl Cl H
C C C C
H H
H Cl
Cis
Trans
In the trans compound the C-Cl bond dipoles are equal and at the same time
acting in opposition cancel each other while Cis compound the dipoles do not
cancel each other resulting in a higher value.
Generally all Trans compounds have a lower dipole moment corresponding to
Cis isomer, when both the substituents attached to carbon atom are either
electron releasing or electron withdrawing.
DIPOLE MOMENT IN AROMATIC RING SYSTEM
The dipole moments of the aromatic compounds present a very good illustration of dipole
moment. We all know when a substituted benzene is treated with a reagent different products
namely ortho, meta and para products are formed. The dipole moments of these products are
different since the orientation of the groups is different at ortho, meta and para position. Let us
take an example which will make it easily digestive for you. Suppose we have three isomers of o-
nitrophenol, m-nitrophenol and p-nitrophenol. We have also the e.g. o-aminophenol, m-
aminophenol and p-aminophenol.
X X X
Para
Y
Ortho Meta Y
In the case X = Y, the para isomer becomes symmetrical and have zero dipole.
Now the obvious question that is peeping through your mind is that which isomer in which case
has got higher dipole moment. The answer lies in the nature of the groups linked to the benzene
ring. In nitrophenol groups one group is electron pushing and the other is electron withdrawing
while in the second case both the groups attached are electron pushing. So depending on the
nature of the groups attached one of the isomer, o, m or p has the largest dipole moment.
Case I: Now when X & Y are both electron pushing or electron withdrawing.
Suppose, bond dipole of C – X = 1
And that of C – Y = 2
Here we have assumed a sign of + when groups are electron pushing and–when groups are
electron withdrawing. The net dipole is the resultant of two bond dipoles at different orientations.
When both X & Y are electron pushing or electron withdrawing.
1
ortho = 12  22  212 cos60o = 12  22  212 
2
0 = 12  22  12
meta = 12  22  212 cos120
m = 12  22  12
para = 12  22  212 cos180 = 12  22  212

p = 1 – 2
From the above expression of 0, m & p it is clear that when both X & Y are of the same nature
i.e. both are electron withdrawing or both are electron pushing the para product has the least
dipole moment and ortho product has the highest. Now when X = Y, p = 1 – 2 = 1 – 1 = 0
Which we have already discussed.
Case II: When X is electron pushing and Y is electron withdrawing or vice versa.
Let C – X dipole = 1
& C – Y dipole = 2
12   2   21  2  cos60
2
0 = = 12  22  12
 
2
= 1  2  312
meta 12   2   21  2  cos120 = 1  2  12

2 2 2
=
 
2
= 1  2  12
para 12   2   21  2  cos180 = 1  2  212 = 1 +2

2 2 2
=
Now if you see the expressions, it is very clear that the para isomer has the highest dipole
moment and ortho is the least.
So to calculate the dipole moments of disubstituted benzene one should consider about the
nature of the groups linked and then only one can predict the dipole moment of the molecule.
Out of NO2
Illustration 13.
and its meta and ortho
isomers which is having
greater dipole moment?
CH3
Solution: Para isomer is having highest dipole moment since two groups attached to
benzene ring have dipole moment directed in the same direction thereby they
reinforce one another in this case.
Exercise 5.
Out of CF3
and its meta and ortho isomers

which is having greater dipole
moment?
CH3
PERCENTAGE OF IONIC CHARACTER
Every ionic compound having some percentage of covalent character according to Fajan’s rule.
The percentage of ionic character in a compound having covalent character, can also be
calculated by the following equation.
Observed dipole moment
The percent ionic character =  100
Calculated dipole moment assuming 100% ionic bond
Illustration 14. Calculate the % of ionic character of a bond having length = 0.92 Å and 1.91 D
as it’s observed dipole moment.
Solution: Calculated  considering 100% ionic bond

= 4.810–10 0.92 10–8esu cm
= 4.8  0.92  10–18 esu cm = 4.416 D
1.91
 % ionic character =  100 = 43.25
4.416
The example given above is of a very familiar compound called HF. The % ionic character is
nearly 43.25%, so the % covalent character is (100 – 43.25) = 56.75%. But from the octet rule HF
should have been a purely covalent compound but actually it has some amount of ionic character
in it which is due to the electronegativity difference of H and F. Similarly knowing the bond length
and observed dipole moment of HCl, the % ionic character can be known. It was found that HCl
has 17% ionic character. Thus it can be clearly seen that although we call HCl and HF as
covalent compounds but it has got appreciable amount of ionic character. So from now onwards
we should call a compound having more of ionic less of covalent and vice versa rather than fully
ionic or covalent.
Exercise 6.
Calculate the percentage of ionic character of HI having bond length = 1.62Å and
observed dipole moment = 0.39 D.
HYDROGEN BONDING
INTRODUCTION
An atom of hydrogen linked covalently to a strongly electronegative atom can establish an extra
weak attachment to another electronegative atom in the same or different molecules. This
attachment is called a hydrogen bond. To distinguish from a normal covalent bond, a hydrogen
bond is represented by a broken line eg X – H…Y where X & Y are two electronagative atoms.
The strength of hydrogen bond is quite low about 2-10 kcal mol–1 or 8.4–42 kJ mol–1 as compared
to a covalent bond strength 50–100 kcal mol–1 or 209 –419 kJ mol–1
Conditions for Hydrogen Bonding:
 Hydrogen should be linked to a highly electronegative element.
 The size of the electronegative element must be small.
These two criteria are fulfilled by F, O, and N in the periodic table. Greater the
electronegativity and smaller the size, the stronger is the hydrogen bond which is evident
from the relative order of energies of hydrogen bonds.
TYPES OF HYDROGEN BONDING
Intermolecular hydrogen bonding:

This type of bonding takes place between two molecules of the same or different types. For
example,
H H H
O—H----- O — H ------ O — H ------
Inter molecular hydrogen bonding leads to molecular association in liquids like water etc. Thus in
water only a few percent of the water molecules appear not to be hydrogen bonded even at 90°C.
Breaking of those hydrogen bonds throughout the entire liquid requires appreciable heat energy.
This is indicated in the relatively higher boiling points of hydrogen bonded liquids. Crystalline
hydrogen fluoride consists of the polymer (HF) n. This has a zig-zag chain structure involving H-
bond.
F F
H H
H H H
F F F
Intramolecular hydrogen bonding:

This type of bonding occurs between atoms of the same molecule present on different sites.
Intramolecular hydrogen bonding gives rise to a closed ring structure for which the term chelation
is sometimes used. Examples are, o-nitrophenol, salicylaldehyde.
H H
O O O
O
N C
O H
o-nitrophenol Salicaldehyde
EFFECT OF HYDROGEN BONDING
Hydrogen bonding has got a very pronounced effect on certain properties of the molecules. As
State of the substance:
H2O exists in liquid state whereas H2S in gaseous state because hydrogen bonding exist in water
and no H-bonding exists in H2S.
Solubility:
The organic compounds like alkane, alkenes, alkynes are insoluble in water due to absence of H-
bonding whereas alcohols, organic acids, amines are soluble in water due to H-bonding.
Boiling point:
High boiling and melting points of NH3 , H2O and HI in comparison to hydrides of other elements of
V, VI and VII groups to which N, O and F belong respectively are due to hydrogen bonding.
Acidity of different isomers:
Strength of certain acids and bases can be explained on the basis of hydrogen bonding eg. when we
compare the acidic strength of o – m – and p – hydroxyl benzoic acid.
OH OH OH
COOH
COOH
pK a  105  10 5
pK a  8.3  105 COOH
pK a  2.9  105
The abnormally high dissociation constant of o – hydroxybenzoic acid is due to the fact that the
conjugate base is stabilised by hydrogen bonding.
These can be evident from the following examples.
Illustration 15. H2O is a liquid at ordinary temperature while H2S is a gas although both O and S
belong to the same group of the periodic table.
Solution: H2O is capable of forming intermolecular hydrogen bonds. This is possible due to
high electronegativity and small size of oxygen. Due to intermolecular H-bonding,
molecular association takes place. As a result the effective molecular weight
increases and hence the boiling point increases. So H 2O is a liquid. But in H2S
no hydrogen bonding is possible due to large size and less electronegativity of S.
So it’s boiling point is that of an isolated H2S molecule and therefore it is a gas.
Illustration16. Ethyl alcohol (C2H5OH) has got a higher boiling point than dimethyl either (CH 3-
O-CH3) although the molecular weight of both are same.
Solution: Though ethyl alcohol and dimethyl ether have the same molecular weight but in
ethyl alcohol the hydrogen of the O-H groups forms intermolecular hydrogen
bonding with the OH group in another molecule. But in case of ether the
hydrogen is linked to C which is not so electronegative to encourage the
hydrogen to from hydrogen bonding.
C2 H5 C H 2 5
O H O H
Due to intermolecular H-bonding, ethyl alcohol remains in the associated form
and therefore boils at a higher temperature compared to dimethyl ether.
Illustration 17. Find the maximum possible number of hydrogen bonds a water molecule can
form.
Solution : O
H
O
H H H
H
H H
H O
O
H
H
A water molecule can form 4 – hydrogen bonds.
Exercise 7.
O-nitrophenol is more volatile than p-nitrophenol. Explain?
IMPORTANCE OF HYDROGEN BONDING IN BIOLOGICAL SYSTEMS
Hydrogen bonding plays a vital role in physiological systems. Proteins contain chains of amino
acids. The amino acid units are arranged in a spiral form somewhat like a stretched coil spring
(forming a helix). The N-H group of each amino acid unit and the fourth C=O group following it
along the chain, establishes the N–H---O hydrogen bonds. These bonds are partly responsible
for the stability of the spiral structure. Double helix structure of DNA also consists of two strands
forming a double helix and are joined to each other through hydrogen bond.
INTERMOLECULAR FORCES
INTRODUCTION
We have enough reasons to believe that a net attractive force operates between molecules of a
gas. Though weak in nature, this force is ultimately responsible for liquefaction and solidification
of gases. But we cannot explain the nature of this force from the ideas of ionic and covalent bond
developed so far, particularly when we think of saturated molecules like H2, CH4, He etc. The
existence of intermolecular attraction in gases was first recognised by Vanderwaal’s (1813) and
accordingly intermolecular forces have been termed as Vanderwaal’s forces. It has been
established that such forces are also present in the solid and liquid states of many substances.
Collectively they have also been termed London forces since their nature was first explained by
London using wave mechanics.
Nature of Vanderwaal’s Forces:
The Vanderwaal’s forces are very weak in comparison to other chemical forces. In solid NH3 it
amount to about 39 KJ mol–1 (bond energy N-H bond = 389 KJ mol–1). The forces are non
directional. The strength of Vanderwaal’s force increases as the size of the units linked increases.
When other factors (like H-bonding is absent), this can be appreciated by comparison of the
melting or boiling points of similar compounds in a group.
Origin of Intermolecular Forces:
Intermolecular forces may have a wide variety of origin.
 Dipole-dipole interaction: This forces would exist in any molecule having a permanent
dipole e.g. HF, HCl, H2O etc.
 Ion-dipole interaction: These interaction are operative in solvation and dissolution of
ionic compounds in polar solvents.
 Induced dipole interaction: These generate from the polarisation of a neutral
molecule by a charge or ion.
 Instantaneous dipole-induced dipole interaction: In non polar molecules dipoles
may generate due to temporary fluctuations in electron density. These transient dipole
can now induce dipole in neighbouring molecules producing a weak temporary
interaction.
MOLECULAR ORBITAL THEORY
In Molecular Orbital Theory (MOT) the atoms in a molecule are supposed to loose their individual
control over the electrons. The nuclei of the bonded atoms are considered to be present at
equilibrium inter-nuclear positions. The orbitals where the probability of finding the electrons is
maximum are multicentred orbitals called molecular orbitals extending over two or more nuclei.
In MOT the atomic orbitals loose their identity and the total number of electrons present are
placed in MO’s according to increasing energy sequence (Aufbau Principle) with due reference to
Pauli’s Exclusion Principle and Hund’s Rule of Maximum Multiplicity.
When a pair of atomic orbitals combine they give rise to a pair of molecular orbitals, the bonding
and the anti-bonding. The number of molecular orbitals produced must always be equal to the
number of atomic orbitals involved. Electron density is increased for the bonding MO’s in the
inter-nuclear region but decreased for the anti-bonding MO’s, Shielding of the nuclei by increased
electron density in bonding MO’s reduces inter nuclei repulsion and thus stabilizes the molecule
whereas lower electron density even as compared to the individual atom in anti-bonding MO’s
increases the repulsion and destabilizes the system.
Anti-bonding MO
Energy
O
Bonding MO
Distance between atom
In denotion of MO’s,  indicates head on overlap and  represents side ways overlap of orbitals.
In simple homonuclear diatomic molecules the order of MO’s ( for molecules having total number
of electrons less than 16) based on increasing energy is
   * 
*  *  2py   2py  *
1s 1s 2s 2s   2px
  2px
2pz 
   *2p 
 z
For molecules having total number of electrons equal to or more than 16 (including O2 and
above) the order is
 * 
*  *  2py 
  2py  *
1s 1s 2s 2s 2p x     2px
 2pz 
   *2p 
 z
If the molecule contains unpaired electrons in MO’s it will be paramagnetic but if all the electrons
are paired up then the molecule will be diamagnetic. Paramagnetic substances are attracted in
magnetic field whereas diamagnetic substances are repelled in magnetic field.
  no. of e s
Bond order= no. of e s occupying bonding MO's occupying antibonding MO's
2
Application of MOT to homonuclear diatomic molecules.
H2 Molecule : Total no. of electrons = 2
Arrangement : 1s2
Bond order : ½ (2 – 0) = 1
H2 Molecule : Total no. of electrons = 1
Arrangement : 1s1
Bond order : ½ (1 – 0) = 1/2
He2 Molecule : Total no. of electrons = 4
Arrangement :  2 * 2
1s 1s
Bond order : ½ (2 – 2) = 0
He2 molecule does not exist.
He2 Molecule : Total no. of electrons = 3
Arrangement :  2 * 1
1s 1s
Bond order : ½ (2 – 1) = 1/2

So He2 exists and has been detected in discharge tubes.
Li2 Molecule : Total no. of electrons = 6
Arrangement :  2 * 2  2
1s 1s 2s
Bond order : ½ (4 – 2) = 1
No unpaired e’s so diamagnetic
Be2 Molecule : Total no. of electrons = 8
Arrangement :  2 * 2  2  *2
1s 1s 2s 2s
Bond order : ½ (4 – 4) = 0
No unpaired e–s so diamagnetic
B2 Molecule : Total no. of electrons = 10
Arrangement :  2 * 2  2 * 2  2  2
1s 1s 2s 2s 1s 2px
Bond order : ½ (6 – 4) = 1 diamagnetic
But observed Boron is paramagnetic
C2 Molecule : Total no. of electrons = 12
 1 
2 *2 2 * 2 2  2p y 
Arrangement : 1s 1s 2s 2s 2p  
x
 12pz 
Bond order : ½ (4 – 0) = 2
It is paramagnetic
But observed C2 is diamagnetic
N2 Molecule : Total no. of electrons = 14
 2 
* * 2  2p y 
Arrangement : 1s 1s 2s 2s 2px 
2 2 2 2

 22pz 
Bond order : ½ (6 – 0) = 3
 It is diamagnetic
O2 Molecule : Total no. of electrons = 16
 2   * 1 
* 2 *2 2  2p y   2py 
Arrangement : 1s2 1s 2s 2s 2p 
2
  
x
 22pz   *2p1 
 z
Bond order : ½ (6 – 2) = 2
It is paramagnetic
F2 Molecule : Total no. of electrons = 18
 2   * 2 
2 *2 2 *2 2  2p y   2py  *
Arrangement : 1s 1s 2s 2s 2p     2px
 *2pz
x
 22pz  2

Bond order : ½ (6 – 4) = 1
 1 
* 2 *2  2p y 
B2 : 1s2 1s 2s 2s 
2

 12pz 
It is paramagnetic
 2 
2 *2 2 *2  2p y 
C2 : 1s 1s 2s 2s  
 22pz 
It is diamagnetic
 2 
N2 :  2 *2  2 *2  2py 
1s 1s 2s 2s  2  22px
2pz 
It is diamagnetic
Illustration 18. Compare the bond energies of O2, O2 & O2
Solution: Higher the bond order greater will be the bond energies.
 * 1 
*2  2 *2  2 2py 
2
Now configuration of O2 = 1s2 1s  2py 
2s 2s 2p   x  
 2pz   *2p1 
2
 z
Now formation of O2 means to remove an electron from anti-bonding one, which
means increase in B.O.
B.O. of O2 = ½ (6-1) = 2.5
O2 means introduction of an e– in the anti-bonding thereby reducing the bond
order.
Bond order of O2 = ½ (6 – 3) = 1.5
So bond energy of O2 > O2 > O2
Exercise 8.
Compare the bond energies of N2, N2 & N2
INERT PAIR EFFECT
Heavier p-block and d-block elements show two oxidation states. One is equal to group number
and second is group number minus two. For example Pb(5s 25p2) shows two O.S, +II and +IV.
Here +II is more stable than +IV which arises after loss of all four valence electrons. Reason - for
more stability of +II 0.S. that 5s2 electrons are reluctant to participate in chemical bonding
because bond energy released after the bond formation is less than that required to unpair these
electrons (lead forms a weak covalent bond because of greater bond length)
BACK BONDING
Sometime surrounding atom in order to make up electron deficiency in the central atom forms a
-bond which is one sided i.e. shared electrons are contributed by surrounding atom only which is
having lone pair of electrons. Overlap involves vacant orbital on central atom and filled orbital on
surrounding atom.
F
B F
Exercise 9.
i) Explain why CCl2 is unstable while PbCl2 is stable?
ii) Trisilyl amine (SiH3)3N is weaker base than (CH3)3N, why?
SOLUTION TO EXERCISES
Exercise 1.
PCl3 will be having greater bond angle since ‘F’ is more electronegative and drags the
shared pair towards itself thereby reducing the b.p. - b.p. repulsion in PF3.
Exercise 2.
i) S ii) S
O F F O O
O –
I
iii) P iv) I
Cl Cl
Cl I
Exercise 3.
Answer is C.
Exercise 4.
The solution lies in the thermal stability of Na2CO3 compared to CaCO3. The
decomposition of a carbonate means formation of an oxide along with CO 2
CaCO3  CaO + CO2 (g)
Now more the carbonate ion is polarised by the cation more is the chance of formation of
CO2 and therefore higher is the probability of decomposition. Now let’s see the case of
CaCO3. The polarising power of Ca2+ is more than Na+ due to higher cationic charge of
calcium ion. Therefore it polarises the carbonate ion more compared to sodium whose 
is insufficient to polarise CO32  and so CaCO3 decomposes but not Na2CO3.
O
++ C
Ca 
  CaO  CO2
O O
O
+
Na C
 No polarization
O O
Exercise 5.
p-isomer will be having highest dipole moment since dipole moment of – CF3 group is
reinforced to maximum extent in this case by – CH3 group. (One is electron withdrawing and
other is electron releasing).
Exercise 6.
Calculate  considering 100% ionic bond
= 4.8  10–14 esu  1.62  10–8 cm = 7.776 D
0.39
 % ionic character =  100 = 5
7.776
 % covalency = (100 – 5) = 95%
Exercise 7.
More volatility means it has got lower boiling point. Now p-nitrophenol remains associated
through intermolecular hydrogen bonding. But in o-nitrophenol only intramolecular H-
bonding formation takes places, as a result of which there is no association. So p-
nitrophenol which remains as an associated species has got higher boiling point and so
less volatile.
O H O H O H
H
O
N
o
o-Isomer O N O
p-isomer
Exercise 8.
The configuration of N2 is
   * 
1s2 *2 2 *2  2py 
1s
 2py 
22px
2s 2s   
 2pz 
 *2p 
 z
Now N2 means removal of an electron from a body M.O. This will decrease the B.O.
B.O. of N2 = ½ (5 – 0) = 2.5
Now again for N2 bond order is ½ (6–1) = 2.5
So from the bond order it may seem that both N2 & N2 may have the same bond energy.
But removal of an electron from a diatomic species tend to decrease the inter electron
repulsion and thereby shorter the bond length. So the bond energy becomes more than
compared to N2
N2 > N2 > N2
Exercise 9.
i) In PbCl2 + II oxidation is more stable than +IV state due to inert pair effect i.e. ns 2
electrons do not participate in bonding.
ii) Due to p – d bonding that exists between fully filled p-orbital of nitrogen and vacant
d-orbital of silicon, availability of lone pair of electrons on nitrogen decreases.
SOLVED PROBLEMS
Subjective:
Problem 1. Predict the shapes of the following ions

a) BeF3-
b) BF4-
c) IF4-
d) IBr2-
Solution: a) Triangular
b) Tetrahedral
c) Square planar
d) Linear
Problem 2. Identify the type of hybridization for each of the carbon atom
CH
H3C
i) ii)
CH2
iii) H3C
OH
Solution: i) CH3 – CH = CH2

sp3 sp2 sp2
sp2 sp2
O sp2 sp2
CH
iii) H3C ii) sp sp
sp2
sp3 sp2 sp2
OH
all the carbon atoms of the benzene
ring are sp2 hybridized
Problem 3. Arrange the following in increasing order of stability O2, O2+, O2-, O22-
Solution: O22- < O2- < O2 < O2+

Calculate first the bond order which is as follows
O2 – 2, O2+ - 2.5, O2- - 1.5, O22- -1 & then arrange according to increasing bond
order.
Problem 4. Which of the following is paramagnetic & why?

a) O2
b) O22-
Solution: O2 –Is2, *Is2, 2S2, *2s2, 2px2- 2py2 2pz2 , * 2py1* 2pz1
O2 has two unpaired electrons & hence paramagnetic. Similarly
O22- - 1s2,*1s2, 2s2, *2s2, 2px2 2py 2pz ,  2py  2pz
2 2 * 2 * 2
O2-2 has no unpaired electron & hence not paramagnetic
Problem 5. A diatomic molecule has dipole moment of 1.2 D. If the bond distance is 1.0 A.
What fraction of an electronic charge ‘e’ exists on each atom?
Dipole moment 1.2  1018 esucm

Solution: Partial charge = = = 1.210-10 esu
Bond dis tance 1.0  108 cm
The fraction of an electronic
1.2x1010
Charge is =  0.25
4.8x1010
= 25% of ‘e’
Problem 6. Interpret the non- linear shape of H2S molecule and non – planar shape of PCl3
using valence shell electron pair repulsion theory (VSEPR)
Solution: In H2S, two bonded pair & two lone pairs are present i.e. sulphur is in sp 3
hybridized state. The angle is less than 10928I as contraction occurs due to
presence of lone pairs. Thus H2S have V shaped structure. In PCl3 three bond
pairs & one lone pair are present i.e. phosphorus is also in sp 3 hybridized state
but it has pyramidal structure.
Problem 7. The C  C bond dissociation energy is 146 kcal/mole whereas C – C bond

dissociation energy is 83 kcal/mole then whey paraffins are less reactive than
olefins.
Solution: In most olefin reactions only 1 bond is broken & it is the  bond that is broken.
This bond has dissociation energy of 146 – 83 = 63 kcal, which is less than the
C – C  bond energy of 83 kcal/mole. This is why olefins are more reactive than
parafins.
Problem 8. Write down geometry for each of each of the following?

a) I3-
b) TeCl4
c )XeF6
d) BrF5
I
Solution: a)
I
I
Linear
Cl
b) Cl
Te
Cl
Cl
see saw shpae
c) XeF6 distorted octahedral
F
d)
F F
Br
F F
square pyramidal
Problem 9. Why Al(OH)3 is amphoteric in nature?
Solution: Since Al – O and O – H bond strength are almost equal, there exist almost
equal probability of their breaking making them amphoteric in nature.
Problem 10. Explain when ClF2- linear but ClF2+ is a bent molecular ion?
Solution: Chlorine atom lies in sp3d hybrid state. Three lone pairs are oriented along the
corners of triangular plane
F Cl F
[ClF2-]
Chlorine atom lies in sp3 hybrid state. Two lone pairs are oriented along two
corners of tetrahedral
Cl
F F
[ClF2+]
Problem 11. Ether R – O – R and water H – O – H have same hybridization at oxygen. What
angle would you expect for them?
Solution: In H2O, bond angle is less than 10928I due to lone pairs and bond pair
repulsion. But in ether due to strong neutral repulsion between two alkyl group
bond angle becomes greater than 10928I
O O
H H R 110 R
105
Problem 12. Explain why?

a) maleate ion is more stable than fumerate ion
b) ortho chlorophenol is less polar than ortho flouro phenol
O
Solution: a)
H
H COOH O
+
H
O
H
H COOH
O
(maleic acid) (maleate ion)
H COOH H COO
+
H
HOOC H HOOC H
(fumaric acid) (fumarate ion)
OH
b)
O Cl
H
(No hydrogen bond)
In ortho flurophenol the angle between the group decreases due to hydrogen
bonding thus ortho fluoro phenol will have greater dipolemoment than ortho
chlorophenol
Problem 13. a) F2O has got a bond angle of 103 but Cl2O has got a angle of 110. Explain
b) Bond angle of H2O is 104 while that of H2S in 92. Explain
O+
Solution : a)
Cl– Cl
In Cl2O delocalisation of lone pair of electrons of oxygen to chlorine decrease
the repulsion by lone pairs and increases the repulsion between bond pairs.
The bond angle thus becomes larger compared to F2O.
b) In H2S it is more or less the pure p orbital that participates in bonding rather
than the sp3 hybrid i.e., the bonding that takes place involves orbitals having
higher percentage of p character. Whereas in H2O it is the sp3 orbitals
participating in bonding and so bond angle of H2S is close to 90°.
Problem 14. a) LiCl is hydrated, but NaCl is always anhydrous. Why?
b) Why is it that although Li+ is far smaller than the other metals ions, it moves
through a solution less rapidly than the others?
Solution: a) Li+ is smaller in size and hence it is more hydrated than Na+ which has a
larger size.
b) Smaller the size of cation, larger the charge, then greater the hydration. The
dense charge of Li+ attracts several layers of water molecules around it. They
increase the effective size of the ion, thus slowing it down.
Problem 15. At room temp., NO2 gas is paramagnetic in nature. When it is cooled below
00 C aquires diamagnetic behaviour. Explain this observation on the basis of
strucuture.
O
Solution : At room temperature N there is unpaired electron at nitrogen.

O
O O
On cooling dimer exist N N and there is no unpaired electron with it.
O O
Objective:
Problem 1. Among LiCl, BeCl2, BCl3 & CCl4 the covalent bond character follows the order
(A) LiC > BeCl2 > BCl3 > CCl4 (B) LiCl < BeCl3 < BCl3 < CCl4
(C) LiCl > BeCl2 > CCl4 > BCl3 (D) LiCl < BeCl2 < BCl3 > CCl4
Solution: Smaller cation causes more polarization of anion

Hence (B) is the correct answer.
Problem 2. PCl5 exists but NCl5 does not because

(A) Nitrogen has no vacant 2 d- orbitals
(B) NCl5 is unstable
(C) Nitrogen atom is much smaller than P
(D) Nitrogen is highly inert
Solution: Excitation of 2s electron in N is not possible

Hence (A) is the correct answer.
Problem 3. Dipole moment is exhibited by

(A) 1, 4 – dichloro benzene (B) 1,2 – dichloro benzene
(C) Trans 1, 2 - dichloroethene (D) None of these
Cl
Solution:
Cl
Except , the vector sum in each is zero
Problem 4. The pair of species having identical shape is

(A) CFl4, SF4 (B) PCl3, BF3
(C) XeF2, CO2 (D) PF5, IF5
Solution: Both are linear molecules

Hence (C) is the correct answer.
Problem 5. KF combines with HF of form KHF2. The compound contains the species
(A) K+, F- & H+ (B) K+, F- & HF
+
(C) K & [HF2] - (D) [KHF]+ & F-
Solution: KHF2 K+ + HF2-

Problem 6. The bond order in O2+ is the same as in

(A) N2+ (B) CN-
(C) CO (D) NO+
1 5
Solution: Bond order of O2+ = 6  1
2 2
1 5
Bond order of N2+ = 5  0 
2 2
Hence (A) is the correct answer.
Problem 7. The hybridization of P in phosphate ion (PO43-) is the same as in

(A) I in ICl4- (B) S in SO3
(C) N in NO3 - (D) S in SO32-
Solution: P in PO43- has sp3 hybridization like S in SO32-

Hence (D) is the correct answer.
Problem 8. The correct increasing bond angle order is

(A) BF3 < NF3 < PF3 < ClF3 (B) ClF3 < PF3 < NH3 < BF3
(C) BF3 = NF3 < PF3 < ClF3 (D) BF3 < NF3 < PF3 < ClF3
Solution: Bond angles of ClF3, PF3, NH3 & BF3 are (180) (101), (106), (120)
respectively
Problem 9. The diamagnetic molecules are

(A) Br, C2, N2 (B) O2, N2, F2
(C) C2, N2, F2 (D) B2, O22-, N2
Problem 10. Which are true statements among the following?

(1) PH5 & BiCl5 do not exist
(2) p - d bonds are present in SO2
(3) SeF4 & CH4 have same shape
(4) I3+ has bent geometry
(A) 1 (B) 1,2 & 4
(C) 1 & 3 (D) 1, 2 & 3
Problem 11. Which molecule is T-shaped?

(A) BeF2 (B) BCl3
(C) NH3 (D) ClF3
Solution: ClF3 has sp3d hybridisation with two lone pairs of electron on central Cl-atom.
Hence (D) is the correct answer.
Problem 12. The species which does not show paramagnetism is

(A) O2 (B) O2+
(C) O2 2– (D) H2+
Solution: O22– has no unpaired electron
Problem 13. CO2 has the same geometry as

(A) HgCl2 (B) NO2
(C) SnCl2 (D) C2H2
Solution: Both HgCl2 and C2H2 are linear like CO2 because of sp2 hybridisation
Hence, (A) & (D) is the correct answer.
Problem 14. Which ion has the highest polarising power?

(A) Mg2+ (B) Al3+
(C) Ca2+ (D) Na+
Solution: Small cation has more polarising power

Problem 15. The correct order of decreasing polarisability of ion is

(A) Cl–  Br–  I–  F– (B) F–  I–  Br–  Cl
(C) I  Br  Cl  F
– – – – (D) F–  Cl–  Br–  I–
Solution: Larger the ion, more is its polarisation

ASSIGNMENT PROBLEMS
Subjective:
LEVEL – I
1. Which among the following has highest boiling point & why?
H2 , He, Ne, Xe, CH4 .
2. Explain why bond angle of NH3 is greater than NF3 while bond angle of PH3 is less than
that of PF3.
3. Explain dipole moment of NH3 is more than that of NF3?
4. Anhydrous AlCl3 is covalent from the data given below, predict whether it would remain
covalent or become ionic in aqueous solution.
Ionization energy of Al = 5137 kJ/mol
Hhydration (Al3+) = – 4665 kJ/mol
Hhydration (Cl–) = – 381 kJ/mol
5. In (CH3)3N nitrogen is sp3 hybridized whereas in (SiH3)3N it is sp2 hybridised why?
6. Though Cs is most electropositive element in periodic table Li has highest oxidation

potential why?
7. Though Li+ ion is smaller than Cs+ ion its mobility in aqueous solution is more than Cs+
ion.
8. On the basis of ground state electronic configuration arrange the following molecules in
increasing N – N bond length order.
NaN2 ,N2
9. CaCO3 dissolves in HCl but not in water.
10. In case of triatomic molecules SO2 & H2O have considerable dipole moment, but no
such moment is possible for CO2 molecule.
LEVEL – II
1. Give the shape of following xenon compound
XeOF4, XeO3
2. SnF4 boils at 705C while SnCl4 boils at 114.
3. a) Compare the dipole moments of CH3Cl, CH2Cl2, CHCl3, CCl4.

b) Compare the dipole moments of H2O and F2O.
4. In water the H – O – H bond angle is 105. Determine the magnitude of the charge on the
oxygen atom in the water molecule.
Given dipole moment of water = 1.85 D
Covalent radii = Hydrogen = 0.28Å
Oxygen = 0.66Å
5. a) BeCl2 in aqueous solution exists as [Be(H2O)4]2+ rather than Be2+ . This is acidic in
nature. Explain
b) Mg3N2 when reacted with water gives NH3 but HCl is not obtained from MgCl2 on
reaction with water at room temperature.
6. In some polar solvents PCl5undergoes an ionisation reaction in which Cl– ion leave one
PCl5 molecule and attaches itself to another
2PCl5 PCl4+ + PCl6–
What are the changes in geometrical shapes that occur in this ionisation?
7. (a) A compound with 2 or more – OH groups present on a carbon is usually unstable.

Explain the stability of chloral hydrate  Cl3  CHCOH2 ?
(b) Indicate the hybridization to the following positively charged carbon atoms:
 2
CH3 , C H2
8. Li+ ion has got the smallest radius among the alkali metals, yet its mobility is less than
other alkali metal ions in aqueous solution.
9. (a) What is the type & number of bonds between 2 carbon atoms in CaC2 .
(b) Using VSEPR theory, identify the type of hybridization & draw the structure of OF2 .
What are the oxidation states of O & F?
10. Discuss the hybridization of carbon atoms in allene  C3H4  & show  -orbital overlap.
LEVEL – III
1. The formula of nitrogen is N2 while that of phosphorous in P4. Explain
2. Compare bond dissociation energy of F2, Cl2, O2, and N2
3. Arrange the following in increasing boiling point and explain

a) H2S, H2O, H2Se, H2Te
b) SiH4, GeH4, SnH4, CH4
4. a) The boiling point of HF is maximum among other halogen acids. Explain.

b) o-nitrophenol is less soluble in water than p-nitrophenol. Why?
5. Compare the bond angles of NH3, PH3 and AsH3.

6. Bond energy of H – H, F – F and H – F bonds are 104, 38 and 135 kcal mol–1
respectively. Calculate resonance energy in H – F molecule.
7. Explain why the measured resultant dipole moment for FNO is 1.81 D, is so much higher
than the value for nitryl fluoride FNO2 (0.47D).
8. A molecular compound is composed of 60.4% of Xe, 22.1% of O and 17.5% of F by

mass. If the molecular weight is 217.3 amu, what is the molecular formula? Predict the
molecular geometry using VSEPR model.
9. A compound of chlorine and fluorine ClF n, reacts at about 75°C with uranium metal to
produce UF6 and ClF(g). A small quantity of uranium produced 3.53g UF 6 and 343 ml ClF
at 75°C and 2.50 atm. What is the formula of the compound? Describe bonding in the
molecule, using valence bond theory.
(U = 239, F = 19)
10. Butanol and butanal has got a large difference in boiling points although they have almost
the same solubility in water. Explain
11. 2Li + O2  Li2O
2Na + O2  Na2O2
Why the number of oxygen atoms combining with each metal increases?
12. a) What type of bonding holds the layer in graphite?

Why will graphite conduct electricity well in a direction parallel to the planes of
hexagons, but not at all well in a direction perpendicular to the planes?
b) PCl5 exists in the solid in the form of [PCl4]+ [PCl6]–, yet it is a non conductor of
electricity. Why?
13. Give MO configuration and bond orders of H 2, H2–, He2 and He2–. Which species among
the above are expected to have same stabilities?
14. In ICl5, the four chlorine atoms on square planar base and the central atom I does not
remain in same plane. Justify the statement.
15. What is the increasing order of the bond angle for?

O O O
H H Cl Cl F F
Objective:
LEVEL – I
1. Which of the following structure is most expected for molecule XeOF 4?

(A) Tetrahedral (B) Square pyramidal
(C) Square planar (D) Octahedral
2. Which of the following species is diamagnetic?

(A) O2+ (B) NO+
(C) NO (D) O2
3. The common features among the species CN–, CO, NO+ are
(A) Bond order three and isoelectronic
(B) Bond order three and weak field ligands
(C) Bond order two and acceptors
(D) Isoelectronic and weak field ligands
4. The correct order of hybridisation of the central atom in the following species NH 3
[PtCl4]2–, PCl5 and BCl3 is
(A) dsp2, dsp3, sp2 and sp3 (B) sp3, dsp2, dsp3, dsp2
2 2 3
(C) dsp , sp , sp , dsp 3 (D) dsp2, sp3, sp2, dsp3
5. KF combines with HF to form KHF2. The compounds contains the species

(A) K+, F–, H+ (B) K+, F– and HF
+
(C) K and HF2 – (D) [KHF]+ and F2
6. The bond energies in NO, NO+ and NO– follow the order
(A) NO+  NO  NO– (B) NO  NO+  NO–
(C) NO–  NO  NO+ (D) NO+  NO+  NO
7. Intramolecular Hbonding is present in

(A) onitrophenol (B) Salicylaldehyde
(C) mnitrophenol (D) Both (A) and (B)
8. Which of the following two are isostructural?

(A) XeF2 IF2– (B) NH3, BF3
(C) CO32–, SO32– (D) PCl5, ICl5
9. The correct order of increasing C – O bond length of CO, CO32– and CO2 is:
(A) CO32–  CO2  CO (B) CO2  CO32–  CO
(C) CO  CO32–  CO2 (D) CO  CO2  CO32–
10. Which one of the following has zero dipole moment?

(A) ClF (B) PCl3
(C) SiF4 (D) CFCl3
11. A molecule XY2 contains two , two  bonds and one lone pair of electrons in the valence
shell of X. The arrangement of lone pair as well as bond pairs is
(A) Square pyramidal (B) Linear
(C) Trigonal planar (D) Unpredictable
12. Identify the false statement

(A) Anhyd. FeCl3 cannot exist in dimeric form
(B) Maximum polarisation is brought about by a cation of high charge
(C) The bond dissociation energy of a metallic bond is greater than that of a hydrogen
bond.
(D) The conversion of Na to Na+ is an endothermic process
13. Which of the following is least ionic?

(A) AgCl (B) KCl
(C) BaCl2 (D) CaCl2
14. Out of the following which has highest dipole moment?

(A) 2, 2-dimethyl propane (B) trans-2-pentene
(C) cis-3-hexene (D) 2, 2, 3, 3-tetramethyl butane
15. The molecule which possesses both sp3 and sp3d2 hybridisation is
(A) Solid PCl5 (B) Gaseous PCl5
(C) PCl4 (D) PCl6
16. There is no S – S bond in

(A) S2O42– (B) S2O62–
(C) S2O32– (D) S2O72–
17. The strongest bond is

(A) C—C (B) C—H
(C) C—N (D) C—O
18. Among KO2, AlO2–, BaO2 and NO2+ unpaired electron is present in
(A) NO2+ and BaO2 (B) KO2 and AlO2–
(C) KO2 only (D) BaO2 only
19. Which of the following is least soluble in H2O?

(A) BaF2 (B) SrF2
(C) CaF2 (D) MgF2
20. Which bond angle () would result in the maximum dipole moment for the triatomic
molecule XY2?
(A)  = 90° (B)  = 120°
(C)  = 150° (D)  = 180°
21. C2 – C3 sigma single bond in vinyl acetylene CH2 = CH – C  CH is due to overlapping of
(A) sp – sp (B) sp2 – sp2
(C) sp – sp2 (D) sp2 – sp
22. Among HF, CH4, CH3OH and N2O4, intermolecular hydrogen bonding is expected
(A) In all (B) In all expect one
(C) In two (D) In none
23. The electronegativity difference between two atoms A and B is 2 then percentage of
covalent character in the molecule is
(A) 54% (B) 46%
(C) 23% (D) 72%
24. For resonance structure a molecule may not have

(A) Identical arrangement of atoms
(B) Nearly same energy contents
(C) The same number of paired electrons
(D) Identical bonding
25. Which of the following diatomic molecules would be stabilized by the removal of an
electron?
(A) C2 (B) CN
(C) N2 (D) O2
26. Molecule in which the distance between two adjacent carbon atoms is largest, is:
(A) Benzene (B) Ethyne
(C) Ethene (D) Ethane
27. Which of the following compounds of IV group elements would you expect to be most
ionic in character?
(A) CCl4 (B) SiCl4
(C) PbCl2 (D) PbCl4
28. Amongst LiCl, RbCl, BeCl2 and MgCl2, the compounds with the greatest and least ionic
character respectively are
(A) LiCl and RbCl (B) RbCl and BeCl2
(C) RbCl and MgCl2 (D) MgCl2 and BeCl2
29. Which of the following is insoluble in water?

(A) AgF (B) AgI
(C) KBr (D) CaCl2
30. In the compounds of type ECl3 where E = B, P, As or Bi the angles Cl – E – Cl for

different E are in the order:
(A) B>P = As = Bi (B) B>P>As>Bi
(C) B<P = As = Bi (D) B<P<As<Bi
LEVEL – II
1. Select correct orders for corresponding property as indicated in bracket for the following.
(A) NH3  BiH3  SbH3  AsH3  PH3 (Boiling point)
(B) H2O  H2Te  H2Se  H2S (Boiling point)
(C) NH3  PH3  AsH3  SbH3 (Basic character)
(D) H2O  H2S  H2Se  H2Te (Acidic character)
2. Which one or more among the following involve(s) p - d bonding?
(A) (SiH3)3N (B) (CH3)3N
(C) CCl3 (D) CF3
3. Which of the following orders are correct for property indicated in brackets
(A) NH3  NF3  BF3 (dipole moment)
(B) Cl  S  O  N (electron affinity)
(C) Si  Mg  Al  Na (first ionization enthalpy)
(D) HClO4  HBrO4  HIO4 (pKa values)
4. Which among the following are having sp3d hybridization of the central atom.
(A) XeF4 (B) XeO2F2
(C) ClO3 (D) BrF3
5. Which of the following statements are correct:
(A) The bond angle of NCl3 is greater than that of NH3.
(B) The bond angle in PH3 is greater than that of PF3.
 2
(C) ClO3 and SO3 are isostructural
(D) It is not necessary that in TBP structure the lone pairs always would occupy the
equatorial positions.
6. Bond angle in PH3 is
(A) much less than NH3 (B) Much less than PF3
(C) slightly more than NH3 (D) much more than PF3
7. Which among the following are isostructural

(A) CO2, I 3 (B) XeO2F2, SF4
2 2
(C) SO3 , CO3 (D) ClF3, XeF2
8. Which are the species in which central atom undergoes sp3 hybridisation?
(A) SF4 (B) SCl2
(C) SO42– (D) H2O
9. Select the correct statements:
(A) the heat of hydration of the dipositive alkaline earth metals ions decrease with an
increase in their ionic size.
(B) hydration of alkali metal ions is less than that of IIA
(C) alkaline earth metal ions, because of their much larger charge to size ratio exert a
much stronger electrostatic attraction on the oxygen of water molecule surrounding
them.
(D) melting point of sodium halides follow order
NaF  NaCl  NaBr  NaI
10. Which of the following are non-polar?

(A) NF3 (B) BF3
(C) SF4 (D) SiF4
Linked Comprehension Type
C1–3 : Paragraph for Questions Nos. 1 to 3

The shape of a molecule is determined by electron-pair repulsions in the valence shell. A lone
pair occupies larger space than a bond pair because it is not shared by two nuclei. Thus the lone
pair-lone pair repulsion is greater than the lone pair-bond pair repulsion, which in trun is greater
than the bond pair-bond pair repulsion. The presence of lone pairs causes distortion of bond
angles and hence a deviation from an ideal shape. The extent of distortion depends upon the
orientation of the lone pairs around the central atom. In a trigonal bipyramid, the lone pairs
occupy equatorial positions than the apical ones.
In ABn type molecules, as the electronegative of A increases, the bond pairs come closer and the
repulsion between them increases. On the other hand, as electro negativity of B increases, the
bond pairs get farther and repulsion decreases.
1. Which of the following statements is true?

(A) F-N-F angle in NF3 is greater than H-N-H angle in NH3
(B) F-N-F angle in NF3 is smaller than H-N-H angle in NH3
(C) H-O-H angle in H2O is greater than H-N-H angle in NH3
(D) F-O-F angle in F2O is greater than H-O-H angle in H2O
2. The shape of which of the following molecules will not be distorted?

(A) BrF3 (B) ClF3
(C) XeF4 (D) XeF6
3. Which of the following species will have the lone pair effects cancelled?
(A) ICl2 (B) ClF3
(C) PCl3 (D) BrF5

The molecular orbital energy diagrams for homonuclear diatomic molecules are given below. For
systems containing up to 14 electrons:
For systems containing more than 14 electrons:
Electrons taken from both the atoms are filled from lower to higher energy molecular orbitals
(MO’s) following Hund’s rules.
The energy diagram of a heteronuculear diatomic molecule is similar. However, the energies of
the atomic orbitals (AO’s) of the atom having higher atomic number being lower, the diagram will
be unsymmetrical, but that will not make a difference in the electron count.
Bond order is given by half the difference in the number of electrons of the bonding ( and ) and
anti-bonding (* and *) molecular orbitals. For a bond to have been formed, the bond order
should be greater than zero. The greater the bond order, the shorter is the bond distance and the
greater is the bond dissociation energy. But if the bond order is the same in two cases, the bond
distance will be greater and the bond dissociation energy smaller in the case which has more
populated anti-bonding orbitals. The presence of unpaired electron(s) in a molecular orbital will
make the system paramagnetic.
4. Which of the following species is not expected to exist?

(A) He2 (B) H2
(C) Be2 (D) Be2
5. Which among the following will have a triple bond order?
(A) CO (B) CN–
(C) NO + (D) All of these
6. Which of the following orders is correct in respect of bond dissociation energy?

(A) N2  N2 (B) O2  O2
(C) NO  NO (D) All of these

In the ionic bond, a cation tend to polarize the electron cloud of the anion by pulling electron
density towards itself. This causes development of covalent character in ionic bond because the
electron density gets localized in between the nuclei. The tendency of cation to bring about the
polarization of anion is expressed as its polarizing power. The ability of ion to undergo
polarization is called its polarisability. The polarizing power of cation and polarisibality of anion
are decided on the basis of Fajan rules as given below:
i) The smaller the cation, the higher is its polarizing power.
ii) Cations with pseudo noble gas configuration (ns 2np6nd10) having relatively high polarizing
power than those with noble gas configuration (ns2np6).
iii) The larger the size of the anion, the higher is its polarisability.
7. Among the following LiCl, BeCl2, BCl3, CCl4 which will have the lowest melting point and
the highest solubility in water.
(A) CCl4, LiCl (B)LiCl, CCl4
(C) BeCl2, BCl3 (D) BCl3, BeCl2
8. The correct order of polarisibility is

I–, Br–, Cl–, F–
(A) I–  Br–  Cl–  F– (B)I–  Br– = Cl–  F–
(C) I– = Br– = Cl–  F– (D) I– = Br–  Cl– = F–
9. The ionic conductance of which of the following is the highest?

(A) Li+ (aq) (B)Na+ (aq)
(C) K+ (aq) (D) Cs+ (aq)
Match the following
1. Match List I (species) with List II (Hybridisation) and select the correct answer using the
codes given below.
List – I List – II
(A) BCl3 (p) sp3
(B) NH3 (q) sp3d2
(C) PCl5 (r) sp2
(D) XeF4 (s) sp3d
2. Match List I with List.

List – I List – II
(A) C—H bond in Ethyne (p) sp-s overlap
(B) P—Cl bond in POCl3 (q) sp3d–p overlap
(C) Br—Br bond in Br – (r) sp3-p overlap
3
(D) C—C bond in Ethane (s) sp3-sp3 overlap
ANSWERS TO OBJECTIVE ASSIGNMENTS
LEVEL – I
1. B 2. B 3. A
4. B 5. C 6. A
7. D 8. A 9. C
10. C 11. C 12. A
13. A 14. C 15. A
16. D 17. B 18. C
19. D 20. A 21. D
22. C 23. B 24. D
25. D 26. D 27. C
28. B 29. B 30. B
LEVEL – II
1. (B), (C), (D) 2. (A), (C)
3. (A), (B), (C) 4. (B), (D)
5. (A), (C) 6. (A), (B)
7. (A), (B) 8. (B), (C), (D)
9. (A), (B), (C), (D) 10. (B), (D)
Linked Comprehension Type
1. (B) 2. (C)
3. (A) 4. (C)
5. (D) 6. (D)
7. (A) 8. (A)
9. (D)
MATCH THE FOLLOWING

1. (A) – (r)
(B) – (p)
(C) – (s)
(D) – (q)
2. (A) – (p)
(B) – (r)
(C) – (q)
(D) – (s)

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K+ Cl– (Ionic bond)

Ca++ O2– (Ionic bond)

Sigma and Pi Bonding:

GENERAL PROPERTIES OF IONIC AND COVALENT BONDS

Lewis base Lewis acid

Ionic Covalent Coordinate

4. solubility in polar High Less in between

VSEPR THEORY (VALENCE SHELL ELECTRON PAIR REPULSION THEORY)

RULE FOR DETERMINATION OF TOTAL NUMBER OF HYBRID ORBITALS

 Detect the central atom along with the peripheral atoms.

1. NCl3 Total valence electrons = 26

Shape : trigonal bipyramidal

Bond order = 3/2 = 1.5

Requirement: 4  bonds +1 lone pairs

19. XeO3 Total valence electrons : 26

 Carbonoxygen bond lengths in carboxylate ion are equal due to resonance.

RULES FOR WRITING RESONATING STRUCTURES

DEVIATION FROM IDEAL BEHAVIOUR

The polarising power of a cation is expressed by an index,  defined as

FACTORS GOVERNING POLARIZATION AND POLARISABILITY (FAJAN’S RULE)

ROLE OF  (IONIC POTENTIAL)

1. Prediction of degree of covalency in an ionic compound.

Deviation from Covalent to Ionic Character:

Illustration 9. CO2 has got dipole moment of zero why?

Solutions: The structure of CO2 is O = C = O . This is a highly symmetrical structure with a

Illustration 11. Compare the dipole moment of H2O and F2O.

DIPOLE MOMENT IN AROMATIC RING SYSTEM

meta = 12  22  212 cos120

m = 12  22  12

para = 12  22  212 cos180 = 12  22  212

meta 12   2   21  2  cos120 = 1  2  12

para 12   2   21  2  cos180 = 1  2  212 = 1 +2

and its meta and ortho isomers

PERCENTAGE OF IONIC CHARACTER

Solution: Calculated  considering 100% ionic bond

TYPES OF HYDROGEN BONDING

Intermolecular hydrogen bonding:

O—H----- O — H ------ O — H ------

Intramolecular hydrogen bonding:

EFFECT OF HYDROGEN BONDING

IMPORTANCE OF HYDROGEN BONDING IN BIOLOGICAL SYSTEMS

Distance between atom

Bond order : ½ (2 – 1) = 1/2

INERT PAIR EFFECT

Problem 1. Predict the shapes of the following ions

Solution: i) CH3 – CH = CH2

Solution: O22- < O2- < O2 < O2+

Problem 4. Which of the following is paramagnetic & why?

O2-2 has no unpaired electron & hence not paramagnetic

Dipole moment 1.2  1018 esucm

Problem 7. The C  C bond dissociation energy is 146 kcal/mole whereas C – C bond

Problem 8. Write down geometry for each of each of the following?

c) XeF6 distorted octahedral

Problem 9. Why Al(OH)3 is amphoteric in nature?

Problem 12. Explain why?

(No hydrogen bond)

Solution : At room temperature N there is unpaired electron at nitrogen.

Solution: Smaller cation causes more polarization of anion

Problem 2. PCl5 exists but NCl5 does not because

Solution: Excitation of 2s electron in N is not possible

Problem 3. Dipole moment is exhibited by

Except , the vector sum in each is zero