CHEMICAL BONDING

In this chapter we shall be studying the following major articles.

(1) Ionic Bond
(2) Covalent Bond
(3) Hydrogen Bond
(4) Polarity of Molecules
So let us start with the study of ionic bond and properties of ionic compounds.
Thus the complete study of ionic bond can be divided into two parts.
A. Conditions of formation of ionic bond.
B. General properties of ionic compounds.
A. CONDITIONS OF FORMATION OF IONIC BOND.
i. The difference of electronegativity between the combining elements must
be large. For example CCl
4
is a covalent substance because the difference
of electronegativity between C (2.5) and Cl (3.0) is only 0.5. But NaCl is an
ionic compound because the difference (Na = 0.9) and (Cl = 3.0) is of 2.1
units. The electronegativities are on Pauling's scale. Approximately if the
difference is more than 1.7 then ionic bond formation is expected. Thus
one element is electropositive then the other the other one must be
electronegative.
ii. Ionisation energy of electropositive element must be low so that it can
easily lose the electron(s) to form the required cation.
iii. Electron affinity or quantitatively known as electron gain enthalpy of
electronegative element must be numerically high so that the
electronegative element may easily gain the required number of
electron(s) to form stable anion.
iv. Since noble gas configurations (eight electrons in the outermost shell,
except He which is only two) are the most stable configurations, hence the
transfer of electron(s) from electropositive atom or group to
electronegative atom or group should be such that cations and anions
acquire stable configurations. For example in the formation of NaCl
sodium atom transfers its valence electron to chlorine atom. The cations
and anions both acquire stable configurations as shown below
Na
+
= 1s
2
, 2s
2
p
6
Cl

= 1s
2
, 2s
2
p
6
, 3s
2
p
6
CHEMICAL BONDING
v. The cations and anions thus formed attract each other to form ionic
crystals. The energy released in this process is called Lattice Energy. For
the formation of stable ionic compound, lattice energy must be high.
LATTICE ENERGY: It is defined as the amount of energy liberated (enthalpy
change) when cations and anions in the gaseous state combine to form one mole
of ionic crystals.
For example:
, , ,
Na g Cl g Na Cl s
+ +
+
1
L.E.
H 777.8 KJ mol

A =
Some more examples of L.E. in KJ mol
1
are given below:
LiF = 1033 KF = 813.4 CsF = 747.7
LiCl = 845.2 KCl = 708.8 CsCl = 652.3
LiBr = 797.9 KBr = 679.5 CsBr = 632.2
LiI = 739.7 KI = 640.2 CsI = 601.2
NaF = 915 RbF = 778 BeF
2
= 3505
NaCl = 777.8 RbCl = 686.2 MgF
2
= 2957
NaBr = 739.3 RbBr = 659 CaF
2
= 2630
NaI = 692.0 RbI = 622.2 AlF
3
= 5215
Calculation of Lattice Energy
It is best calculated with the help of Born-Haber cycle using Hess Law. For
example for NaCl.
, , ,
f
H
s 2 g s
1
Na Cl Na Cl
2
A +
+ =
sub.
H A
H
dissociation
2
A
Na
(g)
Cl
(g)
L.E.
I.E.
e e +
E.A.
, g
Na
+
, g
Cl

rding to Hess Law

CHEMICAL BONDING
diss.
f sub. I.E. EA L.E.
H
H H H H H
2
A
A = A + A + + A + A
since
f
(NaCl) = 411 KJ mol
1
sub.
(Na) = + 107 KJ mol
1
I.E.
(Na) = + 496 KJ mol
1
disso.
(Cl
2
) = + 244 KJ mol
1
E.A.
(Cl) = 355 KJ mol
1
L.E.
244
411 107 496 355 H
2
= + + + A
,
1
L.E. Na Cl
H 781 KJ mol
+

A =
Another convenient but approximate method is by Kapustinskii Equation,
according to this
L.E. =
1
120 200 Z Z
34.5
1 KJ mol
r r
+

v
(

(

where = number of ions per molecule e.g.
NaCl = 2, BaCl
2
= 3
r = inter ionic distance in the crystal
= r
+
+ r

i.e. sum of ionic radii in terms of pm

Z
+
& Z

are the valence charges of ions.

Since for NaCl,
Na Cl
r r
+
+ in NaCl crystal is 281 pm.
,
120 200 2 1 1
34.5
L.E. 1
281 281

| |
=
|
\ .
1
740 KJ mol

~
or
1
L.E.
H 740 KJ mol

A ~
Factors affecting L.E.
I. Inter ionic distance
,
1
r r ; L.E.
r r
+
+
+
+
II. ionic charge; more are the charges ion of the ion more is the L.E. e.g. for
LiF it's value 1033 but for MgO it's is value is 3933 KJ mol
1
.
CHEMICAL BONDING
III. Coordination number of ions in the ionic crystal; more are the
coordination numbers, more is L.E.
IV. There is one important generalization about L.E. specially applicable to
Alkali metal halides (M
+
X

) that if
M
r
+
is kept constant then as
X
r

increases
L.E. decrease. Similarly if
X
r

is constant then as
M
r
+
increases, L.E.
decrease. For example
NaF, NaCl, NaBr, NaI
L.E. (KJ mol
1
) 915, 777.8, 739.3, 692
M
r
+
= constant
X
r

= increasing
L.E. is decreasing.
On this basis we answer the following question
Q.

2
2
RbI Cl
Rb ICl or
RbCl ICl
A
+

The answer is RbCl + ICl because L.E. of RbCl is more than that of RbI, hence RbCl
is more stable, so this is the product with ICl.
General characteristics of Ionic Compounds:
(i) Physical state: Most of the ionic compounds are in solid crystalline state
at ordinary temperatures. Few ionic compounds are found in the
solution phase for example HCl (aq.) consists of H
+
& Cl

in aqueous
medium. In solid crystalline state, the arrangement of ions is regular
depending on the radius ratio
r
r
+

as we have studied in solid state.

Radius of an ion depends on its effective nuclear charge (Zeffe.) i.e.
,
ion
1
r
Zeffe.

But Zeffe. = ZS
where Z = atomic number
CHEMICAL BONDING
and S = screening or shielding constant for the ion. The value of 'S' is
calculated theoretically with the help of some empirical rules given by
slates. These rules give quite good results for ions of lower atomic
number. This is calculated for all electrons except the one that is the
outermost hell electron.
The important rules to be used at present are:
(1) All the other electrons in the (ns, np) group (leaving one) contribute to the
extent of 0.35 (except for is for which the value is 0.30).
(2) (All the electrons in the (n1)
th
shell contribute 0.85 each.
(3) All the electrons in (n2)
th
shell or lower contribute 1.0 each towards
screening constant (s)
let us calculate 'S' for Na
+
Na
+
= 1s
2
, 2s
2
p
6
Leave one electron
S = 7 0.35 + 2 0.85 = 4.15
Isoelectronic ions with same configurations are bound to have same
value of 'S'.
Let us solve the following question
Q. In Na
+
F

crystal, the interionic distance is 2.31 . If 'S' for Na

+
be equal to 4.15
calculate the radius of Na
+
as well as that of F

.
Solution:
ion
1
r
Z S

ion
C
or r
Z S

Where 'C' is simply proportionality constant

Na
C
r
11 4.5
+
=

F
C
and r
9 4.15

,
C C
or 2.31 given
6.85 4.85
+ =
C 6.56 =
CHEMICAL BONDING
Hence
Na
6.56
r 0.9576
6.85
+
= =
F
and r 1.3525

= Ans.
(ii) Melting and boiling points:
Since there are strong electrostatic attractions between the oppositely
charged ions in an ionic solid, hence their melting points and boiling
points are much higher than most of the covalent compounds in which
molecules are held by weak van der Waals attractions.
For example melting point of NaCl is 1073 K while that of Urea is 406 K.
(iii) Ionic Reactions are faster than Molecular Reactions
For example if we add some NaCl to an aqueous solution of AgNO
3
, a
white precipitate of AgCl is formed within no time.
, , , , 3 aq. aq. s 3 aq.
Ag NO Na Cl AgCl Na NO
white ppt.
+ + +
+ +
On the other hand a reaction between H
2 (g)
and I
2 (g)
to form HI
(g)
is
comparatively very slow. Reactions of covalent compounds are called
molecular reactions and these are slow because covalent bonds in
reactants are broken and then new bonds for products are formed. This
all takes time. White in case of ionic solutions ions are readily available
to react.
(iv) Electrical conduction:
Ionic solids cannot conduct electricity through them due to fixed
positions of ions in them. But in molten state or in solution phase they
are very good conductor of electricity due to the movement of ions. But
covalent solids are mostly non-conductors because neither free ions nor
free electrons are available in them for conduction of current. Some
exceptions like graphite are of course available which conduct electricity
due to mobile electrons in that.
(v) Isomorphous nature:
Those substances which have similar type of crystal structures are called
isomorphous. Many ionic compounds show isomorphism for example
FeSO
4
.7H
2
O and ZnSO
4
.7H
2
O generally isomorphous ionic solids have
CHEMICAL BONDING
same formula type, similar relative size of ions and similar polarizing
properties. Thats why BaSO
4
and KMnO
4
are isomorphous but NaClO
3
is
not with NaNO
3
.
It is because
3
ClO

is pyramidal but
3
NO

is planar.
Simple ionic compounds like Na Cl
+
(not the ionic-coordination
compounds) do not show Isomerism. It is a characteristic of many
covalent compounds.
(vi) Hard and Brittle:
Ionic solids, due to strong electrostatic attractions between oppositely
charged ions in them, are hard. But they are brittle also because due to
hammering (some force being applied) a layer of ions in the crystal
moves on the other layer such that similarly charged ions come closer to
each other, where due to repulsion between them the crystal breaks
down. Thus ionic crystals can be brought into the powered form.
Remember metals are also hard but they are ductile i.e. converted into
sheets.
(vii) Solubility :
Ionic compounds prefer a polar solvent for dissolution to a non-polar
solvent. Thats why water is he best solvent for them. However their
solubility in a solvent depends on:
1st. Dielectric constant of the solvent: It is defined as the efficiency of a
solvent to break the electrostatic attractions between oppositely
charged ions of a solute when placed in it. More is the dielectric const. of
a solvent better it is a solvent for ionic compounds Dielectric constant for
H
2
O is about 80, C
2
H
5
OH has value of 27 and C
6
H
6
only about 6 units.
2nd. Heat of salvation of ions:
Once a solute dissociates into its ions in a solvent, then these ions are
immediately solvated molecules. Solvation of ions is always an
exothermic process. If solvent is water it is called hydration. Smaller is
the size of the ion, more is the heat of salvation or hydration.
Thats why the heat of hydration of Mg
2+
is 1908 KJ mol
1
for Na
+
it is 406
KJ mol
1
and for Cs
+
it is 255 KJ mol

because as regards size Mg

2+
< Na
+
<
Cs
+
. Among the alkali and alkaline earth metal ions, the largest heat of
hydration is for Be
2+
, it being the smallest in the entire s-block (except
free H
+
).
CHEMICAL BONDING
Therefore as a general rule we can say that an ionic compound is likely to
be soluble in water of numerically.
heat of hydration of ions > lattice energy.
The dissolution of an ionic compounds may be exothermic or
endothermic, it all depends on the values of H
hydration
and H
L.E.
, as is
clear from the following table.
Table
soln.
of some ionic compounds in water
S.No. Compound H
L.E.
(KJ
mol
1
)
H
hyd.
(KJ
mol
1
)
H
(soln.)
H
hyd.
H
L.E.
(KJ mol
1
)
1. NaCl 777 773 +4
2. LiF 1033 1005 +28
3. KF 813 819 6
4. RbF 778 792 14
Thus we see that dissolution of NaCl and LiF are endothermic but dissolution of
KF and RbF are exothermic.
But an ultimate explanation for the solubility of an ionic compound can be
provided by thermodynamics where we have read that for the occurence of a
spontaneous process G must be negative.
, ,
soln. soln.
G H T S A = A A
and
, , , soln. hyd. L.E.
H H H A = A A
[Put values with sign)
As regards S
(solution)
:
Remember crystal breaking into ions and mixing of ions in water (solvent) are
both S > 0 processes. But ordering (hydration) of water molecules around the
ions is S < 0 process.
Smaller is the ion with more charge, better is the ordering of solvent molecules
around it and hence more negative is 1 charge overall
S
(soln.)
is > 0.
Thus for Na
+
Cl

, H
(soln.)
= + 4 KJ mol
1
and S
soln.
> 0.
Also T is bound to be (+) ve
TS > H
CHEMICAL BONDING
hence G for dissolution of NaCl will be ()ve. Thats why NaCl is readily soluble
in water.
Some important trends of solubility of ionic compounds in water. (Very
important frompractical point of view.)
(i) Many salts of ammonium and alkali metal ions are soluble in water
except LiF, Li
3
PO
4
, Li
2
C
2
O
4
, Li
2
CO
3
.
(ii) All nitrates and almost many perchlorates and acetates are soluble in
water except, the CsCl
4
and acetates of Ag(I) and Fe(III)
(iii) Many halides are water soluble except, chlorides, bromides and iodides
of Ag(I), Hg(I), Pb(II) and Cu(I). Remember AgF is soluble in water but
fluorides of Ca(II), Sr(II) and Ba(II) are insoluble.
(iv) Many sulphates are soluble except sulphates of Ba(II), Ag(I), Sr(II), Pb(II)
and Hg(I).
(v) NH
4
OH, alkalimetal hydroxides, Ba(OH)
2
, Sr(OH)
2
are soluble in water.
Ca(OH)
2
is slightly soluble. Other metal hydroxides are insoluble.
(vi) Ammonium and alkali metal carbonates are soluble.
(vii) (NH
4
)
2
S and alkali metal sulphides are soluble.
(viii) (NH
4
)
3
PO
4
and alkali metal phosphates are soluble.
(ix) Some solubility (g/L) order are given below:
LiF < LiCl < LiBr < LiI
LiF < NaF < KF < CsF
AgI < AgCr < AgCl < AgF
Be(OH)
2
< Mg(OH)
2
< Ca(OH)
2
< Sr(OH)
2
< Ba(OH)
2
CsClO
4
< RbClO
4
< KClO
4
< NaClO
4
< LiClO
4
BaSO
4
< SrSO
4
< CaSO
4
< MgSO
4
< BeSO
4
CHEMICAL BONDING
Part II
COVALENT BOND
We have already noted that if the difference of electronegativity between
combining elements is low then covalent bond is formed. But combining
elements both must be electronegative not electropositive like metals which
form metallic bonds the nature of covalent bond is not so simple as that of ionic
bond. Hence in this part we wish to study, nature of covalent bond and shapes of
molecules or molecular ions formed by covalent bonds. The following four
systematic attempts have been made to do this job. These are known as concepts
of covalent bonds, because it is impossible to view inside a molecule during its
formation that how the bonds are being formed. Of course the final outcome of
the formation of bonds is a molecule or molecular ion which can be analysed for
its shape and geometry with the help of many physical methods including
spectroscopy. Therefore the success of a concept lies in the fact that how much it
can explain the observed physical as well chemical properties of the covalent
compounds?
The four concepts which we must study are:
(i) Lewis concept concept of electron sharing
(ii) Valence shell electron pair repulsion (VSEPR) model
(iii) Valence Bond Theory (VBT)
(iv) Molecular Orbital Theory (MOT)
Let us begin with Lewis concept.
(i) Lewis Concept:
The first systematic approach for explaining the nature of covalent bond
was made by G.N. Lewis. According to this concept, a covalent bond
between two atoms similar or dissimilar is formed by sharing of two
electrons each providing one electron for example:
H
2
: H : H or HH
Further sharing of electrons must be such that each atom acquires an
octet of electrons around it. This is also known as octet rule. The basis of
octet rule is the stable configuration of Noble Gase.
Thus
: F : : F : : F : F : or F F +
CH
4
(Methane)
CHEMICAL BONDING
Diagram here
Octet around carbon is complete 'H' atoms can acquire only He
configuration.
But many exceptions of this octet rule were discovered for example.
BF
3
(Boron trifluoride):
Diagram here
Though octet around is 'F' is complete but not around the control atom
'B'.
NH
3
(Ammonia):
diagram here.
Here octet around 'N' is complete but not & by four bond pairs. There
are three bond pairs and a lone pair.
PCl
5
(Phosphorus pentachloride):
diagram here
There is expansion of octet around 'P'. It has a surrounding of 10
electrons.
Similarly expansions of octet are found in molecules like SF
6
and IF
7
.
Well, all the structures given above and similar are called Lewis
structures or electron dot structures. These are very helpful specially in
Organic Chemistry.
However, the main objections about this concept are that it does not
explain the nature of sharing between two similarly charged particles
and moreover does not given any clue regarding the geometry or shape
of the molecule. It dos not say any thing about the relative strengths of
different covalent bonds.
(ii) Valence-shell Electron Pair Repulsion (VSEPR) model:
This model was given by Gillespie and Nyholm. This is a simple and
reliable method for predicting the shape of molecules and polyatomic
ions. It is based on Lewis dot structures of molecules or ions and takes
into account the bond pairs (shared electron pairs) and lone pairs
present in them.
CHEMICAL BONDING
The central idea of this model is that a molecule or polyatomic ion
would be stable only when the electron pairs are so oriented that
repulsions between them is minimum.
Further, since a bond pair of electrons is concentrated in the bonding
region between the two atoms by the strong attractive forces of two
positive nuclei of the bonded atoms, hence it is relatively compact. On
the other hand for a lone pair present on an atom, there is only one
nucleus attracting this pair, hence lone pair or pairs are less compact
than bond pairs. Therefore the relative strengths of electron-pair
repulsions are
(lone pair lone pair) > (lone pair bond pair) > (bond pair bond pair)
or
LL > LB > BB
Before we proceed for predicting shapes of molecules on the basis of
VSPER model, we must clearly make a distinction between the following
two terms:
(i) Electron pair geometry or simply geometry:
It includes the spatial positions of all the bond pairs and lone pairs of
electrons around a central atom of the molecule or ion, whose structure
we wish to discuss.
(ii) Molecular geometry or shape:
It means arrangement of its atoms in space. Thus the positions occupied
by lone pairs are not specified when we describe the shape of a
molecule.
For example for Ammonia (NH
3
) the geometry is Tetrahedral but shape is
Pyramidal.
Geometrics and shapes of different types of molecules or polyatomic ions:
For this purpose let us suppose 'A' is a central atom and 'B' are atoms bonded
with it. 'L' represents a lone pair on the central atom. So following cases may
arise.
(i) AB
2
:
The central atom A is bonded with two 'B' atoms and 'A' does not have
any lone pair on it. It means there are only two bond pairs in the
molecule; the repulsion between them can be minimum only when they
are maximum far apart. Such a situation can be explained only by linear
geometry or shape of AB
2
. i.e.
B x A x B
linear geometry
linear shape
The bond angle which is defined as the angle between the two adjacent
bond pairs is 180, presently do not consider multiple bonds, we shall
have their study as and bonds later on.
AB
3
(Geometry: Triangular planar or trigonal planar)
Now there can arise following two situations.
(i) AB
3
(ii) AB
2
L
example: BF
3
SnCl
2
For BF
3
For SnCl
2
geometry and shape will geometry will be triangular
be same as shown below: planar but shape is called V-
shape as shown below: A
| 120 B B
The bond angle is expected
to be less than 120 due to
B
B
B
A
Triangular Planar unequal repulsions.
(LB > BB)
AB
4
(Tetrahedral Geometry)
Following four cases are possible.
Formula: AB
4
AB
3
L AB
2
L
2
ABL
3
Shape: Tetrahedral Pyramidal V-shape Linear
diagram here
Regular tetrahedron, bond angle 109.5
Compression by one lone pair
bond angle is less
Compression, by two lone pairs bond angle is further less than 109.5.
AB
5
Trigonal bipyramidal geometry or TBP)
Following four cases are possible.
Formula: AB
5
AB
4
L AB
3
L
2
AB
2
L
3
Shape: TBP Seesaw T-shape Linear
Example: PF
5
SF
4
ClF
3
XeF
2 (Draw images exactly as given in hard copy data)
Now before we draw their figures it is necessary to look at the geometry of
trigonal or triangular bipyramid.
As shown below there are three corners of a equilateral triangle at the centre of
which the atom 'A' is situated. The three 'B' atoms are occupying the three
corners of this triangle. The remaining two 'B' atom are above and below the
centre.
diagram here.
Thus there are two types of positions in th above geometry. The corners of the
triangle are called Equitorial positions. While the positions above and below the
centre are called Axial positions. then in order to have minimum repulsion in the
molecule, lone pair or pairs (maximum three) must occupy the equatorial
positions. Further if all the 'B' atoms are not same then more electronegative
atom/s will occupy the axial positions (This will be explained with the help of
hybridization of orbitals in VBT later on). Finally it is the nature of TBP that axial
bonds are longer than the equatorial bonds.
So now we are in a position to draw molecular shapes for all the four cases of AB
5
types. They are as shown in the following figure:
diagram here.
Fig. Molecular shape for AB
5
, AB
4
L, AB
3
L
2
and AB
2
L
3
It may be further noted that bond angles in all cases except AB
5
will deviate from
their standard values due to the presence of cone or more lone pairs. Thats why,
the equatorial bonds angle in SF
4
is 103 FClF is about 87 in ClF
3
. Ofcourse no
such problem will arise in XeF
2
due to the symmetry.
AB
6
[Octahedral geometry]
Here following three cases are possible.
Formula : AB
6
AB
5
L AB
4
L
2
Shape : Octahedral Square pyramidal Square planar
Example : SF
6
: BrF
5
XeF
4
Now it is to be noted that unlike triangular bipyramid, an octahedron has no
distinct axial and equatorial positions. Here all the six positions are equivalent.
The six 'B' atoms bonded to central atom 'A' can be placed on three axes at right
angles to one another (the x, y and z axes) and are equidistant from the central
atom.
Now in case of AB
5
L, it makes no difference, the lone pair (L) may occupy any of
the six positions. But in AB
4
L
2
, the two lone pairs must be at maximum distance
from each other so as to have minimum repulsion. This is best achieved by
placing the lone pairs above and below the square plane which contains 'A' at the
centre and four 'B' atoms at its four corners.
Therefore the figures for all the three cases can be drawn as given below:
diagram here.
Fig. : Molecular shape for AB
6
, AB
5
L and AB
4
L
2
.
AB
7
(Pentagonal bipyramidal geometry)
So far we have only two types of cases for this
Formula : AB
7
AB
6
L
Shape : pentagonal bi- distorted octahedral
pyramidal
Example : IF
7
XeF
6
A pentagonal bipyramid will have a regular pentagonal in a plane such that atom
'A' is at its centre and five 'B' atoms are occupying its five corners. The remaining
two 'B' atoms are above and below the centre of the pentagon. Thus in AB
7
type
of molecule there are two types of bond angles, 72 in the plane or say between
two equatorial bonds and 90 between an axial and a equatorial bond. Obviously
there are two types of bond lengths also.
But the structure of AB
6
L cannot be predicted correctly by VSEPR model. No
definite location of lone pair can be predicted due to over-crowding of 6 'B'
atoms around the central atom 'A'.
However the structure of an example of the type :XeF
6
is said to be distorted
octahedral as shown below:
diagram here.
pentagonal bipyramidal structure of IF
7
Distorted octahedral structure of : XeF
6
.
(iii) Valence Bond Theory (model) or VBT
This theory was mainly developed by Pauling. According to this theory:
(a) A covalent bond between two atoms is formed by maximum partial
overlapping of two orbitals, each atom providing one orbital containing
one electron. The overlapping means to form a region between the
nuclei of the two atoms in which the probability of finding shared
electrons (bond pair) is maximum.
(b) More is the extent of overlapping, stronger is the bond.
(c) If two atomic orbitals overlap along the molecular axis (the line joining
the nuclei of two bonded atoms) the bond formed is called and if they
overlape perpendicular to the molecule axis, the bond formed is called
.
(d) bond is stronger than .
(e) If there is overlapping between a filled and a vacant orbital then a
coordinate bond is for.
On the basis of above points, e can explain the formation of molecules like H
2
,
HCl(g) and Cl
2
as given below:
H
2
(SS overlapping) : as shown in the figure below:
diagram here.
HCl gas molecule (s-p overlapping)
H = 1s' Cl = 1s
2
, 2s
2
p
6
, 3s
2
p
5
Z = 1 Z = 17
|+ |+ |
Thus we see that H-atom has 1s orbital available for overlapping and Cl-atom has
one of the 3p orbitals (containing one unpaired electron) available for
overlapping. The '3p' orbital may be 3p
x
or 3p
y
or 3p
z
.
If we consider X-axis to be the molecular axis then the orbital or Cl available for
overlapping or bonding will be called a 3p
x
orbital. This overlapping is shown in
the figure below:
diagram here.
Cl
2
molecule (p-p overlapping) : It is shown in the figure given below :
diagram here.
NOTE:
(i) In all the above three cases we are getting one single bond along the
molecular axis. Hence each bond is a
between two atoms in always a
(ii) The overlapping between two atomic orbitals will take place only when
the sign of their wave functions are same. e.g. following overlapping are
not permitted.
diagram here.
Net overlape = Zero Not allowed.
(iii) Provided the principal quantum numbers of s & p orbitals are same, the
extent of overlapping has the order.
p p p s s s
o
o o
> >
But this concept of overlapping of pure orbitals cannot explain the molecular
geometry, bond strengths etc. of all the molecules.
For example let us consider the case of BeF
2
molecule. According to VSEPR model
we have seen that it must be a linear molecule. Let us now develop its structure
with the help of orbital overlapping.
Be = 1s
2
, 2s
2
p
0
Z = 4 |+ |+
(ground state)
Since Be atom has to form two covalent bonds with two fluorine atoms, hence it
must have two unpaired electrons. For this it is supposed that Be atom is first
excited by promotion of a electron from 2s to 2p subshell. The energy needed for
this excitation will be compensated by the energy released due to formation of
bond. We will have to do such excitations at many places in future examples but
one thing in certain that excitation of electron/s with change in principal
quantum number (n) is not permitted because it requires much more energy
which cannot be compensated by bond energy.
Thus,
Be = 1s 2s 2p
Z = 4 |+ | |
(excited state)
and F = 1s
2
, 2s
2
p
5
Z = 9 |+ |+ |
So each 'F' atom has a '2p' orbital say 2p
x
(x-axis being molecular axis) which
contains unpaired electron.
Hence BeF
2
can be viewed as, Be forming two covalent bonds around it linearly
by overlapping of 2s orbital of Be with a 2p orbital of F on one side and 2p orbital
of Be with a 2p orbital of another 'F' on the other side, s shown in the figure
below:
F (2p2s) Be (2p2p) F
Since p-p overlape is more than s-p overlape hence in BeF
2
molecule the two Be-F
bonds must be of different strengths. Is it so really? The answer is no.
Then, how to make the two bonds of equal strength? The only solution is that Be
must provide similar orbitals on both sides of it along the molecular axis to
overlape equally on both sides with 2p orbitals of two 'F' atoms.
To solve such problems, Pauling proposed the concept of hybridization of atomic
orbitals.
According to that, in the case of BeF
2
, if 2s and 2p orbitals of Be combine to form
two new orbitals each possessing 50%, 50% 5 & p character and be linearly
arranged about the Be atom to overlape with 2p orbital of F atoms, then both the
bonds will be of equal strength. Such a mixing of a s-orbital with a p-orbital of the
same atom is called sp hybridization.
So let us now first understand the main points of hybridization of orbitals.
Hybridization of atomic orbitals:
(i) It is a hypothetical concept.
(ii) Only those orbitals of an atom whose energies are comparable take part
in this concept.
(iii) It is a concept of mixing of orbitals, hence it is immaterial whether
orbitals are empty or possess single electron or even pair.
(iv) The number of hybrid orbitals produced will be equal to the total
number of orbitals taking part in hybridization.
(v) The hybrid orbitals produced as result of some type of hybridization will
be of same energy (degenerate).
(vi) The electrons possessed by parent orbitals will be filled in he newly
formed hybrid orbitals according to Hund's rule.
(vii) All hybrid orbitals have directional character i.e. these will be directed in
the space about the atom depending on the type of hybridization.
Since hybrid orbitals can overlape (due to specific direction) to a larger
extent than the pure orbitals, hence bonds formed by hybrid orbitals are
stronger and directional. Following table gives the geometries of
different types of hybridization.
Table (Geometry of different hybrid orbitals)
diagram here.
sp Linear
sp
2
Planar
sp
3
Tetrahedral
sp
3
d Trigonal bipyramidal
sp
3
d
2
Octahedral
NOTE:
(i) Besides sp
3
d
2,
sp
3
d
3
hybridization is also possible; the seven hybrid
orbitals thus produced are directed towards the seven corners of a
pentagonal bipyramid from its centre.
(ii) In case of hybridizations involvingd orbitals i.e. sp
3
d, sp
3
d
2
and sp
3
d
3
,
can also be presented as dsp
3, d+2
sp
3
and d
3
sp
3
respectively for simple
covalent compounds. But in case of metal complexes (coordination
compounds) these will have a difference that in former outer d orbital/s
and in later innerd orbital/s will be used.
(iii) Though in most of the cases, -bonds are formed by pure 'p' ord
orbitals (s-orbitals do not form -bonds) but in some rare cases, hybrid
orbitals can also form -bonds.
(iv) If we can draw Lewis dot structure for a molecular or polyatomic ion,
then the type of hybridization, the central atom will show can be decided
by Steric Number Rule which was given by Gillespic. According to this
rule:
Steric Number of an atom = number of atoms immediately bonded
with that atom + number of lone pairs of electrons on that atom.
(This rule does not work for odd electron molecules and free radicals)
Thus steric number of Nitrogen in NH
3
according to Lewis dot structure is
diagram here.
= 3 + 1 = 4
For 'S' in SO
2
i.e. = 2 + 1 = 3
For 'Xe' in XeF
2
i.e. = 2 + 3 = 5
and so on.
Steric numbers are generally calculated for the central atom of the molecule
because that decides the geometry of the molecule.
Steric number is related to hybridization in the following manner.
Steric Number hybridization
2 sp
3 sp
2
4 sp
3
5 sp
3
d
6 sp
3
d
2
7 sp
3
d
3
Now we shall discuss the individual steric number and the corresponding
hybridization.
sp hybridization (steric No. = 2)
Geometry = Linear; shape = Linear
standard Bond angel = 180
Some examples are given below with their structures:
Example Structure
BeF
2
FBeF
CO
2
O = C = O
CO O C =

C
2
H
2
HC H
CH
2
(Triplet carbine) HCH
N
2
: N
3
N

(azide ion)

sp
:N: N N:
+
= =
2
NO

(nitronium ion) O N: O
+
=
Miscellaneous examples:
SiH
3
HCO (silyl isocyanate)
CH
3
CN ( ethane nitrile or methyl cynide)
sp
2
hybridization (steric No. = 3)
In this, as discussed earlier in VSEPR model following two types of cases are
available.
(i) AB
3
(ii) AB
2
L
geometry: Triangular planer Triangular planar
shape: Triangular planer V-shape
ideal bond angle 120 bond angle < 120
Some example of AB
3
type in which 'A' os central atom which is sp
2
hybridised
are given below:
C
2
H
4
H H
C = C
H H
sp
2
sp
2
C
4
H
6
each (c) is sp
2
2
3
CO

O
||
O

Graphite an allotrope of carbon in

which each (c) is sp
2
(detailed study in IV group
of p-block)
BF
3
F
|
B
F F
SO
3
O
||
S
O O
3
NO

O
NO

O
(oxy acids of Nitrogen)
Some examples of AB
2
L type are : (all with V-shape)
: CH
2
(singlet carbine) C
SO
2
S
O O
SnCl
2
Sn
Cl Cl
NOCl N
Cl O
O
3
O
O O
2
NO

NO

O
Some miscellaneous examples are:
B
3
N
3
H
6
(inorganic benzene or borazine)
(SiH
3
)
3
N (trisilylamine) N
3
H (hydroazoic acid)
CH
3
CONH
2
(acetamide)
H
3
BO
3
(boric acid) FNO
3
(fluorine nitrate)
CH
3
NCO (methyl isocyanate) ClO
2
(Chlorine dioxide)
sp
3
hybridization (steric No. = 4)
Geometry: Tetrahedral; standard bond angle 109.5
Shapes: AB
4
(Tetrahedral) e.g. CH
4
AB
3
L (Pyramidal) e.g. NH
3
AB
2
L
2
(V-shape) e.g. H
2
O
ABL
3
(linear) e.g. ClO

Examples:
Central atom (sp
3
) Examples
Be [BeF
4
]
2
B
4
BF

C alkanes, : CH
3
, diamond, CCl
4
Si SIO
2
, SiCl
4
, silicates like
[Si
3
O
9
]
6
etc.
N
3 4 3 2 2 2
hydrazine
NH , NH , NF , NH , NH NH
+
NH
2
OH,
P
4 4 6 4 10 4
P , P O , P O , PCl ,
+
oxyacids
of phosphorus, POCl
3
O H
2
O, H
2
O
2
, O
2
F
2
S S
8
, SCl
2
, H
3
S
+
, (CH
3
)
2
SO, SOCl
2
,
SO
2
Cl
2
, oxyacids of sulphur
Cl oxyacids of chlorine (in general
(halogens) halogen), Cl
2
O, OF
2
Xe XeO
3
, XeO
4
Miscellaneous examples:
Borax anion [B
4
O
5
(OH)
4
]
2
B
2
H
6
(diborane)
sp
3
d hybridization (steric No. = 5)
Geometry: triangular bipyramidal
standard bond angles 120 and 90
Shapes: AB
5
(Trinagular bipyramidal) e.g. PF
5
, P
AB
4
L (seesaw) e.g. SF
4
, XeO
2
F
2
AB
3
L
2
(T-shape) e.g. ClF
3
,
3
XeF

AB
2
L
3
(Linear) e.g. XeF
2
,
3 2
I , ICl

As we have already read in the study of VSEPR model that in TBP structure there
are two types of positions, equatorial (E) and axial (a). The lone pair/s always
occupy (E) and more electronegative atom/s prefer axial positions.
Thus the structures of some of the examples are:
PCl
5
(g):
diagram here
means covalent bond direction of lone pair.
PCl
3
F
2
:
diagram here
SF
4
:
diagram here
Shape: seesaw, decrease in the equatorial bond angle is due to presence of lone
?????.
ClF
3
:
diagram here.
Shape: T-shape.
XeF
2
:
diagram here.
Shape: Linear.
In all examples of sp
3
d (or dsp
3
) hybridization the five orbitals of the central atom
i.e. s + p + p + p + d combine to form five new hybrid orbitals which are direct
towards the five corners of a TBP.
sp
3
d hybridization involves
2
z
d orbital.
Thus it can be considered as made up of two parts:
, , 2
3
z x y
z
Equitorial axial
sp d p d s p p = + + + +

According to Bent Rule, more negative substitutes prefer hybrid orbitals having
less 'S' character because more is the 'S' character more is the electronegative
character. Hence more electronegative atoms prefer axial positions to equatorial
position.
However if more negative atoms are there i.e. more than two then the third will
naturally occupy one of the 'E' positions. e.g. PCl
2
F
3
will be represented as shown
below:
diagram here.
Well! as regards the positions of lone pairs, we know they occupy 'E' positions
but not axial, why?
Let us consider the case of ClF
3
.We can draw following three structures for it.
diagram here.
We know (c) is considered to be the correct structure. But why this is so? The
answer can be provided if we consider the quantum of repulsions in each
structure. Thus,
In structure (A):
Repulsions are due to:
LL (One) at 180
LB (Six) at 90
BB (Three) at 120
In structure (B):
LL (One) at 90
LB (Three) at 90
and (Two) at 120
BB (Two) at 90
and (One) at 120
In structure (C):
LL (One) at 120
LB (Four) at 90
and (Two) at 120
BB (Two) at 90
Now since LL repulsions are most forceful and less is the angle more is the
repulsion. Hence the structure (B) can be quickly eliminated because it has one L
L repulsion at 90.
Now the choice lies between (A) & (C). Both these have one LL repulsions at
180 and 120 respectively. But then (C) has only 4 LB repulsions as compared to
(A) which has 6 LB repulsions. Obviously the structure (C) must represent
minimum repulsion and hence maximum stability.
This explains, why lone pairs do not occupy axial positions in sp
3
d hybridization.
sp
3
d
2
hybridization (Steric No. = 6)
Geometry: Octahedral
Standard bond angle: 90
Shape: AB
6
(Octahedral)
e.g.
,
2 3 4
6 6 6 6 6
perxenate ion
SF , PF , SiF , AlF , XeO

( ( (

AB
5
L (square pyramidal)
e.g. BrF
5
, XeOF
4
AB
4
L
2
(square planar)
e.g. XeF
4
, [ICl
4
]

sp
3
d
2
or (d
2
sp
3
) hybridization involves
,
2 2 2
x y z
x y z
s p p p d d

+ + + + + orbitals of the central atom.

Since an octahedron has all its six corners equivalent hence presence of cone
lone pair may be anywhere but when there are two lone pairs then they must be
at maximum distance.
With these things in mind, let us drain the structures of some of the examples
listed above.
SF
6
:
diagram here.
Shape: Octahedral.
BrF
5
:
diagram here.
Shape: Square pyramidal.
XeF
4
:
(Xenone tetrafluoride)
diagram here.
Shape: Square planar.
sp
3
d
3
hybridization (Steric No. = 7)
Geometry: Pentagonal bipyramidal
Standard bond angles: 72 and 92
Shapes: AB
7
(pentagonal bipyramidal) e.g. IF
7
AB
6
L (distorted octahedral) e.g. XeF
6
sp
3
d
3
or d
3
sp
3
hybridization involves
,
x y z xy yz zx
s p p p d d d + + + + + + orbitals of the central atom.
Structure of IF
7
(iodine heptafluoride) is as shown below:
diagram here.
Structure of XeF
6
(Xenone hexafluoride):
It has been very difficult to determine the structure of XeF
6
(g). It is supposed
that the lone pair can acquire any position hence it looks like a distorted
octahedron. Another suggestion is that Xe atom is situated at the centre of an
octahedron and six 'F' atoms occupy its six corners as usual. The lone pair in one
of the sp
3
d
3
hybrid orbital of Xe is directed towards one of the faces of this
octahedron as shown below. So it is as distorted octahedron.
diagram here.
distorted octahedron
Otherwise XeF6 solid is found to be an ionic compound consisting of [XeF
5
]
+
units
interlinked through F

. The structure of [XeF

5
]
+
cation will be square pyramidal
due to sp
3
d
2
hybridisation.
NOTE:
Now we shall try to answer some important questions related to some p-block
compounds. The answers will be based on the structure of compounds. We shall
not repeat these explanations later on when we study p-block compounds in the
next chapter.
1 Chemistry 19 September
Some Important Questions and their Answers:
Q.1. Azide ion
,
3
N

is linear but hydroazoic acid (N

3
H) is a bent molecule, why?
Ans. This can be explained by drawing their structures and noting the
hybridization of central atom. Thus,
In
3
N

, the central 'N' is sp hybridized hence it is linear.

sp
2
sp sp
2
Bh = 1.16 , Bh = 1.16
(Bond length)
But in N
3
H, one of the terminal 'N' is attached to 'H' and that (N) is sp
2
hybridized, as shown in the figure:
H 112
N N N
+
= =
sp sp
2
sp
2
1.24

1.13

Q.2. Compounds SiH

3
NCO and CH
3
NCO appear to be similar but their structures
are not same, why?
Ans. The structure of methylisocyanate CH
3
NCO is
H
HCN
H sp
3
sp
2
C
sp
O
Since steric number of 'N' is three hence it is sp
2
hybridized, so CNC angle
cannot be 180. 'N' atom has a lone pair on it. Hybridizations of other has a
lone pair on it. Hybridizations of other atoms are also shown in the above
structure.
Now let us draw the structure of SiH
3
NCO (silylisocyanate). If we draw it at par
with CH
3
NCO then it must be
H
HSiN = C = O
H
2 Chemistry 19 September
But lone pair on 'N' won't allow it to be linear the fact is that, it is linear and 'N'
atom does not possess lone pair. How this is possible? This is possible by
donation of lone pair by 'N' to Si, which has all its '3d' orbitals vacant. This type
of donation which is some times also known as back bonding, will form a -
bond of coordinate nature and is called d -p
hybridization state with a filled 'p' orbital as shown below:
N =
Z = 7
|+ | | | |+
s p p p
sp hybridization
used for p

bond with carbon atom

used for p

bond or Si
Therefore the correct presentation of SiH
3
NCO will be
H d

HSiN = C = O
H sp
3
sp sp
Hence the part of the molecule from Si to O is linear. This type of d p
bonding is not possible in CH
3
NCO because carbon atom does not have any
vacant orbital and moreover it cannot have 'd' orbital in it.
Q.3. Which is a better electron pair donor (Lewis base) and why?
CH
3
NH
2
or CH
3
CN
Ans. Let us compare their structures:
H H
HCN
H H
sp
3
; ('s' is 25%)
H
HCC
H
sp; ('s' is 50%)
Remember more is thes character in the hybridization more is the
electronegativity of that atom and less will be the tendency to donate the
electrons. Hence CH
3
NH
2
is a better donor.
3 Chemistry 19 September
Q.4. The two -bonds in the molecule of CO
2
are coplanar or not. Explain.
Ans. No, they are not coplanar but they are in perpendicular planes, because if
x-axis is the molecular axis then one -bond is formed by p
y
p
y
overlape and
the other by p
z
p
z
.
Q.5. In BF
3
molecule, the BF bond length is found to be less than expected
single bond length. Why?
Ans. Since 'B' in BF
3
is sp
2
hybridized hence it possesses a vacant 'p' orbital,
which can form back bonding (p

) with filled 'p' orbital of F.

This is possible partly with each 'F' atom. It is called delocalized bonding.
Hence each BF bond develops parial double bond character which reduces
the bond length as shown in the figure below :
F
|
B
F G
p p delocalised bond.
Q.6. (SiH
3
)
3
N is planar but (CH
3
)
3
N is not, why?
Ans. The structure of (CH
3
)
3
N (trimethylamine) is as given below:
H
3
C CH
3
N sp
3
(pyramidal shape)
|
CH
3
But in (SiH
3
)
3
N (trisilylamine), 'N' atom does not possess the lone pair, rather it
forms delocalized p d bonding with vacant 'd' orbitals of 'Si' atoms as
shown below:
SiH
3
N
H
3
Si SiH
3
sp
2
.means p d bond (delocalized)
(All the three Si atoms and N atom are in the same plane)
But this is not possible in (CH
3
)
3
N, as (C) atoms do not have vacant orbitals.
Q.7. CO
2
is linear but SO
2
is bent, why?
Ans. It is clear from the hybridization of central atom.
O = C = O
sp
4 Chemistry 19 September
linear
S
O O
bent
Q.8. Why the 'N' atom in CH
3
ONH
2
or in general RCONH
2
(alkanamide) is said t
be in sp
2
hybridized state?
Ans. At first glance the structure of ethanamide CH
3
CONH
2
would be
O H
CH
3
CN
H
Therefore 'N' atom must be in sp
3
hybrid state. But RCONH
2
exhibit following
properties:
(i) There is not free rotation possible about CN bond.
(ii) CN bond length is 1.32 , while the standard CN single bond length is
1.47 .
these observation can be explained if there is double bond between C and N in
CONH
2
group. Infact RCONH
2
is a resonance hybrid of following two
structures:
O H O H
CN
R H R H
sp
2
Q.9. In
2
3
CO

ion, all the CO bond lengths are same or different? Explain.
Ans. These are same, each of 1.29 . Infact standard CO single bond length is
1.43 and C = O is 1.22 . This suggests that
2
3
CO

must be a resonance hybrid
of the following structures.
O

O O

O = C
O O O O O
Q.10. Which of the following is correct with respect to C
O bond length.
(A) COF
2
> CH
3
COCH
3
(B) COF
2
< CH
3
COCH
3
(C) COF
2
= CH
3
COCH
3
(D) COF
2
does not exist hence comparison cannot be done.
5 Chemistry 19 September
Ans. The correct answer is (A). Because in COF
2
partial double bond character
in both CF bonds due to delocalized overlapping between a filled 'p' orbital
of F and vacant 'p' orbital of C, weakens the CO bond and hence its length
increases. This is also known as Synergy Effect. While this is not possible in
CH
3
C = O
CH
3
Q.11. Which is are true about Fluorine nitrate FNO
3
?
(A) Oxidation state of 'N' in it is +5
(B) It contains FN bond
(C) It contains OO bond
(D) It contains a peroxide group.
Ans. The correct answer is (A) only. Its strcture is
O O
F N
O
(sp
2
)
Q.12. Which is a stronger Lewis base NH
3
or PH
3
(Phosphene) and why?
Ans. In NH
3
, 'N' atom is sp
3
hybridized and the lone pair is present in a sp
3
hybrid orbital
N = |+ |+ | | |
Z = 7 s p p p
sp
3
hybridization
|+ | | | all sp
3
and degenerate
in sp
3
(directed) ['S' character
N
H H
H
bond angle
On the other hand the bond angle in PH
3
is about 93.5 which suggests that 'P'
is not hybridized he.
Hence lone pair on 'P' in PH
3
is present in pure 'S' orbital which is compact due
to its spherical nature.
6 Chemistry 19 September
Hence PH
3
cannot donate its lone pair so easily as NH
23
can do through its sp
3
hybrid orbital.
This is ome times known as Drago's rule according which of central atom is in
III period or below in periodic table and electronegativity of atoms attached to
that is < 2.5 then the lone pair will remain inactive in 'S' orbital.
Q.13. The observed NF bond length in NF
3
is found to be more than expected
single bond length. Why?
Ans. This is due to repulsion between lone pair on N and lone pairs on F atoms.
N
F F
F
repulsion
Q.14. In which OO bond length is more and why H
2
O
2
or O
2
F
2
(dioxygen
filuoride)
Ans. Hydrogen peroxide (H
2
O
2
) and dioxygen difluoride (O
2
F
2
) have similar
book like structures.
H F
O O
more repulsion
O O
H F
But bond polarities are in opposite directions. Thus electron pair density on the
two oxygen atoms are more in H
2
O
2
hence repulsion between them increases
OO bond length in H
2
O
2
.
Q.15. The structure of Caro's acid H
2
SO
5
(peroxy monosulfuric acid) is as given
below:
O
HOSOOH
In the first step dissociation this acid which H ( liberated as H
+
?
Ans. The correct answer is '
stable due to charge delocalization (resonance).
Q.16. Which of the following groups contains all its members, paramagnetic?
(A)
2 3
NO, NO , O , CO

(B)
2 3 2 2
O , O , ClO , NO

7 Chemistry 19 September
(C)
2 3 3 3
SO , SO , O , N

(D)
2 2 2
CO , NOCl, Cl O, XeF
Ans. The correct answer is (B)
O
2
molecule is paramagnetic with 2 unpaired electrons.
This cannot be explained by VBT. It will be discussed in the study of MOT.
Others can be identified by their structures.
3
O

(ozonide ion) O
O sp
3
O
number of unpaired electron/s
= 1
ClO
2
(chlorine dioxide) Cl
O O
sp
2
= 1
NO
2
(nitrogen dioxide monomer)
N
O O
= 1
Q.17. How many and bonds are there in a molecule of 1, 3, 5-
Pentanetricarbonitrile.
Ans. Draw its structure and you will find that there are 19
Q.18. Which of the following molecule/ion will have square-pyramidal shape?
(A) [IOCl
4
]

(b) [ICl
2
]
+
(C) FClO
3
(D) XeO
2
F
2
Ans. The correct answer is (A), whose structure is given below:
O
Cl Cl
I
Cl Cl
sp
3
d
2
hybridization.
Q.19. Which of the following reactions is/are almost impossible to occur as per
balanced equations given below:
(A)
3
3 3 2 3 3
H BO 3H O 3H O BO
+ +
+ +
(B)
,
3 3
CF I OH aq. CF OH I

+ +
8 Chemistry 19 September
(C)
4 2 2 3
CCl 3H O H CO 4HCl + +
(D)
, ,
3 3 3 3
3 3
SiH N BF H Si N BF
(
+

Ans. The correct answers is (A), (B), (C) and (D).
Infact none of the above reaction can take place as given above because
H
3
BO
3
(aq.) is a monobasic acid, the bond polarities in CF
3
I does not allow I

to
be released. CCl
4
does not have vacant orbital with (C) so as to interact with
H
2
O.
In (SiH
3
)
3
N, 'N' does not have lone pair due to p d bonding.
Comprehension (I)
Paragraph for Questions No. 20, 21, 22.
According to VBT the percentage of 'S' character in sp, sp
2
and sp
3
hybridizatinos is 50, 33.3 and 25 respectively. But this not true completely for
all species. Depending upon the bond angle (
sp hybrid orbital can be calculated with the help of following formula:
s p 1
cos
s 1 p

u = =

Q.20. In which the s% is maximum. Given

cos 109.5 = 0.3338, cos 107 = 0.29
(A) NH bond in NH
3
(B) PH bond in PH
3
(C) PF bond in PF
3
(D) All have equal s%
Ans. The correct answer can be found out if we know the bond angles which
are
3
,
3
and
3
3
:
s
0.29
s 1
=

s 0.224 or 22.4% =
Further as '
The bond angle in PH
3
and PF
3
both are less than NH
3
hence s% will be less.
Hence correct answer is (A).
On PH
2
it is -orbital.
Q.21. On the basis of your answer of Q.No. 20, which of the following is
correct?
(A) PH
3
is stronger Lewis base than NH
3
9 Chemistry 19 September
(B) NH
3
is stronger Lewis base than PH
3
(C) They are equally strong Lewis bases
(D) PH bond is more polar than NH.
Ans. The correct answer is (B) (refer to Q.No. 12)
Q.22. s% in Phosphorus-halogen bond will be in the order.
(A) PF
3
< PCl
3
< PBr
3
< PI
3
(B) PF
3
> PCl
3
> PBr
3
> PI
3
(C) PF
3
= PCl
3
= PBr
3
= PI
3
(D) None of these
Ans. The correct answer is (A), because in the series PF
3
, PCl
3
, PBr
3
, PI
3
the
bond angle increases. And as '
bond angles are:
PF
3
PCl
3
PBr
3
PI
3
Q.23. In which of the following sets, each member shows 'sp' hybridization of
all its 'c' atoms?
(A) CaC
2
CH
2
(Triplet), (CN)

(B) C
6
H
6
, CH
3
, CH
2
(singlet)
(C) CO
2
, C
2
H
2
, HCN
(D) C
3
O
2
, CO
3
2
, C
2
H
4
Ans. The correct answers are (A) and (C).
Q.24. Which of the following is non-linear.
(A)
3
I

(B)
3
N

(C) XeF
2
(D) SO
2
Ans. The correct answer is (D), SO
2
is a bent molecule with the following
structures. Sulphur is sp
2
.
S S
O O O O
Comprehension (II) [A Quiz]
An element 'J' belongs to 's'-block and another 'Q' belongs to 'p'-block of the
periodic table such that the sum of their atomic numbers in equal to the
atomic number of an element 'X' which belongs to '3d' series of the periodic
table. In the ground state electronic configuration of 'X', the total number of
10 Chemistry 19 September
electrons for which sum of quantum numbers i.e. (n + l) equal to 5.0, is eight.
The element 'J' forms a series of three compounds (R, S, T) with oxygen such
that oxidation number of oxygen increases from R
element 'Q' forms two compounds (G, H) with oxygen in which oxidation
number of oxygen decreases from G to H. The ionic compound JQ is such that
its aqueous solution does not give any precipitate with AgNO
3
solution.
Now answer the following questions:
Q.25. Identify the elements J and Q and the compound JQ.
Q.26. Write the formula of the compounds R, S, T, G and H.
Q.27. What is atomic number of element X?
Solution: The element 'J' can 'K' (Potassiumj) and 'Q' can be F (Fluorine). So
that sum of their atomic numbers become 19 + 9 = 28. Also compound JQ
becomes KF which does not give any precipitate with AgNO
3
(aq.) because AgF
is water soluble. the element X must be Ni (Z = 28) so that
Ni = 1s
2
, 2s
2
p
6
, 3s
2
p
6
d
8
, 4s
2
Z = 28
|+ |+ | | |
For these eight electrons n = l = 3 + 1 = 5
No other electron has n + l = 5
Thus the compounds R, S & T become
K
2
O K
2
O
2
KO
2
Potassium : oxide peroxide superoxide
O.No. of oxygen 2 1 0.5
The compounds G & H will be OF
2
and O
2
F
2
respectively. Oxidation number of
O in OF
2
is +2 and that in O
2
F
2
is +1.
(iv) Molecular Orbital Theory (MOT)
This theory was given by Mulliken. One important limitation of VBT was that is
could not explain the paramagnetic nature of O
2
. MOT is superior to that in this
respect, l it explains the paramagnetic nature of O
2
.
MOT is based on an important principle known as linear combination of atomic
orbitals i.e. LCAO.
The important points or principles of MOT are as follows:
11 Chemistry 19 September
(i) When two atoms combine to form a molecule then their orbitals
undergo linear combination. This combination will be most effective
when the combining orbitals are of similar energy. Thats why in the
formation of a homonuclear diatomic molecule the '1s' orbital of one
atom will combine with '1s' orbital of another atom and so on. Thus
when two atomic orbitals combine they produce two new molecular
orbitals (m.o.).
(ii) Since an atomic orbital is represented by
linear combination of two atomic orbitals means a linear combination
of two atomic orbitals means a linear combination of two
Or more qualitatively we assume that two electron waves interfere
with one another. Since interference can be constructive or
destructive so linear combination of their wave function can be
addition or subtraction.
Therefore if we suppose
a
and
b
be two wave functions then, they
may combine to give two new wave functions as (
a
+
b
) and (
a
~
b
)
(
a
+
b
) will represent bonding molecular orbital. It will be of lower
energy than the average every of
a
&
b
.
But (
a
~
b
) will represent antibonding molecular orbital and its
energy will be higher than the average of atomic orbitals. Infact this
upward energy displacement is slightly greater than the downward
displacement. The antibonding m.o. is identified by putting an asterisk
(*) on its symbol as we are going see soon after.
A bonding molecular orbital is such that electron density increases in
the internuclear region hence the repulsion between the two nuclei is
minimum. that's why it is of lower energy and more stability. It
contributes towards bonding.
But there is a node at the centre of an antibonding nolecular orbital
which reduces the electron density in the internuclear region hence
the electron repulsion between the two nuclei is maximum. Thats
why its energy is higher and stability is less.
In other words it works against bonding, hence the name.
A pictorial presentation of linear combination of 's' and 'p' atomic orbitals is
shown below:
diagram here.
12 Chemistry 19 September
Fig. : Bonding and antibonding bonding molecular orbitals obtained from the
mixing of s and p-orbitals. Note that x-axis is taken as molecular axis hence 2p
x
+ 2p
x
mixing is forming
y
+ 2p
y
and 2p
z
+ 2p
z
(which is
not shown above) will mix similarly to form orbitals.
(iii) A molecular orbital may be further gerade (means symmetrical) or
ungerade means anti-symmetrical. If
moving equal distance from the centre of internuclear region then it is
ungerade otherwise gerade. For example consider.
1s or in general any
diagram here.
nodal plane
We find that on moving equal distances from the centre of nodal plane
in the opposite direction if
m.o.
becomes positive on the left ten it
become negative on the right or vice verse. Hence
m.o. In this manner we can decide their nature. The results will be:
x
gerade
x
ungerade
y
or
z
ungerade
y
or
z
gerade
NOTE:
The principal quantum number may be any other high number but
shape and characgters will remain same. Mind it we have selected x-
axis as molecular axis, thats why p
y
and p
z
are forming -m.o.
(iv) Each molecular orbital irrespective of its nature will behave like an
atomic orbital i.e. it cannot accommodate more than two electrons in
it and that with antiparallel spin as demanded by Pauli exclusion
principle.
(v) For a diatomic molecule in this manner a set of various molecular
orbitals is obtained which are arranged in the increasing order of
energy. Then the total number of electrons of both the atoms are fed
into these molecular orbitals from the molecular orbital of lowest
energy level to higher and higher till all the electrons are exhausted.
During this course Hund's Rule is obyed wherever needed.
13 Chemistry 19 September
(vi) Finally the bond order for the molecule is calculated by the formula:
Bond order =
b a
N N
2

Where N
b
and N
a
means total number of bonding and antibonding
electrons in that molecule. The bond order may come out to be zero,
an integer or even fractional but never negative.
So now we can draw molecular orbital energy level diagrams for various
homonuclear diatomic molecules.
diagram here.
or the molecular orbital configurationof hydrogen molecule can be written as :
H
2
=
2
,
0
From this we derive that
(i) Bond order in H
2
=
2 0
1.0
2

=
(ii) H
2
molecule is diamagnetic as there is no unpaired electron with the
molecule.
diagram here.
2 2
B.O. Zero
2

= =
It means He
2
molecule has no net stability. Indeed it has not been possible to
form He
2
molecule.
diagram here.
2 2 2 0
2
Li 1s , *1s , 2s , *2s = o o o o
4 2
B.O. 1.0
2

= =
Li
2
molecule is diamagnetic. Practically Li
2
molecules have been observed in the
gas phase.
Now we need not to draw a complete diagram for then next molecule Be
2
. It
will be of the same nature as given above for Li
2
. But total number of electrons
being eight [
configuration of Be
2
will be
14 Chemistry 19 September
2 2 2 2
2
Be 1s , *1s , 2s , *2s = o o o o
4 4
B.O. Zero
2

= =
2
is not possible or not stable at all, like He
2
.
So far we have drawn configurations for molecules H
2
, He
2
, Li
2
and Be
2
. But if
we are asked to draw configurations of their cations, then how to draw them
the answer is very simple, we have to first draw the configuration of parent
molecule and then remove the required number of electron or electrons from
the highest occupied m.o. downwards. For anions add e upwards.
Therefore:
1 0
2
1 0
H 1s , *1s ; B.O. 0.5,
2
+

= o o = = paramagnetic
2 1
2
2 1
H 1s , *1s ; B.O. 0.5,
2

= o o = = paramagnetic
2 1
2
2 1
He 1s , *1s ; B.O. 0.5,
2
+

= o o = = paramagnetic
Infact all the above species have been found to exist under some special
circumstances. Since less is the bond order less must be the bond energy and
more bond length. The observed facts are in accordance with it e.g.
Species Bond Energy (KJ mol

) Bond length (pm)

H
2
432 74
2
H
+
255 106
2
He
+
230 108
From these data, it is also clear that relatively
2
H
+
is more stable than
2
He .
+
Now although in the sequence we must draw configurations for B
2
, C
2
, N
2
, but
due to some scientific reason we wish to deal with O
2
, F
2
and Ne
2
before B
2
, C
2
and N
2
. We shall certainly learn in brief the reason also.
So let us draw configuration for O
2
.
diagram here.
NOTE:
X-axis is taken as molecular axis.
15 Chemistry 19 September
2
can be written as
O
2
=
2
,
2
,
2
,
x
2
,
, ,
2 2 1 1
y z y z
2p , 2p , *2p , *2p , *2 t t t t o
At this stage we can introduce two new terms which are:
'HOMO' means highest occupied molecular orbital 'LUMO' means lowest
unoccupied molecular orbital.
Therefore in O
2
molecule 'HOMO' level has two diagenerate orbitals which are
y
and
z
. And the LUMO level is
x
. Infact these terms are applicable
for all electronic configurations in terms of molecular orbitals. You will realize
their significance soon.
Well, so for O
2
we find that Bond order is
10 6
2.0
2

=
And a very important achievement of MOT is that we find two unpaired
electrons in its configuration hence it is paramagnetic.
Now let us draw configurations of some important anions and cations of O
2
.
2 2 2 2 2
2 x
O 1s , *1s , 2s , *2s , 2p ,
+
= o o o o o
, ,
2 2 1 0
y z y z
2p , 2p , *2p , *2p , *2 t t t t o
10 5
B.O. 2.5
2

= =
and it is paramagnetic with one unpaired electron.
2 2 2 2 2
2 x
O 1s , *1s , 2s , *2s , 2p ,
++
= o o o o o
, ,
2 2 0 0
y z y z
2p , 2p *2p , *2p
, , *2
HOMO LUMO
t t t t
o
10 4
3.0, Diamagnetic
2

=
2 2 2 2 2
2 x
O 1s , *1s , 2s , *2s , 2p ,

= o o o o o
, ,
2 2 2 1
y z y z z
2p , 2p , *2p , 2p , *2p t t t t o
(Superoxide ion)
10 7
B.O. 1.5,
2

= = Paramagnetic (one unpaired electric)

16 Chemistry 19 September
2 2 2 2 2 2
2 x
O 1s , 1s , 2s , *2s , 2p ,

= o o o o o
, ,
2 2 2 2 0
y z y z x
2p , 2p , *2p , *2p , *2p t t t t o
(Peroxide ion)
10 8
B.O. 1.0, Diamagnetic
2

= =
All the above results for O
2
and its ions can be presented in the form of a table
given below:
Table
Species
2
2
O
1
2
O

2
O
1
2
O
+ 2
2
O
+
B.O. 1.0 1.5 2 2.5 3.0
Number of
unpaired electrons 0 1 2 1 0
2
F : Since atomic number of Fluorine is 9 hence F
2
molecule will have 18
electrons.
Therefore electronic configuration of F
2
will be like O
2
as given below:
F
2
=
2 2 2 2 2
x
1s , *1s , 2s , *2s , 2p , o o o o o
,
,
2 2
y z
2 2
y z
*2p , *2p
*2p
2p , 2p , ,
HOMO LUMO
t t
o
t t
10 8
B.O. 1.0, Diamagnetic.
2

= =
Similarly for Ne
2
(Total 20 electrons) we have:
Ne
2
=
2 2 2 2 2
x
1s , 1s , 2s , *2s , 2p , o o o o o
, ,
2 2 2 2 2
y z y z x
2p , 2p , *2p , *2p , *2p t t t t o
10 10
B.O.
2

= = zero, which means Ne

2
molecule is not possible. Infact
all noble gases are monoatomic, all the and attempts to form their molecules
have not been successful.
Let us now answer a important question:
17 Chemistry 19 September
Q.1. Geneerally paramagnetic species are colored and diamagnetic colorless,
then why O
2
gas is colorless and F
2
(g) is very light yellow-green gas. Infact all
the halogen molecules are diamagnetic but none of the halogens is colorless,
why?
Answer: Answer of such a question is based on the difference of energy
between HOMO and LUMO level. Since this difference in O
2
molecule is large
enough so that electronic excitation by partial absorption of light cannot take
place in the visible range of the spectrum. No doubt unpaired electrons are
easily excited but the minimum energy needed for this is equal to energy
difference between HOMO and LUMO.
Therefore O
2
does not show absorption in he visible part of the spectrum,
rather it shows this excitation in the U.V. region, where we cannot see hence
oxygen remains colorless.
Remember, when any species absorbs a particular color (wavelengths) then its
complimentary color is exhibited. For example of a specie is absorbs violet
radiations ( 435 nm) and it appears yellow green because this is the
complimentary color of violet.
Since the energy gap between HOMO and LUMO for F
2
is less than that for O
2
,
hence F shows absorption in violet part of the visible spectrum and it appears
light yellow green.
Q.2. Whose ionization energy (I.E.) will be more that of oxygen atom or
oxygen molecule and why?
Ans. We know that I.E. is the energy needed to remove the most loosely
bonded electron in a gaseous atom molecule in ground state, to infinity. So let
us compare the energy levels of most loosely bonded electron in these two
species. Look at the vertical energy level diagram drawn for O
2
earlier. We see
that the most loosely bonded electron must be in HOMO, which are two
unpaired electrons so that any one can be removed to infinity. But the HOMO
level consists of antibonding
than the 2p level of oxygen atom. Hence it is easier to remove a electron from
O
2
than from O.
Therefore I.E. of oxygen atom > I.E. of O
2
. Similarly you can decide for N
2
and
N.
Energy level diagrams for B
2
, C
2
and N
2
:
18 Chemistry 19 September
We had not considered these three molecules in the sequence i.e. just after
Be
2
. Let us see why we did it? Suppose we draw the configuration of B
2
on the
pattern of O
2
, then it will be:
,
2 2 2 2 2 0 0
2 x y z
B 1s , *1s , 2s , *2s , 2p , 2p , 2p = o o o o o t t
[Total 10 electrons]
Z 5 =
Well, if this configuration is correct then B
2
molecule must be a diamagnetic
species, while actually it is a paramagnetic molecule having paramagnetic
moment equivalent to 2 unpaired electrons.
Hence above configuration must not be correct. There must be some change
in the energy order of m.o.s.
Yes, there is a change and that is, that
x
m.o. occupies a place above (
y
and
z
).
the reason behind this change is that energy gap between
x
m.o. in
B
2
, C
2
and N
2
molecules is so small that they can merge with each other to form
two new m.o. This is a different type of hybridization, applicable to m.os. In
this type of mixing the energy gap between the two m.o. increases. Thus we
can say that now
x
s m.o. with the increased energy gap
between them.
x
now occupies a place below the original level of
x
s occupies a place higher than the original
x
, but this new level is now
above the level of
y
and
z
. Similar interaction takes place between
and
x
so that
x
goes down and
x
s goes up but this does not bring
any change with respect to other molecular orbitals. For the sake of
convenience we shall retain the original symbols o molecular orbitals and not
the hybrid symbols.
therefore the increasing energy level order for B
2
, C
2
and N
2
will be:
,
y z
1s, *1s, 2s, *2s, 2p , 2p o o o o t t
,
x y z
2p , *2p , *2p , *2 o t t o
Hence the correct configuration of B
2
will be:
,
1 1
0
y z
2 2 2 2
x
2
2p , 2p
2p
B 1s , *1s , 2s , *2s , ,
HOMO LUMO
t t
o
= o o o o
6 4
B.O. 1.0,
2

= = Paramagnetic with 2-unpaired electrons.