CHEMICAL BOND :
A force that acts between two or more than two atoms to hold them together as a stable moleculeis known
as a chemical bond.
Why chemical bond forms between atoms
(A) Potential energy concept : Every system tries to minimise their energy. Here system of
two or more atom undergoes chemical bond formation to get minimise their P.E.
* Lewis pictured the atom in terms of a positively charged 'Kernel' (the nucleus plus the inner elec-
trons) and the outer shell that could accommodate a maximum of eight electrons.
* Lewis found that octet of electrons, represents a particularly stable electronic arrangement. To
achieve octet of electron atom can combine either by transfer of valence electrons from one
atom to another (gaining or losing) or by sharing of valence electrons. This is known as octet rule
Lewis Symbols: In the formation of a molecule, only the outer shell electrons take part in chemical combi-
nation and they are known as valence electrons.
For example, the Lewis symbols for the elements of second period are as under:
or Mg+2 (F–)2
Page # 2
(ii) The capacity of an element is terms of number of loss of e– or gain of electron to form ionic
bond is termed electrovalency
Cavalent bond
(i) A covalent bond is formed by mutual sharing of one of more electron pairs between two atoms
to aquire nearest noble gas configuration.
(ii) Sharing of one e– single bond
’’ two e– Double bond
’’ three e– Triple bond
(iii) Covalent bond energy arises due to forces of attraction between nuclei and shared pair of
electron.
or Cl – Cl
8e– 8e–
• Thus in water and carbon tetrachloride molecules, formation of covatent bonds can be represented as:
8e
–
Cl
Cl C Cl
H O H
8e
–
8e
–
Cl
–
2e 8e– 2e– 8e
–
For example, in the carbon dioxide molecule, we have two doublebonds between the carbon and oxygen
atoms. Similarly in ethene molecule the two carbon atoms are joined by a double bond.
O C O or O C O
H H H H
C C or C C
H H H H
8e 8e
– –
C2H4 molecule
When combining atoms share three electron pairs as In the case of two nitrogen atoms in the N2 molecule
and the two carbon atoms in the ethyne molecule, a triple bond is formed.
N N or N
8e
–
8e
–
N2 molecule
H C C H or
8e– 8e–
C2H2 molecule
Page # 3
Co-ordinate bond or dative bond is special type of covalent bond is which shared bond pair of
electron is donated by one atom, called doner and other atom is acceptor.
+ or [ A B]
H F H F
| | | |
H–N: B–F H – N B – F
| | | |
H F h F
This does not complete the octed on carbon and hence we have to resort to multiple bonding (in this case
a triple bond) between C and O atoms. This satisfies the octet rule condition for both atoms.
Page # 4
FAVOURABLE CONDITION :
(i) One of the atom must be electro +ve can easily loose e–s or should have few more e–s than a noble gas. It
should have low .E value
(ii) Other element should be a electro –ve element having high .E. value, and more negative value of electron
gain enthalpy, having few e–s less than noble gas.
(iii) Energy released because of the combination of cation and anion should be high.This energy is also defined
in terms of lattice enthalpy.
Lattice Enthalpy
The Lattice Enthalpy of an ionic solid is defined as the energy required to completely separate one mole of
a solid ionic compound into gaseous constituent ions. For example, the lattice enthalpy of NaCI is 788 kJ
mol-1. This means that 788 kJ of energy is required to separate one mole of solid NaCI into one mole of Na+1
(g) and one mole of Cl–(g) to an infinite distance.
This process involves both the attractive forces between Ions of opposite charges and the repulsive forces
between ions of like charge. The solid crystal being three- dimensional; it is not possible to calculate lattice
enthalpy directly from the interaction of forces of attraction and repulsion only.
Factors associated with the crystal geometry have to be included.
Na+(g) + Cl–(g) NaCl(s) H = Hlattice –ve (always)
Mg2+(g) + 2Cl– (g) MgCl2 (s)
LECTURE # 2
FACTORS AFFECTING L.E.
1
(i) Lattice energy (L.E.) r = r+ + r–
r
= interionic distance
(ii) L.E. Z+, Z–
Z+ charge on cation in terms electronic charge
Z– charge on anion in terms electronic charge
CALCULATION OF L.E. :
Page # 5
Born Haber Cycle for NaCl (s)
1 Cl (g) Hf
Na (s) + 2 NaCl(s)
2
Hsub 1( H )
BE
2
Na(g) HL.E.
Cl(g)
HI.E. HEg
+ -
Na (g) + Cl (g)
Hf enthalpy of formation of any compound is defined as the enthalphy change when 1 mol of that
compound is formed form the elements in their standard states
1
Hf = Hsub + H.E. + H + Heg + HL.E.
2 BE
+ve/–ve
Generally +ve +ve +ve +ve/-ve
Q. Born haber cycle for MgCl2(s) & calculate its lattice energy in terms HSub(Mg), HI.E1 (Mg), HI.E 2 (Mg),
Heg(Cl); HB.E.(Cl2(g)) + Hf(Mg Cl2,(s))
+
HL.E
Mg (g) 2 Heg
HI.E 2
2+
Mg (g) + 2Cl–(g)
3
2Al (s) + O (g) Hf Al2O3(s)
2 2
Hsub 3 H
B.E
2
2Al(g) 3O(g)
HI.E 1
Heg 1
+
HL.E
2Al (g) 3O (g)
–
HI.E 2
2+
2Al (g) Heg 2
HI.E 3
3+ 2–
2Al (g) + 3O (g)
3
Hf = 2Hsub + 2 HI.E1 + 2 HI.E 2 + 2HI.E3 + HBE + 3Heg1 + 3Heg2 + HL.E.
2
Page # 6
Q. Born haber for NaBr
1 Br () Hf
Na (s) + 2 NaBr(s)
2
Hsub 1 Hvap
2
Na(g) 1 Br (g)
2
2
1 H H
B.E.
2
HI.E. Br(g)
HEg
+ -
Na (g) + Br (g)
1 I (s) Hf
Na (s) + 2 NaI(s)
2
Hsub 1 H sub(I (s)) 2
Na(g) 1 I2 (g)
2
1 H
B.E.
2
I(g)
Solvation or Hydration :
Whenever any compound generally ionic or polar covalent is dissolved in an polar solvent or in water then.,
different ions of the compound will get separated and will get surrounded by polar solvent molecules. This
process is known as solvation or hydration. Energy released in this process is known as solvation energy or
hydration energy
The ionic compound will be soluble only if solvation energy (H.E.) is more than the lattice energy
Page # 7
Factors affecting solvtion energy or hydration energy.
S.E. Z+ Z–
1 1
r r
1
1 (nature of solvent) where r is dielectric constant.
r
LECTURE # 3
1 1 1
Now we have L.E. r r and S.E.
r r
From these 2 equations, it can be mathematically proved that if the difference between the radii of Cation &
Anion is large then, solvation energy will dominate and if radii are comparable or difference is small, then
lattice energy will dominate
Greater the difference between radii, greater will be solubility
100 10 100 20 100 30 100 40
Cs F > Cs Cl > Cs Br > Cs
1 1 1 1
L.E.
110 120 130 140
1 1 1 1 1 1 1 1
S.E.
100 10 100 20 100 30 100 40
decreament in solvation energy > decreament in lattice energy
Solubility Orders.
Increase difference in radii solubility and viceversa
i. LiF LiI increses
ii. NaF Na increase
iii. LiF CsF increase
iv CsF Cs decrease
v Li Cs decrease
vi Be(OH)2 Ba(OH)2 increase
vii LiOH CsOH increase
viii BeSO4 BaSO4 decrease
white ppt
ix LiClO4 CsClO4 decrease
Page # 8
Explain by Fazan’s rule, because of covalent character solubility
x BeF2 Be2 decrease
xi AgF Ag decrease
Q. NaF Na[BF4]–
which is more soluble
Ans. Na[BF4]– difference will solubility
Q. Which is more soluble Cs3 or [N(CH3)4]+ 3–
Ans. Cs3
Note : It has generally observed that larger cation will be thermally stable with the larger anion and
smaller will be stable with the smaller anion.
e.g. [N(CH3)4]+ I3– more stable than CsI3.
Facts about solubility in H2O :
a All the salts of NH4+ , alkalimetals are soluble except LiF, Li3 PO4, Li2C2O4 , Li2CO3
b All the NO3–, ClO4–, CH3COO– are soluble
c S2– ( sulphides) of NH4+, alkalimetals or alkaline earth metal are soluble
rest are insoluble
d Sulphates of all elements are soluble except Ba 2 , Sr 2 , Ca 2 ,Pb 2
whiteppt .
+
e Hydroxides of NH4 , alkalimetals and Ba(OH)2 are soluble rest are insoluble
f Halides are generally soluble except AgC(white), AgBr(pale yellow), Ag(yellow) and Pb2(yellow)
Ex. Which salt is insoluble in the following reaction
(i) BaCl2 + Na2SO4 BaSO4 + 2NaCl
(ii) BaCl2 + 2AgNO3 2AgCl + Ba(NO3)2
(iii) (NH4)3 PO4 + 3LiCl 3NH4Cl + Li3PO4
(iv) Na2CO3 + (CH3COO)2 Pb PbCO3 + 2CH3COONa
(v) Ba(OH)2 + MgCl2 Mg(OH)2 + BaCl2
Ans. (i) BaSO4 (ii) AgCl (iii) Li3PO4 (iv) PbCO3 (v) Mg(OH)2
Ex. Predict the product of decomposition of given polyhalides
Rb+ [Cl2]– RbCl + Cl
halide with stable lattice ( having ions of comparable radii) are produced
Li Be F
Na Mg Cl Na+ < F– K+
K Ca Br K+ < Cl– Rb+
Rb Sr
Cs Br At
K+ [Br Cl]– KCl + Br
More distortion of anion, more will be polarisation then covalent character increases.
Page # 9
Factors affecting the polarisation :
(i) Small size of cation polarisation.
e.g. BeCl2 MgCl2 CaCl2 SrCl2 BaCl2
e.g.
– Charge of cation
– Polarisation
– Covalent character
(b) Charge on anion :
AlF3 Al2O3 AlN
F– , O–2 , N–3
– Charge on anion
– Polarisation
– Covalent character
(iv) Cation which has pseudo inert gas configuration, shows more polarising power in comparison of cation that
has inert gas configuration. CuCl > NaCl (Covalent character)
Page # 10
(iv) Variation of M.P. [M.P. of covalent < M.P. of ionic] :
BeCl2 , MgCl2 , CaCl2, SrCl2, BaCl2
––––––––––––––> –––––––––––––––––––––> –
ionic charater , r+ ion & r – ion = constant MP
CaF2 , CaCl2 , CaBr2 , Ca2
––––––––––––––> ––––––––––––––––––> –
Covalent character M.P. r ion & r+ ion = constant
–
LECTURE # 4
COVALENT BOND :
Theories explaning the nature of covalent bond are as follows
g
M
g
g
Draw Lewis dot structures
• Each bond Is formed as a result of sharing of an electron pair between the atoms.
• Each combining atom contributes at least one electron to the shared pair.
• The combining atoms attain the outer- shell noble gas configurations as a result of the sharing of electrons.
Page # 11
Formal Charge
Lewis dot structures, in general, do not represent the actual shapes of the molecules. In case of polyatomic
ions, the net charge is possessed by the ion as a whole and not by a particular atom. It is, however, feasible
to assign a formal charge on each atom. The formal charge of an atom in a polyatomic molecule or ion may
be defined as the difference between the number of valence electrons of that atom in an isolated or free state
and the number of electrons assigned to that atom in the Lewis structure. It is expressed as :
The counting is based on the assumption that the atom in the molecule owns one electron of each shared
pair and both the electrons of a lone pair.
Let us consider the ozone molecule (O3 ). The Lewis structure of O3, may be drawn as :
The atoms have been numbered as 1. 2 and 3. The formal charge on:
1
• The central O atom marked 1 = 6 –2 – (6) = + 1
2
1
• The end O atom marked 2 =6–4– (4) = 0
2
1
• The end O atom marked 3 =6– 6– (2) = – 1
2
Hence, we represent O3 along with the formal charges as follows:
We must understand that formal charges do not indicate real charge separation within the molecule. Indicatng
the charges on the atoms in the Lewis structure only helps in keeping track of the valence electrons in
Page # 12
themolecule. Formal charges help in the selection of the lowest energy structure from a number of
possible Lewis structures for a given species. Generally the lowest energy structure is the one with the
smallest formal charges on the atoms. The formal charge Is a factor based on a pure covalent view of bonding
in which electron pairs are shared equally by neighbouring atoms.
Ex. Calculate the formal charge on the all atoms present in the molecules.
(a) NO3– (b) NH4+ (c) N3–
Ans. (a) (b) (c) N = N = N
Li. Be and B have 1,2 and 3 valence electrons only. Some other such compounds are AlCl3 and BF3.
2. Odd-electron molecules
In molecules with an odd number of electrons like nitric oxide. NO and nitrogen dioxide. NO2, the octet rule
is not satisfied for all the atoms
.
Cl O 2
3. The expanded octet/ super octet / hypervalent compound
Elements in and beyond the third period of the periodic table have, apart from 3s and 3p orbitals, 3d orbitals
also available for bonding. In a number of compounds of these elements there are more than eight valence
electrons around the central atom. This is termed as the expanded octet. Obviously the octet rule does not
apply in such cases.
Some of the examples of such compounds are: PF5 SF6 , H2SO4 and a number of coordination compounds.
Interestingly, sulphur also forms many compounds in which the octet rule is obeyed. In sulphur dichloride,
the S atom has an octet of electrons around it.
Page # 13
MODERN CONCEPT OF COVALENT BOND (VBT) :
(Do not take much time here to discuss with the students)
As we know that Lewis approach helps in writing the structure of molecules but it fails to explain the
formation of chemical bond. It also does not give any reason for the difference in bond dissociation enthalpies
and bond lengths in molecules like H2 (435.8 kJ mol – , 74 pm) and F2 (150.6 kJ mol– , 42 pm). although in both
the cases a single covalent bond is formed by the sharing of an electron pair between the respective atoms.
It also gives no idea about the shapes of polyatomic molecules.Similarly the VSEPR theory gives the
geometry of simple molecules but theoretically, it does not explain them and also it has limited applications.
To overcome these limitations the two Important theories based on quantum mechanical principles are
Introduced. These are valence bond (VB) theory and molecular orbital (MO) theory.
Valence bond theory was introduced by Heitler and London (1927) and developed further by Pauling and
others. A discussion of the valence bond theory is based on the knowledge of atomic orbitals, electronic
configurations of elements (Units 2), the overlap criteria of atomic orbitals, the hybridization of atomic orbitals
and the principles of variation and superposition. A rigorous treatment of the VB theory in terms of these
aspects is beyond the scope of this book. Therefore, for the sake of convenience, valence bond theory has
been discussed in terms of qualitative and non-mathematical treatment only. To start with, let us consider
the formation of hydrogen molecule which is the simplest of all molecules. Consider two hydrogen atoms A
and B approaching each other having nuclei N^ and Ny and electrons present in them are represented by e
and e^. When the two atoms are at large distance from each other, there is no interaction between them. As
these two atoms approach each'other, new attractive and repulsive forces begin to operate.
Attractive forces arise between:
(i) nucleus of one atom and its own electron that is NA – eA and NB – eB.
(ii) nucleus of one atom and electron of other atom i.e., NA – eB. NB– eA.
Similarly repulsive forces arise between
(i) electrons of two atoms like eA – eB ,
(ii) nuclei of two atoms NA – NB.
Attractive forces tend to bring the two atoms close to each other whereas repulsive forces tend to push them
apart (Fig. 4.7).
Fig- 4.7 Forces of attraction and repulsion during the formation of H2 molecule.
Experimentally it has been found that the magnitude of new attractive force is more than the new repulsive
forces. As a result, two atoms approach each other and potential energy decreases. Ultimately a stage is
reached where the net force of attraction balances the force of repulsion and system acquires minimum
energy. At this stage two hydrogen atoms are said to be bonded together to form a stable molecule having
the bond length of 74 pm.
Since the energy gets released when the bond is formed between two hydrogen atoms, the hydrogen mol-
ecule is more stable than that of isolated hydrogen atoms. The energy so released is called as bond en-
thalpy, which is corresponding to minimum in the curve depicted in Fig. 4.8. Conversely. 435.8 kJ of energy
is required to dissociate one mole of Hg molecule.
H2(g) + 435.8 kJ mol – H(g) + H(g)
Page # 14
Fig. 4.8 The potential energy curve for the formation of H2 molecule as a function of internuclear distance of
the H atoms. The minimum in the curve corresponds to the most stable state of H2 .
(ii) More is the extent of overlapping between the two atomic orbital, stronger will be bond.
Page # 15
Examples of overlapping of pure atomic orbitals.
(i) H2 (s–s) H= H=
F2 Cl2 Br2 2
2p-2p 3p-3p 4p-4p 5p-5p
s-p overlapping: This type of overlap occurs between half filled s-orbitals of one atom and half filled p-
orbitals of another atom.
p-p overlapping : This type of overlap takes place between half filled p-orbitals of the two approaching
atoms.
(iii) pi() bond : In the formation of bond the atomic orbitals overlap in such a way that their axes remain
parallel to each other and perpendicular to the intemuclear axis. The orbitals formed due to sidewise
overlapping consists of two saucer type charged clouds above and below the plane of the participating
atoms.
Page # 16
4.5.5 Strength of Sigma and pi Bonds
Basically the strength of a bond depends upon the extent of overlapping- In case of sigma bond, the overlaping
of orbitals takes place to a larger extent. Hence, it is stronger as compared to the pi bond where the extent
of overlapping occurs to a smaller extent. Further, it is important to note that pi bond . between two atoms is
formed in addition to a sigma bond. It is always present in the molecules containing multiple bond (double or
triple bonds)
4.5.3 Overlapping of Atomic Orbitals
When two atoms come close to each other. there is overlapping of atomic orbitals. This overlap may be
positive, negative or zero depending upon the properties of overlapping of atomic orbitals. The various ar-
rangements of s and p orbitals resulting in positive, negative and zero overlap are depicted in Fig. 4.9.
The criterion of overlap, as the main factor for the formation of covalent bonds applies uniformly to the
homonuclear/heteronuclear diatomic molecules and polyatomic molecules. In the case of polyatomic mol-
ecules like CH4, NH3 and H2O, the VB theory has to account for their characteristic shapes as well. We know
that the shapes of CH4 , NH3 , and H2O molecules are tetrahedral, pyramidal and bent respectively. It would
be therefore interesting to find out if these geometrical shapes can be explained in terms of the orbital
overlaps.
Following overlappings are not allowed.
(A) Zero overlapping :
(a) (i)
(ii) Also in an s-orbital, is positive throughout but in p-orbital it is positive and negative
not allowed
not allowed
not allowed
Page # 17
LECTURE # 5
4.5.2 Directional Properties of Bonds
As we have already seen the formation of covalent bond depends on the overlapping of atomic orbitals. The
molecule of hydrogen is formed due to the overlap of 1s-orbitals of two H atoms, when they combine with
each other.
In case of polyatomic molecules like CH4 , NH3 and H2O the geometry of the molecules is also important in
addition to the bond formation. For example why is it so that CH4 molecule has tetrahedral shape and HCH
bond angles are 109.5° ? Why is the shape of NH3 molecule pyramidal ?
The valence bond theory explains the formation and directional properties of bonds in polyatomic molecules
like CH4 , NH3 and H2O , etc. in terms of overlap and hybridisation of atomic orbitals.
Hybridisation
Inter Mixing of pure atomic orbitals before bonding to produce new hybrid orbitals, specially for bonding
purpose
Postulates
(i) It is a hypothetical concept
(ii) Only those orbitals can take part in hybridisation which have comparable ( almost equal ) energies. So,
orbitals must be having same principal quantum number or these can be a maximum different of unity (if d
orbitals are involved)
(iii) The number of hybrid orbitals generated will be equal to the number of pure atomic orbitals taking part in
hybridisation.
(iv) All three type of orbitals (having a pair of e– s or having a unpaired e– or completely empty can take part in
hybridisation.
empty orbitals are used in coordination compounds
(v) The hybrid orbital generated will be represented by
Page # 18
s+p 2 new sp hybridised orbitals
(sp hybridisation)
SP
x axis s + pY
180º
120º
s + 2p s + px + py
in x - y plane
s + py + pz in y– z plane
s + px + pz in x– z plane
2 2
sp -sp bond
(unstable)
Page # 19
Ex. (a) CO2
(S+Px+Pz)
:
(SP2) :O C O:
S.N. = 3
S.N of C=2 S.N. = 3 (SP2)
SP
(S+Px) (S+Px+Py)
xy plane
py
(xy) (xz)
:
:
x axis
x-z
plane
:
:
S.N. = 6
(SP3d2)
F
2
B S.N = 3 (SP)
(c)
F F S.N.= 4 (SP)
3
2
S.N = 3 (SP )
:
S
(d) SO2
: :
2
:O O S.N = 3(SP )
<120º
:
:
:
O
2
S.N = 3 (SP )
:
(e) SO3 S
: 2
: :
O : O S.N = 3(SP )
120º
(f) CN–
:C N:
S.N = 2 .x
S.N + 2 (SP) Or
: C N:
(SP)
Out of C & N less E.N. element i.e C will donate its .P.
:
3
N S.N = 4 (SP )
(g) NH3 H
H H
H +
(h) NH4+ N S.N = 4 (SP3)
H
H H
Page # 20
sp hybridisation :
This type of hybridisation involves the mixing of one s and one p orbital rcsull.ingin the formation of two
equivalert sp hybrid orbitals. The suitable orbiials for sp hybridisation are s and pz , if the hybrid orbitals arc to
lie along the z-axis. Each sp hybrid orbitals has 50% s-character and 50% p-character. Such a molecule in
which the central atom is sp-hybridised and linked directly to two other central atoms possesses linear
geometry. This type of hybridisation is also known as diagonal hybridisation.
The two sp hybrids point in the opposite direction along the z-axis with projecting positive lobes and very
small negative lobes, which provides more effective overlapping resulting in the formation of stronger bonds.
Example of a molecule having sp hybridisation
BeCl2 : The ground state electronic configuration of Be is 1s2 2s2. In the exited state one of the 2s-electrons
is promoted to vacant 2p orbital to account for its divalency. One 2s and one 2p-orbitals get hybridised to
form two sp hybridised orbitals. These two sp hybrid orbitals are oriented in opposite direction forming an
angle of 180°. Each of the sp hybridised orbital overlaps with the 2p-orbital of chlorine axially and form two
Be-Cl sigma bonds. This is shown in Fig
Fig.4.10 (A) Formation of sp hybrids from s and p orbitals ; (B) Formation of the linear BeCl2 molecule.
Examples of SP hybridisation.
C
(a) H – C N, H–C C–H
SP
(b) =C= O=C=O H2C = C = CH2
C : CH2
:
S.N. = 3 C
2
(sp ) (sin glet Carbene )
Total spin multiplicity of any molecule = 2S + 1
S = |summation of all the spins|
1 1
Triplet S = = 1
2 2
Total spin multiplicity = 3 (triplet)
Singlet S = zero
Total spin multiplicity = 1 (singlet)
Page # 21
Q. Which is more stable
triplet carbene or singlet carbene?
Ans. triplet carbene
: :
: Cl Be Cl :
S.N= 4(SP3)
:
(f) BeCl2(g) S.N = 2
(SP)
In solid state, BeCl2 is formed in form of polymer (BeCl2)n
Cl Cl Cl Cl Cl
Be Be Be Be Be
Cl Cl Cl Cl
3
S.N = 4 (SP )
(g) N2
:N N:
S.N = 2 (SP)
(h) Azide ion N3 –
N3– (nitride ion)
x.
:N N N:
:
.x
:N N N:
:
x.
:N N N:
SP N = N = N SP
SP
In azide ion, both N–N bond lengths are equal and it is a linear ion.
(i) Hydroazoic acid (HN3)
+
:
N N N
120º H
Its a bent molecule
2 N – N bond length are not equal as in one bond there is extra electrostatic attraction which the bond
length.
It will be planar molecule
Q. CH3CN is a weaker lewis base than CH3NH2
H
:
Sol. CH3 C N : H 3C N
H
3
SP SP
Page # 22