CHEMICAL BONDING JEE-ADV

JEE-ADV CHEM-VOL-I
CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II

CHEMICAL BONDING AND

MOLECULAR STRUCTURE
SYNOPSIS
The electrons present in the inner energy levels
are known as core electrons.
INTRODUCTION -- CHEMICAL BOND
 Nucleus plus inner electrons are called kernel.
 The state of equilibrium between two atoms
 Valency shell electrons of an atom generally
where the force of attraction is equal to force of
occupy corners of a cube.
repulsion is known as chemical bond.  Valence electrons of Sodim and Argon can be
 Atoms participate in chemical bond formation in represented as
order to lose their potential energy and attain
stable electronic configuration
 Atoms having incompletely filled orbital in the
valency shell readily participate in chemical bond
formation
 Atoms are less stable and more energetic hence
they form molecules by losing some energy by
participating in Chemical Bond.
Sodium atom Argon
H + H  H2 + 434.72KJ
Cl + Cl  Cl2 + 239.1KJ  An atom which possess eight electrons
(octet) or two electrons (duplet)in outermost
Potential Energy (KJ / mol)

Potential Energy vs energy level is chemically stable and it is

+ Repulsion

HH Internuclear Distance called stable electronic configuration

Between Two Atoms
 Noble gases are relatively stable because of
Bond length
stable electronic configuration
H H  All other atoms have incompletely filled valence shell .
Bond Energy
- Attraction

 They get stable electronic configuration

either by transfer (or) by sharing of electrons
between atoms.
H H . The Number of electrons transferred per atom
is called Electrovalence and resultant bond is
Internuclear Distance (pm)
called Electrovalent bond.
 Formation of bond is accompanied by decrease . The number of electrons shared per atom is called
in potential energy. co-valence and the resultant bond is called
 Chemical Bond formation is always covalent bond.
 Nature of the bond formed between two atoms
Exothermic
depends on their electronegativity difference.
Kossel - Lewis Theory
 It is also called “Electronic Theory of Valence Electro negativity of Changes occuring
Nature of the
or Chemical bond Theory ” or modern Theory Element Element in the valence
bond formed
of Valence. A B electrons

 This was proposed on the basis of Bohr’s Low High Transfer of e Ionic bond
Atomic theory High High Sharing of e Covalent bond
 Electrons present in the outer most energy level Low Low Sea of e Metallic bond
of an atom are called Valence electrons.

NARAYANA GROUP 1
 CHEMICAL BONDING JEE-ADV CHEM-VOL-I
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LEWIS DOT FORMULAE WITH
DIFFERENT EXAMPLES
In Lewis symbols valence electrons are
represented by dots.
 Single bonds are constructed first with bond
pairs. Then the remaining electron pairs are
utilized either for multiple bonds or remain as the
lone pairs.
 The basic requirement being that each bonded
atom gets an octet of electrons except hydrogen.

O+
–
O O

7 Group VIIA F

 They can be used to calculate the group valence

of the element.
Guidelines to write the Lewis dot Structure
of molecules
 The total number of electrons required for writing
the structure are obtained by adding the valence
electrons of the combining atoms.
eg: CH 4 molecule has 8 valence electrons ( 4
Lewis structures of some important molecules
electrons from carbon and 4 electrons from 4
1. Be F2 F Be F
hydrogen atoms)
 For anions
F
2
eg: CO  4   6  3  2   24
3
B
2
( 2 from negative charge of CO ) 3 F F
 For cations

eg: NH 4 5  1 4   1  8 F

(1 from positive charge of NH ) 4 BF3 B
 Distribute the total number of electrons as F F
bond pairs between the atoms. For this the 2.
skeletal structure of the compound is known or
is presumed.
F
 In general the least electronegative atom is made
the central atom of the molecule or ion. B
eg: In NF3, nitrogen is the central atom and F F
fluorines are bonded atoms.

2 NARAYANA GROUP
 CHEMICAL BONDING JEE-ADV
JEE-ADV CHEM-VOL-I
CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II

F Limitations of Octet Rule

F  It is clear that octet rule is based upon the chemi-
BF4 cal inertness of noble gases but xenon and
3. B
F F krypton can combine with oxygen and fluorine
to form a number of compounds like XeF2,
H KrF2, XeOF2 etc...
 This theory does not account for the shape of
AlH 4 Al
4. molecules.
H H  It does not explain the relative stability of the
H
x x molecules.
F Al 3+ F  There are three types of exceptions to the Octet rule.
5. AlF3 x 6. CO2 O=C=O
F a) In some compounds, the number of electrons
surrounding the central atom is less than eight.
H
(incomplete octet of the central atom)

7. CH 3 C 8. eg: LiCl , BeH 2 , BCl3 etc....
CO C  O
H H b) In some compounds, the number of electrons
Cl surrounding the central atom is more than eight
F
F F (expanded octet (or) super octet of central atom)
2–
CCl4 C SiF6 2 Si
9. 10. F F
eg: PF5 , SF6 , H 2 SO4 , IF7
Cl Cl
Cl F c) In molecules with an odd number of electrons
Cl like NO and NO2 , the octet rule is not satisfied
for all the atoms.
Sn SnCl4 Sn
11. SnCl2 12. N=O; O=N–O
Cl Cl Cl Cl
Cl
H

N  N Total No. of Valence
13. NH 4 14. NH 2 Molecule Electrons in the
H H H H
H Central Atom
xx
15. NO x N = O CH4 C 8 (Octet)

N N NH3 N 8 (Octet)
16. NO2 H2O O 8 (Octet)
O O O O
Cl CO2 C 8 (Octet)
P Cl C2H6 C (each) 8 (Octet)
PCl5 P Cl
17. PF3 F F 18. C2H4 C (each) 8 (Octet)
F Cl
Cl C2H2 C (each) 8 (Octet)
Cl BeCl2 Be 4 (Electron deficient)
F Cl Cl
 P BCl3 B 6 (Electron deficient)
19. PF4 P F 20. PCl6
F Cl Cl PCl5 P 10 (Expanded Octet)
F Cl
O SF6 S 12 (Expanded Octet)

POCl3 P
IF7 I 14 (Expanded Octet)
21. Cl Cl
Cl

NARAYANA GROUP
3
 CHEMICAL BONDING JEE-ADV CHEM-VOL-I
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RESONANCE, Bond order = (Number of Bonds between

CONDITIONS OF RESONANCE two atoms in all resonating structure ) /
 Representation of molecule in more than (Total number of resonating structures)
one structure and none of them explains all
the properties of the molecule singly is O O O
called Resonance
C C C
 When ever a single lewis structure cannot
describe a molecule accurately, a number of O O O O O O
structures with similar energy, positions of atomic
nuclei, bonding and non bonding pair of electrons Resonance Structures of CO32
are taken as the canonical structures of the real 4
2
structures which describes the molecule  Bond order in CO3 is  1.33
3
accurately.
W.E.-1.What is the nitrogen-oxygen bond order
O O in NO 3– ion?
 


Sol: The structure of NO ion is  O  N  O .
3 
O O O O  O 
I II It has four bonds and three canonical structures.
Canonical forms of ozone Bond order = 1.33
O W.E.-2.Write the order of oxygen-oxygen bond
12
pm

energies of O2, O3 and H2O2 molecules.

8
8

pm

Sol: Bond order in O2 is 2.

12

O O Bond order in O3 is 1.5

III
Resonance hybrid of ‘O3’ molecule
 Thus for O3, the two structures (I, II) Shown below
constitute the canonical structures or
resonance structures, and the III strucutre
represents the structure of O3 more accurately,
and it is called resonance hybrid.
Characteristics of Resonance
 Resonance stabilises the molecule
 More the number of resonating structures more
will be the stabiltiy of the molecule
 Because of resonance all the bond lengths
become same.
eg: All the bond lengths in benzene are identical
 The canonical forms have no real existence.
 The resonating structures are inseparable.
 The molecule as such has a single structure which
is the resonance hybrid of all the canonical forms
and which cannot as such be depicted by a single
Lewis structure.
 The lowest energy structure is the one with the
smallest formal charges on the atoms.
 The most stable structure is the one which has
the smallest formal charge on the atoms or zero
formal charge on the atom.
Bond order in H2O2 is 1
Descending order of O – O bond energies:
O2 > O3 > H2O2
FORMAL CHARGE , IMPORTANCE OF
FORMAL CHARGE
 In case of a 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 an atom in a polyatomic
molecule or ion.
 The formal charge of an atom in a polyatomic
molecule (or) ion is the difference between the
number of valence electrons of that atom in an
isolated state and the number of electrons
assigned to that atom in the Lewis structure.
Qf =  N A - N M  =  N A - N LP - 1 / 2N BP 
Q f  Formal charge
NA  number of electrons in the valence shell
in the free atom
N M  number of electrons belonging to the
atom in the molecule
N LP  number of electrons in unshared pairs,
i.e. number of electrons in lone pairs

4 NARAYANA GROUP
 CHEMICAL BONDING JEE-ADV
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CHEM-VOL-I
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N BP  no. of electrons in bond pairs, respectively.. ELECTRO VALENT BOND [Ionic bond]
eg: The Lewis dot formula of PH3 is “The strong electrostatic forces of
attraction between two oppositely charged
ions which are formed due to transfer of
electrons from one atom to another is called
Formal Charge of P Ionic Bond (or) Electrovalent Bond”.
Q f   N A  N M    N A  N LP  1 / 2 N BP   Generally Ionic Bond is formed between a Metal
[5-2-1/2(6)] = (5-5) =0 of groups 1, 2 and Non metals of groups 16 and
Formal Charge of H 17.
Qf =  N A - N M  =  N A - N LP - 1 / 2N BP   Formation of Ionic bond is a redox process.
= [1 - 0 - 2/2] = 0 For example , the formation of NaCl from
 Formal charges on oxygen atoms of ozone sodium and chlorine can be explained as:
(1)
Na  Na   e 
O
 Ne 3s1  Ne
O O
(2) (3) Cl + e  Cl 
 Formal charge of oxygen (1) = +1
Formal charge of end oxygen atom(2) =0  Ne 3s 2 3 p5   Ne 3s 2 3 p 6or  Ar 
Formal charge of end oxygen atom (3)= -1 NaCl or Na  Cl 
Na   Cl  
 The formal charge on an atom may or may not
be same it changes with the structural Similarily the formation of CaF2 may be shown
environment of the atom in the molecule. as:
 In resonance structures electronic environment
changes. Hence the formal charge also may Ca  Ca 2   2e 
change.
 Ar  4s 2   Ar 
eg: Resonance structures of N 2 O
F  e  F
N=N=O NN=O
eg:
1 2 3 4 5 6  He 2s 2 sp5  He 2s 2 sp6 or  Ne
1 F
Qf1  5  4   4   1 2  CaF2 or Ca 2 
2 Ca  2 F  F
1  Number of electrons lost or gained in the
Qf 2  5  0   8   1
2 formation of electrovalent bond is called
1 electrovalency.
Qf3  6  4   4   0  The maximum electrovalency in the formation
2
of Ionic Bond is 3.
1
Qf 4  5  2   6   0  In Mg F2 Electrovalence of Mg = 2, F=1
2
1  In Na2O electrovalence of Na = 1,O = 2
Qf5  5  0   8  1  Most ionic compoiunds have cations derived
2
from metallic elements. The ammonium ion,
1
Qf 6  6  6   2   1 NH 4 ( made up of two non metallic elements)
2
 Formal charges represent a tendency to build is an exception . It forms the cation of a number
up positive (or) negative charges. of ionic compounds.

NARAYANA GROUP 5
 CHEMICAL BONDING
Factors Favourable for the formation of Ionic
Bond
(a) Factors favourable for cation formation
 Low ionisation potential
Atom having very low ionisation potential forms
the cation very easily. Potassium (IP=495.57 kJ/
mole) forms the cation more readily than
sodium(IP=519.82 kJ/mole)
 Low charge on the ion
Formation of cation carrying less positive
charge is easy.( Al 3  Mg 2  Na  )
 Large atomic size
Atoms with large atomic size form cations easily
Cs   Rb   K   Na   Li 
 Formation of cation with Inert gas
configuration.
Formation of cation having inert gas configuration
is very easy.
eg: Of the two cations Zn+2(2, 8, 18) and
Ca+2(2, 8, 8), Ca+2 is more readily formed and
it is more stable than Zn+2and gives compounds
with more ionic character.
(b) Factors favorable for anion formation
 High Electronegativity and Electron affinity
Atom having very high electron affinity / electro
negativity forms anion very easily.
F O N
 Small atomic size
Small non metal atom forms anion very easily.
F   Cl   Br   I 
Low charge on the ion.
 Formation of anion carrying less negative charge
is easy.

F O  N 2 3
Properties of Ionic Compounds
 Ionic compounds exist as solids due to strong
electrostatic forces of attraction.
 They are generally soluble in polar solvents
(having high value of dielectric constant ).
 Generally higher lattice energy salts are lesser
soluble. eg: sulphates and phosphates of Ba
and Sr are insoluble in water due to high lattice
energy.
Solubilities of some salts:
LiClO4  NaClO4  KClO4  RbClO 4  CsClO4
CsF  RbF  KF  NaF  LiF
NARAYANA GROUP
6
JEE-ADV CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
Li 2 CO3  Na 2CO3  K 2 CO 3  Rb 2CO 3  Cs 2 CO3
LiHCO3  NaHCO3  KHCO3  RbHCO3  CsHCO3
CsOH  RbOH  KOH  NaOH  LiOH
Ba  OH 2  Sr  OH  2  Ca  OH  2 
Mg  OH 2  Be  OH 2
BeSO 4  MgSO 4  CaSO4  SrSO4  BaSO4
BeS2O3  MgS2O3  CaS2O3  SrS2O3  BaS2O3
BeCrO4  MgCrO4  CaCrO 4  SrCrO4  BaCrO4
BeF2  BaF2  SrF2  CaF2  MgF2
BeCl2  CaCl 2  MgCl2  SrCl2  BaCl2
 More the heat of hydration, more is the solubility.
eg: AlCl3 though covalent in nature is soluble in
water due to high value of heat of hydration
 Ionic compounds are good electrical
conductors in molten state (or) in aqueous
solutions.
 Ionic compounds undergo chemical reactions
quickly in aqueous solutions.
NaCl aq   AgNO3 aq   AgCl   NaNO3 aq 
White ppt.
 Ionic compounds do not exhibit isomerism
because ionic bond is a non directional bond.
 The melting and boiling points of ionic
compounds are very high.
 If the anion is common in ionic compounds, the
ionic compound which has a cation of higher
atomic weight will have more melting point.
eg: Melting point of BaCl2 > BeCl2 .
 If cation is common in the ionic compounds, then
the compound with high lattice energy will have
high melting point.
eg: Melting point of NaF is more than that of
NaI.
FAJAN’S RULES
 No Bond is 100% ionic in nature. It has
some percentage of covalent character
which is explained on the basis of Fajan’s
rule.
 Polarising Power: The ability of cation to
polarise the near by anion is called polarising
power or polarsing ability.
 Polarisability: The tendency of anion to get
distorted or polarised by the cation is called its
polarisability
 CHEMICAL BONDING JEE-ADV
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 Polarising power relates to cation:  Lattice energy calculation from Born-Lande

1 N 0 Az  z  e 2
Polarising power  charge on cation 
size
 Polarisability relates to anion
Polarisability  charge  size
 As polarising power increases, covalent
character increases.
eg: (i) Covalent character -
NaCl  MgCl2  AlCl3
since the order of polarising power is
Na   Mg 2  Al 3
(ii) Covalent character -
AlF3< AlCl3< AlBr3< AlI3, since the order of
polarisability of halide ions is
F   Cl   Br   I 
 Cation with 18 electrons (pseudo inert gas
configuration ) in outer most shell bring greater
polarisation of the anion than those with inert gas
configuration.
eg: CuCl is more covalent when compared to
KCl
LATTICE ENTHALPY
The amount of energy released when the 
required number of oppositely charged
gaseous ions present at infinite distances
come close and form one mole of ionic
crystalline solid is known as the lattice
energy of the compound.
Eg : Nag   Clg   NaCl crystal  U  782kJ mol 1 
 In ionic solids, the sum of the electron gain
enthalpy and the ionization enthalpy may be
positive but still the crystal structure gets stabilized
due to the energy released in the formation of
the crystal lattice.

 For example the ionization enthalpy for Na
formation from Na(g) is 495.8KJ mol 1 : while
the electron gain enthalpy for the change
Cl  g   e   Cl   g  is , -348.7 KJ mol 1 .
 The sum of the two, 147.1 KJ mol 1 is
compensated for by the enthalpy of lattice
formation of NaCl  s   788 KJ mol  .
1
N0B
U  
equation : r rn
attractive force repulsive force
Az  z  e 2 r0n1
B
n
N 0 Az  z  e 2  1 
U  1  
r0  n
N 0 Az  z  e 2  1 
U  1  
4 0 r0  n 
where z  and z  are the charges on the positive
and negative ions,
e is the charge on an electron,
r is the inter-ionic distance
N 0 is the Avogadro constant
‘A’is the Madelung constant and ‘B’is a repulsion
coefficient, which is a constant which is
approximately proportional to the number of
nearest neighbours (which depends on the
geometry of the crystal)
‘n’ is a constant called the Born exponent.
Born-Lande equation gives a calculated value
of U  778kJ mol 1 for the lattice energy of
sodium chloride, which is close to the
experimental value of 770 kJ mol 1 at 250 C
(obtained using the Born-Haber cycle)
Lattice energy is directly proportional to the
product of Z+ and Z– and inversely proportional
to the sum of the radii of cation and anion.
Z Z 

Lattice energy
 rc  ra  , where Z  is
charge on cation and Z  is charge on anion.
g Calculation of lattice energy
 Lattice energy is calculated based on Born-
Haber cycle which is based on Hess’s law.
Hess’s Law of Constant Heat Summation
 The heat energy released or absorbed in a
process is same whether the process occurs in
one step or in several steps.
 It follows all algebric rules like addition,
multiplication, substraction etc.....

NARAYANA GROUP 7
 CHEMICAL BONDING JEE-ADV CHEM-VOL-I
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All the above energy factors are interrelated in

It can be represented as:
the Born-Haber cycle can be summarized in the
rH
A B following figure.
r H1 r H 3  I Na H 3
Na g 
C r H2
D  E Cl H 4
Cl g 
According to Hess Law
Na   g 
 r H   r H1   r H 2   r H 3  S Na  H
1
Cl   g 
Born-Haber cycle for calculation of lattice 1
 DCl 2  H 2
energy of NaCl(s) : 2
The thermochemical equation for the formation
of solid sodium chloride from its constituest  H 5  U NaCl
elements can be written as follows.
1 NaCls 
1 H r NaCl  Cl
Na s   Cl2 g    NaCls  , 2 2g 
H Na  s
2
H 0f  410.5 kJ mol 1 According to Hess’s Law
This reaction can be assumed to take place in
several steps, which are as follows. H 0f  H1  H 2  H 3  H 4  U  Lattice energy 
i) The heat absorbed in the conversion of solid Substituting the respective values, we get
sodium into gaseous sodium is equal to its 1
410  108.7   239.1  492.8  361.6  U
Sublimation energy  S  . The sublimation 2
Lattice energy of sodium chloride,
energy of sodium is 108.7kJ mol 1 . U=-769.45kJ mol-1.
SNa
Factors that influences lattice energy
Na S 
H r
 Na g  H1  108.7 kJ mol1  Lattice energy increases as cation or anion size
ii) Gaseous sodium atoms ionize by absorbing an decreases.
energy equal to its ionization energy of LiF > NaF > KF
LiF > LiCl > LiBr > LiI
492.82KJ / mol1  Greater the charge on ions more is lattice energy
1Na
Na  g    Na   g  ; NaF < MgO < AlN
H r
 Lattice energy of compounds follows the order
H 2  492.82 kJ mol 1 divalent - divalent > divalent - Monovalent >
Monovalent - Monovalent.
iii) Chlorine molecules should breakup into chlorine
atoms for which the energy absorbed is equal to Eg : MgO  MgCl2  NaCl
its bond energy. To break half the mole of  Greater the lattice energy more is the ionic bond
strength, stability , melting point and low solubility.
Cl2 molecules into atoms the energy absorbed W.E.-3. Lattice energy in sodium chloride is y
is equal to half of its bond energy, i.e., kJ. Assuming the same interionic distance,
239.1 / 2  119.55 kJ what will be the lattice energy of
magnesium sulphide?
1 1/2 DCl2 Sol: The charge magnitudes of ions in NaCl are 1
Cl2 g    Cl g  H3  119.55KJ
2 and 1 respectively.
iv) Chlorine atoms convert into chloride ions by The product of q1 and q2 = 1  1 = 1
The charge magnitudes of ions in magnesium
gaining an electron due to which energy liberated
sulphide are 2 and 2 respectively.
equal to its electron affinity. The product of q1 and q2 = 2  2 = 4
E.a
Cl( g )  Cl  ( g ) H 4  361.60 kJ mol 1 Hence lattice energy of MgS = 4 y kJ

8 NARAYANA GROUP
 CHEMICAL BONDING JEE-ADV
JEE-ADV CHEM-VOL-I
CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II

COVALENT BOND Polar covalent Bond:

 Covalent bond was proposed by G.N. Lewis.  Polar covalent bond is formed by the mutual
 The bond formed between two atoms by the sharing of electron pairs between two atoms of
mutual sharing of their valence electrons is different elements.
known as covalent bond.  Polar covalent bond is present in
 The number of covalent bonds in which an atom HF , HCl , ICl , H 2O, CO2 , SO2 , BeCl2 , SO3
involves is equal to the number of unpaired
electrons present in either ground or excited BCl3 , NH 3 , CH 4 , PCl5 , SF6 etc.
state.  Both Pure and polar covalent bonds are present
 Phosphorus atom has three unpaired electrons in H 2 O2 , N 2 H 4 , H2S2 etc.
in its ground state. So it can form only three  The unpaired electrons present in the valence
covalent bonds in its ground state, shell of an atom involve in covalent bonds, the
 Phosphorus atom has five unpaired electrons in remaining electron pairs present in its valence
its excited state. So it can form five covalent shell are called lone pairs of electrons (or) non
bonds in its excited state. bonded pairs of electrons.
 Single bond is formed by the mutual sharing of  The lone pairs of electrons present in the atom
one pair of electrons between two atoms. involve in the formation of co-ordinate covalent
bonds to satisfy the maximum covalance.
Properties of Covalent Compounds
 Covalent substances exist as solids, liquids and
gases.
eg: I2(s), Br2 (l), Cl2 (g) at room temperature
 Double bond is formed by the mutual sharing of  Covalent substances have low melting and boiling
two pairs of electrons between two atoms. points. Except 3-D network solids like diamond
Carborundum (SiC), Silica (SiO2), Boron Nitride
(BN)n etc.
 Covalent substances dissolve in non-polar
solvents.
 The solubility of a polar covalent substance is
 Triple bond is formed by mutual sharing of 3 pairs
more in a solvent having high dielectric constant
of electrons between two atoms.
and less in a solvent having low dielectric constant.
 The dielectric constant of a solvent is a
measure of its capacity to break the covalent
molecules into ions.
 Polar solvents have high dielectric constants.
 Non polar solvents have low dielectric constants.
 Dielectric constant is high for solvents like water,
 Double and triple bonds are called multiple ammonia, hydrofluoric acid, Methyl alcohol, Ethyl
bonds. alcohol etc....
Types of Covalent Bonds  Dielectric constant is low for solvents like
Pure Covalent Bond: Benzene, Carbon-disulphide, carbon
 Pure covalent bond or non polar covalent bond tetrachloride etc.
is formed by the sharing of electron pairs  Generally covalent substances are not electrical
between two identical atoms. conductors either in molten state or in aqueous
 Pure covalent bond is present in solutions as they do not contain free electrons
H 2 , Cl2 , O2 , N 2 , P4 , S8 etc. (or) ions

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 CHEMICAL BONDING
Exception: Graphite contains delocalised
electrons. So it is a good conductor of electricity.
 Covalent compounds exhibit space isomerism
because covalent bond is a directional bond.
 HCl , HBr , HI , HNO3 and H 2 SO4 etc are
polar covalent compounds. The aqueous 
solutions of these substances are good electrical
conductors because they contain free ions.
 Covalent reactions are slow as they involve
breaking and making of bonds.
 CCl4 , CHCl3 , CH 2 Cl2 etc cannot give white
precipitate with AgNO3 in aqueous solutions
because they do not contain free chloride ions
as they are covalent compounds.
CO-ORDINATE COVALENT BOND
(OR) DATIVE BOND
 The bond formed between two atoms by the
sharing of an electron pair which is 
contributed by only one of the two atoms is
known as the co-ordinate covalent bond.
 Co-ordinate covalent bond is also known as
dative bond or semi polar bond or donor
acceptor bond.
 Co-ordinate covalent bond was proposed by 
Sidgewick. The name dative bond was
proposed by Langmuir.
 Co-ordinate covalent bond is represented by an
arrow   the head of which is close to the
atom which accepts the electron pair.
 For all practical purposes, the co-ordinate
covalent bond is treated as a single covalent
bond.
 The formation of co-ordinate covalent bond 
occurs only after the formation of covalent bond.
Representation of dative bond
Example : Formation of ammonium ion  NH 4  :-

+
H H
H N H+ H NH
H H
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Example : NH 3 .BF3 molecule:-
H H H H
H N B F H N 
H H H H
Co-ordinate covalent bond is present in
Molecules like: N2O, O3, N2O4 , N2O5 CO,
F3B - NH3, B3N3H6, Al2Cl6
Ions like: H3O , NH 4 , NO3 , BF4 ,
N 2 H 5 , C6 H 5 NH 3
 In a hydrated cation the bond between water
molecule and cation is dative bond. Every water
molecule involves in one dative bond only.
3
eg:  Al  H 2 O 6  ion contains 6 dative
bonds.
2
 Be  H 2 O 4  ion contains 4 dative bonds.
The bond between ligand and metal atom (or)
metal ion in complex compounds is dative bond.
2
eg:  Cu  NH 3  4  contains 4 dative bonds.
2
 N i  H 2 O 6  contains 6 dative bonds.
Earlier to account for the octet of the central
atom there is a practice of writing dative bonds
in the structures of
SO2 , SO3 , Cl2O6 , Cl2O7 , H2SO4 , H3PO4 ,
SO42  , PO43 , ClO4 , ClO3 , ClO2 , SO32  etc.
( But as per the modern concepts the dative
bonds in the structures of all these examples must
be shown as double bonds.)
Properties of Coordinate Covalent
Compounds
Compounds containing coordinate covalent
bonds show melting and boiling points higher than
those of pure covalent compounds and lower
than those of ionic compounds.
 Readily soluble in organic solvents and sparingly
soluble in water.
 A coordinate bond acts as a single bond directed
in a specific orientation and hence some
compounds with coordinate bonds show
isomerism.
 Like covalent compounds, they are also poor
conductors.
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W.E.-4.What are the bonds present in ammonium  VBT and MO theory based on quantum
chloride? mechanical principle.
Sol: NH4Cl has ionic, covalent and dative bonds.  V.B.T was extended by pauling and slater to
NH 4 and Cl– bond is ionic, NH3 and H+ bond explain the directional nature of covalent bonds.
is dative, N and H, bond is covalent.  If two atoms A and B approaching each other
W.E.-5.Find the changes in the hybridization of having nuclei NA and NB and electrons present in
B and N atoms as a result of the following them are represented by eA and eB,
reaction. BF3 + NH3  F3B – NH3 Attractive Forces Arise Between
Sol: In BF3 the hybridization of boron is sp2 and in (i) Nucleus of one atom and its own electron i.e.
NH3 the hybridization of nitrogen is sp3. After NA - eA and NB - eB.
the reaction, the hybridization of boron changes (ii) Nucleus of one atom and electron of other
to sp3 but the hybridization of N remains atom i.e. NA - eB and NB - eA.
unchanged. Repulsive forces arise between
W.E.-6. What is the change in hybridization (if (i) electrons of two atoms like eA – eB.
any) of the Al atom in the following (ii) Nuclei of two atoms NA – NB.
reaction. AlCl  Cl   AlCl   Attractive forces tend to bring the two atoms
3 4
2 close to each other where as repulsive forces
Sol: In AlCl3, the central atom is sp hybridised while
tend to push them apart.
in the [AlCl4]–, ‘Al’ atom is sp3 hybridised.
DEVIATION FROM OCTET ,
CONTRACTED AND EXPANDED OCTETS
 A number of molecules shows exception from
octet rule. These are following types
Incomplete octet or Contracted octet
These contain less than 8 electrons at the central
atom
Ex: BeCl2 - 6 electrons
BF3 - 6 electrons
Expanded octet:
In these, the molecules or ions contains more
than 8 electrons in the valance shell of central
atom
Ex: PCl5 - 10 electrons
SF6 - 12 electrons
ICl3 - 10 electrons eA
IF7 - 14 electrons
ODD ELECTRON SPECIES
These contain odd number of electrons AH HBB
A
Examples: NO, NO2 , ClO2
VALANCE BOND THEORY eA
( Orbital over lapping)
Postulates of VBT: Repulsive forces
 V.B.T was proposed by Heitler and London to
Forces of attraction and repulsion during the
explain the shapes of covalent molecules, their
bond angles and bond lengths. formation of H 2 molecule

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Orbital overlap Concept: Directional properties of Bonds:

 The partial merging of atomic orbitals is called  The direction of a covalent bond formed is the
overlapping of atomic orbitals which results in direction of overlaping of atomic orbitals.
the pairing of electrons.
 The valence bond theory expalins the formation
 The extent of overlap decides the strength of a
covalent bond. and directional properties of bonds in polyatomic
 In general, greater the overlap the stronger molecules like CH4, NH3 and H2O, etc.
is the bond formed between two atoms. Types of overlapping and Nature of
Overlapping of Atomic Orbitals Covalent Bonds
 When two atoms come close to each to each  The covalent bond may be classfied into two
other, there is overlapping of atomic orbitals. types depending upon the the types of
 This overlap may be positive, negative or zero overlapping:
depending upon the properties of overlaping of
(i) Sigma(  ) bond, and (ii) pi(  ) bond
atomic orbitals.
 Sigma (  ) bond: This type of covalent bond
is formed by the end to end (head-on) overlap
+ +
+ z of bonding orbitas along the internuclear axis.
Thi is called as head on overlap.
s+s pz + s
This can be formed by any type of atomic orbitals
or even by hybrid orbitals.
z z (i) s-s overlapping
(ii) s-p overlapping
px + px dzx + px
(iii) p-p overlapping
 Dative bond is formed by the overlapping of an
(a) Positive overlap orbital having a pair of electrons and a vacant
orbital.
 pi   overlapping: In the formation of  bond
+ – + z z
the atomic orbitals overlap in sich a way that their
axes remain parallel to each other and
perpendicular to the internuclear axis.
 The orbitals formed due to sidewise overlapping
z z
consists of two saucer type charged clouds
above and below the plane of the participating
px + px dxz + px atoms.
 It is always present in the molecules containing
(b) Negative overlap
multiple bond (double or triple bonds)
 Only ‘p’ or ‘d’ - orbitals can involve in ‘pi’ bond
s px or py s dxy formation.
z x  Single bond is equal to one ‘  ’ bond.
 Double bond is a combination of one ‘ ’ bond
and one ‘pi’ bond.
py d x2  y2
x  Triple bond is a combination of one ‘  ’ bond
px y and two ‘pi’ bonds.
Strength of  and  Bonds:
x
 In case of  bond, the overlapping of orbitals
py takes place to a larger extent. Hence, it is stronger
as compared to the  bond where the extent of
(c) Zero overlap overlapping occurs to a smaller extent.

12 NARAYANA GROUP
 CHEMICAL BONDING
 Strength of the bonds follows the order
σ p -p > σ s -p > σ s -s > π (except  1s 1s in H 2 )
 Strength of the bonds follows the order
triple bond > double bond > single bond.
  electrons are localised,  electrons are mobile
electrons
 Shape of molecule is determined by  bonds
 bonds do not effect shape of molecule
 Reactivity of a multiple bond is always more than
single bond.
W.E.-7.Can Px overlap a Py orbital? Why or why
not?
Sol: No. They cannot overlap because their
orientations are not same.
W.E.-8.Considering x-axis as the internuclear
axis. Which out of the following atomic
orbitals will form a sigma bond?
a) 1S and 1S b) 1S and 2Px
c) 2PY and 2Py d) 1S and 2S
Sol: The  bond is formed by axial overlap along
inter nuclear axis and is present in the following
cases. In the case of a, b & d  bond is possible
and ‘c’ cannot form  bond. 2Py and 2Py
atomic orbitals are involved in the sidewise
overlap leading to the formation of  - bond.
HYBRIDIZATION
 The concept of hybridisation was introduced by
Pauling
 The intermixing of atomic orbitals of almost
same energy and their redistribution into
an equal number of identical orbitals is
known as hybridisation
 The orbitals of one and the same atom only
involve in hybridisation.
 In a molecule the central atom only undergo
hybridisation.
 The orbitals formed in hybridisation process are
called hybrid orbitals.
 The orbitals involving in the hybridisation have
different shapes but almost same energy.
 The hybrid orbitals have same shape and same
energy.
 The no.of hybrid orbitals formed is numerically
equal to no.of orbitals participating in
hybridisation.
 The hybrid orbitals are symmetrically arranged
around the nucleus such that they have maximum
stability.
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 The order of repulsions will be in order of
lp - lp > lp - bp > bp - bp repulsions.
 The angle between any two hybrid orbitals in an
atom is generally same.
 Electron filling in hybrid orbitals obeys, Hunds
rule, Pauli’s rule.
 The hybrid orbitals involve only in ' ' bond
formation. They donot involve in ‘  ’ bond
formation.
 The concept of hybridisation was introduced to
explain the shapes of molecules, bond angles
in the molecules, bond lengths in the molecules.
 A half filled or completely filled or even vacant
orbital can participate in Hybridization..
 The hybrid orbitals are more effective in forming
stronger bonds that leads to the formation of
more stable molecules.
Note: Same atom can undergo different types of
hybridisation under different situations.
 More the directional bond greater is the bond
strength
sp3 - sp3 > sp2 - sp2 > sp- sp > p- p> s - p> s - s
Determination of Hybridisation and Shape
of Molecule or Ion Having Single Central
Atom
 No. of Electron pairs (EP) or steric number or
number of hybrid orbitals = No. of sigma Bond
Pairs(BP) + No. of Lone pairs(LP)
1
EP = S + G - V + A - C 
2
S = No of sigma bond pairs
G = Group no (or) No of valency Electrons of
the central atom
V = Valency of central atom in the compound
C = Charge of cation
A = Charge of Anion
Note: This rule is not applicable to molecules / ions
which have odd e   ClO2 , NO, NO2  , free
radicals , compounds like B2 H 6 which involve
3 centre 2e  bnd (banana bond) and complex
compounds
For example:
O=C=O
S. No = 2 + 0 = 2
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 Example of molecule having sp hybridisation

BeCl2 :
x x
y y 180°
S. No = 2 + 1 = 3
s
z z + z
O O
Linear
O Be
sp hybrids

N S. No = 3 + 0 = 3   
(a)
O O
Clp Be Clp
z z
O
(a) formation of sp hybrid orbitals from s and p
Cl S. No = 3 + 1 = 4 orbitals;
O O (b) Formation of the linear BeCl2 molecule.
BeCl2 is linear molecule with bond angle 1800
sp - Hybridisation in C2 H 2

H H 1s


Steric Type of  C C 
Geometry sp sp
number Hybridisation
sp (a)
2 Linear
2 2px 2px
3 sp Trigonal planar 
3 
4 sp Tetrahedral 2py
C
3 Trigonal  C
5 sp d bipyramidal 2py 
3 2
6 sp d Octahedral (b)
3 3 Pentagonal
7 sp d bipyramidal H 
Types of hybridisation
sp - Hybridisation:
 One s- orbital combines with one p- orbital to 
give two identical orbitals called sp - hybrid 
orbitals. 
c
 The angle between the two sp-hybrid orbitals in 
an atom is 1800 
 sp- hybrid orbital will have 1/2 s- character (or) H
50% s- character.1/2 p- character (or) 50% p-
character. Formation of sigma and pi bonds in ethyne.

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No. of No. of
Molecule Arrangement Reason for the
bonding lone Shape
type of electrons shape acquired
pairs pairs

AB2E 4 1 Bent Theoreticall y the shape

S should have been triangular
S planar but actually it is found
O O O O
119.5° to be bent or v-shaped. The
reason being the lone pair
bond pair repulsion is much
more as compared to the
bond pair bond pair repulsion.
So the angle is reduced
t o 119 .5 ° fro m 1 2 0° .

AB3E 3 1 N Trigonal Had there been a bp in place

H
H 107° py- of lp the shape would have
ramidal been tetrahedral but one
H lone pair is present and due
to the repulsion between
lp-bp (which is more than
bp-bp repulsion) the angle
N bet ween bond pairs is
H
reduced to 107° from 109.5°.
H

AB2E2 2 2 O Bent The shape should have been

tetrahedral if there were all bp
104.5° but two lp are present so the
H H shape is distorted tetrahedral
or angular. The reason is lp-lp
repulsion is more than lp-bp
repulsion which is more than
bp-bp repulsion. Thus, the
O angle is reduced to 104.5° from
109.5°.
H H

AB2E 4 1 F In (a) the lp is present at axial

F position so there are three
(a) F S F S lp-bp repulsions at 90°. In (b)
F See-
F saw the lp is in an equatorial
F F position, and there are two
F lp-bp repulsions. Hence,
F F arrangement (b) is more
F stable. The shape shown in (b)
(b) S is described as a distorted
S
F F tetrahedron, a folded square or
F a see saw.
F
(More stable)

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Note: In N 3 centrala nitrogen atom is in sp sp2 - Hybridisation in C2 H 4

hybridised state. In the formation of ethene molecule each carbon
In N 3 there is a total of two s and two p bonds undergoes sp2 hybridisation.
giving N = N = N and a bond order of two. Thus in ethene molecule, the carbon - carbon
Both N  N bonds are the same length, 1.16 bond consists of one sp 2  sp 2 sigma bond and
A0
The hydrogen azide molecules has a bent one Pi  
structure and two N  N bond length are The bond length 134 pm. The C-H bond is
different. sp 2  s sigma with bond length 108 pm. The H-
H
112O C-H bond angle is 117.6 while the H-C-C angle
is 121. The formation of sigma and pi bonds in
N=N=N ethene is shown in figure
o o
1.24A 1.13A H 1s H 1s 2p x 2px
Other examples: 
 
H H H    H
HCN, HgCl2, NO2+, N2O,BeF2 c c

C C 

sp2 - Hybridisation H 1s H 1s H H
H   H

 One s- orbital combines with two-p-orbitals to (a) (b)

give three identical orbitals called sp2-hybrid

2px 2px
orbitals. 
 The angle between any two sp2-hybrid orbitals H  H

H
in an atom is 1200. H
C C
H H C  C
H
1  
 sp2 hybrid orbital will have rd s- character (d) (e)
3
2
(or) 33.3% s-character. rd p- character (or)
3
66.7% P-character. Type AB3 AB2L
 The hybridisation of central atom in a molecule Shape Trigonal v - shape (bent)
having planar triangle shape is sp2. C =, CH3, CH3,C6H6, – C –, SO , SnCl
2– – 2 2
For example , in BCl3 molecule , CO3 , HCO3 , H2CO3, NOCl, O , NO
3 2
Example graphite, BF3, B(OH)3, NO –
2
x SO3, NO–3 , C60
(Fullerene)
Where A=central atom, B=side atom, L=lone pair of e–

z sp3 - Hybridisation
  One s- orbital combines with three p-orbitals to
 give four identical orbit als called
(s + py + pz)
sp 3 hybridisation.
 BCl3  The angle between any two sp3-hybrid orbitals
120° in an atom is 1090.281.
Planar  sp3 - hybrid orbital will have 1/4 th s- character
sp2 hybrids (or) 25% s- character. 3/4 th p- character (or)
75% p- character.
The geometry of BCl3 is trigonal planar with  The hybridisation of central atom in a molecule
CIBCl bond angle of 120°. having tetrahedral shape is sp3.

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x
Note: PH3 , AsH3 ,SbH 3 are in boding with pure ‘P’
+ +
109.5° orbitals of central atom.
y
+ Water Molecule
z + + In case of H 2 O molecule, the oxygen atom
+
– + +
– undergoes sp 3 hybridisation forming four sp 3
3
sp hybrids
hybrid orbitals out of which two contain one
s + px + py + p z electron each and the other two contain a pair of
electrons.These four sp 3 hybrid orbitals acquire
H a tetrahedral geometry , with two corners
+ occupied by hydrogen atoms while the other two

+
by the lone pairs. The bond angle in this case is
  reduced to 104.50 from 109.50 and the molecule
C
H + + + + H thus acquires a V-shape or angular geometry.
+

 + lp
H

Formation of sp 3 hybrids by the combination of

s, px , p y and pz atomic orbitals of carbon and
lp
the formation of CH 4 molecule
Ammonia Molecule
In NH 3 , nitrogen undergoes sp 3 hybridisation.It H
has 3 bond pairs and one lone pair on nitrogen
atom.The repulsion between a lone pair and a
H H2O
bond pair is more than the force of repulsion
between two bond pairs of electrons. The
molecule thus gets distorted and the bond angle H 2O H 2S H 2Se H 2 Te
is reduced to 1070 from 109.50 The geometry 104.28 93.3 91 90
of such a molecule will be pyramidal as shown in In H 2Se, H 2S, H 2 Te pure ‘P’ orbitals of central
figure
atoms are in bonding.
NH3 PH 3 AsH 3 SbH 3
Nature and types of bonds in ethane C2 H 6 :
107.3 93.3 91.8 91.5
i) one C  C  sp3 sp3 with bond length 154pm
lp
ii) six C  H  sp 3 s with bond length 109pm
Note:Some important molecules in which central atom
involves sp 3 hybridization are
N
H H SOCl2 , XeO4 , H 2 O2 , B2 H 6 , SiO2 , P4 O10 , P4O6

Type AB4 AB3L AB2L2 ABL3

H shape tetrahedral pyramidal Vshape Linear

Example CH 4 XeO3 Br2O OCl 

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Hybridization involving d - orgbital and Type  The axial bonds have been found to be
of ‘d’ orbital involved longer than equatorial bonds since axial P-
Cl bonds experience greater repulsion from
equ ator i al P-Cl bonds. As a r esul t PCl 5
Steric Type of molecule becomes more reactive.
Number Hybridisation Geometry Involving d orbitals
 Maximum number of atoms present in a plane of
square
4 dsp2 planar
d x 2  y2 PCl5 are 4.

sp3d
Trigonal d z2 Type AB5 AB4L AB3L2 AB2L3
5 Bipyramidal
Shape Trigonal T - shape
6 sp3d2 Square d x2  y2 & d z 2 bipyramidal See - saw Linear
Bipyramidal XeF2, I3
–
ClF3,
Example PCl5, PBr5, SF4, – –

sp3d3
Pentagonal d x2  y2 , d z2 , d xy PF5 etc XeO2F2 [XeF3 ] [ICl2]
7 Bipyramidal
Other examples

sp3d - Hybridisation
F
 One S-orbital, three P-orbitals and one d- Cl

orbital combines and gives five identical orbitals

PCl3 F2 P
called sp3d-hybrid orbitals. Cl
Cl
F
The bond angles possible in sp 3 d hybridisation
0
are 900, 1200.
sp3d hybrid orbital will have Cl F

1/5 th s-character (or) 20% s-character.

PF3Cl2 P 0
3/5th p-character (or) 60% p-character.
Cl F
1/5th d-character (or) 20% d-character. F

 The hybridisation of central atom in a molecule F

having trigonal bipyramidal shape is sp3d.

S
Formation of PCl5  sp d hybridisation  :
3 SF4 0
F F
F

Cl
F

Cl P
Cl ClF3 Cl
0
F
Cl F

Cl
Xe
Phosphorus undergoes sp3d hybridization and XeF2 0
molecule has Trigonal bipyramidal geometry. F

Three P-Cl bonds lie in one plane and make an Note:

angle of 1200 with each other; these bonds are
termed as equitorial bonds. The remaining two
P-Cl bonds-one lying above and the other lying
above and the other lying below the equitorial
plane, make an angle of 90° with the plane. These
bonds are called axial bonds.
i) lone pair will occupy equatorial positions but not
axial.
ii) More electronegative atoms will prefer to occupy
axial positions.
iii) Since, double bonds occupy more space.
Therefore, they prefer equatorial positions.

18 NARAYANA GROUP
 CHEMICAL BONDING JEE-ADV
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Note: Note: Since, octahedral is a symmetrical in shape

In solid state (i) a lone pair can occupy any position
PCl5 exists as ionic solid consisting of (ii) if there are two lone pairs , then they occupy
trans postions(opposite).
 PCl4  (tetrahedral) and Other examples
O
 PCl6  (octahedral). 
O O
4
Note: (i)  XeO6  Xe


O O
O
PF5  g  is trigonal bipyramidal and the electron
4
difraction shows that some bond angles are  X eO 6  is perxenate ion & H 4 XeO6 is
90 and others aare 120 , and the axial P - F
° called perxenic acid. But H 2  XeO 4  is called
bond lengths are 1.58 A whilst the equatorial P -
xenic acid.
°
F lengths are1.53 A . But NMR studies suggest O
F
that all five atoms are equivalent because of F

Xe
pseudo rotation. PF5 remains covalent and is (ii) XeOF4 F
F
trigonal bipyramidal in the solid state . ..

PBr5  s  exists as  PBr4  Br  .
sp3d2- Hybridisation F F
 Steric number = 6 ; Geometry = octahedral.
 One s-orbital , three p-orbitals and two d-
orbitals combines to give six identical orbitals Xe
(iii) XeF4
called sp 3 d 2 hybridisation.
F F
 The bond angle possible in sp 3d 2 hybridisation
is 900
 sp3d2 hybrid orbital will have 1/6th s-character, sp 3 d 3 Hybridization
1/2 p-character and 1/3 d-character Steric number = 7
 SF6 : Geometry = Pentagonal bi - pyramidal
In SF6 the sulphur atom undergoes sp3d 2 One s-orbital , three p-orbitals and three d-
orbitals combines to give seven identical orbitals
hybridisation in second excited state.
called sp 3 d 3 hybridisation.
F
 The bond angle possible in sp 3d 2 hybridisation
F F is 720 ,90 0 .
S
 sp3d3 hybrid orbital will have
F F 1/7th s-character,
3/7th p-character and
F 3/7th d-character
Octahedral geometry of SF6 molecule. Ex: IF7
 Maximum number of atoms present in a plane Iodine undergoes sp 3 d 3 hybridisation in the third
of SF6 are 5 excited state.

NARAYANA GROUP 19
CHEMICAL BONDING JEE-ADV CHEM-VOL-I
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F dsp2-Hybrisdisation
F The orbitals involved in dsp2 hybridisation are
d z 2 , s and two p-orbitals, geometry is square
planar bond angle between any two dsp2 orbitals
F F is 900
Eg:  Pt  NH 3 2 Cl2 
I Hybridisation in Carbon Compounds
No of  Bonds Hybridisation
per carbon
0 sp3
F F 1 sp2
2 sp
H 2 C = CH - C  CH
F eg: Vinyl acetylene:
sp 2 sp 2 sp sp
Type AB7 AB6L W.E.-09.Discuss the hybridization of carbon
Pentagonal Distorted atoms in allene(C3H4) and show the 
Shape
bipyramidal Octahedral orbital overlaps.
Example IF7 XeF6 CH 2  C  CH 2
Sol: Allene is :
F F I II III
F F F F Carbon atoms I and III are sp2 hybridised while
XeF6 (g) Xe or Xe carbon II is sp hybridized. The two unhybridised
orbitals of carbon II overlap sidewise with
F F F F unhybridised p orbitals of carbon I and III to
F F form  bonds.
Distorted octahedron with a nonbonding electron
pair either at the center of a face or the midpoint W.E.-10.Predict the shapes of the following
of an edge. species and the type of hybrid orbitals on
the central atom.a) PbCl4, b) SbF6–&c) PCl3.
Structure of XeF5 :
Sol: a) Tetrahedral, hybridization of Pb is sp3
b) Octahedral, hybridization of Sb is sp3d2
F F c) Pyramidal, hybridization of P is sp3
W.E.-11.Write the decreasing order of
(a) carbon – carbon and (b) carbon –
Xe F hydrogen bond lengths in ethane, ethylene
and acetylene molecules.
Sol: Carbon-carbon bond lengths are:
F F
C2H6 > C2H4 > C2H2
154pm 134pm 120pm
Structure of I 2Cl6 : Carbon-hydrogen bond lengths are:
Pentagonal planar ion with two nonbonding C2H6 > C2H4 > C2H2
electron pairs above and below the plane of the 110pm 109pm 106pm
pentagon. Calculation of no. of Hybrid orbitals and
ICl3 does not exist, but the dimer I 2Cl6 is bright Pure orbitals in carbon compounds
yellow solid. Its structure is planar. Hybridisation No. of Hybrid
Orbitals
3
Cl Cl Cl sp 4
I I sp3d3 sp2 3
. sp 2
Cl Cl Cl No.of pure orbitals = 2( )  No. of Hydrogens

NARAYANA GROUP
20
 CHEMICAL BONDING JEE-ADV
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CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II

W.E.-12.Calculate the ratio between hybrid

orbitals (HO)and pure atomic orbitals(PAO)
in Allene. No.of No.of Molecular Example
B.Ps L.Ps Shape
CH 2  C  CH 2
Sol:
SP 2 SP SP 2 BeCl2
No. of HO = 2 (3) + 2 = 8 2 0 AB2 Linear BeF2
No. of PAO = 2 (2) + 4 = 8
C2H2
Ratio between H.O and P.A.O = 1
VSEPR THEORY Planar BF3
It was originally proposed by sidgwick and 3 0 AB3
Triangle BCl3
powell later it was further developed by Nyholm
and Gilliespie, CH4
 The shape of a molecule depends on the +
number of electron pairs in the valence shell NH4
4 0 AB4 Tetrahedral
(bonded or non bonded) of the central atom CCl4
 If the central atom is surrounded by only bond
pairs of electrons the molecule has a regular
5 0 AB5 Trigonal PCl5
shape. bipyramidal
 In addition to bond pairs if the central atom has
one or more lone pairs the molecule has 6 0 AB6 Octahedral SF6
irregular shape.
SO2
 Pairs of electrons in the valence shell repel one 2 1 AB2E Bent
another since their electron clouds are O3
negatively charged.
Trigonal
 These pairs of electrons tend to occupy such 3 1 AB3E NH3
positions in space that minimise repulsion and Pyramidal
then maximise separation between them.
2 2 AB2E2 Bent H2O
 A lone pair of electrons takes up more space
around the central atom than a bond pair because 4 1 AB4E See Saw SF4
the lone pair is attracted to one nucleus while
bond pair is shared by two nuclei. 3 2 AB3E2 T-shape ClF3
 The repulsions between electron pairs on
central atom follows the order Square
5 1 AB5E BrF5
l.p - l.p > l.p - b.P > b.P - b.P Pyramidal
 A multiple bond is treated as if it is a single
Square
electron pair and the two or three electron pairs 4 2 AB4E2 XeF4
of a multiple bond are treated as a single super Planar
pair.
 The magnitude of repulsions between BP of
electrons depends on the electronegativity W.E.-13: What are the types of bonds present in
difference between the central atom and hydrogen cyanide molecule?
other atom. Sol: Lewis dot structure of HCN is H : C  N :
A = Central atom in the compound. The bonds in HCN molecule are one single bond
B = Atom linked to the central atom. and one triple bond. Further, HCN molecule has
E = Lone pairs of electron. two  and two  bonds.

NARAYANA GROUP 21
 CHEMICAL BONDING JEE-ADV CHEM-VOL-I
SR-MAIN-CHEM-VOL-II

Molecular Orbital Theory ψMo = ψ A ± ψB

 It was proposed by Hund and Mulliken to
explain para magnetic nature of oxygen molecule. σ = ψ A + ψ B (Bonding molecular orbital)
 The electrons in a molecule are present in
σ * = ψ A - ψ B (Antibonding molecular orbital)
various molecular orbitals as the electrons of
atoms are present in the various atomic orbitals
 Molecular orbitals are formed by linear Antibonding orbital
combination (LCAO) of atomic orbitals of higher energy than
comparable energies and proper symmetry. that of atomic orbitals
 1s orbital can combine with another 1s orbital
Molecular
but not with 2s orbital because the energy of 2s Atomic
Atomic orbitals

Increasing energy
orbitals is higher than that of 1s orbital. This is orbital orbital
true only for homo nuclear diatomic molecules
 By convention z-axis is taken as the molecular * = A – B
axis, 2pz orbital of one atom can combine with
2pz orbital the other atom but not with the 2px or A B
2py orbitals because they differ in symmetry.
 Molecular orbital is polycentric i.e., an electron * = A + B
in molecular orbital is under the influence of two
Bonding orbital
or more nuclei.
lower energy than that
 The number of molecular orbitals formed is equal of atomic orbitals
to the number of combining atomic
orbitals.
 During the formation of BMO, the two electron
 Linear Combination of two atomic orbitals leads
waves of the bonding atoms reinforce each other
to the formation of BMO and ABMO.
due to constructive interference
 BMO is stabilized to the same extent as to the
 During the formation of ABMO, the electron
ABMO destabilised .
waves cancel each other due to destructive
 Energy lost in the formation of BMO is equal to
interference
energy gained in the formation of ABMO.
 The electron density in a bonding molecular
 Order of energies of various molecular orbitals is
orbital is located between the nuclei of the
bonding orbitals < non bonding orbitals < anti
bonded atoms.
bonding oritals
 The electron density in antibonding molecular
 The molecular orbitals are filled in accordance
orbital is located away from the space between
with the Aufbau principle , Pauli’s exclusion
nuclei (nodal plane)
principle and Hund’s rule.
 The increasing order of relative energies of M.O
 The molecular orbitals are named as  ,  ,  .. etc. having less than or equal to 14 electrons.
 Formation of molecular orbitals by LCAO
method:  1s   *1s   2 s   * 2 s  [ 2 px 
 According to wave mechanics, the atomic  2 py]   2 pz  [ * 2 px   * 2 p y ]   * 2 pz
orbitals can be expressed by wave functions ( ),  The increasing order of relative energies of M.O
which represent the amplitude of waves. having more than 14 electrons.
 The atomic orbitals of two hydrogen atoms A and
 1s   *1s   2 s   * 2 s   2 p z
B may be represented by wave functions  A and
  2 p x   2 p y 
B .
 Mathematically, formation of molecular orbitals   * 2 px   * 2 p y    * 2 p z
may be described as

22 NARAYANA GROUP
 CHEMICAL BONDING JEE-ADV
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CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II

(a) Molecular Antibonding sigma

orbital molecular orbital
Atomic – 1 nodal plane
*1s Atomic + –
orbital + +
orbital
1s 1s
Energy

1s
Bonding sigma
1s 1s molecular orbital
+
1s +
+ +
1s
1s 1s

(b) Molecular Antibonding sigma

orbital molecular orbital

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

Bonding sigma
1s 1s molecular orbital
– + + –
1s
2pz 2pz 2pz

Antibonding pi
Molecular molecular orbital
orbital
+
– +

Atomic – – 2 nodal planes

*2px Atomic
orbital orbital
Energy

2pz 2pz
*-2px
2px 2px Bonding pi
molecular orbital
2px
– +

++

– –

2pz 2pz 2pz

NARAYANA GROUP 23
 CHEMICAL BONDING JEE-ADV CHEM-VOL-I
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Helium Molecule (He2)

Difference between sigma and pi MO’s  The total number of electrons = 4
 12s   1*2s (diamagnetic)

 Nb  N a   2  2  0
Bond order =
2 2
1. Formed by the end 1. Formed by the side
on overlap along wise overlap Hence He2 molecule can not exist
the internuclear perpendicular to  Lithium Molecule (Li2)
axis. inter nuclear axis. no of electrons = 6
2. Overlapped region 2. Overlapped region
is very large. is small.  1s 2  *1s 2  2 s 2 (or)
3. Rotation about the 3. Rotation about the KK 2 s 2 (diamagnatic)
internuclear axis is inter nuclear axis
42
symmetrical. is unsymmetrical. Bond order  1
4. Strong bonds are 4. Weak bonds are 2
favoured. favoured.  Boron Molecule (B2)
no of electrons = 10
 1s 2  *1s 2  2s 2  * 2s 2  2 p1x   2 p1 y (or)
Bond Order
KK  2 s 2  * 2 s 2  2 p1x   2 p1 y
1
 Bond order = It has 2 unpaired electrons, hence paramagnetic
2
Carbon molecule (C2):
[Number of bonding electrons - Number of Number of electrons = 12
antibonding electrons] 2 2
KK  2 s   * 2s    2 px2   2 p 2y  (dia)
Nb  Na
or = C2 consists of both  bonds beacuse of the
2
presence of four electrons in two  molecular
 As bond order increases , bond energy and
orbitals.
stability of the molecule increases but bond
Nitrogen Molecule (N2)
length decreases.  The total number of electrons =14
Magnetic Nature
 If all the electrons in the molecule or ion are paired  
 12s  1*2s  22s  2*2s  22Px   22Pz (or)
it is diamagnetic in nature.If it is unpaired that is
 2 Py 
2

paramagnetic.

Magnetic moment   n  n  2  B.M  2 

KK  22s  2*2s  2 Px   22Pz (dia)
Electronic Configuration / Bond Order of  22Py 
Simple Diatomic Molecules:
Hydrogen Molecule (H2)  N b  N a   10  4  3
Bond order =
 Total number of electrons = 2 2 2
Oxygen Molecule (O2)
 12s   1*0s (diamagnetic)
 Total number of electrons =16
 Nb  N a   2  0  1    
Bond order =  12s  1*2s  22s  2*2s  22Pz  22Px    2*1Px   2*Pz
2 2
 22Py    2 Py 
*1

24 NARAYANA GROUP
 CHEMICAL BONDING JEE-ADV
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CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II

Nitrogen species:
 N b  N a   10  6  2
Bond order = 10  4
2 2 Bond order of N 2  3
3
O2 molecule contains two unpaired electrons
 94
*
Bond order of N 2   2.5
in  hence it is paramagnetic in nature. 2
2p

O2+ Ion 2 84

Bond order of N 2   2.0
2
 Total number of electrons
(16 - 1) = 15,  10  5
Bond order of N 2   2.5
2
   
 12s  1*2s  22s  2*2s  22Pz  22Px    2*1Px   2* Pz 2 10  6
 22Py    2 Py 
* Bond order of N 2  2
2
 As the bond order increases the stability of
10  5
Bond order=  2.5 molecule increase. However, some of the bond
2 orders are identical. In such case, a molecule or
It contains 1 unpaired electron hence it is ion with more number of electrons in their
paramagnetic antibonding orbitals is less stable.
O2– (Super Oxide Ion)
N 22   N 22   N 2  N 2  N 2 .
 Total number of electrons
 Bond dissociation energy order
(16 +1) = 17.
N 2  N 2   N 2   N 2 2
   *2  *  Bond length order
 12s  1*2s  22s  2*2s  22Pz  22Px   2 Px   2 Pz
 2 Py   2*1Py 
2
N 2 2  N 2   N 2   N 2

CN  ion
 Nb  Na   10  7  1.5
Bond order = The CN  ion has totally 14 electrons ( 6 from
2 2
carbon, 7 from nitrogen and 1 due to nagative
It contains 1 unpaired electron hence it is
paramagnetic charge) and is isoelectronic with N 2 . The energy
Peroxide Ion -(O22–) difference in s and p orbitals is less. Therefore,
 Total number of electrons (16 + 2) =18. sp mixing takes place in the formation of

    CN  ion, The MO electronic configuration of

2 
 12s  1*2s  22s  2*2s  22Pz  2 Px 
*2
 2 Px
*
  2 Pz (dia) 2 2 2 2 2
 22Py   2 Py
*2
 CN  is KK*  2s  * 2s 2p x  2p y 2p z  .

Bond order is  8  2  / 2  3 .
10  8
Bond order =  1. HOMO:- Highest occupied molecular orbital
2
LUMO: Lowest unoccupied molecular orbital
Oxygen Species
CO
 Bond dissociation energy order
Bond lengths of CO and CO are 112.9 pm and
O2   O2  O2   O2 2
111.5 pm respectively. This suggests that electron
 Bond length order is removed from nonbonding orbital of carbon
O2 2  O2   O2  O2 which is at higher energy.

NARAYANA GROUP 25
 CHEMICAL BONDING JEE-ADV CHEM-VOL-I
SR-MAIN-CHEM-VOL-II

MO DIAGRAMS WITH AND WITHOUT MIXING OF 2s & 2p ORBITALS

with 2s-2p mixing without 2s-2p mixing
B2 C2 N2 O2 F2 Ne2
 2* p  2* p
Energy

 2* p  2* p

2p 2p
2p 2p
Bond energy / kJ mol–1

 2s* *
 2s
 2s  2s

Bond length/pm
900 159 945
150
143
600 131
110
121 100
620
300 498 50
290 159
Bond length 1 2 3 2 1 0
Magnetic Paramagnetic Diamagnetic Diamagnetic Paramagnetic Diamagnetic –
properties
2 2
Valence  2s   *2 s   2 s 2  *2 s 2  2 s 2  *2s 2  2 s 2  *2 s 2 2
 2 s   *2 s 
2 2
 2s   *2 s 
2

2 4 4 2
electronic  2 p   2 p   2 p   2 p   2 p 2  2 p 4 2 4 2 4
configuration    
2p 2p    
2p 2p
2
 * 
2p
 * 
4
2p
4
 *   *  2p
2

2p

Gerade and Ungerade molecular orbitals

 If the symmetry of a molecular orbital with respect to its centre is symmetrical it is called gerade and it is
represented by symbol ‘g’ , if it is unsymmetrical it is called ungerade and is represented by the symbol
‘u’.
 The symmetry in the orbitals is a point from whch lines when drawn on one side and produced to an
equal distance on the other side will meet the new point if at this new point the sign of the orbital is same
it is gerade otherwise ungerade.
 All  ( bonding MO’S) are gerade whereas all  * ( antibonding MO’s) are ungerade. similarly  *
( antibonding MO’s) are gerade whereas all  ( bonding MO’s ) are ungerade,
for example,
Gerade orbitals:  g 1s  , g  2 s  , g  2 p z  , g  2 p x  , g  2 p y 
* *

Ungerade orbitals:  u 1s  , u  2 s  ,  u  2 p z  ,  u  2 p x  ,  u  2 p y 

* * *

+. +.  + 
(g)
(g)
node
+. –.  
*(u)
(u)

26 NARAYANA GROUP
 CHEMICAL BONDING JEE-ADV
JEE-ADV CHEM-VOL-I
CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II

DIPOLE MOMENT Applications of Dipole Moment

 Polarity of a polar molecule is expressed in terms 
of dipolemoment (  ).
 Dipolemoment (  ) = charge on the pole (q) 
 distance between the poles (d).
 Dipolemoment is usually expressed in Debye
units(D)
 1D = 3.33564 1030C.m (S.I)
where; C = Coulomb and m = meter
 1018 esu.cm  CGS 
 Dipolemoment is vector quantity and is 
represented by crossed arrow( ) pointing
towards more electronegative atom. eg:
H F
 For a polyatomic molecule the net dipole moment
is the vectorial sum of all bond moments.
Calculation of resultant dipole moment
 Let AB&AC are two polar bonds inclined at
angle  , their dipole moments are 1 &  2 . The
resultant dipole moment may be calculated using
B
Dipole moment is helpful in predicting the
geometry of the molecule.
Dipole moment helps in determining the polarity
 Dipole moment can distinguish between
symmetrical and non symmetrical molecules
eg: CO2 has zero dipole moment as it is
symmetrical whereas H2O has a dipole moment
of 1.85 D.
O
O C O 105º
H H
Net dipole moment of water = 1.85 D
 NH3 has higher dipole moment than NF3 because
in NH3 the orbital dipole due to lone pair is in the
same direction as the resultant dipole moment of
the N - H bonds, whereas in NF3 the orbital
dipole is in the direction opposite to the resultant
dipole moment.

A N N N
> >
C
H H Cl Cl F F
2
1
2
μ R = μ + μ + 2μ1μ 2cosθ
2
H Cl F

Type of Geometry
Molecule  Usually cis isomers have higher dipole moment
than trans isomer
HF 1.78 Linear eg:
HC l 1.07 Linear
Molecule H Cl H Cl
HBr 0.79 Linear
(AB) 0.38 Linear C C
HI
H2 0 Linear
C C
H 2O 1.85 Bent
Molecule H Cl Cl H
H 2S 0.95 Bent
(AB 2)
CO 2 0 Linear
 Order of dipole moment in dichlorobenzene:
Trigonal-
NH 3 pyramidal
Molecule 1.47 Trigonal-
NF 3 0.23
(AB 3) pyramidal
BF 3 0 Trigonal-
planar
CH 4 0 Tetrahedral
Molecule
CHC l 3 1.04 Tetrahedral
(AB 4)
CC l 4 0 Tetrahedral

NARAYANA GROUP 27
 CHEMICAL BONDING JEE-ADV CHEM-VOL-I
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The Bond moments donot cancel each other W.E.-14.The dipolemoments of SO2 and CO2 are
when the two groups are different    0  5.37  10–30 C.m and zero respectively. What
can be said about the shapes of the two
molecules?
Sol: SO2 is angular, as the S = O bond moments do
not cancel.
CO2 is linear. Though C = O bonds are polar,
the bond moments cancel each other.
W.E.-15.Dipolemoment of H2S is 0.95 D, Find
the S – H bond moment. Bond angle in H2S
0 is 960 and cos 480 is 0.66.
Sol:  H 2 S  2   S  H cos(960 / 2)
For symmetrical planar molecules   0 .
0.95  2  S  H  0.66
For non planar molecules   0
S-H bond moment = 0.72 D
Ionic Character of a Covalent Bond
CN OH SH  % ionic character of a covalent bond
observed dipole moment of bond
= ×100
calculated dipole moment of bond
W.E.-16.The dipolemoment of HBr is 2.60  10–
CN OH SH 30
C.m and the interatomic spacing is 1.41
0
A . What is the percentage ionic character
of HBr ?
Sol: cal  q  d
  CH3Cl  CH 2Cl2  CHCl3  CCl4
= (1.60  10-19 C) (1.41  10-10m)
 Hybridisation can be determined by dipole = 2.26  10-29 C m
moment The percentage ionic character =

i) If a molecule AB2 has = 0, the  orbitals
2.60 1030 Cm
used by A (z < 21) must be sp hybridised 100  11.5%
2.26 1029 Cm
eg: BeF2
BOND PARAMETERS
F Be F Bond length :
ii) If a molecule AB 3 has  = 0, the  orbitals  The equilibrium distance between the
used by A ( z < 21 ) must be sp2 hybridised nuclei of two bonded atoms in a molecule
eg: BF3 is called bond length.
 Bond length is measured by spectroscopic,
F x-ray diffraction, and electron -diffraction
techniques.
F B  The bond length between a set of same atoms in
F different molecules is always same if hybridised
state is same
 Dipole moment  electronegativity difference
eg:O-H bond length in H 2O, H 2O2 , C2 H 5OH is
HF  HCl  HBr  HI 0
 Dipolemoment  No.of lone pair of electrons. same i.e. 0.97A
HF  H 2O  NH 3  As the p-character of hybrid orbital changes the
bond length changes.

28 NARAYANA GROUP
 CHEMICAL BONDING JEE-ADV
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CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II

C-H bond length in C2 H 6 , C2 H 4 and C2 H 2 are C  F  C  Cl  C  Br  C  I

0 0 0 Si  F  Si  O  Si  Cl  Si  N 
1.09 A,1.08 A and 1.06 A respectively..
Si  Br  Si  S  Si  I  Si  Si
 As number of bonds between two atoms
increases bond length decreases. C  F  C  O  C  B  C  C  C  Cl
485 358 356 346 327

C C ; C C; C C  C  Si  C  N  C  Br  C  S  C  P  C  I
318 305 285 272 264 213
0 0 0
Bond Angle :
1.54 A; 1.34 A; 1.20 A
 Angle between the orbital containing
 As the size of bonded atom increases bond length bonding pair of electrons around the
increases. central atom in a molecule (or) complex ion
HF HCl HBr HI is called bond angle.
92pm 127pm 141pm 160pm  Bond angle is determined by spectroscopic
 It is effected by resonance
methods.
Ex:
 As bond angle increases stability increases.
(i) In benzene, carbon - carbon bond length is
 Bond angle is effected by the presence of lone
intermediate between C  C of ethane and pair of electrons on central atom
C  C of ethene. eg: CH 4  1090 281   0 L.P 
(ii) In O3 , both oxygen - oxygen bonds are
identical. NH 3  1070  1 L.P 
Bond Dissociation Enthalpy : H 2O  1040   2 L.P 
 It is the amount of energy required to break
one mole of bonds of a particular type  Bond angle depends on state of hybridisation
between two atoms in a gaseous state.  As % s character increases bond angle increases
eg: C2H2 > C2H4 > C2H6 (Decreasing order of
H 2  g   2 H  g  ,  a H  435.8kJmol
0 1
bond angle)
 In the case of H 2 O molecule, the enthalpy  If the electronegativity of central atom decreases
needed to break the two O-H bonds is not the bond angle decreases
same due to changed chemical environment. NH3 > PH3 > AsH3 > SbH3
Therefore mean or average bond enthalpy is  Incase the central atom remains same bond angle
used increases with the decrease in electro negativity
of surrounding atoms
H 2 O g   H  g   OH  g   a H 10   502 kJ .mol 1
NI3 > NBr3 > NCl3 > NF3
OH  g   H  g   O g   a H 20  427 kJ .mol 1 Bond order
 Bond order indicates number of bonds
Average bond enthalpy of O-H bond in water
between two atoms in a molecule.
502  427  Greater the bond order more is the strength of
 464.5 kJ
2 the bond.
 The magnitude of bond energy depends upon  With increase in bond order, bond enthalpy
size of the bonded atoms. increases and bond length decreases.
 Bond energy values are less for homolytic fission  Bond order 3 is the highest for a diatomic
when compared to heterolytic fission. molecule.
Bond energies order  Iso electronic species have same bond order
Sn  F  Sn  Cl  Sn  Br  Sn  I eg: N 2 , CO , NO 

NARAYANA GROUP 29
 CHEMICAL BONDING
W.E.-17.Mention the shortest and longest
diatomic molecules.
Sol: The shortest diatomic molecule is hydrogen
The bond length in H2 is only 74 pm.
The longest diatomic molecule is iodine
The bond length in I2 is 267 pm.
W.E.-18.Write the increasing order of bond
energies of H2, F2 and HF molecules.
Sol: Bond in F2 is weak due to lone pair repulsions.
Bond in H2 is strong because bond length is least.
Bond in HF is strongest single bond because of
high polarity. Increasing order of energies:
F2 < H2 < HF
W.E.-19.Dissociation enthalpies of methane,
ethane and ethylene are respectively 400,
680 and 540 k cal m ol -1 . Calculate
 C  H ,  C  C and  C  C bond energies.
Sol: Methane has four  C  H bonds.
400
 C  H bond energy  4  100 kcal mol-1
Ethane has six  C – H bonds and one
 C  C bond.
 C  C bond energy = 680 – (6 x 100)
= 80 k cal mol-1.
Ethylene has four  C  H bonds, one
 C  C bond and one  C  C bond.
  C  C bond energy
= 540 – [(4 x 100) + 80];= 60 kcal mol-1
W.E.-20.The As-Cl bond distance in AsCl3 is 
2.20A0. Estimate the single bond covalent
radius of Arsenic, (Covalent radius of Cl is
0.99A0)
Sol: Internuclear distance -radius of chlorine atom
= radius of arsenic atom
2.20 – 0.99 = 1.21 A0
Covalent radius of As = 1.21 A0
HYDROGEN BONDING
 Hydrogen bond is a weak electrostatic force
present between positively charged
hydrogen atom of a polar molecule and a
highly electronegative atom carrying
negative charge.
 The highly electronegative atom may be present
in the same molecule (or) in a different molecule.
30 NARAYANA GROUP
JEE-ADV CHEM-VOL-I
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 Hydrogen bond is represented by a dotted line
(- - - ).
 The length of the hydrogen bond varies from
1.79A0 to 2.75A0
 The energy of hydrogen bond varies from 2 to
10 K.cals/mole or 10-50 kJ / mole.
 Hydrogen bond is weaker than covalent bond
and stronger than vanderwaals force of attraction.
 Most electronegative atoms like Fluorine,
Oxygen, Nitrogen only can involve in
hydrogen bond. Chlorine atom very rarely
involves in hydrogen bond.
 Strength of hydrogen bond:
H F  H O  H  N
Intra molecular hydrogen bond:
 Hydrogen bond present in the same molecule is
known as intra molecular hydrogen bond.
 Due to intramolecular hydrogen bonding, ring
formation (or) chelation occurs.
For example, in o-nitrophenol the hydrogen is in
between the two oxygen atoms
O
N
O
H
O
Intramolecular hydrogen bonding in o-nitrophenol
molecule
The intra molecular hydrogen bond is present in
substances like o- chlorophenol,
o- nitro phenol, o- nitro aniline,
o- Hydroxy benzaldehyde (Salicylaldehyde),
o- Hydroxy benzoic acid ( Salicylic acid),
Chloral hydrate:
H
Cl O
Cl – C – C – H
Cl O
H
(Cl3 CH(OH)2
 CHEMICAL BONDING
 Substances having intramolecular hydrogen 
bonds are less water soluble and steam volatile
have low boiling points.
Inter molecular hydrogen bond.
 Hydrogen bond formed between different polar
molecules is known as inter molecular
hydrogen bond.
 The inter molecular hydrogen bonds are present
in substances like water, ice, ammonia,
hydrofluoric acid, ortho phosphoric acid, ortho
bo ricacid, p-nitro phenol, p-hydroxy
benzaldehyde, p-hydroxy benzoic acid, Primary
alcohols  CH 3OH , C2 H 5OH  , fatty acids
 HCOOH , CH 3COOH  primary amines and
secondary amines, carbohydrates, proteins and
nucleic acids
 Substances having inter molecular hydrogen
bonds exist as associated molecules.
 Liquids having hydrogen bonds between their
molecules are called associated liquids.
 Water, ammonia, hydrofluoric acid, methyl
alcohol and ethyl alcohol etc., are associated
liquids.
 Liquids which do not contain hydrogen bonds
between their molecules are called normal liquids.
 Benzene, carbondisulphide, carbontetrachloride,
acetone, ether, bromine, nitro benzene etc., are
normal liquids.
 Associated liquids have higher boiling points than
normal liquids.
 Liquids having very low boiling points are called
volatile liquids.
eg: ether, acetone, benzene etc.
 The boiling point of an associated liquid depends
on strength of hydrogen bond present in it and
number of hydrogen bonds present in one mole
of it.
eg: 1) The boiling point of water (1000C) is more
than that of hydrofluoric acid (19.40C) though
the hydrogen bond in HF is very strong. This is
due to the presence of more number of hydrogen
bonds in one mole of water than in one mole of
HF.
NARAYANA GROUP
JEE-ADV
JEE-ADV CHEM-VOL-I
CHEM-VOL-I
SR-MAIN-CHEM-VOL-II
SR-MAIN-CHEM-VOL-II
Effect of Hydrogen Bonding in p-block
Hydrides :
i) The order of boiling points of hydrides of p-
block elements
SnH4 > GeH4 > SiH4 > CH4 (IVA)
ii)The boiling point gradually increases from CH 4
to SnH 4 with increase in molecular weight and
magnitude of Vanderwaal’s forces. (CH4 does
not form hydrogen bonds)
SbH3 > NH3 > AsH3 > PH3 (VA)
H2O > H2Te > H2Se > H2S (VIA)
HF > HI > HBr > HCl (VIIA)
The abnormal high BPs of HF, H 2 O and
NH 3 in their respective groups is due to
intermolecular hydrogen bonding.
 KHF2 exist but KHCl2 , KHBr2 and KHI 2
do not exist because in HF2 ion there is inter

molecular H-bonding  F    H  F .
 Hydrofluoric acid exists as H 6 F6 /  HF 6
molecules in vapour state. Water exists as
only H 2O molecules in vapour state so heat of
vaporisation of hydroflouric acid is less than that
of water.
 The molecular weight of formic acid (or) acetic
acid determined by using its solution in a non
polar solvent like benzene is twice the expected
value. This is due to the dimerisation of acid
molecules in the solution. The dimer formation
takes place with the help of hydrogen bonds.
O_____H_O
_ _
 H C C H
_ ____
O H O
 In ice every water molecule involves in four
hydrogen bonds. The ice is a tetrahedral three
dimensional polymer.
 The two helical strands in the DNA molecule are
joined by Hydrogen bonds.
 Covalent substances like Glucose, Urea, Sugar,
Ammonia, ethyl alcohol etc. dissolve freely in
water because they form hydrogen bonds with
water.
31
 CHEMICAL BONDING JEE-ADV CHEM-VOL-I
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 Substances having inter molecular hydrogen  The metallic bond can account for most of the
bonds are highly water soluble. They have high physical characteristics of metals such as
boiling points and they are not steam volatile. strength, malleability ( ability to be hammered
 Most hydrogen bonds are asymmetric i.e. the into sheets), ductility ( ability to be drawn into
H-atom is not located exactly between X and Y wires), luster and conductance of heat and
atoms, but much closer to X as compared to Y. electricity.
X – H ........ Y
 Hydrogen bonds are Linear or only slightly bent Electron Sea Model
maximising attraction between H and Y, and  In the case of metals, in whcih the valence
minimising repulsion between X and Y. electrons are not tightly bound to the nucleus,
 Valence angle    between H and Y-Z bond, every atom achieves a more stable configuration
varies between 1000 to 1400 by sharing the outer shell electrons with the
 BP of Ortho nitrophenol< Para nitrophenol. various other atoms in the metal lattice.
In Ortho nitrophenol molecules are held by  Quantum mechanically, atomic orbitals on all the
vander walls forces whereas in Para nitrophenol atoms overlap to give a vast number of molecular
molecules are held by intermolecular hydrogen orbitals which extend over the whole metal.
bonds.
 Ortho nitrophenoland Para nitrophenol can 
+ + + + + + + + + +
be separated by steam distillation.     
+  + +  + + + + + + +
W.E.-21:Which one in each of the following    
+ + + + + + + + + +
pairs is expected to exhibit hydrogen  
+  + + + + + + + + +
bonding together? 
Individual atoms with

Positive nuclei embedded in
a) CH3 – CH2 – OH and CH3 – O – CH3 associated electrons a sea of delocalized electrons
b) CH3NH2 and CH3SH Electron sea model
c) CH3OCH3 and (CH3)3N
Sol: a) CH3 – CH2OH forms H-bonds as H is  Hence, the valence electrons become detached
connected to O atoms. from their parent atom and move freely amongst
b) S does not form hydrogen bonds all the atoms within the crystal (delocalized
c) Both do not form hydrogen bonds because H electrons).
atom is absent on ‘O’ and on ‘N’
 The metal lattice is held together by the strong
W.E.-22:Which is expected to have highest
forces of attraction between the positive nuclei
melting point: PH 3 , NH 3 , (CH 3­ ) 3 N?
and the delocalized electrons.This is described
Explain.
as “ an array of positive ions in a sea of electrons.
Sol: NH3 has the strongest intermolecular hydrogen
bonding and it is expected to have the highest  The strength of the metallic bond depends on
melting point. Actual melting points are: the number of valence electrons contributed by
NH3 = 77.70C; PH3 = -1330C & (CH3)3N = -1170C the atoms to the delocalized electrons and the
METALLIC BOND packing arrnagement of the metal atom.
 The theory of covalent bonding cannot be  More number of decocalized electrons and more
extended to explain the bonding mechanism in closely packed atoms result in a stronger bond
metals. and a higher melting point. This explains why
 A theory was proposed to explain the force of group I metals have relatively low melting points
attraction holding the atoms together in a piece compared to other metals.
of metal which is called the metallic bond.

32 NARAYANA GROUP