Chemical Bonding

MONICA BEDI
MONICA BEDI
Ph.D Chemistry
12+ Years of Teaching Experience
Trained Million+ students
Author - Top Ranker’s Series (TRS)
 Bratin Mondal Amaiya Singhal

100 %ile 100 %ile

1. TRANSITION FROM IONIC TO COVALENT BOND - FAJANS' RULE
 Partial Covalent Character in Ionic Bonds

If polarization is more, larger will be covalent character of the bond.

 Deciding Parameters

The extent of polarization depends on both the ions as:

(i) The power of the cation to distort or Polarize the anion.

(ii) The susceptibility of the anion to get polarized by the cation.

 Fajan Rule

1. Small size of the cation. Smaller the size of the cation, greater is its
polarizing power.
Fajan Rule

1
Polarizing Power 
Size of the cation

Cation Radius of the cation, Formula of the Melting point of the

Å chloride chloride, ºC

Be+2 0.31 BeCl2 405

Mg+2 0.65 MgCl2 712

Ca+2 0.99 CaCl2 772

Sr+2 1.13 SrCl2 872

Ba+2 1.35 BaCl2 960

Fajan Rule

2. Large size of anion. Polarization increases with increase in size of anion.

Cation – Ca+2

Anion Radius of the Formula of the Melting point of

Anion, Å Halide the Halide, ºC
F– 1.36 CaF2 1932
Cl– 1.181 CaCl2 772
Br– 1.95 CaBr2 730
I– 2.16 Cal2 730
 Fajan Rule

3. Large charge on cation or anion. Larger the charge on cation greater is

polarizing power and large the charge on anion greater is its tendency to
get polarized.
Compound PbCl2 PbCl4
Oxidation state of Pb +2 +4
Type of bonding More Ionic More Covalent
Melting Point High Low
 Fajan Rule

4. Electronic configuration of the cation. Cation with 18 electrons shell

configuration (known as pseudo inert gas configuration) cause greater
polarization then the cation with 8 electrons shell configuration with the
same size and charge.

Cation Cu+ ion Na+ ion

Electronic 2,8,18 2,8
Configuration
Radius of the cation 0.96 Å 0.95 Å
Melting Point CuCl (442ºC) NaCl (800ºC)
Example :
+3 +2 +1
1. AlCl3 __ MgCl2 ___ NaCl

Covalent character __________, B.P. ____________

2. FeCl2 ____ FeCl3

3. PbCl2 ____ PbCl4
4. BeCl2 ___ MgCl2 ___ CaCl2 ___ SrCl2

covalent character ___ ___ ___ ___ ___

5. AlCl3 ___ AlBr3 ___ AlI3 ___ AlF3

6. CuCl ___ NaCl

2, 8, 8 2, 8
MP=442ºC 800ºC

7. LiF ___ LiCl ___ LiBr ___ LiI

covalent character ___ ___ ___ __ due to large size of anion.

 Crack it

1. Which has maximum covalent character ?

(a) MgCl2 (b) FeCl2
(c) SnCl2 (d) AlCl3
 Crack it
2. Out of the following, maximum covalent nature is in
(a) NaF
(b) MgO
(c) AIN
(d) SiC
 Crack the PYQ

3. Among the following the maximum covalent character is shown by the

compound :-
[AIEEE-2011]
(1) AlCl3 (2) MgCl2
(3) FeCl2 (4) SnCl2
 (2) To determine thermal stability of metal carbonates

From top to bottom thermal stability of carbonates increases

BeCO3
MgCO3 - size of cation increases
CaCO3 - f decreases (covalent character decreases)
SrCO3 - Thermal stability increases
BaCO3
 Crack it

4. Which of the following decomposes at highest temperature ?

(i) SrCO3 (ii) BaCO3
(iii) CaCO3 (iv) MgCO3.
3. HYBRIDISATION AND VSEPR
Methods of Finding Hybrid State and Geometry of Central Atom or
Ion in A Molecules:
STEP - 1:
Predict the number of valence electrons in central atom

Number of Valance Electrons

1 2 3 4 5 6 7 8
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Ga Ge As Se Br Kr
Rb Sr In Sn Sb Te I Xe
Cs Ba Tl Pb Bi Po At Rn
Distribute the number of valance electrons between Bond pairs and Lone pairs.
HYBRIDISATION

two — sp hybridization
three — sp2 hybridization
four — sp3 hybridization
five — sp3d hybridization
six — sp3d2 hybridization
seven — sp3d3 hybridization
Find the sum of BP + LP :
Sum of BP + LP Hybridisation State Geometry

Linear
Trigonal
Planer

Tetrahedral
(Td)

Trigonal
bipyramidal
(TBP)
 Find the sum of BP + LP :

Sum of BP + LP Hybridisation State Geometry

6 sp3d2

Square bipyramidal or
octahedral
1. Predict the shapes and hybridization of the central atom in the following
molecules and ions:
Octahedral Shape
1. Predict the shapes and hybridization of the central atom in the following
molecules and ions:
Octahedral Shape
1. Predict the shapes and hybridization of the central atom in the following
molecules and ions:
Killer Visualization
1. Predict the shapes and hybridization of the central atom in the following
molecules and ions:
Killer Visualization
1. Predict the shapes and hybridization of the central atom in the following
molecules and ions:
Killer Visualization
NH4+
2. IBr6
3. IBr4Q
4. IBr2Q
5. AsF5
CO2
SO2
SO3
CO32–
 Crack the PYQ
5. Which among the following species has unequal bond lengths?
[JEE Main 2021]
(a) XeF4 (b) BF4 –
(c) SF4 (d) SiF4
6. Among the following statements:-
I. PCl5 is trigonal bipyramidal whereas IF5 is square pyramidal.
II. Bond enthalpy of O - H bond in water and ethanol is different.
Ill. All carbon atoms have same hybridization in carbon suboxide (C3O2).

Find out the correct statements.

(A) I & II only (B) II & III only
(C) I & III only (D) I, II & III
Crack the PYQ

7. The correct statement about ICl5 and ICl–4 is :

(a) both are is isostructural. [JEE Main 2019]
(b) ICl5 is trigonal bipyramidal and ICl4 is tetrahedral.
(c) ICl5 is square pyramidal and ICl4 is tetrahedral.
(d) ICl5 is square pyramidal and ICl4 is square planar.
Crack the PYQ
8. The ion that has sp3d2 hydridisation for the central atom, is:
[Main April 8 , 2019 (II)]
(a) [ICl4]– (b) [ICl2] –
(c) [IF6] – (d) [BrF2] –
Crack the PYQ

9. The molecular geometry of SF6 is octahedral. What is the geometry of SF4

(including lone pair(s) of electrons, if any)?
[Main Sep. 02,2020 (II)]
(a) Tetrahedral (b) Trigonal bipyramidal
(c) Pyramidal (d) Square planar
Crack the PYQ
10. The shape of IF6– is :
[Main Online April 23,2013]
(a) Trigonally distorted octahedron
(b) Pyramidal
(c) Octahedral
(d) Square antiprism
Crack the PYQ

11. Identify the pair in which the geometry of the species is T-shape and
square pyramidal, respectively
[Main Online April 15,2018 (1)]
(a) ICl–2 and lCl5 (b) IO – 3 and IO2F – 2
(c) ClF3 and IO – 4 (d) XeOF2 and XeOF4
4. DRAGO GENERALISATION

One considers no hybridization, i.e., overlapping of almost pure atomic

orbitals. In such molecules bond angle is approximately 90°.
Group 15 Bond angle Group 16 Bond angle
NH3 107°48' H2O 104°28’
PH3 93°36' H2S 92°
AsH3 91°48' H2Se 91°
SbH3 91°18' H2Te 90.5°

Right order of bond angle.

(a) H2O > H2S > H2Se > H2Te
(b) NH3 > PH3 > AsH3 > SbH3
 Drago's Rule and Hybridization of Phosphine

Drago's rule states that there is no need for considering the hybridization of an
element in the following cases:
Case 1: At least one lone pair of electrons is present on the central atom of the
molecule.
Case 2: Any of the elements from group 13, 14,15, 16 or from 3rd to 7th
period forms the central atom.
Case 3: The surrounding atom has an electronegativity less than or equal to 2.5.
5. BENT'S RULE

EXPLANATION: As s-orbital is more close to nucleus, the electron pair

present in s-orbital will experience more attraction of the nucleus, i.e.
stability of the system increases, therefore, a lone pair prefers to occupy
that hybrid orbital which has greater percentage of s-character.
A more electronegative atom has tendency to attract the shared pair of
electron towards itself, thus it will prefer to overlap with that hybrid orbital
which has less percentage of s-character (i.e. relatively more distant from
nucleus of central atom) because by doing so, it increases the stability of
the system.
2. Draw the geometry of PCl3F2

Sol.
HYBRIDIZATION IN SOLID STATE

Hybridization in Ionic solid species :

Species Cationic part Anionic part
PCl5 +
PCl4 (sp )3 Pd6– (sp3d2)
PBr5 PBr4+ (sp3) Br –
XeF6 XeF5+ (sp3d2) F–
N2O5 NO2+ (sp) NO4– (sp2)
L2Cl6 (liquid) lCl2+ (sp3) lCl –4(sp3d2)
Cl2O6 Cl2O6+ (sp2) ClO4– (sp3)
(BeCl2)n (BeCl2)n (sp3)
 Crack the PYQ

12. The correct order of hybridization of the central atom in the following
species NH3, [PtCl4]2–, PCl5 and BCl3 is
[IIT JEE 2001]
(a) dsp2, dsp3, sp2, sp3 (b) sp3, dsp2, sp3d, sp2
(c) dsp2, sp2, sp3, dsp3 (d) dsp2, sp3, sp2, dsp3
13. Species like SbCl6–, SnCl62–, XeF5–and IO65– has hybridization as sp3 dx–1.
The value of “x” is
14. The Lewis structure of allene is

Which ol the following statements correctly gives answers for all 3 parts:
(a) Is the molecule planar?
(b) Does 1, 3-dichloro propadiene show geometrical isomerism?
(c) Is the molecule 1.3- dichloro propadiene polar?
(A) (i) Non-planar (B) (i) Planar
(ii) No geometrical isomcrism (ii) No geometrical isomcrism
(iii) Polar (iii) Polar
(C) (i) Planar (D) (i) Non Planar
(ii) Yes geometrical isomerism (ii) No geometrical isomerism
(iii) Polar (iii)Not Polar
CONCEPTS IN BONDING
6. Odd Electronic Species
(1) NO2 :
Structure of NO2:
 CONCEPTS IN BONDING

(2) CIO2 : The Cl-O bond length is in between single bond & double bond
length,
Structure :

Since the free electron is delocalized in d-orbital, its dimer formation

tendency is very less as compared to NO2.
 CONCEPTS IN BONDING

(3) CIO3 :
Bond angle = 119°
Hybridization = sp3
Shape = pyramidal
Structure :
 CONCEPTS IN BONDING

(4) CH3 :
Bond angle = 120°
Hybridisation = sp2
Shape = planer
Structure :
CONCEPTS IN BONDING


(5) CF3 :
Bond angle = 109°28’
Hybridisation = sp3
Shape = pyramidal
Structure :
7. Molecules that do not exist

(i) SF4, SF6, PF5 exists while. OF4, OF6, NF5 do not exists
Reason :- Due to the non avalibility of vacant 2d-orbital, N and O
atom cann't expand their octet.
 7. Molecules that do not exist

(ii) (a) Pl5(vap) & SCI6 do not exist

Reason :- Due to the steric crowding of the surrounding atoms.
(b) SCI6 does not exists while TeCI6 exists
Reason :- Size of Te > Size of S.
 Molecules that do not exist

(iii) SF6. PF5. XeF6, XeF4, XeF2 exists while SH6, PH5, XeH6, XeH4, XeH2
do not exist
Reason :- F is more electronegative
 8. BACK BONDING

There will be pp - pp back bonding between 2p of B atom & 2p of F atom.

BACK BONDING
Boron trlhalides:
BF3 BCl3 BBr3 BI3
   
sp2 sp2 sp2 unstable
(stearic hindrance)
All boron trihalides are lewis acids. Explain their order.

Boron trihalides are electron deficient molecules therefore act as a Lewis acids

But in BCl3  Pp-Pp back bonding 2p of B & 3p of Cl

less effective tendency to accept

L.P in BCI3 > BF3

Lewis acid strength BF3 < BCl3– < BBr3.
BACK BONDING

The extent of back bonding decreases if the atom having vacant orbitals is
also having some non-bonded electron pairs on it. So among the atoms of
third period the extent of back bonding follows the order Si > P > S > Cl.
BACK BONDING

Trisilylamine is a planar molecular and does not act as a lewis base while
trimethyl is a pyramidal and act as lewis base
In a similar compound N(PH3)3 the shape is found to be pyramidal, so N atom
must be sp3 hybridized due to much less extent of back bonding into the
vacant orbitals of P.

Silylisocyanate (SiH3NCO) is linear but methyl isocyanate (CH3NCO) is bent

l.P. of N can be delocalised

(Back bonding)
pp – dp back bonding.
 Crack the PYQ
15. Which one of the following does not have a pyramidal shape ?
[JEE MAINS 2014]
(1) P(CH3)3 (2) (SiH3)3N
(3) (CH3)3N (4) P(SiH3)3
 Crack the PYQ
16. The correct statement among the following is
[JEE MAINS 2019]
(1) (SiH3)3N is pyramidal and more basic than (CH3)3N
(2) (SiH3)3N is planar and more basic than (CH3)3N
(3) (SiH3)3N is pyramidal and less basic than (CH3)3N
(4) (SiH3)3N is planar and less basic than (CH3)3N
 N0. of Bond
N0. of electrons Bond Order
electrons Order
15 2.5
8 0
16 2
9 0.5
17 1.5
10 1
18 1
11 1.5
19 0.5
12 2
20 0
13 2.5
14 3
 Crack the PYQ
Among the following molecules/ions, C22-,N22-, O22-,O2
Which one is diamagnetic and has the shortest bond length?
[JEE Main 2019]

(A) C22- (B) O2 (C) O22- (D) N22-

Crack it

Which of the following pairs will have same bond order?

(a) F2 and O22– (b) N2 and CO2
(c) O2 and C2 2– (d) N2 and N2+
 Crack the PYQ

19. Among the following, the species having the smallest bond is :-
[AIEEE 2012]
(1) NO (2) NO+
(3) O2 (4) NO–
 Crack the PYQ

20. Which of the following is paramagnetic ?

[JEE MAINS 2017]
(1) CO (2) O22–
(3) NO+ (4) B2
 Crack the PYQ

21. Among the following, the molecule expected to be stabilized by anion

formation is C2, O2, NO, F2
[JEE MAINS 2019]
(1) NO (2) C2
(3) F2 (4) O2
 Crack the PYQ

22. The correct order of bond dissociation energy among N2, O2, O2– is shown
in which of the following arrangements?
[JEE MAINS 2014]
(1) N2 > O2 > O2– (2) O2 > O2– > N2
(3) N2 > O2– > O2 (4) O2– > O2 > N2
 Crack the PYQ

23. According to Molecular Orbital Theory,

[IIT-JEE 2016]
(A) C22– is expected to be diamagnetic.
(B) O22+ is expected to have a longer bond length than O2.
(C) N2+ and N2– have the same bond order.
(D) He2+ has the same energy as two isolated He atoms.
 Can you crack it !

24. The bond order and magnetic behaviour of O2– ion are respectively:
[JEE Main 2021]
(a) 1.5 and paramagnetic (b) 1.5 and diamagnetic
(c) 2 and diamagnetic (d) 1 and paramagnetic
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