CHEMISTRY

NMDCAT
Lecture # 18

(CHEMICAL BONDING)
 Contents:
1. Energetics of bond formation 2. Atomic sizes
3. Atomic radii 4. Ionic radii
5. Covalent radii 6. Ionization energy
7. Electron affinity 8. Electronegativity
9. Bond energy 10. Bond length
11. Types of bonds 12. Electrovalent or Ionic Bond
13. Covalent bond
14. Co-ordinate or dative covalent bond
15. Ionic character of covalent bond
16. Sigma and Pi bond 17. Hybridization
18. sp3 - Hybridization 19. sp2 - Hybridization
20. sp-hybridization
21 The Valence Shell Electron Pair Repulsion theory
22. Postulates of VSEPR theory
23 Applications of VSEPR theory
 1. Energetics of Bond Formation 4

Introduction:
When a chemical bond is formed, energy is decreased. Various types of
forces operate during bond formation.
Formation of H2 molecule
• When two hydrogen atoms come closer to distance of 75.4 pm
(equilibrium bond distance), the forces of attraction are greater than the
repulsive forces. The distance of 74.5 pm is called bond distance or
compromise distance or equilibrium bond distance of lowest energy.
• When two hydrogen atoms combine, the amount of energy 436.5 kJmol1
is released.
1
H  H   H 2
 H  4 3 6 .5 k J m o l
• When the distance between the two hydrogen atoms decreases beyond
75.4 pm, the repulsive forces become dominant and system becomes
unstable and potential energy increases as shown in the diagram.
• In the formation of H2 molecule the number of attractive forces are (4) and
repulsive forces are (2).

Potential energy curve for the formation of H2 molecule.

 13

3. Atomic radius (rn)

It is the half distance between the centres of two bonded atoms

of any element
It is the average distance between nucleus of the atom and its
outermost electronic shell. Its unit is pm (1pm = 10-12m)
 14

Q:
Atomic size of an element depends on:
A) Number of inner shells only C) Both A and B
B) Nuclear charge only D) Neither A nor B
 15

Explanation: (C)
With the increase of number of inner shells, atomic
size of an atom increases because nucleus hold on the
valence electrons decreases. e.g. in IIA group size of
Mg is greater than that of Be. This happens in a group.
With the increase of nuclear charge, size of atom
decreases e.g. size of Be is smaller than that Li. This
happens in a period.
 16

Q:
Keeping in view the size of atoms, which order is
correct? 2015
A) N > C C) Ar > Cl
B) P > Si D) Li > Be
 17

Explanation: (D)
The size of atom of an element decreases along the period
because nuclear charge increases.
e.g. Atomic size of Li = 152pm, Atomic size of Be = 112pm
 Q: 18
Following graph shows a physical property along the
period 3 elements. Which physical property is shown
in the graph: 2017

A) Electron affinity C) Atomic radius

B) Non-metallic character D) Melting point upto group IVA
 19

Explanation: (C)
Atomic radius decreases along the period.
(Already Explained)
 20
4. Ionic radius
Cationic radius (r+) Anionic radius (r-)
• With the loss of one or more electrons • With the gain of one or more electrons by
from neutral atom, it becomes positive neutral atom, it becomes negative ion.
ion.
• Then there is loss of the outermost shell • Then repulsion between electrons increases
• There is an imbalance protons-electrons • There is an imbalance protons-electrons
ratio i.e. number of protons > number of ratio i.e. number of electrons > number of
electrons protons
• Nucleus hold increases on the valence • Expansion in size takes place and thus
electrons and thus cationic radius anionic radius increases
decreases
• e.g. Na+ (102pm) < Na (157pm) • e.g. F- (133 pm) > F (72pm)
 21
Striking informations:

Decreasing order of size of isoelectronic species

• N-3 > O-2 > F- > Na+ > Mg+2 > Al+3
• P3- > S-2 > Cl- > K+ > Ca+2 > Sc+3
 22

Q:
Which one of the following will have the smallest
radius? 2015
A) Al+3 C) Mg+2
B) Si+4 D) Na+1
 23

Explanation: (B)
All are the iso-electronic species.
Greater is positive change, smaller is the size of ion.
• Na+1 > Mg+2 > Al+3 > Si+4
 24

Q:
The ionic radius of fluoride ion is: 2016
A) 72 pm C) 133 pm
B) 95 pm D) 157 pm
 5. Covlent radius 20

“Half the length of a single bond between two similar atoms which
are bonded together through covalent bond is called covalent
radius.”
The covalent radius of H2 is 37.7 pm and it is half of the single bond
length which is 75.4 pm. See the following diagram.
 35
6. Ionization energy (I.E)
i. It is
• the minimum amount of energy
• to remove an electron from the outermost shell
• of its isolated gaseous atom in its ground state
ii. Ionization energy of an element is an index of metallic character
iii. Factors:
• Nuclear charge (I.E ∞ nuclear charge)
1
• Atomic size (I.E ∞ )
atomic size
1
• Shielding effect (I.E ∞ )
shielding effect
• Penetration of atomic orbital s > p > d > f
 36
Trends in the periodic table:

I.E increases along the period because nuclear charge

increases along the period
I.E decreases down the group because atomic size and
shielding effect increase down the group
 37
Trends of ionization energy of
elements along period 2
 38

Explanation of Sketch shown above

• More stable electronic configuration of elements at the peak

• s sub-shell completely filled 4Be (1s2, 2s2) I.E = 899kJmol-1

• p sub-shell half filled 7N (1s2,2s2,2p3) I.E = 1402kJmol-1

• p sub-shell is completely filled 10Ne (1s2,2s2,2p6) I.E = 2081kJmol-1

 39
Conclusion:

The above sketch shows

Irregular trend of I.E along period 2
Confirms the evidence of existence of sub-shells
Most stable is the electronic configuration of an atom of element,
greater is the ionization energy
 40
Points to be remembered:

• Be, Mg, N, P and noble gases have relatively higher values of ionization
energy due to their stable electronic configuration
• Alkali metals have the least and noble gases have the highest ionization
energies in the respective periods
• Helium (He) has the highest first ionization energy (2372kJmol-1) among all
the elements in the periodic table
• Caesium (Cs) has the least first ionization energy (376kJmol-1) among all
the elements (EXCEPT Fr which is radioactive)
• Successive ionization energies are always greater than the first ionization
energy ∆𝐢 𝐇𝟑 > ∆𝐢 𝐇𝟐 > ∆𝐢 𝐇𝟏
 41
Some trends of increasing order of first ionization
energy among the elements of second and third
period are given below:
𝐏𝐞𝐫𝐢𝐨𝐝 𝟐: ∆𝒊 𝑯𝟏 : 𝐋𝐢 < 𝐁 < ∗ 𝐁𝐞 < 𝐂 < 𝐎 < ∗ 𝐍 < 𝐅 < ∗ 𝐍𝐞
𝐏𝐞𝐫𝐢𝐨𝐝 𝟑: ∆𝒊 𝑯𝟏 : 𝐍𝐚 < 𝐀𝐥 <∗ 𝐌𝐠 < 𝐒𝐢 < 𝐒 <∗ 𝐏 < 𝐂𝐥 <∗ 𝐀𝐫
Q:
In which of the following pair of elements, the second element has
greater first ionization energy than that of first one?
A) Be, B C) Ne, He
B) N, O D) Cl, Br
Explanation: (C) He (2372kJmol-1) while that of Ne is (2080kJmol-1)
 42

Q:
Energy required to remove an electron from the outermost shell of
an isolated gaseous atom in its ground state is: 2010
A) Electron Affinity C) Crystal Energy
B) lattice Energy D) Ionization Energy

Explanation: (D) Ionization energy

 43

Q: Which of the following elements has smaller 1st

ionization energy:
A) Al C) S
B) Mg D) Cl
Explanation: (A)
Al has comparatively smaller 1st ionization energy (kJmol-1).
A) Al (577) C) S (999)
B) Mg (738) D) Cl (1251)
 44

Q:
A sudden large difference between the values of second and third
ionization energies of elements would be associated with which of
the following electronic configuration:
A) 1s2, 2s2, 2p6 C) 1s2, 2s2, 2p6, 3s2
B) 1s2, 2s2, 2p6, 3s2, 3p2 D) 1s2, 2s2, 2p6, 3s2, 3p6, 3d1, 4s2,
 45

Explanation:
Successive ionization energy increases i.e. third I.E is greater than
second I.E and second I.E is greater than first I.E. In case of electronic
configuration 1s2, 2s2, 2p6, 3s2 after the loss of first electron there is a
sudden large difference between the value of second and third ionization
of the element because after the loss of second electron the positive ion
acquires noble gas configuration such as Ne. So much more energy is
required to remove the electron from a cation having noble gas
configuration. This can be confirmed from the following example:
Mg (1s2, 2s2, 3p6, 3s2).
 46

Explanation: Electronic configuration of Mg (1s2, 2s2, 3p6, 3s2)

Δ H 1 = 7 3 8 k J m o l ....  i 
+  -1
M g g   
 Mg g 
e

Δ H 2 = 1 4 5 1 k J m o l ....  ii 
+1 +2  -1
Mg g 

 Mg g
+ 1e

Δ H 3 = 7 7 3 0 k J m o l ....  iii 
2+ +3  -1
Mg g 

 Mg g 
+ 1e

• Mg+2 (1s2, 2s2, 2p6) stable configuration, much more energy is required to
move electron from p sub-shell.
 7. Electron Affinity (E.A) 31
OUTLINES:
• Definition • Factors
• Example • Trends in the periodic table
• Unit • Striking informations
• MCQs
• Definition:
• It is the energy released or absorbed, when an electron is added to a gaseous atom to form a negative ion
• Examples:
i O g + e− → O− g E.A1 = −141kJmol
−1
(energy is released)
ii O− −
g + e → O −2(𝑔) E.A2 = +780kJmol
−1
(energy is absorbed)
Reason for positive 2nd electron affinity value when a 2nd electron is added to uninegative ion, the incoming
electron is repelled by the already present negative charge and energy is absorbed in this process. That is why
2nd electron affinity has positive value.
 • Warning: 32
• It should be noted that electron is always absorbed by atom or ion in the gaseous state
and this gaseous state should be mentioned in the subscript of atom or ion e.g. O(g) , O-2(g).
• Unit of electron affinity = kJmol-

• Factors affecting E.A:

It depends on the following factors
(i) Atomic radius of atom
𝟏
(E.A ∝ 𝐚𝐭𝐨𝐦𝐢𝐜 𝐫𝐚𝐝𝐢𝐮𝐬 ) i.e. Smaller is the size of an atom, greater is the electron affinity
(ii) Nuclear charge or proton number of the atom
(E.A ∝ magnitude of nuclear charge). Greater is the nuclear charge, greater is the electron affinity
(iii) Shielding effect of inner electrons. Greater is the shielding effect, smaller is the electron affinity
𝟏
(E.A ∞ 𝐬𝐡𝐢𝐞𝐥𝐝𝐢𝐧𝐠 𝐞𝐟𝐟𝐞𝐜𝐭 )
(iv) Electronic configuration: An atom with stable configuration has no tendency to gain an electron. Such
an atom has zero or positive electron affinity. An atom has stable configuration which has:
(a) Fully filled orbitals (ns2) IIA group
(b) Half filled orbitals of the same sub-shell (ns2 np3) VA group
(c) Inert gas configuration (ns2 np6), that is, eight electrons in the outermost orbits (except 1s2
configuration) VIIIA group
 • Trends in the periodic table 33
(i) Along the period: It increases because nuclear charge increases along the period.
(ii) Down the group: It decreases because atomic size and shielding affect increases
down the group.

• Striking informations:
• E.A of Be, Mg and N are almost zero
• Noble gases have zero E.A
• E.A of fluorine is less than that of chlorine. The electron affinity of elements decreases
down the group. But fluorine has less E.A than Cl. The size of fluorine atom (0.71Ao) is very
small. It has only two shells i.e. n = 1, 2 9F = 1s2 2s2 2p5 (2px2 2py2 2pz1).
• Due to small size,
• (a) The 2p-sub shell becomes compact. There is repulsion among electrons of the valence
shell and also with the electron to be added.
• (b) There is a large crowd of electrons around the nucleus. This crowd screens the nucleus. As
a result, effective nuclear charge decreases. Thus, the electron feels less attraction during
addition. Hence, electron affinity decreases.
• Chlorine is the element with maximum electron affinity in the periodic table.
 34
Q: Which of the following element has greater negative first electron
affinity (E.A1)?
A) C C) Li
B) B D) Be

Answer Explanation: (A) Electron affinity of Carbon is greater than that of other
elements as shown in the tabular form.

Options Elements E.A (kJmol-1)

A) C -123
B) B -83
C) Li -1.6
D) Be 240
 35
Q: Which of the following is correct decreasing order of negative
electron affinity of given elements?
A) F > O > N > Ne C) O > F > Ne > N
B) Ne > O > N > F D) N > Ne > F > O

Answer Explanation: (A) The correct decreasing order of negative electron affinity
(E.A1) of given elements is as follow:

Elements E.A (kJmol-1)

F -322
O -141
N 0
Ne +29
 36
Q: Which of the following group of elements have positive first
electron affinity?
A) IA C) VIA
B) IIA D) IIIA

Answer Explanation: (B) IIA group elements have positive first electron affinity
value e.g.
Group Elements E.A1 (kJmol-1)
IA Na -53
IIA Mg +230
VIA S -200
IIIA Al -50
 37
Q: Which of the following halogens has comparatively smaller first
electron affinity?
A) F C) I
B) Br D) Cl

Answer Explanation: (C) Iodine element has smaller first electron affinity value as
shown in the tabular form:

Elements E.A (kJmol-1)

F -322
Br -325
I -295
Cl -349
 8. Electronegativity (E.N) 38

* Trends in Applications of E.N

Factors
Definition Maximum and minimum E.N the periodic
affecting E.N E.N difference Nature of
table
difference bond
• It is the power of F • E. 𝑁 ∝ • Along the • Zero or • Non-polar
an atom to • It has maximum E.N (4.0) in the Nuclear period E.N less than covalent
shared pair of P.T charge increases 0.5 bond
electrons towards • It is the most reactive non-metal • E. 𝑁 ∝ • Down the • 0.5 – 1.6 • Polar
itself in a • It (F2) is the strongest oxidizing 1
group E.N covalent
molecule agent
At size
• E. N ∝ O.S decreases bond
+ −
• e.g. δ H – δ Cl Cs of element • Greater • Ionic bond
• E.N 2.1 3.2 • It has minimum E.N (0.7) in the than 1.7
P.T • If two • Metallic
• It is the most electropositive elements bond
element Note: Greater is the E.N are metals
• It is the strongest reducing difference, greater is the bond
agent energy
 39
Period * Trends of the E.N in the periods of periodic table

IA IIA IIIA IVA VA VIA VIIA VIIIA

2 3Li 4Be 5B 6C 7N 8O 9F 10Ne

E. Conf. (2,1) (2,2) (2,3) (2,4) (2,5) (2,6) (2,7) (2,8)

E.N 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0

3 11Na 12Mg 13Al 14Si 15P 16S 17Cl 18Br

E. Conf. (2,8,1) (2,8,2) (2,8,3) (2,8,4) (2,8,5) (2,8,6) (2,8,7) (2,8,8)

E.N 0.9 1.3 1.5 1.8 2.1 2.5 3.2 0

STRIKING INFORMATIONS:
• All the metals have E.N less than 2
• With the increase of O.S of elements, E.N increases
• It has no unit
• E.N values can be used to estimate the polarity of different bonds
 40
Q: Which one of the following elements has greater electronegativity
value?
A) N C) Br
B) O D) C

Answer Explanation: (B) Oxygen has greater electronegativity value as shown in

the tabular form.

Elements E.A (kJmol-1)

N 3.0
O 3.5
Br 2.8
C 2.5
 41
Q: Which of the following is polar molecule?
A) CO2 C) BF3
B) SO3 D) NO

Answer Explanation : (D) NO is a polar molecule because it has electronegativity

difference 0.5 ( O = 3.5, N = 3.0).
Q: Which of the following periodic properties has no unit?
A) Ionization energy C) Atomic radius
B) Electron affinity D) Electronegativity

Answer Explanation: (D) Electronegativity has no unit.

 42
Q: Which of the following elements has greater
electronegativity?
A) As C) Si
B) S D) P

Answer Explanation: (B) Sulphur has greater electronegativity value. Electronegativity

also depends on valence electrons, greater is the number of valence electrons greater is
the electronegativity.

Elements E.A (kJmol-1)

As 2.0
S 2.5
Si 1.8
P 2.1
 43

Q: Mark the incorrect statement about electronegativity

(E.N)?
A) The maximum E.N is that of F element in the periodic table
B) The minimum E.N is that of Cs element in the periodic table
C) It has no unit
D) It is the property of an element in the isolated form

Answer Explanation : (D) It is the property of an element in the associated

form (i.e. in the molecular form.
 Q: Consider the following applications of electronegativity (E.N): 44
I. If the E.N difference between two bonded atoms is zero or
less than 0.5, then the bond is said to be non-polar covalent
bond
II. If the E.N difference between two bonded atoms is 1.7, then
the bond is said to be 50% covalent and 50% ionic bond
III. If the E.N difference between two bonded atoms is 1.6 or less
than 0.5, then the bond is said to be polar covalent bond
IV. If the E.N difference between two bonded atoms is greater
than 1.7, then the bond is said to be ionic in nature
Which one of the above statements is incorrect?
A) I only C) II and IV
B) III only D) I, II, III and IV
Answer Explanation : (B) It is incorrect statement. The correct statement is as follow.
• If the E.N difference between two bonded atoms is 1.6 or more than 0.4, then the
bond is said to be polar covalent bond
 45
• Comparison between electron affinity and electronegativity

Electron affinity Electronegativity

• It is the energy released or • It is the power of an atom to attract shared pair
absorbed, when an electron is of electrons in a molecule. It is concerned with
added to a gaseous atom to form the attraction for electrons of atoms in
a negative ion molecules
• It is concerned with the attraction for • It is associated with atom of element in the
electrons of single gaseous atoms molecule
• Its unit is kJmol-1 • It has no unit
• It can be measured directly • It cannot be measured directly. It has relative value
 9 and 10 Bond Energy and Bond Length 46

Bond Energy

Factors
Definition Applications
Bond energy ∝ bond order or multiplicity
The bond energy is the e.g. 𝐂 ≡ 𝐂 > 𝐂 = 𝐂 𝐂 − 𝐂 Although the concept of bond energies is
average amount of energy Bond energy ∝
𝟏 rather artificial, corresponding to no
𝐛𝐨𝐧𝐝 𝐥𝐞𝐧𝐠𝐭𝐡 𝐨𝐫 𝐬𝐢𝐳𝐞 𝐨𝐟 𝐚𝐭𝐨𝐦
required to break all bonds physically realizable process, it is
e.g. HF > HCl > HBr > HI
of a particular type in one nevertheless very useful. Four of its
Bond energy ∝ S%
molecule of the substance. e.g. sp > sp2 > sp3
important uses are:
The enthalpy change in 50% > 33% > 25% 1. Comparing the strengths of bonds
splitting a molecule into its 𝟏 2. Understanding the structure and
Bond energy ∝
component atoms is called 𝐥𝐨𝐧𝐞 𝐩𝐚𝐢𝐫 𝐨𝐟 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧𝐬 𝐨𝐫 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧𝐢𝐜 𝐫𝐞𝐩𝐮𝐥𝐬𝐢𝐨𝐧 bonding
e.g. C – C > N – N > O – O > F – F 3. * Estimating the enthalpy changes in
enthalpy of atomization
B.E ---------------------------------- reactions,
Lone pair of electron 4. Understanding the mechanisms of
0 > 1 > 2 > 3
chemical reactions
Q: Which of the following has maximum bond energy (kJ mol-1): 47
A) C – C C) C = C
B) 𝐶 ≡ 𝐶 D) C = O

Explanation : (C) has maximum bond energy (kJ mol-1):

A) C – C (348) C) C = C (614)
B) C ≡ C (839) D) C = O (799)

Q: Which of the following molecules has greater bond energy (kJmol-1):

A) H – H C) N – N
B) O – O D) F – F

Explanation: (A) H – H has greater bond energy (kJmol-1)

A) H – H (436) C) N – N (163)
B) O – O (146) D) F – F (155)
 48

Q: Which of the following has greater bond length (pm):

A) C = O C) C ≡ C
B) C = C D) N ≡ C

Explanation: (B) C = C has greater bond length (pm)

A) C = O (122) C) C ≡ C (120)
B) C = C (133) D) N ≡ C (110)
 Q. Which of the following molecules is the most polar: 49
A) Cl – Cl C) C – F
B) N – F D) O – F
Explanation : (C) : The most polar one is C – F
A) Cl – Cl (3.0 – 3.0) C) C – F (4.0 – 2.5)
B) N – F (4.0 – 3.0) D) O – F (4.0 – 3.5)
Bond length:
The distance between the nuclei of two atoms forming a covalent bond is called the bond length.
Factors:
• Electronegativity difference ∝ 1/bond length
Orbital hybridization (in term of bond order)
• Bond order ∝ 1/bond length (C ≡ C < C = C < C – C)
s-character ∝ 1/bond length (50% < 33.3% < 25%)
• Along the period bond length decreases because nuclear charge increases
C – C bond length > N – N bond length
• Atomic size ∝ bond length
 50

Q: All of the following statements are correctly matched EXCEPT:

Options Compound Hybridization Bond Bond Length
(pm)
A) Propanone sp2 C=O 122
B) Ethene sp2 C=C 133
C) Boron trichloride sp3 B – Cl 160
D) Ethyne sp C≡C 120

Explanation: (C) It is incorrect statement. In fact, the correct statement is

as follows.

Options Compound Hybridization Bond Bond Length

(pm)
C) Boron trichloride sp2 B – Cl 175
 11. Types of Bond 5
•
Comparison of Ionic Bond & Covalent Bond 1
Q: All of the following statement are correctly
matched for ionic and covalent bonds EXCEPT:
Opt. Ionic bond Covalent bond
Ionic bond (Electrovalent bond) (Electron pair bond)
e.g. Na+Cl- It is formed by complete transfer of electron/ It is formed by mutual sharing of
A)
electrons from one atom of element to the other. electrons between two atoms.
Covalent bond
The migrated electron/ electrons belong to only The shared electrons pair belong
e.g. H •• H B)
one of the two bonded atoms. to both the bonded atoms.
C) It is directional bond. It is non-directional bond.
It is shown by positive and negative charge on It is shown by small line ( – ) drawn
D)
the bonded atoms (+ , -). between the two bonded atoms.
Explanation: (C) It is incorrect statement. In fact, the correct statement
about ionic and covalent bond is as given in the tabular form:
Opt. Ionic bond (Electrovalent bond) Covalent bond (Electron pair bond)
C) It is non-rigid and non-directional bond It is rigid and directional bond
 52
Effect of ionic bonding and covalent bonding on the
physical properties of the substances
Ionic Compounds Covalent Compounds
(Ionic bonds are stronger than covalent bonds) (They are weaker than ionic bonds)
• They are present in the solid state • They are present in the gas, liquid or solid state

• They are soluble in polar solvents (H2O) • They are soluble in non-polar solvents (CCl4) and
insoluble in polar solvent
• They give fast reactions • They give slow reactions
• They have higher melting and boiling points • They have lower melting and boiling points
e.g. M.P of NaCl = 801oC e.g. B.P of H2O = 100oC
• They conduct electricity in molten or solution • Generally they are non-conductor
form
 5
• Examples of Ionic Bond (Electrovalent bond): 3
(According to the Lewis theory, ionic bond is formed by the complete transfer of electron or electrons from
an atom with low ionization energy to another atom with high electron affinity.)

Examples of Ionic Bond Formation of Examples of Ionic Bond formation of

NaCl CaO
Steps involved Steps involved
• Formation of positive ion (cation) • Formation of positive ion (cation)
• The element with low ionization form positive ion • The element with low ionization form
i. 11Na(g) Oxidation I.E1 = +496kJmol-1 positive ion and element with high
Na+g + e
(1s2, 2s2, 3p6, 3s1) ( )
(1s2, 2s2, 2p6) (Ne-configuration) electron affinity form negative ion
i. Ca(g) Ca+2(g) + 2e-
Element with high electron affinity form negative ion • Formation of negative ion (anion)
ii. 17Cl(g) + e- Reduction Cl- E.A1 = -349kJmol-1 ii. O(g) + 2e- O-2(g)
(1s2, 2s2, 2p6, 3s2, 3p5) (1s2, 2s2, 3p6, 3s2, 3p6) Formation of ionic bond b/w Ca+2 and O-2
iii. Na+(g) + Cl-(g) EFOA
. . . Na+Cl-(s) (ionic bond) ∆Hlatt = -787 iii. Ca+2 + O-2 CaO (ionic bond)
 54

Q: Which of the following groups of elements

forms ionic bond with each other?
A) IA, IIA with VIA, VIIA C) IA with IVA
B) IIIA, IVA with VA, VIA D) IIA with VIIIA

Explanation: (A) The elements of IA and IIA chemically

combine with the elements of VIA and VIIA to form
ionic bonds (e.g. KI, MgO, Na2S, CsF etc.)
 55

Q: An ionic compound A+B- is most likely to be formed

when:
A) The ionization energy of A is high and electron affinity of B is low
B) The ionization energy of A is low and electron affinity of B is high
C) Both the ionization energy of A and electron affinity of B are high
D) Both the ionization energy of A and electron of B are low

Explanation: (B) The ionization energy of A is low and electron

affinity of B is high.
 56

Q: All of the following are examples of ionic bond

EXCEPT?
A) KBr C) Na2O
B) CaCl2 D) AlCl3

Explanation: (D) AlCl3 does not have ionic bond. It has

covalent bond. AlCl3 acts as Lewis acid.
 57
Q: In ‘H-F’ bond Electronegativity difference is 1.9.
What is the type of this bond? 2012
A) Polar covalent bond C) pi (π) bond
B) Non-polar covalent bond D) Co-ordinate covalent bond
Explanation: (A) Though the electronegativity difference is greater than 1.7
even then the bond is not ionic in nature. In fact in H-F there is polar covalent
bond. H-F does not have ionic bond because of following reasons:
• It is in the liquid state
• In HF there is no complete positive and negative charge
• It is weak acid because it has stronger H-bonding
• It has low boiling point (19.5oC) as compared to ionic compounds
• Those elements form ionic bond in which one has low ionization energy
and other has high electron affinity
 58
Q: No electrovalent bond is 100% ionic in
nature. This is because of:
A) When cations and anions approach each other,
polarizability increases only
e.g. keeping in B) Sharing of electrons takes place to some extent only
view this aspect C) Highest ionic character is present in CsF only
NaCl has 72%
ionic character
D) Both A and B
and CsF has 92%
ionic character Explanation: (D) Ionic bond is not 100% ionic in
and calculations nature because:
tell us that there
is no bond with • When cations and anions approach each other,
100% ionic polarizability increases
character. • Sharing of electrons takes place to some extent
 59
Q: All the ionic compounds have the following
characteristic properties EXCEPT:
A) They have high melting and boiling point
B) They are in the solid state
C) They show polymorphism and isomorphism
D) They also show isomerism

Explanation: (D) They do not show isomerism. It is

generally shown by organic compounds.
 14. Coordinate Covalent Bond
60

Q. Mark the incorrect statement about:


H 3N    B F3
A) NH3 before reaction is in the gaseous state
B) BF3 before reaction is in the gaseous state
C) Adduct product is in the solid state
D) It involves ionic and covalent bond between NH3 and BF3

Explanation: Between (D)

It is incorrect statement. There is Co-ordinate covalent bond between
NH3 and BF3 as shown.

H 3N 
 B F3
 15. Ionic Character of Covalent Bond 20
Covalent bond can be divided into two types from polarity point of
view.
(i) Non-polar covalent bond
(ii) Polar covalent bond
Comparison between Polar and Non-Polar Covalent Bond
Polar Bond Non-Polar Bond
A covalent bond between two different A covalent bond between two similar atoms
i)
atoms is a polar bond is a non-polar bond
In this bond; a pair of electrons ls shared ln this bond, a pair of electrons is shared,
ii)
unequally by the bonded atoms equally by the two bonded atoms
Bonded atoms have partial positive and Bonded atoms remain electrically neutral and
iii)
partial negative charges do not have partial charges
Molecules having polar bonds may or may Molecules having non-polar bonds are always
iv)
not be polar non-polar.
 20

Example: Example:

i)
H–H

ii)
Br – Br

iii)
S=C=S,O=C=O
 63

Q: All of the following are correct statements regarding difference between polar
and non-polar bonds EXCEPT:
Option Non-Polar (Covalent bond) Polar (Covalent bond)
It is a covalent bond which exists It is a covalent bond which exists
between two similar atoms or those between two dissimilar atoms or those
A)
having negligible electronegativity having appreciable electronegativity
difference difference but less than 1.7
B) It is weaker bond It is stronger bond
C) It has no polarity It has always polarity in the molecule
D) It is more reactive It is less reactive
Explanation: (D) In fact, polar bond is more reactive than non-polar bond. Greater is the
electronegative difference between two covalently bonded atoms in a molecule, greater is the polarity,
greater is the reactivity. That is why polar molecules are more reactive than non-polar molecules.
 64
16. Sigma and Pi bond

Valence bond theory:

According to this theory,
• A covalent bond is formed by the overlapping of atomic orbitals (to form
molecular orbitals).
• Atomic orbitals are mixed to get hybrid orbitals
• Important points of this theory are summarized below:
i. Orbitals undergoing overlapping should be half-filled
ii. Half-filled orbitals should contain the electron with parallel spin
iii. Strength of a covalent bond depends upon the extent of overlapping,
for example, axial or lateral overlapping
iv. If the atomic orbitals overlap horizontally, then the bond formed is
called a sigma bond.
 65

v. If atomic orbitals overlap sidewise above and below then the bond formed is called pi
bond
vi. A sigma bond is always stronger than a pi bond
vii. Covalent bonds formed by the overlap of s-s and s-p orbitals are always sigma
s−s<s−p<p−p
viii. Increasing strength of covalent bonds is in the orderincreasing bond strength
ix. A single covalent bond is always a sigma bond. In a double covalent bond, one is
sigma and the other is pi bond. In a triple covalent bond, one is sigma and two are pi
bonds.
x. All the hybrid orbitals form sigma bonds
 • Describe covalent bonding in terms of 66
orbital overlap, giving  and π bonds.

Q: All of the following are correct statements regarding difference between

sigma bond and pi-bond EXCEPT:
Option Sigma bond Pi bond
It is formed by linear overlapping of It is formed by sidewise overlapping of two
A)
two half-filled atomic orbitals half-filled parallel atomic orbitals
It has restricted rotation about the It has free rotation about the inter nuclear axis
B)
inter-nuclear axis
It has one lobe of electron density It has two lobes of electron density on opposite
C)
between the nuclei sides of inter nuclear axis
D) It has symmetrical charge density It has no symmetrical charge density

Examination: (B) Sigma bond has free rotation about the inter-nuclear axis
but pi bond has restricted rotation about the inter-nuclear axis.
 67

Molecules Orbital No of sigma No of pi bonds Shape Angle

Hybridization bonds

Ethane sp3 7 0 Tetrahedral 109.5

Ethene sp2 5 1 Angular 120

Benzene sp2 12 3 Cyclic 120

Hexagonal
Planar
 68

Q. Ethyne molecule is formed when two carbon atoms joined

together to form a sigma bond only: 2010
A) sp-s overlap C) sp2sp2 overlap
B) sp-sp overlap D) 2py-2py overlap

Explanation: (B) Ethyne molecule is formed when two carbon

atoms joined together to form a sigma bond only by sp-sp
overlapping.
 69

Q: The C2H2 molecule is linear which can be deduced from the numbers
of σ and  bond present in the molecule?
Options σ 
A) 2 2
B) 2 3
C) 3 2
D) 3 1
Explanation: (C) H – C ≡ C – H From the structure it is clear that it has three
sigma bonds and two pi bonds having linear structure.
 17. Hybridization, 18. sp3 – Hybridization, 70
19. sp2 – Hybridization, 20. sp-hybridization
Cause for Orbital Hybridization
We have studied overlapping between unmodified (un-hybridized) atomic orbitals in
valence bond theory. There are some problems in explaining the formation of bonds
ሷ 3 and H2 can be
and geometry of molecules. For example, the bond angles of CH4, 𝑁H
explained on basis of concept of hybridization.
Definition
The process in which atomic orbitals of different energies and different shapes
intermix to form an equal number of orbitals, which are identical in all respects like
shape, angle, length and energy except orientation in space, is called hybridization.
Explanation
The nature and shapes of the orbitals in the outermost shell of an atom mix up with
each other. In this way, they get the stability by rearranging the geometries of the
orbitals. For this purpose they are mixed up in definite ratio to give new hybrid
orbitals. The bond so produced are comparatively stable.
Change of valency and hybridization
The hybridization explains valency of elements. In hybridization, usually the first
step is the formation of an excited state. It involves un-pairing of electrons
followed by promotion of an electron to higher energy level. As a result there is
an increase in the number of unpaired electrons. So the valency of the element
changes as explained in the following Table.
Energy for Excitation
The energy required for this excitation comes from the energy which is released
during the process of hybridization and bond formation with other atoms.
Remember that excitation of electron and hybridization are simultaneous
processes.
Significance of Hybridization
Hybridization gives entirely new shape and orientation of valence orbitals of an
atom. It is quite significant in the determination of the geometry of the molecules.
Types of Hybridization
There are various types of hybridizations but we are going to discuss the types of
hybridization due to the mixing of s and p orbitals of small sized atoms.
Hybridization of ‘s’ and ‘p’ orbitals has following types:
(a) sp3-hybridization
(b) sp2-hybridization
(c) sp-hybridization
(a) sp3-hybridization
The type of hybridization in which one 's’ and three ‘p' orbitals mix together to
form four sp3-hybridized orbitals is called sp3-hybridization.
Formation of methane (CH4)
Electronic configuration of valence shell of carbon (6C).

6C (ground state) =

C (excited state) =

In the ground state, C atom has two partially filled orbitals.

When one electron from 2s orbital is promoted to 2pz orbital, carbon changes
from divalent to tetravalent.
At the same time hybridization takes place and tour sp3-hybrid orbitals are
formed.
A tetrahedral geometry is developed. Carbon is at the center and tour equivalent
hybrid orbitals are directed towards the four comers of a regular tetrahedron.
Formation of four sp3 hybrid orbitals from a set of one s and three p orbitals
The hybridized orbitals are oriented in space in such a way that angle between
them is 109.5°. In methane molecule, four sp3 hybrid orbitals overlap with four is
orbitals of four hydrogen atoms at four comers of tetrahedron forming four sigma
bonds.

Four sp3 overlap in tetrahedral structure of gm molecule

Examples of sp3
Formation of water (H2O)
Electronic configuration of valence shell of oxygen is as follow:

In electronic configuration of oxygen, one 2s orbital and three 2p orbitals

hybridize to produce four equivalent sp3 hybrid orbitals.
Two of which are completely filled by two lone pairs of electrons and other two
are half-filled.
These half-filled orbitals overlap with 1s orbitals of two H-atoms. Hence two
sigma bonds are formed. Thus H2O shows tetrahedral geometry in which two
hydrogen atoms are located at two comers and remaining two corners are
occupied by two lone pairs. The HOH bond angle is 104.5° instead of 109.5°. It is
due to the force of repulsion between two lone pairs and two bond pairs of
electrons.
sp3-overlap in H2O to form an angular structure
(b) sp2-Hybridization
The process In which one s and two p orbitals intermix to form three sp2
hybrid orbitals is called sp2-hybridizatien.
Explanation
Let us discuss the structure of boron tri-fluoride (BF3). Electronic configuration
of valence shell of 5B is as follows:

In ground state, boron has only one unpaired electron. In excite state, one electron
from 2s is promoted to 2py. Hence, boron becomes trivalent. New one 2s end two
2p (2px and 2py) orbitals hybridize to give three sp2-hybrid orbitals. Four the p
orbital i.e., 2pz is not taking part in hybridization.
 These three sp2-hybrid orbitals ere half-filled,
planar and oriented at the angle of 120°. Electronic
configuration of valence shell of 9F.
Outermost shell
(b) sp2-Hybridization
The process In which one s and two p orbitals intermix to form three sp2
hybrid orbitals is called sp2-hybridizatien.
Explanation
Let us discuss the structure of boron tri-fluoride (BF3). Electronic configuration
of valence shell of 5B is as follows:

In ground state, boron has only one unpaired electron. In excite state, one electron
from 2s is promoted to 2py. Hence, boron becomes trivalent. New one 2s end two
2p (2px and 2py) orbitals hybridize to give three sp2-hybrid orbitals. Four the p
orbital i.e., 2pz is not taking part in hybridization.

Page No. 39
Note:
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WITH DETAILED EXPLANATION
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