CHEMICAL BONDING AND MOLECULAR STRUCTURE

Octet Rule- During a chemical reaction the atoms tend to adjust their electronic arrangement in such a way
that they achieve 8 e - in their outermost electron. This is called octet rule.

Chemical Bond- the chemical force which keeps the atoms in anymoleculetogether is called a chemical
bond.

Ionic Bond- An ionic bond isformed by the complete transfer of one or more electrons from the atom ofa
metal to an atom of non- metal.

Lattice Enthalpy- The molar enthalpy change accompanying thecompleteseparation of the constituent
particles that compose of the solids (such asions for ionic solid, molecules for molecular solids) under
standard conditions iscalled lattice enthalpy (∆ LH o). The lattice enthalpy is a positive quantity.

Electro Valency: The number of electrons lost or gained by an atom ofanelement is called as
electrovalency.

Formation Of An Ionic Bond: It is favoured by, (i) the lowionisationenthalpy of a metallic element which
forms the cations, (ii) Highelectron gain enthalpy of non- metallic element which forms the anions,
(iii)Large lattice enthalpy i.e; the smaller size and the higher charge of the atoms.

Covalency:The number of electrons which an atom contributestowardsmutual sharing during the formation
of a chemical bond calledits covalency in that compound.

Single Covalent Bond: A covalent bond formed by the mutual sharingof one pair of electrons is called a
single covalent bond, or simply a single bond. Asingle covalent bond is represented by a small line (−)
between the two atoms.

Double Covalent Bond: A covalent bond formed by the mutual sharingof two pair of electrons is called a
double covalent bond, or simply a doublebond. A double covalent bond is represented by two small
horizontal lines (=)between the two atoms. E.g. O=O, O=C=O etc.

Triple Covalent Bond: A covalent bond formed by the mutual sharingofthree pair of electrons is called a
triple covalent bond, or simply a triple bond. Atriple covalent bond is represented by three small horizontal
lines (≡) between the two atoms. eg. N≡N, H-C≡C-H etc.

Formation Of A Covalent Bond: Formation of a covalent bondisfavoured by

 High ionisation enthalpy of the combining elements.

 Nearly equal electron gain enthalpy and equal electro-negativitiesof combining elements.
 High nuclear charge and small atomic size of the combining elements.

Polar Covalent Bond: The bond between two unlike atoms whichdifferin their affinities for electrons is
said to be polar covalent bond. E.g. H-Cl

Coordinate Bond: The bond formed when one sided sharing of electronstakeplace is called a coordinate
bond. Such a bond is also known as dative bond. It isrepresented by an arrow (→) pointing towards the
acceptor atom. E.g. H3N →BF3
Bond Length: Bond length is defined as the equilibrium distance betweenthenuclei of two bonded atoms in
a molecule.

Bond Angle: It is defined as the angle between the orbitals containingbondingelectron pairs around the
central atom in a molecule/complex ion

Bond Enthalpy: It is defined as the amount of energy required to break onemole of bonds of particular type
between two atoms in a gaseous state.

Bond Order: In the Lewis description of covalent bond, the Bond Order isgivenby the number of bonds
between the two atoms in a molecule

Resonance:whenever a single Lewis structure cannot describe amoleculeaccurately, a number of structures

with similar energy, positions ofnuclei, bonding and non-bonding pairs of electrons are taken as
thecanonical structures of the hybrid which describes the molecule accurately.

Dipole moment : The product of the magnitude of the charge and the distancebetweenthe centres of positive
and negative charge. It is a vector quantity and is represented byan arrow with its tail at the positive centre
and head pointing towards a negative centre.

Dipole moment (μ) = charge (Q) × distance of separation (r)

The Valence Shell Electron Pair Repulsion (VSEPR) Theory:

The main postulates of VSEPR theory are as follows:

• The shape of a molecule depends upon the number of valence shell electron pairs (bonded or nonbonded)
around the central atom.

• Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged.

• These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus maximise
distance between them.

The repulsive interaction of electron pairs decrease in the order: Lone pair (lp) – Lone pair (lp) > Lone
pair (lp) -Bond pair (bp) >Bond pair (bp) – Bond pair (bp) .
)>

Sigma Bond: A covalent bond formed due to the overlapping of orbitals ofthetwo atoms along the line
joining the two nuclei (orbital axis) is called sigma(σ) bond. For example, the bond formed due to s-s and s-
p, p-p overlapping alongthe orbital axis are sigma bonds.

Pi - Bond: A covalent bond formed by the side wise overlapping of p- or d-orbitals of two atoms is called as
pi (π) bond. For example, the bond formed dueto the sideways overlapping of the two p- orbitals is a pi-
bond.

Hybridization: The process of mixing of the atomic orbitals to formnewhybrid orbitals is called
hybridization. All hybrid orbitals of a particular kindhave equal energy, identical shapes and are
symmetrically oriented in shape.The hybrid orbitals are designed according to the type and theatomic
orbitals merging together.

Types of Hybridisation:
Molecular Orbital Theory

Energy Level Diagram for Molecular Orbitals

Hydrogen Bond: The bond between the hydrogen atom of one molecule and a more electro- negative
element of same or another molecule is called as hydrogen bond.

Types of H-Bonds:

There are two types of H-bonds

(i) Intermolecular hydrogen bond

(ii) Intramolecular hydrogen bond

QUESTIONS and ANSWERS :-

1. Draw the Lewis structure for CO32- , NO2- , SO42-.

2. Calculate the formal charge on

a) Chlorine in HClO 4. b) Phosphorus in H3PO4

3. Discuss the shapes of the following molecules using VSEPR model

a) BeF2 b) SiF4 c) H3O+ d) BF4-

4. .Account for the following :-

Bond angle in NH3 is larger than bond angle in H2O

5. He2 molecule is not formed – Explain with the help of Valence bond theory.

6. How do the bond length of C - H bond differ in C2H6, C2H4&C2H2 ?

7. .Write the resonating structures for SO3 and NO3-.

8. Although both CO2 and H2O are triatomic molecules, the shape of H2O molecule is bent while that of CO2 is
linear. Explain it on the basis of dipole moment.

9. Arrange the following in order of decreasing bond angle around N atom : NO 2, NO2+ and NO2-.
 10. Which out of NH3 and NF3 has higher dipole moment and why ?

11. Which hybrid orbitals are used by the carbon atoms in the following molecules?
a) H3C – CH3 b) H3C – CH = CH2 c) CH3 – CH2 – OH d) CH3 – CH = O

12. Distinguish between a sigma and a pi bond.

13. Use M.O. theory to explain why Be2 molecule does not exist

14. Compare the relative stability of the following species and indicate their magnetic properties.
O2, O2+, O2-, O22-

15. Describe the hybridization in case of PCl5. Why are the axial bonds longer as compared to equatorial bonds?

16. Why H2O is liquid whereas H2S is gas at room temperature?

17. BCl3 is planar but anhydrous AlCl3 is tetrahedral – Explain

18. KHF2 is known but KHCl2 is not known. Explain

19. All the chlorine – oxygen bond distance in ClO 4- are 144 pm. What explanation can be given for this?
20. Draw molecular structures of XeF2, XeO2F2, XeF4, POCl3, ClF3, BrF5, SF4. Also mention the hybridization of
the central atom for each of the structures.
21. o- nitrophenol is steam volatile while p nitrophenol is not. Discuss.
22. The bond angles inNH4+ and CH4are same, but NH3 has different bond angle. Why?
23. Write the molecular orbital energy level diagram for N2.
24. Why NF3 is pyramidal but BF3 is triangular planar?
25. What angles are associated with the following orbitals? sp, sp 2, sp3
26. Which compound is more covalent AgCl or AgI ?
 Answers

1. , ,

2. Ans. Formal change on Cl = V – ½ S – L = 7 – ½ x (8) – 0 = +3

Formal change on P = 5 – ½ (8) – 0 = +1

3. [Hint : a) Linear b) tetrahedral c) pyramidal d) tetrahedral]

Ans. a) Linear b) Tetrahedral

c) H3O+ Pyradmidal d) Tetrahedral

4. Hint : In H2O, there is lp– lp repulsion which is stronger than lp- bp repulsion
5. Hint : Check the attractive and repulsive forces if He2 is formed

Ans. Attractive forces between He atoms

 Repulsive forces between He atoms
6. Hint : size of hybrid orbitals – Sp3> Sp2>Sp
7. a) SO3

b) NO3-

8. Hint : Bond dipoles of C – O bond cancel in CO2 due to linear shape

Ans.

9. Hint : Consider the number of unpaired electrons on N for NO2, NO2+ and NO2-

Ans.
 Bond angle around N decreases
10. Hint : Check the bond moments of three N-H bonds and the lone pair moment in NH3. Same in NF3

Ans.

11. a) b)

c) d)
12.
Sl Sigma bond Pi bond
No.
1. Formed by axial overlap of atomic orbitals. Formed by sidewise overlap of the atomic orbitals.
2. This bond can be formed by overlap of s-s, s-p or p-p It involves of overlap of p orbitals only.
orbitals.
3. Stronger because overlap cal take place to a larger Weaker because the overlapping occurs to a smaller
extent. extent.
4. There can be a free rotation of atoms around the Free rotation of atoms around the pi bond is not
sigma bond. possible because it involves breaking of the bond.

13. Hint : show bond order = O

M.O. configuration is :

Bond order = ½ (Nb – Na) = ½ ( 4 – 4) = 0

14. Hint : higher bond order, more stability. If unpaired e present is paramagnetic
Bond order of the species –
O2 - 2.0
O2+ - 2.5
O2- - 1.5
O22- - 1.0
Relative stability : O2+ > O2> O2- > O22-
M.O. conf of O2 :

Contains unpaired electrons therefore paramagnetic

 O2+ :
Paramagnetic

O2- :
Paramagnetic

O22- :
No unpaired electron, therefore diamagnetic
15.

16. Hint : H-bond in H2O molecule

17. Hint : BCl3 , sp2,trigonal , planar. AlCl3 exist as dimer
18. Hint : HF2- ion is formed by combination of H - F and F– ions due to H-Bonding
19. Hint : resonance hybrid of ClO4-

Resonance hybrid structure is

All Cl – O bonds are equivalent.

20. XeF2 sp3d XeO2F2 sp3d

XeF4 sp3d2 POCl3 sp3

 ClF3 BrF5 SF4
sp3d sp3d2 sp3d

21 In o nitrophenol, intramolecular hydrogen bonding is present, while intermolecular hydrogen bonding is

present in p nitrophenol. Energy is required to overcome attractive forces in the molecule of p- nitrophenol. So its
boiling point is high and its non volatile in steam.

22 In NH4+ as well as in CH4, the central atom has four shared pair of electrons. So both have similar bond angle.
But in NH3, there are three shared pairs and one loan pair. AS repulsion between the lona pair and bond pair is
stronger than repulsion between the bond pairs, the H-N-H bond angle decreases to 107o..

23.

24 In NF3, N has sp3 hybridization and there is one lone pair of electrons. But in BF 3, B has sp2 hybridization.

25. sp : 180o, sp2 : 120o, sp3 : 109o28’

26. AgI is more covalent than AgCl because I-ion is more polarised than Cl- ion due to bigger
size.
OBJECTIVE TYPE QUESTIONS:-

1. Which of the following is ionic ?

a) HCI (b) CHCI3 (c) IF5 (d) KI

2. When molecule is formed by chemical bonding between atoms then

a)nucleus of combining atoms participate
b)valence electrons and inner cell electrons participate
c)only valence electrons of combining atoms participate
d)only inner cell electrons of combining atoms participate

3. Which is not responsible for the formation of ionic bond?

(a) crystal lattice energy (b) density (c) ionization enthalpy (d) electron gain enthalpy

4. The species having bond order different from that of CO is

a)NO- b)NO+ c) CN- d)N2

5. Who proposed valence-bond theory ?

(a) Mulliken (b) lenus Pauling (c) Hittler and Londan (d) Hund

6. In H2 - C = CH - CH = CH2 molecule C3 - C2 single bond carbons has which type of

hybridization ?
(a) sp2 - sp3 (b) sp - sp2 (c) sp3 - sp (d) sp3 - sp3

7. Which of the following pair of species is iso electronic and same structure ?
(a)NO3- , SO3 2- (b) SO3 2-, CO32- (c) CO32- , ClO3- (d) NO3-, CO32-

8. Which of the following sentence is incorrect for covalent bond ?

(a) Strength of covalent bond depends upon overlapping at atomic orbitals.
(b) Covalent bond is not directional
(c) There is sharing of electrons between atoms bonded by covalent bond
(d) Covalent bond is between atoms having less difference in their electronegativity
9. Which of the following compound possesses covalent bond ?

(a) MgC12 (b) NaH (c) BF3 (d) CsCl

10. Which of the following molecule possesses both polar and nonpolar covalent bond?

(a) NH4Cl (b) CCl4 (c) H2O2 (d) HCN

11. Which of the following compound does not possesses coordinate covalent bond
(a) CO (b) SO2 (c) HNO2 (d) HNO3
12. Which of the following characteristic is not for covalent compound ?
(a) They do not possesses particular geometrical structure
(b) They may be polar or nonpolar
(c) Their boiling and melting point is low
(d) Generally they are insoluble in water
13. Which of the following possesses ionic and covalent bond ?
(a) CO2 (b) H2SO4 (c) NH4CI (d) NaI
14. What is geometrical Structure of ClF3 molecule?
(a) Trigonal bipyramid (b) bent hape (c) see-saw (d) T-shape
15. Which of the following molecule possesses linear structure?
(a) SO2 (b) CO2 (c) H2O (d) C2H4
16 .Correct structure of SF4 is:

16. Numbers of possible resonating structure of carbonate ion is:

(a) 9 (b) 6 (c) 3 (d) 2
17. Which of the following molecule has net zero dipole movement?

(a) NF3 (b) BF3 (c) NH3 (d) H2O

18. Which of the following molecule possesses highest dipole movement ?
(a)CCl4 (b) CHCI3 (c) CH2C12 (d) CH3CI
20. Which of the following molecule possesses dipole movement ?
(a) CO2 (b) BF3 (c) NH3 (d) BeCl2
21. Which of the following molecules has lowest bond space angle ?
(a) NH3 (b) SO2 (c) H2O (d) H2S
22. Which orbital has highest energy ?

(a) σ(2Px) (b) π*(2Py) (c) σ(2S) (d) σ*(1S)

23 Which is the Paramagnetic species?

(a) CN- (b) O2- (c) NO- (d) CO

24.Which of the following statement is incorrect when N2 and O2 are converted into N2+ and O2+ respectively :.
(a) In O2+ , O-O bond order increases (b) In N2+ , N-N bond become weaker. (c) N2+ becomes paramagnetic
(d) Increasing diamagnetism in O2+

25. According to VSEPR theory geometry of which block elements can be explain?
(a) s (b) p (c) d (d) f

ASSERTION-REASON TYPE

In the following questions, a statement of Assertion (A) followed by a statement of Reason (R) is given. Choose the
correct option out of the choices given below.
A. Both A and R are true and R is the correct explanation of A.
B. Both A and R are true but R is not the correct explanation of A.
C. A is true but R is false.
D. A is false but R is true.

26. Assertion (A) : Ionic compounds are usually non-volatile.

Reason (R) : The intermolecular forces in ionic molecules are weak.

27.Assertion (A) : Na2SO4 is soluble in water, but BaSO4 is not

(R) : The lattice enthalpy of BaSO4 is greater than its hydration enthalpy.

28. Assertion (A) : Boron always forms covalent bonds.

Reason (R) : The small size of B3+ is appropriate for covalent bonding.

29. Assertion (A) : The dipole moment of fluoromethane (CH3F, µ = 1.85 D) is less than that of chloromethane
(CH3CI , µ = 1.87 D).

Reason (R) : The negative electron gain enthalpy of fluorine is less than that of chlorine.

30. Assertion (A) : HF2- exists in the solid or liquid state, but not in the aqueous state.

Reason (R) : The intermolecular hydrogen bonding between HF molecules is weaker than the intermolecular
hydrogen bonding between HF and H2O molecules.
 ANSWER KEY

1d 2c 3b 4a 5c

6b 7d 8a 9c 10c

11 c 12a 13b 14d 15b

16 a 17c 18b 19d 20b

21 b 22b 23b 24c 25b

26c 27c 28b 29b 30a