Chemical Bonding and

Chapter

3 Molecular Structure

Topic 1 Ionic and Covalent Bonding, Lewis Structure and Polar Character of Covalent Bond

Revision Notes
 Chemical Bond: The attractive force which holds together the various constituent particles (atoms,

ions of molecules, etc.) in different chemical species is known as chemical bond.
Types of Bonding

Ionic or Electrovalent Bond Covalent Bond

Ionic bonding is a type of chemical bond that involves

→ Cl—Cl
the electrostatic attraction between opposite charged
ions together. Electrovalent compounds are formed by atoms
transfer of electron from a metal to a non-metal.

• Low melting and boiling points: Covalent compound
consists of molecules that are held by weak forces. These
can be easily overcome by heat.
• Non-conductive nature: Covalent compounds do
not conduct electricity, i.e., electricity does not pass
through the covalent compounds. This is because the
• Ionic compounds have high melting points and high covalent compounds do not contain ions of free electrons.
boiling points. • Solubility: Covalent compounds are non-polar and
• Ionic compounds have higher enthalpies of fusion and do not dissolve in polar solvents like water. The covalent
vaporisation than molecular compounds.
compounds however, dissolve in non-polar solvents, like
• Ionic compounds are hard and brittle.
benzene, toulene, etc.
• Ionic compounds conduct electricity when they are
dissolved in water or in molten state. • Slow rate of reaction: The reaction of the covalent
• Ionic compounds have high melting points and high compounds is quite slow. This reaction is molecular, and
boiling points. the molecular reactions are slow.
• Ionic compounds have higher enthalpies of fusion and • Depending upon the number of 2, 4, or 6 electrons
vaporisation than molecular compounds. shared between two atoms, a covalent bond is called
• Ionic compounds conduct electricity when they are single, double or triple covalent bond, respectively.
dissolved in water or in molten state.
• Ionic solids are good insulators.
• The ionic bond is non-directional. This is because each
ion is surrounded by oppositely charged ions uniformly
distributed all around the ion.
CHEMICAL BONDING AND MOLECULAR STRUCTURE

 Coordinate bond: It is a special type of covalent bond

 (ii) Bond energy or bond enthalpy: Energy required to
in which both the shared electrons between two atoms are break one mole of a bond. The unit of bond enthalpy is
donated by one of these atoms. kJ mol–1. For example HH bond enthalpy in hydrogen
X + Y
Coordinate
X Y molecule is 435.8 kJ mol–1.
bond
H2 (g) → H(g) + H(g); ∆H = 435.8 kJmol–1
(i) Bond angle: It is defined as the angle between the
orbitals containing bonding electron pairs around the (iii) Bond order: It is given by number of bonds between
central atom in a molecule/complex ion. For example, the two atoms in a molecule, for example, F2 and N2. CO
bond angle of water molecule is 104.5°. and NO+ have bond order 3.
O
 The stabilities of molecules can be understood by the


104.5° statement ‘’with increase in bond order, bond enthalpy

H H increases and bond length decreases’’.

Types of covalent bond

• Non-polar covalent bond: This type of bond is • Polar covalent bond: This type of bond is formed between
formed between the two atoms of the same element. two atoms of different elements; the shared pair of electrons
Atoms of the same element attract electron equally. So, does not lie exactly midway between the two atoms. In fact
in other words, the shared electron pair will lie exactly it lies more towards the atom which is more electronegative.
midway between the two atoms. This type of covalent The atom with higher affinity for electrons develops a slight
bond is described as a non-polar covalent bond. negative charge and atom with lesser affinity for electrons
For example: H2, O2 and Cl2, etc. develop a slight positive charge. For example: HCl, H2O, etc.

 Polarity of bond : Dipole moment : Dipole moment is

 It is usually expressed in Debye units (D)
defined as : “The product of the magnitude of the charge Dipole moment is also expressed in the units of cm:
and the distance of separation between the charges.” 1D = 3.33564 × 10–30 cm.
Dipole moment (µ) = Charge (q) × Distance of separation (d)

Topic 2 Valence Bond Theory, Resonance, VSEPR Theory and Hybridisation



Revision Notes  Resonance energy = Actual bond – Energy of the most



stable responding structures.

 Resonance : According to the concept
 Valence shell electron pair repulsion (VSEPR) theory:


of resonance, whenever a single Lewis



According to this theory, bonded atoms in a molecule

structure cannot describe a molecule
adopt that particular arrangement in space around the
accurately, a number of structures with
central atom which keeps them on the average as for as
similar energy, positions of nuclei,
possible.
bonding and non-bonding pairs of
electrons are taken as the canonical  Postulates of VSEPR theory:


structures of the hybrid which describes • The geometry of a molecule depends upon the total
the molecule accurately. number of valence shell electron pairs (bonded or non-
bonded) around the central atom in the molecule.
 Conditions for writing resonance structure: The
• Repulsion between valence shell electron pairs


following are essential conditions for writing resonating

structures : determines molecular shape. In order to minimise electron
– electron repulsion or to acquire a state of minimum
• The contributing structures should have same atomic
energy or maximum stability, the valence shell electron
positions.
pairs keep themselves as far apart as possible.
• The contributing structures should have same number • In case more than one geometrical arrangements are
of unpaired electrons. possible for a given number of bonded and non-bonded
• The contributing structures should have nearly same pairs, then the most stable arrangement are consistent
energy. with the following hypothesis:
• The structures should be so written that negative (a) The repulsive interactions, decrease in the order :
charge is present on an electronegative atom and positive Lone pair–Lone pair > Lone pair–Bond pair > Bond pair–
charge is present on an electropositive atom. Bond pair.
• In contribution structures, the like charges should not (b) Repulsive forces decrease sharply with increase in
reside on adjacent atoms. angle between the electron pairs.
 Geometry of Molecules in which the Centre Atom has No Lone Pair of Electrons.


Number of
Arrangement of electron pairs Molecular geometry Examples
electron pairs
180°
B—A—B
2 ——A—— BeCl2, HgCl2
Linear
Linear
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120°
3 A A BF3

B B
Trigonal planar Trigonal planar
B
109.5°

A A
4 B B CH4, NH4+

B
Tetrahedral Tetrahedral
B

90°
B B
A A
5 PCl5
B
120°

B
Trigonal bipyramidal Trigonal bipyramidal
B
90°

B B
90°
A A
6 SF6
B B

B
Octahedral Octahedral
 Shape (geometry) of Some Simple Molecules/Ions with Central Ions having One or More Lone Pairs of Electrons (E)

Arrangement of
Molecule type No. of bonding pairs No. of lone pairs Shape Example
electron pairs

A
AB2E 2 1 Bent SO2, O3
B B
Trigonal planar

A Trigonal
AB3E 3 1 NH3
B B pyramidal
B
Tetrahedral

A
AB2E2 2 2 Bent H2O
B
B
Tetrahedral
CHEMICAL BONDING AND MOLECULAR STRUCTURE

B
B
A
AB4E 4 1 See saw SF4
B
B
Trigonal
bi-pyramidal

B A Distorted
AB3E2 3 2 CIF3
T-shape
B
Trigonal
bi-pyramidal

B B
A
AB5E 5 1 B B Square Pyramidal BrF5
B
Octahedral

B B
A
AB4E2 4 2 B B Square Planar XeF4

Octahedral

 Valence bond theory :

 orbitals with similar energies of each atom containing one
According to V.B.T., a covalent bond is formed between unpaired electron.
the two atoms by the overlap of half-filled valence atomic Greater the overlap, stronger is the bond.
 Types of overlapping and nature of covalent Bond :


Types of Overlapping and Nature of Covalent Bond

Sigma (σ) bond Pi (π) bond

         

• This type of covalent bond is formed by the end to end • For example, px – px overlapping
head on overlap of bonding orbitals along the internuclear x x
axis. The overlap is known as head on overlap or axial
overlap.
+ +
• For example, pz – pz overlapping
z – + + – z
– –
p-orbital p-orbital
p-orbital p-orbital
– + + –

+ + D
p – p-overlap
• This type of covalent bond is formed by the sidewise or
overlap of the half-filled atomic orbitals of bonding
atoms. Such an overlap is known as sidewise or lateral – – D
overlap. The atomic orbitals overlap in such a way that
their axis remain parallel to each other and perpendicular p – p -overlap
to the internuclear axis.

 Hybridisation: The process of intermixing of the

 • The hybridised orbitals are always equivalent in energy
orbitals of slightly different energies so as to redistribute and shape.
their energies resulting in the formation of new set of • The hybrid orbitals are more effective in forming stable
orbitals of equivalent energies and shape. bonds than the pure atomic orbitals.
 Characteristics of hybridisation :

• The hybrid orbitals are directed in space in some preferred
• The number of hybridised orbitals is equal to the directions to have stable arrangement. Therefore, the type of
number of the orbitals that get hybridised. hybridisation indicates the geometry of the molecule.
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 Conditions for hybridisation


• Only the orbitals present in the valence shell of the atom are hybridised.
• The orbitals undergoing hybridisation should have only a small difference in energy. The orbitals which differ largely
in energy cannot take part in hybridisation.
• Promotion is not essential condition prior to hybridisation.
• It is not essential that only half filled orbitals participate in hybridisation. In certain cases, even filled orbitals of
valence shell participate in hybridisation.

Shape of Molecules/ions Hybridisation type Atomic orbitals Example

Linear sp s+p BeF2
Triangular pyramidal sp2 s + p(2) BCl3
3
Tetrahedral sp s + px+ py+pz CH4
Square planar dsp2 d+s+p(2) [Ni(CN)4]2–, [Pt(Cl)4]2–
Trigonal bipyramidal sp3d s+ px +py + pz + d2z PF5, PCl5
Square pyramidal sp3d2 s+px, py, pz+dx2-y2, dz2 BrF5
s+p(3)+d(2) dx2-y2, dz2 SF6, [CrF6]3–
Octahedral sp3d2
dxy, dx2y2+s+p(3) [Co(NH3)6]3+
d2sp3
Pentagonal bipyramidal sp3d3 s+p(3)+dxy, dyz, dxz IF7

3s 3p 3d F
F
(a) I (Ground state)
F

(b) I (Excited state) I

F
hybridisation
sp3d3 hyrbidization
F
(c) IF7
F
Pentagonal bipyramidal
F F F F F F F
(a) (b)

Fig. (a) Formation of IF7 molecule involving sp3d3-hybridisation,

(b) Pentagonal bipyramidal geometry of IF7 molecule.

Topic 3 Molecular Orbital Theory and Hydrogen Bond


Revision Notes
 Molecular orbital theory: The basic idea of molecular orbital theory is that atomic orbital of

individual atoms combine to form molecular orbitals.
 Salient features of molecular orbital theory:

• Just like one atom, molecules have orbitals of definite energy levels.
• Molecular orbitals are formed by the combination of atomic orbitals of proper symmetry and
comparable energies.
• The number of molecular orbitals formed is equal to the number of combining atomic orbitals. When
two atomic orbitals combine they form two molecular orbitals.
• These are called bonding molecular orbitals and antibonding molecular orbitals.
• The bonding molecule has lower energy and hence greater stability whereas corresponding antibonding molecule
has more energy and hence lesser stability.

+ + + + +
+
+
1s 1s 1s
Atomic orbital Molecular orbital

Fig. Formation of bonding molecular orbital

 CHEMICAL BONDING AND MOLECULAR STRUCTURE

+ + + – + –
+

1s 1s *1s
Atomic orbital Node Molecular orbital

Fig. Formation of antibonding molecular orbital

 The main condition for effective combination of atomic orbitals.


• The combining atomic orbitals must have same or nearly the same energies.
• The extent of overlapping between the atomic orbitals of two atoms should be large.
 For homonuclear diatomic molecules of second row elements such as Li2, Be2, B2, C2, N2, the order of increasing


energies for their molecules is

Energy order 1 :
σ1s < σ* 1s < σ 2 s < σ* 2 s < ( π 2 px = π 2 p y ) < σ 2 pz < ( π * 2 p x = π * 2 p y ) < σ* 2 pz
For molecules O2 onwards, the increasing order of energies for molecular orbitals in which they are filled is as follows :
Energy order 2 :
σ1s < σ* 1s < σ 2 s < σ* 2 s < σ 2 pz < ( π 2 px = π 2 p y ) < ( π * 2 p x = π * 2 p y ) < σ* 2 pz
 Hydrogen Bonding :


Hydrogen Bonding
(Force between hydrogen atom and an electronegative atom)

Intermolecular Intramolecular

Intermolecular hydrogen bond is formed Intramolecular hydrogen bond is formed

between two different molecules of the same between the hydrogen atom and the highly
or different substances. electronegative atom (Cl, O, N) present in
For example, the same molecule.
(i) Hydrogen bond between the molecules For example, O
of hydrogen fluoride.
N
(ii) Hydrogen bond in alcohol or water molecules. O
H
O

ortho -nitrophenol


In the light of above statements, choose the most
Topic 1: Previous Year's Questions appropriate answer from the options given below:
(a) Both Statement I and Statement II are true.
1. Given below are two statements: (b) Statement I is false but Statement II is true.
Statement I: pi bonds are weaker than σ bonds. (c) Both Statement I and Statement II are false.
Statement II: pi bonds are formed by the overlapping (d) Statement I is true but Statement II is false.
of p – p orbitals along their axes. 3. The number of σ bonds, π bonds and lone pair of
In the light of above statements, choose the most electrons in pyridine, respectively are
appropriate answer from the options given below: (a) 12, 3, 0 (b) 11, 3, 1
(a) Both Statement I and Statement II are true. (c) 12, 2, 1 (d) 11, 2, 0 [NEET 2023]
(b) Statement I is false but Statement II is true. 4. Amongst the following which one will have
maximum ‘lone pair-lone pair’ electron repulsions ?
(c) Both Statement I and Statement II are false.
(a) ClF3 (b) IF5
(d) Statement I is true but Statement II is false. (c) SF4 (d) XeF2 [NEET 2022]
2. Given below are two statements: 5. Choose the correct statement :
Statement I: NH3 have high dipole moment than PH3 (a) Diamond and graphite have two dimensional
Statement II: Electronegativity of P is more than N. network.
 NEET (UG) Solved Papers Chapterwise & Topicwise CHEMISTRY

(b) Diamond is covalent and graphite is ionic. 17. The electronegativity difference between N and F
(c) Diamond is sp3 hybridised and graphite is sp2 greater than that between N and H yet the dipole
hybridised. moment of NH3 (1.5 D) is larger than that of NF3
(d) Both diamond and graphite are used as dry (0.2 D). This is because:
lubricants. [NEET 2022] (a) In NH3 as well as NF3, the atomic dipole and bond
6. Which of the following molecules is non-polar in dipole are in the same direction.
nature ? (b) In NH3, the atomic dipole and bond dipole are
(a) NO2 (b) POCl3 in the same direction whereas in NF3 these are in
(c) CH2O (d) SbCl5 [NEET 2021] opposite directions
7. Which of the following set of molecules will have (c) In NH3 as well as NF3, the atomic dipole and bond
zero dipole moment ? dipole are in opposite directions.
(a) Boron trifluoride, hydrogen fluoride, carbon (d) In NH3 the atomic dipole and bond dipole are in
dioxide, 1, 3-dichlorobenzene the opposite directions whereas in NF3 these are in
(b) Nitrogen trifluoride, beryllium difluroide, water, 1, the same directions [AIPMT 2005]
3-dichlorobenzene 18. The correct sequence of increasing covalent character
(c) Boron trifluoride, beryllium difluroide, carbon is represented by:
dioxide, 1, 4-dichlorobenzene (a) LiCl < NaCl < BeCl2 (b) BeCl2 < NaCl < LiCl
(d) Ammonia, beryllium difluoride, water, (c) NaCl < LiCl < BeCl2 (d) BeCl2 < LiCl < NaCl
1, 4-dichlorobenzene [NEET 2020 Phase I]  [AIPMT 2005]
8. Identify a molecule which does not exist. 19. Which of the following would have a permanent
(a) Li2 (b) C2 dipole moment?
(c) O2 (d) He2 (a) BF3 (b) SiF4
[NEET 2020 Phase I] (c) SF4 (d) XeF4 [AIPMT 2005]
9. Among the compounds shown below which one


20. Which of the following is isoelectronic?
revealed a linear structure? (a) CO2, NO2 (b) NO2–, CO2
(a) NO2 (b) HOCl –
(c) CN , CO (d) SO2, CO2 [AIPMT 2002]
(c) O3 (d) N2O
21. In PO43– ion, the formal charge on each oxygen atom
[NEET 2020 Phase II]
and PO bond order respectively are:
10. Be2+ is isoelectronic with which of the following
(a) – 0.75, 0.6 (b) – 0.75, 1.0
ions?
(c) – 0.75, 1.25 (d) – 3, 1.25 [AIPMT 1998]
(a) H+ (b) Li+
(c) Na +
(d) Mg2+ [AIPMT 2014] 22. Which one is not paramagnetic among the following?
[Atomic number of Be = 4, Ne = 10, As = 33, Cl = 17]
11. Which of the following molecules has the maximum
(a) Cl– (b) Be+
dipole moment?
(a) CO2 (b) CH4 (c) Ne2+ (d) As+ [AIPMT 1998]
(c) NH3 (d) NF3 [AIPMT 2014] 23. For two ionic solids CaO and KI, identify the wrong
12. Identify the correct order of solubility in aqueous statement among the following:
medium. (a) Lattice energy of CaO is much large than that of KI
(a) CuS > ZnS > Na2S (b) ZnS > Na2S > CuS (b) KI is soluble in benzene
(c) Na2S > CuS > ZnS (d) Na2S > ZnS > CuS (c) KI has lower melting point
 [NEET 2013] (d) CaO has higher melting point [AIPMT 1997]

13. Which of the following is a polar molecule?
(a) BF3 (b) SF4 Answer Key
(c) SiF4 (d) XeF4 [NEET 2013]
1. (d) 2. (d) 3. (b) 4. (d) 5. (c) 6. (d)
14. Which of the following is least likely to behave as
Lewis base? 7. (c) 8. (d) 9. (d) 10. (b) 11. (c) 12. (d)
(a) NH3 (b) BF3 13. (b) 14. (b) 15. (d) 16. (d) 17. (b) 18. (c)
(c) OH– (d) H2O [AIPMT 2011]
19. (c) 20. (c) 21. (c) 22. (a) 23. (b)
15. In the case of alkali metals, the covalent character
decreases in the order :
(a) MCl > MI > MBr > MF Answers with Explanation
(b) MF > MCl > MBr > MI 1. (d) pi bonds are formed by the overlapping of p – p
(c) MF > MCl > MI > MBr orbitals perpendicular to their axis, i.e., sidewise overlap.
(d) MI > MBr > MCl > MF [AIPMT 2009] 2. (d) All the given molecules have same structure.
16. The correct order of C—O bond length among CO, The electronegativity of the central atom of given
CO32–, CO2 is: compounds is in the order
(a) CO2 < CO32– < CO (b) CO < CO32– < CO2 As < Sb < P < N
(c) CO32– < CO2 < CO (d) CO < CO2 < CO32– Thus, the highest bond dipole is for NH bond which
[AIPMT 2007] results in highest dipole moment of NH3.
CHEMICAL BONDING AND MOLECULAR STRUCTURE

3. (b) [2 − 2]
= =0
2
Since, bond order is zero, so He2 molecule does not
exist.
9. (d) N2O is linear.
No. of π bond = 3 10. (b) Electronic configuration of Be2+ = 1s2 i.e., 2 electrons
No. of lone pair = 1 Electronic configuration of H+ = 1s0
No. of σ bond = 11 i.e., zero electron
4. (d) In ClF3, there are 2 lone pairs
Electronic configuration of Li+ = 1s2, i.e., 2 electrons
In IF5, there is 1 lone pair.
Electronic configuration of Na+ = 1s2 2s2 2p6
In SF4, there is 1 lone pair, and
i.e., 10 electrons
In XeF2, there are 3 lone pairs.
So, lone pair – lone pair repulsion is maximum in XeF2. Electronic configuration of Mg2+ = 1s2 2s2 2p6
F i.e., 10 electrons
Thus, Be2+ and Li+ iso electronic as both contains same
number of electrons.
11. (c) In case of CO2 and CH4 though the CO and CH
Xe
bonds are polar but due to their symmetrical structure
they have zero dipole moment.
H
F
5. (c) In diamond, carbon atoms have tetrahedral C
arrangement, so hybridisation is sp3. O C O H H
The shape of graphite is trigonal planar and the H
hybridisation possessed by it is sp2. Net dipole moment = 0 Net dipole moment = 0
6. (d) The molecule which has net dipole moment equal Among NH3 and NF3, the dipole moment of NH3 is
to zero ( = 0) is considered as non-polar molecule. In
m

higher due to direction of dipole of NH bond is in

SbCl5, net vector summation of bond moments will be the similar direction of lone pair but for NF3 the dipole
zero, so it is a non-polar molecule.
moment of NF bond is in opposite direction of lone
Cl
Cl pair which results a lower value of net dipole moment.
Cl Sb =0
Cl N
Cl H H
sp3d, trigonal bipyramidal H
7. (c) Due to their symmetrical structure, BF3, BeF2, CO2 Net dipole moment is of higher
and 1, 4-dichloro benzene molecules have a zero dipole value due to sum of dipoles
moment. in same direction
F F

= 0= 0 N
B B F F
F F F F F
Net dipole moment is lower due to
F F Be Be F =F 0= 0 resultant of 3 N-F bonds is opposite
due to the dipole of lone pair
= 0= 0 12. (d) Water is a polar compound so the salt which is
O O C C O O more polar or having more ionic character will be more
Cl Cl soluble in it. According to Fajans’ rule, ionic character
of compound increases with the increase in the size of
cation. Now, among the given compounds, the size of
= 0= 0 cations are in the order as follows:
Na+ > Zn2+ > Cu2+
Cl Thus, the order of ionic character and the solubility
Cl order in aqueous medium is as follows :
8. (d) For He2 molecule Na2S > ZnS > CuS
Total number of electron = 4 13. (b) The molecules which have symmetrical structure
Electronic configuration is s1s2, s*1s2 are non-polar even they contain polar bonds due
[N b − N a ] to cancellation of bond dipoles. Among the given
Bond order = molecules BF3, SiF4 and XeF4 are symmetric molecules.
2
 NEET (UG) Solved Papers Chapterwise & Topicwise CHEMISTRY

F F value of dipole moment. However, in NF3, the three

F NF bond dipole are in opposite direction of atomic
B Si dipole thus, the net dipole moment for the molecule is
F F F less than the NH3.
F
18. (c) Among the given compounds the anion is same, i.e.,
Bond dipoles Bond dipoles
cancel each other cancel each other chloride ion however the difference is in the cations.
    
Now, according to Fajans’ rule,
F F 1
Xe Covalent character ∝ .
size of cation
F F The size of cations varies as Be2+ < Li+ < Na+. Hence,
Bond dipoles and dipoles of lone covalent character of compounds is in the order as
pairs of electrons cancel each other follows :
But in SF4 there are four Si—F bonds and one lone pair NaCl < LiCl < BeCl2
due to which its structure is unsymmetrical. Hence, it 19. (c) Structures of the given compounds are as follows:
is a polar molecule. F F
F
F B Si
S
Si
F F F F F
F Net dipole moment = 0 Net dipole moment = 0
F
Net dipole moment = 0
F F F F
14. (b) The species which have a lone pair of electrons to S Xe
donate or a negative charge on it can act as a Lewis F F F F
base. Here, N atom in NH3 and O atom in H2O have
lone pair of electrons available for donation. In OH– Due to lone pair there Net dipole moment = 0
the negative charge on it results in to behave it as a is permanent dipole moment
Lewis base. But BF3 is an electron deficient species 20. (c) Number of electrons in CO2 =6 + 2(8) = 22
thus, it is least likely to behave as Lewis base. Number of electrons in NO2 = 7 + 2(8) = 23
15. (d) According to Fajans’ rule, Number of electrons in NO2– = 7 + 2(8) + 1 = 24
Covalent character ∝ size of anion Number of electrons in CN– = 6 + 7 + 1 = 14
1 Number of electrons in CO = 6 + 8 = 14
∝ Number of electrons in SO2 = 16 + 2(8) = 32
size of cation
Thus, species which are isoelectronic are CN– and CO.
    
Now the order of size of anions in the given options is
21. (c) Formula charge on each oxygen atom is as follows :
as follows
Total charge on PO43– ion is –3.
F– < Cl– < Br– < I–
Number of oxygen atoms is 4.
Thus, the covalent character of the given compounds So, average formula charge on each atom
varies as
−3
MF < MCl < MBr < MI or M I > MBr > MCl > MF = = − 0.75
4
16. (d) Bond length between two atoms decreases from
Bond order of P—O
single bond to multiple bonds between them. In CO,
Number of bonds between P and O
there is triple bond between C and O, in CO2 there is =
double bond between C and O. Thus, bond length of Number of resonating structures
CO2 is greater than CO. In CO32–, there are two single O–
O–
bonds between C and O and third oxygen atom forms ||
O- ¾ P ¾ O ↔ O
−
double bond with carbon. These three oxygen atoms – P O–
|

||

are identical due to resonance thus, each C—O bond | |

length is smaller than a single bond but greater than the O– O–
double bond. Thus, the correct order of bond length is as
O− O
follows:
| |
CO < CO2 < CO32– ↔ O−  P  Ο − ↔ O P  
||

17. (b) || |
O O
N N Thus, there are 4 resonating structures of PO43– ion and
F F the number of P—O bonds is
H H
H F 2 + 1 + 1 + 1 = 5
In NH3, all the three bond dipoles are add to the atomic 5
Thus, bond order of P—O = = 1.25
dipole as they are in same direction thus, giving high 4
CHEMICAL BONDING AND MOLECULAR STRUCTURE

22. (a) Electronic configuration of 4. Match List-I with List-II :

Cl– = 1s2 2s2 2p6 3s2 3px2 3py2 3pz2 List-I List-II
Here, all electrons are paired, so it is diamagnetic. (Molecules) (Shape)
Electronic configuration of Be+ = 1s2 2s1 (a) NH3 (i) Square pyramidal
Here, one electron is unpaired, so it is paramagnetic
(b) ClF3 (ii) Trigonal bipyramidal
Electronic configuration of
Ne2+ = 1s2 2s2 2px2 2py1 2pz1 (c) PCl5 (iii) Trigonal pyramidal
Here, there are two unpaired electrons thus, it is (d) BrF5 (iv) T-shape
paramagnetic. Choose the correct answer from the options given
Electronic configuration of below :
As+ = 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4px1 4py1 (a) (a) - (ii), (b) - (iii), (c) - (iv), (d) - (i)
Here, there are two unpaired electrons thus, it is (b) (a) - (iii), (b) - (iv), (c) - (ii), (d) - (i)
paramagnetic. (c) (a) - (iv), (b) - (iii), (c) - (i), (d) - (ii)


(d) (a) - (iii), (b) - (iv), (c) - (i), (d) - (ii) [NEET 2022]
23. (b) According to Fajans’ rule,
5. BF3 is planar and electron deficient compound.
1 Hybridisation and number of electrons around the
covalent character ∝ size of anion ∝
size of cation central atom, respectively are
(a) sp2 and 8 (b) sp3 and 4
Now, size of cation, K+ > Ca2+
(c) sp3 and 6 (d) sp2 and 6 [NEET 2021]
Size of anion, O2– < I–
6. Match List-I with List-II.
Thus, CaO is more covalent than KI. List-I List-II
Lattice energy of KI is lower than that of CaO. Also, KI (a) PCl5 (i) Square pyramidal
has lower melting point than CaO. (b) SF6 (ii) Trigonal planar
Also, KI being ionic in nature is soluble in a polar solvent (c) BrF5 (iii) Octahedral
but benzene is a non-polar solvent thus, KI being polar (d) BF3 (iv) Trigonal bipyramidal
is insoluble in a non-polar solvent like benzene. Choose the correct answer from the options given
below.
Topic 2: Previous Year's Questions (a) (a)-(iv), (b)-(iii), (c)-(ii), (d)-(i)
(b) (a)-(iv), (b)-(iii), (c)-(i), (d)-(ii)
1. Assertion (A): Atoms can combine either by transfer (c) (a)-(ii), (b)-(iii), (c)-(iv), (d)-(i)
of valence of electrons from one atom to another or by (d) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii) [NEET 2021]
sharing of valence electrons. 7. Identify the wrongly matched pair.
Reason (R): Sharing and transfer of valence electrons Molecule Shape or geometry of molecule
is done by atoms to have an octet in their valence shell.
(a) PCl5 Trigonal planar
In the light of the above statements, choose the most
(b) SF6 Octahedral
appropriate answer from the options given below:
(a) Assertion is correct, reason is correct; reason is the (c) BeCl2 Linear
correct explanation for assertion. (d) NH3 Trigonal pyramidal
(b) Assertion is correct, reason is correct; reason is not [NEET 2020 Phase II]
the correct explanation for assertion. 8. Match the coordination number and type of
(c) Assertion is correct, reason is incorrect. hybridisation with distribution of hybrid orbitals in
(d) Assertion is incorrect, reason is correct. space based on valence bond theory.
2. Given below are two statements: Coordination Distribution of
Statement I: Lone pair – lone pair repulsive interactions number and type hybrid orbitals
are greater than lone pair – bond pair and bond pair – of hybridisation in space
bond pair interactions. (A) 4, sp3 (i) trigonal bipyramidal
Statement II: The space occupied by lone pair (B) 4, dsp2 (ii) octahedral
electrons is more as compared to bond pair electrons.
(C) 5, sp3d (iii) tetrahedral
In the light of above statements, choose the most
appropriate answer from the options given below: (D) 6, d2sp3 (iv) square planar
(a) Both Statement I and Statement II are true. Select the correct option:
(b) Statement I is false but Statement II is true. (a) (A)-(ii) (B)-(iii) (C)-(iv) (D)-(i)
(c) Both Statement I and Statement II are false. (b) (A)-(iii) (B)-(iv) (C)-(i) (D)-(ii)
(d) Statement I is true but Statement II is false. (c) (A)-(iv) (B)-(i) (C)-(ii) (D)-(iii)
3. Amongst the following, the total number of species (d) (A)-(iii) (B)-(i) (C)-(iv) (D)-(ii) [NEET 2020 Phase II]
NOT having eight electrons around central atom in 9. The hybridisations of atomic orbitals of nitrogen in
its outer most shell, is NO2+, NO3– and NH4+ respectively are :
NH3, AlCl3, BeCl2, CCl4, PCl5 : (a) sp, sp3 and sp2 (b) sp2, sp3 and sp
(a) 2 (b) 4 2
(c) sp, sp and sp 3
(d) sp2, sp and sp3
(c) I (d) 3 [NEET 2023]  [NEET 2016, Phase II]
 NEET (UG) Solved Papers Chapterwise & Topicwise CHEMISTRY

10. Which of the following pairs of ions is isoelectronic 21. In which one of the following species the central
and isostructural? atom has the type of hybridisation which is not the
(a) CO32–, NO3– (b) ClO3–, CO32– same as they present in the other three?
2– –
(c) SO3 , NO3 (d) ClO3–, SO32– (a) SF4 (b) I3–
 [NEET 2016, Phase II] (c) SbCl52– (d) PCl5 [AIPMT 2010]
11. Which of the following pairs of d-orbitals will have 22. In which of the following molecules/ions BF3, NO2–,
electron density along the axes? NH2– and H2O, the central atom is sp2 hybridised?
(a) dz2 , dxz (b) dxz, dyz (a) NO2– and NH2– (b) NH2– and H2O
(c) dz2, dx2 – y2 (d) dxy, dx2 – y2 –
(c) NO2 and H2O (d) BF3 and NO2–
 [NEET 2016, Phase II]

[AIPMT 2009]
12. Consider the molecules CH4, NH3 and H2O which of

23. The correct order of increasing bond angles in the
the given statements is false? following triatomic species is :
(a) The HOH bond angle in H2O is smaller than (a) NO2– < NO2+ < NO2
the HNH bond angle in NH3.
(b) NO2– < NO2 < NO2+
(b) The HCH bond angle in CH4 is larger than the
(c) NO2+ < NO2 < NO2–
HNH bond angle in NH3.
(c) The HCH bond angle in CH4, the HNH (d) NO2+ < NO2– < NO2 [AIPMT 2008]
bond angle in NH3 and the HOH bond angle 24. The angular shape of ozone molecule (O3) consists
in H2O are all greater than 90°. of:
(d) The HOH bond angle in H2O is larger than (a) 1 sigma and 2 pi-bonds
the HCH bond angle in CH4. (b) 2 sigma and 2 pi-bonds
[NEET 2016, Phase I] (c) 1 sigma and 1 pi-bond

13. Maximum bond angle at nitrogen is present in which (d) 2 sigma and 1 pi-bond [AIPMT 2008]
of the following? 25. In which of the following pairs, the two species are
(a) NO2+ (b) NO3– isostructural?
(c) NO2 (d) NO2– (a) SF4 and XeF4 (b) SO32– and NO3–
(d) BrO3– and XeO3

 [AIPMT 2015] (c) BF3 and NF3
14. Which of the following does not have tetrahedral  [AIPMT 2007]
structure? 26. Which of the following is not isostructural with
(a) BH4– (b) BH3 SiCl4?
(c) NH4+ (d) H2O (a) SCl4 (b) SO42–
15. Which one of the following species has plane (c) PO43– (d) NH4+ [AIPMT 2006]
triangular shape 27. Which of the following species has a linear shape?
(a) N3 (b) NO3– (a) NO2– (b) SO2
(c) NO2– (d) CO2 [AIPMT 2014] (c) NO2+ (d) O3 [AIPMT 2006]
16. Which one of the following molecules contain no 28. In which of the following molecules all the bonds are
π-bond? not equal?
(a) CO2 (b) H2O (a) ClF3 (b) BF3
(c) SO2 (d) NO2 [NEET 2013] (c) AlF3 (d) NF3 [AIPMT 2006]
17. Considering the state of hybridisation of carbon 29. Which of the following is not a correct statement?
atoms, find out the molecule among the following (a) The electron deficient molecules can act as Lewis
which is linear? acids.
(a) CH3 – C ≡ C – CH3 (b) The canonical structures have no real existence.
(b) CH2 = CH – CH2 – C ≡ CH (c) Every AB5 molecule does in fact have square
(c) CH3 – CH2 – CH2 – CH3 pyramid structure.
(d) CH3 – CH = CH – CH3 [AIPMT 2011] (d) Multiple bonds are always shorter than
18. Which of the two ions from the list given below, corresponding single bond.  [AIPMT 2006]
have the geometry that is explained by the same 30. Which of the following molecules has trigonal planar
hybridisation of orbitals. geometry?
  NO2–, NO3–, NH2–, NH4+, SCN–? (a) IF3 (b) PCl3
(a) NH4+ and NO3– (b) SCN– and NH2– (c) NH3 (d) BF3 [AIPMT 2005]
(c) NO2– and NH2– (d) NO2– and NO3– 31. In BrF3 molecule, the lone pairs occupy equatorial
 [AIPMT 2011] positions to minimise:
19. In which of the following pairs of molecules/ions, the (a) Lone pair – bond pair repulsion
central atoms have sp2 hybridisation? (b) Bond pair – bond pair repulsion
(a) NO2– and NH3 (b) BF3 and NO2– (c) Lone pair – lone pair repulsion and lone pair –
–
(c) NH2 and H2O (d) BF3 and NH2– bond pair repulsion
[AIPMT 2010] (d) lone pair – lone pair repulsion [AIPMT 2004]

20. The correct order of increasing bond angles in the 32. H2O is dipolar, whereas BeF2 is not. It is because :
following species is : (a) The electronegativity of F is greater than that of O.
(a) Cl2O < ClO2 < ClO2– (b) H2O involves hydrogen bonding whereas BeF2 is a
(b) ClO2 < Cl2O < ClO2– discrete molecule.
(c) Cl2O < ClO2– < ClO2 (c) H2O is linear and BeF2 is angular.
(d) ClO2– < Cl2O < ClO2 [AIPMT 2010] (d) H2O is angular and BeF2 is linear. [AIPMT 2004]
CHEMICAL BONDING AND MOLECULAR STRUCTURE

33. Among the following pairs which of the two species

are not isostructural is :
Answer Key
(a) SiF4 and SF4 (b) IO3– and XeO3 1. (a) 2. (a) 3. (d) 4. (b) 5. (d) 6. (b)
(c) BH4–and NH4+ (d) PF6– and SF6
7. (a) 8. (b) 9. (c) 10. (a,d) 11. (c) 12. (d)

[AIPMT 2004]
34. In a regular octahedral molecule, MX6 the number of 13. (a) 14. (b) 15. (b) 16. (b) 17. (a) 18. (d)
X—M—X bonds at 180° is : 19. (b) 20. (d) 21. (c) 22. (d) 23. (b) 24. (d)
(a) 3 (b) 2
(c) 6 (d) 4 [AIPMT 2004] 25. (d) 26. (a) 27. (c) 28. (a) 29. (c) 30. (d)
35. Which of the following statement is not correct for 31. (d) 32. (d) 33. (a) 34. (a) 35. (d) 36. (d)
sigma and pi-bonds formed between two carbon
37. (b) 38. (a) 39. (d) 40. (a)
atoms?
(a) Free rotation of atoms about a sigma bond is
allowed but not in case of a pi-bond. Answers with Explanation
(b) Sigma bond determines the direction between
carbon atoms but a pi-bond has no primary in this 1. (a) Atoms combine either by transfer of valence
regard. electrons from one atom to another or by sharing
(c) Sigma bond is stronger than a pi-bond. of valence electrons to have an octet in their valence shell.
(d) Bond energies of sigma and pi-bonds are of the 2. (a) While the lone pairs are localised on the central
order of 264 kJ/mol and 347 kJ/mol respectively. atom, each bonded pair is shared between two atoms.
[AIPMT 2003] As a result, the lone pair electrons in a molecule
36. In NO3– ion number of bond pair and lone pair of occupy more space as compared to the bonding pairs
electrons on nitrogen atom are : of electrons. This results in greater repulsion between
(a) 2, 2 (b) 3, 1 lone pairs of electrons as compared to the lone pair –
bond pair and bond pair – bond pair repulsions.
(c) 1, 3 (d) 4, 0 [AIPMT 2002]
37. In which of the following bond angle is maximum ? 3. (d)
(a) NH3 (b) NH4+
(c) PCl3 (d) SCl2 [AIPMT 2001]
38. Which of the following two are isostructural?

(a) XeF2 and IF2– (b) NH3 and BF3

(c) CO32– and SO32– (d) PCl5 and ICl5


[AIPMT 2001]
39. Main axis of a diatomic molecule is z, molecular

orbital px and py overlaps to form, which of the

following orbitals?
(a) π-molecular orbital (b) σ-molecular orbital
(c) δ-molecular orbital (d) No bond will form

 [AIPMT 2001]
40. Which one of the following is planar?
(a) XeF4 (b) XeO4
(c) XeO3F (d) XeO3F2 [AIPMT 2000]

4. (b)
NH3 ClF3 PCl5 BrF5
bp = 3, lp =1 bp = 3, lp =2 bp = 5, lp =0 bp = 5, lp =1
Steric No. = 4 Steric No. = 5 Steric No. = 5 Steric No. = 6
Hybridisation -sp3 Hybridisation-sp3d Hybridisation-sp3d Hybridisation-sp3d2

.. .. F F
Cl
Cl
Cl
Cl .. ..
f f f f
N N Cl F Cl F P Cl P Cl Br Br
H H H H f ff f
F FCl Cl
H H Cl Cl f f
Trigonal pyramidal T-shaped Trigonal Bipyramidal Square Pyramidal
5. (d) F
Z = 5)
B(z 1s2 2s2 2p1
Ground state B

F F
Excited state Here, boron atom is sp2 hybridised and it contains 6
electrons around the central atom after the formation
sp2 of bond with boron atom.
 NEET (UG) Solved Papers Chapterwise & Topicwise CHEMISTRY

6. (b) In CH4, there is no lone pair of electrons thus it is

Cl
Cl perfectly tetrahedral in shape and has HCH bond
(a) PCl5 – (iv) Trigonal bipyramidal Cl—P angle of 109°28′ but in NH3 there is one lone pair which
sp3d hybridised Cl due to more repulsion with bond pairs of electrons

Cl
pushes them more closer thus bond angle decreases to
F 107°. In H2O, there are two lone pair of electrons which
(b) SF6 – (iii) Octahedral F F
suppress the bond angle more to 104.5°.
sp3d2 hybridised S
13. (a) NO2+→ sp hybridisation, i.e., 180° bond angle.

F F
F
NO3– → sp2 hybridisation, i.e., 120° bond angle
..
(c) BrF5 – (i) Square pyramidal F F NO2– → sp2 hybridisation with two bond pairs and one
sp3d2 hybridised
Br lone pair thus, bond angle is 115°.
F F
NO2 → sp2 hybridisation with two bond pairs and one

F
F orbital contains one electron thus bond angle increases
(d) BF3 – (ii) Trigonal planar B—F to 134°.
sp2 hybridised F Thus, maximum bond angle at nitrogen is of NO2+

7. (a) PCl5 is trigonal bipyramidal. 14. (b) BH4– , NH4+ and H2O all have four electron pairs
8. (b) sp3 is tetrahedral, dsp2 is square planar, sp3d is thus, they have tetrahedral structure but BH3, has three
trigonal bipyramidal, d2sp3 is octahedral. bond pairs of electrons with no lone pairs of electrons
9. (c) Hybridisation of atomic orbitals of nitrogen in the thus, it has trigonal planar shape.
given ions can be calculated by the formula as follows : 15. (b) Hybridisation of N3 is sp thus, it is linear in shape :
1 – –
Hybridisation = (valence electrons + univalent ·
+
2 · N == N == N ··

·
·

·
·
atoms attached to central atom – charge on cation +
Hybridisation of NO3– is sp2 thus, it is plane triangular
charge on anion)
in shape
1 –
For NO2+ = (5 + 0 − 1 + 0) = 2 O
2
Two hybrid orbitals means sp-hybridisation N
1
For NO3– = (5 + 0 − 0 + 1) = 3 O O
2
–
Three hybrid orbitals means sp2-hybridisation Hybridisation of NO2 is sp, thus it is linear in shape
−
1 • • • • • • • • 
For NH4 = (5 + 4 − 1 + 0) = 4
+
 • •O• — N == O • 
2  
4 hybrid orbitals means sp3-hybridisation Hybridisation of CO2 is sp, thus it is linear in shape
10. (a, d) CO32–, number of electrons 5
= 6 + 3(8) + 2 = 32 = = 1.25
4
According to VSEPR theory it is trigonal planar in shape.
16. (b) All the given oxides have oxygen atom with lone
NO3–, number of electrons = 7 + 3(8) + 1 = 32 pair of electrons available to donate to the central atom
According to VSEPR theory it is trigonal planar in which result in -bond. But in H2O the hydrogen
shape.
p
atom attached to oxygen does not have vacant orbital
ClO3–, number of electrons to accept the lone pair of electrons from oxygen
= 17 + 3 (8) + 1 = 42 thus, it cannot form a -bond while carbon, sulphur
p
According to VSEPR theory, it is trigonal pyramidal in and nitrogen have vacant orbitals to form -bond by
p
shape. accepting lone pair of electrons from oxygen atom.
SO32–, number of electrons 17. (a) The carbon atoms which have sp hybridisation
= 16 + 3(8) + 2 = 42 form a linear molecule. Among the given compounds,
CH 3  C ≡≡ C  CH 3 has sp hybridised carbon atoms
According to VSEPR theory, it is trigonal pyramidal in
sp3 sp sp sp3
shape.
which are attached to sp3 hybridised carbon atoms. But
Thus, CO32–, NO3– and ClO3–, SO32– are isoelectronic the whole molecule is linear as shown below :
11. (c) dxy, dyz and dxz orbital have electron density in Must be linear
between their corresponding axes while dx2 – y2 and dz2 H3C—C C—CH3
have electron density along the corresponding axes,
i.e., dx2 – y2 is along x and y axes while dz2 along z-axis. Must be linear
– 2
12. (d) According to the VSEPR theory, the structures of 18. (d) NO2 has sp hybridisation and trigonal planar
CH4, NH3 and H2O are as follows : geometry, NO3– has sp2 hybridisation and trigonal
H planar geometry, NH2– has sp3 hybridisation and
tetrahedral geometry, NH4+ has sp3 hybridisation and
109°28' tetrahedral geometry and SCN– has sp hybridisation
C N O and linear geometry.
H H H 107.1° H H 104.5° H 19. (b) NO2– is sp2 hybridised as it has two bond pairs and
H H one lone pair of electrons.
CHEMICAL BONDING AND MOLECULAR STRUCTURE

NH3 is sp3 hybridised on it has three bond pairs and 1 O 1

one lone pair of electrons. 1
BF3 is sp2 hybridised as it has three bond pairs of O O
electrons only. Thus, there are 2 σ-bonds and 1 pi-bond in O3 molecule.
NH2– is sp3 hybridised as it has two bond pairs and 25. (d) Hybridisation of Br in BrO3–
lone pairs of electrons. H2O is sp3 hybridised as it has 1
two bond pairs and two lone pairs of electrons. = (7 + 0 − 0 + 1)= 4
2
H2O is sp3 hybridised as it has two bond pairs and two

Four hybrid orbital means sp3 hybridisation

lone pairs of electrons.
20. (d) Structure of the given species are as follows : Hybridisation of Xe in XeO3
– 1
Cl O Cl = (8 + 0 − 0 + 0)= 4

2
O O Cl Cl O O Hybridisation of Xe in XeO3
– 1
ClO2 Cl2O ClO2 = (8 + 0 − 0 + 0)= 4
(1 lone pair) (2 lone pair) (2 lone pair)
2
As ClO2 has only one lone pair of electrons thus due Four hybrid orbitals means sp3 hybridisaton.
to lower lone pair – bond pair it has highest bond Thus, both BrO3– and XeO3 are sp3 hybridised with
angle than Cl2O and ClO2– which has two lone pairs of three bond pairs of electrons and one lone pair of
electrons. electrons and results in trigonal pyramidal shape.
Now, among Cl2O and ClO2–, greater bond angle is for
Cl2O due to higher electronegativity of oxygen than
chlorine. As electronegativity of central atom increases Br Xe
the bond pair of electrons are more closer to it and O O– O O
hence more repulsion between them to give a larger O O
bond angle. Thus, the order of increasing bond angle is BrO3– XeO3
ClO2– < Cl2O < ClO2
21. (c) Hybridisation can be evaluated from the formula 26. (a) SCl4 is not isostructural with SiCl4 as SCl4 has four
H=1/2 [Valence electrons + Monovalent atoms– bond pairs of electrons and one lone pair of electrons
Positive charge + Negative charge] and due to this it has see-saw shape. While SiCl4, SO42–,
For SF4 , H = 1/2 [6 + 4 – 0 + 0] = 5 PO43– and NH4+ all have tetrahedral geometry and are
i.e., sp3d hybridisation isostructural.
For I3–, H = 1/2 [7 + 2 – 0 + 1] = 5 27. (c) Among the given species, NO2+ has linear shape
i.e., sp3d hybridisaton due to sp hybridisation of nitrogen atom. While NO2–,
For SbCl52–, H = 1/2 [5 + 5 – 0 + 2] = 6 SO2 and O3 have angular shape due to lone pair of
i.e., sp3d2 hybridisation electrons.
For PCl5, H = 1/2 [5 + 5 – 0 + 0] = 5 N
i.e., sp3d hybridisation +
–
O N O O O
Thus, SbCl52– has different hybridisation than other
three species. NO2
+
NO2–
22. (d) NO2– ⇒ 2 bond pairs + 1 lone pair ⇒ sp2 hybridisation +
NH2– ⇒ 2 bond pairs + 2 lone pairs S O
⇒ sp3 hybridisation
H2O ⇒ 2 bond pairs + 2 lone pairs O O O O–
⇒ sp3 hybridisation SO2 O3
BF3 ⇒ 3 bond pairs only ⇒ sp2 hybridisation
28. (a) The structure of ClF3 is trigonal bipyramid with
23. (b) Structure of the given species are as follows : three bond pairs of electrons and two lone pairs of
N N + electrons.
115° 132° O N O F axial position
O O O O 180°

NO2– NO2 NO2

+ Cl F Equatorial position
–
As NO2 has one lone pair of electrons on nitrogen
F axial position
atom thus, due to bond pair lone pair repulsion it
decreases the bond angle O – N – O than in the NO2 Thus, one Cl–F bond is equatorial bond and two Cl–F
molecule where there is no lone pair of electrons. NO2+ bonds are axial bonds and these two types of bonds
is a linear molecule thus, it has highest O – N – O bond are of different length. While BF3 and AlF3 have
angle of 180°. Hence, order of increasing bond angle is symmetrical trigonal planar structure and NF3 has
NO2– < NO2 < NO2+ pyramidal geometry with one lone pair and three
similar N–F bonds.
24. (d) Ozone has one double-bond and one single-bond.
29. (c) AB5 molecule has generally trigonal bipyramidal
The single-bond is the sigma-bond and in double-bond
structure. Sometimes due to presence of lone pair of
there is one sigma-bond and one pi-bond.
electrons the structure gets distorted.
 NEET (UG) Solved Papers Chapterwise & Topicwise CHEMISTRY

30. (d) IF3 has three bond pairs and two lone pairs, thus, it While in SF4, sulphur atom has four bond pairs of
has sp3d hybridisation electrons and one lone pair of electrons to give a sp3d
F hybridised distorted tetrahedral molecule.

Bent T-Shape F F
I F
S
F F
F Distorted tetrahedral
PCl3 has three bond pairs and one lone pair thus, it has
Thus, SiF4 and SF4 are not isostructural to each other.
sp3 hybridisation
34. (a) The MX6 molecule with regular octahedral geometry
is as follows :
P X X X
Cl Cl X X X X X X
Cl M M M
Pyramidal geometry X 180° X X X X 180°
X
180°
NH3 has three bond pairs and one lone pair thus, it has X X X
sp3 hybridisation Thus, there are 3 XMX bonds with bond angle
180°.
N 35. (d) Free rotation of atoms is possible with sigma bond
and due to overlapping of orbital in pi-bond form
H H
H above and below the plane of the atoms, the free
Pyramidal geometry rotation is not possible. Sigma bond determines the
direction between carbon atoms and not a pi-bond.
BF3 has three bond pairs and no lone pair thus, it has Sigma bond is stronger bond due to head to head axial
sp2 hybridisation. overlap of orbital while pi-bond is weaker due to less
F efficient sideways overlapping. Bond energy of CC
sigma-bond is 347 kJ/mol and for C=C the bond energy
B is 619 kJ/mol.
F F 36. (d) The structure of NO3– ion is as follows:
Trigonal planar geometry – –
O N O or O—N O
31. (d) Lone pair Lone pair repulsion > lone pair – bond
O
pair repulsion > bond pair – bond pair repulsion. O
Thus, in BrF3 molecule where Br is sp3d hybridised, Hence, nitrogen atom has four bond pairs of electrons
i.e., trigonal bipyramidal geometry, the lone pairs of and zero lone pairs of electrons.
electrons are arranged on equatorial position as they 37. (b) Structures of the given molecules are as follows :
are at maximum distance at these positions and hence H
they have minimum repulsion at these positions.
+
32. (d) In H2O the central atom oxygen has two lone pairs N N
of electrons and two bond pairs of electrons. Thus, the H H H H
shape of H2O is bent or V-shape. Thus, the two dipoles H H
of H-O bonds have some resultant value as they are
not exactly in the opposite direction to cancel out
each other. While in BeF2, there are two bond pairs on P S
central atom Be, hence it is linear in shape. Thus, the
Cl Cl
Cl Cl
two dipoles of bonds are exactly in opposite direction Cl
to each other and cancel each other to give net zero All the given molecules have same number of electron
dipole moment. pairs thus, have similar geometry but in NH3, PCl3
and SCl2 due to presence of lone pairs of electrons on
O F Be F central atom there is more repulsion between lone pair
=0
of electrons and bond pair of electrons and hence the
H H bond angle decreases in these cases. Therefore, NH4+
=0 has maximum bond angle.
33. (a) In SiF4 there are four bond pairs of electrons and 38. (a) In XeF2, Xe is sp3d hybridised and linear in shape
no lone pair of electrons thus, it forms a tetrahedral due to three lone pairs on Xe atom.
molecule with sp3 hybridisation. F
F
Xe
Si
F F F
F Linear shape
CHEMICAL BONDING AND MOLECULAR STRUCTURE

In IF2– the I atom is also sp3d hybridised in which there (b) hydration energy.
are two bond pairs of electrons and three lone pairs (c) second ionisation enthalpy.
of electrons to form trigonal bipyramidal geometry in (d) first ionisation enthalpy. [NEET 2023]
which lone pairs are in equatorial position. Thus, the 5. Which amongst the following is incorrect statement ?
shape of IF2– is linear as shown below. (a) The bond orders of O2+, O2, O2– and O22– are 2.5,
F 2, 1.5 and 1, respectively.
– (b) C2 molecules have four electrons in its two
I
degenerate molecular orbitals.
p

(c) H+ 2 ion has one electron.

F
(d) O+2 ion is diamagnetic. [NEET 2022]
39. (d) The molecular orbitals px and py are perpendicular
to each other thus, they cannot overlap each other and 6. Which one of the following diatomic molecular
hence, no bond will be formed. species has only p bonds according of Molecular
40. (a) XeF4 has four bond pairs of electrons and two lone Orbital Theory?
pairs of electrons i.e., it involves sp3d2 hybridisation of (a) N2 (b) C2
Xe atom. The two lone pairs of electrons are arranged (c) Be2 (d) O3

[NEET 2019]
so that they are for a apart from each other so, these 7. Which one of the following pairs of species have the
two lone pairs are positioned at axial positions at 180° same bond order?
angle. Thus, four XeF bonds are in a plane. Thus, the (a) CO, NO (b) O2, NO+
XeF4 molecule is a planar molecule. –
(c) CN , CO (d) N2, O2– [NEET 2017]
F F 8. Which one of the following compounds shows the
Xe presence of intramolecular hydrogen bond?
F F (a) H2O2
(b) HCN
(c) Cellulose
Topic 3: Previous Year's Questions (d) Concentrated acetic acid [NEET 2016, Phase 2]
1. Assertion A: The bond order of helium is always zero. 9. Decreasing order of stability of O2, O2–, O2+ and O22–
Reason R: The number of electrons in bonding molecular is :
orbital and antibonding molecular orbital is equal. (a) O22– > O2– > O2 > O2+
In the light of the above statements, choose the most (b) O2 > O2+ < O22– > O2–
appropriate answer from the options given below: (c) O2– > O22– > O2+ > O2
(a) Assertion is correct, reason is correct; reason is a (d) O2+ > O2 > O2– > O22– [AIPMT 2015]
correct explanation for assertion. 10. Which of the following is paramagnetic?
(b) Assertion is correct, reason is correct; reason is not (a) CO (b) O2–
a correct explanation for assertion. –
(c) CN (d) NO+ [NEET 2013]
(c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct. 11. The pair of species with the same bond order is
(a) O22–, B2 (b) O2+, NO+
2. Assertion A: Bond order of is O2– is 1.5
Reason R: The number of electrons in bonding molecular (c) NO, CO (d) N2, O2 [NEET 2013]
orbital and antibonding molecular orbital is equal. 12. Which of the following has the minimum bond
In the light of the above statements, choose the most length?
appropriate answer from the options given below: (a) O2– (b) O2–
(a) Assertion is correct, reason is correct; reason is a (c) O2 (d) O2+ [AIPMT 2011]
correct explanation for assertion. 13. Which one of the following species does not exist
(b) Assertion is correct, reason is correct; reason is not under normal conditions?
a correct explanation for assertion. (a) Be2+ (b) Be2
(c) Assertion is correct, reason is incorrect.
(c) B2 (d) Li2 [AIPMT 2010]
(d) Assertion is incorrect, reason is correct.
14. What is the dominant intermolecular force on bond
3. The correct order of energies of molecular orbitals of
that must be overcome in converting liquid CH3OH
N2 molecule, is:
to gas?
(a) σ 1s < σ* 1s < σ 2s < σ * 2s < σ 2pz < (π2рx = π2рy)
(a) Hydrogen bonding
< ( π*2px = π*2py) < σ *2pz
(b) Dipole – Dipole interaction
(b) σ 1s < σ* 1s < σ 2s <σ* 2s < σ 2pz < σ *2pz < (π2рx
= π2рy) < (π*2px = π*2py) (c) Covalent bonds
(c) σ 1s < σ* 1s < σ 2s <σ* 2s < (π2px = π2py) < (π*2px (d) London or dispersion forces [AIPMT 2009]
= π*2py) < σ 2pz < σ* 2pz 15. According to Molecular Orbital Theory which of the
(d) σ 1s < σ* 1s < σ 2s < σ* 2s < (π2px = π2py) < σ 2pz following lists rank the nitrogen species in terms of
< (π*2px = π*2py) < σ* 2pz [NEET 2023] increasing bond order?
(a) N2– < N2 < N22– (b) N22– < N2– < N2
4. The stability of Cu2+ is more than Cu+ salts in 2– –
aqueous solution due to (c) N2 < N2 < N2 (d) N2– < N22– < N2
(a) enthalpy of atomisation.  [AIPMT 2009]
 NEET (UG) Solved Papers Chapterwise & Topicwise CHEMISTRY

16. Four diatomic species are listed below in different 26. The ground state electronic configuration of valence
sequences. Which of these presents the correct order shell electrons in nitrogen molecule (N2) is written as
of their increasing bond order? KK, 2s2, σ*2s2, 2p2x = 2p2y 2p2z

s
p
p
s
(a) O2– < NO < C22+ < He2+ Bond order in nitrogen molecule is :
(b) NO < C22– < O2– < He2+ (a) 0 (b) 1
(c) C22– < He2+ < NO < O2– (c) 2 (d) 3 [AIPMT 1995]
(d) He2+ < O2– < NO < C22–  [AIPMT 2008] 27. The correct order of the OO bond length in O2,
17. The number of unpaired electrons in a paramagnetic H2O2 and O3 is :
diatomic molecule of an element with atomic number (a) O2 > O3 > H2O2 (b) O3 > H2O2 > O2
16 is (c) O2 > H2O2 > O3 (d) H2O2 > O3 > O2
(a) 2 (b) 3 [AIPMT 1995]


(c) 4 (d) 1 [AIPMT 2006] 28. Which of the following species is paramagnetic?
18. In X-H----Y, X and Y both are electronegative elements, (a) O22– (b) NO
then : (c) CO (d) CN– [AIPMT 1995]
(a) Electron density on X will increase and on H will
decrease
(b) In both, electron density will increase
Answer Key
(c) In both, electron density will decrease 1. (a) 2. (b) 3. (d) 4. (b) 5. (d) 6. (b)
(d) On X, electron density will decrease and on H, 7. (c) 8. (c) 9. (d) 10. (b) 11. (a) 12. (d)
electron density will increase. [AIPMT 2001]
13. (b) 14. (a) 15. (b) 16. (d) 17. (a) 18. (a)
19. Which one of the following is not paramagnetic?
(a) NO (b) N2+ 19. (c) 20. (c) 21. (d) 22. (c) 23. (a) 24. (d)
(c) CO (d) O2– [AIPMT 2000] 25. (d) 26. (d) 27. (d) 28. (b)
20. The relationship between the dissociation energy of
N2 and N2+ is : Answers with Explanation
(a) Dissociation energy of N2+ > dissociation energy
of N2. 1. (a) B.O. (For Helium) = 1 (Nb – Na) = 1 (2 – 2) = 0
2 2
(b) Dissociation energy of N2 = dissociation energy of
N2+ 1 3
2. (b) Bond order of O2−
= [10 − 7] = = 1.5
(c) Dissociation energy of N2 > dissociation energy of 2 2
N2+ Thus, O2– has the bond order of 1.5.
(d) Dissociation energy of N2 can either be lower or 3. (d) For molecule up to N2 increasing order of energies
higher than the dissociation energy of N2+ in various molecular orbital is
σ1s, σ*1s, σ2s, σ*2s, π2px = π2py, σ2pz, π*2px = π*2py,
 [AIPMT 2000]
σ*2pz
21. Which one of the following molecules will form a
4. (b) Stability of Cu2+ in more than Cu+ salts in aqueous
linear polymeric structure due to hydrogen bonding?
solution. This is due to high hydration energy of
(a) NH3 (b) H2O Cu2+ ion than Cu+.
(c) HCl (d) HF [AIPMT 2000] 5. (d) Molecular orbital electronic configuration of O2 is
22. The number of anti-bonding electron pairs in O22– 1s2 *1s2, 2s2 *2s2, 2pz2, 2px2 = 2py2, *2px1 = *2py1
molecular ion on the basis of molecular orbital theory

s
s
s
s
s
p
­
p
­
p
p
In O2+, the electronic configuration is:
is : (at. no. of O is 8) 1s2 *1s2, 2s2 *2s2, 2pz2, 2px2 = 2py2, *2px1 = *2py1
(a) 5 (b) 2

s
s
s
s
s
p
­
p
­
p
p
Since, there is one unpaired electron in O2+, so it is
(c) 4 (d) 6 [AIPMT 1998]

paramagnetic in nature.
23. The high density of water compared to ice is due to : 6. (b) Molecular orbital configuration C2 is:
(a) hydrogen bonding interactions s1s2, s*1s2, s2s2, s*2s2, 2p2x = 2p2y

p
p
(b) dipole – dipole interactions 7. (c) For any species to have same bond order we can
(c) dipole – induced dipole interactions expect them to have same number of electrons.
(d) induced dipole – induced dipole interactions Calculating the number of electrons in various species :
 [AIPMT 1997] CO = (6 + 8 = 14)
24. N2 and O2 are converted into mono anions N2– and NO = (7 + 8 = 15)
O2– respectively. Which of the following statement is O2 = (8 + 8 = 16)
wrong? NO+= (7 + 8 – 1 = 14)
(a) In N2–, the NN bond weakens CN– = (6 + 7 + 1 = 14)
(b) In O2–, OO length increases O–2 = (8 + 8 + 1 = 17)
(c) In O2–, bond order decreases N2 = (6 + 7 – 1 = 12)
CN– and CO have same number of electrons and have
(d) N2–, becomes diamagnetic [AIPMT 1997]
same bond order equal to 3.
25. The ion that is isoelectronic with CO is : 8. (c) Cellulose is a polymer of glucose which are
(a) O2– (b) N2+ interlinked to each other. The chain of cellulose
+
(c) O2 (d) CN– [AIPMT 1997] is stabilised by two hydrogen bond parallel to the
 CHEMICAL BONDING AND MOLECULAR STRUCTURE

glycosidic linkage. Hydrogen bonding it is considered 14. (a) CH3OH forms intermolecular hydrogen bonding
as intramolecular hydrogen bonding. While H2O2, shown as follows :
HCN and CH3COOH form intermolecular hydrogen H—O H—O H—O
bonding.
1 CH3 CH3 CH3
9. (d) Bond order of O2 = [8 − 4]= 2
2 Intermolecular hydrogen bonding
1 3 This hydrogen bonding must be overcome to convert
Bond order of O2− = [8 − 5]= = 1.5 liquid CH3OH to a gas.
2 2
15. (b) Electronic configuration of N2
1
Bond order of O22 − = [8 − 6]= 1 = 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2px2
2
s s p

= 2py2 < 2pz2

1 5
p s

Bond order of O+2 = [8 − 3]= = 2.5

2 2 1
Bond order= [10 − 4]
= 3
Stability is directly proportional to bond order thus, the 2
correct order is O2+ > O2 > O2– > O22– Electronic configuration of N2–
10. (b) Electronic configuration of CO, CN– and NO+ (14 = 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2px2 = 2py2
s s p p

electrons) < 2pz2 * < 2px1 * = 2py0 * s p p p

= 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2px2 = 2py2 < 2pz2 1
Bond order= [10 − 5]
= 2.5
s s p p s

As no unpaired electrons. Thus, they are diamagnetic 2

in nature.
Electronic configuration of O2– (17 electrons) Electronic configuration of N22–
= 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2pz2
s s s
= 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2px2 = 2py2
s s p p

< 2px2 = 2py2 < π*2px2 = π*2py1

p p
< 2pz2 * < 2px1 * = 2py1 * s p p p

It contains 1 unpaired electron thus, it is paramagnetic 1

Bond order= [10 − 6]
= 2
in nature. 2
11. (a) Electronic configuration of Hence, the increasing bond order is
O22– = 1s2 < σ*1s2 < 2s2 < *2s2 < 2pz2 < 2px2
s s s s p
N22– < N2– < N2
 < 2py2 < π*2px2 = π*2py2
p

16. (d) Electronic configuration of O2–

1 = 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2pz2 < 2px2
Bond order= [10 − 8]= 1 s s s p p

2 = π2py2 < π*2px2 < π*2py1

Electronic configuration of B2 1
Bond order= [10 − 7]
= 1.5
= 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2px1 = 2py1
s s p p 2
1 Electronic configuration of NO
Bond order = [6 − 4]= 1
2 = 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2pz2 < 2px2
s s s p

2–
Thus, both O2 and B2 have same bond order. = 2py2 < π*2px1 < 2py0 p

12. (d) Bond order of O2– = 1.5, O22– = 1; O2 = 2; 1

Bond order= [10 − 5]
= 2.5
O2+ = 2.5 2
1 Electronic configuration of C22–
Now, bond length ∝
bond order = 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2px2 = 2py2 < 2pz2
s s p p s

Thus, the species which has maximum bond order has

1
minimum bond length therefore, O2+ has minimum Bond order= [10 − 4]= 3
bond length. 2
13. (b) According to Molecular Orbital Theory, the Electrons configuration of He2+ = 1s2 < σ*1s1 s

electronic configuration of Be2+ is as follows: 1

Be2+ (7 electrons) = 1s2 < σ*1s2 < 2s2 < σ*2s1 Bond order = [2 − 1]= 0.5
s s

2
1 1
Bond order = [4 − 3]= . Thus, Be2+ can exist. 17. (a) Diatomic molecule of element with atomic number
2 2
16 must have 32 electrons. Therefore, electronic
For Be2 (8 electrons) = 1s2 < σ*1s2 < 2s2 < σ*2s2
configuration of diatomic molecule is as follows :
s s

1
Bond order = [4 − 4]= 0 . Thus, Be2 does not exist 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2pz2 < 2px2
2
s s s p

= 2py2 < π*2px2 = *2py2 < σ2pz2 < 3s2

For B2 (10 electrons) = 1s2 < σ*1s2 < σ2s2 < 2px1
p p s

2
< σ*3s < 3pz2 < 3px = 3py < π*3px = π*3py1
2 2 1
s p

 1 = 2py1 s p p

Bond order = [6 − 4]= 1 . Thus, B2 can exist. Thus, according to the above electronic configuration
2 the diatomic molecule has 2 unpaired electrons.
For Li2 (6 electrons) = 1s2 < σ*1s2 < 2s2
s s
18. (a) As X and Y both are electronegative elements thus
1 both attracts the electron density from H thus, electron
Bond order = [4 − 2]= 1 . Thus, Li2 can exist.
2 density on H decreases and on X it increases.
 NEET (UG) Solved Papers Chapterwise & Topicwise CHEMISTRY

19. (c) Electronic configuration of NO molecules are not too close and it has open structure
= 1s2 < *1s2 < 2s2 < σ*2s2 < 2pz2 < 2px2 having large spaces between the water molecules thus,
s
s
s
s
p
= 2py2 < π*2px2 = π*2py0 the density of ice is less than that of liquid water.
24. (d) Electronic configuration of N2

p
It contains one unpaired electron, hence, it is paramagnetic.
= 1s2 < σ*1s2 < σ2s2 < σ*2s2 < 2px2 = 2py2 < 2pz2
Electronic configuration of N2+

s
p
p
s
Electronic configuration of O2
= 1s2 < σ*1s2 < 2s2 < σ*2s2 < p2px2 = 2py2 < 2pz1 = 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2pz2 < 2px2
s
s
p
s
It contains are unpaired electron, hence, it is

s
s
s
p
= 2py2 < π*2px1 < π*2py1
paramagnetic.

p
When N2– is formed then one extra electron is added
Electronic configuration of CO to anti bonding orbital thus, the bond weakens as one
= 1s2 < σ*1s2 < 2s2 < *2s2 < 2pz2 < 2px2 = 2py2 single unpaired electron is added to anti bonding
s
s
s
s
p
p
It has no unpaired electron, hence, it is diamagnetic. orbitals. Thus, it is paramagnetic and not diamagnetic.
Electronic configuration of O2– When O2– is formed then one extra electron is added
= 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2pz2 < 2px2 to anti bonding orbital thus, bond order decreases and
bond length increases.
s
s
s
p
= 2py2 < π*2px2 < π*2py1
p
It contains one unpaired electron, hence, it is paramagnetic. 25. (d) CO = 6 + 8 = 14 electrons
20. (c) For N2 O2– = 8 + 8 + 1 = 17 electrons;
=1s2 < σ*1s2 < 2s2 < σ*2s2 < 2px2 = 2py2 < 2pz2 N2+ = 7 + 7 – 1 = 13 electrons
s
s
p
p
s
1 O2+ = 8 + 8 – 1 = 15 electrons;
Bond order= [10 − 4]= 3
2 CN– = 6 + 7 + 1 = 14 electrons
26. (d) Bond order of
For N2+ = 1s2 < σ*1s2 < 2s2 < σ*2s2 < 2px2
1
s
s
p
= 2py2 < 2pz1 N2 = [Nb – Na)
2
p
s
1
Bond order = [9 − 4]= 2.5
2 1 6
= [8 − 2] = = 3
2 2
Now, dissociation energy is more for the species
which have higher bond order. Thus, N2 has higher 27. (d) O O O—O
dissociation energy. H H
Bond order = 2 Bond order = 1
21. (d) NH3 and H2O are non-linear molecules. Among
HCl and HF, a linear polymeric structure is formed by + +
O O
HF molecules shown as follows : – –
O O O O
H – F ….. H – F ….. H – F ….. H – F Bond order = 1.5
↓
Hydrogen bonding 1
As bond length ∝
22. (c) According to Molecular Orbital Theory, electronic Bond order
configuration of O22– is as follows : Hence, order of bond length (0 – 0) is
1s2 < σ*1s2 < 2s2 < σ*2s2 < 2pz2 < 2px2
  O2 < O3 < H2O2 or H2O2 > O3 > O2
s
s
s
p
= 2py2 < π*2px2 = π*2py2
28. (b) Electronic configuration of NO (7 + 8 = 15 electrons)
p
Thus, number of anti bonding electron pairs is 4.
is as follows :
23. (a) Water molecule due to presence of hydrogen
1s2 < σ*1s2 < 2s2 < σ*2s2 < 2pz2 < 2px2
atom attached to electronegative oxygen atom shows
s
s
s
p
hydrogen bonding between their molecules. When it = 2py2 < π*2px2 < π*2py0
p
exists in liquid state then their molecules are close to Thus, it contains one unpaired electron in π*2px orbital
each other but when it condenses to ice then the water thus, it is paramagnetic in nature.

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