DAY FOUR

Chemical Bonding &

Molecular Structure
Learning & Revision for the Day

u Ionic or Electrovalent Bond u Coordinate Bonding u VSEPR Theory

u Covalent Bond u Valence Bond Theory u Molecular orbital Theory
u Bond Parameters u Concept of Hybridisation u Hydrogen Bonding
u Resonance Involving s, p and d-orbital u Metallic Bonding

A chemical bond is the attractive force which holds the various constituents (atoms, ions
etc.) together in different chemical species.
The different types of chemical bonds formed between atoms are as follows:
(i) Ionic bond (ii) Covalent bond (iii) Coordinate bond

Kossel-Lewis Approach (Octet Rule)

● According to this approach, the atoms of different elements take part in chemical
combination in order to complete their octet (to have eight electrons in the outermost
valence shell) or duplet (to have two valence electrons) in some cases such as H, Li, Be
etc., or to attain the nearest noble gas configuration. This is known as octet rule.
● In Lewis symbol, the number of dots around the symbol represents the number of
valence electrons. The number of electrons helps to calculate the common valency of
the element.

Limitations of Octet Rule

In accordance to this rule, the shape of the molecule cannot be predicted. The relative
stability of molecule cannot be known by this rule.
However, the octet rule is violated in a significant number of cases. These are:
(i) Electron deficient compounds : BeCl2 , BF3 , AlCl3 etc.
(ii) Hypervalent compounds : PCl5, SF6, IF7 , H2SO 4 etc.
(iii) Compounds of noble gases : XeF2 , XeF6, XeF4 , KrF2 etc.
(iv) Odd electron molecules : NO, NO2 , O2− , O3 etc.
H2+ , He2+ , O2 , NO, NO2 , ClO2 are some of the examples of stable molecules having odd
electron bonds (bonds formed by sharing of usually one or three electrons).
 (d) X (g)+ e – → X – (g ); ∆H 4 = – E
Ionic or Electrovalent Bond
(E = electron affinity)
The attractive forces of ionic bond (i.e. electrostatic force of
attraction) are developed between an electropositive atom and (e) M +( g )+ X – (g )→ MX (s); ∆H 5 = −U
an electronegative atom due to complete transfer of electrons (U = lattice enthalpy)
from former to later. It is generally formed between the atoms Overall enthalpy change of the reaction is given by
having large difference in their electronegativity.
∆H = ∆H1 + ∆H2 + ∆H3 + ∆H 4 + ∆H 5
Formation of Ionic Bond or alternatively, the above equation can be written as:
● Ionic bond is formed by the complete transfer of D
electron(s) from one atom to the other. ∆H = S + I + − E −U
2
e.g. 11 Na 17 Cl
D
(2, 8, 1) (2, 8, 7) or U =S + I + − E − ∆H
2
+
Na + Cl Na [ Cl ]–
NOTE • A number of ionic solids are almost insoluble in water
Na + + Cl − → NaCl because hydration energy is smaller than their lattice energy.
● Ionic bonds are non-directional and also known as Examples of water insoluble salts are AgCl, AgBr, AgI,
electrovalent bonds or polar bonds. Ag 2CrO 4 , PbSO 4 , BaSO 4 , CaCO 3 .
• Both lattice energy and hydration energy decreases with
Factors Affecting the Formation of Ionic Bonds
increase in ionic size.
The formation of an ionic bond is related to cation and anions
• If both anion and cation are of comparable size, the cationic
which depends upon the following factors:
radius will influence the lattice energy.
(i) Low ionisation energy of the electropositive element.
(ii) High electron affinity of electronegative element. Covalent Bond
(iii) High lattice enthalpy
The chemical bonds that are formed by sharing of electrons
 charge on ions  between the elements of almost same electronegativity or
 Lattice enthalpy ∝ 
 size of ion  between the elements having less difference in
electronegativity are called covalent bonds.
NOTE • Elements of group 1 and group 2 on combining with e.g. Formation of O2 molecule.
halogens, oxygen and sulphur generally form ionic bonds.
8O = 2, 6
• Bonding in compounds of transition metals (in lower
oxidation state) is ionic with partial covalent character.
O O Or O O
Lattice Enthalpy and Its Calculation
The lattice enthalpy of an ionic solid is defined as the energy The covalent bond can be of the following two types:
required to completely separate one mole of a solid ionic
1. Non-polar Covalent Bond If the covalent bond is
compound into gaseous constituent ions. This energy is
formed between two homonuclear atoms, i.e. between
calculated by Born-Haber cycle.
atoms of exactly equal electronegativity, the electron
Born-Haber cycle includes pair is equally shared between them. e.g. H2 , Cl2 , F2, Br2
(i) vaporisation of reactants into gaseous state etc.
(ii) conversion of gaseous atoms into ions 2. Polar Covalent Bond If the bond forming entities are
(iii) combination of gaseous ions to form ionic lattice of dissimilar, i.e. heteronuclear or with different
molecules electronegativity, the bond formed has partial ionic
1 character as the electron pair is attracted by more
e.g. M (s) + X 2 (g) → M X (s), ∆H = Q
2 electronegative entity.
Here, ∆H = enthalpy change of the reaction δ+ δ− δ+ δ+ δ−
Q = heat of the reaction. H... O... H H... Cl
The above reaction includes the various steps: The greater the difference in electronegativity, higher is
the polar nature. The relative order of electronegativity
(a) M (s) → M ( g); ∆H1 = S (S = sublimation energy)
of some important elements is
(b) M (g)→ M (g )+ e ; ∆H2 = I (I = ionisation energy)
+ –
F > O > Cl ≈ N > Br > S ≈ C ≈ I > H
1 D
(c) X 2(g )→ X (g ); ∆H3 = (D = dissociation energy) 4.0 3.5 3.0 2.8 2.5 2.1
2 2
 In general,
Calculation of Percentage 1
Ionic Character Polarising power ∝ ∝ size of anion
size of cation
The ionic character in polar bond can be calculated by the
following methods: ∝ charge on ions
1. Pauling equation e.g. In between NaI and NaCl, NaI due to larger size of I−
ion has more covalent character. FeCl2 is less covalent
Percentage ionic character = 18 ( χ A − χ B ) 1. 4
than FeCl3 because polarising power of Fe2+ is less than
2. Hannay and Smith equation
Percentage ionic character = 16 ( χ A − χ B ) + 3. 5 ( χ A − χ B ) 2 that of Fe3+ ion having smaller size and higher oxidation
where, ( χ A − χ B ) = electronegativity difference. state.
● Cation with pseudo noble gas configuration has greater
Dipole Moment ( µ) polarising power than the other noble gas configuration
cation.
● It is defined as the product of the magnitude of charge ( q)
and distance (d) separating the centres of positive and Formal Charge
negative charges.
It is defined as the difference between the number of valence
● Its direction is from positive end to negative end, electrons of that atom in an isolated or free state and the
µ = q ×d number of electrons assigned in the Lewis structure.
● Its unit in CGS system is debye (D). Formal charge (FC) on an atom in a Lewis structure
● A molecule is said to be polar if the net dipole moment of Total number of  Total number of 
the molecule is not equal to zero. e.g. NF3 has lower = valence electrons  − non - bonding (lone pair)
   
dipole moment than NH3 because resulting vector is in the free atom  electrons 
towards the lone pair in NH3 but in NF3 it is opposite of
lone pair, which cancels the resultant moment. 1 Total number of 
−
2 bonding (shared) electrons 
→
→

→
→ N → → N
Bond Parameters
F
→

H F
→

H
The covalent bonds are characterised by the some parameters
H F
which are as follows:
Resultant dipole moment in Resultant dipole moment in 1. Bond Length In general the average distance between the
NH3 = 4.90 × 10−30 cm NF3 = 0.80 × 10−30 cm
centre of nuclei of the two bonded atoms in a molecule is
A comparison dipole moments of NH2 and NF3 known as bond length. It depends upon the size of atoms,
● Percentage ionic character of any molecule can be hybridisation, steric effect, resonance etc. Usually bond
calculated by dipole moment (µ). length of polar bond is smaller as compared to a
µ non-polar bond. Bond length increases as the size of
Percentage ionic character = observed × 100
µ ionic atom or orbital increases.
where, µ ionic = q × d [q = 4.8 × 10 −10 esu] 2. Bond Enthalpy It is the amount of energy required to
break one mole of bonds of a particular type between
two atoms in gaseous state.
Partial Ionic Character of Covalent Bond Bond enthalpy ∝ electronegativity
On the basis of electronegativity difference, partial ionic 1
character of covalent bond can be summarised as : ∝
size of atoms
(i) Electronegativity difference between combining atoms 1
∝
= 1. 7, then bond is 50% ionic and 50% covalent. number of lone pair of electrons
(ii) Electronegativity difference > 1.7, ionic character in
3. Bond Order Bond order is just like number O
bond is more than 50%.
of bond(s) between two atoms in a molecule.
(iii) Electronegativity difference < 1.7, ionic character is less C
1
than 50%. Bond order ∝ ∝ bond stability O O
–
bond length –
Fajan’s Rule Bond order ∝ bond strength (stronger the bond, larger
will be the bond dissociation energy and bond enthalpy)
● It states that the magnitude of covalent character in an
ionic bond depends upon the polarising power. Higher e.g. CO 2−
3 .

the polarising power, more will be the covalent character.

 Number of double bonds Because of orbital overlap the electron density between the
Bond order = 1 +
●

Number of delocalisation position nuclei increases which helps in bringing them closer.
 1  2 The overlapping of orbitals may results in two types of
For O3 , 1 +  = 1.5, SO2−
4 ,  1 +  = 1.5
 2  4 bonds given below :
4. Bond Angle It is defined as the angle between the 1. Sigma ( σ )-Bond It is the result of end to end overlapping
orbitals containing bonding electron pairs around the or axial overlapping between s-s, p -p, s-p orbitals. Single
central atom in a molecule or complex ion. bond is always σ-bond. The electron density accumulates
between the centre of the atoms being bonded.
O
σ-bond
H 104.5° H
+

Resonance s-orbital s-orbital

s-s overlapping
(axial)
There are certain molecules (benzene, ozone, nitric acid
and many more), whose all the properties cannot be σ-bond
explained by a single structure, then two or more +
structures, called resonating structures are required to
s-orbital p-orbital
s-p overlapping
explain all the properties and the actual structure is
(axial)
intermediate of these structures. e.g. CO2–
3 , O3 etc.
2. Pi ( π )-Bond It is formed by the incomplete overlapping of
O O O
orbitals or in other words sidewise or parallel overlapping
O O O O O O of p-p orbitals results in the π-bond formation.
● Resonance is shown by only those molecules which
possess conjugate single and multiple bonds.
+
● It imparts stability to the molecule and hence,
decreases its reactivity (due to resonance).
● Since, the electrons are not localised between any p-orbital p-orbital p-p overlapping
particular atoms and are uniformly distributed in the (sideways)
resonance hybrid, all the bonds are similar and are of
Double bond has one σ-bond and one π-bond. Triple bond
equal bond lengths. has two π-bonds and one σ-bond.
● Resonance averages the bond characteristic as a whole.
● The difference in the energy of a resonance hybrid and Concept of Hybridisation
most stable structure (with least energy) is called
resonance energy. Involving s, p and d-orbital
● Pauling introduced the concept of hybridisation. It is
Coordinate Bonding defined as intermixing of atomic orbitals of nearly the same
energy and resulting in the formation of new atomic
The bonding in which one atom furnishes a pair of
orbitals same in number and identical in all respects
electrons to the other atom, but shared by both the atoms in
(shape, energy and size).
such a manner that both atoms achieve stability, is called
coordinate bonding or dative bonding. e.g.
● sp, sp2 , sp3 hybridisations of atomic orbitals of Be, B, C, N
•• + and O are used to explain the formation and geometrical
H + + NH3 → NH4 shapes of molecules like BeCl2, BCl3, CH 4 , NH3 and H2 O.
Acceptor Donor
2
•• NOTE (i) The d-orbital taking part in dsp -hybridisation is d while
NH3 + BF3 → [H3 N → BF3 ] 3 3 2 x2 − y2
in sp d it is d 2 and in sp d , the two d-orbitals are d 2 and
z z
Donor Acceptor Complex d 2 2.
x − y
(ii) In dsp3 , if d 2 is used, the shape is trigonal bipyramidal. If in
Valence Bond Theory (VBT) z
dsp3 , d 2 2 is used, the shape is square pyramidal.
x − y
(Given by Heitler and London) ● In case of 3rd period elements, the energy of 3d-orbitals are
● It explains bond formation in terms of overlapping of comparable to the energy of 3s and 3 p-orbitals as well as
orbitals, e.g. the formation of H2 molecule from two to the energy of 4s and 4p orbitals.
hydrogen atoms involves the overlap of 1s-orbital of ● As a result of this, hybridisation involves either 3 s, 3 p and
the two H-atoms which are singly occupied. 3d or 3 d, 4s and 4p is possible.
Important hybridisation schemes involving s, p and d orbitals SF6 molecule is a symmetrical molecule and therefore
are as follows: is stable and less reactive.
Shape of Hybridisation F
Atomic orbitals Examples
molecules/ions type F F
Square planar dsp 2
d + s + p (2) [Ni(CN)4 ] 2 − , S
[Pt(Cl)4 ]2 −
F F
Trigonal sp3d s + p (3) + d PF5, PCl 5 F
bipyramidal
The formula for predicting hybridisation of central atom
Square sp3d 2 with s + p (3) + d (2) BrF5, IF5
and the number of hybrid orbitals ( X ) is given below :
pyramidal one lone pair 1
Octahedral sp3d 2 , d 2 sp3 s + p (3) + d (2) SF6, [CrF6]3 − , X = [V + M + A − C]
2
d (2) + s + p (3) [Co(NH3 ) 6]3 + where, V = Number of valence electrons of central atom
Some important examples are : M = Number of monovalent atoms attached
1. sp3 d-hybridisation e.g. PCl5 molecule. In PCl5 the two C = Cation and A = Anion
While determining the type of hybridisation on the
axial bonds are slightly elongated as the axial bond pairs
atom, π-bonds are never taken into account, but lone
suffer more repulsive interaction from equivalent bond
pairs are always considered.
pairs.
Hence, axial bonds found to be slightly longer and weaker
than equatorial bonds. Thus, PCl5 is more reactive. VSEPR Theory
Cl (Given by Gillespie and Nyholm)
Cl ● VSEPR stands for Valence Shell Electron Pair
Equatorial Repulsion. According to this theory, all valence shell
Cl P bonds electron pairs, surrounding, the central atom arrange
themselves in such a manner, so that they are as far
Cl away from each other as possible.
Cl Axial bonds
● There are two types of electron pairs around the central
2. sp3 d2 -hybridisation e.g. SF6 molecule. In SF6, four S—F atom; bonding electron pair (bp) and non-bonding
bonds are in same plane at right angles to one another and electron pairs (lp). The strength of repulsion between
are directed towards the corner of a square. The other two the electron pairs varies as:
F-atom lie at right angle above and below the plane of
lp – lp > lp – bp > bp – bp
F-atoms.

Hybrid orbitals and molecular shapes involving s, p and d-orbitals

Number of electron pairs Geometry Hybridisation Examples
2 bp Linear sp BeF2
3 bp Trigonal planar sp2 BF3
2bp + 1lp Bent sp2 SO2 ,O3
4 bp Tetrahedral sp3 CH 4
3bp+1 lp Pyramidal sp3 ••
NH3
2bp+2 lp Angular or V-shape sp3 ••
H2 O
••

5 bp Trigonal bipyramidal sp3d PF5, PCl 5

4bp + 1lp •
See-saw sp3d • SF4
••
•
3bp + 2lp T-shaped sp3d • ClF3

6bp Octahedral sp3d 2 SF6

5bp + 1 lp Square pyramidal sp3d 2 BrF5
•
4bp+2lp Square planar sp3d 2 • XeF4
3 3
7bp Pentagonal bipyramidal sp d IF7
 There are two types of H-bonds:
Molecular Orbital Theory
1. Intermolecular hydrogen bonding is a type of H-bond that
(Given by Hund and Mulliken) is formed between the different molecules of same
This theory is a method for determining molecular structure substance or different substance.
in which electrons are not assigned to individual bonds +δ −δ +δ −δ +δ −δ
between atoms, but are treated as moving under the e.g. H  F- - - H  F- - - H  F
influence of the nuclei in the whole molecule. Formation of
Intermolecular H-bonding decreases the volatility and
molecular orbitals involve linear combination of atomic
increases the boiling point, viscosity and surface tension
orbitals.
of a substance.
Molecular orbitals (MO) formed are of two types :
2. Intramolecular hydrogen bonding is a type of H-bond that
(i) Bonding MO which are of lower energy, are is formed within the same molecule. Intramolecular
represented as σ or π. These makes bond stronger. H-bonding increases the volatility, decreases the boiling
(ii) Antibonding MO which are of higher energy, are point of the compound and also decreases its solubility in
represented as σ
* or π
* . These reduces the stability of water.
molecules. O
The electronic configuration of molecular orbitals
N –
(MO) are written in the following manner: Oδ
(a) For species like O 2, F2 etc. +
O Hδ
σ 1 s, σ* 1 s, σ 2 s, σ* 2 s, σ 2 pz , (π 2 px = π 2 p y ),
Intramolecular H-bonding
(π* 2 px = π* 2 p y ), σ*2 pz in o-nitrophenol
(b) For species like Li2, Be2, B2 , C2 , N 2 etc. ● Boiling point of H2O is more than that of HF because
σ 1 s, σ* 1 s, σ2 s, σ* 2 s, (π 2 px = π 2 p y ), σ 2 pz , number of H-bonds formed by H2O is more than that by HF.
(π* 2 px = π* 2 p y ), σ
*
2 pz ● Hydrogen bonding is strongest when the bonded structure
is stabilised through resonance.
Bond Order (B.O.) for diatomic molecule or ions,
N − Na Effect of H-Bonding
B.O. = b
2 Various effects arise due to H-bonding in molecules are as
Nb = number of bonding electrons follows:
N a = number of antibonding electrons ● Due to polar nature of H2O, there is association of water
● The molecule is stable if Nb > Na , i. e. if bond order is molecules giving a liquid state of abnormally high boiling
positive. The molecule is unstable if Nb < N a or point.
Nb = Na , i. e. if the bond order is negative or zero. +δ –δ +δ −δ +δ –δ +δ –δ
● Magnetic behaviour of a molecule can also be conveyed
H —O- - - H —O - - - - - - H —O - - - H —O
from its electronic configuration. If any unpaired    
H +δ H +δ H+δ H +δ
electron is present in electronic configuration, the
molecule is paramagnetic and in case of paired Actually, in water, one water molecule is joined to four
electrons, molecule is diamagnetic. water molecules (two with H-atom and other two with
Magnetic moment = n(n + 2) BM O-atoms.)
(BM = Bohr Magneton) Thus, coordination number of water molecule in water is
where, n = number of unpaired electrons four.
● When ice is formed from liquid water, some air gap is
Hydrogen Bonding formed (in tetrahedral packing of water molecules). Due to
Hydrogen bond can be defined as the attractive force, which this, volume of ice is greater than liquid water and thus, ice
binds hydrogen atom of one molecule with the is lighter than water. In another words, we can say that
electronegative atom (F,O or N) of another molecule. Cl has when ice melts, density increases but only upto 4°C, after
same electronegativity as nitrogen but it does not form this intermolecular H-bonding between water molecules
strong H-bonds due to its large size. Strongest H-bond exist breaks, hence volume increases and hence, density
in KHF2 . decreases. Thus, water has maximum density at 4°C.
 In the gaseous state, several polymeric forms of HF
●

molecules exist in which the monomers are held

Metallic Bonding
together through H-bonding. A pentagonal arrangement The attractive force which hold together the constituent
of H—F molecules is shown below: particles in a metal is known as metallic bonding.
The two models which explain metallic bonding are :
δ– δ+
F—H δ – 101 pm
δ+ (i) According to electron sea model, metallic crystal
H 180° F + consists of positive kernels packed together as closely as
δ–
F 180° Hδ
H F– possible in a regular geometric pattern and immersed in a
δ+ F---H δ 150 pm
–
δ
sea of mobile electrons.
δ+
(ii) According to band model, atomic orbitals of atoms with
● Carboxylic acid dimerises in gaseous state due to same energy and same symmetry overlap to form energy
H-bonding. The dimerisation of carboxylic acids is given bands. The highest occupied energy band is valence band
below. and lowest unoccupied energy band is conduction band.
160 pm The gap between these two bands is called energy gap. In
100 pm insulators, energy gap is very large while in
– + H
H δ δ
O---H—O semiconductors it is very small. On increasing
H—C—C C—C—H temperature, electrical conductivity of semiconductors
O —H ---O– increases because some electrons move from valence
H δ + δ H band to conduction band.

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

1 Among the following, electron deficient molecule is 6 Which of the following pairs has zero dipole moment?
(a) CCl 4 (b) PCl 5 (a) CH2 Cl 2 and NF3 (b) SiF4 and BF3
(c) BF3 (d) SF6 (c) PCl 3 and ClF (d) BF3 and NF3
2 Sodium chloride is soluble in water but not in benzene 7 Bond distance in HF is 9.17 × 10 −11 m. Dipole moment of
because HF is 6.104 × 10 −30 cm. The per cent ionic character in HF
(a) ∆HHydration < ∆HLattice energy in water will be (electron charge = 1.60 × 10 −19 C )
∆HHydration > ∆HLattice energy in benzene ª JEE Main (Online) 2013
(b) ∆HHydration > ∆HLattice energy in water (a) 61.0% (b) 38.0%
∆HHydration < ∆HLattice energy in benzene (c) 35.5% (d) 41.6%
(c) ∆HHydration = ∆HLattice energy in water
8 Among the following the maximum covalent character is
∆HHydration < ∆HLattice energy in benzene
shown by the compound ª AIEEE 2011
(d) ∆HHydration < ∆HLattice energy in water
∆HHydration = ∆HLattice energy in benzene (a) FeCl 2 (b) SnCl 2 (c) AlCl 3 (d) MgCl 2

3 Which of the following compounds contain(s) no 9 The correct statement for the molecule,CsI3 is
covalent bond(s)? ª JEE Main 2018 (a) it is a covalent molecule ª JEE Main 2014
(b) it contains Cs + and I−3
KCl, PH3, O 2, B2H6, H2SO4
(c) It contains Cs 3+ and I− ions
(a) KCl, B 2H6 , PH3 (b) KCl, H2SO 4 (d) it contains Cs + ,I− and lattice I2 molecule
(c) KCl (d) KCl, B 2H6
10 Bond order normally gives idea of stability of a molecular
4 The % ionic character in Cs—Cl bond present in CsCl species. All the molecules viz. H 2 , Li 2 and B2 have the
molecule will be, if the electronegativity values for Cs same bond order yet they are not equally stable. Their
and Cl are 0.8 and 3.0 respectively stability order is ª JEE Main (Online) 2013
(a) 62.9% (b) 60% (a) H2 > B 2 > Li 2 (b) H2 >Li 2 > B 2
(c) 75% (d) 52.14% (c) Li 2 > B 2 > H2 (d) B 2 > H2 > Li 2
5 Which one of the following molecule is polar? 11 Which of the following compounds has the smallest bond
ª JEE Main (Online) 2013
angle in its molecule?
(a) XeF4 (b) IF5
(c) SbF5 (d) CF4 (a) H2O (b) H 2 S (c) NH 3 (d) SO 2
 12 Arrange the following molecules in the increasing order 21 In which of the following pairs the two species are not
of bond angle. isostructural? ª AIEEE 2012
−
H 2O H 2S H 2Se H 2 Te (a) CO 2−
3 and NO 3 (b) PCl +4 and SiCl 4
I II III IV (c) PF5 and BrF5 (d) AlF63− and SF6
(a) I < II < III < IV (b) IV < III < II < I
22 Total number of lone pair of electron in I−3 ion is
(c) I < III <II < IV (d) IV < II < III < I
(a) 3 (b) 6 (c) 9 (d) 2
13 Consider the following iodides,
23 In XeF2, XeF4 and XeF6, the number of lone pairs of Xe
PI3 102°, AsI3 100.2, SbI3  99° respectively are
The bond angle is maximum in PI3 which is (a) 2, 3, 1 (b) 1, 2, 3
(a) due to small size of phosphorus (c) 4, 1, 2 (d) 3, 2, 1
(b) due to more bp-bp repulsion in PI3
24 The structure of IF7 is ª AIEEE 2010
(c) due to less electronegativity of phosphorus
(d) None of the above (a) square pyramidal (b) trigonal bipyramidal
(c) octahedral (d) pentagonal bipyramidal
14 Bond energy of H—H, F—F and H—F bonds are 104, 38
and 135 kcal mol −1 respectively. The resonance energy 25 Which has trigonal bipyramidal shape?
in the H—F molecule will be ª JEE Main (Online) 2013
(a) 142 kcal mol −1
(b) 66 kcal mol −1 (a) XeOF4 (b) XeO 3
(c) XeO 3F2 (d) XeOF2
(c) 72.14 kcal mol −1 (d) 79.26 kcal mol −1
15 The species in which the N-atom is in a state of 26 The shape of IF6− is ª JEE Main (Online) 2013
sp- hybridisation is ª JEE Main 2016 (a) trigonally distorted octahedron
(b) pyramidal
(a) NO −2 (b) NO −3 (c) NO 2 (d) NO +2
(c) octahedral
16 The d-orbital involved in sp 3d -hybridisation is (d) square antiprism
(a) dxy (b) dzx (c) d (d) d
z2 x2 −y2 27 The molecular shapes of SF4 , CF4 and XeF4 are
17 The hybridisation of orbitals of N-atom in NO −3 , NO +2 and (a) different with 1, 0 and 2 lone pairs of electrons on the
NH +4 respectively are ª AIEEE 2011 central atoms, respectively
(a) sp, sp 2 , sp 3 (b) sp 2 , sp, sp 3 (b) different with 0, 1 and 2 lone pairs of electrons on the
(c) sp, sp 3 , sp 2 (d) sp 2 , sp 3 , sp central atoms, respectively
18 The states of hybridisation of boron and oxygen atoms in (c) the same with 1, 1 and 1 lone pairs of electrons on the
boric acid (H3BO3 ) are respectively central atoms, respectively
(d) the same with 2, 0 and 1 lone pairs of electrons on the
(a) sp 2 and sp 3
central atoms, respectively
(b) sp 2 and sp 3
(c) sp 3 and sp 2 28 The structure of which of the following chloro species can
(d) sp 3 and sp 3 be explained on the basis of dsp 2-hybridisation ?
19 Match the following and choose the correct option. ª JEE Main (Online) 2013
(a) PdCl 2−
4 (b) FeCl 2−
4
Column I Column II
(c) CoCl 2−
4 (d) NiCl 2−
4
A. SF4 1. sp3d 2
29 XeO 4 molecule is tetrahedral having
B. IF5 2. sp3 ª JEE Main (Online) 2013
C. NO+2 3. sp (a) two pπ − dπ bonds (b) one pπ − dπ bond
(c) four pπ − dπ bonds (d) three pπ − dπ bonds
D. NH+4 4. sp3d
30 Which of the following species is not paramagnetic?
Codes ª JEE Main 2017
A B C D A B C D (a) NO (b) CO (c) O 2 (d) B 2
(a) 4 1 3 2 (b) 1 3 2 4 31 Which of the following order of energies of molecular
(c) 3 2 4 1 (d) 3 1 2 4 orbitals of N2 is correct?
20 Isostructural species are those which have the same (a) σ 2s 2 < σ * 2s 2 < π2 p x2 ≈ π 2 py2 < σ2 pz2
shape and hybridisation. Among the given species (b) σ 2s 2 < σ * 2s 2 < σ 2 pz2 < π 2 px2 ≈ π 2 py2
identify the isostructural pairs. (c) σ * 2s 2 < σ 2s 2 < σ 2 pz2 < π 2 px2 < π 2 py2
−
(a) NF3 and BF3 (b) BF4 and NH+4 (d) σ 2s 2 < σ 2 pz2 < σ 2s 2 < π 2 px2 < π 2 py2
(c) BCl 3 and BrCl 3 (d) NH3 and NO 3−
32 Which one of the following molecules is/are expected to 39 Given,
exhibited diamagnetic behaviour? ª JEE Main 2013
Reaction Energy change (in kJ)
(a) N2 (b) O 2
(c) S2 (d) C 2 Li ( s ) → Li ( g ) 161
+
33 Which of the following statement(s) is/are correct? Li ( g ) → Li ( g ) 520
(a) In the formation of dioxygen from oxygen atoms 1 77
F2 ( g ) → F ( g )
10 molecular orbitals will be formed. 2
(b) All the molecular orbitals in the dioxygen will be
F ( g ) + e − → F − ( g ) (Electron gain enthalpy)
completely filled
(c) Total number of bonding molecular orbitals will not be Li ( g ) + F − ( g ) → LiF ( s ) −1047
same as total number of anti-bonding orbitals in
Li ( s ) +
1
F2 ( g ) → LiF ( s ) − 617
dioxygen
2
(d) Number of filled bonding orbitals will be same as
number of filled anti-bonding orbitals Based on data provided, the value of electron gain
enthalpy of fluorine would be ª JEE Main 2013
34 In accordance to molecular theory,
(a) −300 kJ mol −1 (b) − 350 kJ mol −1
(a) O+2 is diamagnetic and bond order is more than O 2
(b) O+2 is diamagnetic and bond order is less than O 2 (c) − 328 kJ mol −1 (d) −228 kJ mol −1
(c) O+2 is paramagnetic and bond order is more than O 2
Direction (Q. No 40-43) In the following question, a
(d) O+2 is paramagnetic and bond order is less than O 2
statement of Assertion (A) followed by a statement of Reason
35 The stability of the species Li 2 , Li −2 and Li+2 increases in the (R) is given. Choose the correct answer out of the following
order of ª JEE Main 2013 choices.
(a) Li 2− < Li+2 < Li 2 (a) Both A and R are true and R is the correct explanation
of A
(b) Li 2 < Li 2−< Li+2
(b) Both A and R are true but R is not the correct
(c) Li −2 < Li 2 < Li+2
explanation of A
(d) Li 2 < Li+2 < Li −2 (c) A is true but R is false
36 Which of the following pairs of molecules/ions are not (d) Both A and R are false
likely to exist? ª JEE Main 2013 40 Assertion (A) The bond angles in molecules depend
(a) H2+ , He 22 − upon electronegativity of central atom, number of lone
(b) H −2 , He 22 − pairs, odd electrons and multiplicity of bonds.
(c) H 2+
2 , He 2 Reason (R) NO 2 and NO −2 have angles 134° and 115°
(d) H−2 , He 22 + respectively.
37 Ortho-nitrophenol is less soluble in water than 41 Assertion (A) Among the two O—H bonds in H 2O molecule,
p-and m-nitrophenols because ª AIEEE 2012 the energy required to break the first O—H bond and the
(a) o -nitrophenol is more steam volatile than those of other O—H bonds is the same.
m- and p -isomers Reason (R) This is because the electronic environment
(b) o -nitrophenol shows intramolecular H-bonding around oxygen is the same even after breakage of one
(c) o -nitrophenol shows intermolecular H-bonding O—H bond.
(d)melting point of o -nitrophenol is lower than those of
42 Assertion (A) SF4 has a lone pair of electrons at
m- and p-isomers
equatorial position in preference to axial position in the
38 Consider the following compounds, overall trigonal bipyramidal geometry.
I. 1, 2-hydroxybenzene Reason (R) If lone pair of electrons is at equatorial
II. 1, 3-dihydroxybenzene position, repulsion will be minimum.
III. 1, 4-dihydroxybenzene
43 Assertion (A) p-dimethoxy benzene is a polar molecule.
IV. hydroxybenzene
Reason (R) The two methoxy groups at para position are
The increasing order of their boiling points is
located as
(a I < II < III < IV
(b) IV < I < II < III CH3
(c) IV < II < I < III
O O
(d) I < II < IV < III
CH3
52 40 DAYS ~ JEE Main CHEMISTRY DAY FOUR

DAY PRACTICE SESSION 2

PROGRESSIVE QUESTIONS EXERCISE

1 Which of the following statement(s) is/are true? 8 What will be the lattice enthalpy of CaCl2, if the enthalpy of
(a) HF is less polar than HBr (i) sublimation energy of Ca is 121 kJ mol−1
(b) Absolutely pure water does not contain any ions (ii) dissociation energy of Cl2 to Cl is 242.8 kJ mol−1
(c) Chemical bond formation takes place when forces of (iii) ionisation energy Ca to Ca 2+ is 2422 kJ mol−1
attraction overcome the forces of repulsion (iv) electron gain enthalpy for Cl to Cl – is −355 kJ mol−1
(d) In covalency, transference of electrons take place
(v) ∆f H overall is −795 kJ mol−1
2 Consider the Born-Haber cycle for the formation of ionic (a) −3225.8 kJ mol −1 (b) −980.8 kJ mol −1
compound given below and identify the compound (c) −2870.8 kJ mol −1 (d) −2628 kJ mol −1
formed.
9 Select the correct statement(s).
M (s)   ∆H1
→ M (g)   ∆H 2
→ M + (g) 
   ∆H 5 (a) Both lattice energy and hydration energy decrease with
→Z
 1 X (g)  ∆H 3 ∆H 4
→ X (g)   → X − (g) the increase in ionic size
 2 2
 (b) Lattice energy can be calculated using Born-Haber cycle
(a) M + X − (b) M + X − (s) (c) If the anion is larger than the cation, the lattice energy will
(c) MX (d) M + X − (g) remain almost constant within a particular group
3 What is the geometry of nitrogen atom in NH3, N(CH3 )3 (d) All of the above statements are correct
and N[Si(CH3 )3 ]3 molecules? 10 The bond dissociation energy of B—F in BF 3 is
I. Trigonal planar 646 kJ mol −1, whereas that of C—F in CF4 is
II. Trigonal pyramidal 515 kJ mol −1. The correct reason for higher B—F bond
III. Square planar dissociation energy as compared to that of C—F bond is
Choose the correct option. (a)smaller size of B-atom as compared to that of C-atom
(a) II, II and I (b) III, III and I (b) stronger σ bond between B and F in BF 3 as compared
(c) I, II and III (d) I, III and II to that between C and F is CF4
(c) significant pπ-pπ interaction between B and F in BF 3
4 O2 molecule is paramagnetic due to the presence of
whereas there is no possibility of such interaction
(a) two unpaired electrons in anti-bonding MO between C and F in CF4
(b) one unpaired electron in anti-bonding MO
(d) lower degree of pπ-pπ interaction betwen B and F in BF3
(c) two unpaired electrons in bonding MO
(d) one unpaired electron in bonding MO than that between C and F in CF4
5 The BCl3 is a planar molecule whereas NCl3 is pyramidal °
11 If HX bond length is 2A and H−X bond has dipole
because moment 512 −30
. × 10 cm, the percentage of ionic
(a) BCl bond is more polar than NCl bond characters in the molecule will be
(b) NCl bond is more covalent that BCl bond (a) 10% (b) 16%
(c) nitrogen atom is smaller than boron atom (c) 18% (d) 20%
(d) BCl 3 has no lone pair electrons but NCl 3 has
12 The geometrical shapes of XeF5+ , XeF6 and XeF82−
one lone pair of electrons
respectively are
6 H2O is dipolar whereas BeF2 is not. It is because (a) trigonal bipyramidal, octahedral and square planar
(a) the electronegativity of F is greater than that of O (b) square pyramidal, distorted octahedral and square
(b) H2O involves hydrogen bonding whereas BeF2 is angular antiprismatic
discrete molecule (c) planar pentagonal, octahedral and square antiprismatic
(c) H2O is linear and BeF2 is angular (d) square pyramidal, distorted octahedral and octahedral
(d) H2O is angular and BeF2 is linear
13 Suppose the observed value of dipole moment of H 2O
7 In terms of polar character, which one of the following molecule is 1.83 D. What will be the H—O—H bond
order is correct? angle in H 2O molecule? (Given bond moment of O—H
(a) NH3 < H2O < HF < H2 S bond is 1.5 D.)
(b) H2 S < NH3 < H2O < HF (a) 104° 20′′ (b) 105°
(c) H2O < NH3 < H2 S < HF (c) 105 ° 20′′ (d) 104°
(d) HF < H2O < NH3 < H2 S