Inter 1st Year Chemistry

COLLEGE CODE: CEVP
CHAITANYA ENGINEERING COLLEGE

MADHURAWADA, VISAKHAPATNAM
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INTERMEDIATE CEVP
C H A I T A N Y A N A G A R , K O M M A D I V I L L A G E , M A D H U R A W A D A , V S P , A P - 5 3 0 0 4 81
1 ATOMIC STRUCTURE 3 – 52
2 CLASSIFICATION OF ELEMENTS AND PERIODICITYN IN 53 – 95

PROPERTIES
3 CHEMICAL BONDING MOLECULAR STRUCTURE 96 -135
4 STATE OF MATTER : GASES AND LIQUIDS 136 – 182
5 STOICHIOMETRY 183 – 238
6 THERMODYNAMICS 239 – 284
7 CHEMICAL EQUILIBRIUM AND ACIDS BASES 285 – 376
8 HYDROGEN AND ITS COMPOUNDS 377 – 395
9 THE S – BLOCK ELEMNETS 396 – 425

10 THE P – BLOCK ELEMNETS 426 – 442
11 THE P – BLOCK ELEMENTS (GROUP – 14 ) 443 – 467
12 ENVIRONMENTAL CHEMISTRY 468 – 484
14 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND 485 - 552

TECHNIQUES
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Very Short Answer Questions
Question 1.
What is the charge, mass and charge to mass ratio of an electron ?
Answer:
Charge of an electron = – 1.602 × 10-19 coloumbs (or)
-4.8 × 10-19 esu
Mass of an electron = 9.1 × 10-28 gms
Charge to mass ratio of an electron (em) i.e., specific charge = 1.758 ×
1011 coloumbs/kg
Question 2.
Calculate the charge of one mole of electrons.
Answer:
One electron has charge – 1.602 × 10-19 coloumbs.
One mole of electrons has charge -6.023 × 1023 × 1.602 × 10-19
= 9.648846 × 104 = 96488.5 coloumbs.
Question 3.
Calculate the mass of one mole of electrons.
Answer:
Mass of electron = 9.1 × 10-31 kg (or) 9.1 × 10-28 gms.
One mole of electrons has mass 6.023 × 1023 × 9.1 × 10-31 = 54.8 × 10-8 = 5.48 × 10-7 kg.
Question 4.
Calculate the mass of one mole of protons. ”
Answer:
One proton has mass 1.672 × 10-27 kg
One mole protons has mass 6.023 × 1023 × 1.672 × 10-27
= 10.0704 × 10-4
= 1.00704 × 10-3 kg.
3
Question 5.
Calculate the mass of one mole of neutrons.
Answer:
One neutron has mass 1.675 × 10-27 kg
One mole neutrons has mass 6.023 × 1023 × 1.675 × 10-27
= 10.088 × 10-4
= 1.0088 × 10-3 kg.
Question 6.
How many neutrons and electrons are present in the nuclei
of 6C13, 8O16, 12Mg24, 26Fe56 and 38Sr88.
Answer:
Question 7.
What is a black body ?
Answer:
The body which is perfect absorber and emmiter of all type of radiations incident on it
is called a black body.
Question 8.
Which part of electromagnetic spectrum does Balmer series belong?
Answer:
Balmer series (n = 2) belongs to visible region of electromagnetic spectrum.
4
Question 9.
What is an atomic orbital?
Answer:
In an atom, the region around the nucleus where the probability of finding the electron
is maximum is known as atomic orbital.
From the value of magnitude of square of wave function (|ψ2|) this region can be
predicted.
Question 10.
When an electron is transferred in hydrogen atom from n = 4 orbit to n=5 orbit to
which spectral series does this belong?
Answer:
• By the absorption of energy electron jumps from n = 4 orbit to n = 5 orbit.
• The electron present in n = 5 orbit emitts energy and return to n = 4 orbit. Hence
the spectral lines series obtained in Brackett series (IR region)
Question 11.
How many “p” electrons are present in sulphur atom?
Answer:
Sulphur has electronic configuration – 1s2 2s2 2p6 3s2 3p4
∴ Sulphur has 10 ‘p’ electrons.
Question 12.
What are the values of principal quantum number (n) and azimuthal quantum number
(l) for a 3d electron?
Answer:
For a 3d – electron principal quantum number (n) = 3 and
Azimuthal quantum number (l) = 2.
5
Question 13.
What is the complete symbol for the atom with the given atomic number (Z) and
atomic mass (A)?
I) Z = 4, A = 9 ;
II) Z = 17, A = 35 ;
III) Z = 92, A = 233.
Answer:
I) Z = 4, A = 9 Complete symbol is 4Be9
II) Z = 17, A = 35 Complete symbol is 17Cl35
III) Z = 92, A = 233 complete symbol is 92U233.
Question 14.
Draw the shape of dz2 orbital.
Answer:
Question 15.
Draw the shape of dx 2
– y2 orbital.
Answer:
6
Question 16.
What is the frequency of radiation of wavelength 600nm?
Answer:
Formula:
v=cλ
= 3×1086×10−7
= 12×1015
= 0.5 × 1015 = 5 × 1014 sec-1
λ = 600 nm
= 600 × 10-9 m
= 6 × 10-7 m
C = 3 × 108 m/sec.
Question 17.
What is Zeeman effect?
Answer:
The splitting up of spectral lines in presence of strong external magnetic field is called
as Zeeman effect.
Question 18.
What is Stark effect?
Answer:
The splitting of spectral lines in presence of strong electric field is called as Stark effect.
Question 19.
To which element does the following electronic configuration correspond?
I) 1s22s2 2p63s23p1
II) 1s22s22p63s23p6
III) 1s22s22p5
IV) 1s22s22p2.
Answer:
I) 1s22s2 2p6 3s2 3p1 (Atomic no. (Z) = 13) – Aluminium.
II) 1 s22s22p63s23p6(Atomic no. (Z) = 18) – Argon.
III) 1s22s22p5 (Atomic no. (Z) = 9) – Fluorine.
IV) 1s22s22p2 (Atomic no. (Z) = 6) – Carbon.
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Question 20.
Electrons are emitted with zero velocity from a metal surface when it is exposed to
radiation of wavelength 4000 A. What is the threshold frequency (v0)?
Answer:
Formula:
hv = hv0 + 12mv2
hv = hv0 + 12m(0)2
hv = hv0
λ = 4000 A
= 4 × 103 × 10-10 = 4 × 10-7 m.
V=0
C = 3 × 108 m/sec.
⇒ v = v0
∴ v = Cλ = 3×1084×10−7 = 34 × 1015
= 0.75 × 1015
= 7.5 × 1014 sec-1
Question 21.
Explain Pauli’s exclusion principle.
Answer:
Pauli’s exclusion principle:
According to this principle
“No two electrons in an atom can have the same set of four quantum numbers”. This
can also be stated as “only two electrons may exist in the same orbital and these
electrons must have opposite spins”.
This means that the two electrons can have the same value of three quantum numbers
n, l and ml but have the opposite spin quantum number Ex : Consider ‘K’ shell of the
atom having two electrons
8
Question 22.
What is Aufbaus principle ?
Answer:
Aufbau’s principle:
This principle states
“In the ground state of the atoms, the orbitals are filled in order of their increasing
energies”. In other words electrons first occupy the lowest energy orbital available to
them and enter into higher energy orbitals only after the lower energy orbitals are
filled.
The order in which the orbitals are filled as follows :
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 4f < 5d < 6p < 7s
Question 23.
What is Hund’s rule ?
Answer:
Hund’s rule: This rule deals with the filling of electrons in degenerate orbitals. It states
“Pairing of electrons in the orbitals belonging to the same subshell (p, d or f) does not
take place until each orbital belonging to that subshell has got one electron each (i.e.,)
all the orbitals are singly occupied”.
Since there are three ’p’, five ‘d’ and seven ‘f’ orbitals, therefore the pairing of electrons
will start in the p, d and f orbitals with the entry of 4th, 6th and 8th electrons respectively.
Ex : ‘8O’ electronic configuration is
Question 24.
Explain Heisenberg’s uncertainty principle.
Answer:
Heisenberg uncertainty principle : “Simultaneous and exact determination of the
position and momentum of a sub-atomic particle, like electron moving with high speed
is impossible.”
If Δx and Δp represents the uncertainties in the position and momentum respectively.
9
Then according to Heisenberg
Δx. Δp ≥ h4π ——- (1)
The product of uncertainties in position (Δx) and momentum (Δp) of an electron cannot
be less than h4π. It can be equal or greater than h4π.
Since momentum = mass x velocity, the equation (1) can be written as
Δx × m (Δv) ≥ h4π = Δx × Δv ≥ h4πm
If the position is determined accurately Δx = 0 and Δv = ∝. That means the inaccuracy
in measuring the velocity is ∝. If velocity is determined accurately Δv = 0 and Δx = ∝.
Question 25.
What is the wavelength of an electron moving with a velocity of 2.0 × 107m/s ?
Answer:
Formulae:
λ = hmv
= 6.625×10−349.1×10−31×2×107
= 0.3640 × 10-34 × 10+24
= 0.3640 × 1010 m
= 0.3640 A
h = 6.625 × 10-34 J.Sec
m = 9.1 × 10-31 kg
V = 2.0 × 107 m/sec.
Question 26.
An atomic orbital has n = 2, what are the possible values of l and ml?
Answer:
For n = 2, l values are 0, 1
For l = 0 → ml = 0
For l = 1 → ml = -1, 0, +1.
Question 27.
Which of the following orbitals are possible? 2s, 1p, 3f, 2p.
Answer:
2s, 2p orbitals are possible among 2s, 1p, 3f, 2p and 1 p, 3f orbitals are not possible.
10
Question 28.
The static electric charge on the oil drop is – 3.2044 × 10-19 C. How many electrons are
present on it?
Answer:
Given static electric charge on oil drop = – 3.2044 × 10-19 C
Charge of electron = – 1.602 × 10-19 C.
Number of electrons present =
Question 29.
Arrange the following type of radiation in increasing order of frequency:
(a) X – rays
(b) visible radiation
(c) microwave radiation and
(d) radiation from radio waves.
Answer:
Increasing order of frequency of given radiations is
Radio waves < Micro waves < Visible radiation < X – rays.
Question 30.
How many electrons in an atom may have n = 4 and ms = +1/2 ?
Answer:
For n = 4 → l values are 0, 1, 2, 3
l = 0 → s contains 1 electron with ms = + 1/2
l = 1 → p contains 3 electron with ms = + 1/2
l = 2 → d contains 5 electron with ms = + 1/2
l = 3 → f contains 7 electron with ms = + 1/2
∴ Total no.of electrons with ms = +1/2 for n = 4
= 1 + 3 + 5 + 7 = 16.
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Question 31.
How many sub-shells are associated with n = 5 ?
Answer:
For n = 5
l values are 0, 1, 2, 3, 4
l = 0 → s – orbital
l = 1 → p — orbital
l = 2 → d – orbital
l = 3 → f – orbital
l = 4 → g — orbital
→ Five subshells are associated with n = 5.
Question 32.
Explain the particle nature of electromagnetic radiation.
Answer:
• According to earlier days concepts light was supposed to be made of particles.
This assumption was made by Newton in his corpuscular theory. He called the
particles as corpuscales.
• The particle nature of light explains the black body radiations and photo electric
effect satisfactorily.
• The particle nature of light could not satisfactorily explains the phenomenon of
diffraction and Interferance.
Question 33.
Explain the significance of Heisenberg’s Uncertainty principle.
Answer:
Significance of Uncertainty Principle:
1. This principle rules out the existence of definite paths or trajectories of electrons
and other similar particles.
2. This principle is significant only for motion of microscopic objects, and is
negligible for that of macroscopic objects.
3. In dealing with milligram size or heavier objects, the associated uncertainties are
hardly of any real consequence.
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Question 34.
What series of lines are observed in hydrogen spectra?
Answer:
The series of lines observed in hydrogen spectra are
Additional Answer Questions
Question 35.
How many newtrons and electrons are present in the nuclei
of 6C13, 8O16, 12Mg24, 26Fe56, 38Sr88
Answer:
13
Additional Problems
Question 36.
Calculate the wave no. and wave length of first line of lyman series.
Answer:
Question 37.
Calculate the wave no. of and wave length of first line of Balmer series.
Answer:
14
Short Answer Questions
Question 38.
What is the wavelength of light emitted when the electron in a hydrogen atom
undergoes transition from an energy level with n = 5 to an energy level with n = 3 ?
Answer:
Formulae:
R = 1,09,677 cm-1
n1 = 3
n2 = 5.
v¯ = 7799.25 cm-1
λ = 1v¯ = 17799.25 = 1.2821 × 10-4 cm
Question 39.
An atom of an element contains 29 electrons and 35 neutrons. Deduce
1. the number of protons and

2. the electronic configuration of the element.
Answer:
Given no.of electrons ’29’, ∴ Z = 29
1. So, no.of protons = 29
2. Electronic configuration of the element (Z = 29)
= 1s22s22p23s23p64s13d10 [anamalous electronic configuration]
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Question 40.
Explain giving reasons, which of the following sets of quantum numbers are not
possible.
a) n = 0, l = 0, ml = 0, ms = +12
b) n = 1, l = 0, ml = 0, ms = –12
c) n = 1, l = 1, ml = 0, ms = +12
d) n = 2, l = 1, ml = 0, ms = +12
e) n = 3, l = 3, ml = – 3, ms = +12
f) n = 3, l = 1, ml = 0, ms = +12
Answer:
Following set of quantum numbers are not possible.
a) n = 0, l = 0, ml = 0, ms = +12
Reason:
‘n’ is principal quantum number, whose values are from 1 to n. The value of ‘n’ never
equal to zero. But given n = 0.
c) n = 1, l = 1, ml = 0, ms = +12
Reason:
Values of ‘l’ are from 0 to (n – 1).
If n = 1 then the value of ‘l’ is zero not equal to ‘1’.
e) n = 3, l = 3, ml = – 3, ms = +12
Reason:
If n = 3, possible values of ‘l’ are 0, 1, 2, but not equal to ‘3’.
Question 41.
Show that the circumference of the Bohr orbit for the hydrogen atom is an integral
multiple of the de Broglie wavelength associated with the electron revolving around
the orbit.
Answer:
Consider the Bohr’s angular momentum equation.
mvr = nh2π
i.e The angular momentum of an electron is integral multiple of ‘h2π‘
mvr = nh2π
2πr = nhmv
According to de-Broglie’s wavelength λ = hmv
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2πr = n(hmv)
2πr = nλ.
Thus the circumference of the Bohr orbit is integral multiple of de-Broglie’s wave
length.
Question 42.
The longest wavelength doublet absorption transition is observed at 589.0 and 589.6
nm. Calculate the frequency of each transition and energy difference between two
excited states.
Answer:
Given largest wave length doublet absorption transition is observed at 589.0 and 589.6
nm.
∴ v1=cλ1
= 3×108589×10−9 = 0.005093 × 10+7
= 5.093 × 1014 sec-1
λ1 = 589 × 10-9 m
∴ v2=cλ2
= 3×108589.6×10−9
= 0.005088 × 1017
= 5.088 × 1014 sec-1
λ1 = 5.089 × 10-9 m
Energy difference between two states = h[v1 – hv2]
= h[v1 – v2]
= 6.625 × 10-34[5.093 × 10-14 – 5.088 × 1014]
= 6.625 × 10-34 × 0.005 × 1014
= 0.0331 × 10-20 J.
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Question 43.
What are the main features of quantum mechanical model of an atom?
Answer:
Important features of quantum mechanical model of atom:
1. The energy of electrons in an atom is quantized (it can only have certain specific
values).
2. The existence of quantized electronic energý levels is a direct result of the wave
like properties at electrons and are allowed solution at Schrodinger wave
equation.
3. All the information about the electron in an atom is contained in its orbital wave
function ‘Ψ’ and quantum mechanics makes it possible to extract this information
from “Ψ’.
4. The path of the electron can never be determined accurately. Therefore, we find
only the probability of the electron at different points in space, around an atom.
5. The probability of finding an electroñat a point within an atom is proportional to
the square of the orbital wave function i.e., |Ψ|2 at that point. |Ψ|2 is known as
probability density and is always positive. From the value of |Ψ|2 at different
points with in the atom, it is possible to predict the region around the nucleus
where electron will most probably be found.
Question 44.
What is a nodal plane? How many nodal planes are possible for 2p – and 3d – orbitals?
Answer:
The plane at which the probability of finding the electron is zero is called as nodal
plane.
• For 2p orbitaIs one nodal plane is possible for each ‘p’ orbital.
• For 3d orbitais two nodal planes are possible for each ‘d’ orbital.
Question 45.
The Lyman series occurs between 91.2 nm and 121.6 nm, the Balmer series occurs
between 364.7 nm and 656.5 nm and the Paschen series occurs between 820.6 nm and
1876 nm. Identify the spectral regions to which these wavelengths correspond?
Answer:
In electromagnetic spectrum,
a) 91.2 – 121.6 nm (Lyman senes) corresponds to u.v. region.
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b) 364.7 – 656.5 nm (Balmer series) corresponds to visible region.
c) 820.6 – 1876 nm (Paschen series) corresponds to I.R. region.
Question 46.
How are the quantum numbers n, l, ml, for hydrogen atom obtained?
Answer:
Electronic configuration of hydrogen is 1s1
For ns1
Principal quantum no. (n) = 1
Azimuthal quantum no. (l) = 0
Magnetic quantum no. (ml) = 0
and Spin quantum no. (ms) = + 1/2
Question 47.
A line in Lyman series of hydrogen atom has a wavelength of 1.03 × 10-7 m. What is the
initial energy level of the electron?
Answer:
Given λ= 1.03 × 10-7 m = 1.03 × 10-5 cm
n2 = 1 (for Lyman series)
We have, R = 109677 cm-1
⇒ n2 = 3 (i.e.,) original energy level of electron is 3.
Question 48.
If the position of the electron is measured within an accuracy of ±0.002 nm. Calculate
the uncertainty in the momentum of the electron.
Answer:
Formulae:
Δx × Δp = h4π
Δp = hΔx×4π
= 6.625×10−344×3.14×2×10−12
= 0.2637 × 10-22
= 2.637 × 10-23 J/m.
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Δx = 0.002 nm
= 2 × 10-3 × 109 m
= 2 × 10-12 m
h = 6.625 × 10-34 J.sec.
∴ Uncertainity in momentum of electron = 2.637 × 10-23 J/m.
Question 49.
If the velocity of the electron is 1.6 × 106 m/s-1. Calculate de Brogue wavelength
associated with this electron.
Answer:
Formulae:
λ = hmv
= 6.625×10−349.1×10−31×1.6×106
= 0.455 × 10-9 m
= 0.455 nm.
v = 1.6 × 106 m/sec
h = 6.625 × 10-34 J.sec
m = 9.1 × 10-31 Kg.
Question 50.
Explain the difference between emission and absorption spectra. (A.P. Mar. ‘15)
Answer:
Emission spectrum
1. It is produced by analysing the radiant energy emitted by an excited substance.
2. It consists of bright lines on dark back ground.
3. Produced due to the emission of energy by electrons.
4. Emission spectra contains bright ineson dark back ground.
Absorption spectrum
1. It is produced when white light is passed through a substance and the
transmitted light is analysed by a spectrograph.
2. It consists of dark lines on bright background.
3. Produced due to the adsorption of energy by electrons.
4. Absorption spectra contains dark lines on bright back ground.
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Question 51.
The quantum numbers of electrons are given below. Arrange them in order of
increasing energies.
a) n = 4, l = 2, ml = -2, ms = +12
b) n = 3, l = 2, ml = -1, ms = –12
c) n = 4, l = 1, ml = 0, ms = +12
d) n = 3, l = 1, ml = -1, ms = –12
Answer:
a) n = 4, l = 2, → 4d
b) n = 3, l = 2, → 3d
c) n = 4, l = 1, → 4p
d) n = 3, l = 1, → 3p
∴ 3p < 3d < 4p < 4d
According (n + l) values
Hence d < b < c < a is order of increasing energy.
Question 52.
The work function for Cesium atom is 1.9 eV. Calculate the threshold frequency of the
radiation. If the Cesium element is irradiated with a wavelength of 500 nm, calculate
the kinetic energy of the ejected photoelectron?
Answer:
Case-I
Photo electric effect equation is
hv = hv0 + 1/2 mv2
w = hv0
Case-II
Photo electric effect equation is
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E = hcλ
= 6.625×10−34×3×1085×10−7
= 19.878×10−265×10−7
= 3.9756 × 10-19 J.
Given work function hv0 = 1.9 ev
= 1.9 × 1.602 × 10-19J.
Kinetic Energy (KE) = 12mv2
From Photo electric effect
12mv2 = hv – hv0
K.E. = 3.9756 × 10-19 × 1.602 × 10-19
= 3.9756 × 10-19 – 3.0438 × 10-19 = 0.9318 × 10-19 = 9.318 × 10-20J.
Question 53.
Calculate the wavelength for the emission transition if it starts from the orbit having
radius 1.3225 nm and ends at 211.6 pm. Name the series to which this transition
belongs and the region of the spectrum.
Answer:
Given the radius of orbit from which it started = 1.35225 × 10-9 m = 1 3.225Å
In general radius of orbit = 0.529 × n2Å
n2 = 13.2250.529 = 25
n2 = 25 ⇒ n = 5
Given that the
Radius of orbit at which the transition ended = 211.6 pm
= 211.6 × 10-12m
= 2.116A
Similarly as above
n2 = 2.1160.529 = 4
n2 = 4 ⇒ n = 2
∴ transition takes place from n = 5 to n = 2 level
∴ spectral lines are obtained in Balmer series (visible region)
22
Question 54.
Explain the difference between orbit and orbital.
Answer:
Orbit
1. A circular path which is present around the nucleus in which electrons revolve is
called as orbit.
2. Orbits are circular and are non directional paths.
3. The maximum no.of electrons in any orbit is given by the formula 2n2 (n = orbit
number).
Orbital
1. The 3 – dimension space where the probability of finding the electron is maximum
around the nucleus is called as orbital.
2. These have definite shape and these are directional except’s orbital.
3. Each orbital can occupy a maximum of two electrons.
Question 55.
Explain photoelectric effect.
Answer:
The ejection of electrons from a metal surface, when the radiations of suitable
frequency strikes the metal surface is called photoelectric effect.
Explanation using Einstein’s quantum theory:
1) To explain photoelectric effect, Einstein utilised Quantum theory.
2) When a photon strikes metal surface, it uses some part of its energy to eject the
electron from the metal atom. The remaining part of the total energy is given to the
ejected electrons in the form of kinetic energy.
Hence we can write hv = W + KE ⇒ hv = hv0 + 12mev2
where hv = energy of photon,
v0 = Threshold frequency,
me = mass of electron
W = energy required to overcome the attractive forces on the electron in the metal
(work function)
KE = kinetic energy of ejected electron,
V = Velocity of ejected electron.
3) If a photon of sufficient energy struck the metal surface and could eject the electron.
But if a photon has insufficient energy, it cannot eject the electron from the metal.
23
eg. : A photon of violet light [high frequency] can eject the electrons from the surface
of potassium but a photon of red light [low frequency] cannot eject the electrons.
Question 56.
Explain Rutherford’s nuclear model of an atom. What are its drawbacks?
Answer:
Rutherford’s Planetary model: Rutherford drew some conclusions regarding the
structure of atom.
1. Most of the space in the atom is empty (as most of the α – particles passed through
the foil undeflected).
2. A few — positive charges were deflected. The deflection must be due to enormous
repulsive force showing that the positive charge of the atom is not spread
throughout the atom as Thomson predicted. The positive charge is concentrated in
a very small volume. Which is responsible for the deflection of α — particles.
On the basis of the above observations. Rutherford proposed the nuclear model.
According to his model.
1. The positive charge in the atom is concentrated in the small dense portion, called
the NUCLEUS.
2. The nucleus is surrounded by the electrons that move around it in circular paths
called the ORBITS. Thus Rutherford’s model resembles the solar system.
3. Electrons and the nucleus are held together by electrostatic forces of attraction.
Drawbacks of Rutherford model:
1. Rutherford’s atomic model of an atom is like a small scale solar system. This similarity
suggests that electrons should move around the nucleus in well defined orbits.
However, when a body is moving, it undergoes acceleration. According to
electromagnetic theory, charged particles, when accelerated, should emit radiation.
Therefore, an electron in an orbit will emit radiation, thus the orbit will continue to
shrink. But this does not happen. Thus Rutherford’s model cannot explain the stability
of the atom.
2. If we assume that electrons as stationary around the nucleus, the electrostatic
attraction between the nucleus and the electrons would pull the electrons towards the
nucleus to form a miniature version of Thomson’s model.
3. Rutherford model does not explain the electronic structure of the atom i.e., how the
electrons are distributed around the nucleus and what are the energies of these
electrons.
24
Before studying further developments that lead to the formulation of various atomic
models, it is necessary to study about light and its nature.
Question 57.
Explain briefly the Planck’s quantum theory.
Answer:
The postulates. of Planck’s quantum theory are
a) The emission of radiation is due to vibrations of charged particles (electrons) in the
body.
b) The emission is not continuous but in discrete packets of energy called quanta. This
emitted radiation propagates in the form of waves.
c) The energy (E) associated with each quantum for a particular radiation of frequency
V is given by E = hv, Here ‘h’ is Planck’s constant.
d) A body can emit or absorb either one quantum (hv) of energy or some whole
number multiple of it. Thus energy can be emitted or absorbed as hv, 2hv, 3hv etc., but
not fractional values. This is called quantisation of energy.
e) The emitted radiant energy is propagated in the form of waves.
f) Values of Planck’s constant in various units:
h = 6.6256 × 10-27 erg.sec (or) g cm2s-1
= 6.6256 × 10-34J.s (or) kg m2s-1 = 1.58 × 10-34 cal.s.
Success of Planck’s quantum theory: This theory successfully explains the black body
radiations. A black body is a perfect absorber and also a perfect radiator of radiations.
Question 58.
What are the postulates of Bohr’s model of hydrogen atom? Discuss the importance of
this model to explain various series of line spectra In hydrogen atom. Answer:
Niels Bohr quantitatively gave the general features of hydrogen atom structure and it’s
spectrum. His theory is used to evaluate several points in the atomic structure and
spectra.
The postulates of Bohr atomic model for hydrogen as follows
Postulates : –
• The electron in the hydrogen atom can revolve around the nucleus in a circular
path of fixed radius and energy. These paths are called orbits (or) stationary
states. These circular orbits are concentric (having same center) around the
nucleus.
25
• The energy of an electron in the orbit does not change with time.
• When an electron moves from lower stationary state to higher stationary state
absorption of energy takes place.
• When an electron moves from higher stationary state to lower stationary state
emission of energy takes place.
• When an electronic transition takes place between two stationary states that
differ in energy by ΔE is given by
ΔE = E2 – E1 = hv
∴ The frequency of radiation absorbed (or) emitted v = E2−E1h E1 and E2 are
energies of lower, higher energy states respectively.
• The angular momentum of an electron is given by mvr = nh2π
An electron revolve only in the orbits for which it’s angular momentum is integral
multiple of h2π
Line spectra of hydrogen, Bohr’s Theory:
• In case of hydrogen atom line spectrum is observed and this can be explained by
using Bohr’s Theory.
• According to Bohr’s postulate when an electronic transition takes place between
two stationary states that differ in energy is given by
• In case of absorption spectrum nf > ni → energy is absorbed (+ve) energy is

absorbed (+Ve)
26
• In case of emission spectrum ni > nf → energy is emitted (- Ve)
• Each spectral line in absorption (or) emission spectrum associated to the
particular transition in hydrogen atom
• In case of large no.of hydrogen atoms large no.of transitions possible they rsults
in large no.of spectral lines.
The series of lines observed in hydrogen spectra are
27
Question 59.
Explain the success of Bohr’s theory for hydrogen atom.
Answer:
Succes of Bohrs Theory for hydrogen atom:
• Bohr’s theory gave the information about the principal quantum number.
Principal quantum number represents the stationary states. (n = 1, 2, 3 integral
numbers)
• Bohr’s theory gave the information about the radius of the stationary states (or)
orbits.
r = 0.529 × n2 A (or)
r = 52.9 × n2 pm
[r=n2h24π2me2] (for hydrogenation)
• This theory gave the information about the energy of the electron of particular
stationary state.
En = -RH [1n2]n = 1, 2, 3,……
RH = Ryd berg constant
= 1,09,677 cm-1.
• This theory explained the line spectra of hydrogenation.
• This theory can also be applicable to the ions containing only one electron. Eg. :
He+, Li+2, Be+3….
• This theory can also gave information about velocity of electrons moving in the
orbits.
Question 60.
What are the consequences that lead to the development of quantum mechanical
model of an atom?
Answer:
Consequences that lead to development of quantum mechanical model of an atom are
as follows.
• Clàssical mechanics successfully explained the motion of macro scopic objects.
Eg: Falling stone, Planets etc.,.
• Classical mechanics failed to explain the motion of microscopic objects like
electrons, atoms, molecules etc.
• Classical mechanics ignores the concept of dual behaviour of matter and
especially for sub atomic particles
Quantum mechanics:
28
The Branch of science deals with the dual behaviour of matter is called quantum
mechanics.
• This deals with the motions of microscopic objects like electron.
values).
2. The existence of quantized electronic energy levels is a direct result of the wave
like properties at electrons and are allowed solution at schrodinger wave
equations.
function ‘Ψ′ and quantum mechanics makes it possible to extract this information
from ‘Ψ′.
5. The probability of finding an electron at a point within an atom is proportional to
the square of the orbital wave function i.e., |Ψ|2 at that point. |Ψ|2 is known as
probability density and is always positive. From the value of |Ψ|2 at different
points with in the atom, it is possible to
predict the region around the nucleus where electron will most probably be
found.
Question 61.
Explain the salient features of quantum mechanical model of an atom.
Answer:
values).
2. The existence of quantized electronic energy levels is a direct result of the wave
like properties at electrons and are allowed solution at schrodinger wave
equations.
function ‘Ψ′′ and quantum mechanics makes it possible to extract this
information from Ψ′′.
29
5. The probability of finding an electron at a point within an atom is proportional to
the square of the
orbital wave function i.e., |Ψ|2 at that point. |Ψ|2 is known as probability density
and is always positive. From the value of |Ψ|2 at different points with in the atom,
it is possible to predict the region around the nucleus where electron will most
probably be found.
Question 62.
What are the limitations of Bohr’s model of an atom?
Answer:
Limitations:
1. Spectra of multielectron atoms: Bohr’s theory could explain the spectra of
Hydrogen and single electron species like He+, Li2+, Be3+, but it fails to explain the
spectra of multielectron atoms.
2. Fine structure: It fails to explain this fine structure of Hydrogen atom.
3. Splitting up of spectral lines : The theory fails to explain Zeeman effect and Stark
effect.
The splitting up of spectral lines when an atom is subjected to strong magnetic
field is called Zeeman effect.
The splitting up of spectral lines when an atom is subjected to strong electric field
is called Stark effect.
4. Flat model: Bohr’s theory gives a flat model of the orbits. Bohr’s theory predicts
definite orbits for electrons considering them as particles. But according to de
Brogue electron has both wave nature and particle nature. Bohr’s theory cannot
explain this dual role.
5. It fails to support the uncertainty principle proposed by Heisenberg.
6. It could not explain the ability of atoms to form molecules by chemical bonds.
Question 63.
What are the evidences in favour of dual behaviour of electron?
Answer:
• The particle nature of light explains the phenomenon of blackbody radiations and
photo electric effect but it could not explain about wave nature of light.
• Wave nature of light explains the phenomenon of interference and diffraction.
• So, light has dual nature i.e it behaves as a wave (or) as a stream of particles.
30
• According to de-Broglie, light has dual behaviour i.e both particle and wave
nature.
de-Broglies gave the following relationship
λ = hmv = hp
λ = wave length
P = momentum
• Heisen bergs uncertainty principle also a consequence of dual behaviour of
matter and radiation.
Statement :— It is impossible to determine simultaneously, the exact momentum
and exact position of a small particle like lectron.
Δx × Δp ≥ h4π
Δx = uncertainty in position
Δp = uncertainty in momentum
Question 64.
How are the quantum numbers n, l and ml, arrived at? Explain the significance of these
quantum numbers. (A.P. Mar. ‘16)(T.S. Mar. ‘15, ‘14)
Answer:
• In general a large no.of orbitals are possible in an atom.
• These orbitaIs are distinguished by their size, shape and orientation.
• An orbital of smaller size means there is more chance to find electron near the
nucleus.
• Atomic orbitals are precisely distinguished by quantum numbers. Each orbital is
designated by three major quantum numbers.
1) Principal quantum number (n)
2) Azimuthal quantum number (l)
3) Magnetic quantum number (m)
1) Principal quantum number : The principal quantum number was introduced by Neils
Bohr. It reveals the size of the atom (main energy levels). With increase in the value of
‘n’ the distance between the nucleus and the orbit also increases.
It is denoted by the letter ‘n’. It can have any simple integer value 1, 2, 3, ……. but not
zero. These are also termed as K, L, M, N etc.
The radius and energy of an orbit can be determined basing on ”n” value.
The radius of nth orbit is rn = n2h24π2me2
The energy of nth orbet is En = −2π2me4n2h2
31
2) Azimuthal quantum number: It was proposed by Sommerfeld. it is also known as
angular momentum quantum number or subsidiary quantum number.
it indicates the shapes of orbitals. It is denoted by ‘l’. The values of ‘l’ depend on the
values of ‘n’, ‘l’ has values ranging from ‘0 to (n – 1) i.e.. l = 0, 1, 2,….. (n – 1). The
maximum number of electrons present in the subshells s, p, d, f are 2, 6, 10, 14
respectively.
3) Magnetic quantum number: It was proposed by Lande. It shows the orientation of

the orbitals in space. ‘p’ — orbital has three orientations. The orbital oriented along the
x-axis is called px orbital, along the y-axis is called py -orbital and along the z-axis is
32
called pz orbital. In a similar way d – orbital has five orientations. They are dxy, dyz, dzx,
dx – y and dz . It is denoted by ‘m’. Its values depends on azimuthal quantum number,
2 2 2
‘m’ can have all the integral values from -l to +l including zero. The total number of ‘m’
Question 65.
Explain the dual behaviour of matter. Discuss its significance to microscopic particles
like electrons.
Answer:
• The particle nature of light explains the phenomenon of blackbody radiations and
photo electric effect but it couldnot explain about wave nature of light.
• Wave nature of light explains the phenomenon of interference and diffraction.
• So, light has dual nature i.e it behaves as a wave (or) as a stream of particles.
• According to de-Broglie light has dual behaviour i.e both particle and wave
nature.
de-Broglies gave the following relationship
λ = hmv = hp
λ = wavelength
P = momentum
• Heisen bergs uncertainty principle also a consequence of dual behaviour of
matter and radiation.
Statement :— It is impossible to determine simultaneously, the exact momentum
and exact position of a small particle like electron.
Δx × Δp ≥ h4π = uncertainty in position
Δx = uncertainty in position
Δp = uncertainty in momentum
Significance of Uncertainty Principle:
33
1. This principle rules out the existence of definite paths or trajectories of electrons
and other similar
particles.
2. This principle is significant only for motion of microscopic objects and is
negligible for that of macroscopic objects.
3. In dealing with milligram size or heavier objects, the associated uncertainties are
hardly of any real consequence.
Question 66.
What are various ranges of electromagnetic radiation ? Explain the characteristics of
electromagnetic radiation.
(or)
Explain diagrammatically the boundary surfaces for three 2p orbitais and five 3d
Answer:
Electromagnetic radiation : When electrically charged particle is accelerated alternating
electric and magnetic fields are produced and transmitted. These fields are transmitted
in the form of waves called electromagnetic waves or electromagnetic radiation.
Important Characteristics of a wave:
1) These are produced by oscillating charged particles in a body.
2) These radiations can pass through vacuum also. So medium for transmission is not
required.
3) Velocity (c) : It is defined as the linear distance travelled by the wave in one second.
Units : cm sec-1 (or) m see-1
All kinds of electromagnetic waves have the same velocity.
(3 × 108 m sec-1 or 3 × 1010 cm sec-1)
4) Wavelength (λ) : It is defined as the distance between any two successive crests or
troughs of wavez.
Units:A ; m ; cm ; nm or pm 1 A° = 10-10 m
1 nm = 10-9 m = 10-7 cm
1 pm = 10-12m.
5) Frequency (v): It is defined as the number of waves passing through a point in one
34
second.
Units: Hertz (Hz); cycles sec-1 or sec-1.
v = cλ
6) Wave number (v¯): It is defined as the number of waves present in one unit length. It
is equal
to the reciprocal of the wavelength.
v¯=1λ=vc
Relation between wavelength and frequency :
c = v × λ ⇒ v = cλ
7) Amplitude (A) is the height of the crest (or) depth of through of a wave, It
determines intensity (or) brightness of the wave.
Question 67.
Define atomic orbital. Explain the shapes of s, p and d orbitals with the help of
diagrams.
Answer:
Atomic orbital : A three dimensional space around the nucleus in an atom. Where the
probability of finding an electron is maximum (i.e.,) Ψ2 is maximum is called an atomic
orbital.
Shapes of orbitals:
a) s – orbital : Boundary surface diagram for ‘s’ orbital is spherical in shape, ‘s – orbitals
are spherically symmetric (i.e.,) the probability of finding the electron at a given
35
distance is equal in all directions.
b) p – orbitals : p – orbital consists of two sections called lobes that are either side of
the plane that passes through the nucleus. The size, shape and energy of the three
orbitals are identical. They differ only in the orientation. These are mutually
perpendicular to each other and oriented along x, y and z axes. Each p-orbital is of
dumb-bell shape.
36
Question 68.
Illustrate the reasons for the stability of completely filled and half filled subshells.
Answer:
Chromium and Copper shows anamalous electronic configurations
Cr – [Ar] 4s1 3d5
Cu – [Ar] 41 3d10
• Cr — gets half filled 3d— shell electronic configuration.
• Cu — gets full filled 3d— shell electronic configuration.
• Half filled and full filled subshells are more stable than others.
Causes of Stability of Completely filled and Half filled Sub-shells
The completely filled and half filled sub-shells are stable due to the following
reasons :
1. Symmetrical distribution of electrons : It is well known that symmetry leads to
stability. The completely filled or half filled subshells have symmetrical distribution of
electrons in them and are therefore more stable. Electrons in the same subshell (here
3d) have equal energy but different spatial distribution, Consequently, their shielding of
one another is relatively small and the electrons are more strongly attracted by the
nucleus.
2. Exchange Energy: The stabilizing effect arises whenever two or more electrons with
the same spin are present in the degenerate orbitals of a subshell. These electrons tend
to exchange their positions and the energy released due to this exchange is called
exchange energy. The number of exchanges that can take place is maximum when the
subshell is either half filled or completely filled.
As a result the exchange energy is maximum and so is the stability.
37
The extra stability of half-filled and completely filled subshell is due to:
1. relatively small shielding,
2. smaller coulombic repulsion energy and
3. larger exchange energy.
Question 69.
Explain emission and absorption spectra. Discuss the general description of line spectra
in hydrogen atom.
Answer:
Emission spectrum:
1. It is produced by analysing the radiant energy emitted by an excited substance.
2. It consists of bright lines on dark background.
3. Produced due to the emission of energy by electrons.
4. Emission spectra contains bright lines on dark background.
Absorption spectrum:
1. It is produced when white light is passed through a substance and the
transmitted light is analysed by a spectrograph.
2. It consists of dark lines on bright background.
3. Produced due to the adsorption of energy by electrons.
4. Absorption spectra contains dark lines on bright background.
Line spectra of Hydrogen — Bohrs Theory:
• In case of hydrogen atom line spectrum is observed and this can be explained
by using Bohr’s Theory.
• According to Bohrs postulate when an electronic transition takes place
between two stationary states that differ in energy is given by
38
ΔE = Ef – Ei
Ef = final orbit energy
Ei = initial orbit energy
In terms of wave numbers
39
• In case of absorption spectrum nf > ni → energy is absorbed (+ Ve)
• In case of emission spectrum ni > nf → energy is emitted (- Ve)
• Each spectral line in absorption (or) emission spectrum associated to the
particular transition in hydrogen atom
• In case of large no.of hydrogen atoms large no.of transitions possible they results
in large no.of spectral lines.
The Spectral Lines for Atomic Hydrogen
Solved Problems
Question 1.
Calculate the num Notons, neutrons and electrons species?
Solution:
In this case, 8035Br, Z = 35, 80, species is neutral
Number of protons = number of electrons = Z = 35
Number of neutrons = 80 – 35 = 45, Mass number (A) = number of protons (Z) +
number of neutrons (n).
Question 2.
The number of electrons, protons and neutrons in a species are equal to 18, 16 and 16
respectively. Assign the proper symbol to the species.
Solution:
The atomic number is equal to number of protons =16. The element is sulphur (S).
Atomic mass number = number of protons + number of neutrons = 16 + 16 = 32
Species is not neutral as the number of protons is not equal to electrons. It is anion
(negatively charged) with charge equal to excess electrons = 18 – 16 = 2.
Symbol is 3216 s2−
Note: Before using the notation find out whether the speclés is a neutral atom,
40
acation or an anion, If it is a neutral atom, Atomic number (Z) = number of protons in
the nucleus of an atom = number of electrons in a neutral atom is valid, i.e., number of
protons = number of electrons = atomic number. If the species is an ion, determine
whether the number of protons are larger (cation, positive ion) or smaller (anion,
negative ion) than the number of electrons. Number of neutrons is always given by A-
Z, whether the species is neutral or ion.
Question 3.
The Vividh Bharati station of All India Radio, Delhi, broadcasts on a frequency of 1,368
kHz (kilo hertz). Calculate the wavelength of the electro-magnetic radiation emitted by
transmitter. Which part of the electromagnetic specturm does it belong to?
Solution:
The wavelength, λ, is equal to c/v. where c is the speed of electromagnetic radiation in
vacuum and v is the frequency. Substituting the given values, we have
Question 4.
The wavelength range of the visible spectrum extends from violet (400 nm) to red (750
nm). Express these wave
lengths in frequencies (Hz). (1 nm = 10-9 m).
Solution:
Using c = v λ frequency of violet light.
V = cv=3.00×108 ms−1400×10−9 m
= 7.50 × 1014 Hz
Frequency of red light
v = cv=3.00×108 ms−1750×10−9 m = 4.00 × 1014 Hz
The range of visible spectrum is from
4.0 × 1014 to 7.5 × 1014Hz in terms of frequency units.
41
Question 5.
Calculate
(a) wave number and
(b) frequency of yellow radiation having wavelength 5000 A.
Solution:
(a) Calculation of wavenumber (v¯)
λ = 5800 A = 5800 × 10-8 cm
= 5800 × 10-10m
(v¯) = 1λ=15800×10−10 m
= 1.724 × 106m-1
= 1.724 × 104 cm-1
Question 6.
Calculate energy of one mole of photons of radiation whose frequency is 5 × 1014 Hz.
Solution:
Energy (E) of one photon is given by the expression
E = hv .
h = 6.626 × 10-34 J s
v = 5 × 1014 s-1 (given)
E = (6.626 × 10-34J s) × (5 × 1014 s-1)
= 3.313 × 10-19 J
Energy of one mole of photons
= (3.313 × 10-19J) × (6.022 × 1023 mol-1)
= 199.51 kJ mol-1.
Question 7.
A 100 watt bulb emits monochromatic light of wavelength 400 nm. Calculate the
number of photons emitted per second by the bulb.
Solution:
Power of the bulb = 100 watt
= 100 J s-1
Energy of one photon E = hv = hc/λ.
= 6.626×10−34Js×3×108 m s−1400×10−19 m
= 4.969 × 10-19J
42
Number of photons emitted
100 J s−14.969×10−19 J = 2.012 × 1020 s-1
Question 8.
When electromagnetic radiation of wavelength 300 nm falls on the surface of sodium,
electrons are emitted with a kinetic energy of 1.68 × 105 J mol-1. What is the minimum
energy needed to remove an electron from sodium? What is the maximum wavelength
that will cause a photoelectron to be emitted?
Solution:
The energy (E) of a 300 nm photon is given by
hv = hc/λ.
= 6.626×10−34Js×3.0×108 m s−1300×10−9 m
= 6.626 × 10-19 J
The energy of one mole of photons
= 6.626 × 10-19 J × 6.022 × 1023 mol-1
= 3.99 × 105 mol-1
The minimum energy needed to remove one mole of electrons from sodium
= (3.99 – 1.68) 105 J mol-1
= 2.31 × 105 J mol-1
The minimum energy for one electron
= 2.31×105 J mol−16.022×1023 elelctrons mol−1
= 3.84 × 10-19J
This corresponds to the wavelength
∴ λ = hcE
= 6.626×10−34 J s×3.0×108 m s−13.84×10−9 J
= 517 nm
(This corresponds to green light)
Question 9.
The threshold frequency v0 for a metal is 7.0 × 1014 s-1. Calculate the kinetic energy of an
electron emitted when radiation of frequency v = 1.0 × 1015 s-1 hits the metal.
Solution:
According to Einstein’s equation
Kinetic energy = 1/2 mev2 = h(v – v0)
= (6.626 × 10-34 J s)
(1.0 × 1015 s-1 – 7.0 × 1014 s-1)
43
= (6.626 × 10-34 J s)
(10.0 × 1014s-1 – 7.0 × 1014s-1)
= (6.626 × 10-34 J s)
(3.0 × 1014s-1) = 1.988 × 10-19 J
Question 10.
What are the frequency and wave-length of a photon emitted during a transition from
n = 5 state to the n = 2 state in the hydrogen atom?
Solution:
Since n1 = 5 and nf = 2, this transition gives rise to a spectral line in the visible region of
the Balmer series. From ΔE = RH(1n2i−1n2f)
= 2.18 × 10-18J(1n2i−1n2f)
ΔE = 2.18 × 10-18J(152−122)
= -4.58 × 10-19 J.
It is an emission energy.
The frequency of the photon (taking energy in terms of magnitude) is given by
Question 11.
Calculate the energy associated with the first orbit of He+. What is the radius this orbit?
Solution:
44
The radius of the orbit is given by
Question 12.
What will be the wavelength of a ball of mass 0.1 kg moving with a velocity of 10 m s-1?
Solution:
According to de Brogue λ = hmV=hp
λ = hmv = (6.626×10−34Js)(0.1 kg)(10 m s−1)
= 6.626 × 10-34m (J = kg m2 s-2)
Question 13.
The mass of an electron is 9.1 × 10-31 kg. If its K.E. is 3.0 × 10-25 J, calculate its
wavelength.
Solution:
45
Question 14.
Calculate the mass of a photon with wavelength 3.6 A.
Solution:
λ = 3.6 A = 36 × 10-10 m
Velocity of photon = velocity of light
m = hλv=6.626×10−34Js(3.6×10−10 m)(3×108 m s−1)
= 6.135 × 10-29kg
Question 15.
A microscope using suitable photons is employed to locate an electron in an atom
within a distance of 0.1 A. What
is the uncertainty involved in the measurement of its velocity?
Solution:
∆x ∆p = h4π or ∆x m∆v = h4π
∆v = h4πΔxm
∆v = 6.626×10−34Js4×3.14×0.1×10−10 m×9.1×1031kc
= 0.579 × 107 m s-1 (1 J = 1 kg m2 s-2)
= 5.79 × 106 ms-1
Question 16.
A golf ball has a mass of 40g and a speed of 45 m/s. If the speed can be measured
within accuracy of 2%, calculate the uncertainty in the position.
Solution:
The uncertainty in the speed is 2%, i.e.,
4 × 2100 = 0.9 ms-1
Using the λ = hmv=hp
Δx = h4πmΔv
= 6.626×10−34Js4×3.14×40 g×10−3 kg g−1(0.9 ms−1)
= 1.46 × 10-33 m
This is nearly ∼ 1018 times smaller than the diameter of a typical atomic nucleus. As
mentioned earlier for large particles, the uncertainty principle sets no meaningful limit
to the precision of measurements.
46
Question 17.
What is the total number of orbitals associated with the principal quantum number n =
3?
Solution:
For n = 3, the possible values of 1 are 0, 1 and 2. Thus there is one 3s orbital (n = 3, l =
0 and ml = 0); there are three 3p orbitals
(n = 3, 1 = 1 and ml = -1, 0, +1); there are five 3d orbitais (n = 3, l = 2 and ml = -2, -1, 0,
+1, +2).
Therefore, the total number of orbitals is 1 + 3 + 5 = 9
The same value can also be obtained by using the relation; number of orbitals = n2,
i.e. 32 = 9
Question 18.
Using s, p, d, f notations, describe the orbital with the following quantum numbers
(a) n = 2, l = 1,
(b) n = 4, l = 0,
(c) n = 5, l = 3,
(d) n = 3, l = 2
Solution:
Question 19.
Calculate its wave length of 1st line in Balmer series of hydrogen spectrum.
Solution:
Ryd berg’s equation v¯ = 1λ = RH[1n21−1n22]
For the 1st line of Balmer series
n1 = 2, n2 = 3
R = 1,09,677 cm-1
v¯ = 1λ = 1,09,677[122−132]
= 1,09,677 × 536
Wave no. (v¯) = 15232.9 cm-1
Wave length λ = 1v¯ = 115232.9 = 6.5 × 10-5 cm-1
47
Question 20.
Calculate the shortest wave length in lyman series of hydrogen spectrum (RH = 1,09,677
cm-1).
Solution: To calculate shortest wave length
Question 21.
What is the maximum no.of emission lines when the excited electron of a ‘H’ atom in n
=6 drops to ground state.
Solution:
The no. of spectral lines found when an electron return from nth orbit to ground state.
= n(n−1)2 = 6(6−1))2 = 302 = 15
Question 22.
Calculate the longest wavelength transition in the paschen series of He+.
Solution:
48
Question 23.
The no. of waves in the forth Bohr’s orbit of hydrogen is
a) 3
b) 4
c) 9
d) 12
Solution:
Question 24.
It the speed of the electron in 1st Bohr’s orbit of hydrogen is x, then the speed of the
electron in the 3rd orbit of hydrogen is
Solution:
Given
Velocity of electron in 1st Bohr’s orbit of hydrogen = x
Velocity of electron in 3rd Bohr’s orbit of hydrogen = xn = x3
Question 25.
The ratio of radii of the fifth orbits of He+ and Li+2 will be
a) 2 : 3
b) 3 : 2
c) 4 : 1
d) 5 : 3
Solution:
Z2(li)=3
Z1 (He) = 2
r1r2 = Z2Z1 = 32 = 3 : 2
49
Question 26.
What is the lowest value of ‘n’ that allows ‘g’ orbitals to exist ?
Solution:
The lowest value of ‘n that allows ‘g’ orbitals to exist is ‘5’.
Question 27.
What is the orbital angular momentum of a d-electron
Solution:
Orbital angular momentum =√l(l+1)h2π
For a d electron l = 2
= 2(2+1) √h2λ
= 6h√2λ
Question 28.
What is the total spin and magnetic moment of an atom with atomic number 7’?
Solution:
Z = 7 (Nitrogen)
Electronic configuration is 1s2 2s2 2p3 (in ground state)
Question 29.
The quantum number of electrons are given below. Arrange in order of increasing
energies.
50
Solution:
a) 4d
b) 3d
c) 4p
d) 3d
e) 3p
f) 4p
∴ Increasing order of energy
e<b=d<c=f<a
Question 30.
If the value of n + l = 7 then what should be the increasing order of energy of the
possible subshells.
Solution:
Given
n+l=7
∴ The increasing order of energy

4f < 5d < 6p < 7s
(According Aufbau principle)
Question 31.
Which of the following sets of quantum number is not permitted?
a) n = 3, l = 3, m = +1, s = +12
b) n = 3, l = 3, m = +2, s = –12
c) n = 3, l = 1, m = +2, s = –12
d) n = 3, l = 0, m = 0, s = +12
Solution:
Only d is permitted i.e., 3s1
In a, b n = l but n always > l
in c m = + 2 is not permitted
Because l = 1,’m’ has -1, 0, +1 values only.
51
Question 32.
Ground state electronic configuration of nitrogenators can be represented as
Solution:
(a) and (d) are correct representations.
Question 33.
Which of the following is possible
a) 3f
b) 4d
c) 2d
d) 3p
Solution:
4d and 3p are possible.
52
Question 1.
What is the difference in the approach between the Mendeleev’s periodic law and the
modern periodic law ?
Answer:
• According to Mendeleev the physical and chemical properties of elements are
periodic functions of their atomic weights.
• According to modem periodic law the physical and chemical properties of
elements are periodic functions of their atomic numbers.
Question 2.
In terms of period and group, where would you locate the element with Z = 114 ?
Answer:
Element Z = 114 is present in 7th period and IVA group (Group – 14)
Question 3.
Write the atomic number of the element, present in the third period and seven¬teenth
group of the periodic table.
Answer:
The Element present in 3rd period and Group – 17 (VIIA group) is chlorine (Cl). It’s
atomic number is 17.
Question 4.
Which element do you think would have been named by
a) Lawrence Berkeley Laboratory .
b) Seaborg’s group
Answer:
a) Lawrence Berekeley Laboratory – Lanthanide
b) Seaborg’s group – Actinide (Transuranic element).
53
Question 5.
Why do elements in the same group have similar physical and chemical properties ?
Answer:
Elements in the same group have same no. of valency shell electrons and have similar
outer elec¬tronic configuration so these have similar physical and chemical properties.
Question 6.
What are representative elements ? Give their valence shell configuration.
Answer:
• Representative elements are s and p-block elements except zero group.
• These have general electronic configuration ns1-2np1-5.
Question 7.
Justify the position of f-block elements in the periodic table.
Answer:
The two series of elements lanthanides and actinides have been grouped separately
and placed at the bottom of the periodic table, though they belong to the sixth and
seventh periods of third group (III B).
The justification for assigning one place to these elements has been given on the basis
of their similar properties. The properties are so similar that elements from Ce to Lu can
be considered as equivalent to one element. In case these elements are assigned
different positions (i.e.,) arranged in order of their increasing atomic numbers, the
symmetry of the whole arrangement would be disrupted. The same explanation can be
given in the case of actinides.
Question 8.
An element ‘X’ has atomic number 34. Give its position in the periodic table.
Answer:
The element X with atomic no (z) = 34 has electronic configuration
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p4. Hence the element is present in 4,h period and 16th
group (VIA group).
Question 9.
What factors impart characteristic properties to the transition elements ?
Answer:
Transition elements exhibits characteristic properties because
54
• The differentiating electron enters into penultimate d-subshell
• These elements have small size.
• These possess high effective nuclear charge.
Question 10.
Give the outer shells configuration of d-block and f-block elements.
Answer:
• The outer shell electronic configuration of d-block – elements is ns1-2 (n-1)d1-10
• The outer shell electronic configuration of f-block – elements is ns2(n-1)d0 (or) 1 (n –
2) f1-14
Question 11.
State and give one example for Dobereiner’s law of triads and Newland’s law of
octaves.
Answer:
1) Dobereiner law :
• According to Dobereiner in a traid (3 – elements) the atomic weight of the middle
element is the arithmatic mean of the other two elements.
2) Newland’s law of octaves : According to Newlands, the elements arranged in the

increasing order of atomic weights noticed that every eight element had properties
similar to the first element. This relationship was just like every eight note that
resembles the first in octaves of music.
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Question 12.
Name the anomalous pairs of elements in the Mendaleev’s periodic table.
Answer:
In Mendeleev’s periodic table anamalous pairs are the elements whose atomic weights
increasing order is reversed.
Eg:
Question 13.
How does atomic radius vary in a period and in a group ? How do you explain the
variation ?
Answer:
In a period : Atomic radius decreases generally from left to right in a period.
Reason : In periods electrons are entered into same subshells.
In a group : Atomic radius increases generally from top to bottom in a group.
Reason : In groups electrons are entered into new subshells.
Question 14.
Among N-3; O-2, F–, Na+, Mg+2 and Al+3
a. What is common in them ?
b. Arrange them in the increasing ionic radii.
Answer:
Given ions are
N-3, O-2, F–, Na+, Mg+2 and Al+3.
a) The above ions have same number of electrons (All have 10 electrons). So these are
called iso electronic species.
b) The increasing order of ionic radii among above ions is
Al+3 < Mg+2 < Na+ < F– < O-2 < N-3
Reason : – In case of iso electronic species as the nuclear charge increases ionic radii
decreases.
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Question 15.
What is the significance of the term isolated gaseous atom while defining the
ionization enthalpy.
Hint: Requirement for comparison.
Answer:
• Isolated gaseous atom’s ionisation enthalpy is taken as reference value and it is
required to compare this values to various ions of this elements and to compare
this values with various elements.
Question 16.
Energy of an electron in the ground state of the hydrogen atom is – 2.18 × 10-18J.
Calculate the ionization enthalpy of atomic hydrogen in terms of J mol-1.
Answer:
Given that the energy of the electron in the ground state for hydrogen atom = – 2.18 ×
10-18 J.
For 1 mole of atoms is given by – 2.18 × 10-18 J × 6.023 × 1023
= -13.13 × 105 J/Mole
∴ Ionisation enthalpy of hydrogen atom = 13.13 × 105 J/Mole.
Question 17.
Ionization enthalpy, (IE1) of O is less than that of N — explain.
Answer:
• Oxygen has electronic configuration 1s2 2s2 2p4
• Nitrogen has electronic configuration 1s2 2s2 2p3
• Nitrogen has half filled shell and is stable so more amount of energy is required
to remove an electron, than in oxygen.
Hence IE, of ‘O’ is less than that of ‘N’.
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Question 18.
Which in each pair of elements has a more negative electron gain enthalpy?
a. O or Fb. F or Cl
Answer:
a)
has more negative electron gain enthalpy than that of
b)
has more negative electron gain enthalpy than that of
Question 19.
What are the major differences between metals and non-metals ?
Answer:
Metals
• These are generally in solid form (Except Hg)
• These are good conductors of heat and electricity.
• These have high m.pts and b.pts.
• Generally these are electropositive.
• These forms more ionic compounds.
Nón metals
• These may be solids (or) gases (or) liquids.
• These are not good conductors of heat and electricity.
• These have low m.pts and b.pts.
• Generally these are electronegative.
• These forms more covalent compounds.
58
Question 20.
Use the periodic table to identify elements.
a. With 5 electrons in the outer subshell
b. Would tend to lose two electrons
c. Would tend to gain two electrons.
Answer:
a) The elements possessing 5 electrons in the outer most shell are group 15 (VA)
elements.
• General outer electronic configuration is ns2 np3 Eg. : N, P, As………
b) The elements tend to lose two electrons are Group — II elements.
• General outer electronic configuration is ns2 Eg: Mg, Ca, Sr etc.
c) The elements tend to gain two electrons are Group – VIA elements (16th group).
• General outer electronic configuration is ns2 np4 Eg : O, S, Se ………
Question 21.
Give the outer electronic configuration of s, p, d and f – block elements.
Answer:
Question 22.
Write the increasing order of the metallic character among the elements B, Al, Mg and
K.
Answer:
Given elements are B, Al, Mg and K
The increasing order of metallic character is
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Question 23.
Write the correct increasing order of non – metallic character for B, C, N, F and Si.
Answer:
Given elements are B, C, N. F and Si
The increasing order of non- metallic character is
Question 24.
Write the correct increasing order of chemical reactivity in terms of oxidizing property
for N, O, Fand Cl.
Answer:
The correct increasing order of chemical reactivity in terms of oxidizing property for N,
O, F and Cl is F > 0 > Cl > N.
Question 25.
What is electronegativity ? How is this useful in understanding the nature of elements?
Answer:
Electronegativity : The tendency of an element (or) atom to attract the shared pair of
electrons towards itself in a molecule is called electronegativity.
• On the basis of electronegativity values nature of elements can be predicted.
Higher electro-negativity values indicates that element is non metal and lower
values indicates that the element is a metal.
• On the basis of electronegativity values bond nature also predicted
(Ionic/covalent).
Question 26.
What is screening effect? How is it related to lE?
Answer:
The decrease of nuclear attraction on outer most shell electrons due to presence of
inner energy electrons is called screening effect.
• As the screening effect increases LE. values decreases.
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Question 27.
How are electronegativity and metallic & non-metallic characters related?
Answer:
• Greater the electronegativity values of an element indicates that non metallic nature
and low metallic nature of that element.
• Lower the electronegativity value of an element indicates that low non metallic
nature and high metallic nature of that element.
Electronegativity ∝ Non metallic nature
Electronegativity ∝ 1 Metallic Nature
Question 28.
What is the valency possible to Arsenic with respect to oxygen and hydrogen?
Answer:
• The valency of Arsenic with respect to hydrogen is ‘3’
Eg : AsH3
• The valency of Arsenic with respect to oxygen is ‘5’
Eg : As2O5
Question 29.
What is an amphoteric oxide? Give the formula of an amphoteric oxide formed by an
element of group – 13.
Answer:
The oxide which contains both acidic as well s basic nature is called amphoteric oxide.
• The oxides reacts with both acids and bases and forms salts.
Eq : Al2O3 is one of the amphoteric oxide formed by the Group — 13 element
Aluminium.
Question 30.
Name the most electronegative element. Is it also having the highest electron gain
enthalpy? Why or Why not?
Answer:
The most electronegative element is fluorine (F).
•It doesnot have high electron gain énthalpy.
Reasons : —
• Due to small size
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• Due to high inter electronic repulsions.
• Chlorine has high electron gain enthalpý.
Question 31.
What is diagonal relation? Give one pair of elements, that have this relation.
Answer:
On moving diagonally across the periodic table the elements show certain similarities.
An element of group in 2nd period has similar properties with second element of the
next higher group in the 3rd period. This type of resemblance is called diagonal
relationship. e.g. : (Li, Mg); (Be, Al); (B, Si)
Question 32.
How does the nature of oxides vary in the third period?
Answer:
In 3rd period from left to right the oxide nature varies from high basic nature to high
acidic nature.
• Basic nature gradually decreases and acidic nature gradually increases.
Question 33.
Radii of iron atom and its ions follow Fe > Fe2+ > Fe3+ – explain.
Answer:
When the positive charge on the ion increases, the effective nuclear charge on the
outer electrons increases.
Hence the ionic size decreases in the order Fe > F2+ > F3+.
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Question 34.
IE2 > IE1 for a given element — why?
Answer:
IE2 > IE1 for a given element
Reason : —
• IE1 means minimum amount of energy required to remove an electron from
isolated neutral
gaseous atom.
• IE2 means minimum amount of energy required to remove an electron from uni
positive ion.
• In case of unipositive ion nuclear attraction increases on outer most electrons
than in isolated gaseous atom. So more amount of energy needed to remove an
electron from unipositive ion.
Hence IE2 > → IE1.
Question 35.
What is Ianthanide contraction? Give one of its consequences.
Answer:
Lanthanide contraction : Slow decrease in size of the atoms or ions among the
lanthanides is known as lanthanide contraction.
Consequences due to lanthanide contraction:
1. Due to lanthanide contraction, the crystall structure and other properties of the
elements become very closely similar.
2. Due to this, it becomes difficult to separate lanthanides from a mixture.
Question 36.
What is the atomic number of the element, having maximum number of unpaired 2p
electrons ? To which group does it belong ?
Answer:
• The atomic number of the element having maximum no.of unpaired 2p electrons is
7′ (Z = 7)
• Element is nitrogen.
• Electronic configuration is 1s2 2s2 2p3 (3 unpaired 2p electrons)
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Question 37.
Sodium is strongly metallic, while chlorine is strongly non-metallic – explain.
Answer:
Sodium is an alkali metal and it is present in group – I and it has the ability to lose the
valency electron readily.
• It has high electropositive nature. So it has metallic nature.
• Chlorine is a halogen and it is placed in Group – 17 and it has the ability to gain
the electron readily.
• It has high electronegative nature. So it has non metallic nature.
Question 38.
Why are zero group elements called noble gases or inert gases ?
Answer:
• Zero group elements has general outer electronic configuration ns 2 np6 (except for
He).
• These contains stable octet configuration. So these are stable and chemically inert.
Hence these are called inert gases.
• These elements neither lose nor gain electrons. Hence these are called ‘noble
gases’.
Question 39.
Select in each pair, the one having lower ionization energy and explain the reason,
a. I and I–
b. Br and K
c. Li and Li+
d. Ba and Sr
e. O and S
f. Be and B
g. N and O
Answer:
a) I– has lower ionisation energy than I because of increase of size I⊖ ion than ‘I’.
b) K has lower ionisation energy than ‘Br’ because of low electronegative value of K
(0.8) than ‘Br’ (2.8).
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c) ‘Li” has lower ionisation energy than Li+ because of large size of ‘Li’ than Li+.
d) ‘S’ has lower ionisation energy than ‘O’ because of large size of ‘S’ than ‘O’.
e) ‘B’ has lower ionisation energy than ‘Be’ because ‘Be’ has completely filled electronic
configuration (1s2 2s2).
f) ‘O’ has lower ionisation energy than ‘N’ because ‘N’ has half filled electronic
configuration (1s2 2s2 2p3).
Question 40.
IE1 of O < IE1 of N but IE2 of O > IE2 of N – Explain.
Answer:
• ‘N’ has half filled electronic configuration (1s2 2s2 2p3)
So IE1 of O < IE1 of ‘N’.
• O+ ion has half filled electronic configuration (1s2 2s2 2p3)
So IE2 of O > IE1 of N.
Question 41.
Na+ has higher value of ionization energy than Ne, though both have same electronic
configuration – Explain.
Answer:
Na+ has higher value of I.E. than Ne, though both have same electronic configuration.
Reason : –
• Both have electronic configuration 1s2 2s2 2p6
• In case of Na+ ion effective nuclear charge increases and size decreases than in
‘Ne’.
Question 42.
Which in each pair of elements has a more electronegative gain enthalpy ? Explain.
a. N or O
b. F or Cl
Answer:
a) Oxygen has high electronegative gain enthalpy than Nitrogen because ‘N’ has stable
half filled electron configuration.
b) Chlorine (- 349 KJ /mole) has high electronegative gain enthalpy than Fluorine (- 328
KJ/mole) because ‘F’ has small size and more inter electronic repulsions.
65
Question 43.
Electron affinity of chlorine is more than that of fluorine – explain.
Answer:
Chlorine (- 349 KJ / mole) has high electronegative gain enthalpy than Fluorine (- 328
KJ/mole) because ‘F’ has small size and more inter electronic repulsions.
Question 44.
Which in each has higher electron affinity ?
a. F or Cl–
b. O or O-
c. Na+ or F
d. F or F–
Answer:
a) Fluorine has high electron affinity than Cl– ion because of inert gas configuration of
Cl– ion.
b) Oxygen has high electron affinity than O– because O– has positive of 2nd electron
affinity.
c) F has high electron affinity than Na+ because Na+ has inert gas configuration.
d) F has high electron affinity than F– because F– has inert gas configuration.
Question 45.
Arrange the following in order of increasing ionic radius :
a. Cl–, P-3, S-2, F–
b. Al+3, Mg+2, Na+, O-2, F–
c. Na+, Mg+2, K+
Answer:
a) The increasing order of ionic radius is F– < Cl– < S-2 < P-3
b) The increasing order of ionic radius is Al+3 < Mg+2 < Na+ < F– < O-2
c) The increasing order of ionic radius is Mg+2 < Na+ < K+
Question 46.
Mg+2 is smaller than O-2 in size, though both have same electronic configuration –
explain.
Answer:
Mg+2 and O-2 ions are iso electronic species.In case of iso electronic species nuclear
charge increases size of ion decreases. So Mg+2 has small size than O-2.
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Question 47.
Among the elements B, Al, C and Si
a. Which has the highest first ionization enthalpy ?
b. Which has the most negative electron gain enthalpy ?
c. Which has the largest atomic radius ?
d. Which has the most metallic character ?
Answer:
a) Highest I.E. is possessed by the element carbon
b) Most negative gain enthalpy is for carbon (- 122 KJ/mole)
c) Large atomic radius is for Al (1.43 A)
d) Most metallic nature having element is ‘Al’.
Question 48.
Consider the elements N, P, O and S and arrange them in order of ;
a. Increasing first ionization enthalpy
b. Increasing negative electron gain enthalpy
c. Increasing non-metallic character
Answer:
a) Increasing first Ionisation energy order is S < P < O < N.
b) Increasing negative electron gain enthalpy order is N < P < O < S. .
c) Increasing non metallic nature order is P < N < S < O.
Question 49.
Arrange in given order :
a. Increasing EA :O, S and Se
b. Increasing IE1 : Na, K and Rb
c. Increasing radius : I–, I+ and I
d. Increasing electronegativity : F, Cl, Br, I
e. Increasing EA : F, Cl, Br, I
f. Increasing radius : Fe, Fe+2, Fe+3
Answer:
a) Increasing order of electron affinity is O < Se < S.
b) Increasing order of IE1 is Rb < K < Na.
c) Increasing order of radius is I+ < I < I–
d) Increasing order of electronegativity is I < Br < F < Cl
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e) Increasing order of electron affinity is I < Br < F < Cl
f) Increasing order of radius is Fe+3 < Fe+2 < Fe
Question 50.
a. Name the element with highest ionization enthalpy
b. Name the family with highest value of ionization enthalpy.
c. Which element possesses highest electron affinity ?
d. Name unknown elements at the time of Mendeleef
e. Name any two typical elements.
Answer:
a) Highest I.E1 possessing element is ‘Helium’.
b) The family that possess highest values of I.E is Noble gases (or) inert gases.
c) Highest electron affinity element is ‘Chlorine’.
d) Unknown elements at the time of mendeleef are Germanium (Eka silicon). Scandium
(Eka Alu-minium), Gallium (Eka Boron).
e) 3rd period elements are called typical elements
Eg : Al, Si, P, Na, Mg etc
Question 51.
a. Name any two bridge elements.
b. Name two pairs showing diagonal relationship.
c. Name two transition elements.
d. Name two rare earths.
e. Name two transuranic elements.
Answer:
a) Bridge elements 2nd period elements are called Bridge elements Eg : Be, B.
b) i) ‘Li’ diagonally relates with ‘Mg’,
ii) ‘Be diagonally relates with ‘Al’.
c) Scandium, Titanium, Vanadium, Chromium, etc., are examples of transition elements.
d) Lanthanides are called rare earths
Eg : Cerium (Ce), Prasodimium (Pr), Promethium (Pm).
e) Neptunium (Np), Californium (Cf), Fermium (Fm) are examples of transuranic
elements.
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Question 52.
On the basis of quantum numbers, justify that the 6th period of the periodic table
should have 32 elements.
Answer:
6th period contains the subshells 6s, 4f, 5d, 6p
6s can accomodate two electrons (2 elements)
4f can accomodate 14 electrons (14 elements)
5d can accomodate 10 electrons (10 elements)
6p can accomodate 6 electrons (6 elements)
Total no.of electrons can accomodation 6th period are 2 + 14 + 10 + 6 = 32
∴ 6th period of periodic table contains 32 elements.
Question 53.
How did Moseley’s work on atomic numbers show that atomic number is a
fundamental property better than atomic weight ?
Answer:
Mosley’s equation is
where v = frequency, Z = atomic number a, b = constants

A plot of √v against ‘Z’ gives a straight line.
However, no such relationship was obtained when the plot was drawn between
frequency and the atomic mass. The atomic number of the elements, according to
Mosley, stands for serial numbers of the elements in the periodic table. As the atomic
number of the elements increase, the wavelengths of characteristic X – rays decrease.
Mosley concluded that there is a fundamental quantity in an atom which increases in
regular steps with increasing atomic number. The correlation between X – ray spectra
and atomic number indicated that an element is characterized by its atomic number
and not by atomic mass.
69
Question 54.
State modern periodic law. How many groups and periods are present in the long form
of the periodic table ?
Answer:
Modern periodic law : – The physical and chemical properties of elements are periodic
functions of their atomic numbers.
• In modern periodic table 7 periods and 18 groups are present.
Question 55.
Why f-block elements are placed below the main table ?
Answer:
In Lanthanides 4f – orbitals and in Actinides 5f – orbitals are filled. Since these elements
have the same electronic configuration in the ultimate and penultimate shells they have
similar properties. Hence they were placed at the bottom of the periodic table though
they belongs to the sixth and seventh periods of IIIB groups.
Question 56.
Mention the number of elements present in each of the periods in the long form
periodic table.
Answer:
Question 57.
Give the outer orbit general electronic configuration of
a. Noble gases
b. Representative elements
c. Transition elements
d. Inner transition elements
Answer:
Type of elements – General electronic configurations
a) Noble gases – ns2 np6 (except ‘He’ which has 1s2)
b) Representative elements – ns1-2 np0-5
70
c) Transition elements – (n – 1)d1-10ns1-2
d) Inner transition elements – (n – 2) f1-14(n – 1)d0, 1 ns2
Question 58.
Give any four characteristic properties of transition elements.
Answer:
Characteristic properties of elements:
a) They exhibit more than one oxidation state.
b) Most of the elements and their ions exhibit colour.
c) These elements and their compounds are good catalysis for various chemical
processes.
d) They and their ions exhibit paramagnetic properties.
e) They form useful alloys.
Question 59.
What are rare earths and transuranic elements?
Answer:
1. Lanthanides are rare earths. In these elements the differentiating electron enters
into 4f – orbital.
2. The elements present after Uranium are called Transurariic elements. All of these
are radioactive and synthetic elements.
Question 60.
What is isoelectronic series? Name a series that will be isoelectronic with each of the
following atoms or ions.
a. F–
b. Ar
c. He
d. Rb+
Answer:
The species containing same no.of electrons are called Iso electronic species and this
series is called Isoelectronic series.
a) F– relating series
N-3, O-2, F–, Ne, Na+, Mg+2, Al+3
b) Ar relating series P-3, S-2, Cl–, Ar, K+, Ca+2
c) ‘He’ relating series H–, He, Li+, Be+2
71
d) Rb+ relating series
As-3, Se-2, Br–, Kr, Rb+, Sr+2
Question 61.
Explain why cation is smaller and anion is larger in radii than their parent atoms.
Answer:
• Cation means a positively charged species which is formed by an atom (or)
element when an electron is lost.
M → M+ + eΘ
• Cation has high effective nuclear charge and decrease in size observed.
Hence cation has smaller radii.
• Anion means a negatively charged species which is formed by an atom (or)
element when an electron is gained.
M + e– → MΘ.
• Anion has very low effective nuclear charge and increase in size observed.
Hence anion has larger radii.
Question 62.
Arrange the second period elements in the increasing order of their first ionization
enthalpies. Explain why Be has higher IE1 than B.
Answer:
The increasing order of the I.E.s of 2nd period elements are as follows.
• Due to presence of incompletely filled p – orbitals in Boron, its IE value is less.

• Due to presence of completely filled s2 configuration in ‘Be’, it has higher IE value.
Question 63.
IE1 of Na is less than that of Mg but IE2 of Na is higher than that of Mg – explain.
Answer:
IE1 of Na is less than that of ‘Mg’
Reason :-
Na — has electronic configuration [Ne] 31
72
Mg — has electronic configuration [Ne] 3s2
Mg has completely filled configuration so Mg has more IE1 than Na.
IE2 of Na is higher than that of Mg
•
• Na+ has stable inert gas configuration so IE2 of Na is very high
• By the lose of one electron from Mg+ ion forms Mg+2 ion which is more stable so
low amount of energy is required.
∴ IE2 of Na is higher than Mg.
Question 64.
What are the various factors due to which the IE of the main group elements tends to
decrease down a group ?
Answer:
The factors influencing on IE are
1. Atomic radius
2. Nuclear charge
3. Screening effect
4. Half filled, completely filled electronic configurations
5. peretrating power
In main group elements in a group IE decrease from top to bottom.
Reason: –
In groups from top to bottom size of elements increases hence IE values decreases.
Question 65.
The first ionization enthalpy values (in KJ mol-1) of group 13 elements are :
How do you explain this deviation from the general trend ?

Answer:
The given IE, values (in KJ / mole) of group 13 are as follow
73
• In genaral in a group IE values decrease down a group but from the above values
we observe that there is no smooth decrease down the group.
• The decrease from B to Al is due to increase of size.
• The observed discontinuity in the IE values of Al and Ga, and between In and Tl
are due to inability of d- and f – electrons, which have low screening effect to
compensate the increase in nuclear charge.
Question 66.
Would you expect the second electron gain enthalpy of oxygen as positive, more
negative or less negative than the first ? Justify.
Answer:
2nd gain enthalpy means energy released when an electron is added to uni negative ion.
O(g) + e– → O−(g) + 141 KJ/mole
O(g) + e– → O−(2)(g) – 780 KJ/mole
• 2nd gain enthalpy of oxygen is positive because O– ion doesnot accept an electron
readily and the entering electron have to over come the repulsive force.
Question 67.
What is the basic difference between the electron gain enthalpy and electropositivity?
Answer:
• Electron gain enthalpy means energy released when an electron is added to
isolated neutral gaseous atom.
• The tendency to lose the electrons by an element is called electropositivity.
• Electron gain enthalpy is the measure of electronegativity.
• Electron gain enthalpy and electropositivity are inversely related.
Question 68.
Would you expect IE1 for two isotopes of the same element to be the same or different
? Justify.
Answer:
• Isotopes means existance of same elements with different mass no.s
• The isotope with higher mass no. have low I.E value than the normal isotope.
• This is due to the less nuclear attraction on valency electrons in case of heavier
nuclide.
• But overall, the IE values of the isotopes are nearly same and the difference in IE
values is negligible.
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Question 69.
Increasing order of reactivity among group-1 elements is Li < Na < K < Rb < Cs, where
as among group-17 elements it is F > Cl > Br > I- explain.
Answer:
a) Increasing order of reactivity among group -1 elements is Li < Na < K < Rb < Cs
Explanation: –
• Group -1 elements are Alkali metals.
• Group -1 elements have the tendency to lose the electrons
• Group -1 elements forms ionic bonds readily by losing electrons
• Group – 1 elements good reducing agents.
• Electro positive character increases from top to bottom this is due to increase of
size.
b) Increasing order of reactivity among group -17 elements is F > Cl > Br > I
Explanation: –
• These are halogens (Group – 17)
• These have high electronegativity due to small size.
• These have the tendency to gain electrons.
• In a group from top to bottom electronegativity decrease, due to increase of size.
• These are oxidising agents and forms ionic bonds by gaining electrons.
Question 70.
Assign the position of the element having outer electronic configuration.
a. ns2np4 for n = 3
b. (n – 1)d2ns2 for n = 4
Answer:
a) ns2np4 for n = 3 .
• 3s23p4 → element is sulphur
• Sulphur belongs to VIA group (Group – 16) and 3rd period in periodic table,
b) (n – 1 )d2 ns2 for n = 4
3d2 4s2 → element is Titanium
• Titanium belongs to IVB group (Group – 4) and 4th period in the periodic table.
Question 71.
Predict the formulae of the stable binary compounds that would be formed by the
combination of the following pairs of elements.
a. Li and O
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b. Mg and N
c. Al and I
d. Si and O
e. p and Cl,
f. Element with atomic number 30 and Cl
Answer:
a) Stable binary compound formed between Li and O is Li2O (Lithiumoxide).
b) Stable binary compound formed between Mg and N is Mg3N2 (Magnesium nitride).
c) Stable binary compound formed between Al and I is AlI3 (Aluminium Iodide).
d) Stable binary compound formed between Si and I is SiO2 (Silicondioxide).
e) Stable binary compound formed between P and Cl is PCl3 and PCl5 (Phosphorous
trichloride and phosphorous pentain chloride).
f) Stable binary compound formed between element with At. NO – 30 and Cl is
ZnCl2 (Zinc chloride) [At. No – 30 – (Zn)].
Question 72.
Write a note on the variation of metallic nature in a group or in a period.
Answer:
Metals shows electropositive nature (i.e.,) loss of electrons and form positive ions.
Non – metals shows electronegative nature (i.e.,) gain of electrons and form negative
ions.
Periodicity:
a) Down the group : Going down a group of the periodic table, the tendency to form
positive ions, increases. That means there is an increase in metallic nature as the size of
atom increases down the group.
b) Along a period : From left to right in a period, size of atom decreases. So there is
decrease in metallic nature.
Question 73.
How does the covalent radius increase in group- 7 ?
Answer:
• Covalent radius increases in a group from top to bottom
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• The increase of covalent radius in VIIA group elements as follows.
Question 74.
Which element of 3rd period has the highest IE1 ? Explain the variation of IE1 in this
period.
Answer:
• In periods IE values increase from left to right
• Among 3rd period elements Argon (Ar) [Z = 18] possess highest IE,sub>1 value.
• IE1 values of 3rd period elements given below.
Exceptions:
• IE, of ‘Mg’ is higher than ‘Al’ because ‘Mg’ has completely filled ‘s’ subshells.
• IE, of ‘p’ is higher than ‘s’ because ‘p’ has half filled ‘p’ subshells.
Question 75.
What is valency of an element ? How does it vary with respect to hydrogen in the third period?
Answer:
Valency : The combining capacity of an element with another element is called valency.
The number of hydrogen atoms (or) chlorine atoms (or) double the number of oxygen atoms,
with which one atom of the element combine is also called valency.
∴ Valency = no. of hydrogens = no. of chlorine atoms
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= 2 × no. of oxygen atoms present in the molecule.
e.g.:
Periodicity of valency:
1) Each period starts with valency ‘1’ and ends in ‘0’.
2) In a group valency is either equal to the group number (i.e., upto 4th group) or is equal to (8
– group number) (i.e., from 5th group onwards).
Significance :
Valency of an element is useful in writing the formulae of compounds.
Question 76.
What is diagonal relationship ? Give a pair of elements having diagonal relationship. Why do
they show this relation ?
Answer:
On moving diagonally across the periodic table the elements show certain similarities. An
element of group in 2nd period has similar properties with second element of the next higher
group in the 3rd period. This type of resemblance is called diagonal relationship, e.g. : (Li, Mg);
(Be, Al); (B, Si)
Diagonal relationship is due to similar sizes of atoms (or of ions) and similar electronegativities
of the representative elements.
Diagonally similar elements posses the same polarizing power.
Polarizing power = (ionic charge) (ionic radius) 2
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Question 77.
What is lanthanide contraction ? What are its consequences ?
Answer:
Lanthanide contraction : Slow decrease in size of the atoms or ions among the lanthanides is
known as lanthanide contraction.
Consequences due to lanthanide contraction:
1. Due to lanthanide contraction, the crystall structure and other properties of the
elements become very closely similar.
2. Due to this, it becomes difficult to separate lanthanides from a mixture.
Question 78.
The first IP of lithium is 5.41 eV and electron affinity of Cl is – 3.61 eV. Calculate ΔH in kJ mol-
1
for the reaction : Li(g) + Cl(g) → Li(g)+ + Cl−(g)
Answer:
Given reaction is
ΔH = ΔH1 + ΔH2
= 5.41 – 3.61
= 1.8 ev
= 1.8 × 9.65 × 104 J/mole
= 17.37 × 104 J/Mole
= 173.7 KJ/mole
Question 79.
How many Cl atoms can you ionize in the process Cl → Cl+ + e by the energy liberated for the
process Cl + e → Cl– for one Avogadro number of atoms. Given IP = 13.0 eV and EA = 3.60 eV.
Avogadro number = 6 × 1023
Answer:
Given
Cl(g) + e– → Cl−(g) ΔH = – 3.6ev
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1 – atom → Electron affinity = 3.6 ev
6.23 × 1023 atoms → ?
6.23 × 1023 × 3.6 = 21.6828 × 1023
∴ For one avagadro no.of Cl atoms electron affinity = 21.6828 × 1023 eV
Given 13 eV can ionise 1 atom of Cl
21.6828 × 1023 eV ionise -?
21.6828×102313 = 1.667 × 1023 eV
Question 80.
The electron affinity of chlorine is 3.7 eV. How much energy in kcal is released
when 2g of chlorine atoms is completely converted to Cl– ions in the gaseous state
? (1 e V = 23.06 kcal)
Answer:
Given electron affinity of Cl = 3.7 ev
Cl + e– → Cl– ΔH = – 3.7ev
35.5 gms of CZ contains 6.023 × 1023 atoms
2 gms of Cl contains ?
= 2×6.023×102335.5 atoms
6.23 × 1023 atoms can liberate 3.7 eV
2×6.023×102335.5 atom can liberate?
= 2×6.023×1023×3.735.5×6.023×1023 = 2×3.735.5 = 7.435.5
= 0.2084 eV
= 0.2084 × 23.06 kcal/mole
= 4.81 k.cal/mole
Long Answer Questions
Question 1.
Discuss the classification of elements by Mendaleev’
Answer:
The periodic classification of elements based on “atomic weights” was done by “Lothar
Meyer” and “Mendeleev” independently.
Mendeleev’s periodic law : “The physical and chemical properties of elements and their
compounds are a periodic function of their atomic weights”.
Mendeleev arranged the 65 elements in a periodic table. He did not blindly follow the atomic
weight but gave more importance to their chemical properties in arranging them in the table.
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Explanation of the periodic law : When the elements are arranged in the increasing order of
their atomic weights, elements with similar properties appear again and again, at regular
intervals. This is called, periodicity of properties.
Mendeleev’s table : Mendeleev introduced a periodic table containing the known 65 elements.
In this table, while arranging the elements, he gave importance only to their atomic weights,
but also to their physical and chemical properties. This table was defective in some responses.
Then he introduced another table, after rectifying the defects of that table. lt is called, “short
form of periodic table”. He named the horizontal rows as ‘periods’ and the vertical columns, as
‘groups’. It has in all ‘9’ groups, I to VIII and a ‘O’ group. The first ‘7’ groups were divided into A
and B sub groups. There are ‘7’ periods in the table. The VIII group contains three triods,
namely, (Fe, Co, Ni), (Ru, Rh, Pd) and (Os, Ir, Pt).
Mendeleev’s observations :
1. When the elements are arranged according to their atomic weights, they exhibit
periodicity of properties.
2. Elements with similar chemical properties have nearly equal atomic weights: Iron
(55.85),. Cobalt (58.94) and Nickel (58.69).
3. The group number corresponds to the valency of element in that group.
4. Most widely distributed elements like H,C, O, N, Si, S etc., have relatively low atomic
weights.
5. The atomic weight of an element may be corrected if the atomic weights of the adjacent
elements are known. The properties of an element are the average properties of the
neighbouring elements.
6. The atomic weights of beryllium. Indium, Uranium etc. were corrected, based on this
observation.
Merits of Mendeleev’s table:
1. Actually it formed the basis for the development of other modern periodic tables.
2. Mendeleeffs left some vacant spaces in his periodic table, for the unknown elements.
But the predicted the properties of those elements. Later on, when these elements
were discovered, they exactly fitted into those vacant places having properties,
predicted by Mendeleev.
Ex : Eka – boron (Scandium), EKa – Silicon (germanium)
EKa – aluminium (gallium) etc.
3. ‘O’ group elements were not known at the time of Mendeleeff. Later when they were
discovered, they found a proper place in that table under ‘0’ group of elements.
Similarly, the radioactive elements.
4. In case of these pairs of elements Tellurium – Iodine Argon – Potassium and Cobalt –
Nickel, there is a reversal of the trend. The first element has higher atomic weight than
the second one. These are called anomalous pairs.
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However, based on their atomic numbers, and chemical properties, this arrangement
proves quite justified.
Draw-backs of Mendeleev’s periodic table :
1. Dissimilar elements were placed in the same group.
Ex : The coinage mentals Cu, Ag and Au are placed along with the alkali metals K, Rb, Cs
etc. in the I group. The only common property among them is that they are all univalent
(Valency = 1).
2. The 14 rare earths having different atomic weights are kept in the same place.
3. Hydrogen could not be given a proper place, as it resembles alkali metals and halogens
in its properties.
Question 2.
From a study of properties of neighbouring elements, the properties of an unknown element
can be predicted – Justify with an example.
Answer:
From a study of adjacent elements and their compounds, it is possible to predict the
characteristics of certain elements. These predictions were found to be very accurate. These
predicted properties helped the future scientists in the discovery of unknown elements, e.g. :
EKa Aluminium (EKa Al) (now known as Gallium); EKa Silicon (EKa Si) (now known as Germanium);
EKa Boron (EKa B) (now known as Scandium).
Illustration : Following table shows a comparison of the properties predicted by’Mendeleeff’

for the elements and those found experimentally after their discovery.
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Question 3.
Discuss the construction of long form periodic table.
Answer:
The elements are arranged in the long form of the periodic table in the increasing order of
atomic numbers. ‘Neils Bohr’ constructed the long form of the periodic table based on
electronic configuration of elements.
The important features of the long form of the periodic table are :
It consists seven horizontal rows called periods and 18 vertical columns which are classified
into 16 groups only.
Periods : Every period starts with an alkali metal and ends with an inert gas. The first period
consists of two elements only (H, He) and is called very short period. Second period consists 8
elements (Li to Ne) and is called first short period. The third period consists (Na to Ar) 8
elements and is called second short period.
Fourth period contains 18 elements (K to Kr) and is called first long period. Fifth period is the
second long period with 18 elements (Rb to Xe).
Sixth period is the longest period with 32 elements which starts with Cs and ends with Rn. This
period includes 14 lanthanides.
Seventh period is an incomplete period with 20 radioactive elements.
Groups : There are 16 groups in the long form of the periodic table (in transition elements
three vertical columns are fused and designated as VIII group). These groups are IA, IIA, NIB,
IVB, VB, VIB, VIIB, VIII, IB, MB, IMA, IVA, VA, VIA, VIIA and zero group.
The elements of IA, IIA, IIIA, IVA, VA, VIA, VIIA groups are called representative elements or
normal elements. Elements of IB, MB, NIB, IVB, VB, VIB, VIIB and VIII groups have their
ultimate and penultimate shell incomplete. These are called transition elements. MB elements
have (n – 1) d10 ns2 outermost electronic configuration.
Zero group elements have stable electronic configuration. These elements are called inert
gases, noble gases. These elements have been grouped at the extreme right of the periodic
table.
In this long periods have been expanded and short periods are broken to accommodate the
transitional elements in the middle of the long period.
Lanthanides and actinides have been grouped separately and placed at the bottom of the
periodic table.
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Question 4.
Discuss the relation between the number of electrons filled into the sub energy levels of an
orbit and the maximum number of elements present in a period.
Answer:
Elements have been accommodated in these periods according to the following scheme.
1st period : The first main energy shell (K – shell) is completed. As the maximum capacity of K-
shell is of 2 electrons, it consists of only two elements, hydrogen (1s1)and helium (1s2).
2nd period : The second main energy shell is completed (i.e.,) 2s and 2p are completed. It
includes eight elements from Li (2s1) to Ne (2s22p6).
3rd period : The 3s and 3p energy shells are completed. It includes also eight elements from
Na(3s1) to Ar (3s2 3p6).
4th period : The 4s, 3d and 3p energy shells are completed. It includes 18 elements from K(4s1)
to Kr (3d10 4s24p6). It includes two s – block elements, ten d – block elements and six p – block –
elements.
5th period : The 5s, 4d and 5p energy shells are completed. It includes 18 elements from Rb
(5s) to Xe (4d10 5s1 5p6). 1st also includes two s – block elements, ten d – block elements and six
p – block elements.
6th period : The 6s, 4f, 5d and 6p energy shells are completed, (i.e.,) it includes 32 elements
from Cs (6s1) to Rn (4f14 5d10 6s26p6). It consists of two s – block elements, ten d – block
elements, six p – block elements and fourteen f – block elements.
As this period can accommodate only 18 elements in the table, 14 members of 4f – series are
separately accommodated in a horizontal row below the periodic table.
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7th period : This period at present consists 26 elements. The 7s, 5f and 6d are completed (i.e.,)
twenty six elements. Seven of the elements from atomic numbers 106 to 112 have recently
been reported.
Question 5.
Write an essay on s, p, d and f block elements .
Answer:
According to the electronic configuration of elements, the elements have been classified into
four blocks. The basis for this classification is the entry of the differentiating electron into the
subshell. They are classified into s, p, d and f blocks.
‘s’ block elements : If the differentiating electron enters into ‘s’ orbital, the elements belongs
to ‘s’ block.
In every group there are two ‘s’ block elements. As an ‘s’ orbital can have a maximum of two
electrons, ‘s’ block has two groups IA and IIA.
‘p‘ block elements : If the differentiating electron enters into ‘p’ orbital, the elements belongs
to ‘p’ block.
‘p’ block contains six elements in each period. They are IIIA to VIIA and zero group elements.
The electronic configuration of ‘p’ block elements varies from ns2np1 to ns2np6.
‘d‘ block elements : It the differentiating electron enters into (n – 1) d – orbitals the elements
belongs to’d’ block. These elements are in between ‘s’ and ‘p’ blocks. These elements are also
known as transition elements. In these elements n and (n – 1) shells are incompletely filled.
The general electronic configuration of’d’ block elements is (n – 1) d1-10 ns1-2. This block consists
of IIIB to VIIB, VIII, IB and IIB groups.
‘f’ block elements : If the differentiating electron enters into ‘f’ orbitals of antipenultimate
shell (n – 2) of atoms of the elements belongs to ‘f block. They are in sixth and seventh periods
in the form of two series with 14 elements each. They are known as lanthanides and actinides
and are arranged at the bottom of the periodic table. The general electronic configuration is (n
– 2)f1-14 (n – 1)d0 – 1 ns2.
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In these shells the last three shells (ultimate, penultimate and anti penultimate) are
incompletely filled. Lanthanides belongs to 4f series. It contains Ce to Lu. Actinides belong to
5f series. It contains Th to Lr.
Advantages of this kind of classification :
As a result of this classification of elements were placed in correct positions in the periodic
table. It shows a gradual gradation in physical and chemical properties of elements. The
metallic nature gradually decreases and non – metallic nature gradually increases from’s1′
block to ‘p1 block. This classification gave a special place for radioactive elements.
Question 6.
Relate the electronic configuration of elements and their properties in the Classification of
elements.
Answer:
The chemical properties of all elements depends upon the electronic configuration. Upon the
basis of complete and incomplete electron shells and chemical properties, the elements are
classified into four types. (Type -1, Type – II, Type – III and Type – IV).
Type – I(inert gas elements): All the elements with an electronic configuration ns2 np6 including
He belongs to this type, nth shell of those elements are completely filled.
The elements show chemical inertness due to completely filled shells and hence they have
extra stability. Because of their stability, they are chemically inactive.
e.g. : He, Ne, Ar, Kr, Xe and Rn.
Type – II (Representative elements) : Except inert gases, the remaining elements of s and p –
blocks are called representative elements. All the elements with an electronic configuration
ns1 to ns2 np5 excluding. He comes under this type. These are atoms in which all except the
outermost shells (nth) are complete. Elements of this type enter into chemical combination by
loosing, gaining or sharing electrons to get stable inert gas configuration. Many of the metals,
all non – metals and metalloids come under this type. Chemically these elements are reactive.
Type – III (Transition elements): All the elements with an electronic configuration (n – 1) d1 –
9
ns1or2 belongs to this type. Atoms in which the two outermost shells are incomplete. These
elements show variable oxidation states, form complex ions and coloured ions. The electronic
configuration of d – block elements is (n – 1) d1 – 10 ns1 – 2. Small size, high nuclear charge and
unpaired’d’ orbitals impart characteristic properties to be transition elements.
Type- IV (Inner transition elements): All the elements with an electronic configuration (n – 2) f1
– 14
(n -1) d0, 1 ns2 belongs to this type. Atoms in which three outermost shells are incomplete.
Lanthanides and Actinides belong to this type.
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Question 7.
What is a periodic property ? How the following properties vary in a group and in a period ?
Explain
a) Atomic radius
b) Electron gain enthalpy.
Answer:
Recurrence of similar properties of elements at definite regular intervals with increasing
atomic number i.e., according to their electronic configurations is known as periodicity. Any
property which is periodic in nature is called periodic property.
a) Atomic radius : The atomic radius decreases from left to right in a period. With an increase
in the atomic number in a period the nuclear charge increases. As a result the effective nuclear
charge over the outermost electrons increases, due to this the orbitals are pulled closer to the
nucleus causing in a decrease in the atomic radius.
The atomic radius increases from top to the bottom in a group because – with an increase in
the atomic number the electrons are added to new shells resulting an increase in the number
of inner shells. Hence atomic radius increases from top to bottom in a group.
b) Electron gain enthalpy : Electron gain enthalpy increases in a period from left to right
because the size of the atom decreases and the nature of the element changes from metallic
to non – metallic nature when we move from left to right in a period.
Electron gain enthalpy decreases from top to bottom in a group because there is an increase in
the atomic size. But the second element has greater electron gain enthalpy than the first
element.
e.g. : Chlorine has more electron affinity value (- 348 kJ mol-1) than Fluorine (-333 kJ mol-1). It is
because fluorine atom is smaller in size than chlorine atom. There is repulsion between the
incoming electron and electrons already present in fluorine atom i.e., due to stronger inter
electronic repulsions.
Question 8.
What is a periodic property ? How the following properties vary in a group and in a period ?
Explain
a. IE
b. EN
Answer:
a) IE : In groups and periods of the periodic table the ionization enthalpy values are
periodically change depend upon the electronic configuration and size of elements.
In a group of elements ionization energy decreases from top to bottom because atomic radius
increases.
In general, in a period the atomic size decreases. Because of this, the ionization energy
increases across a period.
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b) Electro negativity : Electronegativity increases from left to right in a period since the atomic:
radii decreases and nuclear attraction increases.
In a group electronegativity decreases from top to bottom due to an increase in atomic radii
and a decrease in nuclear attraction.
Question 9.
Write a note on
a. Atomic radius
b. Metallic radius
c. Covalent radius
Answer:
a) Crystal Radius (Atomic radius or Metallic radius): The term is used for metal atoms. A
metallic crystal contains metal atoms in close packing. These metal atoms are considered
spherical. They are supposed to touch each other in the crystal.
The crystal radius is half the internuclear distance between two adjacent atoms.
e.g.: The internuclear distance between two adjacent sodium atoms in a crystal of sodium
metal is 3.72 A. So crystal radius of sodium is 3.722 = 1.86 A
For potassium it is 2.31 A.
b) Covalent radius : It is used generally for non – metals. Covalent radius is half the equilibrium
distance between the nuclei of two atoms with a covalent bond.
Covalent radii of two atoms can be added to give internuclear distance between them.
e.g. : Covalent radius of H is 0.37A and for chlorine it is 0.99A. Hence internulear distance
between H and Cl in HCl is 1.36A.
c) Vander Waals radius (Collision radius): The Vander Waals radius is half the equilibrium
distance between the nuclei of two atoms bound by Vander Waals forces.
It is used for molecular substances in solid state and for inert gases.
e.g. : The Vander Waals radius for hydrogen is 1.2 A and that of chlorine is 1.80 A.
The Vander Waals radius of an atom is 40% larger than its covalent radius.
Question 10.
Define IE1 and IE2. Why is IE2 > IE1 for a given atom? Discuss the factors that effect IE of an
element. (A.P. Mar. ’16)(T.S. Mar. ’13)
Answer:
1) Ionization energy is the amount of energy required to remove the most loosely held
electron from isolated a neutral gaseous atom to convert it into gaseous ion. It is also known
as first ionization energy because it is the energy required to remove the first electron from
the atom.
It is denoted as I1, and is expressed in electron volts per atom, kilo calories (or) kilo joules per
mole.
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M(g) + I1 → M(g)+ + e–
I1 is first ionization potential.
2) The energy required to remove another electron from the unipositive ion is called the
second ionization energy. It is denoted as I2.
M+(g) + I2 → M(g)2+ + e–
3) The second ionization potential is greater than the first ionization potential. On removing an
electron from an atom, the unipositive ion formed will have more effective nuclear charge
than the number of electrons. As a result the effective nuclear charge increases over the
outermost electrons. Hence more energy is required to remove the second electron. This
shows that the second ionization potential is greater than the first ionization potential.
For sodium, I1 is 5.1 eV and I2 is 47.3 eV.
I1 < I2 < I3 ….. In
Factors affecting ionization potential:
1. Atomic radius : As the size of the atom increases the distance between the nucleus and the
outermost electrons increases. So the effective nuclear charge on the outermost electrons
decreases. In such a case the energy required to remove the electrons also decreases. This
shows that with an increase in atomic radius the ionization energy decreases.
2. Nuclear charge : As the positive charge of the nucleus increases its attraction increases over
the electrons. So it becomes more difficult to remove the electrons. This shows that the
ionization energy increases as the nuclear charge increases.
3. Screening effect or shielding effect: In multielectron atoms, valence electrons are attracted
by the nucleus as well as repelled by electrons of inner shells. The electrons present in the
inner shells screen the electrons present in the outermost orbit from the nucleus. As the
number of electrons in the inner orbits increases, the screening effect increases. This reduces
the effective nuclear charge over the outermost electrons. It is called screening or shielding
effect. With the increase of screening effect the ionization potential decreases. Screening
efficiency of the orbitals falls off in the order s > p > d > f.
(Magnitude of screening effect) ∝ 1( Ionization enthalpy)
TREND IN A GROUP : The ionisation potential decreases in a group, gradually from top to
bottom as the size of the elements increases down a group.
TREND IN A PERIOD : In a period from left to right I.P. value increases as the size of the
elements decreases along the period.
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Question 11.
How do the following properties change in group-1 and in the third period ? Explain with
example.
a. Atomic radius
b. IE
c. EA
d. Nature of oxides
Answer:
a) Atomic radius
• In Group – 1 atomic radius from Li to Cs increases
→ In 3rd period from Na to Cl atomic radius decreases.
b) Ionization energy : In a group ionization energy values decreases with an increase in the size
of the atom. In IA group Li is the element with highest ionization potential and Cs is the
element with lowest ionization potential.
In third period the ionization potential increases from Na to Mg and then decreases at Al and
increases upto P and decreases in case of S and then increases upto argon, i.e., Al has a lower
value than Mg and S has a lower value than P, due to stable electronic configurations of Mg
and P Among these elements argon has highest ionization potential.
c) Electron affinity :
• In 3rd period E.A > from ‘Si’ to ‘P’ decreases and P to Cl increases.
‘Mg’ and ‘Ar’ has positive values.
• In 1st group from Li to Cs electron affinity decreases due to increase of size.
d) Nature of oxides of elements : All IA group elements are alkali metals. Their oxides are basic
in nature. They dissolve in water to give basic solutions which changes fed litmus blue.
e.g. : Na2O, CaO , MgO etc.
Na2O + H2O → 2 NaOH
CaO + H2O → Ca(OH)2
MgO + H2O → Mg (OH)2
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The basic nature of these oxides increases from top to bottom in the group. In a period basic
properties decreases and acidic properties increases.
Question 12.
Define electron gain enthalpy. How it varies in a group and in a period? Why is the electron
gain enthalpy of O or F is less negative than that of the succeeding element in the group ?
Answer:
1. Electron affinity is the amount of energy released when an electron is added to a neutral
gaseous atom in its ground state. It is known as first Electron affinity EA,sub>1. It has -ve
value.
X(g) + e → X(g)− + EA1
2. Energy can be absorbed when an other electron is added to uni negative ion. It is
because to overcome the repulsion between negative ion and electron. Hence second
electron affinity, EA2 has +ve value.
X(g)− + e → X2−(g) + EA2
3. It can be indirectly determined from Born —Haber cycle. Its units are kJ/mole.
4. Trend in a group : Generally EA decreases down the group. In a group the second
element has higher EA value than the first member.
e.g. : EA of Cl is more than that of F
Fluorine possess lower EA value than chlorine. It is due to inner electron repulsions in
Fluorine.
5. Trend in a period : Generally EA value increases across a period, but some irregularities can
be observed.a) I A group elements possess low EA values than the corresponding III A
elements, e.g. : Be has EA value zero, it is due to completely filled 2s2 orbital.
b) VA elements have low EA values than that of VI A elements.
e.g. : Due to presence of half filled p – orbitals [2s2 2p3], nitrogen has lower EA value than
that of oxygen.
c) For inert gases EA value is zero.
d) The element with the highest EA value is chlorine.
• The electron gain enthalpy of O and F is less negative than the succeeding element in the
group because. These have small size and inter electronic repulsions are high in these
elements
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O → 141 KJ / mole and S → 200 kJ/Mole
F → 328 KJ / mole and Cl → 349 kJ/Mole
Question 13.
a. What is electronegativity ?
b. How does it vary in a group and in a period ?
Answer:
a) Electronegativity : ‘The tendency of the atom of an element to attract the shared electron
pair(s) more towards itself in a hetronuclear diatomic molecule or in a polar covalent bond.”
Measuring electronegativity Pauling scale : Pauling scale is based on the values of bond
energy. The bond energy of a compound A – B is the average of bond energies of A – A and B –
B molecules.
EA – B = 12(EA−A+EB−B)
But the experimental value of EA – B is found to exceed the theoretical value. The difference is ∆.
∴ ∆ = E’A – B – EA – B
∆ indicates the polarity of the covalent bond. It is measured in k. cal. mol-1.
Pauling gave the relation XA – XB = 0.208 × Δ−−√
In S.l. units XA – XB = 0.1017 Δ−−√ where ∆ is measured in kJ/mole
XA and XB are the electronegativities of A and B. Pauling arbitrarily fixed 2.1 as the
electronegativity value of Flydrogen and calculated the electronegativities of other elements.
On Pauling scale Fluorine has the highest EN value 4.0.
From the values of the electronegativity of elements, the nature of the chemical bond formed
can be understood. If two bonded atoms differ by 1.70 or more ion their EN values, the bond
between them would be either 50% or more than 50% ionic in nature. Similarly if the
difference in the EN values of the atoms is less than 1.70, the bond formed is more than 50%
covalent in nature.
b) Variation in a group and period : Electronegativity increases from left to right in a period
since the atomic: radii decreases and nuclear attraction increases. In a group electronegativity
decreases from top to bottom due to an increase in atomic radii and a decrease in nuclear
attraction.
Question 14.
Explain the following
a. Valency
b. Diagonal relation
c. Variation of nature of oxides in the Group -1
Answer:
a) Valency : The combining capacity of an element with another element is called valency. The
number of hydrogen atoms (or) chlorine atoms (or) double the number of oxygen atoms, with
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which one atom of the element combine is also called valency.
∴ Valency = no. of hydrogens
= no. of chlorine atoms
= 2 × no. of oxygen atoms present in the molecule
Periodicity of valency :
1) Each period starts with valency’11 and ends in ‘O’.
e.g.:
2) In a group valency is either equal to the group number (i.e., upto 4th group) or is equal to (8
– group number) (i.e., from 5th group onwards).
Significance :
Valency of an element is useful in writing the formulae of compounds.
b) Diagonal relation : On moving diagonally across the periodic table the elements show
certain similarities. An element of group in 2nd period has similar properties with second
element of the next higher group in the 3rd period. This type of resemblance is called diagonal
relationship,
e.g. : (Li, Mg); (Be, Al); (B, Si)
c) Nature of oxides of elements : All IA group elements are alkali metals. Their oxides are basic
in nature. They dissolve in water to give basic solutions which changes red litmus blue.
e.g. : Na2O, CaO , MgO etc.
CaO + H2O → Ca(OH)2
MgO + H2O → Mg (OH)2
The basic nature of these oxides increases from top to bottom in the group. In a period basic
properties decreases and acidic properties increases.
Solved Problems
Question 1.
What would be the IUPAC name and symbol for the element with atomic number 120?
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Solution:
The roots for 1, 2 and 0 are un, bi and nil, respectively. Hence, the symbol and the name
respectively are Ubn and unbinilium.
Question 2.
How would you justify the presence of 18 elements in the 5t” period of the Periodic Table ?
Solution:
When n = 5, l = 0, 1, 2, 3. The order in which the energy of the available orbitals 4d, 5s and 5p
increases is 5s < 4d < 5p. The total number of orbitals available are 9. The maximum number of
electrons that can be accommodated is 18; and therefore 18 elements are there in the
5th period.
Question 3.
The elements Z = 117 and 120 have not yet been discovered. In which family / group would
you place these elements and also give the electronic configuration in each case.
Solution:
we see from that element with Z = 117, would belong to the halogen family (Group 17) and
the electronic configuration would be [Rn] 5f146d107s27p5. The element with Z = 120, will be
placed in Group 2 (alkaline earth metals), and will have the electronic configuration [Uuo]8s2
Question 4.
Considering the atomic number and position in the periodic table, arrange the following
elements in the increasing order of metallic character: Si, Be, Mg, Na, P.
Solution:
Metallic character increases down a group and decreases along a period as we move from left
to right. Hence the order of increasing metallic character is : P < Si < Be < Mg < Na.
Question 5.
Which of the following species will have the largest and the smallest size ?
Mg, Mg2+, Al, Al3+.
Solution:
Atomic radii decrease across a period. Cations are smaller than their parent atoms. Among
isoelectronic species, the one with the larger positive nuclear charge will have a smaller radius.
Hence the largest species is Mg; the smallest one is Al3+.
Question 6.
The first ionization enthalpy (∆iH) values of the third period elements, Na, Mg and Si are
respectively 496, 737 and 786 kJ mol-1. Predict whether the first ∆iH value for Al will be more
close to 575 or 760 kJ mol-1 ? Justify your answer.
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Solution:
It will be more close to 575 kJ mol-1. The value for Al should be lower than that of Mg because
of effective shielding of 3p electrons from the nucleus by 3s-electrons.
Question 7.
Which of the following will have the most negative electron gain enthalpy and which the least
negative ? P, S, Cl, F. Explain your answer.
Solution:
Electron gain enthalpy generally becomes more negative across a period as we move from left
to right. Within a group, electron gain enthalpy becomes less negative down a group.
However, adding an electron to the 2p-orbital leads to greater repulsion than adding an
electron to the larger 3p-orbital. Hence the element with most negative electron gain enthalpy
is chlorine; the one with the least negative electron gain enthalpy is phosphorous.
Question 8.
Using the Periodic Table, predict the formulas of compounds which might be formed by the
following pairs of elements;
(a) silicon and bromine
(b) aluminium and sulphur.
Solution:
(a) Silicon is group 14 element with a valence of 4; bromine belongs to the halogen family with
a valency of 1. Hence the formula of the compound formed would be SiBr4.
(b) Aluminium belongs to group 13 with a valence of 3; sulphur belongs to group 16 elements
with a valence of 2. Hence, the formula of the compound formed would be Al2S2.
Question 9.
Are the oxidation state and covalency of Al in [AICI(H2O)5]2+ same ?
Solution:
No. The oxidation state of Al is +3 and the covalency is 6.
Question 10.
Show by a chemical reaction with water that Na2O is a basic oxide and Cl2O7 is an acidic oxide.
Solution:
Na2O with water forms a strong base Whereas Cl2O7 forms strong acid.
Na2O + H2O → 2NaOH
Cl2O7 + H2O → 2HClO4
Their basic or acidic nature can be qualitatively tested with litmus paper.
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Question 1.
What is Octet rule?
Answer:
Every atom must possess 8 electrons in its outer most energy level for its stability.
Atoms combine in two ways to get octet either by transfer of electrons (or) by mutual
sharing of electrons. They can attain ns2 np6 configuration.
The tendency of an atom to achieve eight electrons in their outer most shell is known
as octet rule.
Question 2.
Write Lewis dot structures for S and S2-.
Answer:
• Lewis dot structure for ‘s’ is
Electronic configuration — 1s2 2s2 2p6 3s2 3p4

• Lewis dot structure for s-2 is
Electronic configuration of s-2 is 1s2 2s2 2p6 3s2 3p6
Question 3.
Write the possible resonance structures for SO3.
Answer:
The resonance structures of SO3 as follows
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Question 4.
Predict the change, if any, in hybridization of Al atom in the following reaction
AlCl3 + Cl– → AlCl−4.
Answer:
In AlCl3 Aluminium undergoes sp2 hybridisation
In AlCl−4 Aluminium undergoes sp3 hybridisation
Question 5.
Which of the two ions Ca2+ or Zn2+ is more stable and why ?
Answer:
• Ca+2 has electronic configuration 1s22s22p63s23p6. This configuration is noble gas
(or) inert gas configuration.
• Zn+2 has electonic configuration 1s22s22p63s23p64s03d10. This configuration is
psuedo inert gas configuration.
∴ Ca+2 is more stable than Zn+2 ion.
Question 6.
Cl– ion is more stable than Cl atom—Why ?
Answer:
The electronic configurations of Cl and Cl– is :
Cl = 1s2 2s2 2p6 3s2 3p5
Cl– = 1s2 2s2 2p6 3s2 3p6.
This electronic configuration clearly shows that chlorine atom has 7 electrons in the
outermost orbit. Whereas chloride has a stable octet electronic configuration (3s2 3p6).
After gaining one electron, chloride ion attains the electronic configuration of Argon.
Hence chloride ion has greater stability than chlorine atom.
Question 7.
Why argon does not form Ar2 molecule ?
Answer:
Ar2 represents diatomic molecule. But Argon does not form diatomic molecule. So it
cannot represented as ‘Ar2‘.
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Reason : Since Ar’ has only paired electrons with stable octet configuration. It cannot
share its electrons with another Ar atom and does not form diatomic molecule.
Question 8.
What is the best possible arrangement of four bond pairs in the valence shell of an
atom to minimise repulsions ?
Answer:
The best possible arrangement of four bond pairs in the valency shell of an atom to
minimise repulsions is Tetrahedral. (Bond angle 109°.28′)
Eg. : Methane (CH4).
Question 9.
If A and B are two different atoms when does AB molecule become Covalent ?
Answer:
1. If the difference in electronegativity values between A and B is less than 1.7, then
covalent compound formation is possible (according to Allred – Rochow scale).
2. If A and B are sharing one or more electron pairs mutually then AB will be a
covalent compound.
Question 10.
What is meant by localized orbitals?
Answer:
The molecular orbital with bonded electron cloud localised between the two nuclei of
bonded atoms is called localized orbital, (or) The orbitals which are involved in bond
formation are called localized orbitals.
Question 11.
How many Sigma and Pi bonds are present in
(a) C2H2 and
(b) C2H44?
Answer:
a) C2H2
H–C≡C–H
C2H2 contains 3 – sigma bonds and 2 – pi bonds.
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b) C2H4
C2H4 contains 5 – sigma bonds and 1-pi bond.
Question 12.
Is there any change in the hybridization of Boron and Nitrogen atoms as a result of the
following reaction? BF3 + NH3 → F3BNH3
Answer:
a) Ammonia – Boron trifluoride formation (H3N → BF3):
Ammonia molecule contains Nitrogen atom with a lone pair of electrons (in sp3 orbital).
BF3 has ‘B’ atom with an incomplete octet (with a vacant Pz orbital). Therefore, nitrogen
of ammonia donates its lone pair to Boron and thus forms coordinate covalent bond.
During this bond formation, the sp3 orbital of nitrogen having a lone pair overlaps the
vacant ‘p’ orbital of Boron. The equation corresponding to the reaction is written as
follows :
b) Change in hybridised states N and B during [H3N → BF3] formation :

Boron in BF3 undergoes (sp2 hybridization with one vacant unhybrid ‘p’ orbital. This
orbital also undergoes) hybridization in presence of NH3 so that the hybridised state of
‘B’ changes from sp2 to sp3. This vacant hybrid orbital is bonded to NH3 through dative
bond. During this process there is no change in the hybridized state of Nitrogen in NH3.
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Question 13.
Give reasons for the following.
a) Why H2O Boiling point is more than H2S
b) Why H2O Boiling point is more than HF
Answer:
a) H2O has high boiling point than H2S
Reason:
In H2O inter molecular hydrogen bonding is present where as in case of H2S such
bonding is absent.
b) H2O has high boiling point than HF
Reason:
In H2O and H2S inter molecular hydrogen bonding is present but in H2O the no. of
hydrogen bonds are more than in HF.
Question 1.
Explain Kossel-Lewis approach to Chemical bonding.
Answer:
Kossel – Lewis Theory : This theory was also called as electronic theory of valency (or)
chemical bond theory.
Postulates of Kossel – Lewis Theory : Kossel explained the formation of electrovalent
bond while Lewis explained the formation of covalent bond. Their explanation of
valency is mainly based on the inertness of noble gases.
Postulates:
• The chemical inertness of noble gases is due to the presence of octet structure.
Octet rule was stated as follows “An atom must possess eight electrons in the
outermost energy level for its stability”.
• Even though ‘He’ has only two electrons in the valency shell, it is highly stable
and chemically inert.
• Elements other than zero group are chemically reactive because of having less
than 8 electrons in their outer most shells.
• Every atom try to acquire the Eight electron configuration (octet) in its outer most
shell. This can be possible by losing (or) sharing (or) gaining electrons.
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• According to Lewis the valency electrons are represented by dots. These are
called Lewis symbols.
• Lewis dot structures can be used to calculate the group valency of the element.
Eg:
has four electrons.

∴ Valency of ‘c’ is ‘4’.
Question 2.
Write the general properties of Ionic Compounds.
Answer:
1. Physical state : Due to close packing of ions, ionic compounds are crystalline
solids.
2. Melting and Boiling points : In ionic crystals the oppositely charged ions are
bound by strong electrostatic force of attraction. To overcome these attractive
force between ions, more thermal energy is required. Hence the melting and
boiling points of ionic compounds are high.
3. Solubility : Ionic compounds are soluble in polar solvents like water, liquid
ammonia etc., but are insoluble in non – polar solvents like benzene, carbon
disulphide etc.,
4. Reactivity: Reactions between ionic compounds in aqueous solution are very fast
due to strong attraction among ions.
e.g. : When AgNO3 solution is added to NaCl solution, a white precipitate of AgCl
is formed.
5. Isomerism : Ionic bond is non-directional.

So ionic compounds cannot exhibit isomerism.
6. Electrical conductivity : Ionic substances conduct electricity in molten state and in
aqueous solution. The ionic compounds are, therefore, electrolytes.
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Question 3.
State Fajan’s rules and give suitable examples.
Answer:
Fajan’s rules:
1. Ionic nature of the bond increases with increase in the size of cation, e.g.: The
ionic nature increases in the order
Li+ < Na+ < K+ < Rb– < Cs+
2. The formation of ionic bond is favoured with the decrease of the size of anion.
e.g.: CaF2 is more ionic than CaI2.
3. If the charge on cation (or) anion (or) both is less, then they can form ionic bonds,
e.g.: The ionic nature increases in the order
4. Cations with inert gas configurations form ionic compounds while those cations
with pseudo inert gas configurations favour covalent bond formation.
e.g.: Na+ in Na+Cl– has an inert gas configuration. So Na+Cl– is ionic. But CuCl is
more covalent because Cu+ has not acquired inert gas configuration in this
compound, instead it has acquired pseudo inert gas configuration.
5. The cation with inert gas configuration is more stable, e.g.: Ca2+ is more stable
than Zn2+ ion.
6.
Question 4.
What is Octet rule ? Briefly explain its significance and limitations.
Answer:
Octet rule: Every atom must possess 8 electrons in its outermost energy level for its
stability. Atoms combine in two ways to get octet either by transfer of electrons (or) by
mutual sharing of electrons. They can attain ns2 np6 configuration.
e.g.:
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1. Na loose one electron to get Ne configuration by possessing 8 electrons.
Na : 1 s2 2s2 2p6 3s1 and Na+ : 1 s2 2s2 2p6.
2. ‘Cl’ atom take one electron to get “Ar” configuration. Cl– : 1s2 2s2 2p6 3s2 3p6.
Here Na+ and Cl– ions obey octet rule.
3. In H2O molecule oxygen obey octet rule.
It is therefore, concluded that s2p6 configuration in the outer energy level constitutes a
structure of maximum stability and therefore, of minimum energy.
The atoms of all elements when enter into chemical combination try to attain noble gas
configuration (i.e.,) they try to attain 8 electrons in their outermost energy level which is
of maximum stability and hence of minimum energy.
The tendency of an atoms to achieve eight electrons in their outermost shell is known
as OCTET RULE.
Limitations : There are 3 types of exceptions to the octet rule. These are mentional
below.
• Central atoms containing incomplete octet.
Eg : BeH2, BCl3 etc.,
• Molecules containing odd number of electrons.
• Central atoms possessing more than 8 electrons which istermed as expanded

octet.
Eg : SF6, H2SO4 etc.,
• This theory does not explained about shape of molecules.
• This theory does not explained about the formation of noble gas compounds like
XeF2, XeOF2 etc.,
Question 5.
Write the resonance structures for NO2 and NO−3
Answer:
Resonance structure of NO2
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Question 6.
Use Lewis symbols to show electron transfer between the following pairs of atoms to
form cations and anions:
(a) K and S
(b) Ca and O
(c) Al and N.
Answer:
a) Between the atoms K and S
b) Between Ca and O
c) Between Al and N
Question 7.
Explain why H2O has dipole moment while CO2 does not have.
Answer:
• H2O molecule is a polar molecule and it has un symmetrical structure i.e. Angular
(or) V – shape
• CO2 molecule is non polar and it is linear molecule.
• SO H2O has dipolemoment (μ = 1 ,835D) and CO2 does not have dipolemoment
(μ = 0)
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Question 8.
Define Dipole moment. Write its applications.
Answer:
Dipole moment : The product of magnitude of the charge and the distance between
the two poles (bond length) is called dipole moment.
• Dipole moment μ = q × d
q = charge
d = bond length
• Units : Debye (D), 1 Debye = 3.34 × 10-30 coulombs metres.
Applications : –
• Dipole moment is used to calculate the percentage of ionic character in a
molecule.
• It is used to know the shape of the molecule.
• Symmetry (symmetrical (or) non symmetrical) of the molecule can be known by
dipole moment.
Question 9.
Explain why BeF2 molecule has zero dipole moment although the Be-F bonds are polar.
Answer:
• Even though Be-F bonds in BeF2 are polar, the dipole moment of BeF2 molecule is
zero. Because BeF2 has linear shape.
• Flere the vectrorial sum of the dipole moment of two Be-F bonds is zero. Hence
dipole moment
(μ) = 0.
Question 10.
Explain the structure of CH4 molecule.
Answer:
Formation of Methane molecule :
1. The central atom of methane is carbon.
2. The electronic configuration of carbon in ground state is and
on excitation it is During excitation the 2s pair splits and the
electron jumps into the adjacent vacant 2pz orbital.
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3. The undergo sp3 hybridisation giving four equivalent
sp3 hybridised orbitals.
4. Each sp3 hybrid orbital overlaps with the 1s orbitals of hydrogen
forming σsp3−s bond.
5. In case of methane four σsp3−s bonds are formed. The bonds are directed towards
the four corners of a regular tetrahedron. The shape of methane molecule is
tetrahedral with a bond angle 109°28’.
Question 11.
Explain Polar Covalent bond with a suitable example.
Answer:
The covalent bond which is formed by the mutual sharing of electron pairs between
two dissimilar atoms is called polar covalent bond.
• Dissimilar atoms means two atoms having different electronegativity values (or)
atoms of different elements.
Eg : HF, HCl, H2O, CO2 etc.,
Formation of HCl :
• In the above example H and Cl are two atoms of different elements having
different electro negativities.
• These two atoms (H, Cl) mutually share the electron pairs and form the polar
covalent bond.
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Question 12.
Explain the shape and bond angle In BCl3 molecule in terms of Valence Bond Theory.
Answer:
Boron trichloride molecule formation :
1. The electronic configuration of ‘B’ in the ground state is

2. On excitation the configuration is Now there are three half
filled orbitals are available for hybridisation.
3. Now sp2 hybridisation takes place at boron atom giving three sp2 hybrid orbitals.
4. Each of them with one unpaired electron forms a ‘σ’ bond with one chlorine
atom. The overlapping is σsp – p (Cl atom has the unpaired electron in 2pz orbital).
2
In boron trichloride there are three ‘σ’ bonds.
Question 13.
What are σ and π bonds ? Specify the differences between them.
Answer:
Definition of σ bond : “σ – bond is along the internuclear axis. It has a cylindrical
symmetry”.
Definition of π bond : “A covalent bond formed by a sidewise overlap of ‘p’ orbitals of
atoms that are already bonded through a σ – bond, and in which the electron clouds
are present above and below the internuclear axis is known as π – bond”.
Sigma bond (σ)

1. A ‘σ’ bond is formed by the axial overlap of two half filled orbitals belonging to
the valence shells of the two combining atoms.
2. The ‘σ’ bonding electron cloud is symmetric about the inter-nuclear axis.
3. It is strong bond since the extent of overlap is much.
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4. It allows free rotation of atoms or groups about the bond.
5. It can exist independently.
6. It determines the shape of the molecule.
7. There can be only one ‘σ’ bond between two atoms.
8. Hybrid orbitaIs form only ‘σ’ bonds.
Pi — bond (π)
1. A π-bond is formed by the lateral overlap of orbitals.
2. The π-bonding electron cloud lies above and below the flame of the internuclear
axis.
3. It is a weaker than ‘σ’ bond, since the extent of overlap is less.
4. π-bond restricts such free rotation.
5. It is formed only after a ‘σ’ bond is formed.
6. It does not determine the shape of the molecule.
7. There can be one or two π-bonds between the atoms.
8. Hybrid orbitals cannot form π-bonds.
Question 14.
Even though nitrogen in ammonia is in sp3 hybridization, the bond angle deviate from
109°28. Explain.
Answer:
In NH3 molecule the central nitrogen atom shares its ‘3’ unpaired electrons with three
hydrogen atoms to form 3σ bonds. Hence NH3 molecule contains one lone pair, three
bond pairs.
a) Because of the repulsion between the lone pair and the bond pairs the angle reduces
to 107°.
b) According to VSEPR theory the geometry of the molecule is pyramidal with bond
angle 107°.
108
Question 15.
Show how a double and triple bond are formed between carbon atoms in
(a) C2H4 and
(b) C2H2 respectively.
Answer:
Formation of double bond between the carbon atoms of C2H4 : –
C – Ground state electronic configuration 1s2 2s2 2p2
• In ethylene two carbons undergo sp2 hybridisation.

• One of sp2 hybrid orbital of carbon overlaps with sp2 hybrid orbital of another
carbon atom to form C – C sigma bond.
• The two other sp2 hybrid orbitals of each carbon overlap with ‘s’ orbital of
hydrogen atoms to form C – H bonds.
The unhybridised orbital of one carbon atom overlap side wisely with the similar orbital
to form weak π bond.
Formation of triple bond between the carbon atoms of C2H2 : –
109
C – Ground state electronic configuration 1s2 2s2 2p2
• In acetylene two carbons undergoes sp hybridisation.

• One of sp hybrid orbital of carbon overlaps with sp hybrid orbital of another
carbon atom to form C – C sigma bond.
• another sp hybrid orbitals of each carbon overlap with s orbital of hydrogen
atoms to form C – H bonds.
• The un hybridised orbitals of two carbon atom overlap side wisely to form two
weak π bonds.
Question 16.
Explain the hybridization involved in PCl5 molecule. (T.S. Mar. ’16, ’15)
Answer:
1) In PCl5 the electron configuration of phosphorus is
2) Phosphorus undergoes sp3d – hybridisation by intermixing of one s-orbital [3s], three

p – orbitals [3px, 3py, 3pz] and one d – orbital.
These five hybrid orbitals overlap. The pz orbitals of chlorine atoms forming
five σsp3d−s bonds. Out of these five p – Cl bonds three are coplanar and the remaining
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two are in the axial position. There by PCl5 acquires the trigonal bipyramidal shape. The
molecule contains two bond angles 90° and 120°.
Question 17.
Explain the hybridization involved in SF6 molecule.
Answer:
In this hybridisation one ‘s’ orbital, three ‘p’ orbitals and two ‘d’ orbitals of the excited
atom combine to form six equivalent sp3d2 hybrid orbitals.
e.g. : SF6
These six sp3 d2 hybrid orbitals overlap six 2pz orbitals of fluorine atoms to form
six σsp3d2 bonds. The directions of the bonds give an octa-hedral shape to the molecule.
The bond angle is 90° or 180° & 90°.
111
Question 18.
Explain the formation of Coordinate Covalent bond with one example.
Answer:
Co-ordinate covalent bond (dative bond) is a special type of covalent bond. It is
proposed by Sidgwick. It is formed by the sharing of electrons between two atoms in
which both the electrons of the shared electron pair are contributed by one atom and
the other atom nearly participates in sharing.
The bond is represented as (“→”) an arrow starting from the donar atom and directed
towards the acceptor atom.
Examples :
1) Ammonia – Boron trifluoride H3N : → BF3
Ammonia combines with boron trifluoride to give ammonium boron trifluoride.
In ammonia nitrogen has a complete octet and also it has a lone pair of electrons. In
BF3 the boron atom has a total of six electrons after sharing with fluorine. Nitrogen
donates the electron pair to boron to form a co-ordinate covalent bond between
ammonia and boron trifluoride.
2) Ammonium ion (NH+4)
3) Hydronium ion (H3O+)
Properties of co-ordinate covalent bond :

1. The bond do not ionise in water.
2. The compounds are generally soluble in organic solvents and are sparingly
soluble in water.
3. These compounds exhibit space isomerism because the bond is rigid and
directional.
4. The bond is semipolar in nature – so their volatility lies in between covalent and
ionic bonds.
112
Question 19.
Which hybrid orbitals are used by Carbon atoms in the following molecules?
(a) CH3 -CH3
(b) CH3 – CH = CH2
(c) CH3 – CH2 – OH
(d) CH3 – CHO
Answer:
a) CH3 -CH3 (ethane)
The two carbons of ethane undergo sp3 hybridisation.
Carbon – (1) – undergoes sp2 hyrbidisation

Carbon (1) and (2) both undergo ‘sp3‘ hybridisation.
Question 20.
What is Hydrogen bond ? Explain the different types of Hydrogen bonds with
examples.
Answer:
Hydrogen bond is a weak electrostatic bond formed between partially positive charged
hydrogen atom and an highly electronegative atom of the same molecule or another
molecule.
Hydrogen bond is formed when the Hydrogen is bonded to small, highly
electronegative atoms like F, O and N. A partial positive charge will be on hydrogen
atom and partial negative charge on the electronegative atom.
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The bond dissociation energy of hydrogen bond is 40 KJ/mole. Hydrogen bond is
represented with dotted lines (—–). Hydrogen bond is stronger than Vander Waals’
forces and weaker than covalent bond.
Hydrogen bonding is of two types.
(1) Intermolecular hydrogen bond and
(2) Intramolecular hydrogen bond.
1) Intermolecular hydrogen bond :
If the hydrogen bond is formed between two polar molecules it is called intermolecular
hydrogen bond, i.e., the hydrogen bond is formed between hydrogen atom of one
molecule and highly electronegative atom of another molecule is known as
intermolecular hydrogen bond.
Ex. : Water (H2O) ; HF : NH3 ; p – nitrophenol, CH3COOH, ethyl alcohol etc.
Water molecule forms oi. associated molecule through intermolecular hydrogen bond.
Due to molecular association water possess high boiling point.
m or p – nitrophenol :
2) Intramolecular hydrogen bond:

If the hydrogen bond is formed within the molecule it is known as intramolecular
hydrogen bond.
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Ex. : o – nitrophenol; o – hydroxy benzaldehyde.
Abnormal behaviour due to hydrogen bond:

1. The physical state of substance may alter. They have high melting and boiling
points.
2. Ammonia has higher boiling point than HCl eventhough nitrogen and chlorine
have same electronegativity values (3.0). Ammonia forms an associated molecule
through intermolecular hydrogen bond.
3. p – hydroxy benzaldehyde have higher boiling point than o- hydroxy
benzaldehyde. This is due to intermolecular hydrogen bonding in para isomer.
4. Ethyl alcohol is highly soluble in water due to association and co-association
through intermolecular hydrogen bonding.
Question 21.
Explain the formation of H2 molecule on the basis of Valence Bond theory.
Answer:
Postulates of valency bond theory:
1. Covalent bond is formed by the overlap of an half filled atomic orbital of one
atom with an half filled atomic orbital of the other atom involved in the bond
formation.
2. The electrons in these two orbitals involved in the overlap shall have opposite
spins.
3. Greater the overlap stronger the bond formed.
4. The bonds are formed mostly in the direction in which the electron clouds are
concentrated.
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Formation of H2 molecule:
Hydrogen molecule is formed due to overlaping of s – s orbitals. When two Hydrogen
atoms come together, is orbitals of the Hydrogen atoms overlap to form a strong ‘σ”
bond. This is σs-s’
Question 22.
Using Molecular Orbital Theory explain why the B2 molecule is paramagnetic ?
Answer:
Boron electronic configuration is – 1s2 2s2 2p1
The molecular orbital energy level sequence for B2 is
• Bond order = 6−42 = 22 = 1

• In the above sequence unpaired electrons are present.
• Presence of unpaired electrons leads to paramagnetic nature.
∴ B2 molecule is paramagnetic.
Question 23.
Write the important conditions necessary for linear combination of atomic orbitals.
Answer:
1. The molecular orbitals are formed when the atomic orbitals combine linearly (i.e.,)
when the atoms approach each other. The no. of molecular orbitals resulting are
equal to the no.of atomic orbitals combining.
2. Only such atomic orbitals which are of similar energies and symmetry with
respect to the inter nuclear axis combine to form molecular orbitals.
3. The total no. of molecular orbitals produced will be numerically equal to the no.
of combining orbitals.
4. The order of energies of bonding, anti bonding and non bonding orbitals can be
written as bonding orbitals < non bonding orbitals < anti – bonding orbitals.
116
Question 24.
What is meant by the term Bond order? Calculate the bond orders in the following
(a) N2
(b) O2
(c) O+2 and
(d) O−2
Answer:
Bond order : The half of the difference between the no.of bonding electrons and anti
bonding electrons is known as bond order. ’
a) N2 : Molecular orbital energy level sequence.
→ Bond Order = 10−42 = 62 = 3

b) O2 : Molecular orbital energy level sequence.
Question 25.
Of BF3 and NF3, dipole moment is observed for NF3 and not for BF3. Why ?
Answer:
Of BF3 and NF3 dipole moment is observed for NF3 and not for BF3.
Reasons:
• BF3 molecule is non polar and is a symmetrical molecule. Symmetrical molecules
have zero dipole moment.
• NF3 molecule is polar and it is a unsymmetrical molecule so it has dipole moment.
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• BF3 molecule has trigonal planar structure.
NF3 molecule has pyramidal shape.
• NF3 has dipole moment µ = 0.8 × 10-30 coloumb × meter.
Question 26.
Eventhough both NH3 and NF3 are Pyramidal, NH3 has a higher dipole moment
compared to NF3. Why? (A.P. Mar.’16)
Answer:
• Both NH3 and NF3 molecules have pyramidal shape and in two molecules N atom
has lone pair of electrons.
• Even though fluorine has more electronegativity than nitrogen the dipole
moment of NH3 is greater than that of NF3
µ (NH3) = 4.9 × 10-30 coloumbs × meter.
µ (NF3) = 0.8 × 10-30 coloumbs × meter.
• In case of NH3 the orbital dipole due to lone pair is in the same direction as the
resultant dipole moment of N – H bonds.
Where as in case of NF3 the orbital dipole is in the direction opposite to the resultant
dipole
moment of the three N – F bonds.
118
Question 27.
How do you predict the shapes of the following molecules making use of VSEPR
Theory ?
(a) XeF4
(b) BrF5
(c) ClF3 and
(d) ICl−4
Answer:
According to VSEPR theory the shape of the molecule can be predicted by counting
no.of electron pairs (bond pairs, lone pairs) around the central atom.
a) XeF4:
In XeF4 No.of bond pairs present are ‘4’.
No.of lone pairs present are ‘2’.
According to VSEPR theory shape of molecule is square planar (Actual shape
octahedral).
b) BrF5 :
In BrF5 No.of bond pairs present are ‘5’
No.of lone pairs present are ‘1’
According to VSEPR theory shape of the molecule is square pyramid (actual shape
octahedral)
119
c) ClF3:
In ClF3 No.of bond pairs present are ‘3’

According to VSEPR Theory shape of ClF3 Molecule is T – shape (Actual shape TBP)
d) ICl−4:
In ICl−4 No.of bond pairs present are ‘4’
According to VSEPR Theory shape of ICll−4 is square planar
(Actual shape octahedral)
Question 1.
Explain the formation of Ionic Bond with a suitable example.
Answer:
The electrostatic force that binds the oppositely charged ions which are formed by the
transfer of electrons from one atom with low ionization potential to the other with high
electron affinity is called ionic bond or electrovalent bond.
It is formed when the electronegativity difference between the two atoms is more tha
1.7.
Example :
Formation of sodium chloride in terms of orbital concept:
1) Na (Z = 11). The electronic configuration is 1s2 2s2 2p6 3s1.
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This can be expressed as
2) Cl (Z = 17). The electronic configuration is = 1s2 2s2 2p6 3s2 3p5

This can be expressed as
3) The configurations after the transfer of electrons forming ions can be expressed as:
In the formation of sodium chloride the 3s electron of sodium atom is transferred to

the 3p2 orbital of chlorine atom. The Na+ ion and Cl– ion so formed are now bound by
strong coulombic electrostatic forces of attraction forming sodium chloride.
Question 2.
Explain the factors favourable for the formation of Ionic Compounds.
Answer:
Factors favour the ionic bond formation:
a) Cation formation:
1. Lower ionization energy: Lower ionization energy of an atom greater is the ease
of formation of cation
e.g. : The ionization energy of sodium is 117.9 kcal/mole and that of potassium is
100 kcal/mole So K+ ion can readily form than Na+ ion.
2. Large size of the atom : Large atoms can easily lose the valence electrons. If the
size large, the distance between the nucleus and the valence electrons is more
and so the force of attraction is less. Therefore the electron can be removed
easily from the atom forming cation.
3. Ion with lower charge: Small magnitude of charge favours the formation of ions
easily.
e.g. : The ease of ion formation increases in the order Na+ > Mg2+ > Al3+.
4. Cations with inert gas configuration : Ion possessing electronic configuration
similar to zero group elements are more stable than those ions which do not
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have such configuration.
eg.: Ca2+ (2, 8, 8) is more stable than Zn2+ (2, 8, 18) because the former has inert
gas
configuration.
b) Anion formation:
1. High electron affinity: If the electron affinity of an element is high its anion can be
easily formed.
e.g.: Cl + e— → Cl–
2. Smaller size of atom : Smaller the size of the atom lesser is the distance between
the nucleus and the valence orbit. Hence the nuclear attraction on incoming
electron is more. So the anion is readily formed.
3. Lower charge : Ions with lower charge are more readily formed than those with
higher charge.
e.g.: Cl– > O 2- > N3-
4. The ions with inert gas electronic configuration are more readily formed than
others with the same charge. .
c) If the two bonded atoms differ by more than 1.70 in their EN values, the bond
between them is ionic in nature.
Question 3.
Draw Lewis Structures for the following molecules.
(a) H2S
(b) SiCl4
(c) BeF2
(d) HCOOH
Answer:
Lewis structures:
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Question 4.
Write notes on
(a) Bond Angle
(b) Bond Enthalpy
(c) Bond length and
(d) Bond order.
Answer:
a) Bond angle : The angle between the orbitals containing bonding electron pairs
around the central atom in a molecule (or) complex ion is known as Bond angle.
• it is expressed in degrees.
• It is determined experimentally by spectroscopic methods.
Eg: In H2O (H — 0 — H) bond angle is 104.5° .
b) Bond Enthalpy : The amount of energy required to break one mole of bonds of a
particular type between two atoms in a gaseous state is known as Bond Enthalpy.
Units: KJ/Mole.
Eg: H – H bond enthalpy in hydrogen is 435.8 KJ/mole
H2(g) → H(g) + H(g) ∆H = 435.8 KJ/mole
• In case of poly atomic molecules average bond enthalpy is used.
c) Bond length : The distance between the nuclei of the atoms in a molecule is known
as bond length.
• Bond length is equal to the sum of the covalent radii of the two atoms that are
bonded.
• Units of Bond length A° (or) cm (or) m (or) pm
• As the number of bonds between two atoms increases the bond length decrease.
d) Bond Order:
According to Lewis the bond order is given by the number of bonds between the two
atoms in a covalent molecule.
Eg: Bond order of N2 – 3
Bond order of O2 – 2
Bond order of H2 – 1
123
• In case of Iso electronic species and ions bond orders are same.
• Bond order is useful in predecting stabilities of molecules.
• Bond order increases bond enthalpy increases and Bond length decreases.
Question 5.
Give an account of VSEPR Theory and its applications.
Answer:
VSEPR theory was proposed by Sidgwick and Powell and later extended by Gillespie
and Nyholm. It was developed by Ronald and Nyholm.
This theory explains the shapes of simple molecules having electron pairs bonded or
non-bonded. The repulsions among the electron pairs present in the valence shell of
the central atom decides the shape of the molecules.
According to this theory :
a) The shape of the molecule is determined by repulsions between all of the electron
pairs present in the valency shell of central atom.
b) The electron pairs orient in space so as to have minimum repulsions among them.
c) The magnitude of repulsions between bonding pairs of electrons depends on the
electronegativity difference between the central atom and the other atoms.
d) The order of repulsions between various electron pairs is lone pair – lone pair > lone
pair – bond pair > bond pair – bond pair.
e) The repulsive forces between different bonds is of the order triple bond > double
bond > single bond.
f) The shapes of molecules can be predicted as.
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In NH3 molecule the central nitrogen atom shares its ‘3’ unpaired electrons with three
hydrogen atoms to form 3σ bonds. Hence NH3 molecule contains one lone pair, three
bond pairs.
a) Because of the repulsion between the lone pair and the bond pairs the angle reduces
to 107°.
b) According to VSEPR theory the geometry of the molecule is pyramidal with bond
angle 107°.
Question 6.
How do you explain the geometry of the molecules on the basis of Valence bond
Theory ?
Answer:
Postulates of valency bond theory :
1. Covalent bond is formed by the overlap of an half filled atomic orbital of one
atom with an half filled atomic orbital of the other atom involved in the bond
formation.
2. The electrons in these two orbitals involved in the overlap shall have opposite
spins.
3. Greater the overlap stronger the bond formed.
4. The bonds are formed mostly in the direction in which the electron clouds are
concentrated.
Formation of H2 molecule :
Hydrogen molecule is formed due to overlapping of s – s orbitals. When two Hydrogen
atoms come together, 1s orbitals of the Hydrogen atoms overlap to form a strong “σ”
bond. This is σs-s.
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Formation of Cl2 molecule :
The electronic configuration of Chlorine atom is It has one half

filled 3pz orbital. The pz orbital of one chlorine atom overlaps the pz orbital of the other
chlorine atom and the two electrons of opposite spins pair up to form covalent bond.
As the overlap along the internuclear axis is maximum a strong bond is formed. The
bond is formed due to σp−p overlap.
Formation of O2 molecule:
The electronic configuration of oxygen atom is It has two half filled

2p orbitals i.e., 2py and 2pz.
The py orbital of one atom overlaps the py orbital of the second atom to form a ‘σ’
bond σpy−py.
The pz orbital in the two atoms will be at right angles to the internuclear axis. These two
can have lateral overlap. The electron density of the bonded pair is distributed in two
banana like regions lying on either side of the internuclear axis. Thus the oxygen
molecule has a double bond. The molecule has one σp – p and one πp – p between the two
atoms.
126
Question 7.
‘What do you understand by Hybridisation? Explain different types of hybridization
involving s and p orbitals. (Mar. ’13)
Answer:
Hybridisation is defined as the process of mixing of atomic orbitals of nearly equal
energy of an atom to give the same number of new set of orbitals of equal energy and
shapes.
Depending on the number and nature of orbitals involving hybridisation it is classified
into different types. If ‘s’ and ‘p’ atomic orbitals are involved three types are possible
namely sp3, sp2 and sp.
1. sp3 hybridisation : In this hybridisation one’s and three ‘p’ atomic orbitals of the
excited atom combine to form four equivalent sp3 hybridised orbitals.
This hybridisation is known as tetrahedral or tetragonal hybridisation.
Each sp3 hybridised orbital possess 25% ‘s’ nature and 75% of ‘p’ nature. The shape of
the molecule is tetrahedral with a bond angle 109°28′, e.g. : Formation of Methane
molecule :
1. The central atom of methane is carbon.
2. The electronic configuration of carbon in ground state is and on
excitation it is During excitation the 2s pair splits and the
electron jumps into the adjacent vacant 2pz orbital.
3. The undergo sp3 hybridisation giving four equivalent sp3 hybridised
orbitals.
4. Each sp3 hybrid orbital overlaps with the 1s orbitals of hydrogen
forming σsp3−s bond.
5. In case of methane four σsp3−s bonds are formed. The bonds are directed
towards the four corners of a regular tetrahedron. The shape of methane
molecule is tetrahedral with a bond angle 109°28′.
127
2. sp2 hybridisation : In this hybridisation one ‘s’ and two p’ atomic orbitals of the
excited atom
combine to form three equivalent sp2 hybridised orbitals.
This hybridisation is also known as trigorial hybridisation. In sp2 hybridisation each
sp2 hybrid orbital has 33.33% ‘s’ nature and 66.66% ‘p’ nature. The shape of the
molecule is trigonal with a bond angle 120°.
E.g.: Boron trichioride molecule formation:
1. The electronic configuration of ‘B’ in the ground state is
2. On excitation the configuration is Now there are three half filled

orbitals are available for hybridisation.
3. Now sp2 hybridisation takes place at boron atom giving three sp2 hybrid orbitals.
4. Each of them with one unpaired electron forms ‘σ’ bond with one chlorine atom.
The overlapping is σsp2−p (Cl atom has the unpaired electron in 2Pz orbital).
Inboron trichloride there are three ‘σ’ bonds.
3. sp hybridisation : In this hybridisation one ‘s and one ‘p’ atomic orbitals of the
excited atom combine to form two equivalent sp hybridised orbitals.
This hybridisation is also known as diagonal hybridisation. In sp hybridisation each sp
hybrid orbital has 50% ‘s’ character and 50% ‘p’ character. The shape of the molecule is
linear or diagonal with a bond angle 180°.
Ex. : Beryllium chloride molecule formation:
1. Be atom has electronic configuration.

2. In ground state it has no half filled orbitais. On excitation the configuration
becomes 1s22s12P1x2p0y2p0z.
128
3. Now sp hybridisation takes place at beryllium atom giving two sp hybrid orbitais.
Each of them with one unpaired electron forms a ‘σ’ bond with one chlorine
atom.
4. The overlaping is σsp-p (Cl atom has the unpaired electron in 2pz orbital). In
beryllium chloride there are two ‘σ’ bonds.
Question 8.
Write the salient features of Molecular Orbital Theory.
Answer:
Molecular orbital theory:
Hund and Mulliken.
1. Theory was proposed by
2. Atomic orbitals (AO) of the bonded atoms combine loose their identity to form
molecular orbitals (MO).
3. The electrons in a molecule reside in molecular orbitals.
4. Molecular orbital is the region around the nuclei where the probability of finding
electon is maximum (or) the wave function of a molecule.
5. The electrons of all the atoms in a molecule are revolving under the influence of
all the nuclei in the molecule.
6. The molecular orbitals are formed when the atomic orbitals combine linearly.
7. The shape of the molecular orbitals depends on the shape of the atomic orbitals.
8. Each molecular orbital can accommodate two electrons with opposite spins.
9. The molecular orbitals are arranged in the increasing order of energy, and
electrons are filled in the same order.
10. Hund’s rule of maximum multiplicity is to be followed while filling
molecular orbitals.
129
11.Atomic orbitals with similar energy and symmetry can combine to give molecular
orbitals.
12.Molecular orbitals with energy lower than A.O are known as bonding molecular
orbital; while those with higher energy are known as anti bonding molecular
orbitals. Those which are not involved in combination are called non bonding
orbitals.
The order of energies of molecular orbital is : bonding < nonbonding < antibonding
molecular orbitals.
The bonding orbitals are designated a σ and π.
The antibonding orbitals are designated σ* and π*.
Filling of electrons into molecular orbitals :
The sequence of energy levels of molecular orbitals is given by
sequence is valid for oxygen and other heavier elements.
This sequence is valid for lighter elements like B.CandN.
Question 9.
Give the Molecular Orbital Energy diagram of
(a) N2 and
(b) O2. Calculate the respec- five bond order. Write the magnetic nature of N2 and
O2 molecules.
Answer:
Molecular orbital energy level diagram (MOED) of ‘N2‘ ; Electronic configuration of
nitrogen (z = 7) is 1s2 2s2 2p3. Since nitrogen atom has 7 electrons, the molecular
orbitals of nitrogen molecule (N2) has 14 electrons which are distributed as below :
130
• Bond order = 8−22 = 3 ( N ≡ N)
• Absence of unpaired electrons showed that N2 molecule is diamagnetic.
MOED of O2:
Electronic configuration of Oxygen (Z = 8) is 1s2 2s2 2p4. Since Oxygen atom has 8
electrons, the molecular orbitais of Oxygen molecule (O2) has 16 electrons, which are
distributed as below:
131
• Bond order = 10−62 = 2 (O = O)
• Presence of two unpaired 6 electrons (π⋆2p1y,π⋆2p1z) showed that O2 molecule is
paramagnetic.
132
Solved Problems
Question 1.
Write the Lewis dot structure of CO molecule.
Solution:
Step 1. Count the total number of valence electrons of carbon and oxygen atoms. The
outer (valence) shell configurations of carbon and oxygen atoms are: 2s2 2p2 and
2s2 2p4, respectively. The valence electrons available are 4 + 6 = 10.
Step 2. The skeletal structure of CO is written as: C O
Step 3. Draw a single bond (one shared electron pair) between C and O and complete
the octet on O, the remaining two electrons are the lone pair on C.
This does not complete the octet on carbon and hence we have to resort to multiple
bonding (in this case a triple bond) between C and O atoms. This satisfies the octet rule
condition for both atoms.
Question 2.
Write the Lewis structure of the nitrite ion, NO−2.
Solution:
Step 1. Count the total number of valence electrons of the nitrogen atom, the oxygen
atoms and the additional one negative charge (equal to one electron).
N(2s2 2p3), O (2s2 2p4)
5 + (2 × 6) + 1 = 18 electrons
Step 2. The skeletal structure of NO−2 is written as: O N O
Step 3. Draw a single bond (one shared electron pair) between the nitrogen and each
of the oxygen atoms completing the octets on oxygen atoms. This, however, does not
complete the octet on nitrogen if the remaining two electrons constitute lone pair on
it.
133
Hence we have to resort to multiple bonding between nitrogen and one of the oxygen
atoms (in this case a double bond). This leads to the following Lewis dot structures.
Question 3.
Explain the structure of CO2−3 ion interms of resonance.
Solution:
The single Lewis structure based on the presence of two single bonds and one double
bond between carbon and oxygen atoms is inadequate to represent the molecule
accurately as it represents unequal bonds. According to the experimental findings, all
carbon to oxygen bonds in CCO2 are equivalent.
Therefore the carbonate ion is best described as a resonance hybrid of the canonical
forms I, II, and III shown below.
Question 4.
Explain the structure of CO2 molecule.
Solution:
The experimentally determined carbon to oxygen bond length in CO2 is 115 pm. The
lengths of a normal carbon to oxygen double bond (C = O) and carbon to oxygen triple
bond(C ≡ O) are 121 pm and 110 pm respectively. The carbon-oxygen bond lengths in
CO2 (115 pm) lie between the values for C = O and C ≡ O. Obviously, a single Lewis
structure cannot depict this position and it becomes necessary to write more than one
Lewis structures and to consider that the structure of CO2 is best described as a hybrid
134
of the canonical or resonance forms I, II and III.
Additional Problems
Question 1.
The experimental dipole moment of HCl is 1.03D and its bond length (distance) is
1.27Å. Calculate the % of ionic character of HCl.
Answer:
Calculated dipole moment = q × d
= 4.8 × 10-10 × 1.27 × 10-8 cm
= 6.09 Debye
% of ionic character = μods μcalc × 100
= 1.036.09 × 100
= 16.9%
Question 2.
The dipole moment of H2S is 0.95D. Find the bond moment if the bond angle is 97°
(Cos 48.5° = 0.662).
Answer:
μobs = 2 (bond moment) (cosθ2)
0.95 = 2 (bond moment) (Cos 48.5°)
0.95 = 2 × bond moment × 0.662
Bond moment = 0.952×0.662 = 0.72D
135
Question 1.
Name the different intermolecular forces experienced by the molecules of a gas.
Answer:
The different inter molecular forces experienced by the molecules of a gas are London
(or) dispersion forces, Dipole – Dipole forces, Dipole- induced dipole forces, hydrogen
bond.
Question 2.
State Boyle’s law. Give its mathematical expression.
Answer:
At constant temperature, the pressure of a given mass (fixed amount) of gas varies
inversely with it’s volume. This is Boyle’s law.
• Mathematically it can be written as
P ∝ 1v (At constant T and no.of moles (n))
⇒ Pv = kv (constant).
Question 3.
State Charle’s law. Give its mathematical expression.
Answer:
At constant pressure the volume of a fixed mass of a gas is directly proportional to it’s
absolute temperature. This is charle’s law.
• Mathematically it can be written as
V ∝ T (At constant P and no.of moles (n))
⇒ V = kT
⇒ VT = k (constant).
136
Question 4.
What are Isotherms?
Answer:
At constant temperature the curves which shows the relationship between variation of
volume of a given mass of gas and pressure are called isotherms.
Question 5.
What is Absolute Temperature?
Answer:
It is also called thermodynamic temperature (or) Kelvin temperature. It is a temperature
on the absolute (or) kelvin scale in which zero lies at – 273.16°C.
T = (t° C + 273.16) K
Question 6.
What are Isobars?
Answer:
The curves (or) graphs that can be drawn at constant pressure are called Isobars.
Eg : Graph drawn between volume and temperature.
Question 7.
What is Absolute Zero?
Answer:
It is the lowest temperature theoretically possible at which volume of a perfect gas is
zero.
Question 8.
State Avogadro’s law.
Answer:
Equal volumes of all gases under the same conditions of temperature and pressure
contains equal number of molecules
V ∝ n (mathematically)
v = kn
137
Question 9.
What are Isochores ?
Answer:
At constant volume a line on a graph showing the variation of temperature of a gas
with its pressure is called Isochores.
• It is also called Isoplere.
Question 10.
What are S T P Conditions ?
Answer:
STP means Standard Temperature and Pressure conditions.
• Standard temperature is 0° C = 273 K
• Standard pressure is 1 atmosphere = 76 cm = 760 mm. of Hg.
At S.T.P. one mole of any gas occupy 22.4 lit. of volume.
Question 11.
What is Gram molar Volume ?
Answer:
The volume occupied by one gram molecular weight (or) one gram mole of an element
(or) compound in the gaseous state is called gram molar volume.
(or)
• At STP one mole of any gas occupy 22.4 lit. of volume This is known as gram
molar volume.
Question 12.
What is an Ideal gas ?
Answer:
A gas which obeys gas laws i.e. Boyle’s law, charle’s law and avagadro’s law exactly at
all temperatures is called an ideal gas.
Question 13.
Why the gas constant ‘R’ is called Universal gas constant ?
Answer:
Gas constant ‘R’ is called universal gas constant because the value of ‘R‘ is same for all
gases.
138
Question 14.
Why Ideal gas equation is called Equation of State ?
Answer:
Ideal gas equation is a relation between four variables (p, v, n, T) and it describes the
state of any gas. Hence it is called equation of state.
Question 15.
Give the values of gas constant in different units.
Answer:
Gas constant ‘R’ has values in different units as follows.
R = 0.0821 lit. atm. k-1 mol-1
= 8.314 J. k-1 mol-1
= 1.987 (or) 2 cal. k-1 mol-1
= 8.314 × 107 ergs. k-1 mol-1.
Question 16.
How are the density and molar mass of a gas related?
Answer:
Pv = n RT
Pv = wm RT m
P = (wv)RTM
Molar mass M = dRTP [∴ wv = density(d)]
P = Pressure of gas
R = Universal gas constant
T = Temperature of gas in kelvins scale.
Question 17.
State Graham’s law of diffusion.
Answer:
The rate of diffusion of a given mass of gas at a given pressure and temperature is
inversely proportional to the square root of its density
rate of diffusion r ∝ 1d√.
139
Question 18.
Which of the gases diffuses faster among N2, O2 and CH4? Why? (T.S. Mar. ‘15)
Answer:
CH4 gas diffuse faster among N2, O2 and CH4.
Reason : CH4 (16) has low molecular weight than N2 (28) and O2 (32).
Question 19.
How many times methane diffuses faster than sulphurdioxide?
Answer:
According to Graham’s law of diffusion.
Hence methane gas diffuses 2 times faster than SO2.
Question 20.
State Dalton’s law of Partial pressures. (Mar. ‘14)
Answer:
The total pressure exerted by a mixture of chemically non – reacting gases at given
temperature and volume, is equal to the sum of partial pressures of the component
gases.
P = P1 + P2 + P3.
Question 21.
Give the relation between the partial pressure of a gas and its mole fraction.
Answer:
Partial pressure of a gas = mole fraction of the gas × Total pressure of the mixture of
gases
Eg : Consider A and B in a container which are chemically non reaction.
∴ Partial pressure of A (PA) = XA × PT
Partial pressure of B (PB) = XB × PT
XA = nAnA+nB, XB = nBnA+nB
XA, XB are mole fractions
PT = Total pressure.
140
Question 22.
What is aqueous tension?
Answer:
The pressure exerted by the water vapour which is equilibrium with liquid water is
called aqueous tension.
(or)
The pressure exerted by the saturated water vapour is called aqueous tension.
Question 23.
Give the two assumptions of Kinetic molecular theory of gases that do not hold good
in explaining the deviation of real gases from ideal behaviour.
Answer:
The two assumptions of kinetic molecular theory of gases that do not hold good in
explaining the deviation of real gases from ideal behaviour are
1. There is no force of attraction between the molecules of a gas.
2. Volume of the gas molecules is negligible when compared to the space occupied
by the gas.
Question 24.
Give the Kinetic gas equation and write the terms in it.
Answer:
Kinetic gas equation is PV = 13mnu2rms
P = Pressure of the gas
V = Volume of the gas
m = Mass of 1 mole of the gas
urms = RMS speed of the gas molecules.
Question 25.
Give an equation to calculate the kinetic energy of gas molecules.
Answer:
Kinetic energy for ‘n1 moles of gas is given by
K.E. = 32nRT
T = absolute temperature.
141
Question 26.
What is Boltzman’s constant ? Give its value.
Answer:
Boltzman’s constant is the gas constant per molecule.
Boltzman’s constant K = RN
= 1.38 × 10-16 erg/k. molecule
= 1.38 × 10-23 J/k. molecule.
Question 27.
What is RMS speed ?
Answer:
The square root of mean of the squares of the speeds of all molecules of a gas is
known as RMS speed (uRMS)
Question 28.
What is Average speed ?
Answer:
The arithematic mean of speeds of gas molecules is known as average speed (uav).
Question 29.
What is Most probable speed ?
Answer:
The speed possessed by the maximum number of molecules of the gas is known as
most probable sPeed (ump).
Question 30.
What is the effect of temperature on the speeds of the gas molecules ?
Answer:
Temperature and speeds of the gases are directly related.
∴ By the rise of temperature the speeds of the gas molecules also increases.
142
Question 31.
What is the effect of temperature on the kinetic energy of the gas molecules ?
Answer:
According to the postulates of kinetic molecular theory of gases.
The kinetic energy of gas molecules is directly proportional to the absolute
temperature.
K.E. ∝ Tabs
Question 32.
Give the ratio of RMS average and most probable speeds of gas molecules.
Solution:
Question 33.
Why RMS speed is taken in the derivation of Kinetic gas equation ?
Answer:
RMS speed is the mean of squares of speeds of all molecules of gas. Hence RMS speed,
is taken into the derivation of kinetic gas equation.
PV = 13mnu2rms
Question 34.
What is Compressibility factor ?
Answer:
The ratio of the actual molar volume of a gas to the molar volume of a perfect gas
under the same conditions is called compressibility factor.
Compressibility factor Z = PVnRT
For a perfect gas Z = 1.
Question 35.
What is Boyle Temperature?
Answer:
The temperatue at which a real gas exibits ideal behaviour for a considerable range of
pressure is called Boyle’s temperature.
143
Question 36.
What is critical temperature ? Give its value for CO2.
Answer:
The temperature above which no gas can be liquified how ever high the pressure may
be applied is called critical temperature.
• Critical temperature of CO2 gas is 31.98° C.
Question 37.
What is critical Volume ?
Answer:
The volume occupied by one mole of gas at critical temperature and critical pressure is
known as critical volume.
Question 38.
What is critical Pressure ?
Answer:
The pressure required to liquify a gas at critical temperature is known as critical
pressure.
Question 39.
What are critical constants ?
Answer:
Critical temperatue (TC), critical volume (VC) and critical pressure (PC) are called as critical
constants.Question 40.
Define vapour Pressure of a liquid.
Answer:
The pressure exerted by the vapour on the liquid surface. When it is in equilibrium with
the liquid at a given temperature is known as vapour pressure of the liquid.
Question 41.
What are normal and standard boiling points ? Give their values for H2O.
Answer:
• The boiling points at 1 atm. pressure are called normal boiling points.
• The boiling points at 1 bar pressure are called standard boiling points.
• For water normal boiling point is 100° C.
• For water standard boiling point is 99.6° C.
144
Question 42.
Why pressure Cooker is used for cooking food on hills ?
Answer:
At hill areas pressure cooker is used for cooking food because low atmospheric
pressure is observed at high altitudes. At high altitudes liquids boil at low temperature.
So water boils at low temperature on hills.
Question 43.
What is surface tension ?
Answer:
The force acting at right angles to the surface of the liquid along unit length of surface
is called surface tension.
• Units : dynes / cm.
Question 44.
What is laminar flow of a liquid ?
Answer:
In liquids a regular gradation of velocity for layers in passing from one layer to the next
observed. This flow of liquid is called Laminar flow.
Question 45.
What is coefficient of Viscosity ? Give its units.
Answer:
The force of friction required to maintain velocity difference of 1 cm. sec-1 between two
parallel layers of a liquid 1 cm. apart and each layer having an area 1cm2 is called
coefficient of viscosity.
• It is denoted by η
• F = η A dudx
• Units : Poise : In CGS system 1 poise = 1g. cm-1 sec-1.
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Question 1.
State and explain Boyle’s law.
Answer:
Boyle’s law : At constant temperature, the volume of a given mass of gas is inversely
proportional to pressure of the gas.
If ‘V’ is the volume of a given mass of the gas and its pressure, then the law can be
written as
V ∝ 1P at constant temperature
V = kP
∴ PV = k
or P1V1 = P2V2 = k.
Boyle’s law may also be stated as, “at constant temperature the product of the’
pressure and volume of a given mass of gas is constant.”
Question 2.
State and explain Charle’s law.
Answer:
Charles’ law : At constant pressure, the volume of a given mass of gas is directly
proportional to absolute temperature.
V ∝ T at constant pressure
V = kT
VT = k
Where V is the volume and T is the absolute temperature. V1 and V2 are the initial and
final volumes of a given mass of the gas at the absolute temperatures T1 and
T2 respectively at constant pressure.
V1T1 = k; V2T2 = k
or v1T1 = V2T2 = k
Question 3.
Derive Ideal gas equation.
Answer:
Ideal gas equation : The combination of the gas laws leads to the development of an
equation which relates to the four parameters volume, pressure, absolute temperature
and number of moles. This equation is known as ideal gas equation.
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In this Boyle’s law and Charles’ law combined together and an equation obtained is
called the gas equation.
V ∝ 1p (Boyle’s law)
V ∝ T (Charles law)
V ∝ n (Avogadro’s law)
Combining above three laws, we can write
V ∝ 1p ∝ T ∝ n (or) V = R × 1P × T × n
(Or) PV = nRT
Where V = volume of the gas
P = pressure of the gas
n = no. of moles of gas
T = absolute temperature
R = Universal gas constant.
Question 4.
State and explain Graham’s law of Diffusion. (A.P. Mar.’16) (Mar.’13)
Answer:
Graham’s law of diffusion : At a given temperature and pressure, the rate of diffusion of
a gas is inversely proportional to the square root of density, vapour density or
molecular weight.
If r1 and r2 are the rates of diffusion of two gases d1 and d2 are their densities
respectively, then
r1r2 = √d2d1
This eqaution can be written as:
Comparison of the volumes of the gases that diffuse in the same time. Let V 1 and V2 are
the volumes of two gases that diffuse in the same time ‘t’.
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When time of flow is same then : r1r2 = v1v2
When volume is the same then : r1r2 = t2t1.
Applications:
• This principle is used in the separation of isotopes like U235 and U238.
• Molar mass of unknown gas can be determined by comparing the rate of
diffusion of a known gas molecular mass.
• Ansil’s alarms which are used in coal mines to detect the explosive maršh gas
works on the principle of diffusion.
Question 5.
State and explain Dalton’s law of Partial pressures.
Answer:
Dalton’s law of Partial pressures : The total pressure exerted by a mixture of chemically
non-reacting gases at given temperature and volume, is equal to the sum of the partial
pressures of the component gases.
Explanation: Consider a mixture of three gases ¡n a vessel. Let P1, P2, P3 be the partial
pressures of the three gases in the mixture. According to Dalton’s law of partial
pressures, the pressure (P) of the gaseous mixture is at the same temperature.
P = P 1 + P2 + P3
Let n1, n2, n3 be the number of moles of three gases respectively in the mixture. Let ‘V’
be the volume of the mixture of gases at T K temperature.
According to ideal gas equation,
∴ P 1 = x1 P
In a similar way P2 = x2 P and P3 = x3P
∴ Partial pressure = mole fraction × total pressure
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Question 6.
Deduce
(a) Boyle’s law and
(b) Charle’s law from Kinetic gas equation.
Answer:
a) Deduction of Boyle’s law:
Kinetic gas equation is PV = 13mnu2
PV = 13 mnu2
= 13 × 22 mnu2
= 23 × 12 mnu2
PV = 23 [Kinetic energy (KE)] [∵ KE‘n; moles = 12 mnu2]
PV = 23 KT [∵ KE = KT According to kinetic theory]
PV = 23KT
According to Boyle’s law T is constant
∴ PV = 23(constant)
∴ PV = constant
(or)
P ∝ 1V
Hence Boyle’s law proved from kinetic gas equation.
b) Deduction of Charle’s law:
Kinetic gas equation is PV = 13 mnu2
PV = 13 mnu2
= 22 × 13 mnu2
= 23 × 12 mnu2
= 23(KE) [Kinetic energy (KE) = 12 mnu2]
PV = 23KT [According to kinetic theory KE = KT]
VT = 23 × KP
According to Charles law ‘P is constant
∴ VT = constant (or) V ∝ T
Hence Charle’s law proved from kinetic gas equation.
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Question 7.
Deduce
(a) Graham’s law and
(b) Dalton’s law from Kinetic gas equation.
Answer:
a) Graham’s law: At constant temperature and pressure the rate of diffusion of a gas is
inversely proportional to the square root of its density, r ∝ 1d√
Deduction : Kinetic gas equation is
PV = 13 mnu2 = 13 mu2
u2 = 3PVM = 3d
∴ u =√ 3Pd
At constant pressure u = k. √1d
k = constant; or u ∝ √1d
∴ The rate of diffusion of gases depends upon the velocity of the gas molecules.
So r ∝√ 1d
This is Graham’s law.
b) Dalton’s law of partial pressures : The total pressure exerted by a mixture of
chemically non-reacting gases at given temperature and volume, is equal to the sum of
the partial pressures of the component gases.
Deduction :
Consider a gas present in vessel of volume = V
no. of molecules = n1
mass of each molecule = m1
RMS velocity = u1
According to kinetic gas equation the pressure of the gas. P1 = 13m1n1u21v
When this gas is replaced by another gas in the same vessel, P2 = 13m2n2u22V
When these two gases are mixed in the same vessel, the total pressure of the mixture is
P = 13m1n1u21V+13m2n2u22V = P1 + P2
∴ P = P1 + P2.
This is Dalton’s law of partial pressures.
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Question 8.
Derive an expression for Kinetic Energy of gas molecules.
Answer:
Kinetic gas equation is PV = 13mnu2
For one mole of gas ‘n’ the no.of molecules will be equal to Avagadro’s number ‘N’.
∴ m × N = ‘M’ (gram molar mass of the gas)
∴ PV = 13 Mu2
= 22 × 13 Mu2
= 23 × 12 Mu2
= 23 (K.E)
Ideal gas equation for 1 mole of gas is PV = RT
∴ 23 KE = RT
⇒ KE = 32 RT
For ‘n’ moles KE = 32 nRT
Question 9.
Define
(a) RMS
(b) average and
(c) most probable speeds of gas molecules. Give their interrelationship.
Answer:
a) RMS speed:
The square root of mean of the squares of the speeds of all molecules of a gas is
known as RMS speed (uRMS)
b) Average speed:
The arthematic mean of speeds of gas molecules is known as average speed (uav).
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c) Most probable speed:
The speed possessed by the maximum number of molecules of the gas is known as
most probable speed (ump).
ump√2RTM= √2PVM =√ 2Pd
Inter relationships : –
• ump : uav : urms = √2RTM: √8RTπM :√ 3RTM
= 1 : 1.128 : 1.224.
• uav = 0.9213 × urms
• ump = 0.8166 × urms
Question 10.
Explain the physical significance of Vander Waals paramaters.
Answer:
Vander Waals equation : [P + an2 V2] [V – nb] = nRT
Where P = Pressure of the gas
n = Number of moles of the gas
a, b = Vander Waals parameters (or) empirical parameters
V = Volume of the container
R = Gas constant
T = Absolute temperature
Units of ’a’: – bar lit-2 mole-2
Units of ’b’: – lit. mol-1
Significance : –
• ‘a’ is the measure of magnitude of inter molecular forces (attractive) with in the
gas and is independent of temperature and pressure. If ‘a’ value is high the gas
can be easily liquified.
• ‘b’ is the effective volume of the gas molecule. It indicates the effective size of the
gas molecules. If the value of ‘b’ is constant over a long range of temperature and
pressure then the gas cannot be compressed easily.
Question 11.
What is Surface Tension of liquids ? Explain the effect of temperature on the surface
tension of liquids.
Answer:
Surface tension property (γ): ‘It is defined as the force acting along the surface of a
liquid at right angles to any line of 1 unit length.”
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It is numerically and dimensionally equal to surface energy. It has dimensions kg. s-
2
and in SI unit Nm-1.
If we consider a molecule in the bulk of the liquid it experiences equal intermolecular

forces in all directions. Hence there is no net force acting on it. But a molecule at the
surface has intermolecular forces from inside only. Therefore there is a net attractive
force on it towards the interior of the liquid. Due to this the surface area of the liquid
tends to minimise. That is the molecules experience a downward force and have more
energy than the molecules in the bulk.
Surface tension decreases with increase of temperature because of increase in K,E. of
molecules and decrease in intermolecular forces,
e.g.:
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Question 12.
What is Vapour Pressure of liquids? How the Vapour Pressure of a liquid is related to its
boiling point ?
Answer:
The pressure exerted by vapour of a liquid when it is in equilibrium with liquid is known
as vapour pressure.
Effect of temperature : When the temperature of a liquid increased the average kinetic
energy of molecules increases. This increase in kinetic energy overcomes the attractive
forces between the liquid molecules so that liquid molecules rapidly escape into air.
Thus rise in temperature raises the escaping tendency of molecules. Hence the vapour
pressure of a liquid increases with increase in temperature.
The vapour pressure of a liquid increases with increase of temperature. This goes on
until the critical temperature of the liquid is reached. Above the critical temperature
liquid state does not exist when the vapour pressure of the liquid becomes equal to the
external (atmospheric) pressure the liquid is said to be boiling and the temperature at
which this happens is known as boiling point.
For water the boiling point is 100°C at 1. atm pressure. If the external pressure is
reduced, the liquid boils at lower temperature. The boiling point of a liquid can be
increased by increasing the external pressure.
Question 13.
Define Viscosity and Coefficient of Viscosity. How does the Viscosity of liquids varies
with temperature.
Answer:
Viscosity : Viscosity is a measure of resistance to flow of liquids. This arises due to
internal friction between layers of fluids as they slip past one another while liquid flows.
Coefficient of Viscosity:
The force of friction required to maintain velocity difference of 1 cm. sec-1 between two
parallel layers of a liquid 1 cm. apart and each layer having an area 1 cm2 is called
• F = ηAdudx
• Viscosity of liquids decrease with increase of temperature due to high kinetic
energy of molecules that over come the inter molecular forces.
154
Question 1.
Write notes on Intermolecular Forces.
Answer:
Intermolecular forces :
a) Ion – Dipole forces : Ion dipole forces are mainly important in aqueous solutions of
ionic substances such as NaCl in which dipolar water molecules surround the ions.
Water molecules are polar and in them hydrogen atoms possess partial positive
charges and oxygen atoms possess partial negative charges due to electronegativity
difference between hydrogen and oxygen atoms. When ionic compounds like NaCl
dissolve in water, they dissociate into component ions like Na+ and Cl–. Now the water
molecules orient in the presence of ions in such a way that the positive end of the
dipole is near an anion and the negative end of the dipole is near a cation.
b) Dipole-Dipole forces : Neutral but polar molecules experience dipole-dipole forces.
These are due to the electrical interactions among dipoles on neighbouring molecules.
These forces are again attractive between unlike poles and repulsive between like poles
and depend on the orientation of the molecules. The net force in a large collection of
molecules results from many individual interactions of both types. The forces are
generally weak and are significant only when the molecules are in close contact.
c) London dispersion forces : These forces result from the motion of electrons around
atoms. Take, for example, atoms of helium. The electron distribution around a helium
atom is for averaged over time spherically symmetrical. However, at a given instant the
electron distribution in an atom may be unsymmetrical giving the atom a short – lived
dipole moment. This instantaneous dipole on one atom can affect the electron
distribution is neighbouring atoms and induce temporary dipoles in those neighbours.
As a result, weak attractive forces develop known as London forces or dispersion forces.
155
London forces are generally small. Their energies are in the range 1 – 10k J mol-1.
d) Dipole – Induced Dipole forces : These forces are between polar molecules with
permanent dipole moments and the molecules with no permanent dipole moment.
Permanent dipole of the polar molecule induces dipole on the electrically neutral
molecule by deforming into electronic cloud.
Magnitude of these forces depends on the magnitude of the dipole moment of
permanent dipole and polarisatricity of neutral molecule. This interaction is
proportional to (1r2), where r = distance between molecules.
Question 2.
State Boyle’s law, Charle’s law and Avogadro’s law and derive Ideal gas equation.
Answer:
Boyle’s law : At constant temperature, the volume of a given mass of gas is inversely
proportional to pressure of the gas.
If ‘V is the volume of a given mass of the gas and ‘P’ its pressure, then the law can be
written as V ∝ 1P at constant temperature
V = kP
∴ PV = k or P1V1 = P2V2 = k
Boyle’s law may also be stated as, “at constant temperature the product of the pressure
and volume of a given mass of gas is constant.”
Charles’ law: At constant pressure, the volume of a given mass of gas is directly
proportional to absolute temperature.
V ∝ T at constant pressure
V = kT
TT = k
Where V is the volume and T is the absolute temperature. V1 and V2 are the initial and
final volumes of a given mass of the gas at the absolute temperatures T1 and
T2 respectively at constant pressure.
V1T1 = k ; V2T2 = k
or V1T1 = V2T2 = k
Avogadro’s law : Equal volumes of all gases contain equal number of moles at constant
temperature and pressure.
V ∝ n (pressure and temperature are constant).
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Ideal gas equation : The combination of the above gas laws leads to the development
of an equation which relates to the four parameters volume, pressure, absolute
temperature and number of moles. This equation is known as ideal gas equation.
In this Boyle’s law and Charles’ law combined together and an equation obtained called
the gas equation.
V ∝ 1P (Boyle’s law) ‘
V ∝ T (Charles law)
V ∝ n (Avogadro’s law)
Combining above three laws, we can write
V ∝ 1P ∝ T ∝ n (or) V = R × 1P × T × n
(Or) PV = nRT
Where V = volume of the gas
P = pressure of the gas
n = no. of moles of gas
T = absolute temperature
Question 3.
Write notes on diffusion of Gases.
Answer:
Diffusion : The property of gases to spread and occupy the available space is known as
diffusion.
• It is a non – directional phenomenon.
Effusion : The escape of a gas from high pressure region into space through a
fine hole is called effusion.
• It is uni directional phenomenon.
Rate of diffusion : No. of molecules diffused per unit time is called rate of diffusion.
Graham’s law of diffusion : At a given temperature and pressure, the rate of diffusion of
a gas is inversely proportional to the square root of density, vapour density or
molecular weight.
r ∝ 1d√ ; r ∝ 1VD√ ; r ∝ 1M√
If r1 and r2 are the rates of diffusion of two gases d1 and d2 are their densities
respectively, then
r1r2 = √d2 d1
This equation can be written as :
157
Comparison of the volumes of the gases that diffuse in the same time. Let V 1, and
V2 are the volumes of two gases that diffuse in the same time t’.
When time of flow is same then r1r2 = V1V2

When volume is the same then : r1r2 = t2t1
Applications :
• This principle is used in the separation of isotopes like U235 and U238.
• Molar mass of unknown gas can be determined by comparing the rate of
diffusion of a known gas molecular mass.
• Ansil’s alarms which are used in coal mines to detect the explosive marsh gas
works on the principle of diffusion.
Question 4.
State and explain Dalton’s law of Partial Pressures.
Answer:
Dalton’s law of Partial pressures : The total pressure exerted by a mixture of chemically
non-reacting gases at given temperature and volume, is equal to the sum of the partial
pressures of the component gases.
Explanation: Consider a mixture of three gases in a vessel. Let P1, P2, P3 be the partial
pressures of the three gases in the mixture. According to Dalton’s law of partial
pressures, the pressure (P) of the gaseous mixture is at the same temperature.
P = P 1 + P2 + P3
Let n1, n2, n3 be the number of moles of three gases respectively in the mixture. Let V be
the volume of the mixture of gases at T K temperature.
According to ideal gas equation,
P1 = n1RTV ; P2 = n2RTV ; P3 = n3RTV
∴ Total pressure of the mixture P = P1 + P2 + P3
P = n1RTV + n2RTV + n3RTV
P = RTV(n1 + n2 + n3)
Since nn1 + n2n2 + nn3 = n
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∴ P 1 = x1 P
In a similar way P2 = x2 P and P3 = x3P
∴ Partial pressure = mole fraction × total pressure
Question 5.
Write the postulates of Kinetic Molecular Theory of Gases.
Answer:
Assumptions:
1. Gases are composed of minute particles called molecules. All the molecules of a
gas are identical.
2. Gaseous molecules are always, at a random movement. The molecules are
moving in all possible directions in straight lines with very high velocities. They
keep on colliding against each other and against the walls of the vessel at very
small intervals of time.
3. The actual volume occupied by the molecules is negligible when compared to the
total volume occupied by the gas.
4. There is no appreciable attraction or repulsion between the molecules.
5. There is no loss of kinetic energy when the molecules collide with each other or
with the wall of vessel. This is because the molecules are spherical and perfectly
elastic in nature.
6. The pressure exerted by the gas is due to the bombardment of the molecules of
the gas on the walls of the vessel.
7. The average kinetic energy of the molecules of the gas is directly proportional to
the absolute temperature, Average K.E. ∝ T.
8. The force of gravity has no effect on the speed of gas molecules.
Boyle’s law : According to kinetic theory of gases, the pressure of a gas is due to
collisions of gas molecules on the walls of the vessel. At a particular temperature the
molecules make definite number of collisions with the walls of the vessel; When the
159
volume of the vessel is reduced the molecules have to travel lesser distance only before
making collisions on the walls. As a result the number of collisions per unit increases.
The pressure then increases, i.e., the pressure increases when the volume is reduced at
constant temperature. This explains Boyle’s law.
Charles’ law : According to kinetic theory of gases, the average kinetic energy of the
molecules is directly proportional to the absolute temperature of the gas.
K.E. ∝ T
but K.E. = 12 mc2
As temperature increases, the velocity of the molecules also increases. As a result the
molecules make more number of collisions against the walls of the vessel. This results
in an increase of pressure if the volume is kept constant. If the volume is allowed to
increase the number of collisions decrease due to the increased distance between the
molecules and the walls of the vessel. The pressure then decreases. In other words, with
rise of temperature, the volume should increase in order to keep the pressure constant.
V ∝ T at constant pressure.
This is Charles’ law.
Question 6.
Deduce gas laws from Kinetic gas equation.
Answer:
a) Deduction of Boyle’s law :
PV = 13 mnu2
= 13 × 22 mnu2
= 23 × 12 mnu2
PV = 23[Kinetic energy (KE)] [∵ KE‘n’ moles = 12 mnu2]
PV = 23KT [∵ KE = KT According to kinetic theory]
PV = 23KT
According to Boyle’s law T is constant
∴ PV = 23(constant)
∴ PV = constant
(or)
P ∝ 1V
Hence Boyle’s law proved from kinetic gas equation.
b) Deduction of Chartes law:
160
PV = 13 mnu2
= 22 × 13 mnu2
= 23 × 12 mnu2
= 23 (KE) [Kinetic Energy (KE) = 12 mnu2]
PV = 23KT [According to kinetic theory KE = KT]
VT = 23 × KP
According to Charles law P’ is constant
∴ VT = constant (or) V ∝ T
Hence Charles law proved from kinetic gas equation.
c) Graham’s law: At constant temperature and pressure the rate of diffusion of a gas is
inversely proportional to the square root of its density, r ∝ 1d√
Deduction: Kinetic gas equation is
Pv = 13 mnu2 = 13 Mu2
At constant pressure u = k. 1d√

k = constant; or u ∝ 1d√
∵ The rate of diffusion of gases depends upon the velocity of the gas molecules.
So r ∝ 1d√
This is Graham’s law.
d) Dalton’s law of partial pressures : The total pressure exerted by a mixture of
chemically non-reacting gases at given temperature and volume, is equal to the sum of
the partial pressures of the component gases.
Deduction:
Consider a gas present in vessel of volume = V
no. of molecules = n1
mass of each molecule = m1
RMS velocity = u1
According to kinetic gas equation the pressure of the gas. P1 = 13m1n1u21V
When this gas is replaced by another gas in the same vessel, p2 = 13m2n2⋅u22V
When these two gases are mixed in the same vessel, the total pressure of the mixture is
P = 13m1n1u21v + 13m2n2u22V = P1 + P2
∴ P = P 1 + P2
This is Dalton’s law of partial pressures.
161
Question 7.
Explain Maxwell-Boltzmann distribution curves of molecular speeds and give the
important conclusions. Discuss the effect of temperature on the distribution of
molecular speeds.
Answer:
According to kinetic gas equation it was assumed that all the molecules in a gas have
the same velocity. But it is not correct. When any two molecules collide exchange of
energy takes place and hence their velocities keep on changing. At any instant few
molecules may have zero velocity, a few molecules may be at high velocities and some
may be with low velocities.
The distribution of speeds between different molecules were worked out by Maxwell by
applying probability considerations.
If one plots a graph between fraction of molecules ΔNN vs velocity one gets distribution
curve of the type.
These curves are shown at different temperatures T1 T2 (T1 < T2)

The graph reveals that
1. There are no molecules with zero velocity and only very few molecules possess
the highest velocity.
2. The velocities of most of the molecules lie near a mean value.
3. As the temperature of the gas is increased, the curve becomes more flattened
and shifts towards higher velocity. It means that at higher temperature the
number of molecules possessing higher velocities is more than at lower
temperature.
162
The peak point corresponds to the most probable velocity. It is the velocity possessed
by maximum number of molecules.
The average velocity of the molecules is slightly higher than the most probable velocity.
The RMS velocity is slightly higher than the average velocity.
Question 8.
Write notes on the behaviour of real gases and their deviation from ideal behavior.
Answer:
Real gases are also called non – ideal gases; A gas which does not obey ideal gas
equation PV = nRT is called Real gas.
• Real gases show ideal behaviour at low pressure and high temperature.
The deviation of real gas from ideal behaviour can be measured in terms
compressibility factor (Z), which is the ratio of product PV and nRT. (i.e.,) Z
= PVnRT
For ideal gas, Z = 1 at all temperatures and pressures because PV = nRT. The graph of
Z Vs P will be a straight line parallel to pressure axis. For gases which deviate from
ideality, value of Z deviates from unity. At very low pressures all gases shown Z = 1 and
behave as ideal gas. At low pressures, inter molecular forces are negligible hence show
ideal behaviour. At high pressures all the gases have Z > 1. These are more difficult to
compress. At intermediate pressures, most gases have Z < 1.
Question 9.
Derive the Vander Waals equation of state. Explain the importance of Vander Waal’s
gas eqaution.
Answer:
Vander Waal’s equation of state : Vander Waal’s proposed an approximate equation of
state which involves the intermolecular interactions that contribute to the deviations of
a gas from perfect gas law. It may be explained as follows. The repulsive interactions
between two molecules cannot allow them to come closer than a certain distance.
Therefore, for the gas molecules the available volume for free travel is not the volume
of the container V but reduced to an extent proportional to the number of molecules
present and the volume of each exclude.
Therefore, in the perfect gas equation a volume correction is made by changing v to (v
– nb). Here, ‘b’ is the proportionality constant between the reduction in volume and the
amount of molecules present in the container. P = nRTV−nb If pressure is low, the
volume is large compared with the volume excluded by the molecules (V > > nb). The
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nb can be neglected in the denominator and the equation reduces to the perfect gas
equation of state.
The effect of attractive interactions between molecules is to reduce the pressure that
the gas exerts. The attraction experienced by a given molecule is proportional to the
concentration n/V of molecules in that container. As the attractions slow down the
molecules, the molecules strike the waals less frequently and strike with a weaker
impact. Therefore, we can expect the reduction in pressure to be proportional to the
square of the molar-concentration, one factor of n/V showing the reduction in
frequency of collisions and the other factor the reduction in the strength of their
impulse.
Reduction in pressure ∝ (nV)2
Reduction in pressure = a. (nv)2,
Where a = the proportionality constant.
Vander Waals equation is
The equation is called Vander Waals equation of state.

The constants ‘a’ and ‘b’ known as Vander Waals parameters (or) empirical parameters.
They depend on the nature of the gas independent of temperature.
Significance : –
• ‘a’ is the measure of magnitude of inter molecular forces (attractive) with in the
gas and is independent of temperature and pressure. If ‘a’ value is high the gas
can be easily liquified.
• ‘b’ is the effective volume of the gas molecule. It indicates the effective size of the
gas molecules. If the value of ‘b’ is constant over a long range of temperature and
pressure then the gas cannot be compressed easily.
164
Question 10.
Explain the principle underlying the liquefacation of gases.
Answer:
Liquifacation of gases can be done by decreasing the temperature and increasing the
pressure.
Liquefaction of gases: Any gas, if it to be liquefied, it must be cooled below its critical
temperature. A gas liquefies if it is cooled below its boiling point at given pressure. For
example, chlorine at room pressure say 1 atmosphere can be liquefied by cooling it to
– 34.0°C in a dry ice bath. For N2 and O2 that have very low boiling points -196°C and -
183°C. Such simple technique is not possible. Then, to liquify such type of gases the
technique based on intermolecular forces is used. It is as follows. If the velocities of
molecules are reduced to such lower values that neighbours can attract each other by
their interaction or intermolecular attractions, then the cooled gas will condense to a
liquid.
For this, the molecules are allowed to expand into available volume without supplying
any heat from outside. In this, the molecules have to overcome the attractions of their
neighbours and in doing so, the molecules convert some of their kinetic energy into
potential energy and now travel slowly. The average velocity decreases and therefore
the temperature of the gas decreases and the gas cools down compared to its
temperature before its expansion. For this the gas is allowed to expand through a
narrow opening called throttle. This way of cooling of gas by expansion from high
pressure side to low pressure is called Joule – Thomson effect.
Question 11.
Write notes on the following properties of liquids
(a) Vapour Pressure
(b) Surface Tension
(c) Viscosity.
Answer:
(a) Vapour Pressure : The pressure exerted by vapour of a liquid when it is in
equilibrium with liquid is known as vapour pressure.
Effect of temperature : When the temperature of a liquid increased the average kinetic
energy of molecules increases. This increase in kinetic energy overcomes the attractive
forces between the liquid molecules so that liquid molecules rapidly escape into air.
165
Thus rise in temperature raises the escaping tendency of molecules. Hence the vapour
pressure of a liquid increases with increase in temperature.
The vapour pressure of a liquid increases with increase of temperature. This goes on
until the critical temperature of the liquid is reached. Above the critical temperature
liquid state does not exist when the vapour pressure of the liquid becomes equal to the
external (atmospheric) pressure the liquid is said to be boiling and the temperature at
which this happens is known as boiling point.
For water the boiling point is 100°C at 1. aim pressure. If the external pressure is
reduced, the liquid boils at lower temperature. The boiling point of a liquid can be
increased by increasing the external pressure.
b) Surface tension property (γ) : “It is defined as the force acting along the surface of a
liquid at right angles to any line of 1 unit length.”
It is numerically and dimensionally equal to surface energy. It has dimensions kg. s-
2
and in SI unit Nm-1
If we consider a molecule in the bulk of the liquid it experiences equal intermolecular

forces in all directions. Hence there is no net force acting on it. But a molecule at the
surface has intermolecular forces from inside only. Therefore there is a net attractive
force on it towards the interior of the liquid. Due to this the surface area of the liquid
tends to minimise. That is the molecules experience a downward force and have more
energy than the molecules in the bulk.
Surface tension decreases with increase of temperature because of increase in K, E. of
molecules and decrease in intermolecular forces.
e.g.:
166
c) Viscosity : Viscosity is a measure of resistance to flow of liquids.
Coefficient of Viscosity:
The force of friction required to maintain velocity difference of 1cm. sec-1 between two
parallel layers of a liquid 1 cm. apart and each layer having an area 1cm2 is called
• F = η A dudx
• Viscosity of liquids decrease with increase of temperature due to high kinetic
energy of molecules that over come the inter molecular forces.
Solved Problems
Question 1.
What will be the minimum pressure required to compress 500 dm3 of air at 1 bar to 200
dm3 at 30°C?
Solution:
Formula:
P1y1 = P2y2
P1 = 1 bar
V1 = 500 dm3
V2 = 200 dm3
P2 = ?
1 × 500 = P2 × 200
P2 = 52 = 2.5 bar.
Question 2.
A vessel of 120 mL capacity contains a certain amount of gas at 35°C and 1.2
bar pressure. The gas is transferred to another vessel of volume 180 mL at
35 °C. What would be its pressure ?
Solution:
Formula:
167
P1V1 = P2V2
P1 = 1.2 bar
V1 = 120 ml
V2 = 180 ml
P2 = ?
1.2 × 120 = P2 × 180
P2 = 1.2×1218
= 2.43 = 0.8 bar
Question 3.
Using the equation of state pV = nRT; show that at a given temperature
density of a gas is proportional to gas pressure p.
Solution:
Consider the equation of state .
PV = nRT
PV = wMRT
P = WV×RTM
P = dRTM (∵ d = wV)
From the above relation
P∝d
Question 4.
At 0°C, the density of a certain oxide of a gas at 2 bar is same as that of dinitrogen at 5
bar. What is the molecular mass of the oxide?
Solution:
• Given two gases one is unknown oxide and another one is dinitrogen.
• Density of two gases is same
168
Question 5.
Pressure of 1 gm. of an ideal gas A at 27 °C is found to be 2 bar. When 2 g of another
ideal gas B is introduced in the same flask at same temperature the pressure becomes
3 bar. Find a relationship between their molecular masses.
Solution:
Given
Weight of gas A = 1 gm
Weight of gas B = 2 gms
Molecular mass of A = MA
Molecular mass of B = MB
Pressure of A = PA = 2 bar
Given Total pressure = 3 bar (PA + PB)
∴ PB = 3 – 2 = 1 bar
Question 6.
The drain cleaner, Drainex contains small bits of aluminum which react with caustic
soda to produce dihydrogen. What volume of dihydrogen at 20°C and one bar will be
released when 0.15 g of aluminium reacts?
Solution:
Chemical equation is
2Al + 2 NaOH + 2H2O → 2 NaAlO2 + 3H2
From the above equation
2 gram atom of Al liberates 3 moles of H2 at NTP
2 × 27 gms Al liberates 3 × 22.4 lit.
0.15 gms of Al liberates?
= 0.15×3×22.42×27
169
= 0.1866 li.t = 186.6 ml
P1 = 1.013 bar P2 = 1 bar
V1 = 186.6 ml V2 = ?
T1 = 273 K T2 = 20° C = 293 K
Formulae:
Question 7.
What will be the pressure extracted by a mixture of 3.2 g of methane and 4.4 g of
carbon dioxide contained in a 9 dm3 flask at 27 °c?
Solution:
Formula:
Given 3.2 gmš of CH4
no.of moles of CH4 = wt GMW = 3.216 = 0.2
no.of moles of CO2 = 4.444 = 0.1
∴ n = nCH4 + nCO2
= 0.2 + 0.1 = 0.3
R = 8.314
T = 27°C = 300 K
V = 9 dm3
PV = nRT
P = nRTV
= 0.3×8.314×3009 = 83.14
= 83.14 × 103 pa
= 83.14 × 104 pa
∴ P = 8.314 × 104 pa
170
Question 8.
What will be the pressure of the gaseous mixture when 0.5 L of H2 at 0.8 bar and 2.0 L
of dioxygen at 0.7 bar are introduced in a 1 L vessel at 27°C?
Solution:
Case – I
Hydrogen gas
P1 = 0.8 bar
P2 = ?
V1 = 0.5 lit
V2 = 1.0 lit
P1y1 = P2V2
P2 = 0.8×0.51
P2 = 0.4 bar
Partial pressure of H2 = 0.4 bar. [PH2]
Case-II:
Oxygen gas
P1 = 0.7 bar
V1 = 2 lit
V2 = 1.0 lit
P2 = ?
P1V1 = P2V2
P2 = P1V1V2=0.7×21
= 1.4 bar
Partial pressure of O2 = 1.4 bar. [PO2]
∴ Total pressure = PH2 + PO2
= 0.4 + 1.4 = 1.8 bar
Question 9.
Density of a gas is found to be 5.46 g/dm3 at 27 °c at 2 bar pressure. What will be its
density at STP?
Solution:
d1 = 5.46 gm/dm3
T1 = 27° C = 300 K
P1 = 2 bar
P2 = 1.013 bar (STP)
171
T2 = 273 K(STP)d2 = ?
Question 10.
34.05 mL of phosphorus vapour weighs 0.0625 g at 546 °c and 0.1 bar pressure. What is
the molar mass of phosphorus ?
Solution:
P = 0.1 bar
W = 0.0625 gms
R = 0.083 bar dm3 k-1 mol-1
V = 34.05 × 10-3 lit
T = 546°C = 819 K
Formula:
PV = nRT
PV = wMRT
0.1 × 34.05 × 10-3 = 0.0625M × 0.083 × 819
M = 0.0625×0.083×8190.1×34.05×10−3
= 0.0625×83×81934.05
= 124.77 gm/mole.
172
Question 11.
A student forgot to add the reaction mixture to the round bottomed flask at 27 °C but
instead he/she placed the flask on the flame. After a lapse of time, he realized his
mistake and using a pyrometer he found the temperature of the flask was 477 °C. What
fraction of air would have been expelled out ?
Solution:
Formula:
T1 = 27° C – 300 K
T2 = 477° C = 750 K
V1T1 = V2T2
V1300 = V2750
V2 = 750×V1300
V2 = 2.5 V1
The volume of air expelled = V2 – V1
= 2.5V1 – V1
= 1.5V1
Fraction of air expelled out
= 1.5 V12.5 V1 = 1.52.5 = 1525 = 35
Question 12.
Calculate the temperature of 4.0 mol of a gas occupying 5 dm3 at 3.32 bar.
(R = 0.083 bar dm3 k-1 mol-1)
Solution:
Formulae: —
P = 3.32 bar
V = 5 dm3
R = 0.083 bar dm3 k-1 mol-1
n = 4 moles
PV = nRT
T = PVnR
= 3.32×54×0.083
= 16.60.332
= 50
∴ T = 50 k
173
Question 13.
Calculate the total number of electrons present in 1.4 g of dinitrogen gas.
Solution:
14 gms of N2 gas contains
6.023 × 1023 atoms
1.4 gms of N2 gas contains
6.023 × 1022 atoms
Each ‘N’ atom contains 7 electrons.
∴ Number of electrons present in 1.4 gms of Nitrogen
= 6.023 × 1022 × 7
= 42.161 × 1022
= 4.2161 × 1023 electrons.
Question 14.
How much time would it take to distribute one Avogadro number of wheat grains, if
1010 grains are distributed each second ?
Solution:
Given that
1010 grains are distributed in each second i.e., one second Avagodro number means
6.023 × 1023
6.023 × 1023 grains distributed in ?
X seconds
x = 6.023×10231010 = 6.023 × 1013 seconds
The time taken to distribute the one Avagadro number of grains
= 6.023×101360×60×24×365
= 6.023×10133.153×107 = 1.909 × 10 years.
6
174
Question 15.
Ammonia gas diffuses through a fine hole at the rate 0.5 lit min-1. Under thé same
conditions find the rate of diffusion of chlorine gas.
Solution:
Rate of diffusion of ammonia (r1)
= 0.5 lit min-1
Molecular weight of ammonia (M1) = 17
Rate of diffusion of chlorine (r2) = ?
Molecular weight of chlorine (M2) = 71
According to Graham’s law of diffusion
∴ Rate of diffusion of Cl2 = 0.245 lit/min.
Question 16.
Find the relative rates of diffusion of CO2 and Cl2 gases.
Solution:
175
Question 17.
If 150 mL carbon monoxide effused in 25 seconds, what volume of methane would
diffuse in same time?
Solution:
Rate of diffusion of CO (r1)
Molecular weight of CO (M1) = 28

Rate of diffusion of methane (r2)
Molecular weight of methane (M2) = 16

According to Graham’s law of diffusion
Question 18.
Hydrogen chloride gas is sent into a 1oo metre tube from one end ‘A’ and ammonia
gas from the other end ‘B’, under similar conditions. At what distance from ‘A’ will be
the two gases meet?
Solution:
The two gases HCl and NH3 diffuse into the pipe from the ends A and B respectively to
meet at a point O as indicated by formation of white ring of NH4Cl. If the distance AO is
x meters, the distance OB will be (100 – x) metres.
According to Graham’s law of diffusion. Ration of rates of diffusion of HCl and NH3 gas
is given by
735 mm×101.3kPa1760 mm = 98 k Pa
It means that the two gases meet at the point O such that the ratio of the distances
from the end A to O and B to O is 0.68 : 1.00
∴ 0.681 = x(100−x)
176
or 0.68 (100 – x) = x or 68 – 0.68 x = x
or 68 = x + 0.68 x or 68 = x (1 + 0.68)
= 1.68 x
x = 681.68 = 40.48 metres.
Hence, the two gases meet at a distance of 40.48 metres from the end ‘A’.
Question 19.
Calculate the total pressure in a mixture of 8 g of dioxygen and 4 g of dihydrogen
confined in a vessel of 1 dm3 at 27°C. R = 0.083 bar dm3 K-1 mol-1.
Solution:
Formula:
Question 20.
Calculate the total pressure in a mixture of 3.5g of dinitrogen 3.0g of dihydrogen and
8.0g dioxygen confined in vessel of 5 dm3 at 27°C (R = 0. 083 bar dm3 k-1 mol-1)
Solution:
Formula:
V = 5 dm3
177
Question 21.
Pay load is defined as the difference between the mass of displaced air and the mass of
the balloon. Calculate the pay load when a balloon of radius 10m, mass 100 kg is filled
with helium at 1.66 bar at 27°C. (Density of air = 1.2 kg m-3 and R = 0.083 bar dm3 k-
1
mol-1).
Solution:
Formula :
r = 10 m
m = 100 kg
T = 27° C = 300 K
d = 1.22 kg/m3
Volume of the ballon = 43πr3
= 43×227×103
= 4190.5 m3
P = 1.66 bar
T = 300 K
V = 4190.5 m3
R = 0.083 bar dm3 k-1 mol-1
PV = nRT
n = PVRT = 1.66×4190.50.083×10−3×300
= 2793.70 moles
= 0.083 × 10-3 bar m3k-1mol-1
∴ Weight of 279370 moles of He
= 279390 × 41000
= 1117.48 kg
Total weight of balloon = 100 + 1117.48
= 1217.48 kg
Maximum weight of He = V × d
=4190.5 × 1.2
= 5028.6 kg
∴ Payload = 5028.6 – 1219.48
= 3811.12 kg.
178
Question 22.
Calculate the volume occupied by 8.8 g of CO2 at 31 .1°C and 1 bar pressure. R = 0.083
bar L K-1 mol-1.
Solution:
Formula:
Question 23.
2.9 g of a gas at 95 °C occupied the same volume as 0.184 g of dihydrogen at 17°C, at
the same pressure. What is the molar mass of the gas?
Solution:
Given unknown gas and dihydrogen
For unknown gas
V1 = V
n1 = 2.9 m
T1 = 95° C = 368 K
P1V1 = n1RT1
P1 = n1RT1V1
= 2.9m×R×368
Question 24.
A mixture of dihydrogen and dioxygen at one bar pressure contains 20% by weight of
dihydrogen. Calculate the partial pressure of dihydrogen.
Solution:
Given 20% by wt of dihydrogen so 80% oxygen remained for dihydrogen
n = wt GMwt = 0.22 = 0.1
179
For dioxygen
n = wt GMwt = 0.832 = 0.025
mole fraction of H2
= 0.10.1+0.025 = 0.10.125 = 0.8
Partial pressure of dihydrogen
= mole fraction of H2 × Ptotal
= 0.8 × 1 = 0.8 bar
Question 25.
What would be the SI unit for the quantity PV2 T2n?
Solution:
Given quantity PV2 T2n = N/m2( m3)2( K)2 mole
= N × mole-1m4k2
∴ The given quantity has SI units Nm4k2 mole-1.
Question 26.
In terms of Charles’ law explain why — 273°C is the lowest possible temperature.
Solution:
According to Charles law if we put the value of t = -273°C
in the equation Vt = V0 [273.15+t273.15].
In this case the volume of the gas becomes zero.
V0 = Volume at 0° C
Vt = Volume at t° C
• This means the gas will not exist
• In fact all gases liquified before this temperature.
Question 27.
Critical temperature for carbon dioxide and methane are 31.1°C and – 81.9°C
respectively. Which of these has
stronger intermolecular forces and why?
Solution:
Given Critical temperatures of CO2, CH4
180
TC (CO2) = 31.1°C
TC (CH4) = -81.9°C
• The gas with highest critical temperature value can be easily liquified because of
high inter molecular forces.
∴ TC(CO2) is very high.
So CO2 gas liquified easily.
• ‘He’ gas has low T value so it is highly difficult to liquify.
Question 28.
Air is cooled form 25°C to 0°C. Calculate the decrease in rms speed of the molecules.
Solution:
181
Question 29.
Find the RMS. average and most probable speeds of O2 at 27°c.
Solution:
uaverage = 0.9213 × urms

= 0.9213 × 4.835 × 104
= 4.455 × 104 cm/sec.
ump = 0.8166 × urms
= 3.948 × 104 cm/sec.
Question 30.
Give the values of Gas constant ‘R’ in different units.
Answer:
R = 0.0821 lit. atm. K-1 .mol-1
= 8.314 J.K-1. mole-1
= 1.987 (or) 2 cal.K-1.mol-1
= 8.314 × 107 erg.K-1.mol-1
182
Question 1.
How many number of moles of glucose are present in 540 gms of glucose ?
Answer:
Formulae:
No. of moles = Weight G.M. Wt
= 540180
=3
Given
Weight of glucose = 540 gms
G.M. wt = 180 (C6H12O6)
No. of moles of glucose in 540 gms = 3 moles.
Question 2.
Calculate the weight of 0.1 mole of sodium carbonate.
Answer:
Formulae:
No. of moles = Weight GMWt, 0.1 = Weight 106
Weight = 10.6 × 0.1 = 10.6 gms
Given
No. of moles = 0.1
G.M. Wt of Na2CO3 = 106
Question 3.
How many molecules of glucose are present in 5.23g of glucose (Molecular weight of
glucose 180 u).
Answer:
Formulae:
No. of molecules = No. of moles × Avagadro no
No. of moles = Weight GM Wt = 5.23180 = 0.02906 moles
No. of molecules = 0.02906 × 6.023 × 1023
183
= 1.75 × 1022 molecules
Given
Wt of glucose = 5.23 gms
G.M. Wt = 180
Question 4.
Calculate the number of molecules present in 1.12 × 10-7 c.c. of a gas at STP (c.c. cubic
centimeters = cm3).
Answer:
1 mole of any gas occupies 22400 cc of volume
1 mole of any gas contains 6.023 × 1023 molecules
∴ 22400 cc of gas at STP contains 6.023 × 1023 molecules
1.12 × 10-7 cc of a gas at STP contains ——–?
1.12×10−7×6.023×102322400 = 3.015 × 1012 molecules
Question 5.
The empirical formula of a compound is CH2O. Its molecular weight is 90. Calculate the
molecular formula of the compound. (A.P. Mar. ‘16) (Mar. 13)
Answer:
Formulae:
∴ Molecular formula = 3(CH2O) = Cr (NO3)3(aq) + Pb(s).

Given
Molecular wt = 90
Emperical formula = CH3O
∴ Emperical wt = 30
Question 6.
Balance the following equation by the oxidation number method
Cr(S) + Pb(NO3)2(aq) → Cr (NO3)3(aq) + Pb(s).
Answer:
So the balanced equation is 2Cr + 3Pb(NO3)2 → 2Cr(NO3)3 + 3Pb

184
Question 7.
What volume of H2 at STP is required to reduce 0.795 g of CuO to give Cu and H2O.
Answer:
Balance equation is
CuO + H2 → Cu + H2O
79.5 gms → 1 mole H2 gas for reduction → 22.4 lit of volume at STP
∴ 79.5 gms of CuO require 22.4 lit of H2 at STP
Then 0.795 gms of CuO require ——-?
0.795×22.479.5 = 0.224 lit.
Question 8.
Calculate the volume of O2 at STP required to completely burn 100 ml of acetylene.
Answer:
Balanced chemical equation for combustion of acetylene is
2C2H2 + 5O2 → 4CO2 + 2H2O
2 moles of C2H2 require 5 moles of O2 for complete combustion at STP
2 × 22400 ml of C2H2 require 5 × 22400 ml of O2 at STP
Then 100 ml of C2H2 require ————?
100×5×224002×22400 = 5002 = 250 ml
Question 9.
Now-a-days it is thought that oxidation is simply decrease in electron density and
reduction is increase in electron density. How would you justify this?
Answer:
Oxidation : The process of removing electrons from an element is called oxidation. It is
also called
as de-electronation.
• Oxidation means decrease in electron density
e.g. : 2Cl– → Cl2 + 2e⊖
• Oxidation process occurs at anode in the electrolysis process.
• Reduction : The process of addition of electrons to an element is called reduction.
It is also called as electronation.
• Reduction means increase in electron density.
e.g.: Mg2+ + 2e– → Mg
• Reduction process occurs of cathode in the electrolysis process.
185
Question 10.
What is a redox concept? Give an example.
Answer:
Redox reactions are the reactions in which reduction and oxidation both takes place.
e.g.:
Question 11.
Calculate the mass per cent of the different elements present in sodium sulphate
(Na2SO4).
Answer:
Given compound is sodium sulphate (Na2SO4)
Molecular weight of the compound = 2(23) + 1(32) + 4(16)
= 46 + 32 + 64
= 142
Step – I:
Mass percent of Na
142 gms of Na2SO4 → 46 gms of Na
100 gms of Na2SO4 → ?
100×46142 = 32.39%
Step – II:
Mass percent of ‘S’
142 gms of Na2SO4 → 32 gms of ‘S’
100×32142 = 22.53%
Step-III:
Mass percent of ‘0’
142 gms of Na2SO4 → 64 gms of oxygen
100×64142 = 45.07%
∴ Mass percents of Na, S, O are 32.39, 22.53, 45.07.
186
Question 12.
What do you mean by significant figures?
Answer:
The meaningful digits which are known with certainty are called significant figures.
• The uncertainty in the experimental (or) calculated values is indicated by
mentioning the number of significant figures.
Question 13.
If the speed of light is 3.0 × 108 ms-1. Calculate the distance covered by light in 2.00 ns.
Answer:
Given the speed of light 3 × 108 m/sec.
i.e., 1 sec → 3 × 108 m
In 2 nano seconds → ?
2 × 10-9 sec
2×10−9×3×1081 = 6 × 10-1 = 0.6 m
Question 1.
The approximate production of sodium carbonate per month is 424 × 108 g, while that
of methyl alcohol is 320 × 106 g. Which is produced more in terms of moles?
Answer:
Given that weight of Na2CO3 produced per month = 424 × 106 gms
No. of moles of Na2CO3 = wt GMwt = 424×106106 = 4 × 106 moles per month
Given weight of CH3OH produced per month = 320 × 106 gms
No. of moles of CH3OH = = 320×10632 = 107 moles per month
Methyl Alcohol is produced more (per month) in terms of moles.
Question 2.
How much minimum volume of CO at STP is needed to react completely with 0.112 L
of O2 at 1.5 atm pressure and 127°C to give CO2.
Answer:
Formula P1V1T1 = P2V2T2
At STP
P1 = 1 atm
V1 = ?
T1 = 0°C = 273 K
187
Given P2 = 1.5 at m
V2 = 0.112 lit
T2 = 127°C = 400 K
1×V1273 = 1.5×0.112400
V1 = 1.5×0.112×273400
= 0.1147 lit
Chemical equation
2CO + O2 → 2CO2
2 moles of CO → 1 mole of O2 at STP
2 × 22.4 lit → 1 × 22.4 lit
? ← 0.1147 lit
0.1147×2×22.422.4 = 0.2294 lit
The volume of CO required at STP = 0.2294 lit = 229.4 ml
Question 3.
Chemical analysis of a carbon compound gave the following percentage composition
by weight of the elements present, carbon = 10.06%, hydrogen = 0.84%. chlorine =
89.10%. Calculate the empirical formula of the compound.
Answer:
∴ Emperical formula of given compound = C1H1Cl3

= CHCl3
188
Question 4.
A carbon compound on analysis gave the following percentage composition, carbon 14.5%,
hydrogen 1.8%, chlorine 64.46%, oxygen 19.24%. Calculate the empirical formula of the
compound.
Answer:
∴ The formula of the compound = C1 H1.5 Cl1.5 O1

Emperical formula of the compound = C2 H3 Cl3 O2
Question 5.
Calculate the empirical formula of a compound having percentage composition : Potassium (K)
= 26.57, chromium (Cr) = 35.36; oxygen (0) 38.07. (Given the atomic weights of K. Cr and O as
39; 52 and 16 respectively).
Answer:
Formula of the compound = K1 Cr1 O3.5

Emperical formula of the compound = K2 Cr2 O7
189
Question 6.
A carbon compound contains 12.8% carbon, 2.1% hydrogen, 85.1% bromine. The molecular
weight of the compound is 187.9. Calculate the molecular formula.
Answer:
∴ Emperical formula of the compound = C1 H2 Br

Molecular formula = n (Emperical formula)
Given molecular wt = 187.9

Emperical wt = 94 (CH2 Br)
∴ Molecular formula = 2 (CH2Br)
= C2H4Br2
Question 7.
0.188 g of an organic compound having an empirical formula CH2Br displaced 24.2 cc. of air at
14 °C and 752 mm pressure. Calculate the molecular formula of the compound. (Aqueous
tension at 14°C is 12mm).
Answer:
Given Emperical formula CH2Br
Wt. of compound = 0.188 gms
Volume of displaced air = 24.2 CC
Temperature = 14°C = 287 K
Pressure = 752 mm.
STP conditions
P1 = 760 mm
v1 = ?
T1 = 273 K
Given conditions
P2 = Pressure – aqueous tension
190
= 752 – 12mm = 740 mm
V2 = 24.2K
T2 = 287 K
Formula
P1V1T1 = P2V2T2 ⇒ 760×V1273 = 740×24.2287
V1 = 740×24.2287×273760 = 22.414ml (or) 22.414 CC
∴ 0.188 gms of organic compound displaced 22.414 CC of air gms of organic compound
displaced 22400 CC of air
2240022.414×0.188 = 188 ∴ Gram molecular wt of compound = 188
Molecular formula = n (Emperical formula)
= n (CH2Br)
n = Molecular wt Emperical wt = 18894 = 2 ∴ Molecular formula = C2 H4 Br2
Question 8.
Calculate the amount of 90% H2S04 required for the preparation of 420 kg HCl.
2 NaCl + H2SO4 → Na2SO4 + 2 HCl
Answer:
Given equation is
2NaCl + H2SO4 → 4 Na2SO4 + 2HCl
1 Mole H2SO4 → 2 Moles HCl
98 gms of H2SO4 → 2 × 36.5 = 73 gms of HCl
? → 420 × 103 gms of HCl
420×103×9873 = 563.84 × 103 gms
For 100% H2SO4 → 563.84 × 103
For 90% H2SO4 → 563.84 × 103 × 10090
= 626.5 × 103 gms of H2SO4
∴ 626.5 × 103 gms of 90% H2SO4 is required to produce 420 × 103 gms of HCl
Question 9.
An astronaut receives the energy required in his body by the combustion of 34g of sucrose per
hour. How much oxygen he has to carry along with him for his energy requirement in a day ?
Answer:
Given sucrose quantity required per hour = 34 gms
Sucrose quantity required per a day = 34 × 24 gms
Chemical equation of combustion of sucrose
C12 H22 O11 + 12O2 → 12CO2 + 11 H2O + Energy
1 mole sucrose → 12 moles of Oxygen
342 gms of sucrose → 12 × 32 gms of oxygen
34 × 24 gs of sucrose → ?
191
34×24342 × 12 × 32 = 916.21 gms
∴ The astronaut require 916.21 gms of Oxygen per a day
Question 10.
What volume of CO2 is obtained at STP by heating 4g of CaCO3 ?
Answer:
Chemical Equation is
CaCO3 CaO + CO2
1 mole CaCO3 → 1 mole CO2 at STP
100 gms of CaCO3 → 22.4 lit of CO2 at STP
4gms of CaCO3 → ?
4×22.4100 = 0.896 lit
Question 11.
When 50g of a sample of sulphur was burnt in air 4% of the sample was left over. Calculate the
volume of air required at STP containing 21% oxygen by volume.
Answer:
Given that when a 50 gms of sample of sulphur was burnt 4% of the sample was left over.
∴ 50 gms of S → 48 gms of ‘S’ burnt.
Chemical equation is S + O2 → SO2
32 gm of ‘S’ 22.4 lit of O2 at STP
48 gms of S →
100 ml air contains 21 ml of oxygen
100 lit of air contains 21 lit of oxygen
33.6 lit of oxygen is present in 33.6×10021 = 160 lit
∴ The volume of air needed for combustion = 160 lit
Question 12.
Calculate the volume of oxygen gas required at STP conditions for the complete combustion of
10 cc of methane gas at 20°C and 770 mm pressure.
Answer:
Given 10 cc of methane (CH4) undergoes combustion at 20°C and 770 mm pressure
STP Conditions
P1 = 760 mm
V1 = ?
T1 = 273 k
Given conditions
P2 = 770 mm
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V2 = 10 cc
T2 = 20°C = 293 k
Formulae
P1V1T1 = P2 V2 T2
760×V1273 = 770×10293
V1 = 770×10×273293×760 = 9.44 cc ∴ Volume of methane (CH4) at STP = 9.44 cc.
CH4 + 2O2 → CO2 + 2H2O
1 mole CH4 → 2 moles of oxygen
22,400 cc of CH4 → 2 × 22400 cc of oxygen
9.44 cc of CH4 → ?
9.4422400 × 2 × 22400 = 18.88 cc ∴ Volume of oxygen gas required STP = 18.88 cc.
Question 13.
Calculate the volume of H2 liberated at 27°C and 760 mm of Hg pressure by action by 0.6g of
magnesium with excess of dil HCl.
Answer:
Mg + 2HCl → MgCl2 +H2
24 gms. of Mg → 1 mole of H2 at STP
= 22.4 lit at STP
0.6 gms. of Mg → ?
0.6×22.424 = 0.56 lit = 560 ml
Formula
P1V1T1 = P2V2T2
760×V1300 = 760×560273
V1 = 560×300273 = 615.4 ml
∴ volume of H2 liberated at 27°C and 760 mm of presence = 615.4 ml = 0.6154 Lit.
Given conditions
P1 = 760 mm
V1 = ?
T1 = 27° mm
STP conditions
P2 = 760 mm
V2 = 560 ml
T2 = 0° C = 273 k
193
Question 14.
Explain the role of redox reactions in titrimetre processes and galvanic cells.
Answer:
a) Redox reactions in titrimetric quantitative analysis : In titrimetric analysis the substance of
known concentration is called the titrant and the substance being titrated is called the titrand.
The standard solution is generally added from a long graduated tube called burette. The
process of adding the standard solution until the reaction is just complete is called titration.
The substance to be estimated is titrated. The point at which the titrand just completely reacts
is called the equivalence point (or) the theoretical point (or) stoichiometric end point. In the
redox reactions the completion of the titration is detected by a suitable method like
1. Observing a physical change, for example, the light pink colour of KMnO4 titrations.
2. By using a reagent known as indicator which gives a clear visual change like colour
change, formation of turbidity etc. The point at wh’ch this is observed is called the end
point of the titration which should coincide with theoretical end point.
Examples:
1. In Cr2O2−7 titrations dippenyl amine is used as indicator and at the end poirtt it
produces intense blue colour due to oxidation by Cr2O2−7.
2. In the titration of Cu+2 with I–
2Cu2+ (aq) + 4I– (aq) → Cu2I2 (s) + I2 (aq)
A redox reaction I2 gives a deep blue colour with starch solution.
3. In the titration of I2 (aq) S2O−23 as per the stoichiometric reduce equation.
In this way redox reactions are taken as the basis for titrimetric analysis with MnO−4,
Cr2O−27 etc., as oxidising agents and S2O−3 etc., as a reducing agents,
b) Redox Reactions – Galvanic cells : Redox reaction (i.e) cell reaction that takes place in
gavamic cell is
The process of transfer of electrons from Zn(s) to Cu+2 take place directly. To make this transfer
indirectly, Zn rod is kept in ZnSO4 solution in one beaker and in the other beaker
CuSO4 solution is taken and a copper rod is dipped in it. Now the redox reaction takes place in
either of the beakers. Each beakers contains both oxidised and reduced forms of the
respective species in the beakers containing CuSO4 solution & Cu rod at the interface Cu and
Cu+2 and in the other beaker at the interface Zn and Zn+2. The two forms i.e., oxidised and
reduced forms of a species participating in oxidation and reduction half reactions is called
redox couple. Both the beakers contains each a redox couple. The oxidised form and reduced
194
form are separated by a vertical line (or) a slash that represent an interface, e.g.: Zn (s) /
Zn+2 (aq)
In the above arrangement, the two redox couples are represented by Zn+2 / Zn and Cu+2 / Cu.
halvamic cell is represented as : Zn/Zn2+//Cu+2/Cu.
Question 15.
Define and explain molar mass.
Answer:
Molar mass : The mass of one mole of any substance in gms is called its molar mass,
e.g. :
1. Molar mass of sulphuric acid = 98 g
2. Molar mass of hydrogen is one gram for gram atomic mass and two grams for gram
molecular mass.
Question 16.
What are disproportionation reactions ? Give example. (T.S. Mar. ’16)
Answer:
Disproportionation Reaction : Reactions in which same element in the given form to undergo
both oxidation and reduction simultaneously.
Here Cl2 undergoes both oxidation and reduction reactions. So, above reaction is
disproportionation reaction.
Question 17.
What are comproportionation reactions ? Give example.
Answer:
Comproportionation reactions : In these reactions, two species with the same element in two
different oxidation states form a single product in which the element is in an intermediate
oxidation state. Reverse of disproportionation is comproportionation.
e.g.:
195
Question 18.
Determine the empirical formula of an oxide of iron which has 69.9% iron and 30.1% dioxygen
by mass.
Answer:
∴ Formula of compound = Fe1O1.5

Emperical formula = Fe2O3
Question 19.
Calculate the mass of sodium acetate (CH3COONa) required to make 500 ml of 0.375 molar
aqueous solution. Molar mass of sodium acetate is 82.0245 g mol-1.
Answer:
Formula
Molarity = WtGMwt × 1000V(ml)
Molarity = 0.375M
V = 500 ml
GMwt of CH3COONa = 82.0245
0.375 = Wt82.0245 × 1000500
Wt = 82.0245×0.3752
= 15.3795 gms
∴ Mass of CH3COONa required = 15.3795 gms
Question 20.
What is the concentration of sugar (C12H22O11) in mol L-1 if 20g are dissolved in enough water to
make a final volume up to 2L ?
Answer:
Formula
Molarity = WtGMWt×1V( lit )
= 20342×12
= 0.02924 M
Wt = 20 gms
GMWt = 342
[C12H22OH]
V = 2 lit
196
Question 21.
How many significant figures are present in the following ?
1. 0.0025
2. 208
3. 5005
4. 126,000
5. 500.0
6. 2.0034
Answer:
1. 0.0025 has 2 significant figures
2. 208 has 3 significant figures
Question 22.
Round up the following upto three significant figures :
1. 34.216
2. 10.4107
3. 0.04597
4. 2808
Answer:
1. 34.216 becomes 34.2
2. 10.4107 becomes 10.4
3. 0.04597 becomes 0.046
4. 2808 becomes 281
Question 23.
Calculate the molarity of a solution of ethanol in water in which the mole fraction of ethanol is
0.040 (assume the density of water to be one)
Answer:
The relation between Molarity and mole fraction is given by
Given data, x2 = 0.040, M = ?

M1 = 18(H2O), M2 = 46 (C2H5OH), Cl = 1
0040 = M×18M(18−46)+1000×1 = M×18−28M+1000
18 M = -0.040 × M × 28 + 0.040 × 1000
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18 M = -1.12M + 40
(18 + 1.12)M = 40
19.12 M = 40
M = 4019.12 = 2 09 M ∴ Molarity of Ethanol = 2.09 M
Given data
Question 24.
A welding fuel gas contains carbon and hydrogen only. Burning a small sample of it in oxygen
gives 3.38 g carbon dioxide, 0.690 g of water and no other products. A volume of 10.0 L
(measured at STP) of this welding gas is found to weigh 11.6 g. calculate
(i) empirical formula,
(ii) molar mass of the gas and
(iii) molecular formula.
Answer:
Assuming 1 gm. of gas is burnt
The weight % of ‘C’ = 3.38×1244 × 100 = 92.18%
The weight % of ‘H’ = 0.69×218 = 7.67%
i)
Experical formula of compound = C1H1

ii) Given 10 lit of gas at STP weighs – 11.6 gas
22.44 lit of gas at STP weights = 22.4×11.610 = 25.984
∴ Molecular weight of given gas = 25.984
iii) Molecular formula = n(emperical formula)
n = Mol. wt Emp. wt = 25.98413 = 2 ∴ Molecular formula = 2(CH) = C2H2.
198
Question 25.
Calcium carbonate reacts with aqueous HCl to give CaCl2 and CO2 according to the reaction
CaCO3(5) + 2 HCl(aq) → CaCl2(aq) + CO2(g) + H2O (L). What mass of CaCO3 is required to react
completely with 25 mL of 0.75 M HCl?
Answer:
Given chemical reaction
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)
Molarity = WtGMWt×1000 V( m)
0.75 = Wt36.5×100025
M = 0.75 M
W=?
Wt = 0.75×36.5×251000
= 0.6844 gms of HCl
GMwt = 36.5
V = 25 ml
From the equation
1 mole of CaCO3 – 2 moles of HCl
100 gms of CaCO3 – 2 × 36.5 gms of HCl
? – 0.6844 gms of HCl
∴ Mass of CaCO3 = 0.68442×36.5 × 100 = 0.937 5 gms
Question 26.
Chlorine is prepared in the laboratory by treating manganese dioxide (MnO2) with aqueous
hydrochloric acid according to the reaction
4 HCl (aq) + MnO2(s) → 2 H2O (l) + MnCl2(aq) + Cl2(g)
How many grams of HCl react with 5.0 g of manganese dioxide?
Answer:
Given chemical reaction is
4HCl(aq) + MnO2(s) → MnCl2(aq) + 2H2O(l) + Cl2(g)
4 moles of HCl – 1 mole of MnO2
4 × 36.5 gms. of HCl – 87 gms. of MnO2
∴ Weight of HCl required = 5×4×36.587 = 8.39 gms.
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Question 27.
To 50 ml of 0.1 N Na2CO3 solution 150 ml of H2O is added. Then calculate a normality of
resultant solution.
Answer:
Formulae N1V1 = N2V2
0.1 × 50 = N2 × 200
N2 = 0.14
= 0.025 N
N1 = 0.1 N
V1 = 50 ml
N2 = ?
V2 = 150 + 150 = 200 ml
Question 28.
Calculate the volume of 0.1 N H2SO4 required to neutralize 200 ml of 0.2 N NaOH solution. It is
an acid base neutralisation reaction. Hence, at the neutralisation point. Number of equivalents
of acid = Number of equivalents of base.
Answer:
Formula N1V1 = N2V2
0.1 × V1 = 0.2 × V2
V2 = 2 × 200
= 400 ml
N1 = 0.1 N
V1 = ?
V2 = 200 ml
N2 = 0.2 N
Question 29.
Calculate normality of H2SO4 solutions if 50 ml of it completely neutralises 250 ml of 0.1 N
Ba(OH)2 solutions.
Solution:
Formulae N1V1 = N2V2
N × 50 = 0.1 × 250
N1 = 0.5 N
N1 = ?
V1 = 50 ml
N2 = 0.1 N
V2 = 250 ml
200
Question 30.
Calculate the volume of 0.1 M KMnO4 required to react with 100 ml of 0.1 M H2C2O4.2H2O
solution in presence of H2SO4.
Answer:
Balanced chemical equation for the given data is
Formulae
M1V1n1 = M2V2n2
0.1×V12 = 0.1×1008
V1 = 40 ml
KMnO4
M1 = 0.1 M
V1 = ?
n1 = 2
Oxalic acid
M2 = 0.1 M
V2 = 100 ml
n2 = 5
Question 31.
Assign oxidation number to the underlined elements in each of the following species:
a) NaH2PO4
b) NaHSO4
c) H4P2O7
d) K2MnO4
e) CaO2
f) NaH4
g) H2S2O7
h) KAl(SO4)2.12 H2O
Answer:
a) NaH2PO4
1(+1) + 2(+1) + x + 4(-2) = 0
1+2+x–8=0
x–5=0
x= + 5
Oxidation no. of ‘P in NaH2PO4 = + 5
b) NaHSO4
1(+1) + 1(+1) + x + 4(-2) = 0
1+1+x–8=0
201
x = +6
Oxidation no. of ‘S in NaHSO4 = + 6
c) H4P2O7
4(+1) + 2x + 7(-2) = 0
4 + 2x – 14 = 0
2x – 10 = 0.
x = +5
Oxidation no. of ‘P’ in H4P2O7 is +5
d) K2MnO4
2(+1) + x + 4(-2) = 0
2+x–8=0
x=+6
Oxidation no of Mn is K2MnO4 = +6
e) CaO2
+ 2 + 2x = 0
2x = -2
x = -1
Oxidation no. of oxygen in CaO2 = -1
f) NaBH4
1(+1) + x + 4 (-1) = 0
1+x–4=0
x = +3
Oxidation no. of ‘B’ in NaBH4 = + 3
But B’ most probably exhibits – 3 oxidation state.
g) H2S2O7
2(1) + 2x + 7(-2) = 0
2 + 2x – 14 = 0
2x – 12 = 0
x = +6
Oxidation state of ‘S’ in H2S2O7 = + 6
h) K Al(SO4)2 12H2O :
General formula of above compound is K2SO4 Al2 (SO4)3 2 + H2O (Potash alum)
Consider Al2(SO4)3 from the above double salt
2x + 3 (-2) = 0
2x – 6 = 0
x=+3
202
Question 32.
What are the oxidation number of the underlined elements in each of the following and how
do you rationalise your results ?
a) KI3
b) H2SO4O6
c) Fe3O4
Answer:
a) KI3
It is formed by the combining KI, I2
∴ Oxidation no. of ‘I’ in KI = – 1
[1 + x = 0
x = – 1]
In I2 oxidation no. of. I = 0
b) H2S4O6
According to H2S4O6 structure
2(1) + 4x + 6(-2) = 0 ⇒ 4x – 10 = 0
x = 2.5
‘S’ average Ox. No = 2.5
c) Fe3O4
3x + 4(-2) = 0
3x – 8 = 0
x = 83
In general Fe3O4 obtained by FeO + Fe2O3
∴ In FeO → x = + 2 [x – 2 = 0 ⇒ x = + 2]
In Fe2O3 → x = + 3 [2x – 6 = 0 ⇒ x = + 3]
203
Question 33.
Justify that the following reactions are redox reactions :
Answer:
a) CuO(s) + H2(g) → Cu(s) + H2O(g)
b) Fe2O3(s) + 3CO(g) → 2 Fe(s) + 3 CO2(g)
c) 4 BCl3(g) + 3 LiAlH4(s) → 2 B2H6(g) + 3 LiCl(s) + 3 AlCl3(s)
d) 2 K(s) + F2(g) → 2 K+F–(s)
e) 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g)
a)
Hence it is a Redox reaction.
b)
Hence it is a Redox reaction.
c) 4BCl3(g) + 3LiAlH4(s) → 2 B2H6(g) + 3LiCl(s) + 4AlCl3(s)

Here in the above reaction the oxidation states of all elements doesnot changed. So it is not a
redox reaction.
204
d)
Hence it is a redox reaction.
e)
Question 34.
Fluorine reacts with ice and results in the change
H2O(S) + F2(g) → HF(g) + HOF(g)
Justify that this reaction is a redox reaction.
Answer:
Given chemical equation
205
Question 35.
Calculate the oxidation number of sulphur, chromium and nitrogen in H2SO5,
Cr2O−27 and NO−3. Suggest structure of these compounds.
Answer:
a) H2SO5 Structure:
2(1) + x + 2(-1) + 3(-2) = 0 (One peroxy linkage)

2+x–2–6=0
x = +6
b) Cr2O−27 Structure:
2(x) + 7(-2) = -2
2x – 14 = -2
x = +6
c) NO−3 Structure:
x + 3(-2) = -1
x – 6 = -1
x = +5
206
Question 36.
Write formulas for the following compounds: .
a) Mercury (II) chloride
b) Nickel (II) sulphate
c) Tin (IV) oxide
d) Thallium (I) sulphate
e) Iron (III) sulphate
f) Chromium (III) oxide
Answer:
Formula
a) Mercury (II) Chloride — HgCl2
b) Nickel (II) Sulphate — NiSO4
c) Tin (IV) Chloride — SnCl4
d) Thallium (I) Sulphate — Tl2SO4
e) Iron (III) Sulphate — Fe2(SO4)3
f) Chromium (III) Oxide — Cr2O3
Question 37.
Suggest a list of the substances where carbon can exhibit oxidation states from -4 to +4 and
nitrogen from -3 to +5.
Answer:
207
Question 38.
While sulphur dioxide and hydrogen peroxide can act as oxidising as well as reducing agents in
their reactions, ozone and nitric acid act only as oxidants. Why ?
Answer:
SO3 and H2O2 both acts as oxidising as well as reducing agents.
• Ozone acts as strong oxidising agent in acidic medium (Ozone acts as reducing agent
also in some cases).
• HNO3 acts as strong oxidising agent because in HNO3. He H+ ion readily released and the
oxidation state of ‘N’ is +5 in HNO3. So it is a good oxidising agent.
Question 39.
Consider the reactions :
a) 6 CO2(g) + 6 H2O (l) → C6H12O6 (aq) + 6 O2(g)
b) O3 (g) + H2O2 (l) → H2O () + 2 O2 (g)
Why it is more appropriate to write these reactions as :
a) 6 CO2 (g) + 12 H2O(l) → C6H12O6(aq) + 6 H2O(l) + 6 O2(g)
b) O3(g) + H2O2(l) → H2O2(l) + O2(g) + O2(g)
Also suggest a technique to investigate the path of the above (a) and (b) redox reactions.
Answer:
a) 6CO2 + 12 H2O → C6H12O6 + 6 H2O + 6 O2
This equation is more appropriate writing equation of photosynthesis.
Because of evolution of oxygen from H2O but not from CO2.
b) O3(g) + H2O2(l) → H2O(l) + O2(g) + O2(g)
This is the more appropriate equation to write because in this reaction clearly mentioned that
which is oxidised and which is reduced.
Question 40.
The compounds AgF2 is unstable compound. However, if formed, the compound acts as a very
strong oxidising agent. Why ?
Answer:
• AgF2 is an unstable compound.
• If suppose it is formed it acts as good oxidising agent.
Reason :
AgF2 releases fluorine gas which is a powerful oxidising agent.
∴ AgF2 is a good oxidising agent.
208
Question 41.
Whenever a reaction between an oxidising agent and a reducing agent is carried out, a
compound of lower oxidation state is formed if the reducing agent is in excess and a
compound of higher oxidation state is formed if the oxidising agent is in excess. Justify this
statement giving three illustrations.
Answer:
The above equations illustrates the given statement.
Question 42.
How do you count for the following observations ?
a) Though alkaline potassium permagnate and acidic potassium permanganate both are used
as oxidants, yet in the manufacture of benzoic acid from toluene we use alcoholic potassium
permanganate as an oxidant. Why ? Write a balanced redox equation for the reaction.
b) When concentrated sulphuric acid is added to an inorganic mixture containing chloride, we
get colourless pungent smelling gas HCl, but if the mixture contains bromide then we get red
vapour of bromine. Why ?
Answer:
a) Balanced equation of KMn04/H+ (Acidic medium)
MnO−4 + 8 H+ + 5 e– → Mn+2 + 4 H2O
Balanced equation of KMnO4/ H+ (Basic medium)
MnO−4 + 2 H2O + 3 e– → MnO2 + 4 OH–
• Toluene is oxidised to benzoic acid in alcoholic medium.
• Toluene is easily oxidised in presence of alcoholic KMnO4
209
b) When Conc. H2SO4 reacts with NaCl then HCl vapours are evolved.
2 NaCl + H2SO4 → Na2SO4 + 2 HCl
When Conc. H4SO4 reacts with KBr than HBr vapours are evolved which on further oxidation
gives reddish brown Br2 vapours.
2 KBr + H2SO4 → Na2SO4 + 2 HBr
2MBr + H2SO4 → 2 H2O + SO2 + Br2 (Reddish brown)
Question 43.
Identify the substance oxidised, reduced, oxidising agent and reducing agent for each of the
following reactions :
a) 2 AgBr (s) + C6H6O2 (aq) → 2 Ag (s) + 2 HBr (aq) + C6H6O2 (aq)
b) HCHO(l) + 2[Af(NH3)2]+(aq) + 3 OH–(aq) → 2 Ag(s) + HCOO–(aq) + 4 NH3(aq) + 2 H2O(l)
c) HCHO(l) + 2 Cu2+(aq) + 5 OH–(aq) → Cu2O(s) + HCOO–(aq) + 3 H2O(l)
d) N2H4 (l) + 2 H2O2(l) → N2(g) + 4 H2O(l)
e) Pb(s) + PbO2(s) + 2 H2SO4(aq) → 2 PbSO4(s) + 2 H2O(l)
Answer:
a) Given equation is
2 AgBr(s) + C6H6O2(aq)
• 2 Ag(s) + 2 HBr(aq) + C6H4O2 (aq)
• C6H6O2 oxidised to C6H4O2
• Ag+Br– reduced to Ag
• Oxidising agent is Ag+
• Reducing agent is C6H6O2
b) Given equation is HCHO(l) + 2[Ag(NH3)2]+(aq) + 3OH−(aq)
• 2 Ag(s) + 3OH−(aq) + 4NH3(aq) + 2 H2O(l)

• HCHO oxidised to HCOO–
• [Ag(NH3)2]+ reduced to Ag
• [Ag(NH3)2]+ is oxidising agent
• HCHO is reducing agent
c) Given equation is
HCHO(l) + 2Cu+2(aq) + 5OH– → Cu2O(s) + HCOO−(aq) + 3H2O(l)
• HCHO oxidised to HCOO–
• Cu+2 reduced to Cu+(in Cu2O)
• Oxidising agent is Cu+2 ions (In Fehling’s reagent)
• Reducing agent is HCHO
d) Given equation is
N2H4(l) + 2K2O2(l) → N2(g) + 4H2O(l)
210
• N−2 oxidised to N 2
• O−22 reduced to O -2
• Oxidising agent is H2O2

• Reducing agent is N2H4
Pb(s) + pbO4(s) + 2H2SO4(aq)
e)
• 2PbSO4(s) + 2H2O
• Pb oxidised to Pb+2
• PbO2 reduced to Pb+2
• Oxidising agent is PbO2
• Reducing agent is Pb
Question 44.
2S2O−23 (aQ) + I2 (s) → S4O−26 (aQ) + 2I– (aQ)
S2O−23 (aQ) + I2(s) + 5H2O(l) → 2SO−24 (aq) + 4Br−(aq)(aq) + 10H+(aq)
Why does the same reductant, thiosulphate react differently with iodine and bromine ?
Answer:
• Thio sulphate ion is not a strong reducing agent.
• I2 is not a strong oxidising agent.
• The reaction between I2 and thio sulphate form tetrathionate (S4O−26) ion.
• The above reaction has high rate of reaction.

• The reaction between Thiosulphate and Bromine involves the formation of sulphate ion.
• Br2 is some what better oxidising agent than I2.

Hence the difference observed in the above reactions.
211
Question 45.
Justify giving reactions that among halogens, fluorine is the best oxidant and among hydrohalic
compounds, hydroiodic acid is the best reductant.
Answer:
a)
• The oxidising capacity of any substance depends on the net result of several
contributing energy factors like enthalpy change in a reaction, standard Electrode
potential.
• With reference to Born-Haber type energy cycle the change in enthalpy value is greater
for fluorine.
• Greater the magnitude of negative change in enthalpy greater is the oxidising power.
Supporting reaction :
• Fluorine reacts with carbon while the other elements of group do not combine even
under drastic conditions.
C + 2 F2 → CF4
• Fluorine is also called as superhalogen.
b)
• Hydrohalic compounds acts as reducing agents. Their stability order is
HF >> HCl > HBr > HI
• HI is least stable and acts as strons reducing agent among these halides.
H2 + I2 ⇌ 2 HI
Question 46.
Why does the following reaction occur ?
What conclusion about the compound Na4XeO6(of which is a part) can be drawn from
the reaction.
Answer:
Given equation is
• In the above reaction ‘Xe’ under go reduction (+8 to +6)

• F– oxidised to F2 here perxenate ion acts as powerful oxidising agent.
• Perxenates are stable in alkali solutions.
• Na4XeO6 is a powerful oxidant.
212
Question 47.
(a) H3PO2(aq) + 4 AgNO3(aq) + 2 H2O(1) → H3PO4(aq) + 4Ag(s) + 4HNO3(aq)
(b) H3PO2(aq) + 2 CuSO4(aq) + 2 H2O(1) → H3PO4(aq) + 2Cu(s) + H2SO4(aq)
(c) C6H5CHO(l) + 2[Ag (NH3)2]+(aq) + 3OH–(aq) → C6H5COO–(aq) + 2Ag(s) + 4NH3(aq) + 2H2O(l)
(d) C6H5CHO(l) + 2Cu2+(aq) + 5OH–(aq) → No Change observed.
what inference do you draw about the behaviour of Ag+ and Cu2+ from these reactions ?
Answer:
• H3PO2 is a strong reducing agent hence it reduce Ag+ to Ag and Cu+2 to Cu.
• C6H5CHO is also a reducing agent it just reduced.
Ag+ to Ag in tollen’s reagent but it does not reduced Cu+2 in alkaline solution.
Question 48.
Balance the following redox reactions by ion – electron method :
(a) MnO−4 (aq) + I– (aq) → MnO2(s) + I2 (s) (in basic medium)
(b) MnO−4 (aq) + SO2 (g) → Mn2+ (aq) + HSO4 (aq) (in acidic solution)
(c) H2O2 (aq) + Fe2+ (aq) → Fe3+ (aq) + H2O(l) (in acidic solution)
(d) Cr2O2−7SO2 (g) → Cr3+ (aq) + SO2−4 (aq) (in acidic solution)
Answer:
a) MnO−4 (aq) + I−(aq) → MnO2(s) + I2(s) (Basic medium)
Reduction half cell
MnO−4 → MnO2
MnO−4 → MnO + 2H O (Oxygens balanced)
2 2
MnO−4 + 4H O → MnO + 2H O + 4OH

2 2 2
–
(Hydrogens balanced)
MnO−4 + 2H2O → MnO2 + 4OH–
MnO−4 + 2H O + 3e
2
–
→ MnO2 +4OH–]
(Charge balanced)
2 × [MnMnO−4 + 2H2O + 3e– → MnO2 + 4OH-1]
3 × [2 I– → I2 + 2e–]
Oxidation half cell
I – → I2
2 I– → I2 (Iodines balanced)
2 I– → I2 + 2 e– (Charge balanced)
213
The above equation is balanced equation.
b)
Above equation is balanced chemical equation.
c)
214
d)
Question 49.
Balance the following equations in basic medium by ion-electron method and oxidation
number methods and identify the oxidising agent and the reducting agent
(a) P4(s) + OH–(aq) → PH3(g) + HPO−2
(b) N2H4(l) + ClO−3(aq)(aq) → NO(g) + Cl–(g)
(c) Cl2O7 (g) + H2O2 (aq) → ClO2 (aq) + O2 (g) + H+
Answer:
a) P4 + OH– → PH3 + HPO−2
Reduction half cell
P4 → PH3
P4 → 4PH3
P4 + 12H2O → 4PH3 + 12 OH– (H balanced)
P4 + 12H2O + 12e– → 4PH3 + 12 OH–
215
Oxidation half cell
P4 → H2PO−2
P4 → 4H2PO−2 (‘P’ balanced)
P4 + 8H2O → 4H2PO−2 (Oxygen balanced)
P4 + 8H2O + 8 OH– → 4H2PO−2 + 8H2O
(Hydrogen balanced)
P4 + 8OH– → 4H2PO−2 + 4e–
(Charge balanced)
Here P4 is oxidising agent as well reducing agent.
b)
ClO−3 is oxidant
N2H4 is reductant
c)
216
Question 50.
What sorts of informations can you draw from the following reaction ?
(CN)2(g) + 20H(aq → CN–(aq) + CNO(aq) + H2O(1)
Answer:
(CN)2(g) + 2(OH–) → CN−(aq) + CNO−(aq) + H2O(l)
(CN)2 + 2e– → 2 CN– (Reduction)
(CN)2 + 2H2O → 2 CNO– + 4H+ + 2e– (Oxidation)
Here (CN2) undergo oxidation as well as reduction.
It is a dis proportionation reaction.
Question 51.
The Mn3+ ion is unstable in solution and undergoes disproportionation to give Mn2+. MnO2+ and
H+ ion. Write a balanced ionic equation for the reaction.
Answer:
• Above equation is a dis proportionation reaction
Question 52.
Consider the elements :
Cs, Ne, I and F
(a) Identify the element that exhibits only negative oxidation state.
(b) Identify the element that exhibits only positive oxidation state.
(c) Identify the element that exhibits both postive and negative oxidation states.
217
(d) Identify the element which exhibits neither the negative nor does the positive oxidation
state.
Answer:
a) ‘F’ Exhibits negative oxidation state i.e. ‘-1’
b) ‘Cs’ Exhibits only positive oxidation state
c) ‘I’ Exhibits positive as well as negative oxidation states
d) ‘Ne’ doesnot exhibit any oxidation state in ground state
(Neither positive nor negative)
Question 53.
Chlorine is used to purify drinking water. Excess of chlorine is harmful. The excess of chlorine is
removed by treating with sulphur dioxide. Present a balanced equation for this redox change
taking place in water.
Answer:
Balanced equations for the given data is
Cl2 + SO2 + H2O → SO3 + 2H+ + Cl–
Question 54.
Refer to the periodic table given in your book and now answer the following questions :
a) Select the possible non metals that can show disproportionation reaction.
b) Select three metals that can show disproportionation reaction.
Answer:
a) Non metals
Chlorine, Bromine, Oxygen, Sulphur, Phosphorous, Iodine undergo disproportionations
b) Metals Cr, Mn and pb undergo disproportionation.
Question 55.
In Ostwald’s process for the manufacture of nitric acid, the first step involves the oxidation of
ammonia gas by oxygen gas to give nitric oxide gas and steam. What is the maximum weight of
nitric oxide that can be obtained starting only with 10.00 g, of ammonia and 20.00 g of oxygen
?
Answer:
Chemical reaction is
4NH3 + 5O2 → 4NO + 6H2O
4 moles NH3 – 5 moles of O2
Given 10 gms of NH3
∴ No. of moles = 1017 = 0.588 moles
Given 20 gms of NH3
∴ No. of moles = 2032 = 58 = 0.4
218
4 moles of ammonia reacts with 5 moles of O2
0.588 moles of NH3 …. ?
0.5884 × 5 = 0.735 moles
5 moles of O2 reacts with 4 moles of NH3
0.4 moles of O2…. ?
0.45 × 4 = 1.65 = 0.32
• Here O2 is not present in sufficient amount NH3 has sufficient in amount
5 moles of O2 → 4 moles of NO.
5 × 32 gms of O2 → 4 × 30 gms of NO.
20 gms of O2 → ?
20×4×305×32 = 20×2432 = 1208 = 15 gms
Question 56.
Arrange the following metals in the order in which they displace each other from the solution
of their salts.
Al, Cu, Fe, Mg and Zn.
Answer:
According to electro chemical series electrode potentials of given elements as follows
Al – -1.66 V
Cul – + 0.34 V
Fe – -0.40 V
Mg – -2.37 V
Zn – -0.76 V
∴ The order of the above metals in which they displace each other from the solution of their
salts. Mg > AZ > Zn > Fe > Cu
Question 1.
Wtire the balanced ionic equation which represents the oxidation of iodide (I-) ion by
permanganate ion in basic medium at give iodine (I) and managanese dioxide (MnO 2)
Answer:
Basic equation is
219
The above equation is balanced equation.
Question 2.
Write the balanced equation for the oxidation of suiphite ions to sulphate ions in acid medium
by permanganate ion.
Answer:
220
Question 3.
Oxalic acid is oxidised by permanganate ion is acid medium of Mn2+ balance the reaction by ion
— electron method.
Answer:
Question 4.
Phosphorus when heated with NaOH solution gives phosphine (PH3) and H2PO−2. Give the
balanced equation.
Answer:
Here P4 is oxidising agent as well reducing agent.

221
Question 5.
Balance the following equation
Answer:
Oxidation half reaction Cr(OH)3 → CrO2−4
(The ox. no of Cr changes from +3 to +6)
Reduction half reaction IO−3 → I– (The ox. no. of ‘I’ changes from +5 to —1)
222
Question 6.
Balance the following equation by the oxidation number method.
MnO−24 + Cl2 → MnO−24 + Cl–
Answer:
Question 7.
Exaplain the different types of redox reactions.
Answer:
Redox reaction : “The reaction that involves loss of electrons is called an oxidation reaction
and that involving gain of electrons is called a reduction reaction. The overall reaction is called
as oxidation – reduction reaction” or simply ‘redox reaction’.
Types of redox reactions:
a) Chemical combination reactions: In these reactions one species combine with another
species to form product. In this conversion one species undergo oxidation and other species
undergo reduction.
e.g.:
As the oxidation state of carbon increases from ‘0’ to ‘+4’ in the reaction. So, carbon
undergoes oxidation.
Oxygen changes from ‘0’ to ‘-2’ oxidation state. So, it undergoes reduction. Therefore, the
above overall combination reaction is redox reaction.
b) Decomposition reactions : Chemical compounds chemically split into two or more simpler
substances during decomposition reactions. These are again redox reactions.
223
Here, water decomposes. H2 undergoes reduction from +1 to 0 in the reaction. Oxygen on the
other hand changes its oxidation state from -2 to 0 (or) it undergoes oxidation.
Therefore, decomposition of H20 is a redox reaction.
c) Displacement reactions : In these reactions the place of one species in its compound is taken
up by other species.
‘Zn’ displaces ‘Cu’ from CuSO4 solution. In this reaction Zn undergoes oxidation and Cu
undergoes reduction. Therefore overall reaction is a redox reaction.
d) Disproportionation reactions : These reactions involve the same element in the given form
to undergo both oxidation and reduction simultaneously.
In the above reaction ‘Cl2‘ undergoes both oxidation and reduction. It is a special type of redox
reaction.
e) Comproportionation reactions : Reverse of disproportionation is comproportionation. In
comproportionation reactions, two species with the same element in two different oxidation
states form a single product in which the element is in an intermediate oxidation state.
e.g.:
Question 8.
Calculate the amount of carbon dioxide that could be produced when
(i) 1 mole of carbon is burnt in air.
(ii) 1 mole of carbon is burnt in 16 g of dioxygen,
(iii) 2 moles of carbon are burnt in 16 g of dioxygen.
Answer:
i) C + O2 → CO2
224
1 mole of ‘C’ → 1 mole of CO2
∴ 44 gms of CO2
ii) C + O2 → CO2
Given 1 mole of O2 burnt in 16 gms of di oxygen
iii) C + O2 → CO2
2 moles of ‘C’ burnt in 16 gms of O2
∴ 1 mole of O2 → 44 gms of CO2
32 gms of O2 → 44 gms of CO2
16 gms of O2 → 22 gms of CO2
Question 9.
Dinitrogen and dihydrogen react with each other to produce ammonia according to the
following chemical equation :
N2(g) + H2(g) → 2NH3 (g)
(i) Calculate the mass of ammonia produced if 2.00 × 103 g dinitrogen reacts with 1.00 × 103 g
of dihydrogen.
(ii) Will any of the two reactants remain unreacted ?
(iii) If yes, which one and what would be its mass ?
Answer:
i) N2 + 3H2 → 2NH3
Given Nitrogen = 2 × 103 gms
No. of moles = 200028 = 71.4285
Given hydrogen = 1 × 103 gms
No. of moles = 10002 = 500 moles
N2 is limiting agent
∴28 gms of N2 → 2 × 17gms NH3
2000 gms of N2 →
2000×1728 = 2428.57 gms
ii) Used amount of hydrogen
28 → 6 gms
100 gms → ?
1000×628 = 214.285 gms
iii) Remaining amount of hydrogens
= 1000 – 2140.285
= 785.715 gms
225
Question 10.
Assign oxidation number to the underlined elements in each of the following epecies :
(a) NaH2PO4
b) NaHSO4
c) H4P2O7
d) K2MnO4
(e) CaO2
(f) NaBH4
(g) H2S2O7
(h) KA1(SO4)2.12 H2O
Answer:
(a) NaH2PO4
1(+1) + 2(+1) + x + 4 (-2) = 0
1+2+x–8=0
x–5=0
x = +5
Oxidation no. of ‘P’ in NaH2PO4 = + 5
b) NaHSO4
1(+1) +1(+1) + x + 4(-2) = 0
1+1+x–8=0
x=+6
Oxidation no. of ‘S’ in NaHSO4 = + 6
c) H4P2O7
4(+1) + 2x + 7(-2) = 0
4 + 2x – 14 = 0
2x – 10 = 0
x=+5
Oxidation no. of ‘P’ in H4P2O7 is +5
d) K2MnO4
2(+1) + x + 4(-2) = 0
2+x+8=0
x=+6
Oxidation no of Mn is K2MnO4 = + 6
e) CaO2
+ 2 + 2x = 0.
2x = -2
x = -1
Oxidation no. of oxygen in CaO2 = -1
226
f) NaBH4
1(+1) + x+ 4(-1) = 0
1+x–4=0
x = +3
Oxidation no. of ‘B’ in NaBH4 = +3
But ‘B’ most probably exhibits -3 oxidation state.
g) H2S2O7
2(1) + 2x + 7(-2) = 0
2 + 2x – 14 = 0
2x – 12 = 0
x = +6
Oxidation state of ‘S’ in H2S2O7 = + 6
h) k Al(SO4)2 12H2O :
General formula of above compound is
k2SO4 Al2 (SO4) 24 H2O (Potash alum)
Consider Al2(SO4)3 from the above double salt
2x + 3(-2) = 0
2x – 6 = 0
x = +3
Question 11.
What are the oxidation number of the underlined elements in each of the following and how
do you rationalise your results?
(a) H2S4O6
(b) Fe3O4
(c) CH3CH2OH
(d) CH3COOH
Answer:
a) 45 (b)
b) 45 (c)
c) CH3 CH2 – OH
C2H6O
2x + 6(1) + (-2) = 0
2x + 6 – 2 = 0
2x + 4 = 0
x = -2
d) CH3COOH
C2H4O2
2x + 4(+1) + 2(-2) = 0
227
2x + 4 – 4 = 0
x=0
Solved Problems
Question 1.
Calculate molecular mass of glucose (C6H12O6) molecule.
Solution:
Molecular mass of glucose (C6H12O6)
= 6(12.011 u) + 12(1.008 u) + 6(16.00.u)
= (72.066 u) + (12.096 u) + (96.00 u)
= 180.162 u
Question 2.
A compound contains 4.07% hydrogen, 24.27% carbon and 71.65% chlorine. Its molar mass is
98.96 g. What are its empirical and molecular formulae ?
Solution:
Step 1.
Conversion of mass per cent to grams :
Since we are having mass percent, it is convenient to use 100 g of the compound as the
starting material. Thus, in the 100 g sample of the above compound, 4.07 g hydrogen; 24.27 g
carbon; and 71.65 g chlorine are present.
Step 2.
Convertion into number of moles of each element:
Divide the masses obtained above by respective atomic masses of various elements.
Moles of hydrogen = 4.07 g1.008 g mol−1 = 4.04
Moles of carbon = 24.27 g12.01 g mol−1 = 2.021 Moles of chlorine = 71.65 g35.453 g mol−1 = 2.021
Step 3.
Divide the mole value obtained above by the smallest number:
Since 2.021 is smallest value, division by it gives a ratio of 2:1:1 for H:C:Cl.
In case the ratios are not whole numbers, then they may be converted into whole number by
multiplying by the suitable coefficient.
Step 4.
These numbers indicate the relative number of atoms of the elements. Write empirical
formula by mentioning the numbers after writing the symbols of respective elements :
CH2Cl is thus, the empirical formula of the above compound.
Step 5.
Writing molecular formula :
228
a) Determine empirical formula mass.
Add the atomic masses of various atoms present in the empirical formula.
For CH2Cl, empirical formula mass is 12.01 + 2 × 1.008 + 35.453 = 49.48 g
b) Divide Molar mass by empirical formula mass
= 2 = (n)
c) Multiply empirical formula by n obtained above to get the molecular formula.
Empirical formula = CH2Cl, n = 2. Hence molecular formula is C2H4Cl2.
Question 3.
Calculate the amount of water (g) produced by the combustion of 16 g of methane.
Solution:
The balanced equation for combustion of methane is :
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
1. 16 g of CH4 corresponds to one mole.
2. From the above equation, 1 mol of CH4(g) gives 2 mol of H2O(g).
2 mol of water (H2O) = 2 × (2 + 16)
= 2 × 18 = 36 g
1 mol H2O = 18g H2O ⇒ 18 gH2O1 molH2O = 1
Hence 2 mol H2O × 18 gH2O1 molH2O
= 2 × 18 g H2O = 36 g H2O
Question 4.
How many moles of methane are required to produce 22 g CO2(g) after combustion ?
Solution:
According to the chemical equation
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
44 g CO2 (g) is obtained from 16 g CH4(g).
[∵ 1 mol CO2(g) is obtained from 1 mol of CH4(g)]
Mole of CO2(g)
= 22 g CO2(g) × 1 molCO2( g)44gCO2( g)
= 0.5 mol CO2(g)
Hence 0.5 mol CO2(g) would be obtained from 0.5 mol CH4(g) or 0.5 mol of CH4(g) would be
required to produce 22g CO2(g).
229
Question 5.
50.0 kg of N2(g) anfd 10.0 kg of H2(g) are mixed to produce NH3(g). Calculate the NH3 (g)
formed. Identify the limiting reagent in the production of NH3 in this situation.
Solution:
A balanced equation for the above reaction is written as follows :
Calculation of moles:
N2 + 3H2(g) ⇌ 2HN3(g)
Moles of N2
According to the above equation, 1 mol N2(g) requires 3 mol H2(g), for the reaction. Hence, for
17.86 × 102 mol N2, the moles of H2(g) required would be
17.86 × 102 mol N2 × 3 molH2( g)1molN2( g)
= 5.36 × 103 mol H2
But we have only 4.96 × 103 mol H2. Hence, dihydrogen is the limiting reagent in
this case. So NH3(g) would be formed only from that amount of available dihydrogen i.e.,
4.96 × 103 mol.
Since 3 mol H2(g) gives 2 mol NH3(g)
4.96 × 103 mol H2 (g) × 2 molNH3( g)3molH2( g)
= 3.30 × 103 mol NH3 (g)
3.30 × 103 mol NH3 (g) is obtained.
If they are to be converted to grams, it is done as follows :
1 mol NH3(g) = 17.0 g NH3(g)
3.30 × 103 mol NH3 (g) × 17.0 gNH3( g)1 molNH3( g)
= 3.30 × 103 × 17 g NH3 (g)
= 56.1 × 103 g NH3 (g)
= 56.1 kg NH3
Question 6.
A solution ¡s prepared by adding 2 g of a substance A to 18 g water. Calculate the mass
percent of the solute.
Solution:
230
Question 7.
Calculate the molarity of NaOH in the solution prepared by dissolving 4 g in enough water to
form 250 mL of the solution.
Solution:
Since molarity
Note that molarity of a solution depends upon temperature because volume of a solution is
temperature dependent.
Question 8.
The density of 3 M solution of NaCl is 1.25 g mL-1. Calculate molality of the solution.
Solution:
M = 3 mol L-1
Mass of NaCl in 1 L solution
= 3 × 58.5 = 175.5 g
Mass of
1 L solution = 1000 × 1.25 = 1250 g
(Since density = 1.25 gmL-1)
Mass of water of solution = 1250 – 175.5
= 1074.5 g = 1.0745 kg
Often in a chemistry laboratory, a solution of a desired concentration is prepared by diluting a

solution of known higher concentration. The solution of higher concentration is also known as
stock solution. Note that molality of a solution does not change with temperature since mass
remains unaffeoted with temperature.
231
Question 9.
Calculte the normality of oxalic acid solutions containing 6.3g of H2C2O4.2H2O in 500 ml of
solutions.
Solution:
Weight of solute = 6.3 g
GEW of solute = 1262 = 63
∴ Normality (N) = ωGEW×1000 V( mL)
Normality (N) = 6.363×1000500 = 0.2 N
Question 10.
Calculate the mass of Na2CO3 required to prepare 250 ml of 0.5 N solution.
Solution:
Normality of required solution = 0.5 N
Volume of required solution = 250 ml
Equivalent wt.of. Na2CO3 = 1062 = 53
Normality (N) = WGEW×1000 V( mL)
wt. of solute = N × GEW × V(ml)1000
= 0.5 × 53 × 2501000 = 538 = 6.62 g
Question 11.
In the reactions given below, identify the species undergoing oxidation and reduction :
(i) H2S (g) + Cl2 (g) → 2HC (g) + S (s)
(ii) 3Fe3O4 (s) + 8Al (s) → 9Fe (s) + 4Al2O3 (s)
(iii) 2Na (s) + H2 (g) → 2NaH (s)
Solution:
(i) H2S is oxidised because a more electronegative element, chlorine is added to hydrogen (or a
more electropositive element, hydrogen has been removed from S). Chlorine is reduced due to
addition of hydrogen to it.
(ii) Aluminium is oxidised because oxygen is added to it. Ferrous ferric oxide (Fe3O4) is reduced
because oxygen has been removed from it.
(iii) This reaction is very interesting. It may be said from the above definitions that the reaction
is only a reduction reaction as it involves the addition of sodium (electropositive metal) or
hydrogen whereas sodium undergoes oxidation and hydrogen undergoes reduction. It is to say
that the above definitions for oxidation and reduction can not explain this and they have
limitations like this. Therefore a new concept has to be considered for the oxidation and the
reduction.
232
Question 12.
Justify that the reaction :
2Na (s) + H2 (g) → 2NaH (s) is a redox change.
Solution:
Since in the above reaction the compound formed is an ionic compound, which may also be
represented as Na+H– (s), this suggests that one half reaction in this process is :
2Na (s) → 2Na+ (g) + 2e– and the other half reaction is H2 (g) + 2e– → 2H– (g)
This splitting of the reaction under examination into two half reactions automatically reveals
that here sodium is oxidised and hydrogen is reduced, therefore, the complete reaction is a
redox change.
Question 13.
Using stock notation, represent the following compounds : HAuCl4, Tl2O, FeO, Fe2O3, Cul, CuO,
MnO and MnO2.
Solution:
By applying various rules of calculating the oxidation number of the desired element in a
compound, the oxidation number of each metallic element in its compound is as follows:
HAuCl4 → Au has 3
Tl2O → Tl has 1
FeO → Fe has 2
Fe2O3 → Fe has 3
Cul → Cu has 1
CuO → Cu has 2
MnO → Mn has 2
MnO2 → Mn has 4
Therefore, these compounds may be represented as :
HAu (III) Cl4, Tl2(I)O, Fe(II)O, Fe2(III)O3, Cu(I)I, Cu(II)O, Mn(II)O, Mn(IV)O2.
Question 14.
Justify that the reaction :
2Cu2O(S) + Cu2S(s) → 6Cu(s) + SO2(g) is a redox reaction. Identify the species oxidised/reduced,
which acts as an oxidant and which acts as a reductant.
Solution:
Let us assign oxidation number to each of the species in the reaction under examination. This
results into :
233
We therefore, conclude that in this reaction copper is reduced from +1 state to zero oxidation
state and sulphur is oxidised from -2 state to +4 state. The above reaction is thus a redox
reaction.
Further, Cu2O helps sulphur in Cu2S to increase its oxidation number, therefore Cu (I) is an
oxidant; and sulphur of Cu2S helps copper both in Cu2S itself and Cu2O to decrease its
oxidation number ; therefore, sulphur of Cu2S is reductant.
Question 15.
Which of the following species, do not show disproportionation reaction and why ? ClO–,
ClO−2, ClO3 and ClO4. Also write reaction for each of the species that disproportionates.
Solution:
Among the oxoanions of chlorine listed above, ClO4 does not disproportionate because in this
oxoanion chlorine is present in its highest oxidation state that is, +7. The disproportionation
reactions for the other three oxoanions of chlorine areas follows :
Question 16.
Suggest a scheme of classification of
the following redox reactions
(a) N2 (g) + O2 (g) → 2NO (g)
(b) 2Pb(NO3)2(s) → 2PbO(s) + 2NO2(g) + 1/2 O2(g)
(c) NaH(s) + H2O (l) → NaOH (aq) + H2(g)
(d) 2NO2(g) + 2OH–(aq) → NO−2 (aq) + NO−3 (aq) + H2O(l)
Solution:
In reaction
(a) the compound nitric oxide is formed by the combination of the elemental substances,
nitrogen and oxygen ; therefore, this is an example of combination redox reactions. The
reaction.
(b) involves the breaking down of lead nitrate into three components, therefore, this is
categorised under decomposition redox reaction. In reaction.
234
(c) hydrogen of water has been displaced by hydride ion into dihydrogen gas. There-fore, this
may be called as displacement redox reaction.
(d) The reaction involves disproportionation of NO2 (+4 state) into NO2 (+3 state) and NO3 (+5
state). Therefore reaction (d) is an example of disproportionation redox reaction.
Question 17.
Why do the following reactiolns proceed differently ?
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O and
Pb3O4 + 4HNO3 → 2Pb(NO3)3 + PbO2 + 2H2O
Solution:
Pb3O4 is actually a stoichiometric mixture of 2 mol. of PbO and 1 mol. of PbO2. In PbO2, lead is
present in +4 oxidation state, whereas the stable oxidation state of lead in PbO is +2.
PbO2 thus can act as an oxidant (oxidising agent) and, therefore, can oxidise Cl ion of HCl into
chlorine. We may also keep in mind that PbO is a basic oxide. Therefore, the reaction
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O can be splitted into two reactions namely :
2 PbO + 4HCl → 2PbCl2 + 2H2O (acid base reaction)
Question 18.
Write the net ionic equation for the reaction of potassium dichromate (VI) K2Cr2O7 with sodium
sulphite, Na2SO3 in an acid solution to give chromium (III) ion and the sulphate ion.
Solution:
Step – 1 :
The skeletal ionic equation is :
Cr2O2−7 (aq) + SO−23 (aq) → Cr3+ (aq) + SO2−4 (aq)
Step – 2 :
Assign oxidation numbers for Cr and S
This indicates that the dichromate ion is the oxidant (it oxidises sulphite ion to sulphate ion)
and the sulphite ion is the reductant. (it reduces dichromate ion to chromium (III).
Step – 3 :
Calculate the increase and decrease of oxidation numbers of respective species and make
235
them equal.
As reduction is total 6 units due to two Cr3+ formed, oxidation also must be 6 units. This is
obtained by multiplying SO−23 with 3.
Step – 4 :
Adjust the coefficients of the products accordingly
Step – 5 :
a) Add H+ ions in acid medium or H2O molecules in basic medium in the required number to
hydrogen atoms deficient side.
b) Add H2O molecules in acid medium or OH– ions in basic medium in the required number to
oxygen atoms diffident side, (a) and (b) may be repeated any number of times by hit and trial
method until hydrogen and oxygen atoms are same in number on both the sides of the redox
reaction.
The given reaction is in acid medium
Question 19.
Permanganate ion reacts with bromide ion in basic medium to give manganese dioxide and
bromate ion. Write the balanced ionic equation for the reaction.
Solution:
Step – 1 : The skeletal ionic equation is :
MnO−4 (aq) + Br– (aq) → MnO2 (s) + BrO−3 (aq)
Step – 2 : Assign oxidation numbers for Mn and Br.
This indicates that permanganate ion is the oxidant and bromide ion is the reductant.
Step – 3 :
Calculate the increase or decrease in the oxidation number per atom and for the entire
molecule/ion in which it occurs. The number units of oxidations change must be equal to the
number units of reduction change. If this is not observed then multiply the oxidising agent
236
with the number of units of oxidation and the reducing agent with the number of units of
reduction i.e., multiply oxidant MnO4 by 2 and reductant Br– by I.
Know number of units oxidation number of units reduction.

Step – 4:
Adjust the coefficients of products accordingly.
2MnO−4 (aq) + Br (aq) → 2MnO2 (s) + BrO3 (aq)
Step – 5 :
a) Add H+ ions in acid medium or H2O molecules in basic medium in the required number to
hydrogen atoms deficient side.
b) Add H2O molecules in acid medium or OH– ions in basic medium in the required number to
oxygen atoms dificient side, (a) and (b) may be repeated any number of times by hit and trial
method until hydrogen and oxygen atoms are same in number on both the sides of the redox
reaction. This reaction is basic medium.
2MnO−4 (aq) + Br (aq) + H2O (I)
• 2MnO2 (s) + BrO−3 (aq) + 2OH– (aq)
Question 20.
Permanganate (VII) ion, MnO4 in basic solution oxidises iodide ion. I to produce molecular
iodine (I2) and manganese (IV) oxide (MnO2). Write a balanced ionic equation to represent this
redox reaction.
Solution:
Step – 1 :
First we write the skeletal ionic equation, which is
MnO−4 (aq) + I– (aq) → MnO2 (s) + I2 (s)
Step – 2 :
The two half-reactions are :
-1 0
Oxidation half :
Reduction half : MnO−4 (aq) → MnO2 (s)

Step – 3 :
To balance the I atoms in the oxidation half reaction, we rewrite it as:
2I– (aq) → I2 (s)
237
Step – 4:
As the reaction takes place to basic medium, to balance the 0 atoms in the reduction half
reaction, we add OH– ions in required number.
MnO−4 (aq) → MnO2 (s) + 2HO– (I)
To balance the H atoms, we add two H2O molecules on the left.
MnO−4 (aq) + 2H2O (aq) → MnO2 (s) + 2 HO– (I)
Balance H and 0 atoms by bit and trial method even if it requires morethan once we haye to
do it.
The resultant equation is :
MnO−4 (aq) + 2H2O (I) → MnO2 (s) + 4OH– (aq)
Note : While balanceing H atom 0 atoms do not disturb the coefficients of other species
(oxidant and reduCtant and the products).
Step-5 :
In this step we balance the charges of the two half-reactions in the manner depicted as:
2I– (aq) → I2 (s) + 2e–
MnO−4 (aq) + 2H2O (I) + 3e– → MnO2 (s) + 4OH– (aq)
Now to equalise the number of electrons, in the two half reactions we multiply the oxidation
hatf-reaction by 3 and the reduction half-reaction by 2.
6I– (aq) → 3I2 (s) + 6e–
2MnO4 (aq) + 4H4O (I) + 6e– → 2MnO2 (s) + 8OH–(aq)
Step-6:
Add two half-reactions to obtain the net reaction and canceel the electrons on both sides.
6I– (aq) + 2MnO−4 (aq) + 4H2O (I) → 3I2 (s) + 2MnO2 (s) + 8 OH– (aq)
Step – 7:
A final verification shows that the equation is balanced in respect of the number of atoms and
charges on both sides.
Question 21.
Calculate the normality of H2So4 solution. If 50 ml of it completely neutralised 250 ml of 0.2 N
sodium hydroxide (NaoH) solution.
Answer:
∴ Normality of H2So4 solution = 1 N.

238
Question 1.
What is the information given by the term thermodynamics ?
Answer:
• Thermodynamics gives information of energy changes involved in a chemical
reaction (or) process.
• The laws of thermodynamics deal with energy changes of macroscopic systems
involving a large no.of molecules.
Question 2.
What is the relationship between the laws of thermodynamics and equilibrium state ?
Answer:
• Laws of thermodynamics apply only when a system is in equilibrium (or) moves
from one equilibrium state another equilibrium state.
• Macroscopic properties like pressure and temperature do not change with time
for a system in equilibrium state.
Question 3.
Define a system. Give an example.
Answer:
System : A small part of the universe chosen for thermodynamic study is called system.
Question 4.
The wall is adiabatic and AU = Wad. What do you understand about the heat and work
with respect to the system ?
Answer:
• In adiabatic process there is no transfer of heat between system and
surroundings.
• Work done adiabatic process is the change in internal energy of the system.
Work done in adabatic process Wad = U2 – U1 = ∆U
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• Here work done on the system is positive and work done by the system is
negative.
Question 5.
The system loses ‘q’ amount of heat though no work is done on the system. What type
of wall does the system have ?
Answer:
• Here heat is transferred through a thermally conducting walls.
• In this case charge in internal energy ∆U = q can be measured interms of
temperature difference.
q = TB – TA
• Here no work is done at constant volume,
q = +ve → heat transferred from surrounding to system.
q = -ve → heat transferred from system to surrounding.
Question 6.
Work is done by the system and ‘q’ amount at heat is supplied to the system. What
type of system would it be ?
OR
Work is done by the system and heat (q) is supplied to the system. What type of
system would it be ?
Answer:
The system is closed system .
Mathematical form
∆U = q – W
∆U = Change in internal energy
q = heat supplied
W = Workdone by the system.
Question 7.
What is the workdone in the free expansion of an ideal gas in reversible and irreversible
processes ?
Answer:
In case of free expansion of an ideal gas pressure becomes zero, (into vaccum) .
∴ No workdone during free expansion of an ideal gas in case to reversible as well as
irreversible process.
240
Question 8.
From the equation ∆U = q-pex∆V, if the volume is constant what is the value of ∆U.
Answer:
Suppose volume is constant change in volume ∆V = 0
∆U = q = pex∆V
∆U = q – 0
∆U = q
∴ Internal energy change = heat supplied.
Question 9.
In isothermal free expansion of an ideal gas find the value of q and ∆U.
Answer:
∆U = q + W
In case of free expansion of a gas in isothermal process.
W = 0, q = 0, ∆U = 0
Work done W = 0 (∵ Pexp = 0)
∴ q = 0, U = 0
Question 10.
In isothermal irreversible change of ideal gas what is value of q ?
Answer:
In case of an isothermal irreversible change,
q=W=0
q = -W
= pexp(Vf – Vi)
Question 11.
In isothermal reversible change of an ideal gas, what is the value of q ?
Answer:
In case of isothermal irreversible change
q=W
q = nRTln VfVi
q = 2.303 nRT log VfVi
Question 12.
For an adiabatic change is an ideal gas what is the relationship between its ∆U and W
241
(adiabatic) ?
Answer:
For an adiabatic change q = 0
∆U = q + W
∆U = 0 + W
∆U = W
Change in internal energy = Work done in adiabatic process.
Question 13.
State the first law of the thermodynamics.
Answer:
First law of thermodynamics :
The law of conservation of energy is taken as the first law of thermodynamics.
Statements :
1. “Energy can neither be created nor destoyed, although it can be transformed
from one form to another”.
2. “It is impossible to construct perpetual motion machine of first kind”.
3. “The total energy of the system, and surroundings in constant”.
Question 14.
What are the sign conventions of the work done on the system and work done by the
system ?
Answer:
• Work done on the system uses positive sign.
• Work done by the system uses negative sign.
Question 15.
Volume (V), pressure (P) and Temperature (T) are state functions. Is the statement true
?
Answer:
Volume (V), Pressure (P) and Temperature (T) are state functions. These do not depends
upon path or reaction but only depends upon state of reaction.
242
Question 16.
What are the heat (q) sign conventions when heat is transferred from the surroundings
to the system and that transferred from system to the surrounding ?
Answer:
q = positive → Heat transferred from surrounding to the system.
q = negative → Heat transferred from system to the surroundings.
Question 17.
No heat is absorbed by the system from the surroundings, but work (w) is done on the
system. What type of wall does the system have ?
Answer:
No heat is absorbed by the system from the surroundings but work (w) is done on the
system. It is adiabatic change. Hence the wall is called adiabatic wall.
Question 18.
No work is done on the system, but heat (q) is taken out from the system by the
surroundings. What type of wall does the system have ?
Answer:
No work is done on the system, but heat (q) is taken out from the system by the
surroundings. Then the containing wall is thermally conducting wall.
Question 19.
q = w = -Pext (vf – vi) is for irreversible ………… change.
Answer:
q = w = -Pext (vf – Vi) is for irreversible isothermal change.
Question 20.
q = -w = nRT in (vf/vi) is for isothermal change.
Answer:
q = -w = nRT/n vfvi is for isothermal reversible change.
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Question 21.
What are the ‘∆H’ sign conventions for exothermic and endothermic reactions ?
Answer:
Compounds which liberate heat in their formation reaction from the constituent
elements are called exothermic compounds.
For this reactions, ∆Hf = negative
Compounds which absorb heat in the formation reaction from the constituent
elements are called endothermic compounds.
For this reactions, ∆Hf = positive.
Question 22.
What are intensive and extensive properties ?
Answer:
Measurable (or) macroscopic properties such as mass, pressure, volume, temperature,
surface tension, viscosity etc., can be subdivided into two categories as below :
i) Extensive properties : The properties whose magnitude depends upon the quantity of
matter present in the system are called extensive properties. Examples of such
properties are mass, volume, heat capacity, internal energy, entropy, heat content,
Gibbs free energy etc. These properties change with quantity of matter present in the
system. These properties are additive in nature.
ii) Intensive properties : The properties which do not depend upon the quantity of
matter present in the system are called intensive properties. Examples of such
properties are density, molar volume, molar entropy, molar heat capacity, surface
tension, viscosity, specific heat, refractive index, pressure, temperature, boiling point,
freezing point, vapour pressure etc. These properties depends only on the nature of the
substance.
Question 23.
In the equation q = c. m. ∆T. If ∆T is change in temperature’m1 mass of the substance
and ‘q1 is heat required, what is ‘c’ ?
Answer:
Given q = c × m × ∆T.
In the above equation c = Specific heat.
Specific heat: The amount of heat required to raise the temperature of 1gm of
substance by 1°C is called specific heat.
244
Question 24.
Give the equation that gives the relationship between ∆U and ∆H.
Answer:
The equation that gives the relationship between ∆U and ∆H.
∆H = ∆U + ∆nRT
∆H = Change in Enthalpy
∆U = Change in Internal energy
∆n = nP – nR, R = Universal gas constant :
T = Temperature
Question 25.
What is the relationship between Cp and Cv ?
Answer:
Cp – Cv = R
Cp = Heat capacity at constant pressure
Cv = Heat capacity at constant volume
R = Universal gas constant.
Question 26.
1g of graphite is burnt in a bomb calorimeter in excess of O2 at 298K and 1 atm.
pressure according to the equation.
C(graphite) + O2(g) → CO2(g)
During the reaction the temperature rises from 298K to 299K. Hat capacity of the bomb
calorimeter is 20.7kJK-1. What is the enthalpy change for the above reaction at 298 K
and 1 atm ?
Answer:
Given equation C(graphite) + O2(g) → CO2(g)
∆T = 299 – 298 = 1K
q = Cv × ∆T = -20.7 × 1 = -20.7 KJ
Given 1 gm of graphite ∴ ∆H = ∆U (∵ ∆h = 0)
∴ ∆U = – 20.7 KJ/k
For 1 mole
∆U = 12 × -20.7 = -248 KJ/mole
245
Question 27.
For the above reaction what is the internal energy change, ∆U ?
Answer:
For the above reactions
Internal Energy change ∆U = – 20.7 KJ/k
Question 28.
What is ∆rH for CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) interms of molar enthalpies of the
respective reactants and products ?
Answer:
∆rH = Sum of enthalpies of products – sum of enthalpies of reactants
= ∆Hp – ∆Hr
∆rH = (H(CO2) + 2 × H(H2O)) – (H(CH4) + 2 × H(O2))
Question 29.
Enthalpy decrease is not the criterion for spontaneity. Why ?
Answer:
Change in enthalpy “(∆H) = negative” may be a condition but not a necessary and
sufficient condition for the spontaneous nature of a reaction.
Question 30.
Is increase of entropy the criterion for spontaneity ? Why ?
Answer:
Change in entropy “(∆S) = positive” is a condition but is not necessary and sufficient
condition for the spontaneous nature of a reaction.
Question 31.
Explain the relationship between Gibbs energy change and equilibrium constant.
Answer:
∆G° =2.303 RT logk
∆G = Change in Gibbs free energy
K = Equilibrium constant
246
Question 32.
If we measure ∆Hθ and ∆Sθ it is possible to estimate ∆Gθ. Is it true ? why ?
Answer:
∆G° = ∆H° – T ∆S°
If we can measure ∆H° and ∆°S° then we can estimate ∆G° by the above equation, the
given statement is true.
Question 33.
Equilibrium constant ‘K’ is measured accurately in the laboratory at given temperature.
Is it possible to calculate ∆G° at any other temperature ? How ?
Answer:
It is possible to calculate ∆G° from the measurement of ∆H° and ∆S° and we can
calculate K at any temperature.
∆G° = ∆H° – T ∆S°
Question 34.
Comment on the thermodynamic stability of NO(g) given that
12 N2(g) + 12 O2(g) → NO(g); ∆rH° = 90kJ mol-1
NO(g) + 12 O2(g) → NO2(g); ∆rH° = -74kJ mol-1
Answer:
12 N2(g) + 12 O2(g) → NO(g); ∆rH° = 90kJ mol-1
NO(g) + 12 O2(g) → NO2(g); ∆rH° = -74kJ mol-1
NO(g) formation is endothermic (∆H = + ve)
NO2(g) formation is exothermic (∆H = -ve)
∴ NO(g) is thermodynamically unstable.
Question 35.
Calculate the entropy change in surroundings when 1.00 mole of H2O(1) is formed under
standard conditions ∆fH° = – 286k J mol-1.
Answer:
Formula ∆S = ΔfH∘T=−286273 = -1.0476 KJ/mole.K
∆Ssurrounding = 1.0476 KJ/mole.k
247
Question 36.
The equilibrium constant for a reaction is 10. What will be value of ∆G°? R = 8.314JK-
1
mol-1,T = 300K.
Answer:
Formulae ∆G° = —RTlnk
K = 10
R = 8.314 J/K.mole
T = 300 K
= – 2.303 RT logK
= – 2.303 × 8.314 × 300 × log 10 = – 5774.14 J/mole
Question 37.
State the third law of thermodynamics. [T.S. Mar. 16]
Answer:
Third law of thermodynamics: “The entropy of a pure and perfectly crystalline
substance is zero at the absolute zero of a temperature (- 273° C)”.
Slim T → 0 = 0
This law imposes a limitation on the value of entropy.
ST = ∫T0CpT⋅dT
Question 1.
What are open, closed and isolated systems ? Give one example for each.
Answer:
Types of systems : The systems are classified into three types. These are :
a) Open system : A system which can exchange matter as well as energy with the
surroundings is called an open system.
Ex :Evaporation of water from a beaker presents as open system.
Here vapours of water (matter) go into the atmosphere and heat (energy) required is
absorbed by water from the surroundings.
248
b) Closed system : A system which may exchange energy but not matter with
surroundings is called a closed system.
Ex : Consider boiling of water in a closed metallic vessel. Here, heat is transferred from
the burner (surroundings) to the system. Steam remains inside the vessel. Thus, matter
is not exchanged.
c) Isolated system : A system which can neither exchange matter nor energy with the
surroundings is called an isolated system.
Ex : Take some water in an insulated vessel and put a small piece of sodium metal in it.
An exothermic reaction takes place.
Neither hydrogen gas (matter) nor heat (energy) is transferred to the surroundings.
Question 2.
Define the state function and state variables, Give examples.
Answer:
State function : Properties of the systems which depends on the initial and the final
states of the system but are independent of the path are called state functions.
Eg. : Energy, Volume, Enthalpy, Gibbs Energy.
State variables : Variables like P, V, T are called state variables. These are used to
describe a system completely.
249
Question 3.
“Internal energy is a state function”. Explain.
Answer:
Internal energy (E) : ‘The total energy stored in the substance at constant temperature
and pres-sure is called its internal energy (E)”.
It is a state function and is an extensive property.
Internal energy change (∆E) is considered as the difference between the internal
energies of products and reactants.
∆E = (Ep – Er)
In any path taken (Q – W) is equal to ∆E.
Where Q = heat and W = Work.
Internal energy is a state function it depends on initial state and find state of the
system.
Question 4.
“Work is not a state function”. Explain.
Answer:
Work is not a state function.
• One state of a system can be changed to another in a several ways. Work
involved in different paths differ in their quantity.
• Work depends on the path of the reaction but not on the state of the system.
• Work is dependent on the capacity factor and intensity factor.
Question 5.
What is heat ? Explain.
Answer:
The internal energy of a system can be change by transfer of heat from the
surroundings to system (or) vice versa with out consumption of work.
This exchange of energy which results of temperature difference is called heat (q).
Question 6.
Derive the equation for ‘Wrev‘ in isothermal reversible process.
Answer:
Derivation of equation for Wrev in isothermal reversible process :
Let the work done against the pressure Sw = -P.dv
Assume that expansion isothermally from volume V1 to volume V2
250
[P = pressure (External)
dv = change in volume]
Question 7.
Two litres of an ideal gas at a pressure of 10 atm expands isothermally into a vacuum
until its total volume is 20 litres. How much heat is absorbed and how much work is
done in the expansion ?
Answer:
Heat absorbed = 0
‘P‘ of gas = 10 at m
PExp = 0
V1 = 2 lit
V2 = 20 lit
Because the given process is isothermal
∴ ∆U = 0
q+w=0
q = -w
= pex (V2 – V2)
= Pex(20 – 2) = 0
= 0 (18) = 0
q = 0 and work done also zero
∴w=0
251
Question 8.
If the ideal gas given in the problem 45 expands against constant external pressure of 1
atm what is the q value ?
Answer:
Formula
q=–W
pex = 1 atm
pgas = 10 atm
V1 = 2 lit
V2 = 20 lit
= pex(VV2 – V2)
= 1 (20 – 2)
= 18 lit. atm
Question 9.
If the ideal gas given in the problem 45 expands to a final volume of 10L conducted
reversibly what is q value ?
Answer:
V1 = 2 lit, V2 = 10 lit.
The expression for reversible isothermal expansion; q = 2.303 log v2v1
q = -w = 2.303 × log 202 = 2.303 × 20 log 10
= 46.06 lit. atm.
Question 10.
Explain the state function enthalpy, H’. What is the relationship between ∆U and ∆H ?
Answer:
Enthalpy (H) : “Enthalpy is the amount of heat exchanged by a system with its
surroundings at constant pressure and temperature”.
The energy change taking place at constant pressure and at a constant temperature is
called enthalpy change (∆H).
Mathematically, ∆H = ∆U + P. ∆N. When ∆U = Internal energy change.
Enthalpy is state function. Thus, the magnitude of enthalpy change depends only upon
the enthalpies in the initial and the final states.∆H = [HProducts – HReactants]
For gaseous reactions, ∆H = ∆U + ∆nRT
252
Question 11.
Show that ∆H = ∆U + ∆n(g), RT
Answer:
Mathematically, ∆H = ∆U + P. ∆V. When ∆U = Internal energy change.
the enthalpies in the initial and the final states.
∆H = [HProducts – Hreactants]
For gaseous reaction, ∆H = ∆U + ∆nRT
Consider PV1 = n1 RT
PV2 = n2 RT
PV2 – PV1 = n2 RT – n1 RT
P(V2 – V1) = (n2 – n11)RT
P × ∆V = ∆ ng RT
[We know that ∆H = ∆U + P∆V]
∆H = ∆U + ∆ng RT
Question 12.
If Water vapour is assumed to be a perfect gas, molar enthalpy change for
vapourisation of 1 mole of water at 1 bar and 100° C is 41 kJ mol-1. Calculate the
internal energy change when
a) 1 mol of water is vapourised at 1 bar and 100° C
b) 1 mol of water liquid is converted into ice.
Answer:
∆H = 41kJ
∆ng = 1
a) H2O ⇌ H2O(g)
∆H = ∆U + ∆n(g) RT
41 = ∆U + 8.314 × 10-3 × 373
∆U = 41 – 3.101 = 37.899 KJ / mole
b) H2O ⇌ H2O(ice)
∆H = ∆U + ∆n(g) RT,∆H = ∆U [∵ ∆n = 0]
∆H = ∆U = 41 kJ /mole
253
Question 13.
Explain extensive and intensive properties.
Answer:
Measurable (or) macroscopic properties such as mass, pressure, volume, temperature,
surface tension, viscosity etc., can be subdivided into two categories as below :
i) Extensive properties: The properties whose magnitude depends upon the quantity of
matter present in the system are called extensive properties. Examples of such
properties are mass, volume, heat capacity, internal energy, entropy, heat content,
Gibbs free energy etc. These properties change with quantity of matter present in the
system. These properties are additive in nature.
ii) Intensive properties: The properties which do not depend upon the quantity of
matter present in the system are called intensive properties. Examples of such
properties are density, molar volume, molar entropy, molar heat capacity, surface
tension, viscosity, specific heat, refractive index, pressure, temperature, boiling point,
freezing point, vapour pressure etc. These properties depends only on the nature of the
substance.
Question 14.
Define heat capacity. What are Cp and Cv ? Show that Cp – Cv = R.
Answer:
Heat capacity (C) : “Heat capacity (G) of a substance is defined as the amount of heat
required to raise its temperature through one degree”.
(or)
It is the ratio of heat absorbed (q) to the resulting increase in temperature (dT)
∴ C = qdT
Heat capacity (C) is a state function. Hence to evaluate ‘C’, the conditions such as
volume or constant pressure have to be specified in order to define the path. Thus
there are two different types of heat capacities. These are :
i) Heat capacity at constant volume (Cv)
ii) Heat capacity at constant pressure (Cp).
From first law of thermodynamicsl,
q = dE + W = dE + P.dV (∵ W = PV)
∴ C = qdT = dE+P⋅dVdT
If the absorption of heat takes place at constant volume, Cv (i.e.,) dV = 0
∴ Cv = qVdT=∂E+O∂T=(∂E∂T)V
∴ Cv = (∂E∂T)V
254
Definition for “Cv“: Heat capacity of a system at constant volume (Cv) may be defined as
rate of change of internal energy with temperature at constant volume.
If heat is absorbed by the system at constant pressure, heat capacity is denoted by ‘Cp‘
and is called heat capacity at constant pressure.
Cp = qpdT=(∂E∂T)p+P(∂V∂T)p ………… (1)
But H = E + PV
Differentiating this equation w.r.to T at constant pressure, we get
(∂H∂T)p=(∂E∂T)p+(∂V∂T)p ………………. (2)
From equation (1) and (2), we get
Cp = (∂H∂T)p
Definition for Cp: Heat capacity of a system at constant pressure (Cp) may be defined as
rate of change of enthalpy with temperature at constant pressure.
Derivation of Cp – Cv = R
H = E + PV (For an ideal gas)
differentiating w.r.t. T.
dHdT=dEdT+d(PV)dT
⇒ dHdT=dEdT+d(RT)dT [∵ PV = RT]
dHdT=dEdT+R
Cp – Cv = R
Question 15.
Explain the determination of ‘∆U’ of a reaction calorimetric
Answer:
• The technique of measuring heats of reactions is called calorimetres. The
apparatus used is calorimeter.
• Calorimeter is a vessel properly insulated and contains water as the calorimetric
liquids.
• A combustioble substance is burnt in oxygen.
• Heat evolved during the reaction is measured from the rise in temperature.
• Here there is no worke done as ∆V = 0
• By the raise of temperature of water bath and calorimeter the amount of heat
evolved can be determined.
255
Internal Enegy ∆U = Q. ∆t × Mm
Q = heat capacity
∆t = t2 – t1
M = molar mass of substance
m = mass of the substance
Question 16.
Explain the determination of ∆H of a reaction calorimetrically.
Answer:
Heat change at constant pressure can be measured in a calorimeter at constant
pressure ∆H = qp
∴ For Exothermic reaction ∆H = -ve
For Endothermic reaction ∆H = +ve
256
Question 17.
What is enthalpy of a reaction ? Explain the standard enthalpy of a reaction.
Answer:
Mathematically, ∆H = ∆U + P. ∆V. When ∆U = Internal energy change.
the enthalpies in the initial and the final states.
∆H = [HProducts – HReactants]
For gaseous reactions, ∆H = ∆U + ∆nRT
Question 18.
What is the standard enthalpy of formation ? Explain it with example.
Answer:
The heat change involved in the reaction of formation of one mole of a compound is
called enthalpy of formation.
If all the substances are in the standard states the enthalpy of formation is called
standard enthalpy of formation.
In the above reactions the substances are in standand states
Question 19.
Define and explain enthalpy of phase transformation.
Answer:
Enthalpy of phase transformation : The heat change involved in the change of phase
(or) physical state of one mole of compound at atmospheric pressure.
a) Standard molar enthalpy of fusion (∆fusH0) : The enthalpy change that accompanies
melting of one mole of a soild substance in standard state is called Standard molar
enthalpy of fusion.
Eg : H2O(s) → H2O(l) ∆fusH0 = 6.00 KJ mol-1
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b) Standard molar enthalpy of vapourisation (∆vapH0): Amount of heat required to
vapourise 1 mole of a liquid at constant temperature and under standard pressure (1
bar) is called its standard molar enthalpy of vapourisation (∆vapH0).
Eg : H2O(l) → H2O(g) ∆vapH0 = + 40.79 KJ mol-1
c) Standard enthalpy of sublimation (∆subH0): It is the change in the enthalpy when are
mole of a solid substance sublimes at a constant temperature under standard pressure.
Question 20.
Define and explain the standard enthalpy of vapourisation (Molar enthalpy of
vapourisation)
Answer:
Standard molar enthalpy of fusion (∆fusH0) : The enthalpy change that accompanies
melting of one mole of a soild substance in standard state is called Standard molar
enthalpy of fusion.
Eg : H2O(s) → H2O(l) ∆fusH0 = 6.00 KJ mol-1
Question 21.
Define and explain the standard enthalpy of vapourisation (Molar entghalpy of
vapourisation)
Answer:
Standard molar enthalpy of vapourisation (∆vapH0) : Amount of heat required to
vapourise 1 mole of a liquid at constant temperature and under standard pressure (1
bar) is called its standard molar enthalpy of vapourisation (∆vapH0).
Eg : H2O(l) → H2O(g) ∆vapH0 = + 40.79 KJ mol-1
Question 22.
Define and explain the standard enthalpy sumlimation.
Answer:
Standard enthalpy of sublimation ∆subH0 : It is the change in the enthalpy when are mole
of a solid substance sublimes at a constant temperature under standard pressure.
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Question 23.
Define and explain the standard enthalpy of formation (∆f Hθ).
Answer:
The heat change involved in the reaction of formation of one mole of a compound is
called Enthalpy of formation
If all the substances are in the standard states the enthalpy of formation is called
standard enthalpy of formation.
Question 24.
State and explain the Hess’s law of constant Heat summation. [Mar. ’13]
Answer:
Hess’s law states that the total amount of heat evolved or absorbed in a chemical
reaction is always same whether the reaction is carried out in one step (or) in several
steps.
Illustration : This means that the heat of reaction depends only on the initial and final
stages and not on the intermediate stages through which the reaction is carried out.
Let us consider a reaction in which A gives D. The reaction is brought out in one step
and let the heat of reaction be ∆H.
A → D; ∆H
Suppose the same reaction is brought out in three stages as follows :
A → B : ∆H1
B → C : ∆H2
C → D : ∆H3
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The net heat of reaction is ∆H1 + ∆H2+ ∆H3.
According to Hess law ∆H = ∆H1 + ∆H2 + ∆H3.
Ex : Consider the formation of CO2. It can be prepared in two ways.
1) Direct method : By heating carbon in excess of 02.
C(s) + O2(g) → CO2(g); ∆H = – 393.5 kJ
2) Indirect method : Carbon can be converted into CO2 in the following two steps.
C(s) + 12O2(g) → CO2(g); ∆H1 = – 110.5 kJ
CO (g) + 12 O2(g) → CO2(g); ∆H2 = – 283.02 kJ
Total ∆H = -393.52 kJ (∆H1 + ∆H2)
The two ∆H values are same.
Question 25.
Define and exlain the enthalpy of combustion (∆cHθ).
Answer:
Standard enthalpy of combustion is defined as the enthalpy change per mole (or per
unit amount) of a substance, when it undergoes combustion and all the reactants and
products being in their standard states at the specified temperature.
Cooking gas in cylinders contains mostly butane (C4 H10). During complete combustion
of one mole of butane, 2658 kJ of heat is released. We can write the thermochemical
reactions ofr this as :
C4 H10 (g) + 132 O2 (g) → 4CO2 (g) + 5H2O(1);
∆cHθ = -2658.0 kJ mol-1
Question 26.
Define and explain enthalpy of atomisation (∆aHθ).
Answer:
• The heat required to dissociate 1 mole of a simple molecule in the gaseous state
into its constituent atoms.
• This is an endothermic process.
Ex: O2(g) → 2O(g) ∆H = 489.5 KJ
N2(g) → 2N(g) ∆H = 937.4 KJ
260
Question 27.
Define and explain the Bond enthalpy (∆bondHθ)
Answer:
Bond Enthalpy : The change in enthalpy when one mole of covalent bonds of a gaseous
covalent compond is broken to from gaseous products is called Bond dissociation
Enthalpy.
Ex : H2(g) → 2H(g) ∆H = 435.9 KJ / mole
Question 28.
What is the bond enthalpy of C-H bond of CH4 ?
Answer:
The bond dissociation enthalpy for step wise dissociation of CH4 molecule are CH.
CH4(g) → CH3(g) + H(g) ; ∆ H0 = 427.0 kJ
CH3(g) → CH2(g) + H(g) ; ∆ H0 = 418.4kJ
CH2(g) → CH(g) + H(g) ; ∆ H0 = 460.2 kJ
CH(g) → C(g) + H(g) ; ∆ H0 343.1 kJ
The enthalpy for each step is different due to the reason that in each step of
dissociation different fragments of CH4 are involved.
But the average bond dissociation enthalpy is 1/4 of the total energy required to break
one mole of CH4 into C(g) + 4H (g).
C-H bond dissociation Enthalpy = 427.0+418.4+460.2+343.14
= 1648.74 = 412.2 kJ
Question 29.
Define heat of solution (∆solHθ) and heat of dilution.
Answer:
i) Enthalpy of solution : Definition : The amount of heat evolved or absorbed when 1
mole of a solute is dissolved completely in large excess of solvent is called Enthalpy of
solution.
(Or)
The change of enthalpy when a solution containing 1 mole of a solute is diluted from
one concentration to another.
Ex : KCl (s) + aq → KCl (aq), DH = + 19.75 kJ
This is measured per mole of solute. If solvent is water then it is called enthalpy of
dilution.
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ii) Enthalpy of dilution : The change of enthalpy when a solution containing 1 mole of a
solute is diluted from one concentration to another.
Ex : HCl (g) + aq → HCl (aq), ∆H = – 75.4 kJ
Question 30.
Define ionisation enthalpy and electron affinity.
Answer:
Ionisation Enthalpy : The enthalpy change observed by the removal of an electron from
the neutral isolated gaseous atom is called ionisation enthalpy.
Electron affinity : The enthalpy evolved by the addition of electron to neutral gaseous
atom is called electron affinity.
X(g) + e– → X–(g) + EA
Observe the following spontaneous reactions
1) H2(g) + 1/2 O2(g) H2O = -285.8 kJ / mole
2) c(graphite) + 2S(g) → CS2(g) ∆ H0 = 91.91 kJ / mole
In reaction (1) ∆H = -ve, in reaction (2) ∆H = +ve
∴ The decrease in Enthalpy may be a condition but not a necessary and sufficient
condition for spontaneity of a reaction.
Ionization Energy and Electron Affinity : Ionization energy and electron affinity are
defined at absolute zero. At any other temperature, heat capacities for the reactants
and the products have to be taken into account. Enthalpies of reactions for
M(g) → M+(g) + e– (for ionization)
M(g) + e– → M–(g) (for electron gain) at temperature, T is
∆rHΘ(T) = ∆rHΘ(0) + ∫T0ΔrCΘpdt
The value of Cp for each species in the above reaction is 5/2 R (Cv = 3/2R)
So, ∆rCpΘ = 5/2 R (for ionization)
∆rCpΘ = -5/2 R (for electron gain)
Therefore,
∆rHΘ = (Ionization enthalpy)
= E0 (ionization energy) + 5/2 RT
∆rHΘ = (electron gain enthalpy)
= -A (electron affinity) = 5/2 RT
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Question 31.
Explain the spontaneity of a process.
Answer:
Spontaneous reaction :
A process is said to be spontaneous if it occurs on its own without intervention of any
external agency of any kind.
All natural processes are spontaneous.
Entropy increases in all spontaneous processes.
At this juncture, “Gibbs” introduced another thermodynamic function which involves
both enthalpy (H) and entropy (S) functions. This is known as free energy function (G).
This is given by the equation.
G = H – TS. .’G1 is now referred as ‘Gibbs energy (or) Gibbs function.
“∆Gsys is negative” for spontaneous reactions (or) processes. Thus the spontaneity of a
reaction and the algebraic signs of ∆H, ∆S, ∆G and the magnitude of T can be related
as follows :
Question 32.
Is decrease in enthaply a crieterion for spontaneity ? Explain. [A.P. Mar. 16]
Answer:
sufficient condition for the spontaneous nature of a reaction. ;
Observe the following spontaneous reactions
1. H2(g) + 1/2 O2(g) ⇌ H2O ∆ H0 = -285.8 kJ/mole
2. C(graphite) + 2S(g) → CS2(g) ∆ H0 = 91.91 kJ/mole
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In reaction (1) ∆H = -ve, in reaction (2) ∆H = +ve
∴ The decrease in enthalpy may be a condition but not a necessary and sufficient
condition for spontaneity of reaction.
Question 33.
What is entropy ? Explain with examples.
OR
Explain “Entropy” concept.
Answer:
Entropy (S): Entropy is taken as a measure of disorder of molecules (or) randomness of
the system. Greater the disorder of molecules in a system, the higher is the entropy.
Entropy is a state function. It depends on the temperature, pressure of the state.
Entropy change, ∆S = qrevT [qrev = heat absorbed by the system isothermally and
reversibly at T]
For a spontaneous process in an isolated system the entropy change is positive.
(∆S = positive)
∆Stotal = ∆Ssystem + ∆Ssurroundings
Question 34.
Is increase in entropy a criterion for spontaneity ? Explain.
Answer:
For a spontaneous process change in entropy is positive
∆S = +ve (spontaneous)
∆S = -ve (backward reaction is spontaneous)
∆S = 0 (Equilibrium reaction)
∴ ∆H = -ve, ∆S = +ve, ∆G = -ve then the reaction
Spontaneous at all T values (Reaction is irreversible)
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Question 35.
Can All and ∆S discriminate between irreversible and reversible processes ? Explain.
Answer:
• Change in internal energy (∆U)
• In exothermic process and internal energy lowered (Reaction is Spontaneous)
• In case of reversible reaction the reaction favoured in the direction where there is
decrease in the internal energy.
For a spontaneous process change in entropy is positive
∴ ∆H = -ve, AS = +ve, ∆G = -ve then the reaction
Question 36.
In which of the following processes entropy increases ?
a) A liquid evaporates to vapour.
b) Temperature of a crystalline solid lowered from 115K to OK
c) CaCO3(s) → CaO(s) + CO2(g)
d) Cl2(g) → 2Cl(g)
Answer:
a) When a liquid evaporates to vapour randomness increases in the vapour state ∆S is
+ve. Hence the process is spontaneous.
b) If the temperature of the crystalline solid is lowered to OK it becomes perfectly
ordered. No disorder is noticed. Hence such a process is not spontaneous.
c) CaCO3(s) → CaO(s) + CO2(g)
∆S is very slightly positive. If temp is increased ΔS becomes more positive.
d) Cl2(g) → 2Cl(g)
It is an endothermic process there is no considerable increase in entropy. The process is
not spontaneous.
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Question 37.
For the oxidation of iron
4Fe(s) + 3O2(g) → 2Fe(2)O3(s), the entropy change is -549.45JK-1 mol-1 at 298K. Though it has
negative entropy change the reaction is spontaneous. Why ?
(∆rHΘ = -1648 × 103 J mol-1)
Answer:
One decides the spontaneity of a reaction by considering
∆Stotal i.e< (∆Ssys + ∆Ssurr). For calculating ∆Ssurr, we have to consider the heat absorbed by
the surroundings which is equal to -∆rHΘ. At temperature T, entropy change of the
surroundings is
∆Ssurr = ΔrHθT (at constant pressure)
= −(−1648×103Jmol−1298 K = 5530 JK-1 mol-1
Thus, total entropy change for this reaction
∆rStotal = 5530 JK-1 mol-1 + (-549.4 JK-1 mol-1) = 4980.6 JK-1 mol-1
This shows that the above reaction is spontaneous.
Question 38.
Which formalae in the following are correct ?
a) G = H – TS
b) ∆Gsys = ∆Hsys = ∆Hsys – ∆Ssys
c) ∆Ssurr = ΔHsur T=−ΔHsys T
d) ∆Ssurr = ∆Hsys + −ΔHsys T
e) TASTotal = T∆Hsys – ∆Hsys
Answer:
a) Correct
b) Correct at constant temperature
c) Correct
d) Correct
e) Not correct
Question 39.
Calculate ∆rGθ for conversion of oxygen to ozone ∆rGθ=163 kJ mol-1 O2(g) → O3(g) at 298K.
Kp for the 32 the reaction is 2.43 × 10-29
Answer:
∆G0 = -2.303 RT log Kp
= -2.303 × 8.314 × 298 × log 2.43 × 10-29
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= -16300 J/mole
= 163 kJ/mole
Question 40.
State the second law of thermodynamics and explain it.
Answer:
II law of thermodynamics :
Statements :
• “It is impossible for a self acting machine unaided by any external agency to
convert heat from a body at low temperature to a body at higher temperature”.
• “All spontaneous processes are thermodynamically irreversible and entropy of the
system increases in all spontaneous processes.”
• “For any spontaneous process taking place in an isolated system, the change in
entropy (∆S) is positive.”
Question 41.
State the third law of thermodynamics. What do you understand by it ?
Answer:
Third law of thermodynamics: “The entropy of a pure and perfectly crystalline
substance is zero ; at .the absolute zero of a temperature (-273° C)”.
Slim T → 0 = 0
This law imposes a limitation on the value of entropy.
ST = ∫T0CpT⋅dT
Thus entropy (S) of a substance at any temperature is calculated if the temperature
dependence of ‘Cp‘ is known in evaluating absolute entropy of any substance.
Importance of this law : One of the most important applications of third law is the
calculation of entropy changes in chemical reactions.
Question 42.
Explain spontaneity of a process in terms of Gibbs energy.
Answer:
∆G = ∆H – T∆S
∆Gsys = negative for spontaneous reactions (∆G < 0)
∆Gsys = positive for non – spontaneous reactions (∆G > 0)
∆Gsys = zero for equilibrium reactions (∆G = 0)
∆G =-ve, ∆S =+ve, ∆H =-ve are the conditions for the sponaneity of reaction.
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Question 43.
The sign and magnitude of Gibbs energy change of a chemical process tells about its
spontaneity and useful work that could be extracted from it. Explain.
Answer:
To predict about the spontaneity of the reaction and
To redict the useful work that could be extract is the sign and magnitude of the
quantities in Gibb’s equation is useful.
When a reaction is reversible it cannot proceed in both the direction with same case. In
general the system would spontaneously change to configuration of lower free energy.
At equilibrium ∆G = 0
0 = ∆G° + RTLnK
∆rG° = -RTLnK = -2.303 RT log k
We know ∆rG° = ∆rH° – T∆rS° = -RT log k
For endothermic reaction ∆rH° may be large and positive
In such a case K is much less (K < 1)
In exothermic reactions ∆rH° is large and negative (K >1)
∴ For exothermic reaction
a) K must be large
b) ∆rG° is highly negative
c) ∆S° is highly positive
Hence with the sign and magnitude of the factors the yield of the product may be
estimated.
Question 44.
In a process 701 J of heat is absorbed by a system and 394J of work is done by the
system. What is the change in internal energy for the process ?
Answer:
q = 701 J
w = -394 J
∆U = q + w
∆U = 701 – 394
= 307 J
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Question 45.
The reaction of cyanamide (s). with dioxygen was carried out in a bomb calorimeter and
∆U was found to be – 742, 7kJ mol-1 at 298K. Calculate the enthalpy change for the
reaction at 298k.
NH2CN(g) + 32 O2(g) → N2(g) + H2O(1)
Answer:
NH2CN(g) + 32 O2(g) → N2(g) + H2O(1)
∆n = 2 – 52
= 0.5
∆U = – 742 kJ/mol
∆H = ∆U + ∆n RT
∆H = – 742 + (-0.5) × 8.314 × 10-3 × 298
= -742.7 – 1.238
= – 743.94 kJ/mol4.
Question 46.
Calculate the number of kJ of heat necessary to rise the temperature of 60.0 g of
aluminium from 35°C to 55°C. Molar heat capacity of aluminimum is 24 J mol-1 K-1.
Answer:
Given molar heat capacity of Al = 24 J/mole.k
= 2427 J/gm. k
The heat necessary to raise the temp, of 60 g. of Al from 35°C to 55°C
= 60 × 2427 × 55 – 35
= 60 × 2427 × 20 = 1.067 Kj
Question 47.
Calculate the enthalpy change on freezing of 1.0 mol of water at 10.0°C to ice at 10.0°C.
∆fus H = 6.03 kJ mol-1 at 0°C.
Cp [H2 O(1)] = 75.3J mol-1 K-1
Cp [H2O(s)] = 36.8 J mol-1 K-1
Answer:
∆Hfus = 6.03 kJ
1 mole of water taken to -10°C from 0°C
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∆H = Cp ∆T = 36.8 × -10 = – 3685
= 0.368 kJ.
Total enthalpy = 6.03 + 0.753 – 0.368
= 6.415 kJ/mole.
Question 48.
Enthalpy of combustion of carbon to CO2 is – 393.5 kJ mol-1. Calculate the heat released
upon formation of 35.2 g of CO2 from carbon and dioxygen gas.
Answer:
C(s) + O2(g) → CO2(g) ∆H = -393.5 kJ/mole
44gms of CO2 → -393.5 kJ
35.2 gms of CO2 → ?
35.2×393.544 = -314.8 kJ
Question 49.
Enthalpies of formation of CO(g), CO2(g) and N2O4(g) are – 110, -393, 81 and 9.7 kJ mol-
1
respectively. Find the value of ∆rH for the reaction :
N2O4(g) + 3CO(g) → N2O(g) + 3CO2(g)
Answer:
N2O4(g) + 3CO(g) → N2O(g) + 3CO2(g)
∆HCO = -110 KJ
∆HCO = -393 KJ
2
∆HN O = -81 KJ
2
∆HN O = -9.7 KJ
2 4
∆H = sum of enthalpies of products – sum of enthalpies of reactants

= -1017 – (-320.3)
∆H = -696.7kJ
Question 50.
Given N2(g) + 3H2(g) → 2NH3(g); ∆rH° = – 92.4 kJ mol-1 What is the standard enthalpy of
formation of NH3 gas ?
Answer:
N2(g) + 3H2(g) → 2NH3(g)
2 moles of NH3 → -92.4kJ
For 1 mole of NH3 → −92.42 = -46.2
∆H°(NH ) = -46.2 KJ l mole
3
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Question 51.
Calculate the standard enthalpy of formation of CH3OH(l) from the following data :
CH3OH(l) + 32O2(g) → CO3(g) + 2H3OΘ; ∆rH° = -726 kJ mol-1
C(graphite) + O2(g) → CO2(g); ∆cH° = – 393 kJ mol-1
H2(g) + O2(g) → H2O(l); ∆fH° = -286 kJ -mol-1.
Answer:
Given ∆fH° (CO2) = -393 KJ mol-1
∆fH° (H2O(1)) = -286 KJ mol-1
∆rH° = -726 KJ mol-1

∆rH°= ∆H°total total of the products – ∆H°total total of the reactants
-726 = [-393 + 2 (-286)] – [∆fH° CH3OH].
∆rH° (CH3OH) = 726 + [-393 + 2(-286)] KJ mol-1
= – 239 KJ mol-1
Question 52.
Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4 Cl(g)
and calculate bond enthalpy of C – Cl in CCl4(g).
∆vap H°(CCl4) = 30.5 kJ mol-1.
∆fH°(CCl4) = – 135.5 kJ mol-1.
∆aH° (C) = 715.0 kJ mol-1, where ∆aH° is enthalpy of atomisation
∆aH° (Cl2) = 242 kJ mol-1
Answer:
CCl4(1) → CCl4(g) → C(g) + 4Cl(g)
∆vap H°(CCl4) = 30.5 kJ mol-1.
∆fH°(CCl4) = – 135.5 kJ mol-1.
∆H°(C) = 715.0 kJ mol-1
∆rH° (Cl2) = 242 kJ mol-1
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∆rH° = 715 + 484 + 135.5 – 30.5
∆rH° = 1334.5 – 30.5 KJ mol-1 = 1304 KJ
C – Cl bond enthalpy = 13044 = 326 KJ mol-1
Question 53.
For an isolated system, ∆U = 0, what will be ∆S ?
Answer:
Given an Isolated system
For isolated system ∆U = 0
∴ ∆H = ∆U + ∆nRT
∆H = ∆nRT
∆H = ΔHT=ΔnRTT
∴ ∆S > 0 ∆S = + ve
Question 54.
For the reaction at 298 K.
2A + B → C
∆H = 400 kJ mol-1 and ∆S = 0.2 kJ K-1 mol-1
At what temperature will be reaction become spontaneous considering ∆H and ∆S to
be constant over the temperature range.
Answer:
Formula ∆S = ΔHT
T = ΔHΔS=4000.2 = 2000K
Question 55.
For the reaction, 2 Cl(g) → Cl2(g), what are the signs of ∆H and ∆S ?
Answer:
2 Cl(g) → Cl2(g)
Here in the above reaction chlorine atoms (reactive)
Converted into stable Cl2 molecule It is an exothermic reaction
∆H = – ve, ∆S = + ve
Question 56.
For the reaction 2 A(g) + B(g) → 2D(g)
∆U° = – 10.5 kJ and ∆S° = – 44.1 JK-1.
Calculate ∆G° for the reaction and predict whether the reaction can occur
272
spontaneously or not.
Answer:
2A(g) + B(g) → 2D(g)
ng = 2 – 3 = -1
∆H = ∆v + ng RT
∆H = – 10.5 + (-1) × 8.314103 × 298
– 10.5 – 2.477 = – 12.977 KJ mol-1
∆S = -44.1 JK-1
∆G° = ∆H – T∆S
∆G° = – 12.977 – 298 (-44.1)
= – 12977 + 13141.8 = 1648 J or + 0.1648 J
∴ ∆G° is +ve the reaction is non spontaneous.
Question 57.
The equilibrium constant for a reaction is 10. What will be the value of ∆G° ? R = 8.314
JK-1 mol-1, T = 300 K.
Answer:
Formula ∆G° = – RT lnk
∆G° = – 2.303 RT log k
∆G° = – 2.303 × 8.314 × 300 × log 10
= – 5744 J/mole
∆G° = -5.744 KJ/mole
Question 58.
State the first law of thermodynamics. Explain its mathematical notation.
Answer:
First law of thermodynamics :
The law of conservation of energy is taken as the first law of thermodynamics.
Statements :
1. “Energy can neither be created nor destroyed, although it can be transformed
from one form to another”.
2. “It is impossible to construct a perpetual motion machine of first kind (which
produce work without consuming energy)”.
3. “The total energy of the system and surroundings is constant”.
Mathematical form :
Let a system in state “A”, of internal energy EA absorb from the surroundings acertain
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amount of heat (Q) and undergo a change in its state to B. Let the internal energy in
the state B is EB. If W is the work done by the system in the process, the increase in
internal energy ∆E of the system is given by the equation, ∆E = EB – EA
From first law, net gain of energy (Q – W) must be equal to ∆E

∆E = (EB – EA) = (Q – W)
(or) Q = ∆E + W For infinitesimally small changes
∴ q = increase in internal energy + energy used in doing work.
Above equation is mathematical form of I law of thermodynamics.
Question 59.
State the 2nd law of thermodynamics in any two ways.
Answer:
II law of thermodynamics :
Statements :
1. “It is impossible for a self acting machine unaided by any external agency to
convert heat from a body at low temperature to a body at higher temperature”.
2. “All spontaneous processes are thermodynamically irreversible and entropy of the
system increases in all spontaneous processes.”
3. “For any spontaneous pirocess taking place in an isolated system, the change in
entropy (∆S) is positive.”
Question 60.
Explain Gibbs energy.
Answer:
Gibbs energy (∆G) : The amount of energy available from a system which can be put to
useful work at constant temperature and pressure is called Gibb’s energy. For
explaining the criteria for spontaneity of a reaction, Gibb’s introduced thermodynamic
function which involved both enthalpy (H) and entropy (S) functions. This is known as
free energy function (G). This is given by the equation,
G = H – TS
Where ‘G’ is known as Gibbs energy (or) Gibbs function.
∆G = ∆H – T ∆S
∆Gsys = positive for non – spontaneous reactions (∆G >0)
∆Gsys = zero equilibrium reactions (∆G = 0)
274
Question 61.
Explain the sponteneity of a reaction interms of Gibbs energy.
Answer:
To predict about the spontaneity of the reaction and
To redict the useful work that could be extract is the sign and magnitude of the
quantities in Gibb’s equation is useful.
When a reaction is reversible it cannot proceed in both the direction with same case. In
general the system would spontaneously change to configuration of lower free energy.
At equilibrium ∆G = 0
0 = ∆G° + RTLnK
∆rG° = -RTLnK = -2.303 RT log k
We know ∆rG° = ∆rH° – T∆rS° = -RT log k
For endothermic reaction ∆rH° may be large and positive
In such a case K is much less (K < 1)
In exothermic reactions ∆rH° is large and negative (K >1)
∴ For exothermic reaction
a) K must be large
b) ∆rG° is highly negative
c) ∆S° is highly positive
Hence with the sign and magnitude of the factors the yield of the product my be
estimated.
∆Gsys = positive for non – spontaneous reactions (∆G > 0)
∆Gsys = zero equilibrium reactions (∆G = 0)
Question 1.
State and explain Hess’s Law of constant heat summation. Give example.
Answer:
Hess’s Law : Hess’s law states that the total amount of heat evolved or absorbed in a
chemical reaction is always same whether the reaction is carried out in one step (or) in
several steps. Illustration : This means that the heat of reaction depends only on the
initial and final stages and not on the intermediate stages through which the reaction is
carried out. Let us consider a reaction in which A gives D. The reaction is brought out in
one step and let the heat of reaction be ∆H.
275
A → D; ∆H
Suppose the same reaction is brought out in three stages as follows –
A → B : ∆H1
B → C : ∆H2
C → D : ∆H3
The net heat of reaction is ∆H1 +∆H2+∆H3.
According to Hess law ∆H = ∆H1 + ∆H2 + ∆H3.
Ex : Consider the formation of CO2. It can be prepared in two ways.
1) Direct method : By heating carbon in excess of O2.
C(s) + O2(g) → CO2(g); ∆H = – 393.5 kJ
2) Indirect method : Carbon can be converted into C02 in the following two steps.
C(s) + 12O2(g) → CO2(g); ∆H1 = – 110.5 kJ
CO (g) + 12 O2(g) → CO2(g); ∆H2 = – 283.02 kJ
Total ∆H = -393.52 kJ
The two ∆H values are same.
Question 2.
Explain the experiment to determine the internal energy change of a chemical reaction.
Answer:
Internal energy (U): “The total energy stored in the substance at constant temperature
and pressure is called its internal energy (U)”.
It is state function and is an extensive property.
Internal energy change (∆U) is considered as the difference the internal energies of
products and reactants.
∆U = (Up – Uf)
In any path taken (Q – W) is equal to ∆U.
Where Q = heat and W = work.
276
• The technique of measuring heats of reactions is called calorimetres. The
apparatus used is calorimeter.
• Calorimeter is a vessel properly insulated and contains water as the calorimetric
liquids
• A combustioble substance is burnt in oxygen.
• Heat evolved during the reaction is measured from the rise in 5 temperature.
• Here there is no worke done as ∆V = 0
• By the raise of temperature of water bath and calorimeter the amount of heat
evolved can be determined.
Internal Enegy All = Q. ∆t × Mm

Q = heat capacity
∆t = t2 – t1
M = molar mass of substance
m = mass of the substance
Question 3.
Explain the experiment to determine the enthalpy change of chemical reaction.
Answer:
277
Mathematically, change in enthalpy ∆H = ∆E. P∆V
the enthalpies in the initial and final states.
∆H = [Hproducts – Hreactants]
Heat change at constant pressure can be measured in a calorimeter at constant
pressure ∆H = qp
∴ For Exothermic reaction ∆H = -ve
For Endothermic reaction ∆H = +ve
Question 4.
Explain the spontaneity of a reaction interms of enthalpy change, entropy change and
Gibb’s energy change.
Answer:
Spontaneous reaction :
A process is said to be spontaneous if it occurs on its own without intervention of any
external agency of any kind.
All natural processes are spontaneous.
Entropy increases in all spontaneous processes.
At this juncture, “Gibbs” introduced another thermodynamic function which involves
both enthalpy (H) and entropy (S) functions. This is known as free energy function (G).
This is given by the equation, G = H – TS. ‘G’ is now referred as ‘Gibbs energy (or) Gibbs
function.
“∆Gsys is negative” for spontaneous reactions (or) processes. Thus the spontaneity of a
reaction and the algebraic signs of ∆H, ∆S, ∆G and the magnitude of ‘T’ can be related
as follows :
278
For a spontaneous process change in entropy is- positive
∴ ∆H = -ve, ∆S = +ve, ∆G = -ve then the reaction
Solved Problems
Question 1.
Express the change in internal energy of a system when
1. No heat is absorbed by the system from the surroundings, but work (w) is done
on the system. What type of wall does the system have?
2. No work is done on the system, but q amount of heat is taken out from the
system and given to the surroundings. What type of wall does the system have?
3. w amount of work is done by the system and q amount of heat is supplied to the
system. What type of system would it be?
Solution:
1. ∆U = wad wall is adiabatic
2. ∆U = -q, thermally conducting walls
3. ∆U = -q – w, closed system.
Question 2.
Two litres of an ideal gas at a pressure of 10 atm expand isothermally into a vacuum
until its total volume is 10 litres. How much heat is absorbed and how much work is
done in the expansion ?
Solution:
We have q = – w = pex (10 – 2) = 0(8) = 0
No work is done; no heat is absorbed.
279
Question 3.
Consider the same expansion, but this time against a constant external pressure of 1
atm.
Solution:
We have q = – w = pex (8) = (8) = 8 litre-atm
Question 4.
Consider the same expansion, to a final volume of 10 litres conducted reversibly.
Solution:
We have q = – w = 2.303 × 20 log 102
= 32.2 litre-atm
Question 5.
If water vapour is assumed to be a perfect gas, molar enthalpy change for
vapourisation of 1 mol of water at 1 bar and 100°C is 41 kJ mol-1. Calculate the internal
energy change, when
i) 1 mol of water is vaporised at 1 bar pressure and 100°C.
ii) 1 mol of water is converted into ice.
Solution:
i) The change H2O (l) → H2O (g)
∆H = ∆U + ∆ngRT
or ∆U = ∆H – ∆ngRT, substituting the values, we get
∆U = 41.00 kJ mol-1 -1 × 8.3 J mol-1 K-1× 8.3 J mol-1 K-1 × 3731 |K|
= 41.00 kJ mol-1– 3.096 kJ mol-1
= 37.904 kJ mol-1
ii) The change H2O (l) → H2O (s)
There is negligible change in volume,
So, we can put p∆V = ∆ngRT ≈ 0 in this case,
∆H ≅ ∆U
so, ∆U = 41.00 kJ mol-1
280
Question 6.
1g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1
atmospheric pressure according to the equation
C (graphite) + O2 (g) → CO2 (g)
During the reaction, temperature rises from 298 K to 299 K. If the heat capacity of the
bomb calorimeter is 20.7 kJ / K, what is the enthalpy change for the above reaction at
298 K and 1 atm ?
Solution:
Suppose q is the quantity of heat from the reaction mixture and Cv is the heat capacity
of the calorimeter, then the quantity of heat absorbed by the calorimeter.
q = Cv × ∆T
Quantity of heat from the reaction will have the same magnitude but opposite sign
because the heat lost by the system (reaction mixture) is equal to the heat gained by
the calorimeter.
q = -Cv × ∆T = -20.7 kJ/K × (299 – 298)K
= -20.7 kJ
(Here, negative sign indicates the exothermic nature of the reaction)
Thus, ∆U for the combustion of the 1g of graphite = -20.7 kJ
For combustion of 1 mol of graphite,
= 12.0 g mol−1×(−20.7 kJ)1 g
= -2.48 × 102 kJmol-1, Since ∆ng = 0,
∆ H = ∆ U = -2.48 × 102kJ mol-1
Question 7.
A swimmer coming out from a pool is covered with a film of water weighing about 18g.
How much heat must be supplied to evaporate this water at 298 K ? Calculate the
internal energy of vaporisation at 100°C.
∆vapH° for water at 373k = 40.66 kJ mol-1
Solution:We can represent the process of evaporation as
281
Question 8.
The combustion of one mole of benzene takes place at 298 K and 1 atm. After
combustion, CO2(g) and H2O (l) are produced and 3267.0 kJ of heat is liberated.
Calculate the standard enthalpy of formation. ∆f H° of benzene. Standard enthalpies of
formation of CO2(g) and H2O(l) are -393.5 kJ mol-1 and -285.83 kJ mol-1respectively.
Solution:
The formation reaction of benezene is given by:
6C (graphite) + 3H2 (g) → C6H6 (l);
∆fH° = ? ………………… (i)
The enthalpy of combustion of I mol of benzene is :
C6H6 (l) + 152 O2 (g) → 6CO2 (g) + 3H2O(l);
∆cH° =-3267 kJ mol-1 …………… (ii)
The enthalpy of formation of 1 mol of CO2 (g):
C(graphite) + O2 (g) → CO2 (g);
∆f H° = -393.5 kJ mol-1 ………………. (iii)
The enthalpy of formation of 1 mol of H2O(l) is:
H2 (g) + 12 O2 (g) → H2O(l) .
∆fH° = -285.83 kJ mol-1 ………………….. (iv)
Multiplying eqn. (iii) by 6 and eqn. (iv) by 3 we get:
6C (graphite) + 6O2 (g) → 6CO2 (g);
∆fH° = – 2361 kJ mol-1
3H2 (g) + 32 O2 (g) → 3H2O(l) .
∆fH° = – 857.49 kJ mol-1
Summing up the above two equations :
6C(graphite) + 3H2 (g) + 152 O2 (g) → 6CO2 (g) + 3H2O(l)
∆fH° = -3218.49 kJ mol-1 ………………. (v)
Reversing equation (ii);
6CO2 (g) + 3H2O(l) → C6H6 (l) + 152 O2
∆fH° = – 3267.0 kJ mol-1 ………………….. (vi)
adding equations (v) and (vi), we get
6C(graphite) + 3H2 (g) → C6H6 (l);
∆fH° = 48.51 kJ mol-1
282
Question 9.
Predict in which of the following, entropy increases/decreases :
i) A liquid crystallizes into a solid.
ii) Temperature of a crystalline solid is raised from 0 K to 115 K.
iii) 2NaHCO3 (s) → Na2 CO3 (s) + CO2 (g) + H2 O (g)
iv) H2 (g) → 2H(g)
Solution:
i) After freezing, the molecules attain an ordered state and therefore, entropy
decreases.
ii) At 0 K, the contituent particles are static and entropy is minimum. If temperature is
raised to 115 K, these begin to move and oscillate about their equilibrium positions in
the lattice and system becomes more disordered, therefore entropy increases.
iii) Reactant, NaHCO3 is a solid and it has low entropy. Among products there are one
solid and two gases. Therefore, the products represent a condition of higher entropy.
iv) Here one molecule gives two atoms i.e., number of particles increases leading to
more disordered state. Two moles of H atoms have higher entropy than one mole of
dihydrogen molecule.
Question 10.
For oxidation of iron,
4Fe(s) + 3O2 (g) → 2Fe2 O3 (s) entropy change is – 549.4 JK-1 mol-1 at 298 K. Inspite of
negative entropy change of this reaction, why is the reaction spontaneous ?
(∆fH° for this reaction is -1648 × 103 J mol-1)
Solution:
One decides the spontaneity of a reaction by considering.
∆Stotal i.e., (∆Ssys + ∆Ssurr)- For calculating ∆Ssurr. we have to consider the heat absorbed by
the surroundings which is equal to – ∆r ,H°. At temperature T, entropy change of the
surroundings is ∆Ssurr = – ΔrH∘T (at constant pressure)
= –(−1648×103 J mol−1)298 K
= 5530 JK-1 mol-1
Thus, total entropy change for this reaction.
∆rStotal = 5530 JK-1 mol-1 + (-549.4JK-1 mol-1)
= 4980.6 JK-1 mol-1
This shows that the above reaction is spontaneous.
283
Question 11.
Calculate ∆rG° for conversion of oxygen to ozone, 3/2 O2(g) → O3(g) at 298 K. if Kp for
this conversion is 2.47 × 10-29.
Solution:
We know ∆rG° = – 2.303 RT log Kp and
R = 8.314 JK-1 mol-1
Therefore, ∆rG° = – 2.303 (8.314 J K-1 mol-1) × (298 K) (log 2.47 × 10-29)
= 163000 J mol-1
= 163 kJ mol-1
Question 12.
Find out the value of equilibrium constant for the following reaction at 298 K.
2NH3 (g) + CO2 (g) ⇌ NH2 CONH2 (aq) + H2O(l)
Standard Gibbs energy change, ∆rG° at the given temperature is – 13.6 kJ mol-1.
Solution:
Question 13.
At 60°C, dinitrogen tetroxide is fifty percent dissociated. Calculate the standard free
energy change at this temperature and at one atmosphere.
Solution:
N2O4(g) ⇌ 2NO2(g)
If N2O4 is 50% dissociated, the mole fraction of both the substances is given by
xN O = 1−0.51+0.5 ; xNO = 2×0.51+0.5
2 4 2
PN O = 0.51.5 × 1 atm, PNO = 11.5 × 1 atm.

2 4 2
The equilibrium constant Kp is given by

Kp = (pNO2)2pN2O4=1.5(1.5)2(0.5)
= 1.33 atm.
Since
∆rG° = – RT l n Kp
∆rG° = (-8.314 JK-1 mol-1) × (333 K) × (2.303) × (0.1239)
= – 763.8 kJ mol-1
284
Question 1.
State law of chemical equilibrium.
Answer:
The ratio of product of molar concentrations of the products to the product of molar
concentrations of the reactants has a constrant value. This is known as the equilibrium
law (or) law of chemical equilibrium.
Question 2.
Can equilibrium be achieved between water and its vapours in an open vessel. Explain.
Answer:
Equilibrium does not acheived between water and its vapour in an open vessel.
But the equilibrium achieved between water and its vapour in a closed vessel.
H2Ol) ⇌ H2O(g)
Question 3.
Why the concentrations of pure liquids and pure solids are ignored from equilibrium
constant expressions ?
Answer:
The concentrations of pure solids and pure liquids are ignored from equilibrium
constant expres-sions because the concentrations of pure solids and pure liquids are
taken as unity.
Question 4.
What is homogenous equilibrium ? Write two homogenous reactions.
Answer:
It the physical states of the participating substances are same they the equilibrium is
homogeneous equilibrium
e.g.: H2 + I2 ⇌ 2HI(g))
(g) (g)
N2 + 3H2 ⇌ 2NH3
(g) (g) (g)
285
Question 5.
What is heterogeneous equilibrium? Write two heterogeneous reactions.
Answer:
If the physical states of all (or) some of the participating substances are same then the
equilibrium is Heterogeneous equilibrium.
Question 6.
Write reaction quotient, Q, for each of the following reactions.
a) 3O2(g) ⇌ 2O3(g)
b) 4NH3(g) + 7O2(g) ⇌ 4NO2(g) + 6H2O(g)
Answer:
a) 3O2 ⇌ 2O3
(g) (g)
Q = (O3)2t(O2)2t
b) 4NH3 + 7O2 ⇌ 4NO2 + 6H2O(s)
(g) (g) (g)
Q = [NO2]4t[H2O]6t[NH3]4t[O2]7t
Question 7.
Define equilibrium constant.
Answer:
The ratio of product of molar concentrations of products to the product of molar
concentrations of reactants is called equilibrium constant (Kc)
Question 8.
The equilibrium constant expression for a gas reaction is Kc = [NH3]4[O2]5[NO]4[H2O]6 Write
the balanced chemical equation corresponding to this expression.
Answer:
Given Kc = [NH3]4[O2]5[NO]4[H2O]6
Balanced chemical equation is
4NO + 6H2O ⇌ 4NH3 + 5O2
286
Question 9.
Write the relation between Kp and Kc.
Answer:
Kp = Kc(RT)∆n
∆n = No. of gaseous products – No. of gaseous reactants
Question 10.
Under what conditions for a reaction Kp and Kc are numerically equal?
Answer:
If ∆n = 0 i.e. No. of gaseous products = No. of gaseous reactants
then Kp = Kc (RT)∆n
Kp = Kc(RT)0
then Kp = Kc
Question 11.
Give two chemical equilibrium reactions for which Kp = Kc
Answer:
1. H2 + I2 ⇌ 2 HI(g)
(g) (g)
Here ∆n = 0
∴ K p = Kc
2. N2 + O2 ⇌ 2NO(g)
(g) (g)
Here ∆n = 0
∴ K p = Kc
Question 12.
Give two chemical equilibrium reactions for which Kp > Kc.
Answer:
1) 2NH3 ⇌ N2 + 3H2
(g) (g) (g)
∆n = np – nR = (3 + 1) – 2 = 2
∆n = 2 (+ve)
∴ K p > Kc
2) 2SO3 ⇌ 2SO2 + O2
(g) (g) (g)
∆n = np – nR = (2 + 1) – 2 = 1
∆n = 1 (+ve)
∴ K p > Kc
287
Question 13.
Give two chemical equilibrium reactions for which Kp < Kc
Answer:
1) N2 + 3H2 ⇌ 2NH3
(g) (g) (g)
∆n = np – nR = 2 – (1 + 3) = -2
∆n = -2 (- ve)
∴ K p < Kc
2) 2SO2 + O2 ⇌ 2SO3
(g) (g) (g)
∆n = np – nR
= 2 – (1 + 2) = -1
∆n = -1 (-ve)
∴ K p < Kc
Question 14.
Write the equations for the conversion of Kc to Kp for each of the following reactions.
a) CO(g) + H2O (g) ⇌ CO2 (g) + H2 (g)
b) C3H8(g) + 5O2(g) ⇌ 3CO2 (g) + 4H2O (g)
Answer:
a) CO(g) + H2O(g) ⇌ CO2 + H2 (g) (g)
Kp = PCO2×PH2PCO×PH2O
Kc = [CO2][H2][CO][H2O]
Kc to Kp conversion
b) C3H8(g) + 5O2(g) ⇌ 3CO2 (g) + 4H2O (g)
Kp = P3CO2×PH2O4PC3H8×P5O2
Kc = [CO2]3[H2O]4[C3H8][O2]5
Kc to Kp conversion
Question 15.
What are the factors which influence the chemical equilibrium?
Answer:
The factors influencing chemical equilibrium are
1. Concentration of reactants and the products
2. Temperature of reaction
3. Pressure of reaction
4. Inert gas addition etc.
288
Question 16.
What is the effect of pressure on a gaseous chemical equilibrium?
Answer:
Increase of external pressure of the reaction at equlibrium favours the reaction in the
direction in which the volume (or) the No. of molecules decreases.
Decrease of external pressure of reaction at equilibrium favour the reaction in the
direction in which the volume (or) no. of molecules increase.
Question 17.
What is the effect of increase in concentration of reactants of a chemical reaction at
equilibrium?
Answer:
Increase of concentration of the reactants in the reaction mixture at equilibrium favours
the forward reaction (Reactants → products)
Question 18.
Can catalyst disturb the state of equilibrium?
Answer:
Addition of catalyst to the reaction does not effect the equilibrium position. It only
speedy up the attainment of the equilibrium.
Question 19.
On which factor, the equilibrium constant value changes?
Answer:
The numerical value of equilibrium constant depends on the standard state of products
and reactants chosen.
Question 20.
The equilibrium constants of a reaction at 27° C and at 127°C are 1.6 × 10-3 and 7.6 ×
10-2 respectively. Is the reaction exothermic or endothermic.
Answer:
Given equilibrium constants
At 27°C – 1.6 × 10-3
At 127°C -7.6 × 10-2
From the above values as the temperature raised euilibrium constant value increased.
289
Here ∆H = +ve
∴ The reaction is endothermic.
Question 21.
What is the effect of temperature on a system at equilibrium?
Answer:
• Increase in temperature of the reaction mixture at equilibrium favours the
endothermic reaction.
• Decrease in temperature of the reaction mixture at equilibrium favours the
exothermic reaction.
Question 22.
For an exothermic reaction, what happens to the equilibrium constant if temperature is
raised?
Answer:
For an exothermic reaction when the temperature is raised equilibrium constant value
decreased.
Question 23.
What kind of equilibrium constant can be calculated form ∆G° value for a reaction
involving only gases?
Answer:
Mathematical expression in the thermodynamic view of equilibrium is
∆G = ∆G° + RTlnQ
At equilibrium ∆G = 0 and Q = K
∴ ∆G = ∆G° + RTlnK = 0
∆G° = -RTlnK
knK = −ΔG∘R
K = e-∆G°/RT
K = Equilibrium constant using the above equation the sponteinity of reaction can be
predicted.
Question 24.
What is a Bronsted base ? Give one example.
Answer:
The substance which accepts a proton from the other substance is called Bronsted base
e.g.: NH3, H2O etc.
290
Qeustion 25.
What is Lewis acid ? Give one example.
Answer:
A substance which can accept an electron pair to from a co-ordinate covalent bond
with donor is called Lewis acid.
e.g. : H+, BF3, SnCl2 etc.
Question 26.
What is meant by ionic product of water ?
Answer:
At a given temp, the product of the concentrations of H+ and OH– ions in water is called
ionic product
Ionic product Kw = [H+] [OH–]
At 25°C Kw = 1.008 × 10-14 mole2/lit2
Question 27.
What is the value of Kw? What are its units ?
Answer:
At 25°C Ionic product of water Kw = 1.008 × 10-14 mole2/lit2
Units : mole2/lit2
Question 28.
What is the effect of temperature on ionic product of water ?
Answer:
As the temperature increases ionisation of water increases and hence Ionic product
alue (Kw) also increases.
Question 29.
H2O + H2O ⇌ H2O+ + OH–
The ionic product of water is 1 × 10-14 at 25°C and 3.0 × 10-14 at 40°C.
Is the above process endothermic or exothermic ?
Answer:
Given reaction
H2O + H2O ⇌ H2O+ + OH–
Kwat25°C – 1 × 10-14 mole2/lit2
291
Kwat40°C – 3 × 10-14 mole2/lit2
The above reaction is endo thermic reaction because Kw value increases with increase of
temperature.
Question 30.
All Bronsted bases are Lewis bases. Explain.
Answer:
Bronsted base means proton acceptor and lewis base means electron pair donor.
But according to two theories base provides a lone pair.
∴ All bronsted bases are lewisbases
Question 31.
All Lewis acids are not Bronsted acids. Why ?
Answer:
• Lewis acid means electron pair acceptor and bronsted acid means proton donar.
• According to Lewis concept many acids donot have proton.
So all Lewis acids are not Bronsted bases.
Question 32.
What is degree of ionization?
Answer:
• It is the expression used to find the extent of ionisation of electrolytes.
• It is devoted by ‘α’.
Question 33.
What is the measure of strength of an acid and base ?
Answer:
• Strength of an acid can be measured by the acid disociation constant (Ka)
• Strength of a base can be measured by the base disaciating constant (kb)
Question 34.
Give two examples of salts whose aqueous solutions are basic.
Answer:
Sodium acetate (CH3COONa), Sodium carbonate (Na2CO3) salts aqueous solutions are
basic in nature due to anionic hydrolysis.
292
Question 35.
Give two examples of salts whose aqueous solutions are acidic.
Answer:
Ammonium chloride (NH4Cl), Ammonium sulphate [(NH4)2 SO4] salts aqueous solutions
are acidic in nature.
Question 36.
What equation is used for calculating the pH of an acid buffer ?
Answer:
Hendersen’s equation is used to calculate the PH of an acid buffer
PH = PKa + log [Salt] [ Acid]
Question 37.
Phosphoric acid (H3PO4) have three ionization constants Ka , Ka and Ka . Among these
1 2 3
ionization constants which has a lower value ? Give reason for it ? Answer:
Phosphoric acid (H3PO4) has
Ka1 – 7.5 × 10-3
Ka2 – 6.2 × 10-8
Ka3 – 4.2 × 10-13
Ka3 has lower value.
Reason :
• It is more difficult to remove a proton from the negativeion due to electro static
forces.
• It is difficult to remove a proton from HPO−24 anion.
Question 38.
Ice melts slowly at high altitudes. Explain. Why ?
Answer:
Ice melts slowly at high altitudes
Reason :
• Ice and water are equilibrium only at a particular temperature and pressure
conditions.
• At high attitude temp and pressure conditions are changed.
293
Qeustion 1.
Write expression for the equilibrium constant, Kc for each of the following reactions.
(i) 2NOCl(g) ⇌ 2NO(g) + Cl2(g)
(ii) 2Cu(NO3)2(s) ⇌ 2CUO(s) + 4NO2(g) + O2(g)
(iii) CH3COOC2H5(aq) + H2O(l) ⇌ CH3COOH(aq) + C2H5OH(aq)
(iv) Fe+3(aq) + 3OH–(aq) ⇌ Fe(OH)3(s)
Answer:
i) Given equation
2NOCl(g) ⇌ 2NO(g) + Cl2 (g)
Equilibrium constant Kc = [NO2[Cl2][NoCl]

ii) Given equation
2Cu(NO3)2 ⇌ 2CUO(s) + 4NO2 + O2
(s) (g)
Kc = (NO2)4 (O2)
iii) CH3COOC2H5(aq) + H2O(l) ⇌ CH3COOH(aq) + C2H5OH(aq)
Kc = [CH3COOH][C2H5OH][CH3COOC2H5]
iv) Fe+3(aq) + 3OH–(aq) ⇌ Fe(OH)3(s)
Kc = 1[Fe+3][OH−]3
Question 2.
Derive the relation between Kp and Kc for the equilibrium reaction
N2(g) + 3H2(g) ⇌ 2NH3(g) [Mar. 13]
Answer:
Given equation (Equilibrium reaction)
N2 + 3H2 ⇌ 2NH3
(g) (g) (g)
We can make the following generalisation concerning the composition of equilibrium

mixtures : If Kc > 103 products predominate over reactants, i.e., if Kc is very large, the
reaction proceeds nearly to completion. Consider the following examples :
a) The reaction of H2 with O2 at 500 K has a very large equilibrium constant Kc = 2.4 ×
1047
b) H2 + Cl2 ⇌ 2Hl(g) at 300 K has Kc = 4.0 × 1031
(g) (g)
c) H2 + Br2 ⇌ 2HBr(g) at 300 K. Kc = 5.4 × 1018

(g) (g)
If Kc < 10-3 reactants predominate over products i.e, if Kc is very small the reaction
proceeds rarely.
294
Consider the following examples :
a) The decomposition of H2O into H2 and O2 at 500 K has a very small equilibrium
constant.
Kc = 4.1 × 10-48
b) N2 + O2 ⇌ 2NO(g)
(g) (g)
at 298 K has Kc = 4.8 × 10-31

If Kc is in the range of 10-3 to 103 appreciable concentrations of both reactants and
products are present. Consider the following examples :
a) For reaction of H2 with I2 to give HI.
b) Also, gas phase decomposition of N2O4 to NO2 is another reaction with a value of
Kc = 4.64 × 10-3 at 25°C which is neither too small nor too large. Hence equilibrium
mixtures contain appreciable concentrations of both N2O4 and NO2.
These generarlisations are illustrated.
Question 3.
State law of chemical equilibrium ? What is Kc for the following equilibrium when the
equilibrium concentration of each substance is [SO2] = 0.60 M,
[O2] = 0.82 M and [SO3] = 1.90 M
2SO2(g) + O2(g) ⇌ 2SO3(g)
Answer:
The ratio of product of molar concentrations of the products to the product of molar
concentrations of the reactants has a constrant value. This is known as the equilibrium
law (or) law of chemical equilibrium.
Given equation is
2SO2 + O2 ⇌ 2SO3
(g) (g) (g)
Given [SO2] = 0.60M, [O2] = 0.82M, [SO3] – 1.90 M

Kc = [SO3]2[SO2]2[O2]=(1.9)2(0.6)2(0.82)
= 3.610.36×0.86=3.610.2952
= 12.22
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Question 4.
Why sealed soda water bottle on opening shows the evolution of gas with
effervescence ?
Answer:
• Sealed soda bottle on opening shows evolution of gas with effervescence
• This is due to difference in solubility of CO2 at different pressures there is
equilibrium between molecules of gaseous state and molecules of dissolved in
the liquid state.
CO2 ⇌ O2 (Jusolutcoiny)
(g)
Question 5.
Explain the significance of
a) a very large value of K,
b) a very small value of K and
c) a value of K of about 1.0
Answer:
a) A very large value of K indicates reaction proceeds almost to complete.
b) A very small value of K indicates reaction hardly proceeds.
c) A value of K about 1.0 indicates that reactants and products are at equilibrium.
Qeustion 6.
Why is it useful to compare Q with K ? What is the situation when
(a) Q = K
(b) Q < K (c) Q > K
Answer:
Q and K are compared to predict the direction of reaction
a) Q = K indicates that the reaction mixture is already at equilibrium
b) Q < K indicates that the reaction proceeds in the direction. c) Q > K indicates that
the reaction proceeds in the direction of reactants (Reverse reaction)
Qeustion 7.
For the reaction Cl2(g) + F2(g) 2Cl F (g), Kc = 19.9
What will happen in a mixture originally containing [Cl2] = 0.4 mol L–; [F2] = 0.2 mol L-
1
and [Cl F] = 7.3 mol L–?
Answer:
Given reaction
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Cl2 + F2 ⇌ 2ClF(g), Kc = 19.9
(g) (g)
Given [Cl2] = 0.4 mole/lit, [F2] = 0.2 mole/lit

[ClF] = 7.3 moles/lit
∴ [ClF]2[Cl2][F2]=[7.3]20.4×0.2=53.290.8 = 66.6125
Qc > Kc
∴ The reaction proceeds in the backward direction (Reactants side, Reverse Reaction)
Question 8.
Predict which of the following reaction will have appreciable concentration of reactants
and products :
a) Cl2(g) 2Cl (g), Kc = 5 × 10-39
b) Cl2(g) + 2NO(g) ⇌ 2NOG (g), Kc = 3.7 × 108
c) Cl2(g) + 2NO2 (g) ⇌ 2N02a(g) Kc = 1.8
Answer:
a) Cl2 ⇌ 2ClF(g) Kc = 5 × 10-39
(g)
b) Cl2 +2NO(g) ⇌ 2NOCl(g) Kc = 3.7 × 108

(g)
c) Cl2 + 2 NO2 ⇌ 2NO2Cl(g) Kc = 1.8

(g) (g)
• This equation (c) have appreciable concentrations of reactants and products.

• ‘Kc‘ value is neither too small nor too large. Hence equilibrium mixtures contain
appreciable concentrations of reactants and products.
Question 9.
How to recognise the conditions under which changes in pressure would effect system
in equilibrium.
Answer:
Effect of pressure charge : A pressure change obtained by changing the volume can
affect the yield of products in case of a gaseous reaction where the total number of
moles of gaseous reactants and total number of moles of ga seous products are
different. In applying Le Chatelier’s principle to a heterogeneous equilibrium the effect
of pressure changes on solids and liquids can be ignored because the volume (and
concentration) of a solution/liquid is nearly independent of pressure.
Consider the reaction.
CO(g) + 3H2 ⇌ CH4 + H2O(g)
(g) (g)
Here, 4 mol of gaseous reactants (CO + 3H2) become 2 mol of gaseous products (CH4 +
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H2O). Suppose equilibrium mixture (for above reaction) kept in a cylinder fitted with a
piston at constant temperature is compressed to one half of its original volume. Then,
total pressure will be doubled (according to pV = constant). The partial pressure and
therefore, concentration of reactants and products have changed and the mixture is no
longer at equilibrium. The direction in which the reaction goes to re-establish
equilibrium can be predicted by applying the Le Chatelier’s principle.
Since pressure is doubled, the equilibrium now shifts in the forward direction, a
direction in which the number of moles of the gas or pressure decreases (we know
pressure is proportional to moles of the gas). The can also be understood by using
reaction quotient, Qc. Let [CO], [H2], [CH4] and [H2O] be the molar concentrations at
equilibrium for methanation reaction. When volume of the reaction mixture is halved,
the partial pressure and the concentration are doubled. We obtain the reaction
quotient by replacing each equilibrium concentration by double its value.
QC = [CH4( g)][H2O(g)][CO(g)][H2(g)]3
As QC < KC, the reaction proceeds in the forward direction.
In reaction C(s) + CO2 ⇌ 2CO(g), when pressure is increased, the reaction goes in the
(g)
reverse direction because the number of moles of gas increases in the forward
direction.
Question 10.
What property of a reaction can be used to predict the effect of a change in
temperature on the magnitude of an equilibrium constant ?
Answer:
• Change in temperature leads to the charge in the value of equilibrium constant
(Kc)
• The temperature dependence of the equilibrium constant depends on the sign of
∆H for the reaction.
• The equilibrium constant for an exothermic reactions (∆H = -ve) decreases as the
temperature increases.
• The equilibrium constant for an endothermic reaction (∆H = +ve) increases as the
temperature increases.
• Temp changes affect the equilibrium constant and rates of reactions.
298
Question 11.
Does the number of moles of reaction products increase, decrease or remains same
when each of the following equilibria is subjected to a decrease in pressure by
increasing the volume ?
i) PCl5(g) ⇌ PCl3 (g) + Cl2 (g)
ii) CaO(s) + CO3(g) ⇌ CaCO3 (s)
Answer:
i) PCl5 ⇌ PCl3 + Cl2
(g) (g) (g)
Decrease in pressure by increasing volume leads to the reaction goes in forward

direction be cause no. of moles of gas decrease in the forward direction.
∴ No. of moles of reaction products decreases.
ii) CaO(s) + CO2 ⇌ CaCO3 (g) (s)
Decrease in pressure by increasing volume the reaction does not move in any direction
because only one gaseous product present i.e. CO2 . So nochange in no. of moles of
(g)
reaction products.
Question 12.
Which of the following reactions will get affected by increasing the pressure ? Also
mention whether change will cause the reaction to go into forward or back ward
direction.
i) COCl2(g) ⇌ CO(g) + Cl2 (g)
ii) CH4(g) + 2S2(g) ⇌ CS2 (g) + 2H2S(g)
iii) CO2(g) + C(s) ⇌ 2CO(g)
iv) 4NH3(g) + 5O2(g) ⇌ 4NO(g) + 6H2O(g)
Answer:
i) COCl2 ⇌ CO(g) + Cl2 (affected by pressaure)
(g) (g)
Increase in pressure the reaction goes in reverse direction and No. of moles of gas
increase in the forward direction.
ii) CH4 + 2S2 ⇌ CS2 + 2H2
(g) (g) (g) (s)
No. of reactants and No. of products are same, pressure has no affect.
iii) CO2 + C(s) ⇌ 2 CO(g) (affected by pressure)
(g)
iv) 4NH3 + 5O2 ⇌ 4 NO(g) + 6H2O(g) (affected by pressure)

(g) (g)
Increase in pressure, the reaction goes in reverse direction and No. of moles of gas
increase in the forward direction.
299
Question 13.
How will an increase in pressure affect each of the following equilibria ? An increase in
temperature ?
i) 2NH3(g) ⇌ N2(g) + 3H2(g) ∆ H = 92 kJ
ii) N2(g) + O2(g) ⇌ 2NO(g) ∆ H = 181 kJ
iii) 2O3(g) ⇌ 3O2(g) ∆ H = – 285 kJ
iv) CaO(S) + CO2(g) ⇌ CaCO2(s) ∆ H = – 176 kJ
Answer:
i) 2NH3 ⇌ N2 + 3H2 ∆H = +92KJ
(g) (g)
• Increase in pressure favours backword reaction

• Increase in temperatures favours to shift the equilibrium right.
ii) N2 + O2 ⇌ 2NO(s) ∆H = 181 KJ
(g) (s)
• Pressure has no effect. NP = NR

• Increase in temperature favour to shift the equilibrium right
jjj) 2O3 3O2 ⇌ ∆H = -285 KJ .
(g) (g)
• Increase in pressure favours backward reaction

• Increase in temperative favours to shift the equilibrium left
iv) CaO(s) + CO2 ⇌ CaCO3 ∆H = -176 KJ
(g) (s)
• Pressure has no effect.

• Increase in temperature favour to shieft the equilibrium left.
Question 14.
The dissociation of HI is independent of pressure, while the dissociation of
PCl5 depends upon the pressure applied explain.
Answer:
Dissociation of HI
2HI(g) ⇌ H2 + I2 (g) (g)
Here np = nR
∴ Pressure has no effect on the above reaction.
Dissociation of PCl5
PCl5 ⇌ PCl3 + Cl2
(g) (g) (g)
Here np ≠ nR
∴ This reaction has affected by pressure
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Question 15.
Explain the terms :
1. electrolyte
2. Non-electrolyte
3. strong and weak electrolytes
4. ionic equilibrium
Answer:
1. Electrolyte: The substances either in molten state (or) in solution conducts
electricity and at the same time undergoes chemical decomposition, e.g.: HCl,
HNO3 etc.
2. Non-electrolytes: The substances which donot ionise (or) chemical decomposed
when dis-solved in a solvent.
e.g.: Sugar, urea etc.
3. Strong Electrolytes: The electrolytes which readily under go chemical
decomposition are called strong electrolytes.
eg.: NaOH, HG, H2SO4 etc.,
Weak electrolystes : The electrolytes which donot readtions undergo chemical
decomposition are called weak electrolytes.
eg. : CH3COOH, NH4OH etc.,
4. Ionic equilibrium is a state of equilibrium set up between ionised and unionised
molecule. In weak electrolytes, equilibrium is established between ions and the
unionized molecules. This type of equilibrium involving ions in aq. solution is
called ionic equilibrium.
Question 16.
Explain the terms :
i) extent of ionization and on what factors it depends
ii) dissociation
iii) ionization
Answer:
Acids are generally represented as ‘HX’ and bases are represented as ‘BOH’.
Ionization of acids and bases : HX H+ + X–
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BOH B+ + OH–
This process of splitting of acids and bases when dissolved in water is called ‘ionization’
or ‘dissociation1. The extent of ionization of acids and bases depends on the polarity of
the molecule. For strong acids and strong bases extent of ionization is large. The extent
of ionization is less for weak acids or bases.
This extent of ionization depends on the concentration of the solution of the
substance. Process of ionization is an equilibrium process.
Hence, the equilibrium constants are expressed as Ka = [H+][X−][HX]

Ka = acid ionization constant (or) acid dissociation constant.
Kb = [B+][OH−][BOH]
Kb = base ionization constant (or) base dissociation constant.
Question 17.
Explain the Arrhenins concept of acids and bases.
Answer:
According to Arrhenius
Acid : Acids are the substances that dissociates in water to gave H+ ions.
e.g. : HCl, H2SO4 etc..
H x(aq) → H+(aq) + x–(aq)
Base : Bases are the substances that produce hydrorylions (OH–) ion dissociation in
water
e.g. : NaOH, KOH MOH,
MOH(aq) → M+(aq) + OH–(aq)
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Question 18.
What is a, conjugate acid – base pair ? Illustrate with examples. [A.P. Mar. 16]
Answer:
Conjugate acid – base pair:
A pair of a Bronsted acid and a base that differs by one proton (H+) is known as
conjugate acid – base pair.
Consider the following reaction :
CH3COOH + H2O ⇌ H3O⊕ + CH3COO⊖
It involves two conjugate pairs. The acid – base pairs are :
Question 19.
Acetic acid is a weak acid. List, in order of descending concentration, all of the ionic and
molecular species present in 1 M aqueous solution of acetic acid.
Answer:
[H2O] > [CH3COOH] > [H3O+] [CH3COO–] > [OH–]
Question 20.
Show by suitable equations that each of the following species can act as a Brostead
acid.
a) H3O+
b) HCl
c) NH3
d) HSO4–
Answer:
a) H3O+ → H2O + H+
Proton donar Hence a Bronsted acid
b) HCl → H+ + Cl–
Proton donar Hence a Bronsted acid
c) NH3 is bronsted base it’s not an acid
(Sometimes NH3 → NH–2 + H+ as acid]
d) HSO4– → H+ + SO4-2
proton donar Hence Bronsted acid.
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Question 21.
Show by suitable equations that each of the following spices can act as a Bronsted
base.
a) H3O
b) OH–
c) C2H5OH
d) HPO4-2
Answer:
a) H2O + H+ → H3O+
Proton acceptor Hence a Bronsted base
b) OH– + H+ → H2O
Proton acceptor Hence a Bronsted base
c) C2H5OH is a proton donar
So it is not a bronsted base it is acid
d) HPO4-2 + H+ → H2PO4–
proton acceptor Hence it is Bronsted base.
Question 22.
The species H2O, HCO4–, HSO4– and NH3 can act both as Bronsted acids and bases. Give
the corresponding conjugate acid and base for each of them.
Answer:
The answer is given in the following Table :
Question 23.
Write equation that shows H2PO4– acting both as an acid and as a base.
Answer:
As an acid :
H2Po4– → H+ + HP2PO4-2
Proton donar
As a base:
H2Po4– + H+ → H3PO4
Proton acceptor
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Question 24.
Write the conjugate acid and conjugate base of each of the following :
a) OH–
b) H2O
c) HCO3–
d) H2O2
Answer:
Question 25.
Identity and label the Bronstead acid and its conjugate base, the Bronsted base and its
conjugate acid in each of the following equations.
a) H2SO4 + Cl– → HCl + HSO4–
b) H2S + NH2 → HS– + NH3
c) CN– + H2O → HCN + OH–
d) O-2 + H2O → 2OH–
Answer:
305
Question 26.
Classify the species AlCl3, NH3, Mg+2 and H2O into Lewis acids and Lewis bases and
justify your answer ?
Answer:
• AlCl3, Mg+2 are lewis acids because These are electron pair acceptory
• NH3, H2O are lewis bases becuse. These are electron pair donors.
Question 27.
What are the strengths of conjugate bases of a strong acid and a weak acid ?
Answer:
A strong acid has a weak conjugate base
Eg : HCl, Cl–
A weak acid has a strong conjugate base
Eg : CH3COOH, CH3COO–
Question 28.
What are the strength of conjugates acids of a strong base and weak base ?
Answer:
Strong base has a weak conjugate acid
Eg : HS–, H2S
A weak base has a stong conjugatge acid
Eg : ClO–4, HClO4
Question 29.
Define ionic product of water. What is its value at room temperature ?
Answer:
At a given temp, the product of the concentrations of H+ and OH– ions in water is called
ionic product
Ionic product Kw = [H–] [OH–]
At 25°C Kw = 1.008 × 10-14 mole2/lit2
At 25°C Ionic product of water Kw = 1.008 × 10-14 mole2/lit2
Units: mole2/lit2
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Question 30.
Define pH. pH cannot be calculated directly from the molar concentration of a weak
acid or weak base. Why ? Derive an equation for the pH of a weak acid.
Answer:
The negative logarithm on value to the 10 of the hydrogen ion concentration
expressed in moles/lit, in a solution is know as pH. of the solution.
pH : – log (H+) = – log10 1(H+)
In case of a weak acid (or) weak base extent of ionisation is low so pH cannot be
calculated directly from their molar concentrations.
Derivation of pH of a weak acid :
A general step wise approch can be adopted to evaluate the pH of the weak acid as
follows.
Step 1. The species present before dissociation are identified as Bronsted – Lowry
acids/ bases.
Step 2. Balanced equations for all possibel reactions i.e., with a species acting both as
acid as well as base are written.
Step 3. The reaction with the higher Ka is identified as the primary reaction whilst the
other is a subsidiary reaction.
Step 4. Enlist in a tabular form the following values for each of the species in the
primary reaction.
a) Initial concentration. C.
b) Change in concentration on proceeding to equilibrium in terms of a, degree of
ionization.
Step 5. Substitute equilibrium concentrations into equilibrium constrant equation for
principal reaction and solve for α.
Step 6. Calculate the concentration of species in principal raction.
Step 7. Calculate pH = – log [H3O+]
The above mentioned methodology has been elucidated in the following examples.
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Question 31.
Write equations to show the step wise ionization of the polyprotic acids H2SO4 and
H2PO4.
Answer:
Step wise Ionisation H2SO4
Question 32.
Explain how acid strength changes among
1. the hydrides of the group elements and
2. the hydrides in the same row of the periodic table.
Answer:
1. The hydrides of the group elements acid strength decreases from top to bottom.
2. The hydrides in the same row of Periodic table i.e., in a period the acid strength
increases from left to right.
Question 33.
Justify the statement that water behaves like an acid and also like base on the basis of
protonic concept.
Answer:
• Water has the ability to acts as an acid and as well as a base i.e., it behaves as an
amphoteric substance.
• The following are the supporting reactions for the fact that water behaves as an
• As an acid :
H2O(l) + NH3(aq) ⇌ OH–(aq) + NH4+(aq)
H2O is proton do nor i.e., an acid according to Bronsted sense
308
• As a base:
H2O(l) + H2S(aq) ⇌ H3O+(aq) + HS–(aq)
H2O is proton acceptor i.e., a base according to Bronsted Sense
Question 34.
What is common ion effect ? Illustrate.
Answer:
Common ion effect : The decrease in the ionisation (dissociation) of a weak electrolyte,
by the addition of a strong electrolyte having an ion common with the weak
electrolyte, is known as common ion effect.
Example : The dissociation of NH4OH is diminished by the addition of NH4Cl due to the
common ion, NH4+ ion
NH4OH ⇌ NH4⊕ + OH⊖
NH4OH NH4+ + OH⊖ (addition of NH4Cl)

Importance of this effect In qualitative analysis :
1. This principle is used in the systematic qualitative analysis of cations.
2. The concentration of S2- in II group or OH– ion in III group of chemical analysis is
controlled by HCl and NH4OH on the basis of common ion effect.
H+ ion is common to H2S (II group)
NH4+ ion is common to NH4OH (IV group) .
3. The common ion effect principle is also used in controlling the H+ ion
concentration in buffer solutions.
4. It is also used in the purification of common salts by passing dry HCl gas into
impure salt solution.
Question 35.
Define solubility product ? Write solubility product expressions for the following :
(i) Ag2Cr2O7
ii) Zr3(PO4)4
Answer:
Solubility product (KSP) : The product of the concentrations of the cation and the anion
in a saturated solution of a salt at room temperature is called solubility product (Ksp).
Ksp = [Mn+][An-]
Significance of solubility product in chemical analysis : In any solution of a salt, if the
product of [Mn+] and [An-] is greater than the solubility product (KSP) of the salt, then
309
only the salt gets precipitated. For example,
i) If the product of [Cu 2+] & [S-2] in the II group (in presence of acid) of chemical
analysis exceeds the value of KSP of CuS, then only CuS will be precipitated in the group.
Similar argument applies to other metal ions in the group namely (Cd2+, Bi3+, Hg2+, Sb2+,
etc).
ii) If the product of [Zn2+] and [S2-] in ammonical medium in IV group of chemical
analysis exceeds the value of KSP of ZnS, it will be precipitated. Similar arguments apply
to Mn2+, Ni2+ etc.
a) Solubility product expression for Ag2Cr2O7
Question 36.
Give the classification of salts. What type of salts undergo hydrolysis ?
Answer:
The following are the types of salts : –
1. Salts of a strong acid and a strong base. Ex : NaCl
2. Salts of a strong acid and a weak base. Ex : NH4Cl
3. Salts of a weak acid and a strong base. Ex : CH3COONa
4. Salts of a weak acid and a weak base. Ex : CH3COONH4
Types 2, 3, 4 under go hydrolysis reactions.
Question 37.
What must be true of the value of ∆G° for a reaction if
a) K > 1
b) K = 1
c) K < 1
Answer:
a) If K > 1 then ∆ G° < 0
b) If K = 1 then ∆ G° = 0
c) If K < 1 then ∆ G° > 0
310
Question 38.
Aqueous solution of NH4Cl is acidic. Explain.
Answer:
Given salt NH4Cl is obtained by the reaction of strong acid (HCl) and weak base
(NH4OH).
The ionisation of NH4Cl as follows
NH+4 + Cl– ⇌ NH4Cl
The above salt under goes cationic hydrolysis
NH+4 + H2O ⇌ NH4OH + H+
∴ The equation solution of salt is acidic due to greater H+ ion concentration than
OH– ion concentration.
∴ PH < 7
Question 39.
Aqueous solution of CH3COONa is basic explain.
Answer:
Given salt CH3COONa is obtained by the reaction of weak acid (CH3COOH) and strong
base (NaOH).
The ionisation CH3COONa as follows
CH3COONa ⇌ CH3COO– + Na+
The above salt under go anionic hydrolysis
CH3COO– + H2O ⇌ CH3COOH + OH–
∴ The equation solution of salt is basic due to greater OH– ion concentration than
H+ ion concentration.
∴ PH > 7
Question 40.
Give reason that acetic acid is less acidic in sodium acetate solution than in sodium
chloride solution.
Answer:
Acetic acid in sodium acetate solution is less acidic.
Reasons:
• Because of common ion effect ionisation process is decreased.
• Sodium acetate is obtained by the reaction of weak acid and strong base:
Acetic acid in NaG solution is more acidic.
311
Here no common ion effect observed.
NaCl is the salt obtained by strong acid and strong base.
Question 41.
AgCl is less soluble in AgNO3 solution than in pure water explain.
Answer:
• AgCl is less soluble in AgNO3 because of common ion effect solubility is
decreased.
• AgCl is more soluble in pure water because common ion effect not observed
here.
Question 42.
Predict whether the following reaction will proceed from left to right to any measurable
extent:
CH3COOH (aq) + Cl–(aq) →
Answer:
Given CH3COOH(aq) + Cl−(aq) →
The reaction does not proceed from left to right because Cl– ion is obtained from
strong acid do not under go hydrolysis and CH3COOH has low extent of ionisation.
Question 43.
Aqueous solution of H2S contains H2S, HS–, S-2, H3O+, OH– and H2O in varying
concentrations. Which of these species can act only as a base ? Which can act only as
an acid ? Which can act both an acid and as a base ?
Answer:
• H23S, H3O+ acts as only acids
• HS–, OH–, H2O acts as acids as well as bases
• S-2 acts as only base
Question 1.
What are equilibrium processes ? Explain equilibrium in Physical and Chemical pro-
cesses with examples.
Answer:
Equilibrium State (or) Equilibrium Process : The state at which the velocity of forward
312
reaction becomes equal to the velocity of backward reaction or reverse reaction is
called ‘equilibrium state’. Consider a reversible reaction.
A + B ⇌ C + D taking place in a closed vessel. At the beginning we have only the

reactants A and B. Their concentrations are maximum. As the reaction proceeds the
reactants A and B change into the products C and D. The concentrations of the
products increase gradually.
The rate of forward reaction diminishes while the reverse reaction sets in and proceeds
with increasing speed. A state is soon reached where the speeds of forward and
backward reactions become equal. If the rate of forward reaction Vf = The rate of
reverse reaction (Vb).
The system is said to have attained a state of equilibrium. Once equilibrium is reached
there is no further change in the composition of the system. The system appears to be
stand still although it is dynamic. The products are formed by forward reaction just as
fast as they change back into reactants by the reverse reaction.
The state at which the rate of forward reaction is equal to the rate of the reverse
reaction in a reversible reaction is known as the equilibrium state or chemical
equilibrium.
Examples :
i) Equilibrium physical processes :
a) Equilibrium between two phases (i.e.,) physical transformation processes.
Solid ⇌ Liquid (melting or fusion)
Solid ⇌ Vapour (sublimation)
b) Equilibrium between two different allotropic forms of same substance
α – Sulphur ⇌ β – Sulphur
ii) Equilibrium chemical processes :
a) N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
b) 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
c) H2(g) + I2(g) ⇌ 2HI(g)
313
Question 2.
What is meant by dynamic equilibrium ? Explain with suitable examples.
Answer:
Dynamic equilibrium : The forward and reverse reactions of a reversible reaction
continue to take place with equal rates simultaneously at the equilibrium stage also.
Hence the equilibrium is called Dynamic equilibrium.
Explanation : In order to understand the dynamic nature of the reaction, synthesis of
ammonia is carried with exactly the same starting conditions but using D2 (deuterium)
in place of H2. The reaction mixtures starting either with H2 or D2 reach equilibrium with
the same composition, except that D2 and ND3 are present instead of H2 and NH3. After
equilibrium is attained, these two mixtures (H2, N2, NH3 and D2, N2, ND3) are mixed
together and left for a while. Later when this mixture analysed, it is found that the
concentration of ammonia is just the same as before.
However, when this mixture is analysed by a moss spectrometer, it is found that
ammonia and all deuterium containing forms of ammonia (NH3, NH2D, NHD2 and ND3)
and dihydrogen and its deutrated forms (H2, HD and D2) are present. Thus one can
conclude that scrambling of H and D atoms in the molecules must result from a
continuation of the forward and reverse reactions in the mixture. If the reaction had
simply stopped when they reached equilibrium, then there would have been no mixing
of isotopes in this way.
Use of isotope (deuterium) in the formation of ammonia clearly indicates that chemical
reaction react a state of dynamic equilibrium in which the rates of forward and reverse
reactions are equal and there is no net change in composition.
Question 3.
Give the General characteristics of equilibria involving physical processes ?
Answer:
Characteristics of general equilibria :
1. The rate of the forward reaction is equal to the rate of the reverse reaction (uf =
ub).
2. The concentrations of the reactants and the products remain unchanged with
time.
3. The observable properties such as pressure, concentration, density, colour also
remain unchanged with time.
4. The equilibrium is dynamic in nature. Both the forward reaction and the reverse
reaction continue to take place simultaneously with equal rates.
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5. A catalyst does not alter the state of equilibrium or the composition of the
chemical substances of the reaction at the equilibrium. It only speeds up the
attainment of the equilibrium.
6. Chemical equilibrium can be established from either side of the reversible
reaction.
Question 4.
What are the important features of equilibrium constant ? Discuss any two applications
of equilibrium constant.
Answer:
The ratio of product of molar concentrations of products to the product of molar
concentrations of reactants is called equilibrium constant (Kc)
Ex : aA + bB ⇌ cC + dD
KC = [C]c[D]d[A]a[B]b
KC for reverse reaction is the inverse of the KC for the reaction in the forward direction.
Concentration equilibrium constant (KC) and pressure equilibrium constant (Kp) are
related as follows
Kp = KC(RT)∆n
∆n = np – nR
While writing KC expression pure liquids, pure solids concentration are ignored
Applications :
a) In predicting the extent of reaction :
The numerical value of the equilibrium constant for a reaction indicates the extent of
the reac-tion. But it is important to note that an equilibrium constant does not give any
information about the rate at which the equilibrium is reached the Magnitude of ke or
Kp is directly proportional to the concentrations of products (as these appear in the
numerator of equilibrium constant expression) and inversely proportional to the
concentrations of the reactants (these appear in the denominator). This implies that a
high value of K is suggestive of a high concentration of products and vice- versa.
We can make the following generalisation concerning the composition of equilibrium
mixtures : If Kc > 103 products predominate over reactants, i.e., if Kc is very large, the
reaction proceeds nearly to completion. Consider the following examples :
a) The reaction of H2 with O2 at 500 K has a very large equilibrium constant Kc = 2.4 ×
1047
b) H2(g) + Cl2(g) ⇌ 2HCl(g) at 300 K has Kc = 4.0 × 1031
c) H2 + Br2 ⇌ 2HBr(g) at 300 K. Kc = 5.4 × 1018
(g) (g)
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If Kc = < 10-3 reactants predominate over products i.e, if Kc is very small the reaction
proceeds rarely. Consider the following examples : –
a) The decomposition of H2O into H2 and O2 at 500 K has a very small equilibrium
constant.
Kc = 4.1 × 10-48
b) N2 + O2 ⇌ 2NO(g)
(g) (g)
at 298 K has Kc = 4.8 × 10-31

If Kc is in the range of 10-3 to 103 appreciable concentrations of both reactants and
products are present. Consider the following examples :
a) For reaction of H2 with I2 to give HI.
b) Also, gas phase decomposition of N2O4 to NO2 is another reaction with a value of
Kc = 4.64 × 10-3 at 25°C which is neither too small nor too large. Hence equilibrium
mixtures contain appreciable concentrations of both N2O4 and NO2.
These generarlisations are illustrated.
b) In predicting the direction of reaction : A and K are compared to predict the
direction of reaction
a) Q = K indicates that the reaction mixture is already at equilibrium
b) Q < K indicates that the reaction proceeds in the direction. c) Q > K indicates that
the reaction proceeds in the direction of reactants (Reverse reaction)
Question 5.
What is Lechatlier’s principle ? Discuss briefly the factors which can influence the
equilibrium.
Answer: Le Chatelier’s Principle – Statement: “If a system at equilibrium is subjected to
the change of pressure, temperature (or) concentration, the system is shifted in such a
way as to nullify the effect of change”.
Explanation:
1) Concentration: Increase of reactant concentrations pushes the equilibrium state to
the products side and increase of the reactions concentrations pushes to the
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equilibrium to the reactants side. For example in the chemical equilibrium
H2(g) + I2(g) ⇌ 2HI(g)
Increase of H2 or I2 concentrations pushes the equilibrium in favours of HI and similarly
the increase of HI concentrations pushes the equilibrium in favour of H2 and I2.
2) Pressure : Pressure will have no effect on the equilibrium reactions in which there is
no change in the number of moles of the reactants and the products.
For example pressure will have no effect on
H2(g) + I2(g) ⇌ 2HI(g) equilibrium
(or) N2 (g) + O2 (g) ⇌ 2NO (g) equilibrium
But in the case of reactions in which there is a change in the number of moles of the
reactants and the products increase of pressure pushes the reaction equilibrium in the
direction in which there is a decrease in the number of moles.
For example in the reaction PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
Increase of pressure favours the backward reaction PCl3 (g) + Cl2(g) → PCl5 (g) and the
decrease of pressure favour the forward reaction PCl5 (g) → PCl3 (g) + Cl2 (g)
3) Temperature : Increase of temperature favour the endothermic reaction and
decrease of temperature favours exothermic reactions.
For example .
N2 (g) + O2 (g) ⇌ 2N0(g) – 180.8 kJ
Increase of temperature favours The forward reaction
N2 (g) + O2 (g) → 2NO (g) (since endothermic)
decrease of temperature favour the dissociation of NO into N2 and O2 since it is
exothermic.
The backward reaction
2NO (g) → N2 (g) + O2 (g) (since exothermic)
Question 6.
Discuss the application of Lechaterlier’s principle for the industrial synthesis of
Ammonia and sulphur trioxide.
Answer:
Applications of Le Chatelier’s principle to synthesis of Ammonia by Haber’s process :
Nitrogen and Hydrogen combine to form ammonia. The formation of ammonia is

reversible and exothermic reaction. It is accompanied by decrease in volume.
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Effect of Pressure: 1 volume of N2 combines with 3 volumes of H2 to form 2 volumes of
NH3. There is decrease in volume in the forward reaction (4 volumes to 2 volumes).
According to Le Chatelier’s principle increase of pressure favours the reaction where
there is decrease in volume. So higher the pressure, greater the yield of ammonia. In
practice 200 atmospheres are used in the manufacture of ammonia by Haber’s process.
Low pressures favour the reverse reaction i.e., decomposition of NH3 already formed.
Effect of Temperature : The formation of ammonia (forward reaction) is exothermic
reaction
N2 + 3H2 → 2 NH3; ∆H = – 92 kJ.
Low temperatures favour the forward reaction. But at low temperatures the reaction is
too slow. Therefore an optimum temperature (725 K- 775 K) is chosen in Haber’s
process. To speed up the reaction, a catalyst, finely divided iron is used. To increase the
activity of the catalyst molybdenum or a mixture of oxides of K after Al is used as
promoter.
The reverse reaction (i.e.,) decomposition of NH3 is an endothermic reaction. High
temperatures favour the decomposition of NH3. Therefore high temperatures are
avoided in Haber’s process. Thus the optimum conditions are
Pressure : 200 atm
Temperature : 725-775 K
Catalyst : Fe (Powered)
Promoter : Mo (or) (K2O + Al2O3)
Application of Le Chatelier’s principle to the synthesis of SO3 :
The formation of SO3 is reversible and exothermic reaction. It is accompanied by

decrease in volume.
1. Effect of Pressure : 2 volumes of SO2 and one volume of O2 combine to give 2
volumes of SO3. According to Le Chatelier’s Principle increase of pressure favours the
reaction where there is decrease in volume. The formation of SO3 is accompanied by
decrease in volume (3 volumes to 2 volumes). Higher the pressure greater is the yield
of S03. But in contact process high pressures are not used because towers used in the
manufacture are corroded by the acid at these high pressures.
Low pressures favour the decomposition of SO3 as there is increase in the volume of (2
volumes to 3 volumes). Therefore optimum pressures are used (1.5 to 1.7 atmosphere).
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2. Effect of Temperature : The formation of SO3 is exothermic. 189 Id of heat is evolved.
High temperatures favour the reverse reaction which is endothermic and do not favour
the forward reaction which is exothermic. Low temperatures are favourable for the
formation of SO3. At low temperature the reaction is too slow. Therefore an optimum
temperature 673 K is used. To speed up the reaction V205 is used as catalyst.
Thus the optimum conditions are
Pressure : 1.5 to 1.7 atm
Temperature : 673 K
Catalyst : V2O5 (or) Platinised asbestos
Question 7.
Dihydrogen gas is obtained from natural gas by partial oxidation with steam as per the
following endothermic reaction. .
CH4(g) + H2O(g) ⇌ CO(g) + 3H2 (g)
a) Write an expression for Kp for the above reaction.
b) How will the values of Kp and composition of equilibrium mixture be affected by
1. increasing the pressure
2. increasing the temperature
3. using a catalyst ?
Solution:
a) Given equation
CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)
Kp = PCO×P3H2PCH4×PH2O
b)
1. Increase of pressure the reaction proceeds in reverse direction because the no. of
moles of gas increases in the forward direction.
Increase pressure Kp value increases.
2. Increase of temperature of the reaction mixture at equilibrium favours the
reaction in the direction in which heat is absorbed.
Increase of temperature Kp value increases.
3. A catalyst does not disturbs (or) change the chemical reaction it just speed up the
attaining of equilibrium.
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Question 8.
Describe the effect of :
a) addition of H2
b) addition of CH3OH
c) removal of CO
d) removal of CH3OH on the equilibrium of the reaction
2H2(g) + CO(g) ⇌ CH3OH(g)
Solution:
a) Addition of H2 (Reactant):
Increasing the concentration of reactants in the reaction mixture at equilibrium favours
the forward reaction.
b) Addition of CH3OH (Product):
Increasing the concentration of products in the reaction mixture at equilibrium favours
the reverse reaction.
c) Removal of CO (Reactant):
Decreasing the concentration of reactants in the reaction mixture at equilibrium favours
the reverse reaction.
d) Removal of CH3OH (Product):
Decreasing the concentration of products in the reaction mixture at equilibrium favours
the forward reaction.
Question 9.
At 473K, equilibrium constant Kc for the decomposition of phosphorous pentachloride,
PCl5, is 8.3 × 10-3. If the decomposition is depicted as :
pCl5 (g) pCl3 (g) + Cl2 (g) ∆H = 124.0 kJ mol-1.
a) Write an expression of Kc for the reaction
b) What is the value of Kc for the reverse reaction at the same temperature ?
c) What would be effect on Kc if
(i) more PCl5 is added
(ii) pressure is increased
(iii) the temperature is increased.
Solution:
Given
PCl5(g) ⇌ PCl3(g) + Cl2(g) ∆H = 124.0 kJ/mole
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KC = 8.3 × 10-3
a) KC = [PCl3][Cl2][PCl5]
b) Given KC = 8.3 × 10-3
We have to calculate KC for reverse reaction
i.e., PCl3 + Cl2 ⇌ PCl5
(g) (g) (g)
∴ Kc for the reverse reaction = 18.3×10−3

= 0.12048 × 103
= 120.48
c) i) More PCl5 is added KC value is decreased.
ii) By the increase of pressure KC value is increased.
iii) Given reaction is Endothermic so increase of temperature increases KC value.
Question 10.
Explain the concept of Bronsted acids and Bronsted bases. Illustrate the answer with
suitable examples.
Answer:
According to Bronsted theory o substance which can donate a proton to the other
substance is known as acid. A substance which accept a proton from other substance is
a base.
Here HCl donates a proton to water and behaves as Bronsted Lowry acid. Similarly
NH3 accepts a proton from H2O and acts as Bronsted Lowry base.
Above reaction is a reversible reaction so that H3O+ can donate proton to act as acid.
Cl– can accept a proton to act as base. Thus each acid base reaction equilibrium
involves two acids and two bases. Each pair differs by a proton, such acid base pair is
called Conjugate acid base pain.
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According to this theory strengths of acids and bases can be explained.
An acid which show great tendency to donate protons is a strong acid and an acid
which shows less tendency to donate proton is a weak acid.
A base which shows great tendency to accept a proton is a strong base and a base
which shows less tendency to accept a proton is a weak base.
Question 11.
Explain Lewis acid-base theory with suitable example. Classify the following species into
Lewis acids and Lewis bases and show these act as Lewis acid / base.
a) OH–
b) F–
c) H+
d) BCl3
Answer:
Lewis theory of acids and bases : G.N. Lewis proposed a more generalised theory of
acids and bases. According to this theory.
Acid : A substance that can accept an electron pair to form a co-ordinate covalent bond
is called an acid.
Types of Lewis acids :
Lewis acids are of 5 types.
1) All Cations : Simple cations Ag⊕, CO+3, Cu+2, Fe+3, Al+3 can act as Lewis acids.
2) Compounds in which the central atom has an incomplete octet and possessing an
empty orbital can act as Lewis acids.
Ex : BF3, BCl3, AlCl3, FeCl3.
3) Compounds in which the central atom has vacant d-orbitals and may expand its
octet can act as lewis acids.
Ex : SiF4, SF4, TeF4, SnCl4, FeCl3.
4) Molecules having multiple bonds between atoms of dissimilar electronegativities can
behave like Lewis acids.
Ex : CO2, SO2, SO3, NO2, Cl2O7, P4O10
5) Elements with six electrons in the valence shell or electron sextet can act as Lewis
acids.
Ex : O, S
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Base : According to Lewis theory a base is a substance which can donate an electron
pair to form a co-ordinate covalent bond.
Types of Lewis bases : Lewis bases are divided into three types.
1) All anions
Ex: Cl⊖, OH⊖, CN⊖, NH⊖2, F⊖, SCN⊖ All simple anions can act as Lewis bases.
2) Molecules with one or two lone pairs on the central atom can act as Lewis bases.
Ex :
a) Hydrenyl ion is a lewis base as it can donate an electron lone pair (:OH–).
b) Flouride ion acts as a Lewis base as it can donate any one of its four electron lone
pairs.
c) A Proton is a lewis acid as it can accept alone pair of electrons from bases like
hydrenyl ion and flowride ion.
d) BCl3 acts as a lewis acid as it can accept a lane pair electrons from species like
ammenia or amine molecules.
Question 12.
What is degree of ionization in respect of weak acids and weak bases ? Derive the
relationship between degree of ionization (α) and ionization constant (Ka) for the weak
acid HX.
Answer:
Degree of ionization (α):
The extent of ionization (or) dissociation of a weak acid or weak base is termed as its
Degree of ionization (α). Let the concentration of weak acid (HX) be ‘C moles/lit and
the degree of ionization be ‘α’. Hence at equilibrium,
If ‘α’ is neglected compared to ‘one’ in the denominator.

We have Ka = Cα2 ⇒ α2 = KaC⇒α=√KaC
Similar equation can be written for the ionization of weak base (BOH) in aq. solution.
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Therefore strengths of two acids or two bases are compared generally by their Ka or
Kb values. Higher Ka or Kb value, stronger is the acid or base.
Question 13.
Define pH. What is buffer solution ? Derive Henderson – Hasselbalch equation for
calculating the pH of an acid buffer solution.
Answer:
pH : “The negative value of the logarithm to the base 10, of the hydrogen ion
concentration, expressed in moles / lit, in a solution is known as the pH of the solution”.
Mathematically, pH = – log10 [H+]
Buffer Solution:
“A buffer solution is that solution which resists any change in its pH value on dilution
(or) on addition of a small amount of a strong acid or a strong base
Ex : Acidic buffer: (CH3COOH + CH3COONa)
Basic buffer: (NH4OH + NH4Cl)
Preparation of buffer solutions :
1) Acid buffer solutions : An acid buffer consists of weak acid and its salt with strong
base.
Ex : (CH3COOH + CH3COONa)
Acid buffer solutions are normally prepared by mixing either equal or different volumes
of equimolar solutions of a weak acid and its salt.
2) Base buffer solutions : A basic buffer solution consists of a mixture of a weak base
and its salt with a strong acid.
Ex : (NH4OH + NH4Cl)
Base buffer solutions are prepared generally, by mixing either equal or different
volumes of equimolar solutions of a weak base and its salt.
Derivation of Hendersen’s equation for an acid buffer :
i) Consider the acid buffer HA + NaA
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HA ⇌ H+ + A-
NaA ⇌ Na+ + A–
Acid dissociation constant Ka = [A+][A−][HA]
Here due to common ion effect
Question 14.
Explain the term “Hydrolysis of salts” with examples. Discuss the pH of the following
types of salt solutions.
(i) Salts of weak acid and strong base.
(ii) Salts of strong acid and weak base. [T.S. Mar. 16]
Solution:
It may be defined as a phenomenon in which the anion or cation or both of a salt react
with water producing excess of OH⊖ ions or H⊕ ions or both in aq. solution”.
i) -4 Given salt CH3COONa is obtained by the reaction of weak acid (CH3COOH) and
strong base (NaOH).
-4 The ionisation CH3COONa as follows
The above salt undergo anionic hydrolysis
The aq solution of salt is basic due to greater OH– ion concentration than H+ ion
concentration.
∴ PH > 7
ii) -4 Given salt NH4;C3 is obtained by the reaction of strong acid (HCl) and weak base
(NH4OH).
-4 The ionisation of NH4Cl as follows
-4 The above salt under goes catioric hydrolysis
NH+4 + H2O ⇌ NH4OH + H+
325
∴ PH < 7
Question 15.
What is solubility product ? Explain the common ion effect on solubility of ionic salts.
Solution:
Solubility product (KSP) : The product of the concentrations of the cation and the anion
in a saturated solution of a salt at room temperature is called solubility product (KSP).
KSP = [Mn+][An-]
Significance of solubility product in chemical analysis :
In any solution of a salt, if the product of [Mn+] and [An-] is greater than the solubility
product (KSP) of the salt, then only the salt gets precipitated. For example,
i) If the product of [Cu2+] & [S-2] in the II group (in presence of acid) of chemical analysis
exceeds the value of KSP of CuS, then only CuS will be precipitated in the group. Similar
argument applies to other metal ions in the group namely (Cd2+, Bi3+, Hg2+, Sb2+, etc).
ii) If the product of [Zn2+] and [S2-] in ammonical medium in IV group of chemical
analysis exceeds the value of Ksp of ZnS, it will be precipitated. Similar arguments apply
to Mn2+, Ni2+ etc.
• Given salt CH3COONa is obtained by the reaction of weak acid (CH3COOH) and
strong base (NaOH).
• The ionisation CH3COONa as follows
• The above salt undergo anionic hydrolysis
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∴ The aq solution of salt is basic due to greater OH– ion concentration than H+ ion
concentration.
∴ PH > 7
Given salt NH4Cl is obtained by the reaction of strong acid (HCl) and weak base
(NH4OH).
The ionisation of NH4Cl as follows
The above salt under goes catioric hydrolysis
NH+4 + H2O ⇌ NH4OH + H+
∴ PH < 7
Common ion effect on solubility of ionic salts
The common ion effect is used for almost complete precipitation of a particular ion as
its sparingly soluble salt, with every low value of solubility product for gravimetric
estimation. Thus we can precipitate silver ion as silver chloride, ferric ion as its
hydroxide (or hydrated ferric oxide) and barium ion as its sulphate for quantitative
estimations.
Question 16.
Write notes on
(i) Common ion effect.
(ii) The relation between Ksp and solubility (S) of a spaningly soluble salt BaSO4.
Solution:
i) Common ion effect : The decrease in the ionisation (dissociation) of a weak
electrolyte, by the addition of a strong electrolyte having an ion common with the
weak electrolyte, is known as common ion effect.
Example : The dissociation of NH4OH is diminished by the addition of NH4Cl due to the
common ion, NH4+ ion
NH4OH ⇌ NH4⊕ + OH⊖
NH4OH NH4+ + OH⊖ (addition of NH4Cl)

Importance of this effect In qualitative analysis :
1. This principle is used in the systematic qualitative analysis of cations.
2. The concentration of S2- in II group or OH– ion in III group of chemical analysis is
controlled by HCl and NH4OH on the basis of common ion effect.
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H+ ion is common to H2S (II group)
NH4+ ion is common to NH4OH (IV group) .
3. The common ion effect principle is also used in controlling the H+ ion
concentration in buffer solutions.
4. It is also used in the purification of common salts by passing dry HCl gas into
impure salt solution.
ii) Relation between KSP and ‘S’ of salt at BaSO4
Problems
Question 1.
1 Mole of PCl5 is heated in a closed vessel of 1 litre capacity. At equilibrium 0.4 moles of
chlorine is found. Calculate the equilibrium Constant.
Solutioni:
PCl5 ⇌ PCl3 + Cl2
(g) (g) (g)
Initial [PCl5] = 1 mole/lit

At equilibrium [Cl2] = 0.4 moles/lit
[PCl3] at equilibrium = 0.4 moles/lit
[PCl5] at equilibrium = 0.6 moles/lit
KC = [PCl3][Cl2][PCl5]
= 0.4×0.40.6=0.160.6
= 0.2606
Question 2.
Nitrogen dioxide forms dinitrogen tetroxide according to the equation 2 NO2 (g) ⇌
N2O4 (g) when 0.1 mole of NO2 as added to a 1 litre flask at 25°C, the concentration
changes so that at equilibrium [NO2] = 0.016M and [N2O4] = 0.042 M
a. What is the value of the reaction Quotient before any reaction occurs.
b. What is the value of the equilibrium constant for the reaction.
Solution:
Given equation
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2NO2 ⇌ N2O4
(g) (g)
a) The value of reaction quotient before any reaction occurs = 0

b) KC = [N2O4][NO2]2
= 0.042(0.016)2=0.0420.000256
= 164.06
= 1.64 × 102
Question 3.
The equilibrium constant for the reaction:
N2(g) + 3H2(g) ⇌ 2 NH3(g) at 725K is 6.0 × 10-2. At equilibrium, [H2] = 0.25 mol L-1 and
[NO3] = 0.06 mol L-1. Calculate the equilibrium concentration of N2.
Solution:
Given
N2 + 3H2 ⇌ 2NH3
(g) (g) (g)
KC = 6 × 10-2
[H2] = 0.25 moles/lit
[NH3] = 0.06 moles/lit
KC = [NH3]2[ N2][H2]3
6 × 10-2 = (0.06)2(N2)(0.25)3
[N2] = (0.06)26×10−2×(0.25)3
= 0.00360.015625×6×10−2
= 0.00360.09375×10−2
= 3.84 moles/lit
Question 4.
At certain temperature, Kc for the re action.
SO2 (g) + NO2 (g) ⇌ SO3 (g) + NO (g)
is 16. If intially one mole each of all the four gases are taken in one litre vessel. What
are the equilibrium con centrations of NO and NO2.
Solution:
Given equations is
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x = 8 – 4x
5x = 8
x = 1.6 moles/lit ∴ (NO] = 1.6 moles/lit
2 – x = 2 – 1.6 = 0.4 moles/lit
[NO2] = 0.4 moles/lit
Question 5.
Under certain conditions, the equilibrium constant for the decomposition of PCl5 (g)
into PCl3 (g) and Cl2 (g) is 00211 mol L-1. What are the equilibrium concentrations of
PCl5, PCl3 and Cl2, if the intial concentration of PCl5 was 1.00 M?
Solution:
PCl5 ⇌ PCl3 + Cl2
(g) (g)
0.0211 (1 – x) = x2
0.0211 – 0.0211 x = x2
x = 0.14 M
∴ 1 – x = 1 – 0.14
= 0.86 M
∴ 1 [PCl5] = 0.86 M
∴ [PCl3] = 0.86 M
[PCl3] = [Cl2] = 0.14 M
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Question 6.
For the reaction A + B ⇌ 3C at 25°C, a 3 litre vessel contains 1, 2, 4 mole of A, B and C
respectively predict the direction of reaction if
a. Kc for the reaction is 10
b. Kc for the reaction is 15
c. Kc for the reaction is 10.66
Answer:
A + B ⇌ 3C at 25°C
a) Given Kc = 10
Kc< Qc
∴ Backward reaction takes place
b) Given Kc = 15
Kc > Qc
∴ Forward reaction takes place
c) Given Kc = 10.66 Q = Kc
∴ Represents equilibrium state
Question 7.
A mixture of H2, N2 and NH3 with molar concentrations 5.0 × 10-3 mol L-1, 4.0 × 10-3 mol
L-1 and 2.0 × 10-3 mol L-1 respectively was prepared and heated to 500K. The value of
Kc for the reaction : 3H2 (g) + N2 (g) ⇌ 2NH3 (g) at this temperature is 60. Predicts
whether ammonia tends to form or decompose at this stage of concentration.
Answer:
331
Given Kc = 60
Kc < Qc
∴ Backward reaction i.e decomposition of NH3 takes place
Question 8.
At 500 K, Kp value for the reaction
2 SO2 (g) + O2 (g) ⇌ 2SO3 (g) is 2.5 × 1010.
Find the value of Kp for each of following reactions at the same temperature.
a. SO2(g) + 1/2O2(g) ⇌ SO3 (g)
b. SO3(g) ⇌ SO2(g) + 1/2O2(g)
c. 3SO2(g) + 3/2 O2(g) ⇌ 3SO3(g)
Solution:
2SO2 + O2 ⇌ 2SO3
(g) (g) (g)
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Question 9.
Kc for the reaction N2O4 (g) ⇌ 2NO2 (g) is 4.63 × 10-3 at 25°C.
a. What is the value of K at this termperature
b. At 25°C, if the partial pressure of N2O4 (g) at equilibrium is 0.2 atm1 calculate
equilibrium pressure of NO2(g).
Solution:
a) Given
Na2O4(g) ⇌ 2NO2(g)
kc = 4.63 × 10-3
kp = kc (RT)∆n
= 4.63 × 10-3 × 0.0821 × 298 [∆n = 1]
= 113.27 × 10-3
= 0.1132
b) kp = PNO22PN2O4
0.1132 = PNO220.2
PNO 2 = 0.2264
2
PNO = 0.15 atm

2
Question 10.
At 27°C, Kp value for the reversible reaction PCl5(g) PCl5(g) + Cl2(g) is 0.65, calculate Kc
Solution:
PCl5 ⇌ PCl3 +Cl2
(g) (g) (g)
Given kp = 0.65 .
kp = k<subC (RT)∆n
0.65 = k<subC 0.082 1 × 300 [T =27°C = 300K; ∆n = 1]
k<subC = 0.6524.63 = 0.02639
Question 11.
Kc for the reaction, N2 (g) + 3H2 (g) 2NH3(g) is 0.5 at 400K, find Kp.
Solution:
N2(g) + 3 H2(g) ⇌ 2 NH3(g)
Given kC = 0.5
T = 400 K
kp = kc (RT)∆n
kp = 0.5 × (0.0821 × 400)-2 ∆n = -2
kp = 0.5 × (8.21 × 4)-2 = 0.5 × (32.84)-2
0.51078.46 = 4.63 × 10-4
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Question 12.
1 mole of A and 1 mole of B are taken in a 5 litre flask, 0.5 mole of C is formed in the
equilibrium of
A + B ⇌ C + D.
What is molar concentration of each species if the reaction is carried with 2 mole of A 1
mole of B in a 5 litre flask at the same temperature.
Solution:
= 0.2 – 0.133 = 0.067 M

[C] = [D] = 0.133 M
Question 13.
For the following reaction
PCl5(g) ⇌ PCl3(g) + Cl2(g) 0.4 mole of PCl5 0.2 mole of PCl3 and 0.6 mole of Cl2 are taken
in a 1 litre flask. If Kc = 0.2, Predict the direction in which reaction proceeds.
Solution:
Given
PCl(g) ⇌ PCl3(g) + Cl2 (g)
QC = [PCl3][Cl2][PCl5]
= 0.2×0.60.4
= 0.03
Given KC = 0.2
QC < KC
∴ Reaction proceds in forward direction.
334
Question 14.
In an equilibrium A + B C + D; A and B are mixed in a vessel at temperature T. The
initial concentration of A was twice the initial concentration of B. After the attainment
of equilibrium, concentration of C was thrice concentration of B, calculate Kc.
Solution:
Given
A+B⇌C+D
The initial concentrations of A was twice the initial concentration of B and after the
Question 15.
A mixture of SO2, SO3 and O2 gases are maintained at equilibrium in 10 litre flast at a
temperature at which Kc for the reactin 2SO2(g) + O2(g) ⇌ 2SO3(g) is 100. At equilibrium.
a. If no. of moles of SO3 and SO2 inflask are same, how many moles of O2 are present.
b. If no. of moles of SO3 in flask is twice the no. of moles SO2, how many moles of
O2 are present.
Solution:
a) Given
2 SO2 + O2 ⇌ 2 SO3
(g) (g) (g)
Given KC = 100 attaining of equilibrium concentration of ‘C’ was thrice the

concentration of ‘B’.
335
a) Given no.of moles of SO3 = No. of moles of SO2
y = 410 = 0.4
∴ 0.4 moles of O2 present.
Question 16.
For A + B ⇌ C, the equilibrium concentrations of A and B at a temperature are 15 mol
L-1. When volume is doubled the reaction has euilibrium concentration of A as 10 mol L-
1
. Calculate.
a) Kc
b) Concentration of C in original equilibrium
Solution:
a) Given
A+B⇌C+D
a) KC
b) Concentration of C in original equilibrium
a) KC = [C][A][B]
[A] = 10 moles/lit
[B] = 10 moles/lit
[CI = 20 moles/lit
= 2010×10
= 20100 = 0.2
b) KC = [C][A][B]
[AI = [B] = 15 moles/lit
0.2 = [C]15×15
[C] = 225 × 0.2
= 45 M.
336
Question 17.
A vessel at 100 K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted
into CO on addition of graphite. Calculate the value of K, if total pressure at equilibnum
is 0.8 atm.
Solution:
0.5 – x + 2x = 0.8
x = 0.3
∴ PCO = 0.2 atm
PCO = 0.6 atm
2
K = PCO22PCO
= 0.360.2 = 1.8
Question 18.
The K1, va)ue for the reaction H2(g)+ I2(g) ⇌ 2 HI(g) at 460°C is 49. If the initial pressure
of H2 and I2 are 0.5 atm respectively, determine the partial pressure of each gases a
equilibrium.
Solution:
x = 3.59
= 0.3888
337
∴ PHI = 2 × 0.3888
= 0.7788 atm
PH = 0.5 – 0.388
2
= 0.111 atm
PI = 0.5 – 0.3888
2
= 0.111 atm.
Question 19.
0.5 mol of H2 and 0.5 mole of I2 react in 10 litre flask at 448°C. The equilibrium constant
Kc is 50 for
H2(g) + I2(g) ⇌ 2HI(g).
a) What is the value of Kp
b) Calculate mole of I2 at equilibrium.
Solution:
∴ No of moles of I2 = 0.5 – 0.3888

= 0.111 moles
338
Question 20.
How much PCl5 must be added to a one little vesel at 250°C in order to obtain a
concentration of 0.1 mole of Cl2 at equilibrium. Kc for
PCl5(g) ⇌ PCl3(g) + Cl2(g) is 0.0414 M.
Solution:
∴ KC = [PCl3][Cl2][PCl5]
0.0414 = 0.1×0.1x−0.0414
0.0414 x – 0.00414 = 0.01
0.0414 x = 0.01 + 0.00414
x = 0.34154 moles
Question 21.
K for the reaction
N2(g) + 3H2(g) ⇌ 2NH3(g) at 400°C is 1.64 × 10-4.
a) Calculate Kc
b) Calculate ∆G° value using Kc value.
Solution:
Given equation N2(g) + 3H2(g) ⇌ 2NH3(g)
a) Kp = Kc (RT)∆n
∆n = 2 – (4)
= -2
1.64 × 10-4 = Kc (0.0821 × 673)-2
Kc = 1.64 × (55.2533)2 × 10-4
Kc = 0.5006
b) ∆G° = -2.303 RT log K
= -2.303 × 0.0821 × 673 × log 0.5005
= 3874 J
339
Question 22.
Calculate the pH of
a) 10-3 M HCl
b) 10-3 M H2SO4
c) 10-6 M HNO3
d) 0.02 M H2SO4
Solution:
a) 10-3 M HCl
pH = -log (H+)
= – log 10-3
=3
b) 10-3 M H2SO4
pH = – log10 [H+]
= 0.001 × 2
= 0.002
pH = – log 0.002
= – log2 × 10-3
= – log2 – log 10-3
= 3 – log2
= 3 – 0.3010
= 2.699
c) 10-6 M HNO3
0.0008 M Ba(OH)2)
pOH = – log [OH–]
[OH–] = 0.0008 × 2
= 0.0016 N
∴ pOH = – log 0.0016
= – log 16 × 10-4
= – log 16 + 4 log 10
= – log24 + 4
= – 4 log 2 + 4 = 2.796
pH + pOH = 14
pH = 14 – 2.796
pH = 11.204
340
d) 0.02 M H2SO4
pH = -log10(H+)
[H+] = 0.02 × 2
= 0.04N
pH = – log 0.04
= -log 4 × 102
= -log4 – log 10-2
= 2 – log4
= 1.3010
Question 23.
Calculate of pH for
a) 0.001 M NaOH
b) 0.01 M Ca (OH)2
c) 0.0008 M Ba(OH)2
d) 0.004M NaOH
Solution:
a) 0.001 M NaOH
pOH = -log[OH–]
pOH = – log (0.001)
= – log 10-3
=3
pH = 14 – pOH = 14 – 3 = 11
b) 0.01 M Ca (OH)2
pOH = -log [OH–]
[OH–] = 0.01 × 2
= 0.02 N
pOH = – log 0.02
pOH = -log 2 × 10-2
pOH = – log2 + 2 log 10
= 2 – 0.3010
= 1.699
∴ pH = 14 – pOH
= 14 – 1.699 = 12.301
341
c) 00008M Ba(OH)2
pOH = -log [OW]
[OH–] = 0.0008 × 2
= 0.0016N
∴ pOH = – log 0.0016
= -log 16 × 10
= -log 16 + 4log 10
= – log 24 + 4
= -4 log 2 + 4 = 2.796
pH + pOH = 14
pH = 14 – 2.796
pH = 11.204
10-6M HNO3
PH = -log [H+]
= -log 10-6
= 6 log 10
=6
d) 0.004M NaOH
pOH = – log[OH–]
= – log 0.004
= – log 4 × 10-3
= 3 – log22
= 3 – 0.6020
= 2.398
pH = 14 – POH
= 14 – 2.398
= 11.602
Question 24.
The pH of a solution is 3.6 Calculate H3O+ ion concentration.
Solution:
pH = – log [H+]
log [H+] = – 3.6 (or) 4¯¯¯.4000
[H+] = anti log of 4¯¯¯.4
= 2.512 × 10-4.
342
Question 25.
The pH of a solution is 8.6 calculate the OH ion concentration.
Solution:
pH = 8.6
∴ pOH = 14 – pH
= 14 – 8.6
= 5.4
∴ pOH = – log [OH–]
log [OH–] = -5.4 (or) 6¯¯¯.6000
[OH–] = anti log of 6¯¯¯.6000
= 3.981 × 10-6
Question 26.
What is [H+] for a solution in which
a) pH = 3
b) pH = 4.75
c) pH = 4.4
Solution:
a) Given
pH = 3
∴ pH = – log [H+]
log [H+] = -3
∴ [H+] = 10-3 M
b) Given
pH = 4.75
PH = – log [H+]
log [H++] = – 4.75 (or) 5¯¯¯.2500
[H+] = anti log of 5.2500
= 1.77 × 10-5 M
c) Given
pH = 4.4
PH = – log [H+]
log [H+] = – 4.4 (or) 5¯¯¯.6
[H+] = anti log of 5¯¯¯.6
= 2.512 × 10-6 M
343
Question 27.
A solution of 0.005 M H2SO4 is diluted 100 times. Calculate the pH of diluted solution.
Solution:
0.005 M H2SO4
[H+] = 0.005 × 2 = 0.01
It is diluted to 100 times
[H+] = 0.01100 = 0.0001
pH = – log [H+]
= – log 0.0001
= – log 10-4 = 4
Question 28.
A solution of HCl has a pH = 3. If one ml of it is diluted to 1 litre, what will be the pH of
the resulting solution ?
Solution:
Given
pH = 3 for HCZ solution
∴ [H+] = 10-3 M
It is diluted to litre
∴ [H+] = 10−3103 = 10-6
∴ pH = – log [H+]
= – log 10-6 = 6
Question 29.
What is the pH of 10-8 M HCl ?
Solution:
The given acid solution is very dilute. Hence the H+ obtained from the acid and water
must be taken into consideration.
H+ ion concentration of acid is 10-8 M
H+ ion concentration of water is 10-7 M
Total [H+] = 10-8 + 10-7
= 1.1 × 10-7 or 1.1 × 10-7 M
∴ pH = – log 1.1 × 10-7
= 7 – log 1.1 = 7 – 0.0414 = 6.995
344
Question 30.
Calculate the pH of the following basic solutions.
a. [OH–] = 0.05 M
b. [OH–] = 2 × 10-4 M
Solution:
a) [OH–] = 0.05 M
pOH = – log (0.05)
= – log 5 × 10-2
= – log 5 + 2 log 10
= 2 – log 5
= 1.3010
pH = 14 – pOH
pH = 14 – 1.3010
= 12.699
b) [OH–] = 2 × 10-4 M
pOH = – log 2 × 10-4
= – log 2 + log 10
= 4 – log 2
= 4 – 0.3010
= 3.699
pH = 14 – 3.699 = 10.301
Question 31.
2g of NaOH is dissolved in water to give 1 litre solution. What is the pH of the solution
?
Solution:
N = wtG∈w×11
= 240 = 120 = 0.05 N = [OH–]
∴ pOH = – log 0.05
= – log 5 × 10-2
= 2 – log 5
= 1.3010
pH = 14 – pOH
= 13 – 1.3010
= 12.699
345
Question 32.
Calculate the pH of the following solutions.
a. 0.37 g of Ca(OH)2 dissolved in water to give 500 ml solution
b. 0.3 g of NaOH dissolved in water to give 200 ml solution
c. 0.1825% HCl aqueous solution
d. 1ml of 13.6 M HCl is diluted with water to give 1 litre solution.
Solution:
a) 0.37 gms of Ca(OH)2 in 500 ml
N = wt/G×w×1/1
N = 0.37/37×1000/500
= 0.01 × 2
= 0.02 = pOH
pOH = – log 0.02
= 1.699
pH = 14 – pOH = 12.301
b) 0.3 gms of NaOH in 200 mZ solution
N = 0.3/40×1000/200
= 0.3×5/40=1.5/40
= 0.375 = [OH–]
= – log 0.375
= 1.426
pH = 14 – pOH
= 14 – 1.426
= 12.574
c) 0.1825% HCl solution means 100 ml
solution contain 0.1825 g. of HCl
Normality (N) = W/EW×1000/V
= 0.1825/36.5×1000/100 = 0.05 N
∴ [H+] = 0.05 N
∴ pH = – log[H+]
= – log [0.051
= – log [5 × 10-2]
= 2 – log 5
= 2 – 0.692
∴ pH = 1.308
346
d) ∴ [H+] = 13.6
Diluted with water to 1 litre solution
∴ [H+] = 13.6/1000 = 0.016
pH = – log [H+]
= – log 0.0136 = 1.87
Question 33.
How many grams of NaOH are present in 100 ml solution if pH of the solution is 10?
Solution:
Given
pH = 10
pOH = 14 – 10 = 4
∴ Normality = 10-4 N
N = wt/GMw×1000/V(ml)
10-4 = wt/40×1000/100
∴ wt = 4 × 10-4 gms
347
Question 35.
Calculate the pH of 10-8 M NaOH.
Solution:
The given box solution is very dilute. Hence OH– obtained from the box and water must
be taken into consideration.
∴ [OH–] = 10-8 + 10-7 = 1.1 × 10-7
pOH = -log 1.1 × 10-7
pOH = 6.995
∴ pOH = 14 – 6.995 = 7.005
348
Question 38.
100 ml of pH = 4 solution is mixed with 100 ml of pH = 6 solution. What is the pH of
resulting solution.
Solution:
349
350
351
Question 44.
40 ml of 0.2 M HNO3 when reacted with 60 ml of 0.3 M NaOH, gave a mixed solution.
What is the pH ofo the resulting solution.
Solution:
VBNB > VANA
Question 45.
50 ml of 0.1 M H2SO4 were added to 100 ml of 0.2 M HNO3. Then the solution is diluted
to 300 ml. What is the pH of the solution.
Solution:
V1 = 50 ml ; V2 = 100 ml
N1 = 0.1 × 2 = 0.2N ; N2 = 02N
352
Question 46.
What is the Kw value in an aqueons solution of pKw = 13.725
Solution:
Given pKw = 13.725
pKw = – log Kw
Kw = antilog of 13.725
= 1.884 × 10-14
Question 48.
The ionization constant for water is 2.9 × 10-14 at 40°C. Calculate [H3O+], [OH]. pH and
pOH for pure water at 40C.
Solution:
Kw = [H-1] [OH–]
2.9 × 10-14 = [H+] [OH–]
For pure water [H+] = [OH–]
∴ [H+]2 = 2.9 × 10-14
[H+] = 1.7 × 10-7 = [H3O+]
∴ [OH–] = 1.7 × 10-7
pH = – log [H+]
= -log [1.7 × 10-7]
= 7 – log 1.7 = 6.7689
= – log [1.7 × 10-7]
= 7 – log 1.7 = 6.7689
353
Question 49.
Calculate the pH of
a. 0.002 M acetic acid having 2.3% dissociation.
b. 0.002 M NH4OH having 2.3% dissociation.
Solution:
a) [H+] = Cα
= 0.002 × 2.3 = 0.0046
pH = – log [H+]
= – log 0.0046
= 4.3372
b) [OH–] = Cα
= 0.002 × 2.3
= 0.0046
= – log 0.0046
= 4.3372
pH = 14 – pOH
= 14 – 4.3372
= 9.6628
354
Question 51.
Calculate pH of 0.1 M acetic acid having Ka =1.8 × 10-5.
Solution:
Question 52.
The pH of 0.1 M solution of weak mono protic acid is 4.0 calculate its [H+] and Ka.
Solution:
Given pH = 4.0
∴ [H+] = ?
pH = – log[H+]
[H+] = 10-pH
= 10-4
∴ [H+] = C × α
α = 10−4/0.1
= 10-3
Ka = C × α2
= 0.1 × (10-3)2
= 0.1 × 10-6
= 10-7.
355
Question 53.
Ka of 0.02 M CH3 COOH is 1.8 × 10-5. Calculate
a. [H3O+]
b. % ionization
c. pH
Solution:
(a), (b)
d2 = Ka/C
= 1.8×10−5/0.02
α2 = 9 × 10-4
α = 3 × 10-2
% of ionisation
[H3O+] = C × α
= 0.02 × 3 × 10-2 = 6 × 10-4
c) pH = -log[H3O+]
= -log(6 × 10-4) = 3.24.
Question 54.
Calculate the pH of 0.01 M solution of CH3 COOH. Ka for CHa OOH at 298K is 1.8 × 10-5.
Solution:
α2 = Ka/C
= 1.8×10−5/0.01
= 180 × 10-5
= 18 × 10-4
α = 4.1 × 10-2
∴ [H3O+] = 0.01 × 4.1 × 10-2
= 4.1 × 10-4
pH = – log [H3O+]
= -log (4.1 × 10-4) = 3.38.
Question 55.
The pH of 0.1 M solution of an organic acid is 4.0 calculate the dissociation constant of
the acid.
Solution:
Given pH = 4.0
∴ [H+] = ?
356
pH = – log[H+]
∴ [H+] = 10-pH = 10-4
∴ [H+] = C × α
α = 10−4/0.1 = 10-3
Ka = C × α2
= 0.1 × (10-3)2 = 0.1 × 10-6 = 10-7
357
358
Question 60.
The pH of a buffer prepared by mixing 50 ml of 0.2 M CH3 COOH and 25 ml of
CH3 COONa is 4.8. If the PKa is 4.8. What is the strength of CH3 COONa.
Solution:
The given solution is an acid buffer.
∴ The pHof the buffer is given by,
359
Question 63.
One litre of buffer solution contains 0.1 mole of aceticacid add 1 mole of sodium
acetate. Find its pH if PKa of CH3COOH is 4.8.
Solution:
For an acid buffer pH = PKa + log[ Salt ]/[ Base ]
pH = 4.8 + log 10.1 = 4.8 + log 10
pH = 4.8 + 1 ⇒ pH = 5.8
360
.
361
Question 71.
In a 0.1 M solution, acetic acid is 1.34% ionized. Calculate [H+], [CH3COO–] and
[CH3COOH] in the solution and Calculate Ka of acetic acid.
Solution:
Given 1.34 % ionised
[H+] = C × α
= 0.1 × 1.34 × 10-2 = 1.34 × 10-3 M
∴ [CH3COOH] =1.34 × 10-3 M
[H+] = Cα = 1.34 × 10-3]
α = 1.34×10−3/0.1 = 1.34 × 10-2]
[CH3COO–] (1 – α) = 0.1 (1 – 0.0134)
= 0.09866 M
Ka = α2 × C
= (1.34 × 10-2) × 0.1 = 1.79 × 10-5
Solved Problems
Question 1.
The following concentrations were obtained for the formation of NH3 from N2 and H2 at
equilibrium at 500 K. [N2] = 1.5 × 10-2 M. [H2] = 3.0 × 10-2 M and [NH3] = 1.2 × 10-2 M.
Calculate equilibrium constant.
Solution:
362
The equilibrium constant for the reaction. N2(g) + 3 H2 (g) ⇌ NH3(g) can be written as,
Question 2.
At equilibrium, the concentrations of N2 = 3.0 × 10-3 M, O2 = 4.2 × 10-3 M and NO = 2.8
× 10-3 M in sealed vessel at 800K. What will be Kc for the reaction
N2(g) + O2 (g) ⇌ 2 NO(g)
Solution:
For the reaction equilibrium constant, KC can be written as,
KC = [NO]2[ N2][O2]
= (2.8×10−3M)2(3.0×10−3M)(4.2×10−3M)
= 0.622.
Question 4.
The value of KC = 4.24 of 800 K for the reaction
CO (g) + H2O (g) ⇌ CO2 (g) + H2 (g)
Calculate equilibrium concentrations of CO2, H2, CO and H2O at 800 K, if only CO and
H2O are present initially at concentrations of 0.10 M each.
Solution: For the reaction
363
Question 5.
For the equilibrium, 3 NOCl (g) ⇌ 2 NO(g) + C2 (g) the value of the equilibrium
constant, KC is 3.75 × 10-6 at 1069 K. Calculate the Kp for the reaction at this temperature
?
Solution:
We know that,
KP = KC(RT)∆n
For the above reaction,
∆n = (2 + 1) – 2 = 1
KP = 3.75 × 10-6 (0.0831 × 1069)
KP = 0.033.
364
Question 6.
The value of KP for the reaction.
CO2 (g) + C(s) ⇌ 2CO (g) is 3.0 at 1000 K. If initially PCO = 0.48 bar and PCO = 0 bar and
2
pure graphite is present, calculate the equilibrium partial pressures of CO and CO2.
Solution:
For the reaction,
let ‘x’ be the decrease in pressure of CO2, then
= (-3 ± 5.66)/8
= (-3 + 5.66)/8 (as value of x cannot be negative hence we neglect that value)
x = 2.66/8 = 0.33
The equilibrium partial pressures are,
PCO = 2x = 2 × 0.33 = 0.66 bar
PCO = 0.48 – x = 0.48 – 0.33 = 0.15 bar
2
Question 7.
The value of Kc for the reaction
2A ⇌ B + C is 2 × 10-3. At a given time, the composition of reaction mixture is [A] = [B]
= [C] = 3 × 10-4 M. In which direction the reaction will proceed ?
Solution:
For the reaction the reaction quotient QC is given by.
QC = [B] [C] / [A]2
as [A] = [B] = [C] = 3 × 10-4 M
QC = (3 × 10-4) (3 × 10-4)/ (3 × 10-4)2 = 1
as QC > KC so the reaction will proceed in the reverse direction.
365
Question 8.
13.8 g of N2O4 was placed in a 1L reaction vessel at 400 K and allowed to attain
equilibrium
N2O4(g) ⇌ 2 NO2(g)
The total pressure at equilbrium was found to be 9.15 bar. Calculate KC, KP and partial
pressure at equilibrium.
Solution:
We know pV = nRT
Total volume (V) = 1 L
Molecular mass of N2O4 = 92 g
Number of moles = 13.8 g / 92 g = 0.15 of the gas (n)
Gas constant (R) = 0.083 bar L mol-1K-1
Temperature (T) = 400 K
pV = nRT
p × 1L = 0.15 mol × 0.083 bar L mol-1K-1 × 400 K
p = 4.98 bar
Hence,
ptotal at equilibrium = pN O + pNO
2 4 2
9.15 = (4.98 – x) + 2x
9.15 = 4.98+ x
x = 9.15 – 4.98 = 4.17 bar
Partial pressures at equilibrium are,
pN O = 4.98 – 4.17 = 0.81 bar
2 4
pNO = 2x = 2 × 4.17 = 8.34 bar

2
Kp = (pNO )2 / pN O
2 2 4
= (8.34)2 / 0.81 = 85.87

Kp = KC (RT)∆n
85.87 = KC(0.083 × 400)1
KC = 2.586 = 2.6
366
Question 9.
300 mol of PCl5 kept in 1L closed reaction vessel was allowed to attain, equilibrium at
380K. Calculate composition of the mixture at equilibrium. Kc = 1.80
Solution:
Question 10.
The value of ∆G° for the phosphorylation of glucose in glycolysis is 13.8 kJ/mol. Find
the value of Kc at 298 K.
Solution:
∆G° = 13.8 ki/ mol = 13.8 × 103J/mol
Also, ∆G° = – RT Inkc
Hence, In Kc = – 13.8 × 103 J/mol
(8.314 Jmol-1K-1 × 298 K)
In Kc = 5.569
Kc = e-5 569
Kc = 3.81 × 10-3
367
Question 11.
Hydrolysis of sucrose gives.
Sucrose + H2O ⇌ Glucose + Fructose Equilibrium constatnt Kc for the reaction is 2 ×
1013 at 300K. Calculate ∆GΘ at 300K.
Solution:
∆G° = -RT InKc
∆G° = -8.314J mol-1K-1 × 300K × In (2 × 1013)
∆G° = – 7.64 × 104J mo-1
Question 12.
What will be the conjugate bases for the following Bronsted acides: HF,
H2SO4 and HCO−3 ?
Solution:
The conjugate bases should have one proton less in each case and therefore the
corresponding conjugate bases are: F–, HSO−3 and CO2-3 respectively.
Question 13.
Write the conjugate acids for the following Bronsted bases: NH–2, NH3 and HCOO–.
Solution:
The conjugate acid should have one extra proton in each case and therefore the
corresponding conjugate acids are : NH3, NHO+4 and HCOOH respectively.
Question 14.
The species; H2O, HCO−3′, HCO−4′ and NH3 can act both as Bronsted acids andbases.
For each case give the corresponding conjugate acid and conjugate base.
Solution:
The answer is given in the following Table:
368
Question 15.
Classify the following species into Lewis acids and Lewis bases and show how these act
as such :
(a) HO–
(b) F–
(c) H+
(d) BCl3
Solution:
(a) Hydroxyl ion is a Lewis base as it can donate an electron lone pair (: OH–).
(b) Flouride ion acts as a Lewis base as it can donate any one of its four electron lone
pairs.
(c) A proton is a Lewis acid as it can accept a lone pair of electrons from bases like
hydroxyl ion and fluoride ion.
(d) BCl2 acts a Lewis acid as it can accept a lone pair of electrons from species like
ammonia or amine molecules.
Question 16.
The concentration of hydrogen ion in a sample of soft drink is 3.8 × 10-3M. What is its
pH ?
Solution:
pH = – Log[3.8 × 10-3]
= -{log[3.8] + log[10-3}]
= – {(0.58) + (-3.0)} = -2.42} = 2.42
Therefore, the pH of the soft drink is 2.42 and it can be inferred that it is acidic.
Question 17.
Calculate pH of a 1.0 -8 M solution of HCl.
Solution:
2H2O(1) H3O+ (aq) + OH–(aq)
Kw = [OH–][H3O+]
= 10-14
Let, x = [OH–] = [H3O+] from H2O. The H3O+ concentration is generated (i) from the
ionization of HCl dissolved i.e., HCl (aq) + H2O (1) ⇌ H3O+ (aq) + Cl–(aq), and (ii) from
ionization of H2O. Inthese very dilute solutions. both sources of H3O+ must be
considered:
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[H3O+] = 10-8 + X
Kw = (10-8 + x)(x) = 10-14
or x2 + 10-8 x – 10-14 = 0
[OH–] = x = 9.5 × 10-8
So, pOH = 7.02 and pH = 6.98
Question 18.
The ionization costant of HF is 3.2 × 10-4. Calculate the degree of dissociation of HF in
its 0.02 M solution. Calculate the concentration of all species present (H3O+.F– and HF) in
the solution and its pH.
Solution:
The following proton transfer reactions are possible :
1) HF + H2O ⇌ H3O+F–Ka = 3.2 × 10-4
2) H2O + H2O H3O+ + OH– Kw = 1.0 × 10-14
As ka >> Kw, [1] is the principle reaction.
Substituting equilibrium concentrations in the equailibrium reaction for principal

reaction gives.
Ka (0.02α)2/ (0.02 – 0.02α)
= 0.02α2/(1 – α) = 3.2 × 10-4
We obtain the following quadratic equation:
α2 + 1.6 × 10-2α – 1.6 × 10-2 = 0
The quadratic equation in α can be solved and the two values of the roots are :
α = + 0.12 and – 0.12
The negative root is not acceptable and hence.
a = 0.12
This means that the degree of ionization α = 0.12, then equilibrium concentrations of
other species viz., HF, F– and H3O+ are given by:
[H3O+] = [F] = cα = 0.02 × 0.12
= 2.4 × 10-3M
[HF] = c(1 – α) = 0.02(1 – 0.12)
= 17.6 × 10-3M
pH = -log[H+] = -log (2.4 × 10-3) = 2.62
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Question 19.
The pH of 0.1 M monobasic acid is 4.50. Calculate the concentration of species H+,
A– and HA at equilibrium. Also, determine the value of Ka and pKa of the monobasic
acid.
Solution:
pH = – log [H+]
Therefore [H+] = 10-pH = 10-4.50
= 3.16 × 10-5
[H+] = [A–] = 3.16 × 10-5
Thus, Ka = [H+] [A–] / [HA]
[HA]eqlbm = 0.1 – (3.16 × 10-5) ≅ 0.1
Ka = (3.16 × 10-5)2/0.1 = 1.0 × 10-8
pKa = – log (10-8) = 8
Alternatively, “Percent dissociation” is another useful method for measure of strength
of a weak acid and is given as : Percent dissociation
= [HA]dissociated × 100/[HA]initial (7.32)
Question 20.
Calculate the pH of 0.08M solution of hypochlorous acid. HOCI. The ionization
Constant of the acid is 2.5 × 10-5, Determine the percent dissociation of HOCl
Solution:
[H+] = 1.41 × 10-3 M Therefore,
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Percent dissociation
= {[HOCI]dissociated × 100/[HOCI]initial}
= 1.41 × 10-3 /0.08 = 1.76%,
pH = -log (1.41 × 10-3) = 2.85
Question 21.
The pH of 0.004 M hydrazine solution is 9.7. Calculate is ionization constant Kb and pKb.
Solution:
NH2NH2 + H2O ⇌ NH2NH+3 +OH–
From the pH we can calculate the hydrogen ion concentration. Knowing hydrogen ion
concentration and the ionic product of water we can calculate the concentration of
hydroxyl ions. Thus we have :
[H+] = antilog (-pH)
= antilog (-9.7) = 1.67 × 10-10
[OH–] = Kw/[H+] = 1 × 10-14/ 1.67 × 10-10
= 5.98 × 10-5
The concentration fo the corresponding hydrazinium ion is also the same as that of
hydroxyl ion. The concentrations of both these ions are very small so the concentration
of the undissociated base can be taken equal to 0.004 M.
Thus,
Kb = [NH2NH3+] [OH–] / [NH2NH2]
= (5.98 × 10-5)2/0.004 = 8.96 × 10-7
pKb = -logKb = -log(8.96 × 10-7 ) = 6.04
Question 22.
Calculate the pH of the solution in which 0.2M NH4Cl and 0.1 M NH3 are present. The
pKb of ammonia solution is 4.75.
Solution:
NH3 + H2O ⇌ NH+4 + OH–
The ionization constant of NH3,
Kb= antilog (-pKb) i.e.
Kb = 10-4.75 = 1.77 × 10-5 M
3 + H2O ⇌ NH+4 + OH Initial concentration (M)
–
Change in concentration to reach equilibrium (M)
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Kb = [latex]\mathrm{NH}_4^{+}[/latex][OH-1] / [NH3]
= (0.20 × x) (x) / (0.1 – x) = 1.77 × 10-5
As Kb is small, we can neglect x in comparison to 0.1 M and 0.2 M. Thus
[OH–] = x = 0.88 × 10-5
Therefore, [H+] = 1.12 × 10-9
pH = -log [H+] = 8.95 .
Question 23.
Determine the degree of ionization and pH of a 0.05M of ammonia solution. The
ionization constant of ammonia can be taken from Table 7.7. Also, calculate the
ionization constant of the conjugate acid of ammonia.
Solution:
The ionization of NH3 in water is represented by equation :
NH3 + H2O ⇌ NH+4 + OH–
We use equation (7.33) to calculate hydroxyl ion concentration,
[OH–] c α = 0.05 α
Kb = 0.05 α2/(1 – α)
The value of α is small, therefore the quadratic equation can be simplified by
neglecting a in comparison to 1 in the denominator on right hand side of the equation,
Thus,
Kb = C α2 or α =√ (1.77×10−5/0.05)
= 0.018.
[OH–] = C α = 0.05 × 0.018 = 9.4 × 10-4 M.
[H+] = Kw/[OH–] = 10-14 / (9.4 × 10-4)
= 1.06 × 10-11
pH = -log (1.06 × 10-11) = 10.97
Now, using the relation for conjugate acid-base pair,
K a × K b = Kw
using the value of Kb of NH3 from Tabel 7.7.
We can determine the concentration of con-jugate acid NH+4
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Ka × Kw/ Kb = 10-14/ 1.77 × 10-5
= 5.64 × 10-10.
Question 24.
Calculate the pH of a 0.10M ammonia solution. Calculate the pH after 50.0 mL of this
solution is treated with 25.0 mL of 0.10M HCl. The dissociation constant of ammonia,
Kb = 1.77 × 10-5.
Solution:
NH3 + H2O ⇌ NH+4 + OH–
Kb = [latex]\mathrm{NH}_4^{+}[/latex] [OH–] / [NH3] = 1.77 × 10-5
Before neutralization,
[latex]\mathrm{NH}_4^{+}[/latex] [OH–] = x
[NH3] = 0.10 – x – 0.10, x2 / 0.10 = 1.77 × 10-5
Thus, x= 1.33 × 10-3 = [OH–]
Therefore, [H+] = Kw / [OH–] = 10-14 / (1.33 × 10-3)= 7.51 × 10-12
pH = -log (7.5 × 10-12 ) = 11.12
On addition of 25 mL of 0.1 M HCl solution (i.e., 2.5 mmol of HCl) to 50 mL of 0.1 M
ammonia solution (i.e., 5 mmol of NH3), 2.5 mmol of ammonia molecules are
neutralized. The resulting 75 mL solution contains the remaining unneutralized 2.5
mmol of NH3 molecules and 2.5 mmol of NH+4
The resulting 75 mL of solution contains 2.5 mmol of NH+4 ions (i.e., 0.033M) and 2.5
mmol (i.e., 0.033M) of uneutralised NH3 molecules. This NH3 exists as NH4OH in the
following equilibrium :
The final 75 mL solution after neutralisation already contains 2.5 m mol

[latex]\mathrm{NH}_4^{+}[/latex] ions (i.e. 0.033M), thus total concentration of
[latex]\mathrm{NH}_4^{+}[/latex] ions is given as : [NHJ] = 0.033 + y
As y is small, [NH4OH] ≃ 0.033 M and [latex]\mathrm{NH}_4^{+}[/latex] ≃ 0.033M.
We know,
Kb = [latex]\mathrm{NH}_4^{+}[/latex] [OH–] / [NH4OH]
= y(0.033)/(0.033) 1.77 × 10-5 M
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Thus, y = 1.77 × 10-5 = [OH–]
[H+] = 10-14/ 1.77 × 10-5 = 0.56 × 10-9
Hence, pH = 9.24.
Question 25.
The pKa of acetic acid and pKa of ammonium hydroxide are 4.76 and 4.75 respectively.
Calculate the pH of am-monium acetate solution.
Solution:
pH = 7 + 1/2 [pKa – pKb]
= 7 + 1/2 [4.76 – 4.75]
= 7 + 1/2 [0.01] = 7 + 0.005 = 7.005
Question 26.
Calculate the solubility of A2X3 in pure water, assuming that neither kind of ion reacts
with water. The solubility product of A2X3, Ksp = 1.1 × 10-23.
Solution:
A2X3 ⇌ 2A3+ + 3X2-
Ksp = [A3+]2 [X2-]3 = 1.1 × 10-23
If S = solubility of A2X3, then
[A3+] = 2S; [X2-] = 3S
therefore, Ksp = (2S)2 (3S)3 = 108S5
= 1.1 × 10-23
thus, S5 = 1 × 10-23
S = 1.0 × 10-5 mol/L.
Question 27.
The values of Ksp of two sparingly soluble salts Ni(OH)2 and AgCN are 2.0 × 10-15 and 6
× 10-17 respectively. Which salt is more soluble ? Explain.
Solution:
AgCN ⇌ Ag+ + CN–
Ksp = [Ag+] [CN–] = 6 × 10-17
Ni(OH)2 ⇌ Ni2 + 2OH–
Ksp = [Ni2+] [OH–]2 = 2 × 10-15
Let [Ag+] = S1 then [CN–] = S1
Let [Ni2+] = S2 then [OH–] = 2S2
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S12 = 6 × 10-17 = S1 = 7.8 × 10-9
(S2) (2S2)2 = 2 × 10-15, S2 = 0.58 × 10-4
Ni(OH)2 is more soluble than AgCN.
Question 28.
Calculate the molar solubility of Ni(OH)2 in 0.10 M NaOH. The ionic product of
Ni(OH)2 is 2.0 × 10-15.
Solution:
Let the solubility of Ni(OH)2 be equal to S. Dissolution of S mol/L of Ni(OH)2 provides S
mol/L of Ni2+ and 2S mol/L of OH–, but the total concentration of OH– = (0.10 + 2S)
mol/L because the solution already contains 0.10 mol/L of OH– from NaOH.
Ksp = 2.0 × 10-15 = [Ni2+] [OH–]2
(S) (0.10 + 2S)2 As Ksp is small, 2S < < 0.10,
thus, (0.10 + 2S) ≈ 0.10
Hence,
2.0 × 10-15 S(0.10)2
S = 2.0 × 10-13 M = [Ni2+]
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Question 1.
The three isotopes of hydrogen differ in their rates of reaction. Give the reasons.
Answer:
The three isotopes of hydrogen differ in their rates of reactions due to their different
enthalpies of bond dissociation.
Question 2.
Why is dihydrogen used in welding of high melting metals ?
Answer:
Dihydrogen is used in welding of high melting metals because the atomic hydrogens
which are formed by the dissociation of dihydrogen are recombined on the surface of
the metal to be welded and produce the high temperature of 4000 K.
Question 3.
Describe one method of producing high purity hydrogen.
Answer:
Highly pure hydrogen is obtained by the electrolysis of hot aq.Ba(OH)2 solution
between nickel electrodes. The purity of hydrogen is about more than 99.95%.
Question 4.
Explain the term “SYNGAS”.
Answer:
The mixture of CO and H2 which is used for the synthesis of methanol and a number of
hydrocar-bons is called “SYNGAS”. It is also called as synthesis gas.
Preparation :
This reaction is called ‘Coal gasification’.
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Question 5.
What is meant by coal gasification ? Explain with relevant, balanced equation.
Answer:
The process of producing synthesis gas (SYNGAS) by using coal at 1270K temperature
is called coal gasification.
Balanced equation :
Question 6.
Define the term Hydride. How many categories of hydrides are known ? Name them.
Answer:
The binary compounds of hydrogen formed by the other elements except noble gases
are called hydrides.
Hydrides are categorised into three types.
1. Ionic hydrides
2. Covalent hydrides
3. Metallic hydrides
Question 7.
The unusual property of water in condensed phase leads to its high heat of
vapourization. What is that property ?
Answer:
In water inter molecular hydrogen bonding is present. Due to this unusual property
water has high Freezing point. Boiling point and high heat of vapourization.
Question 8.
During photosynthesis, water is oxidised to O2. Which element is reduced ?
Answer:
During photosynthesis, the element reduced is carbon.
Oxidation state change from +4 to 0 [Reduction]
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Question 9.
What do you mean by autoprotolysis ? Give the equation to represent the
autoprotolysis of water.
Answer:
Water has the ability to behave as an acid as well as base. It behaves as an amphoteric
substance. The self-ionising property of water is called auto protolysis.
The equation that represent the auto protolysis of water is as follows.
Question 10.
Water behaves as an amphoteric substance in the Bronsted sense. How do you explain
?
Answer:
According to Bronsted proton donor is acid and acceptor is base. Water has the ability
to behave as an acid as well as base. So it is an amphoteric substance.
Eg :
1. Water acts as acid with ammonia.
H2O(l) + NH3(aq) ⇌ OHΘ(aq) + NH⊕4 (aq)
Here water is proton donor.
2. Water acts as base with H2S.
H2O(l) + H2S(aq) ⇌ H3O⊕(aq) + HSΘ(aq)
Here water is proton acceptor.
Question 1.
The boiling points of NH3 ; H2O and HF are higher than those of hydrides of the
subsequent members of the group. Give your reasons.
Answer:
The boiling points of NH3, H2O and HF are higher than those of hydrides of the
subsequent mem-bers of the group.
Reasons :
• NH3, H2O and HF are electron rich hydrides and these have 1, 2 and 3 lone pairs
respectively.
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• Due to the presence of lonepairs on the high electronegative elements results in
the formation of hydrogen bond [i.e. intermolecular hydrogen bonding].
• Due to the formation of hydrogen bond association of molecules takes place.
Hence these hydrides has high boiling points.
Question 2.
Discuss the position of hydrogen in the periodic table on the basis of its electronic
configuration.
Answer:
Hydrogen is the simplest element with one electron and proton. Its electronic
configuration is 1s. The configuration is responsible for its dual nature. It behaves both
like alkali metals and halogens. So it can be placed along with alkali metals (IA) or
along with halogens (VIIA).
Points in support of placing it in IA group :
a) Like alkali metals hydrogen also has a single electron in the outer shell 1s1,
b) Its ability to form hydrated unipositive ion, H+ (aq).
c) It is quite reasonable to start the periodic table with an element having the least
atomic number (Z = 1).
Points in support of placing it in VIIA group :
a) Hydrogen is a gas like fluorine or chlorine.
b) It can form diatomic molecule like halogens.
c) It has a tendency of gaining an electron and attains a stable electronic configuration
of He forming H+ ion like halogens.
At the same time it should be noted that hydrogen has not such a great tendency to
lose electron like alkali metals and gain an electron like halogens. In view of this it is
difficult to assign any definite position to hydrogen. Sometimes it is placed in IA group
and sometime with VIIA group.
Question 3.
How is the electronic configuration of hydrogen suitable for its chemical reactions ?
Answer:
Electronic configuration of hydrogen is 1s1.
• The atomic hydrogen obtained from dihydrogen by the treatment with UV rays
does combine with allmost all the elements.
• This atomic hydrogen successfully complete the reactions,
a) By the loss of one electron to give H⊕.
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b) By the gain of one electron to form HΘ and
c) By the sharing of electrons to form a single covalent bond.
Eg : 1) H2(g) + F2(g) → 2HF(g)
2) 2Li(s) + H2(g) → 2LiH
Question 4.
What happens when dihydrogen reacts with
a) Chlorine and
b) Sodium metal. Explain.
Answer:
a) Reaction of dihydrogen with chlorine : Hydrogen reacts with chlorine to form
hydrogen chloride gas. This reaction occurs in presence of sun light.
b) Reaction of dihydrogen with sodium metal : Hydrogen reacts with highly reactive
metal like sodium and forms sodium hydride. The reaction occur at a high temperature.
2Na(s) + H2(g) → 2NaH(s)
Question 5.
Write a note on heavy water.
Answer:
Deuterium oxide (D2O) is known as heavy water.
Peparation : Heavy water is obtained by the exhaustive electrolysis of water.
The physical properties like molecular mass, melting point, Boiling point etc., of D2O are
heavier than watet. But dielectric constant and solubility are low for heavy water when
compared to water.
Chemical properties :
a) Heavy water reacts with calcium carbide and forms Deuteroacetylene.
CaC2 + 2D2O → C2D2 + Ca(OD)2
b) Heavy water reacts with sulphur trioxide and forms Deutero sulphuric acid.
SO3 + D2O → D2SO4
c) Heavy water reacts with Aluminium carbide and forms Deutero methane.
Al4C3 + 12D2O → 3CD4 + 4Al (OD)3
Uses :
• It is used as a moderator in nuclear reactors to decrease the speed of neutrons.
• It is used to study the reaction mechanism in exchange reactions.
• It is used for the preparation of deuterium and deuterium compounds.
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Question 6.
Name the isotopes of hydrogen. What is the ratio of masses of these isotopes ?
Answer:
Hydrogen has three isotopes.
1. Protium (1H1)
2. Deuterium (1H2 (or) D)
3. Tritium (1H3 or T)
Tritium is radioactive isotope.
• The ratio of masses of these isotopes is 1 : 2 : 3 respectively for protium,
deuterium and Tritium.
• Protium has no neutrons, deuterium has one neutron and tritium has two
neutrons.
Question 7.
What is water – gas shift reaction? How can the production of dihydrogen be increased
by this reaction?
Answer:
The mixture of CO and H2 is called water gas. It is also called ‘Syngas’.
Water-gas shift reaction : When carbon monoxide of the syngas mixture reacted in
presence of Iron chromate as catalyst then the reaction is called as water-gas shift
reaction.
By using this reaction dihydrogen production can be increased.
In this reaction CO2 gas is removed by using sodiumarsenite solution by scrubbing.
Question 8.
Complete and balance the following reactions :
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Answer:
Question 9.
What is the nature of the hydrides formed by elements of 13 group ?
Answer:
Group 13 elements are belongs to p-block of periodic table.
Generally p-block elements forms covalent (or) molecular hydrides.
These molecular hydrides are further classified into 3 types
1. Electron deficient hydrides
2. Electron – precise hydrides
3. Electron – rich hydrides
Group – 13 elements forms electron deficient hydrides. Electron deficient hydrides are
the molecular hydrides which have less no.of electrons to write the lewis structure.
Eg : Diborane (B2H6)
These hydrides acts as Lewis acids. Lewis acids accepts electron pairs and forms co-
ordinate covalent bonds with donors.
Question 10.
Discuss the principle and the method of softening of hard water by synthetic, ion-
exchange resins.
Answer:
Synthetic ion – exchange resins method :
• In present days, this method is mostly used for softening the hard water by using
synthetic resins.
• This method is more useful than zeolite (or) permutit process.
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Principle : Formation of de-ionised water (or) de mineralised water by passing the water
successively through cation exchange and anion exchange resins.
De-ionised water means, water which is free from all soluble mineral salts.
Process : The de-ionization of water can be done in two steps by this process.
Step – I: Cation exchange process.
Step – II: Anion exchange process.
Step – I: Cation exchange process
In this process synthetic resins used are – So3H group containing large organic
molecule. (R-SO3H)
Here R = organic group (or) resin anion.
• At first the synthetic resin converted to RNa by reacting it with NaCl.
• This resin i.e; RNa exchanges Ca+2 and Mg+2 ions of hard water and the softening
of water takes place.
2RNa(s) + M+2(aq) → R2M(s) + 2Na+(aq)
• The resin can be regenerated by using aq.NaCl solution.
• In this step H+ ions exchanges Na+, Ca+2, Mg+2 and proton formation takes place.
2RH(s) + M+2(aq) ⇌ MR2(s) + 2H+(aq)
Step – II: Anion exchange process :
• In this process resins used are RNH3OH i.e., a basic compound.
• The OH– ions of resin exchanges the’anions Cl–, SO4-2, HCO3– etc., and OHΘ ion
formation takes place.
• The H+ ions and OH– ions obtained in the two steps are get neutralised to form
de-ionised water.
H+(aq)+OH−(aq)⟶H2O(l)
• The cation exchange resins and anion exchange resins are regenerated by
treatment with dil.acid and base respectively.
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Question 11.
Write a few lines on the utility of hydrogen as a fuel. [Mar. 13]
Answer:
Hydrogen as a fuel :
The heat of combustion of hydrogen is high i.e about 242kj/mole. Hence hydrogen is
used as industrial fuel.
• The energy released by the combustion of dihydrogen is more than the petrol (3
times).
• Hydrogen is major constituent in fuel gases like coal gas and water gas.
• Hydrogen is also used in fuel cells for the generation of electric power.
• 5% dihydrogen is used in CNG for running four-wheeler vehicles:
• By hydrogen economy principle the storage and transportation of energy in the
form of liquid (or) gaseous state. Here energy is transmitted in the form of
dihydrogen and not as electric power.
Question 12.
A 1% solution of H2O2 is provided to you. What steps do you take to prepare pure
H2O2 from it ?
Answer:
To obtain pure H2O2 from the provided 1% H2O2 the following steps are involved.
Step -1:
The provided 1% H2O2 solution is carefully evoparated on a water bath under reduced
pressure by distillation.
Here approximately 30% H2O2 solution is obtained.
Step – II :
The obtained solution in the above step is heated in a distillation flask at a low pressure
of 15mm. Here approximately 85% H2O2 solution is obtained.
Step – III :
The above sample (obtained in the step – II) crystallised by freezing and pure H2O2 is
obtained (≅ 100%).
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Question 13.
Mention any three uses of H2O2 in modern times.
Answer:
Uses of H2O2 in modern times :
• H2O2 is used in modern times in Green chemistry to control the pollution.
Eg : It is used in the treatment of domestic and industrial effluents and in the
oxidation of cyanides.
• H2O2 is used in manufacturing of Sodium perborate and sodium per carbonates.
These are used in high quality detergents.
• H2O2 is used in certain food products and in certain pharmaceuticals.
• H2O2 is used as bleaching agent to bleach paper pulp, leather etc.
• H2O2 is used as an antiseptic and in hair bleach.
Question 1.
Write an essay on the commercial preparation of dihydrogen. Give balanced equations.
Answer:
Commercial methods of preparation of dihydrogen
i) From Hydrocarbons : When hydrocarbons undergo reaction with steam at high
temperatures in presence of catalyst liberates hydrogen gas.
Eg : C3H 8 + 3H2°(g)
(g) 3CO + 7H2
ii) By the electrolysis of water : Acidified (or) alkaline water undergo electrolysis using
platinum electrodes liberates hydrogen gas.
Highly pure hydrogen is liberated by the electrolysis of hot aq. Ba(OH)2 by using ‘Ni’
electrodes.
iii) By Nelson’s Process : Hydrogen gas is obtained as a Byproduct by the electrolysis of
brine solution. This process is mainly used for the manufacturing of NaOH, Cl−2 gas.
Cell Reactions : –
2NaCl → 2Na+ + 2Cl–
2Cl– → Cl2 + 2e– (Anode)
2H2O + 2e– → H2 + 2OH– (Cathode)
2Na+ + 2OH– → 2 NaoH
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iv) By water gas shift reaction : Water gas is the mixture of CO and H2. It is also called as
syngas. The process of producing syngas from coal is called as coal gasification.
The dihydrogen production can be increased by the reaction of steam with syngas in
presence of catalyst.
This reaction is called as water gas shift reaction.
Question 2.
Illustrate the chemistry of dihydrogen by its reaction with
i) N2
ii) Metal ions and metal oxides and
iii) Organic compounds. How is dihydrogen used in the manufacture of chemicals ?
Answer:
i) Reaction with N2: Dihydrogen reacts with nitrogen in presence of iron catalyst to form
ammonia.
This process is called as Haber’s process. Here temperature used is around 700K and
pressure used is 200 atm.
ii) a) Reaction with metal ions : Hydrogen reduces metal ions in aqueous solution into
metals.
H2 + Pd+2(aq) → Pd(s) + 2H+(aq)
(g)
b) Reaction with metal oxides : Hydrogen reduces metal oxides into metals.
WO3 + 3H2 → W + 3H2O
iii) Reaction with organic compounds :
a) Vegetable oils undergoes hydrogenation in presence of ‘Ni’ catalyst and forms
vanaspathi.
b) Alkenes undergo hydro formylation and forms aldehydes. These aldehydes undergo
reduction to form alcohols.
CH2 = CH2 + CO + H2 → CH3 – CH2CHO (Aldehyde)
CH3CH2CHO + H2 → CH3CH2CH2OH (Alcohol )
Use of Dihydrogen in the manufacture of chemicals
Dihydrogen is used in the manufacturing of industrial cherfiicals like methanol,
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ammonia, hydrogen chloride etc.
Question 3.
Explain, with suitable examples, the following :
1. electron deficient
2. electron – precise and
3. electron – rich hydrides.
Answer:
Molecular hydrides (or) covalent hydrides are formed by the p-block elements.
These molecular hydrides are divided into three types.
1. Electron deficient hydrides
2. Electron – precise hydrides
3. Electron – rich hydrides
1) Electron – deficient hydrides : These are the molecular hydrides in which the
available no.of valency electrons is less than the number-required for normal covalent
bond formation.
(or) .
These are the molecular hydrides in which the available valency electrons are lessthan
the required for writting the Lewis structure of the molecule.
Eg : (AlH3)n, B2H6 etc.
These hydrides acts as Lewis acids i.e. electron pair acceptors. These forms dative bond
with donors.
2) Electron – precise hydrides : These are the molecular hydrides in which all the
valency electrons of the central atom are involved in bond formation.
(or)
These are the molecular hydrides which contains the required no.of valency electrons
to write the Lewis structure of the molecule.
Eg : Group 14 elements forms this type of hydrides CH4, C2H6 etc., are examples of this
type.
These have tetrahedral geometry.
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3) Electron – rich hydrides :
These are the molecular hydrides in which the valency electrons on the central atom
are more than that are required for bond formation.
(or)
• These are the molecular hydrides in which the available valency electrons are
more than the required for writting the Lewis structure of the molecule.
• These hydrides contains lone pairs on central atoms.
Eg :
These hydrides have high boiling points than those of the hydrides of the
subsequent members of group because of hydrogen bond formation.
Question 4.
Write in brief on
i) ionic hydrides
ii) interstitial hydrides.
Answer:
i) Ionic hydrides : These are also called as saline hydrides (or) salt like hydrides.
* These are the hydrides formed by combining di hydrogen with s-block elements
(Electro posi-tive elements).
* These are stoichiometric compounds.
Eg : LiH, NaH, CaH2 etc.
NaH is formed by the direct union of Na and H2
Physical properties :
• These hydrides are crystalline.
• These hydrides are non volatile and non – conducting in solidstate.
• These conducts electricity in moltenstate.
• These have high melting points.
These hydrides on electrolysis, liberates dihydrogen gas at anode.
2H– → H2(g) + 2e– [Anode]
Lithium hydride is used in the synthesis of other useful hydrides like LiAlH4 and LiBH4.
8LiH + Al2CL6 → 2LiAlH4 + 6LiCl
2LiH + B2H6 → 2LiBH4
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2NaH + B2H6 → 2NaBH4
These hydrides react with acids and water vigorously and liberate dihydrogen.
LiH + H2O → LiOH + H2 ↑
ii) Interstitial hydrides : These are the hydrides formed by the reaction of hydrogen with
d-block and f-block elements. These are also called as metallic hydrides.
Eg : CrH, CrH2, ZnH2, ThH2
• The hydrogen of the metallic hydride occupy the intersticies of metallic lattice.
Hence these are called as Interstitial hydrides.
• These are non-stiochiometric compounds
Eg : TiH1.5-1.8 LaH2.87 etc-
• In these hydrides law of constant composition does not found.
• Metals of group 7, 8 and 9 do not form hydrides and in group 6 only chromium
forms hydrides.
• The conductivity of these hydrides is less than the parent metals.
• The formation of metallic hydrides and their capacity to release hydrogen at high
temperature are utilised in the purification of H2.
• Some metals can accomodate a very large volume of hydrogen and acts as
storage media.
Question 5.
Explain any four of the chemical properties of water.
Answer:
i) Hydrolysis Reaction : The chemical interaction of a compound with water is called as
hydrolysis. -» Water has high hydrating ability because of high dielectric constant.
Covalent as well as ionic compounds undergo hydrolysis.
Eg: P4O10(s) + 6H2O(l) → 4H3PO4(aq) (orthophosphoric acid)
NCl3 + 3H2O → NH3 + 3HOCl
SiCl4 + 2H2O → SiO2 + 4HCl
ii) Formation of hydrogen : Water can be reduced to dihydrogen by reacting with
highly elec-tropositive metals.
2Ma(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
Water is an important source of dihydrogen.
iii) Photosynthesis reaction : During photo synthesis reaction water gets oxidised to O2.
6CO2 + 6H2O(l) → C6H12O6 + 6O2
(g) (aq) (g)
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iv) Hydrates formation : By the association of water molecules of different types
hydrated salts formed from the crystallisation of salts.
Eg : BaCl2.2H2O, CuSO4. 5H2O
v) Amphoteric Nature : Water has the ability to act as an acid as well as base. It is an
Eg: i) H2O(l) + NH3(aq) ⇌ OH–(aq) + NH4+(aq)
In this reaction H2O acts as Bronsted acid.
ii) H2O(l) + H2S(aq) ⇌ H3O+(aq) + HS–(aq)
In this reaction H2O acts as Bronsted base.
Question 6.
Explain the terms hard water and soft water. Write a note on the
i) ion-exchange method and
ii) calgon method for the removal of hardness of water.
Answer:
Hard water : Water does not give lather readily with soap is called hard water.
Hard water contains hardness. This hardness is due to presence of Ca, Mg soluble salts.
Presence of Ca, Mg – bicarbonates causes temporary hardness.
Presence of Ca, Mg – chlorides, sulphates causes permanent hardness.
Soft water: Water which give lather immediately with soap is called soft water.
(or)
Water which is free from soluble salts of Ca, Mg is called soft water.
i) Ion – Exchange method :
This method is useful to remove the permanent hardness of water.
• This method is also named as permutil (or) zeolite process.
• Permutit is the artificial zeolite, j.e sodium aluminium orthosilicate.
(Na2Al2Si2O8xH2O (or) NaAlSiO4)
• Permutit is written in short form as Naz.
• When permutit is added to hard water, the following ion-exchange reactions
takes place.
• Caz2 and Mgz2 are called as exhausted permutit. These are regenerated to
permutit by the treatment with brine solution.
Caz2(5)+2Na+(aq)⟶2Naz(s)+Ca+2(aq)
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ii) Calgon process :
• Calgon is sodium hexametaphosphate. [Na6P6O18 (or) (NaPO3)6]
• Calgon does not precipitate the Ca (or) Mg – salts but removes Ca+2 and
Mg+2 ions from water. -4 The removal of Ca+2 (or) Mg+2 ions from water may takes
place either by adsorption (or) by complex formation.
• Reactions :
Question 7.
Write the chemical reaction to justify that hydrogen peroxide can function as on
oxidizing as well as reducing agent. [T.S. Mar. 16]
Answer:
• H2O2 has the ability to function as an oxidising agent as well as reducing agent in
both acid and alkaline solutions.
• In H2O2 oxidation state of oxygen is -1. It oxidised to O2. Here H2O2 is reductant.
• H2O2 can be reduced to H2O (or) OH–. Here H2O2 is oxidant.
1. Oxidising action in acidic medium :
2Fe+2(aq)+2H+(aq)+H2O2(aq )⟶2Fe+3(aq )+2H2O(l)
2. Reducing action in acidic medium :
2MnO−4+6H++5H2O2⟶2Mn+2+8H2O+5O2
3. Oxidising action in basic medium :
2Fe+2 + H2O2 → 2Fe+3 + 2OH–
4. Reducing action in basic medium :
2MnO−4+3H2O2⟶2MnO2+3O2+2H2O+2OH−
Question 8.
Complete and balance the following chemical reactions :
i) PbS(s) + H2O2 →
ii) MnO−4(aq) + H2O2 →
(aq)
iii) CaO(s) + H2O(g) →

(iv) Ca3N2(s) + H2O(l) →
Classify the above into
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a) hydrolysis
b) redox and
c) hydration reactions.
Answer:
iii) CaO(s) + H2O(g) → Ca(OH)2

(iv) Ca3N2(s) + H2O(l) → 3Ca(OH)2 + 2NH3
(iii) and (iv) reactions are hydrolysis reactions
Question 9.
Discuss, with relevant chemical equations, various methods of preparing hydrogen
peroxide. Which of these methods is useful to prepare D2O2 ?
Answer:
Preparations of H2O2:
i) From Acidified BaO2 removing the excess of water by evaporation under reduced
pressure gives H2O2.
BaO2 . 8H2O(s) + H2SO4(aq) → BaSO4(s) + H2O2(aq) + 8H2O(l)
ii) Auto oxidation method : H2O2 is prepared industrially by the auto oxidation of 2-
ethyl anthraquinol.
iii) Electrolysis of peroxo disulphuric acid : H2O2 is obtained by the electrolysis of 50%
H2SO4 solution, peroxo disulphuric acid obtained undergo hydrolysis to form H2O2.
Preparation of D2O2: D2O2 is obtained by the reaction of K2S2O8 with heavy water. This is
similar to above method (iii).
K2S2O8(s) + 2D2O(l) → 2KDSO4(aq) + D2O2(l)
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Question 10.
In how many ways can you express the strength of H2O2 ? Calculate the strength of 15
volume solution of H2O2 in g/l. Express this strength in normality and molarity.
Answer:
Strength of H2O2 can be expressed majorly in two ways.
H2O2 strength can be expressed in terms of i) Molarity ii) Normality.
Problem :
Solution:
15 volume H2O2 solution means 1 lit, of H2O2
will give 15 lit, of O2 at STP
22.4 lit, of 02 produced from 68 gms of H2O2

15 lit, of 02 produced from x gms of H2O2
x = 68×1522.4 = 45.53 gms. of H2O2
∴ Strength of 15 volume H2O2 = 45.53 gms/lit.
= 4.5% H2O2
→ Molarity of the 15 volume H2O2 solution
= WtGMW×1 lit.
= 45.5334×1 = 1.339M.
→ Normality of the 15 volume H2O2 solution
= Wt G.E.W ×1 lit. =45.5317×1 = 2.678 N.
Solved Problems
Question 1.
Comment on the reactions of dihydro-gen with
1. chlorine
2. sodium and
3. copper (II) oxide.
Solution:
1. Hydrogen reacts with chlorine to form hydrogen chloride. An electron pair is
shared between H and Cl leading to the formation of a covalent molecule.
2. Hydrogen is reduced by sodium to form NaH. An electron is transferred from Na
to H leading to the formation of an ionic compound, Na+ H .
3. Hydrogen reduces copper(ll) oxide to copper and itself gets oxidised to H2O.
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Question 2.
H2O has a higher boiling point than that of H2S. Give reasons.
Solution:
On the basis of molecular mass of H2O. Its boiling point is expected to be lower than
that of H2S. However, due to higher electronegativity of O, the magnitude of hydrogen
bonding in H2O will be quite appreciable. Hence, the boiling point of H2O will be higher
than that of H2S.
Question 3.
How many hydrogen – bonded water molecule(s) are associated in CuSO4. 5H2O ?
Solution:
Only one water molecule, which is outside the brackets (coordination sphere), is
hydrogen-bonded. The other four molecules of water are coordinated.
Question 4.
Calculate the strength of 10 volume solution of hydrogen peroxide.
Solution:
10 volume solution of H2O2 means that 1L of this H2O2 solution will give 10 L of oxygen
at STP.
On the basis of above equation 22.4 L of O2 is produced from 68 g H2O2 at STP 10 L of

O2 at STP is produced from 68×1022.4 g = 30.36g
≈ 30g H2O2
Therefore, strength of H2O2 in 10 volume H2O2 solution = 30.36 g/L = 3% H2O2 solution.
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Question 1.
Give reasons for the diagonal relationship observed in the periodic table.
Answer:
• Diagonal relationship is due to similar sizes of atoms (or) ions
• Diagonal relationship is due to similar electro negativities of the respective
elements. Diagonally similar elements possess same polarising power.
• Polarizing Power = ionic charge/ (ionic radius) 2
Question 2.
Write completly the electronic configurations of K and Rb.
Answer:
The electronic configuration of ‘K’ is 1s2 2s2 2p6 3s2 3p6 4s2
The electronic configuration of ‘Rb’ is 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1.
Question 3.
Lithium salts are mostly hydrated. Why ?
Answer:
Hydration enthalpy of Li+ ion is very high. It has very high degree of hydration. So ‘Li’
salts are mostly hydrated.
Eg : LiCl . 2H2O.
Question 4.
Which of the alkali metals shows abnormal density ? What is the order of the varia-tion
of density among the IA group elements.
Answer:
• ‘K’ has abnormal density among alkalimetals due to high inter atomic distances in
crystal lattice.
• The order of the variation of density among the IA group elements as follows.
Li < Na > K < Rb < Cs.
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Question 5.
Lithium reacts with water less vigorously than sodium. Give your reasons.
Answer:
Lithium reacts with water less vigorously than sodium.
Reasons :
• Lithium has small size.
• Lithium has very high hydration energy.
Question 6.
Lithium Iodide is the most covalent among the alkali metal halides. Give the reasons.
Answer:
Lithium iodide is the most covalent among the alkalimetal halides.
Reasons :
• The polarising capability of lithium ion is high.
• Li+ ion has very small size.
• Li+ ion has high tendency to distort electron cloud around the iodide ion.
Question 7.
In what respects lithium hydrogen carbonate differs from other alkali metal hydrogen
carbonates.
Answer:
Lithium hydrogen carbonate cannot exist in solid form but remaining alkali metal
hydrogen carbonates exist as solids.
Question 8.
Write the complete electronic configurations of any two alkaline earth metals.
Answer:
1. The electronic configuration of ‘Mg’ is 1s2 2s2 2p6 3s2
2. The electronic configuration of ‘Ca’ is 1s2 2s2 2p6 3s2 3p6 4s2.
Question 9.
Tell about the variation of m.pts., and b.pts among the alkaline earth metals.
Answer:
1. The m.pts and b.pts of alkaline earth metals are higher than corresponding alkali
metals due to smaller sizes.
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2. Due to low I.P. values the variation of m.pts and b.pts among alkaline earth
metals is not sys-tematic.
Question 10.
What are the characterstic colours imparted by the HA elements ?
Answer:
Elements – Imparted colours towards flame
Calcium – Brick red
Strontium – Crimson red
Barium – Apple green
Beryllium – No colour
Magnesium – No colour
Question 11.
What happens when magnesium metal is burnt in air ?
Answer:
Magnesium metal burns with dazzling brilliance in air to give MgO and Mg3N2.
2 Mg + O2 → 2 MgO
3 Mg + N2 → Mg3N2.
Question 12.
Lithium carbonate is not so stable to heat as the other alkali metal carbonates. Explain.
Answer:
Lithium carbonate is not so stable to heat because Lithium has very small size and it
polarises the large CO3-2 ion which leads to the formation of more stable Li2O and CO2.
As the electro positive character increases down the group, the stability of carbonats
increase.
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Question 13.
Write a balanced equation for the formation of ammoniated IIA metal ions from the
metals in liquid ammonia.
Answer:
Alkaline earth metals dissolve in liquid ammonia to give deep blue black solutions
forming ammoniated ions.
M + (x + y) NH3 → [M(NH3)x]2+ + 2 [e(NH3)y]–
From the above solutions, ammoniates [M(NH3)x]2+ can be recovered.
uestion 14.
The fluorides of alkaline earth metals are relatively less soluble than their respective
chlorides in water. Why ?
Answer:
Because of their high lattice energies fluorides of alkaline earth metals are relatively
less soluble than their respective chlorides in water.
Question 15.
What happens when hydrated Mg (NO3)2 is heated ? Give the balanced equation.
Answer:
When hydrated Mg(NO3)2 is heated, it first loses the six water molecules and on further
heating
decomposes to give the oxide.
2 Mg (NO3)2 → 2 MgO + 4NO2 + O2.
Question 16.
Why does the solubility of alkaline earth metal hydroxides in water increases down the
group ?
Answer:
Among alkaline earth metal hydroxides, the anion being common the cationic radius
will influence the lattice enthalpy. Since lattice enthalpy decreases much more than the
hydration enthalpy with increasing ionic size, the solubility increases as we go down the
group.
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Question 17.
Why does the solubility of alkaline earth metal Carbonates and sulphates in water
decrease down the group ?
Answer:
The size of anions being much larger compared to cations, the lattice enthalpy will
remain almost constant within a particular group. Since the hydration enthalpies
decrease down the group, solubility will decrease as found for alkaline earth metal
carbonates and sulphates.
Question 18.
Write the average composition of Portland cement.
Answer:
Composition of port land cement is
Cao – 50 – 60%
Sio2 – 20 – 25%
Al2O3 – 5 – 10%
Mgo – 2 – 3%
Fe2O3 – 1 – 2% and
SO2 – 1 – 2%
Question 19.
Why is gypsum added to cement ?
Answer:
Gypsum is added to cement to slow down the process of setting of the cement and to
get sufficiently hardened cement.
Question 20.
Why are alkali metals not found in the free state in nature ? Answer:
Alkali metals are not found in the free state in nature because they readily lose their
valency electron to form M+ ion (a nonvalent ion).
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Question 21.
Potassium carbonate cannot be prepared by Solvay process. Why ?
Answer:
Potassium carbonate cannot be prepared by solvay process because potassium bi
carbonate is more soluble and to be precipitated by the addition of ammonium bi
carbonate to a saturated solution of potassium chloride.
Question 22.
Describe the important uses of caustic soda.
Answer:
Uses:
• It is used in petrol refining
• It is used in the purification of bauxite.
• It is used in manufacturing of soap, paper.
• It is used in manufacturing of antificial silk.
• It is used in manufacturing of so many chemically.
• It is used in textile industries for mercerising cotton fabrics.
• It is used in preparation of pure fats and oils.
• It is used in as laboratory reagent.
Question 23.
Describe the important uses of sodium carbonate.
Answer:
Uses:
• Na2CO3 is used in the manufacturing of glass.
• Na2CO3 is used in the manufactuing of borax, caustic soda.
• Na2CO3 is used in paper, paints and textile industries.
• Na2CO3 is used in softening of water.
• Na2CO3 is used in laundries.
• Na2CO3 is used an important laboratory reagent both in qualitative and
quantitative analysis.
401
Question 24.
Describe the important uses of quick line.
Answer:
Uses:
• Quick lime is used in the purification of sugar.
• Quick lime is used in the manufacture of dyestuffs.
• Quick lime is used in the manufacture of Na2CO3 from NaOH.
• It is an important material for manufacturing of cement and it is the cheapest
form of alkali.
Question 25.
Draw the structures of
1. BeCl2 (vapour) and
2. BeCl2 (Solid).
Answer:
1. In vapour phase BeCl2 forms a bridged dimer which disociates into monomer at
high temperatures (around 1200 k)
Cl – Be – Cl
2. In solid state BeCl2 has a chain structure.
Question 26.
Describe the importance of Plaster of Paris.
Answer:
1. Plaster of paris has an important property of setting with water.
2. It forms a hard solid in 5 to 15 min. When it is mixed with suitable quantity of
water.
3. It is majorly used in building industry and as well as plasters.
4. It is used in the bone fractures (or) sprain conditions.
5. It is used in dentistry.
6. It is used in manufacturing status and busts.
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Question 27.
Which of the alkaline earth metal carbonates is thermally the most stable ? Why ?
Answer:
Among Alkaline earth metal carbonates BaCO3 is thermally most stable.
Reason :
As the cationic size increases thermal stability also increases. So BaCO3 is most stable
thermally.
Question 28.
Write balanced equations for the reactions between
1. Na2O2 and water
2. K2O and water.
Answer:
1. Na2O2 + 2H2O → 2 NaOH + H2O2
2. K2O + H2O → 2 KOH.
Question 1.
Alkali metals and their salts impart characteristic colours to an oxidizing flame. Explain
the resonizing flame. Explain the reason.
Answer:
Alkali metals and their salts impart characterstic colours to an oxidizing flame.
Reasons :
The heat from the flame excites the outer most orbital electron to a higher energy
level. When the excited electron emitts the radiation and comes back to the ground
state. This falls in the visible region.
Question 2.
What makes caesium and potassium useful as electrodes in photoelectric cells ?
Answer:
• Alkali metals can be detected by the respective flame tests and can be
determined by the flame photo metry (or) atomic absorption spectroscopy.
• Alkali metals when irradiated with light, the light energy absorbed may be
sufficient to make an atom lose electron.
• This makes caesium and potassium useful as electrodes in photo electric cells.
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Question 3.
Write a short note on the reactivity of alkali metals towards air.
Answer:
• The alkali metals forms their oxides in presence of dry air and tarnished.
• These oxides reacts with moisture to form hydroxides.
• They burn vigorously in oxygen and forms oxides.
• Lithium forms Lithium monoxide.
• Sodium forms monoxide with limited supply of oxygen and peroxide with
excess of oxygen.
• Other metals of this group forms super oxides. The super oxide ion (O2–) is
stable only in presence of large cations.
Reactions :
4Li + O2 → 2 Li2O
4Na + O2 (Limited) → 2 Na2O2
2Na + O2 (Excess) → Na2O2
K + O2 (Excess) → KO2
Lithium shows a different character. It reacts directly with nitrogen of air and forms Li3N
(Lithium nitride).
Question 4.
Give any two uses for each of the following metals.
1. Lithium
2. Sodium.
Answer:
1. Uses of Lithium : –
• ‘Li’ metal is used to make alloys.
Eg: 1) Lithium with lead forms an alloy which is used for making white metal
bearings for motor engines.
2) Lithium with aluminium forms alloys which are used to make air craft parts.
• ‘Li’ metal is used in thermo nuclear reactions.
• ‘Li’ metal is used to make electro chemical cells.
2) Uses of sodium : –
• Sodium metal is used to make Na and Pb alloy needed to make TEL. this TEL
(tetra ethyl lead) is used as antiknock additives to petrol.
• Liquid ‘Na’ metal is used as a coolant in fast breeder nuclear reactors.
• ‘Na’ metal is used in the manufacturing of rabber.
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Question 5.
Give an account of properties of washing soda.
Answer:
Properties of washing soda : –
• Na2CO3 is a white crystalline solid.
• Na2CO3 exists as a decahydrate Na2CO3. 10H2O which is called washing soda.
• Na2CO3 is readily soluble in water.
• Na2CO3 (deca hydrate) when heated it loses the water molecules and forms
monohydrate. This monohydrate on heating above 373 K it forms anhydrous
form which is called soda ash, a white powder.
Reactions : –
• Na2CO3 (aq) solution is alkaline (basic) in nature Because it under goes anionic
hydrolysis. (PH > 7).
CO3-2 + H2O → HCO3– + OH–
Question 6.
Mention some uses of sodium carbonate.
Answer:
Uses :
• Na2CO3 is used in the manufacturing of glass.
• Na2CO3 is used in the manufacturing of borax, caustic soda.
• Na2CO3 is used in paper, paints and textile industries. .
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Question 7.
How do you obtain pure sodium chloride from a crude sample ?
Answer:
1. Crude sodium chloride is obtained by the crystallisation of brine solution.
2. Crude sodium chloride contains sodium sulphate, calcium sulphate, calcium
chloride and magnesium chloride.
3. CaCl2 and MgCl2 are the impurities in the Crude NaCl because these absorb
moisture easily from the atmosphere.
4. Pure sodium chloride’s obtained by dissolving Crude NaCl in minimum amount of
water and filtered to remove insoluble impurities.
5. This solution is saturated with HCl gas. Then crystals of pure NaCl are separated
out.
6. Ca and Mg chloride are more soluble in solution than NaCl and these remained
in the solution.
Question 8.
What do you know about Castner – Kellner process ? Write the principle involved in it.
Answer:
• Castner – Kellner process is a commercial method used for the preparation of
sodium hydroxide.
• In this process sodium hydroxide is prepared by the electrolysis of sodium
chloride in Castner – Kellner cell.
• Brine solution is electrolysed using a mercury cathode and a carbon anode.
• Sodium metal is formed at cathode and it combine with mercury to form sodium
amalgam. Chlorine gas is evolved at anode.
• The amalgam is treated with water to form, sodium hydroxide.
Cell Reactions :
2Na+ + 2e– 2Na – amalgam
2Cl– → Cl2 + 2e–
2Na – amalgam + 2H2O → 2NaOH + 2Hg + H2
• This process is also called as mercury cathode process.
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Question 9.
Write a few applications of caustic soda.
Answer:
Uses :
• It is used in petrol refining
• It is used in the purification of bauxite.
• It is used in manufacturing of soap, paper.
• It is used in manufacturing of antificial silk.
• It is used in manufacturing of so many chemically.
• It is used in textile industries for mercerising cotton fabrics.
• It is used in preparation of pure fats and oils.
• It is used in as laboratory reagent.
Question 10.
Give an account of the biological importance of Na+ and K+ ions.
Answer:
• Na+ ions participate in the transmission of nerve signals.
• Na+ ions regulates the flow of water accross cell membranes.
• Na+ ions responsible for transport of sugars and amino acids into cells.
• K+ ions are useful in activating enzymes.
• K+ ions participate in the oxidation of glucose to produce ATP.
• K+ along with Na+ responsible for the transmission of nerve signals.
Question 11.
Mention the important uses of Mg metal.
Answer:
1. Magnesium forms so many useful alloys with Al, Zn, Mn and Sn.
2. Mg – Al alloys are useful in air – craft construction.
3. Mg powder and ribbon is used in flash powders bulbs.
4. Mg is used in incendiary bombs and signals.
5. Milk of magnesice is used as antacid in medicine.
6. MgCO3 is the main ingradient in tooth pastes.
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Question 12.
Show that Be(OH)2 is amphoteric in nature.
Answer:
1. Be(OH)2 is amphoteric in nature. This can be evidented by the following reactions.
2. Be(OH)2 reacts with both acids and alkalis.
Be(OH)2 + 2OH– [Be(OH)4]2- (Beryllation)
Be(OH)2 + 2HCl + 2H2O → [Be(OH)4]Cl2
3. Hence Be(OH)2 is amphoteric in nature.
Question 13.
Write a note on anomalous behaviour of beryllium.
Answer:
Anomalous characters of Be:
As was already discussed in the earlier sections, the first element shows some
differences from the properties of the other elements in the group. Be differs from the
other alkaline earth metals because of its small size and high electronegativity. Be
differs from the other elements in the following aspects.
1. Be compounds are predominantly covalent due to its high polarizing power and
its salts are readily Hydrolyzed.
2. Be is not easily affected by dry air and does not decompose water at ordinary
temperature.
3. Be is an amphoteric metal. It dissolves in alkali solutions forming beryllates.
4. Be SO4 is soluble in water whereas the sulphates of Ca, Sr and Ba are not soluble.
5. Be and its salts do not respond to flame test while Ca, Sr and Ba give
characteristic flame colours.
6. Be forms many complexes while the heavier elements do not show a great
tendency to form complexes.
7. Be has a maximum covalency of 4 while other can have a maximum covalency of
Question 14.
Be shows diagonal relationship with Al. Discuss.
Answer:
1. ‘Be’ shows diagonal relation ship with ‘Al’.
2. The ionic radius of Be+2 is nearly same as that of Al+3 so ‘Be’ resembles ‘Al’ in
several ways.
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3. Al, Be both not readily reacts with acids. This is due to the presence of an oxide
film on the surface of metal.
4. Al(OH)3, Be(OH)2 both similarly dissolves in excess of alkali and forms Beryllate ion
[Be(OH)3]2- and Aluminate [Al(OH)4] ions respectively.
5. The chlorides of Be, Al have bridged chloride structures in vapour phase.
6. Both the chlorides of Be, Al used as strong Lewis acids.
7. Both the chlorides of Be, Al used in Friedal craft catalysts.
8. Be, Al ions have strong tendency to form complexes.
Question 15.
What is Plaster of Paris ? Write a short note on it. [T.S. Mar. 16]
Answer:
Plaster of paris is the hemi hydrate of CaSO4 with formula CaSO4. 12H2O.
Preparation: –
Plaster of paris is obtained by heating gypsum at 393 K.
1. If temperature is used greater than 393 K then an hydrous CaSO4 is formed which
is called ‘dead burnt plaster’.
2. Plaster of paris has an important property of setting with water.
3. It forms a hard solid in 5 to 15 min. when it is mixed with suitable quantity of
water.
4. It is majorly used in building industry and as well as plasters.
5. It is used in the bone fractures (or) sprain conditions.
6. It is used in dentistry.
7. It is used in manufacturing status and busts.
Question 16.
In what ways lithium shows similarities to magnesium in its chemical behaviour ?
Answer:
Diagonal relationship of Li : In the periodic table an element of a group in the
2nd period shows similar properties with the second element of the next group in the
third period. This relation is known as diagonal relationship. For examples. Lithium and
Magnesium show diagonal relationship. The elements show that diagonal relationship
have similar polarizing powers, electronegativities, nature of the compounds. The
diagonal similarity may be due to the effects of size and charge. For example, charge
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per unit area.
Lithium shows similarity to Magnesium in the following respects.
a) Lithium is slow to react with water. Magnesium decomposes water only in the hot
condition.
2Li + 2H2O → + H2;
Mg + 2H2O → Mg(OH)2 + H2
b) Lithium combines directly with N2 forming nitride.
6Li + N2 → 2Li3N
c) Both Lithium and Magnesium give only monoxides Li2O, MgO.
d) Lithium chloride is deliquescent like MgCl2, LiCl undergoes hydrolysis to a smaller
extent in hot water in a similar way to MgCl2.
e) Due to their covalent nature, the halides Lithium and Magnesium are soluble in
organic solvents.
f) Both Li+ and Mg+2 are highly hydrated.
g) The Carbonates, Phosphates and Fluorides of both Li and Mg are sparingly soluble in
water.
h) Lithium alkyls (Li+ R–) are chemically similar to Grignard reagents in organic synthesis.
Question 17.
When an alkali metal dissolves in liquid ammonia the solution can acquire different
colours. Explain the reasons for this type of colour change.
Answer:
• The alkali metals dissolve in liquid NH3 and gives deep blue solutions. These are
conducting in nature.
• The blue colour of the solution is due to the ammoniated electrons which
absorbs energy in the visible region of light and thus imparts blue colour to the
solution.
• These solutions are paramagnetic and on standing liberate hydrogen resulting in
the formation of amide.
M + (x + y) NH3 → [M(NH3)x]+ + [e(NH3)y]–
M(am)+ + e– + NH3 → MNH2(am) + 1/2 H2(g)
• In concentrated solution the blue colour Changes to bronze.colour on warming
and becomes did magnetic.
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Question 18.
What happens when
1. Sodium metal is dropped in water ?
2. Sodium metal is heated in a free supply of air ?
3. Sodium peroxide dissolves in water ?
Answer:
1. Sodium metal when dropped in water it reacts with water vigourously and
liberates H2 gas.
2Na + 2H2O → 2NaOH + H2
2. Sodium metal is heated in free supply of air to form sodium peroxide.
2Na + O2 → Na2O2 (sodium peroxide)
3. Sodium peroxide dissolves in water and forms NaOH and hydrogen peroxide.
Na2O2 + 2H2O → 2NaOH + H2O2
Question 19.
States as to why
i) An aqueous solution of Na2CO3– is alkaline ;
ii) Alkali metals are prepared by the electrolysis of their fused chlorides ?
Answer:
i) An aqueous solution of Na2CO3 is alkaline. This is due to anionic (CO3-2) hydrolysis.
CO3-2 + H2O → HCO3-2 + OH–
∴ PH > 7. So the solution is alkaline in nature.
ii) Chemically alkali metals are highly reactive and they are placed at top in the electro
chemical series.
∴ Common methods of extraction of the metals are not applicable for the alkali metals.
So electrolytic reduction of their used chlorides is the possible method for extracting
alkali metals.
Eg: ‘Na’ metal obtained from fused ‘NaCl’.
Question 20.
How would you explain the following observations ?
1. BeO is almost insoluble but BeSO4 is soluble in water ?
2. BaO is soluble but BaSO4 is insoluble in water ?
Answer:
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1. BeO has amphoteric nature and the solubility in water is low because of its
covalent nature.
BeSO4 is soluble in water. This is due to greater hydration energy of Be+2 ion.
2. BaO is soluble in water because of its ionic nature.
BaSO4 is insoluble in water because of low hydration energy of Ba+2 ion.
Question 1.
Justify the inclusion of alkali metals in the same group of the periodic table with
reference to the following :
i) Electronic configuration
ii) Reducing nature
iii) Oxides and hydroxides.
Answer:
i) Electronic configuration : All the alkali metals have one valence electron, ns1.
ii) Reducing nature :

• Alkali metals are strong reducing agents.
• ‘Li’ is most powerful reducing agent and ‘Na’ is poor reducing agent. .
The standard electrode potential (E°) is the measure of reducing power.
• ‘Li’ has highest hydration enthalpy. It has high negative S.E.P. (E°) hence it has
high reducing power.
iii) Oxides and hydroxides : –
• These oxides reacts with , .noisture to form hydroxides.
1. Lithium forms lithium monoxide.
2. Sodium forms monoxide with limited supply of oxygen and peroxide with’
excess of oxygen
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3. Other metals of this group forms super oxides. The super oxide ion (O2–) is
Reactions:
4Li + O2 → 2 Li2O
4Na + O2 (Limited) → 2 Na2O
2 Na + O2 (Excess) → Na2O2
Lithium shows a different character. It reacts directly with nitrogen of air and forms Li3N
(Lithium nitride).
• Alkali metal oxides easily hydrolysed by water to form the hydroxides.
Monoxide : M2O + H2O → 2MOH
Peroxide : M2O2 + 2H2O → 2MOH + H2O2
Superoxide : 2MO2 + 2H2O → 2MOH + H2O2 + O2
• Oxides, peroxides are colourless whereas superoxides are coloured because of
their para mag-netic property.
• Hydroxides are white crystalline solids.
• Hydroxides are strong bases and dissolved freely in water and evolve much heat.
Question 2.
Write an essay on the differences between lithium and other alkali metals.
Answer:
Anomalous properties of Lithium : In the periodic table some representative elements
of different series show similarities, known as diagonal relationship. Li, of the alkali
metals, show such a similarity with Mg of II group. That means it differs from alkali
metals. Some of the important abnormal characters of lithium are given below.
a) Lithium is hard metal while other alkali metals are soft and can be cut with the knife.
Its melting point and boiling point are high.
b) Lithium directly unites with N2 while no other alkali metal combines directly.
6Li + N2 → 2Li3N
c) Lithium element forms a carbide on direct combination. Group IA elements do not
form directly. But all these elements are known to give carbides.
d) The solubilities of Lithium Hydroxide (LiOH), Lithium Carbonate (Li2CO3), Lithium
Phosphate (Li3PO4) and Lithium Fluoride (LiF), are very less compared to the high
solubilities of the other alkali metal compounds.
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e) Lithium Hydroxide is a weaker alkali than the alkali metal Hydroxides. Basic nature of
other alkali metal Hydroxides is more than Li(OH). Because of this Lithium Hydroxide
Carbonate, nitrates are thermally unstable.
Question 3.
Discuss the preparation and properties of sodium carbonate.
Answer:
Preparation :
• Sodium carbonate is prepared by solvay process.
• In this process sodium chloride reacts with ammonium bicarbonate and gets
precipitated the low soluble sodium bicarbonate.
• The lather is prepared by passing CO2 into a concentrated solution of NaCl
saturated with ammonia. Here (NH4)2CO3 followed by NH4 HCO3 are formed.
Chemical equations involved :
2NH3 + H2O + CO2 → (NH4)2 CO3
(NH4)2 CO3 + H2O + CO2 → 2NH4HCO3
NH4HCO3 + NaCl → NH4Cl + NaHCO3
• The separated NaHC03 Crystals heated to get Na2CO3.
2NaHCO3 → Na2CO3 + H2O + CO2
• In this process ammonia is regenerated by Ca(OH)2.
2NH4Cl + Ca(OH)2 → 2NH3 + CaCl2 + H2O
Properties of washing soda :
• Na2CO3 is a white crystalline solid.
• Na2CO3 exists as a decahydrate Na2CO3. 10H2O which is called washing soda.
• Na2CO3 is readily soluble in water.
• Na2CO3 (decahydrate) when heated it loses the water molecules and forms
monohydrate. This monohydrate on heating above 373 K it forms anhydrous
form which is called soda ash, a white powder.
Reactions : –
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• Na2CO3 (aq) solution is alkaline (basic) in nature Because it under goes anionic
hydrolysis. (PH > 7).
CO3-2 + H2O → HCO3– + OH–
Uses :
• Na2CO3 is used in the manufactuing of glass.
• Na2CO3 is used in the manufactuing of borax, caustic soda.
• Na2CO3 is used in paper, paints and textile industries.
Question 4.
Discuss the similarities between alkaline earth metals and gradation in the following
aspects.
i) Electronic configuration
ii) Hydration enthalpies
iii) Nature of oxides and hydroxides.
Answer:
i) Electronic configuration :
The general electronic configuration of alkaline earth metals represented by [noble gas]
ns2.
ii) Hydration Enthalpies :

• The hydration enthalpies of alkaline earth metal ions decrease with increase in
ionic size down the group.
Be+2 > Mg+2 > Ca+2 > Sr+2 > Ba+2
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• Hydration enthalpies of these elements ions are larger than those of alkali metal
ions.
Eg : MgCl2 MgCl2 . 6H2O
CaCl2 CaCl2 . 6H2O
iii) Nature of oxides and hydroxides : –
• Alkaline earth metals forms oxides of type MO.
• These are formed by burning in oxygen.
• BeO is amphoteric and covalent in nature whereas other oxides are ionic and
basic in nature. Other oxides i.e., except BeO forms hydroxides with water.
Eg : MgO + H2O → Mg(OH)2
• The solubility, thermal stability and the basic character of these hydroxides
increase with increase of atomic no. from Mg(OH)2 to Ba(OH)2. H
• These hydroxides are less basic, less stable than alkali metal hydroxide.
• Be(OH)2 is amphoteric in nature. This can be evidented by the following reactions.
• Be(OH)2 reacts with both acids and alkalis.
• Hence Be(OH)2 is amphoteric in nature.
Question 5.
Discuss on;
i) Carbonates
ii) Sulphates and
iii) Nitrates of alkaline earth metals.
Answer:
i) Carbonates :
• Alkaline earth metals forms MCO3 type carbonates.
• These Carbonates are insoluble in water.
• The solubility of these carbonates in water decreases as the atomic no.of the
element increases.
• The thermal stability increases with increasing cationic size.
• These carbonates decompose on heating to give CO2
CaCO3 Cao + CO2
• BeCO3 is unstable and kept only in at atmosphere of CO2.
ii) Sulphates :
• Alkaline earth metals forms MSO4 type sulphates.
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• These are white solids and are stable to heat.
• BeSO4 and MgSO4 are readily soluble in water due to high hydration enthalies of
Be2+, Mg2+.
• The solubility decrease from CaSO4 to BaSO4.
iii) Nitrates :
• Alkaline earth metals forms M(NO3)2 type Nitrates.
• These are formed by the reaction of carbonates in dil.HNO3.
• Mg(N03)2 crystallises with six water molecules and Ba(NO3)2 is an hydrous.
• All of these decompose on heating to give the respective oxides.
2M(NO3)2 → 2MO + 4NO2 + O2
M = Be, Mg, Ca, Sr, Ba.
Question 6.
What are the common physical and chemical features of alkali metals ?
Answer:
Physical features :
• Alkali metals are silvery white, soft and light metals.
• These elements have low density which increases down the group from Li to Cs.
(one exception density of K < density of Na).
• The m.pts, b.pts of alkali metals are low.
• Alkali metals and their salts impart characterstic colours to an oxidizing flame.
Reasons :
The heat from the flame excities the outer most orbital electron to a higher energy
level. When the excited electron emitts the radiation and comes back to the ground
state. This falls in the visible region.
• Alkali metals can be detected by the respective flame tests and can be
determined by the flame photo metry (or) atomic absorption spectroscopy.
• Alkali metals when irradiated with light, the light energy absorbed may be
sufficient to make an atom lose electron. .
• This makes calsium and potassium useful as electrodes in photo electric cells.
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Chemical features : –
i) Reactivity towards Air : —
• These oxides reacts with moisture to form hydroxides.
1. Lithium forms Lithium monoxide.
2. Sodium forms monoxide with limited supply of oxygen and peroxide with
excess of oxygen.
3. Other metals of this group forms super oxides. The super oxide ion (O2–) is
• Reasons :
4Li + O2 → 2 Li2O
4Na + O2 (Limited) → 2 Na2O
2Na + O2 (Excess) → Na2O2
• Lithium shows a different character. It reacts directly with nitrogen of air and
forms Li3N (Lithium nitride).
ii) Reactivity with H2: Alkali metals react with H2 directly at 300 – 600° C and form
hydrides. The reaction can be written as follows :
Where M = Li, Na, K, Rb or Cs. These hydrides are ionic in nature. Their ionic nature
increases with the metalic nature of alkali metals.
iii) Reactivity with halogens : All the alkali’ metals react with halogens to give the binary
compounds. The chemical reactivity in the alkali metals increases with increase in
atomic number.
2M + X2 → 2MX (where M is any alkali metal)
All the metal halides are ionic compounds.
iv) Reactivity with water : The alkali metals decompose water vigorously and liberate
hydrogen gas! The chemical reactivity of these metals increases as the atomic number
increases. The metal hydroxides are formed.
2M + 2H2O → 2MOH + H2
Where M = any one of the alkali metals.
ii) Reducing nature :
• Alkali metals are strong reducing agents.
• ‘Li1 is most powerful reducing agent and ‘Na’ is poor reducing agent.
• The standard electrode potential (E°) is the measure of reducing power.
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• ‘Li’ has highest hydration enthalpy. It has high negative S.E.P. (E°) hence it has
high reducing power.
• The alkali metals dissolves in liquid NH3 and gives deep blue solutions. These are
conducting in nature.
• The blue colour of the solution is due to the ammoniated electrons which
absorbs energy in the visible region of light and thus imparts blue colour to the
solution.
• These solutions are paramagnetic and on standing Liberate hydrogen resulting in
the formation of amide.
M + (x + y) NH3 → [M(NH3)x]+ + [e(NH3)y]–
M(am)+ + e– + NH3 → MNH2(am) + 1/2 H2(g)
• In concentrated solution the blue colour Changes to bronze.colour on warming
and becomes did magnetic.
Question 7.
Discuss the general characterstics and gradation in properties of alkaline earth metals.
Answer:
The general characterstics and gradation in properties of alkaline earth metals follows.
i) Oxides and hydroxides :
• Alkaline earth metals forms oxides of type Mo.
• These are formed by burning in oxygen.
• BeO is amphoteric and covalent in nature where as other oxides are ionic and
basic in nature.
• Other oxides i.e., except Beo forms hydroxides with water.
Eg : MgO + H2O → Mg(OH)2
• The solubility, thermal stability and the basic character of these hydroxides
increase with increase of atomic no. from Mg(OH)2 to Ba(OH)2.
• These hydroxides are less basic, less stable than alkali metal hydroxide.
• Be(OH)2 is amphoteric in nature. This can be evidented by the following reactions.
• Be(OH)2 reacts with both acids and alkalis.
• Hence Be(OH)2 is amphoteric in nature.
ii) Halides:-
• These forms MX2 type halides.
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• Except Be – halides, all other halides of these metals are ionic.
• Be – halides are covalent and soluble in organic solvents.
• In vapour phase BeCl2 forms a bridged dimer which disociates into monomer at
high temperatures (around 1200 k)
Cl – Be – Cl
• In solid state BeCl2 has a chain structure.
• The tendency to form halide hydrates gradually decreases – down the group.
Eg : MgCl2, 8H2O, CaCl2, 6H2O, BaCl2. 2H2O.
• Ca, Sr and Ba halides, dehydration can be done by heating.
• Fluorides are less soluble than the chlorides due to their high lattice energies.
i) Carbonates :
• Alkaline earth metals forms MCO3 type carbonates.
• These Carbonates are insoluble in water.
• The solubility of these carbonates in water decreases as the atomic no.of the
element increases.
• The thermal stability increases with increasing cationic size.
• These carbonates decompose on heating to give CO2
CaCO3 Cao + CO2
• BeCO3 is unstable and kept only in at atmosphere of CO2.
ii) Sulphates:
• Alkaline earth metals forms MSO4 type sulphates.
• These are white solids and are stable to heat.
• BeSO4 and MgSO4 are readily soluble in water due to high hydration enthalpies of
Be2+, Mg2+.
• The solubility decrease from CaSO4 to BaSO4.
iii) Nitrates:
• Alkaline earth metals forms M(NO3)2 type Nitrates.
• These are formed by the reaction of carbonates in dil.HNO3.
• Mg(NO3)2 crystallises with six water molecules and Ba(NO3)2 is an hydrous.
• All of these decompose on heating to give the respective oxides.
2M(NO3)2 → 2MO + 4NO2 + O2
M = Be, Mg, Ca, Sr, Ba.
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Question 8.
Discuss the various reactions that occur in the solvay process. [A.P. Mar. 16]
Answer:
Preparation:
• Sodium carbonate is prepared by solvay process.
• In this process sodium chloride reacts with ammonium bicarbonate and gets
precipitated the low soluble sodium bicarbonate. ‘
• The lather is prepared by passing CO2 in to a concentrated solution of NaCl
• Chemical equations involved:
2NH3 + H2O + CO2 → (NH4)2 CO3
(NH4)2 CO3 + H2O + CO2 → 2NH4HCO3
NH4HCO3 + NaCl → NH4Cl + NaHCO3
• The separated NaHCO3 Crystals heated to get Na2CO3.
2NaHCO3 → Na2CO3 + H2O + CO2
• In this process ammonia is regenerated by Ca(OH)2.
2NH4Cl + Ca(OH)2 → 2NH3 + CaCl2 + H2O
Question 9.
Starting with sodium chloride how would you proceed to prepare
i) Sodium metal
ii) Sodium hydroxide
iii) Sodium peroxide
iv) sodium carbonate.
Answer:
i) Fused NaCl on electrolysis gives sodium metal.
2Na+ + 2e– → 2Na (Cathode)
2Cl– → Cl2 + 2e– (anode)
ii)
• Castner-Kellner process is a commercial method used for the preparation of
sodium hydroxide.
• In this process sodium hydroxide is prepared by the electrolysis of sodium
chloride in Castner – Kellner cel..
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• Brine solution is electrolysed using a mercury cathode and a carbon anode.
• Sodium metal is formed at cathode and it combine with mercury to form sodium
amalgam. Chlorine gas is evolved at anode.
• The amalgam is streated with water to form sodium hydroxide.
Cell Reactions:
2Na+ + 2e– 2Na – amalgam
2Cl– → Cl2 + 2e–
2Na-amalgam + 2H2O → 2NaOH + 2Hg + H2
• This process is also called as mercury cathode process.
iii) The obtained Na – metal reacts with excess of oxygen to form sodium peroxide.
2Na + O2 → Na2O2 (Sodium peroxide.)
iv) Preparation:
1. Sodium carbonate is prepared by solvay process.
2. In this process sodium chloride reacts with ammonium bicarbonate and gets
precipitated the low soluble sodium bicarbonate.
3. The lather is prepared by passing CO2 into a concentrated solution of NaCl
Question 10.
What happens when
i) Magnesium is burnt in air ?
ii) Quick lime is heated with silica
iii) Chlorine reacts with slaked lime
iv) calcium nitrate is strongly heated.
Answer:
i) Magnesium burns with dazzling brilliance in air to give MgO and Mg3N2.
2Mg + O2 →2MgO
3Mg + N2 → Mg3N2
ii) Quick lime heated with silica to form calcium silicate
Cao + SiO2 → CaSio3
iii) Slaked lime reacts with chlorine gas to form bleaching powder.
iv) Calcium nitrate on strong heating to form respective oxide

2Ca(NO3)2 → 2CaO + 4NO2 + O2.
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Question 11.
Explain the significance of sodium, potassium, magnesium and calcium in biological
fluids.
Answer:
Biological importance of Na, K.
• Na+ ions participate in the transmission of nerve signals.
• Na+ ions regulates the flow of water accross cell membranes.
• Na+ ions responsible for transport of sugars and amino acids into cells.
• K+ ions are useful in activating enzymes.
• K+ ions participate in the oxidation of glucose to produce ATP.
• K+ along with Na+ responsible for the transmission of nerve signals.
Biological importance of Mg and Ca :
Role of Mg2+ in biology :
1. Mg2+ ions are concentrated in animal cells.
2. Enzymes like “phosphohydrolases1 and ‘Phospho transferases’ contain Mg2+ ions.
These enzymes participate in ATP reactions and release energy in the process.
Mg2+ forms a complex with ATP.
3. Mg2+ is a constituent of chlorophyll, the green component of plants.
Role of Ca+2:
About 99% of body calcium is present in bones and teeth. It also plays important roles
in neuromuscular function, interneuronal transmission, cell membrance integrity and
blood coaqulation.
The calcium concentration in plasma is regulated at about 100 mg/Lit. It is maintained
by two hormones, calcitonin and parathyroid hormone. Ca2+ ion are necessary for
muscle contraction.
Question 12.
Write few lines about cement ?
Answer:
• Cement is an important building material.
• It is also called portland cement.
• Cement is obtained by combining a material rich in lime, CaO with other material
such as clay which contains Sio2 along with the oxides of Al, Fe and Mg.
• Composition of port land cement is
Cao – 50 – 60%
Sio2 – 20 – 25%
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Al2O3 – 5 – 10%
Mgo – 2 – 3%
Fe2O3 – 1 – 2%
and SO2 – 1 – 2%
• For a good quality of cement the ratio of SiO2 to Al2O3 is between 2.5 and 4 and
the ratio of lime (Co) to the total of the oxides of SiO2, Al2O3 and Fe2O3 is as close
as ‘2’.
• The raw materials used for the manufacture of cement are lime stone and clay.
Clay + lime cement clinker.
• This cement clinker mixed with 2 – 3% by wt. of gypsum to form cement.
• Important ingradients in portland cement are
Ca2SiO4 – 26%, Ca3SiO5 – 51 % and Ca3Al2O6 – 11 %
Setting of Cement: –
• Cement mixed with water to give a hard mass i.e setting of cement takes place.
• This is due to the hydration of molecules of the cement.
• The purpose of adding gypsum is to slow down the process of setting and to get
sufficiently hardness.
Uses:
• It is used in concrete and rein forced concrete.
• It is used in plastering.
• It is used in construction of bridges, dams and buildings.
Solved Problems
Question 1.
What is the oxidation state of K in KO2 ?
Solution:
The superoxide species is represented as O2–; since the compound is neutral, the
oxidation state of potassium is +1.
Question 2.
The EΘ for Cl2 / Cl– is + 1.36, for I2/I– is + 0.53, for Ag+/Ag is + 0.79, Na+/Na is – 2.71 and
for Li+/Li is – 3.04. Arrange the following ionic species in decreasing order of reducing
strength : I–, Ag, Cl–, Li, Na
Solution:
The order is Li > Na > I– > Ag > Cl–.
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Question 3.
Why is KO2 paramagnetic ?
Solution:
The superoxide O2– is paramagnetic because of one unpaired electron in π*2p
molecular orbital.
Question 4.
Why does the solubility of alkaline earth metal hydroxides in water increases down the
group ?
Solution:
Among alkaline earth metal hydroxides, the anion being common the cationic radius
will influence the lattice enthalpy. Since lattice enthalpy decreases much more than the
hydration enthalpy with increasing ionic size, the solubilit y increases as we go down
the group.
Question 5.
Why does the solubility of alkaline earth metal carbonates and sulphates in water
decrease down the group ?
Solution:
The size of anions being much larger compared to cations, the lattice enthalpy will
remain almost constant within a particular group. Since the hydration enthalpies
decrease down the group, solubility will decrease as found for alkaline earth metal
carbonates and sulphates.
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Question 1.
Discuss the pattern of variation in the oxidation states of Boron to Thallium.
Answer:
• Boron exhibits – 3 oxidation state due to its small size and non metalic nature.
• Aluminium exhibits +3 oxidation state.
• Gallium, Indium and Thallium exhibits both +1 and +3 oxidation states.
• In Thallium +1 oxidation state is more stable than +3 due to inert pair effect.
Question 2.
How do you explain higher stability of TlCl3 ?
Answer:
[TlCl3 is not stable because Tl doesnot exist in Tl3 stable state.] [TlCl is stable because of
inertpair effect Tl+1 is stable].
Question 3.
Why does BF3 behave as a Lewis acid ?
Answer:
BF3 is a electron deficient molecule. It has the tendency to accept an electron pair.
Electron pair acceptors are Lewis acids. Hence BF3 behave as a Lewis acid.
Question 4.
Is boric acid a protic acid ? Explain.
Answer:
Boric acid is a weak mono basic acid. In Boric acid plannar BO3 units are joined by
hydrogen bonds. It has layer structure (polymeric). Hence it is not a protic acid. It does
not give up a proton.
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Question 5.
What happens when boric acid is heated ?
Answer:
Boric acid when heated above 370 K forms meta boric acid. This on heating forms Boric
oxide.
Question 6.
Describe the shapes of BF3 and BH4–. Assign the hybridization of boron in these species.
Answer:
• Shape of BF3 molecule is Trigonal planar
Hybridisation of ‘B’ in BF3 is sp2
• Shape of BH4– molecule is Tetrahedral
Hybridisation of ‘B’ in BH4– is sp3
Question 7.
Explain why atomic radius of Ga is less than that of ‘Al’.
Answer:
In Gallium penultimate shell contains 10-d electrons. Due to this 10-d electrons
shielding effect becomes poor on outer most electrons. So nuclear charge increased in
Gallium. Hence atomic radius of Ga is lessthan that of ‘Al’.
Question 8.
Explain inert pair effect.
Answer:
The reluctance of ‘ns’ pair of electrons to take part in bond formation is called inert pair
effect.
(or)
The occurrence of oxidation states two unit lessthan the group oxidation states is called
inert pair effect.
Eg : In Group – 13 Tl exhibits +1 oxidation state instead of +3 oxidation state due to
inert pair effect.
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Question 9.
Write balanced equations for
a) BF3 + LiH →
b) B2H6 + H2O →
c) NaH + B2H6 →
d) H3BO3
e) B2H6 + NH3
Answer:
a) 2BF3 + 6LiH → B2H6 + 6 LiF
b) B2H6 + 6H2O → 2B(OH)3 + 6H2
c) B2H6 + 2NaH → 2NaBH4
d) H3BO3 HBO2 B2O3
e) B2H6 + 6NH3 → 3[BH2(NH3)2]+ (BH4)– 2B3N3H6 + 12H2
Question 10.
Why is boric acid polymeric ?
Answer:
Boric acid has layer like lattice. In this structure planar BO3 units are joined by hydrogen
bonds and forms a polymeric structure.
Question 11.
What is the hybridization of B in diborane and borazine ?
Answer:
• In diborane ‘B’ hybridisation is sp3
• In Borazine ‘B’ hybridisation is sp2
Question 12.
Write the electronic configuration of group – 13 elements.
Answer:
General outer electronic configuration of Group – 13 elements is ns2np1
• B – 1s22s22p1
• Al – [Ne] 3s23p1
• Ga – [Ar] 3d104s24p1
• In – [Kr] 4d105s25p1
• Tl – [Xe] 5d10 6s26p1
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Question 13.
Give the formula of borazine. What is its common name ?
Answer:
• The formula of borazine is B3N3H6.
• It’s common name is “In organic benzene” because it is – iso structural with
benzene.
Question 14.
Give the formulae of
a) Borax
b) Colemanite.
Answer:
a) Formula of Borax is Na2B4O7. 10H2O
b) Formula of Colemanite is Ca2B6O11.5H2O
Question 15.
Give two uses of aluminium.
Answer:
Uses of Aluminium :
• Aluminium is used in packing.
• Aluminium is used in utensil making.
• Aluminium alloys are used in shaping of pipes, tubes, wires etc.
• Aluminium alloys are used in making air craft bodies.
Question 16.
What happens when
a) LiAlH4 and BCl3 mixture in dry ether is warmed and
b) Borax is heated with H2SO4 ?
Answer:
a) When LiAlH4 and BCl3 mixture is warmed in dry ether diborane is formed.
4BF3 + 3 LiAlH4 → 2B2H6 + 3 LiF + 3 AlF3
b) Borax is heated with H2S04 then boric acid is formed
Na2B4O7 + H2SO4 + 5H2O → Na2SO4 + 4H3BO3
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Question 17.
Sketch the structure of Orthoboric acid.
Answer:
Question 18.
Write the structure of AlCl3 as a climer.
Answer:
Question 19.
Metal borides (having 10B) are used as protective shield – Why ?
Answer:
Boron – 10 (10B) has the capacity to absorb neutrons. Hence metal borides (having 10B)
are used as protective shields in nuclear industry.
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Question 1.
Write reactions to justify amphoteric nature of aluminium.
Answer:
• Amphoteric nature means having acidic as well as basic nature.
• Aluminium reacts with both mineral acids as well as aqueous alkalis.
a) Reaction with mineral acid :
‘Al’ reacts with dil.HCl and liberates hydrogen gas.
2Al + 6HCl → 2AlCl3 + 3H2 ↑
b) Reaction with aqueous alkali :
‘Al’ reacts with aqueous alkali (NaOH) and liberates hydrogen gas.
2Al + 2NaOH + 6H2O → Na2[Al(OH)4] + 3H2 ↑
Question 2.
What are electron deficient compounds ? Is BCl3 an electron deficient species ? Explain.
Answer:
These are the compounds in which the available no.of valence electrons is lessthan the
number required for normal covalent bond formation (or) for writting the Lewis
structure of the molecule.
• These compounds are electron pair acceptors and acts as Lewis acids.
• BCl3 is an electron deficient compound.
• In BCl3 ‘B’ contains only six electrons instead of eight electrons.
• BCl3 has the tendency to accept an electron pair and acts as Lewis acid.
Eg : Formation of BCl3 . NH3 :-
BCl3 accepts an electron pair from NH3 and forms the compound
BCl3.NH3 (Tetrahedral)
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Question 3.
Suggest reasons why the B – F bond lengths in BF3 (130 pm) and BF4– (143 pm) differ.
Answer:
About BF3 :
• In BF3 the central atom ‘B’ contains three bond pairs in the valency shell.
• ‘B’ under goes sp2 hybridisation.
• Shape of the molecule is trigonal planar.
About BF4– :
• In BF4– the central atom ‘B’ contains four bond pairs in the valency shell.
• ‘B’ under goes sp3 hybridisation.
• Shape of the molecule is tetrahedral.
• The above reasons suggent that the difference in bond lengths of BF3 (130 pm)
and BF4– (143 pm).
Question 4.
B – Cl bond has a bond moment. Explain why BCl3 molecule has zero dipolemoment.
Answer:
• B – Cl bond is a polar bond so it has bond moment.
• BCl3 molecule is non-polar because of its symmetrical structure. (Trigonal planar
structure)
• Symmetrical molecules has zero dipole moment.
∴ Dipole moment of BCl3 (μ) = 0
Question 5.
Explain the structure of boric acid.
Answer:
• Boric acid has a layer lattice.
• In this layer lattice planar BO3 units are joined by hydrogen bonds.
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• The structure of Boric acid is polymeric as shown in following figure.
• In the above structure dotted lines represents the hydrogen bonds
Question 6.
What happens when
a) Borax is heated strongly
b) Boric acid is added to water
c) Aluminium is heated with dilute NaOH
d) BF3 is treated with ammonia
e) Hydrated alumina is treated with aq.NaOH solution.
Answer:
a) Borax on heating first loses water molecules and forms sodium tetraborate. This on
further heating forms a mixture of sodium metaborate and boric an hydride. This
mixture is solidifies into glass like substance.
b) Boric acid is added to water, boric acid accepts a hydroxyl ion from water.
B(OH)3 + 2H2O → [B(OH)4]– + H3O+
c) Aluminium is heated with dilute NaOH, sodium metaluminate is formed with the
liberation of hydrogen gas.
2Al + 2NaOH → 2NaAlO2 + H2 ↑
d) BF3 is treated with NH3 an addition compound BF3. NH3 is formed. BF3 accepts an
electron pair from NH3 and forms a dative bond.
BF3 + → [BF3 ← NH3] → [BF3.NH3]
e) Hydrated Alumina is treated with aq.NaOH to form sodium metaluminate.
Al2O3.2H2O + 2NaOH(aq) → 2NaAlO(aq) + 3H2O
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Question 7.
Give reasons
a) Conc.HNO3 can be transported in aluminium container.
b) A mixture of dil. NaOH and aluminium pieces is used to open drain.
c) Aluminium alloys are used to make aircraft body.
d) Aluminium utensils should not be kept in water overnight.
e) Aluminium wire is used to make transmission cables.
Answer:
a) Cone. HNO3 can be transported in Aluminium containers because Al is passive
towards Conc.HNO3 due to the formation of thin layer of Al2O3 on the surface.
b) A mixture of dil.NaOH and aluminium pieces is used to open drain because it acts as
cleaning agent.
2Al + 2NaOH → 2NaAlO2 + H2
c) Aluminium alloys are used to make air craft body because it is a light metal, soft,
malleable, ductile and tenacious. It shows resistance to atmosphere corrosion.
d) Aluminium utensils should not be kept in water overnight because Aluminium reacts
with water and liberates hydrogen gas and heat. It makes colour dissolving and
sometimes Aluminium compounds are toxic in nature.
e) Aluminium wire used to make transmission cables because of it’s good conductivity
(electrical) and resistance to atmospheric corrosion.
Question 8.
Explain why the electronegativity of Ga, In and Tl will not vary very much.
Answer:
1. Ga, In and Tl have the electro negativity values 1.6, 1.7 and 1.8 respectively.
2. In Ga, In and Tl the d-electrons (d10) in penultimate shell do not shield the outer
most electrons from nuclear attraction effectively.
3. The reason for the above fact is.the shielding effect of various electrons in the
orbitals follows the order
s > p > d > f.
4. Hence the outer electrons are held more firmly by the nucleus. Because of this,
atoms with d- electrons in the penultimate shell (d10) are smaller in size. Ga, In
and Tl has same number of penultimate shell electrons.
5. So, Ga, In and Tl will not vary very much in their electronegativities.
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Question 9.
Explain Borax bead test with a suitable example.
Answer:
Borax bend test: This test is useful in the identification of basic radicals in qualitative
analysis. On heating borax swells into a white, opaque mass of anhydrous sodium tetra
borate. When it is fused, borax glass is obtained. Borax glass is sodium meta borate
and B203. The boric anhydride, B203, combined with metal oxides to form metal
metaborates as coloured beads. The reactions are as follows :
Question 10.
Explain the structure of diborane. [A.P. Mar. 16] [A.P. & T.S. Mar. 15]
Answer:
Diborane is an electron deficient compound. It has ’12’ valency electrons for bonding
purpose instead of ’14’ electrons.
In diborane each boron atom undergoes sp3 hybridization out of the four hybrid
orbitals one is vacant.
Each boron forms two, σ – bonds (2 centred – 2 electron bonds) bonds with two
hydrogen atoms by overlapping with their ‘1s’ orbital.
The remaining hybrid orbitals of boran used for the formation of B-H-B bridge bonds.
In the formation of B-H-B bridge, half filled sp3 hybrid ofbital of one boron atom and
vacant sp3 hybrid orbital of second boron atom overlap with 1s orbital of H-atom.
These three centred two electron bonds are also called as banana bonds. These bonds
are present above and below the plane of BH2 units.
Diborane contains two coplanar BH2 groups. The four hydrogen atoms are called
terminal hydrogen atoms and the remaining two hydrogens are called bridge hydrogen
atoms.
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Bonding in diborane, Each B atom uses sp3 hybrids for bonding. Out of the four
sp3 hybrids on each B atom, one is without an electron shown in broken lines. The
terminal B-H bonds are normal 2-centre-2- electron bonds but the two bridge bonds
are 3-centre-2- electron bonds. The 3-centre-2-electron bridge bonds are also referred
to as banana bonds.
Question 11.
Explain the reactions of aluminium with acids.
Answer:
Reactions of ‘Al’ with adds :
i) DiS. (or) cone. HCl dissolves Al and gives H2.
ii) a) Dil.H2SO4 liberates H2.
b) Cone. H2SO4 dissolves the metal ‘Al’ and gives SO2.
iii) a) Very dil.HNO3 is reduced to NH4 NO3 by Al.
b) Cone. HNO3 makes ‘Al’ passive due to the formation of a thin film of oxide layer on
the metal surface.
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Question 12.
Write a short note on the anamalous behaviour of boron in group – 13.
Answer:
• Among Group – 13 elements ‘B’ is only the non metal.
• ‘B’ forms only covalents compounds.
• ‘B’ doesnot displaces hydrogen from acids.
• ‘B’ shows diagonal relationship with ‘Si’.
• ‘B’ forms acidic oxide where as other elements of group forms amphoteric oxides
and basic oxides.
• ‘B’ has only two electrons in the penultimate shell.
• ‘B’ has covalency ‘4’ where as other elements has covalency of maximum ‘6’.
Question 13.
Aluminium reacts with dil.HNO3 but not with conc.HNO3 – explain.
Answer:
• Dilute HNO3 reacts with Aluminium slowly and forms aluminium nitrate and
ammonium nitrate.
8Al + 30 HNO3 → 8 Al(NO3)3 + 3NH4NO3 + 9H2O
• Aluminium doesnot react with cone. HNO3.
Reasons :
• Aluminium is passive towards cone. HNO3 due to the formation of thin film of
Al2O3 layer on the surface.
• Because of this passivity between Al and conc.HNO3, conc.HNO3 is transported in
Aluminium containers.
Question 14.
Give two methods of preparation of diborane.
Answer:
1. In industries diborane is prepared by the reaction between boron tri fluoride and
lithium hydride.
2. Boron trichloride and hydrogen mixture subjected to silent electric discharge at

low pressure to from diborane.
2BCl3 + 6H2 → B2H6 + 6HCl
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3. Boron trichloride undergo reduction with LiAlH4 to form diborane.
Question 15.
How does diborane react with
a) H2O
b) CO
c) N(CH3)3 ?
Answer:
a) Diborane reacts with water to form boric acid and hydrogen.
B2H6 + 6H2O → 2H3BO3 + 6H2↑
b) Diborane reacts with CO at 100° C and 20 atm. pressure to form borane carbonyl.
c) Diborane reacts with N(CH3)3 and form a adduct.

B2H6 + 2N(CH3)3 → 2BH3.N(CH3)3 (adduct)
Reactions b, c are cleavage reactions.
Question 16.
Al2O3 is amphoteric – explain with suitable reactions.
Answer:
• Amphoteric oxides are the oxides which possess both acidic as well as basic
nature.
Al2O3 possess both acidic as well as basic behaviour.
• Al2O3 react with both acids as well as bases to produce salts and water.
Supporting reactions for amphoteric nature of Al2O3
a) With acids:
b) With bases:
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Question 17.
Na2B4O7 + Cone. H2SO4 → A > B (Green edged flame) Identify A and B

Hint: A = H3BO3 B = (C2H5)3 BO3.
Answer:
Na2B4O7 + Cone. H2SO4 + 5H2O → 4H3BO3 A) B) 4(C2H5)3BO3

• ‘A’ is H3BO3
• ‘B’ is (C2H5)3 BO3.
Question 1.
How are borax and boric acid prepared ? Explain the action of heat on them.
Answer:
Preparation of Borax:
Boric acid on heating first forms tetraboric acid. This on reaction with sodium hydroxide
to form borax.
Preparation of Boric acid : Borax is treated with conc.H2SO4 boric acid is formed.
Na2B4O7 + H2SO4 + 5H2O → 4H3BO3 + Na2SO4.
Heating of Borax :
Borax on heating first loses the water molecules and forms sodium tetraborate. This on
further heating forms a mixture of sodium meta borate and boric anhydride.
Na2B4O7.10H2O Na2B4O7 imgg 2 2 NaBO2 + B2O3.
Heating of Boric acid :
Boric acid on heating forms boric anhydride. The reaction depends on the temperature
used.
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Question 2.
How is diborane prepared ? Explain its structure.
Answer:
In industries diborane is prepared by the reaction between boran tri fluoride and
lithium hydride.
Boron trichioride and hydrogen mixture subjected to silent electric discharge at low
pressure to from diborane.
2BCl3 + 6H2 → B2H6 + 6HCl
Boron trichloride undergo reduction with LiAlH4 to form diborane.
Diborane is an electron deficient compound. It has ’12’ valency electrons for bonding
purpose instead of ’14’ electrons.
In diborane each boron atom undergoes sp3 hybridization out of the four hybrid
orbitals one is vacant.
Each boron forms two, σ – bonds (2 centred – 2 electron bonds) bonds with two
hydrogen atoms by overlapping with their ‘1s’ orbital.
The remaining hybrid orbitals of boran used for the formation of B-H-B bridge bonds.
In the formation of B-H-B bridge, half filled sp3 hybrid ofbital of one boron atom
and vacant sp3 hybrid orbital of second boron atom overlap with 1s orbital of H-
atom.
These three centred two electron bonds are also called as banana bonds. These
bonds are present above and below the plane of BH2 units.
Diborane contains two coplanar BH2 groups. The four hydrogen atoms are called
terminal hydrogen atoms and the remaining two hydrogens are called bridge
hydrogen atoms.
Bonding in diborane, Each B atom uses sp3 hybrids for bonding. Out of the four sp3 hybrids on
each B atom, one is without an electron shown in broken lines. The terminal B-H bonds are
normal 2-centre-2- electron bonds but the two bridge bonds are 3-centre-2- electron bonds. The
3-centre-2-electron bridge bonds are also referred to as banana bonds.
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Question 3.
Write any two methods of preparation of diborane. How does it react with
a) Carbon monoxide and
b) Ammonia ?
Answer:
Preparation of diborane:
In industries diborane is prepared by the reaction between boroh tri fluoride and
lithium hydride.
Boron trichloride and hydrogen mixture subjected to silent electric discharge at

low pressure to from diborane.
2BCl3 + 6H2 → B2H6 + 6HCl
Boron trichloride undergo reduction with LiAlH4 to form diborane.
a) Reaction with carbon monoxide :

Diborane reacts with CO at 100° C and 20 atm. pressure to form borane carbonyl.
b) Reaction with ammonia

Diborane reacts with ammonia at 120° C first forms B2H6.2NH3 (or)
[BH2(NH3)2]+[BH4]– and on further heating forms borazole (or) borazine. Which is
also called as “In organic benzene”. It has iso structural with benzene. Flence it is
named as “Inorganic Benzene”.
Solved Problems
Question 1.
Standard electrode potential values, EΘ for Al3+ / Al is – 1.66 V and that of Tl3+ / Tl is
+ 1.26 V. Predict about the formation of M3+ ion in solution and compare the
electropositive character of the two metals.
Solution:
Standard electrode potential values for two half cell reactions suggest that
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aluminium has high tendency to make Al3+ (aq) ions, whereas Tl3+ is not only
unstable in solution but is a powerful oxidising agent also. Thus Tl+ is more stable
in solution than Tl3+. Aluminium being able to form +3 ions easily, is more
electropositive than thallium.
Question 2.
White fumes appear around the bottle of anhydrous aluminium chloride. Give
reason.
Solution:
Anhydrous aluminium chloride is partially hydrolysed with atmospheric moisture
to liberate HCl gas. Moist HCl appears white in colour.
Question 3.
Boron is unable to form BF3−6 ion. Explain.
Solution:
Due to non – availability of d orbitals, boron is unable to expand its octet.
Therefore, the maximum covalence of boron cannot exceed 4.
Question 4.
Why is boric acid considered as a weak acid ?
Solution:
Because it is not able to release H+ ions on its own. It receives OH+ ions from water
molecule to complete its octet and in turn releases H+ ions.
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Question 1.
Discuss the variation of oxidation states in the group -14 elements.
Answer:
• The common oxidation states exhibited by group – 14 elements are +4 and +2.
• Carbon exhibits negative oxidation states.
• Heavier elements exhibits +2 oxidation state.
• The tendency to show +2 oxidation state increases in the order Ge < Sn < pb.
• pb exhibits +2 oxidation state as stable state because of inert pair effect.
Question 2.
How the following compounds behave with water
a) BCl3
b) CCl4.
Answer:
a) BCl3 reacts with water (hydrolysis) to form boric acid.
b) CCl4 does not undergo hydrolysis due to lack of d-orbitals in the central atom ‘C1
and due to its highly non polar nature, CCl4 does not acts as Lewis acid.
Question 3.
Are BCl3 and SiCl4 electron-deficient compounds ? Explain.
Answer:
• BCl3 and SiCl4 are electron-deficient compounds.
• These two compounds behave as Lewis acids.
• These compounds are electron pair acceptors.
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• The following reacts support the electron deficiency of BCl3 and SiCl4.
Question 4.
Give the hybridization of carbon in
a) CO3-2
b) diamond
c) graphite
d) fullerene
Answer:
a) In C03-2 carbon atom undergoes sp2 hybridisation.
b) In Diamond carbon atom undergoes sp3 hybridisation.
c) In Graphite carbon atom undergoes sp2 hybridisation.
d) In Fullerenes carbon atom undergoes sp2 hybridisation.
Question 5.
Why is’CO’poisonous ? [T.S. Mar. 16]
Answer:
‘CO’ gas is highly poisonous because it has the ability to form a stable complex with
haemoglobin.
Carboxy haemoglobin is 300 times more stable than oxyhaemoglobin.
Question 6.
What is allotropy ? Give the crystalline allotropes of carbon. [Mar. 13]
Answer:
• The phenomenon of existence of an element in different physical forms having
similar (or) same chemical properties is called allotropy.
• Crystalline allotropes of carbon are
a) Diamond
b) Graphite
c) Fullerenes.
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Question 7.
Classify the following oxides as neutral, acidic, basic or amphoteric,
a) CO
b) B2O3
c) SiO2
d) CO2
e) Al2O3
f) PbO2
g) Tl2O3
Answer:
a) CO is neutral oxide.
b) B2O3 is acidic oxide.
c) SiO2 is acidic oxide.
d) CO2 is acidic oxide.
e) Al2O3 is amphoteric oxide.
f) PbO2 is amphoteric oxide.
g) Tl2O3 is basic oxide.
Question 8.
Name any two manmade silicates.
Answer:
Glass and cement are man made silicates.
Question 9.
Write the outer electron configuration of group -14 elements.
Answer:
The general outer most electronic configuration of group – 14 elements is ns2np2.
1) Carbon – [He] 2s22p2
2) Silicon – [Ne] 3s23p2
3) Germanium – [Ar] 3d104s24p2
4) Tin – [Kr] 4d10 5s2 5p2
5) Lead – [Xe] 4f4 5d10 6s2 6p2
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Question 10.
How does graphite function as a lubricant ?
Answer:
Graphite is soft and it has layer lattice. In this structure one of the layer slided over
another due to weak Vander Waal’s force of attraction. These layers are slippery. Hence
it is greasy and function as lubricant.
Question 11.
Graphite is a good conductor – explain.
Answer:
In graphite carbon undergoes sp2 hybridisation. Each carbon forms three a – bonds
with three neighbouring carbon atoms. Fourth electron forms TC – bond and it is
delocalised. Due to the presence of these moving (or) free electrons graphite acts as
good conductor.
Question 12.
Explain the structure of silica.
Answer:
• Silica is a giant molecule with 3 – dimensional structure.

• In Silica eight membered rings are formed with alternate Silicon and Oxygen
atoms.
• Each ‘Si’ is tetrahedrally surrounded by four Oxygen atoms.
• Each Oxygen at the vertex of the tetrahedron is shared by two Silicon atoms.
• In SiO2 Silicon atom undergoes sp3 hybridisation.
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Question 13.
What is ‘Synthesis gas’?
Answer:
• Water gas is also called as synthesis gas.
• It is a mixture of CO and H2.
• It s prepared by passing steamover hot coke.
• It is used for the synthesis of methanol and a number of hydrocarbons. Hence it
is called synthesis gas.
Question 14.
What is producer gas?
Answer:
• Producer gas is mixture of CO and N2.
• It is prepared by passing air over hot coke.
Question 15.
Diamond has high melting point – Explain.
Answer:
• In Diamond each carbon undergoes sp3 hybridisation and it is surrounded by four
other carbon atoms with strong a – bonds tetrahedrally.
• The C – C bond energy in diamond is very high and it has 3 – dimensional
structure.
• Due to these reasons diamond has high melting point.
• It has melting point 4200 K.
Question 16.
Give the use of CO2 in photosynthesis.
Answer:
The process of converting the atmospheric CO2 into Carbohydrates by green plants is
known as ‘photosynthesis’.
In Photosynthesis CO2 changes to carbohydrates such as glucose.
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Question 17.
How does CO2 increase the green house effect ?
Answer:
• Green plants absorbs CO2 gas for photosynthesis and releases O2 gas.
• Due to deforestation, decomposition of lime stone and burning of fossil fuels
CO2 concentration is increased in atmosphere.
• The increase of CO2 level disturbs the O2 – CO2 balance in the atmosphere and it
is responsible for green house effect (or) global warming.
Question 18.
What are silicones ?
Answer:
• Silicones are the organo Silicon polymers containing R2 SiO – repeating unit.
• These are synthetic compounds containing Si – O – Si.
• Linkage preparation : These are formed by the hydrolysis of chlorosilanes.
Question 19.
Give the uses of silicones.
Answer:
Uses of silicones :
• These are used in surgical and cosmetic plants.
• These are used in preparation of silicone rubbers.
• These are used as sealoant, greases etc.
• These are used in preparing water proof clothes and papers.
• These are used as insulators.
• These are used in paints and enamels.
Question 20.
What is the effect of water on tin ?
Answer:
• Tin metal reacts with steam to form tin dioxide and dihydrogen gas.
• In this reaction steam is decomposed.
Sn + 2H2O SnO2 + 2H2
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Question 21.
Write an account of SiCl4.
Answer:
• Silicon tetrachloride (SiCl4) is also called as tetra chloro silico methane.
• SiCl4 can acts as Lewis acid due to availability of 3d orbital in ‘Si’.
• SiCl4 undergoes hydrolysis due to presence of vacant 3d-orbital. Here water
molecules forms dative bonds with empty 3d-orbitals of Siratom.
Uses :
• SiCl4 and NH3 mixture used to produce smoke screens.
• Ultra pure Silicon is used to make transistors.
• SiO2 prepared from SiCl4 used in epoxypaints, resis etc..
Question 22.
SiO2 is a solid while CO2 is a gas – explain.
Answer:
• Silica (SiO2) has giant molecular structure.
• In SiO2 ‘Si’ undergoes sp3 hybridisation.
• It is a 3 – dimension structure in which each ‘Si’ atom is tetrahedrally surrounded
by four oxygen atoms.
• Hence it exists as solid compound.
• CO2 has linear structure.
• In CO2 ‘C’ undergoes sp hybridisation.
• In between CO2 molecule weak Vander Waal’s forces are present.
• In CO2 molecule two double bonds are present.
• Hence CO2 exists as a gas.
Question 23.
Write the use of ZSM – 5.
Answer:
1. ZSM – 5 is a zeolite.
2. It is used to convert alcohols directly into gasoline.
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Question 24.
What is the use of dry ice ?
Answer:
1. Solid CO2 is called as dry ice.

2. It is used as refrigirent for frozen food and ice – creams.
Question 25.
How is water gas prepared ?
Answer:
Water gas is prepared by passing superheated steam over hot coke.
Question 26.
How is producer gas prepared ?
Answer:
Producer gas is prepared by passing air over white not coke.
Question 27.
C-C bond length in graphite is shorter than C-C bond length in diamond – explain.
Answer:
1. In graphite each carbon undergoes sp2 hybridisation and hence bond length is
1.42 A° (or) 141.5 pm.
2. Graphite has hexagonal layer like lattice. It is a 2-dimensional structure.
3. In diamond each carbon undergoes sp3 – hybridisation and hence bond length is
1.54 A° (or) 154 pm.
4. Diamond has regular tetrahedral giant polymeric structure. It is a 3-dimensional
structure.
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Question 28.
Diamond is used as precious stone – explain.
Answer:
• Diamonds are used as precious stones.
• Diamonds are clear, colourless form of pure carbon.
• These are hardest substances occurring naturally.
• The weight of diamond expressed in carats.
1 carat = 200 mg.
Question 29.
Carbon never shows co-ordination number greater than four while other members of
carbon family show co-ordination number as high as six – explain.
Answer:
Carbon never shows co-ordination number greater than four because of absence of d-
orbitals in carbon atom.
The other members of carbon family show co-ordination number as high as six
because of availability of d – orbitals.
Question 30.
Producer gas is less efficient fuel than water gas – explain.
Answer:
1. Producer gas has calorific value 5439.2 KJ/m3
2. Water gas has calorific value 13000 KJ/m3.
3. Due to high calorific value of watergas, it is more efficient fuel than producer gas
(or) producer gas is less efficient than watergas.
Question 31.
SiF6-2 is known while SiCl6-2 is not. Explain. [A.P. Mar. 16]
Answer:
SiF6-2 is known while SiCl6-2 is not because
• Si+4 has small size so it cannot be accomodate six large chloride ions.
• The interaction between lone pairs of Cl– ion and Si+4 is not very strong.
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Question 1.
Explain the difference in properties of diamond and graphite on the basis of their
structure.
Answer:
Diamond
a) Each carbon is sp3 hybridised.
b) Each carbon is bonded to 4 other carbons tetrahedrally.
c) It has a 3 dimensional structure.
d) C – C bond length is 1.54 Å and bond angle is 109° 28′.
e) Carbon atoms are firmly held with strong covalent bonds.
f) Diamond is very hard.
g) Density = 3.5 g/cc.
h) Graphite is a conductor due to the presence of free electrons.
i) It is transparent to light and X-rays. It has high refractive index (2.45).
Graphite
a) Each carbon is sp2 hybridised.
b) Each carbon is bonded to 3 other carbon atoms to form hexagonal rings. It has sheet
like structure.
c) It has a 2 dimensional structure.
d) C – C bond length in hexagonal rings is 1.42 A° and bond angle is 120°.
e) The distance between two adjacent layers is 3.35 A°. These layers are held by weak
Vander Waal’s forces.
f) Graphite is soft.
g) Density – 2.2g/cc.
h) Diamond is an insulator due to the absence of free electrons.
i) It has layer, lattice. The layers are slippery. Hence it is greasy.
Question 2.
Explain the following.
a) PbCl2 reacts with Cl2 to give PbCl4
b) PbCl4 is unstable to heat,
c) Lead is not known to form PbI4.
Answer:
a) PbCl2 + Cl2 → PbCl2
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But PbCl4 is unstable than PbCl2. Because compounds of lead in +2 oxidation state are
stable than +4 oxidation state.
b) PbCl4 is unstable to heat:
• In PbCl4 lead exhibits +4 oxidation state.
• he compounds of lead in +2 oxidation state are stable than +4 oxidation state.
Hence PbCl4 is unstable to heat.
c) Lead is not known to form PbI4:
• Pb – I bond formed initially during the reaction does not release enough energy
to unpair the 6s electrons.
• Lead compounds in +2 state are stable than +4 state.
Due to inert pair effect Pb exhibits stable +2 oxidation state.
Question 3.
Explain the following :
a) Silicon is heated with methyl chloride at high temperature in presence of copper.
b) SiO2 is treated with HF.
c) Graphite is a Lubricant
d) Diamond is an abrasive.
Answer:
a)
• Methyl chloride reacts with silicon at high temperature in presence of copper
catalyst to form various types of methyl substituted chlorosilane of formula
MeSiCl3, Me2SiCl2, Me3SiCl with small amount Me4Si.
• Hydrolysis of dimethyl dichloro silane followed by condensation polymerisation
forms a straight chain polymer (silicone) (Me = CH3 – group)
b) SiO2 is treated with HF to form SiF4. Which on hydrolysis to form H4SiO4 and H2SiF6.
SiO2 + 4HF → SiF4 + 2H2O
SiF4 + 4H2O → H4SiO4 + 2H2SiF6
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c) Graphite is soft and it has layer lattice. In this structure one of the layer slided over
another due to weak Vander Waal’s force of attraction. These layers are slippery. Hence
it is greasy and function as lubricant.
d) The covalent bonds in diamond are very strong and difficult to break, Hence
diamond is used as an abrasive for sharpening hard tpols, in making dyes and in the
manufacturing of tungsten filaments etc.
Question 4.
What do you understand by
a) Allotropy
b) Inert pair effect
c) Catenation.
Answer:
a) Allotropy :
The phenomenon of existence of an element in different physical forms having similar
(or) same chemical properties is called allotropy.
Crystalline allotropes of carbon are
a) Diamond
b) Graphite.
b) Inert pair effect : The reluctance of ‘ns’ pair of electrons to take part in bond
formation is known as inert pair effect.
(or)
The occurrence of oxidation states two units less than the group oxidation states is
known as inert pair effect.
Eg : Lead exhibits +2 oxidation state as stable oxidation state due to inert pair effect.
(Instead of +4 state).
c) Catenation : The phenomenon of self linkage of atoms among themselves to form
long chains (or) rings is called as catenation.
Carbon has highest catenation tendency due to its high bond energy (348 KJ/mole).
Question 5.
If the starting material for the manufacturing of Silicons is RSiCi3. Write the structure of
the product formed.
Answer:
When RSiCl3 type of compound is used for the manufacturing of silicones a cross –
linked silicon is formed.
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Eg : When Methyl trichloro silane (CH3SiCl3) undergoes hydrolysis to give monomethyl
silane triol. This undergoes polymerisation to form a very complex cross-linked polymer
(Silicone).
Question 6.
Write a short note on Zeolites.
Answer:
Zeolites : The three dimensional structure contain no metal ions. If some of the Si+4 in
them is replaced by Al+3 and an additional metal ion an infinite three dimensional
lattice is formed. Replacements of one or two silicon atoms in [Si2O8]-2n form zeolites.
Zeolites act as ion exchanges and as molecular sieves. The structures of zeolites permit
the formation of cavities of different sizes. Water molecules and a variety of other
molecules like NH3, CO2 and ethanol can be trapped in these cavities. Then zeolites
serve as molecular sieves. They trap Ca+2 ions from hard water and replace them by
Na+2 ions.
Uses of Zeolites :
Zeolites are used as catalysts in petrochemical industries for cracking of hydrocarbons
and in Isomerisation.
Zeolite ZSM – 5 is used to convert alcohols directly into gasoline.
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Question 7.
Write a short note on Silicates.
Answer:
Silicates : Many building materials are silicates.
Ex : Granites, slates, bricks and cement. Ceramics and glass are also silicates. The Si – O
bonds in silicates are very strong. They do not dissolve in any of the common solvents
nor do they mix with other substances readily.
The silicates can be divided into six types. They are mentioned here.
1. Orthosilicate or Nesosilicates : Their general formula may be M211 (SiO4).
Ex : Willemite Zn2 (SiO4).
2. Pyrosilicates or sorosilicates or Disilicates : These contain SiO7-6 units. Pyrosilicates
are rare.
Ex: Thorveitite Ln2 (Si2O7).
3. Chain silicates : They have the units (SiO3)n2n-
Ex : Spodumene LiA/ (SiO3)2.
Amphiboles are one type chain silicates. Generally double chains are formed in
them.
4. Cyclic silicates : They are silicates having ring structures. They may be formed of
general formula (SiO3)n2n-. Rings containing three, four, six and eight tetrahedral
units are known. But rings with three and six are the most common.
Ex : Beryl Be3Al2 (Si6O18)
5. Sheet silicates : When SiO4 units share three corners the structure formed is an
inifinite two dimensional sheet. The empirical formula (Si2O5)n2n-. These
compounds appear in layer struc-tures. They can be cleaved.
Ex : Kaolin Al2 (OH)4 Si2O5.
6. Frame work silicates or three dimensional silicates : Sharing all the four corners of
a SiO4 tetrahedron results in three dimensional lattice of formula SiO2.
Ex : Quartz, Tridymite; Cristobalite; Feldspar and ultramarine (Na8 [Al6 Si6 O24] S2),
zeolites.
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Question 8.
What are Silicones ? How are they obtained ?
Answer:
• Silicones are the organo silicon polymers containing R2 SiO – repeating unit.
• These are synthetic compounds containing Si – 0 – Si.
Preparation : These are formed by the hydrolysis of chlorosilanes.
• Methyl chloride reacts with Silicon at high temperature in presence of copper
MeSiCl3, Me2SiCl2, Me3SiCl with small amount Me4Si
• Hydrolysis of dimethyl dichloro silane followed by condensation polymerisation
forms a straight chain polymer (Silicone) (Me = CH3 – group).
Question 9.
Write a short note on Fullerene.
Answer:
Fullerenes :
• Fullerenes are one type of crystalline allotropes of carbon.
• These are formed by heating graphite in an electric arc in presence of inertgases
such as Helium (or) Argon.
• These have smooth structure without dangling bonds. Hence Fullerenes are the
only pure forms of carbon.
• C60 molecule is called Buck minster fullerene and it’s shave was like a soccer ball.
• C60 contains twenty 6 – membered rings and twelve 5 – membered rings.
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• In C60 6 – membered rings can combine with 5 (or) 6 – mem-bered rings while 5
– membered rings only combine with 6 – membered rings.
• In Fullerens each carbon undergoes sp2 hybridisation.
• Fullere has aromatic nature due to delocalisation of electrons in unhybrid p-
orbitals.
• The C – C bond length in these compound lies between single and double bond
lengths.
• Spherical fullerene are also named as bucky balls.
• The ball shaped molecule has 60 vertices.
• The C – C bond distances are 1,43A° and 1.38A° respectively.
Question 10.
Why SiO2 does not dissolve in water ?
Answer:
Silica (SiO2) is a non reactive compound in it’s normal state.
1. This non reactivity is due to very high Si – O bond enthalpy.
2. Silica is a giant molecule with 3-dimensional structure.
3. In Silica each silicon atom is covalently bonded in a tetrahedral manner to four
oxygen atoms
4. Hence SiO2 is insoluble in water.
5. But slightly dissolves at high pressures when heated.
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Question 11.
Why is diamond hard ?
Answer:
In diamond, each carbon undergoes sp3 hybridization. A carbon atom is bound to four
carbon atoms, arranged in a tetrahedral symmetry, with single bonds. A three
dimensional arrangement of the tetrahedral structures result in giant molecule. The
bond energy is very high (348 kJ mol-1). It is very difficult to break the bonds. So,
diamond is hard.
Question 12.
What happens when the following are heated
a) CaCO3
b) CaCO3 and SiO2
c) CaCO3 and excess of coke.
Answer:
CaCO3 up on heating gives Quick lime.
Quick lime (CO) with silica gives Calcium silicate.
Coke reacts with Quick lime and form Carbides.
Question 13.
Why does Na2CO3 solution turn into a suspension, when saturated with CO2 gas.
Answer:
An aq. solution of Na2CO3 when saturated with CO2, gives Sodium bicarbonate
(NaHCO3).
Na2CO3 + H2O + CO2 → 2NaHCO3
NaHCO3 is less soluble compared to Sodium carbonate, hence suspension is
formed.
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Question 14.
What happens when
a) CO2 is passed through slaked lime
b) CaC2 is heated with N2.
Answer:
a) Slaked lime, Ca(OH)2 is turned milky on passing CO2 with the formation of
insoluble calcium
carbonate Ca(OH)2 + CO2 → CaCO3 + H2O on passing more ‘CO2‘, CaCO3 is
converted into Calcium bicarbonate.
CaCO3 + H2O + CO2 → Ca(HCO3)2
b) CaC2 on heating with N2 gives calcium cyanamide.
Question 15.
Write a note on the anomalous behaviour of carbon in the group -14.
Answer:
Carbon shows ariamalous behaviour in group – 14 elements. The following facts
support that anamalous behaviour.
Except carbon all other elements of group -14 has available d-orbitals and can
expand octet in valency shell.
Carbon occurs in free state but not the other elements of this group.
• Maximum covalency of carbon is four but for silicon is six.
• C – C bond energy is very high (348 kJ/Mde).
• Carbon can form multiple bonds with C, O, S, etc.
• Hydrocarbons are more stable thermally than silanes.
Question 1.
What are Silicones ? How are they prepared ? Give one example. What are their
uses?
Answer:
• Silicones are the organo silicon polymers containing R2 SiO – repeating unit.
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• These are synthetic compounds containing Si – 0 – Si.
Preparation : These are formed by the hydrolysis of chlorosilanes.
• Methyl chloride reacts with Silicon at high temperature in presence of copper
MeSiCl3, Me2SiCl2, Me3SiCl with small amount Me4Si
• Hydrolysis of dimethyl dichloro silane followed by condensation
polymerisation forms a straight chain polymer (Silicone) (Me = CH3 – group).
Uses of Silicones:
• These are used in surgical and cosmetic plants.
• These are used in preparation of Silicons rubbers.
• These are used as sealoant, greases etc.
• These are used in preparing water proof clothes and papers.
• These are used as insulators.
• These are used in paints and enamels.
Question 2.
Explain the structure of Silica. How does it react with
a) NaOH and
b) HF.
Answer:
• Silica is a giant molecule with 3 – dimensional structure.
• In Silica eight membered rings are formed with alternate Silicon and Oxygen
atoms.
• Each ‘Si’ is tetrahedrally surrounded by four Oxygen atoms.
• Each Oxygen at the vertex of the tetrahedron is shared by two Silicon atoms.
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• In SiO2 Silicon atom under goes sp3 hybridisation.
a) Silica reacts with NaOH and forms Sodium Silicate (Na2SiO3)

SiO2 + 2 NaOH → Na2SiO3 + H2O
b) SiO2 is treated with HF to form SiF4. Which on hydrolysis to form H4SiO4 and
H2SiF6.
SiO2 + 4HF → SiF4 + 2H2O
SiF4 + 4H2O → H4SiO4 + 2H2SiF6
Question 3.
Write a note on the allotropy of carbon.
Answer:
The property of an element to exist in two or more physical forms due to
difference in the arrangement of atoms is called Allotropy. Allotropes have more
or less similar chemical properties but different physical properties.
Diamond, graphite and fullerenes are the crystalline allotropes of carbon.

Structure of Diamond : In diamond, each carbon atom bonded to four carbon
atoms situated tetrahydrally around it.
In diamond, each carbon atom is in sp3 hybridisation and is linked to four carbon
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atoms by single covalent bonds.
C – C bond distance in diamond is 1.54 A°.
bond angle in diamond is 109° 28″.

Uses of Diamond :
1. Diamonds are used as precious stones for jewellery because of their ability to
reflect light.
2. Diamonds are used for cutting glass and drilling rocks due to their
remarkable hardness.
Structure of Graphite : Graphite consists of a series of layers in which hexagonal
rings made up of carbon atoms.
In Graphite, each carbon atom undergo sp2 hybridisation and forms three covalent
bonds with three other carbon atoms.
The fourth electron present in the pure ‘p orbitaI which is unhybridised. The
electron become Free Electron.
The C — C bond length in graphite is 1.42 A°.
The distance between the two layers in graphite is 3,4 A°.

These layers are held together by Vander Waal’s forces which are weak.
Graphite is a layer lattice structure.
Uses of Graphite:
1. Graphite is used as a lubricant.
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2. It is used in the manufacturing of lead pencils.
3. It is used in the manufacturing of Electrodes and Refractory crucibles.
Fullerenes :
• These are formed by heating graphite in an electric arc in presence of
inertgases such as Helium (or) Argon.
• These have smooth structure without dangling bonds. Hence Fullerenes are
the only pure forms of carbon.
• C60 molecule is called Buck minster fullerene and it’s shave was like a soccer
ball.
• C60 contains twenty 6 – membered rings and twelve 5 – membered rings.
• In C60 6 – membered rings can combine with 5 (or) 6 – membered rings while
5 – membered rings only combine with 6 – membered rings.
orbitals.
• The C – C bond length in these compound lies between single and double
bond lengths.
• The C – C bond distances are 1.43A° and 1.38A° respectively.
• Amorphous allotropes of carbon are coal, coke, animal charcoal wood
charcoal, lamp black, carbon black, gas carbon, petroleum coke and sugar
charcoal.
Question 4.
Write a note on
a) Silicates
b) Zeolites
c) Fullerenes.
Answer:
a) Silicates : Many building materials are silicates.
Ex : Granites, slates, bricks and cement. Ceramics and glass are also silicates. The Si
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– O bonds in silicates are very strong. They do not dissolve in any of the common
solvents nor do they mix with other substances readily.
The silicates can be divided into six types. They are mentioned here.
1. Orthosilicate or Nesosilicates : Their general formula may be M211 (SiO4).
Ex : Willemite Zn2 (SiO4).
2. Pyrosilicates or sorosilicates or Disilicates : These contain SiO7-6 units.
Pyrosilicates are rare.
Ex : Thorveitite Ln2 (Si2O7).
3. Chain silicates : They have the units (SiO3)n2n-
Ex : Spodumene LiAl (SiO3)2.
Amphiboles are one type chain silicates. Generally double chains are formed
in them.
4. Cyclic silicates : They are silicates having ring structures. They may be formed
of general formula (SiO3)n2n-. Rings containing three, four, six and eight
tetrahedral units are known. But rings with three and six are the most
common.
Ex : Beryl Be3Al2 (Si6O18)
5. Sheet silicates : When SiO4 units share three corners the structure formed is
an inifinite two dimensional sheet. The empirical formula (Si2O5)n2n-. These
compounds appear in layer struc-tures. They can be cleaved.
Ex : Kaolin Al2 (OH)4 Si2O5.
6. Frame work silicates or three dimensional silicates : Sharing all the four
corners of a SiO4 tetrahedron results in three dimensional lattice of formula
SiO2.
Ex : Quartz, Tridymite; Cristobalite; Feldspar and ultramarine (Na8 [Al6 Si6 O24]
S2), zeolites.
b) Zeolites : The three dimensional structure contain no metal ions. If some of the
Si+4 in them is replaced by Al+3 and an additional metal ion an infinite three
dimensional lattice is formed. Replacements of one or two silicon atoms in [Si 2O8]-
2n form zeolites. Zeolites act as ion ex-changes and as molecular sieves. The
structures of zeolites permit the formation of cavities of different sizes. Water

molecules and a variety of other molecules like NH3, CO2 and ethanol can be
trapped in these cavities. Then zeolites serve as molecular sieves. They trap
Ca+2 ions from hard water and replace them by Na+2 ions.
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Uses of Zeolites :
• Zeolites are used as catalysts in petrochemical industries for cracking of
hydrocarbons and in Isomerisation.
• Zeolite ZSM – 5 is used to convert alcohols directly into gasoline.
c) Fullerenes :
• These are formed by heating graphite in an electric arc in presence of
inertgases such as Helium (or) Argon.
• These have smooth structure without dangling bonds. Hence Fullerenes are
the only pure forms of carbon. .
• C60 molecule is called Buck minster fullerene and it’s shave was like a soccer
ball.
• C60 contains twenty 6 – membered rings and twelve 5 – membered rings.
•
• In C60. 6 – membered rings can combine with 5 (or) 6 – membered rings while
5 – membered rings only combine with 6 – membered rings.
orbitals.
• The C – C bond length in these compound lies between single and double
bond lengths.
• The C – C bond distances are 1.43A° and 1.38A° respectively.
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Solved Problems
Question 1.
Select the member(s) of group 14 that
1. forms the most acidic dioxide
2. is commonly found in +2 oxidation state
3. used as semiconductor.
Solution:
1. Carbon
2. lead
3. Silicon and germanium
Question 2.
[SiF6]2- is known whereas [SiCl6]2- not. Give possible reasons.
Solution:
The main reasons are :
1. Six large chloride ions cannot be accommodated around Si4+ due to limitation
of its size.
2. Interaction between lone pair of chloride ion and Si4+ is not very strong.
Question 3.
Diamond is covalent, yet it has high melting point. Why ?
Solution:
Diamond has a three – dimensional network involving strong C – C bonds, which
are very difficult to break and in turn has high melting point.
Question 4.
What are Silicones ?
Solution:
Simple Silicones consist of chains in which alkyl or phenyl groups occupy

the remaining bonding positions on each silicon. They are hydrophobic (water
repellant) in nature.
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Question 1.
Define the terms atmosphere, biosphere.
Answer:
Atmosphere : The blanket of gases present around the earth is called the atmosphere.
It maintains the heat balance on earth. Atmosphere contains nitrogen and oxygen in
large proportions.
Biosphere : The living organisms like plants, animals and human beings constitute the
biosphere.
Biosphere is related to other environment segments.
Question 2.
Explain the terms Lithosphere, Hydrosphere.
Answer:
Lithosphere : The outer mantle of the solid earth consists of minerals present in earth
gust and soil. The earth inner surface contains minerals and deeper inner layers contain
natural gas and soil. Mountains and hills these are all constitutes lithosphere.
Hydrosphere : All the natural water resources together constitute the hydrosphere.
Hydrosphere include oceans, seas, rivers, lakes, streams etc.
Question 3.
Define the term Soil Pollution.
Answer:
The concentration (or) accumulation of natural bodies is called as soil. Soil gets
polluted due to industrial wastes, urban wastes, agricultural pollutants, chemical, radio
active pollutants etc.
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Question 4.
What is Chemical Oxygen demand (COD).
Answer:
The amount of oxygen required to oxidise organic substances present in polluted water
is called Chemical Oxygen Demand (COD).
It is an index for amount of organic substances present in water.
Question 5.
What is Bio Chemical Oxygen Demand (BOD) ?
Answer:
The amount of oxygen used by the suitable micro organisms present in water during
five days at 20° C is called as Bio Chemical Oxygen Demand (BOD).
Question 6.
What are Troposphere and Stratosphere ?
Answer:
Troposphere : The major portion of the atmosphere which contains air is called
troposphere.
It is present 0-11 Km from the earth.
Stratosphere : Stratosphere present 11 – 50 Km from the earth and it mainly contains
ozone layer. It absorbs the harmful UV radiations coming from sun.
Question 7.
Name the major particulate pollutants present in Troposphere.
Answer:
The major particulate pollutants present in troposphere are dust, mist, fumes, smoke,
smog etc.
Question 8.
List out four Gaseous Pollutants present in the polluted air.
Answer:
Oxides of Sulphur,Nitrogen and Carbon, Ozone, Hydrocarbons etc., are gaseous
pollutants present in polluted air.
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Question 9.
Green house effect is caused by and gases.
Answer:
Green house effect is caused by gases such as CO2, CH4, O3, CFCs (Chloro Fluoro
Carbons) and water vapour in the atmosphere.
Question 10.
Which oxides cause acid rain ? and What is its pH value ? [Mar. 13]
Answer
• Oxides of Nitrogen, Sulphur and Carbon dissolved in rain water forms acid rain.
• Acid rain has pH value lessthan 5.6.
Question 11.
Name two adverse effects caused by acid rains. [A.P. Mar. 16] [T.S. Mar. 15]
Answer:
Effects of acid rains
• Acid rains are harmful for agriculture, trees and plants because it dissolves and
washes away nutrients needed for their growth.
• Acid rains affects the plants and animal life in aquatic ecosystem.
• Acid rains damages the old buildings and historical monuments like Taj mahal.
• Acid rains corrodes water pipes which lead to decrease the quality of drinking
water.
Question 12.
What are smoke and mist ?
Answer:
Smoke : The solid particles (or) mixture of solid and liquid particles formed by the
combustion of organic matter are called smoke particulates.
Eg : Cigarette smoke, oil smoke etc.
Mist: The particles produced by the spray liquids and by condensation of vapours in air
is called mist.
Eg : H2SO4 – mist, herbicides, insecticides etc.
These miss their targets and travel through atmosphere to form mist.
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Question 13.
What is classical smog ? and What is its Chemical Character (Oxidizing / reducing) ?
Answer:
• The mixture of smoke, fog and sulphur dioxide is called classical smog. It exists in
cool humid climate.
• The chemical character of classical smog is reducing character. Hence it is also
called as reducing smog.
Question 14.
Name the common components of Photo Chemical smog.
Answer:
The common components of Photo Chemical smog are O3, NO, acrolein, formaldehyde
and Peroxy Acetyl Nitrate (PAN).
Question 15.
What is PAN ? What effect is caused by it ?
Answer:
• Peroxy Acetyl Nitrate is called as PAN.
• Peroxy Acetyl Nitrate is (PAN) is a powerful eye irritant.
Question 16.
How is Ozone formed in the Stratosphere ?
Answer:
• UV radiations react with dioxygen (O2) molecules and split into free oxygen (O)
atoms. These free oxygen atoms (0) combined to form ozone molecule.
• The following are the reactions that takes place during the formation of ozone in
stratosphere.
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Question 17.
Give the Chemical equations involved in the Ozone depletion by CF2Cl2.
Answer:
CF2Cl2 which is released in the atmosphere mix with the normal atmospheric gases and
reaches the stratosphere.
• In stratosphere CF2Cl2 react with powerful UV radiations and liberates chlorine
free radicals.
• These chlorine radical reacts with ozone present in stratosphere to form chlorine
monoxide radicals and molecular dioxygen.
Cl* + O3 → ClO* + O2
• ClO radical react with atomic oxygen and produce more Cl – radicals.
ClO* + O → Cl* + O2
Question 18.
What is Ozone hole ? Where was it first observed ?
Answer:
The depletion of ozone layer is commonly known as ozone hole.
• It was first observed in Antarctica over the south pole.
• It was reported by atmospheric scientists working in Antarctica.
Question 19.
What is the value of dissolved Oxygen in pure cooled, water ?
Answer:
The value of dissolved oxygen in pure cooled water is around 10 ppm.
Question 20.
Give the possible BOD values of clean water and the polluted water.
Answer:
• The BOD value of clean water is less than 3 ppm.
• The BOD value of water is greaterthan 4 ppm then it is said to be polluted.
• Highly polluted water has BOD value more than 17 ppm.
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Question 21.
Name three industrial Chemicals that pollute water.
Answer:
Detergents, paints, pesticides, dyes and pharmaceuticals etc.
Question 22.
What agrochemicals are responsible for water pollution ?
Answer:
Agrochemicals like chemical fertilisers, chemicals used for killing insects, fungi and
weeds in crop etc., are responsible for water pollution.
Question 1.
What are different segments of the earth’s environment ?
Answer:
Environment can be divided into four segments.
1. Atmosphere
2. Hydrosphere
3. Lithosphere
4. Biosphere
1) Atmosphere : The layer of air present around the Earth is called the atmosphere. The
atmospheric air contains N2 and O2 in large proportions, while the rest of the gases like
C02 are present only in smaller proportions. Atmosphere absorbs harmful radiations
coming from the Sun. It plays an important role in maintaining the heat balance on
Earth. If the proportions of the gases, especially O2 and N2 are disturbed by human
activity, the equilibrium of the echo system is lost. It leads to disastrous consequences.
2) Hydrosphere : Hydrosphere includes all the surface and ground water resources i.e.,
oceans, rivers, lakes, polar ice caps etc., 97% of earth’s water is locked up in oceans. 3%
is trapped in polar ice caps. Only small percentage of water is available for drinking,
agricultural and industrial purpose. 80% of the earth’s surface is covered with water.
3) Lithosphere : One fifth of the total Earth surface is in the form of land. Inner layers of
Earth contain minerals. Deeper inner layers of Earth contain Natural gas and oil. All
these things, including hills and mountains come under Lithosphere. Plants, animals
and human beings are occupied by it.
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4) Biosphere : All living organisms like plants, animals and human beings constitute the
Biosphere. Biosphere and other segments of the environment are interrelated.
Biosphere is dependent on Atmosphere and Hydrosphere. Polluted atmosphere arrest
the plant growth and bring health hazards among animals and human beings.
Contaminated water causes many diseases and also death of aquatic animals.
Question 2.
Define the terms Sink, COD, BOD and TLV. [T.S. Mar. 16]
Answer:
Sink : The medium which retains and interacts with long lived pollutant is called the
sink.
Eg : Oceans are important sinks for atmospheric CO2.
COD : The amount of oxygen required to oxidise organic substances present in
polluted water is called Chemical Oxygen Demand (COD).
It is an index for amount of organic substances present in water.
BOD : The amount of oxygen used by the suitable micro organisms present in water
during five days at 20° C is called as Bio Chemical Oxygen Demand (BOD).
TLV : (Threshold Limit Value): The permissiable level of the toxic substances (or)
pollutants in the atmosphere which affects a person adversly when he is exposed to
this for 7 – 8 hrs. in a day is called TLV.
Question 3.
Name the gaseous pollutants present in the air and explain their formation.
Answer:
Gaseous pollutants present in air are
a) Oxides of sulphur
b) Oxides of nitrogen
c) Oxides of carbon
d) Hydro carbons
a) Oxides of sulphur :
• The oxides of sulphur formed by the fossil fuel containing sulphur are burnt.
S + O2 → SO2
• Sulphur dioxide oxidises to form sulphur trioxide in presence of catalyst.
2SO2 + O2 ⇌ 2SO3
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• Sulphur trioxide can also be formed by the reaction of SO2 with O3 (or) H2O2.
SO2 + O3 ⇌ SO3 + O2
SO2 + H2O2 → H2SO4
• SO2 is the most common oxide and causes the following adverse effects.
a) It causes respiratory problems like asthma, bronchitis etc.
b) It is poisonous to both animals and plants.
c) It causes irritation to the eyes which results in tears and redness.
b) Oxides of nitrogen :
The major gases present in air are oxygen and nitrogen.
• These do not combine at normal temperature.
• Dinitrogen and dioxygen combined at high altitudes in presence of light to form
oxides of nitrogen.
• No reacts with oxygen to form NO2.

2NO + O2 → 2NO2
• NO2 is quickly formed by the reaction of NO with O3.
NO + O3 → NO2 + O2
Adverse Effects
• NO2 damages the leaves of plants and effects the efficiency of photosynthesis.
• NO2 causes lung problems.
• NO2 causes respiratory problems.
• NO2 affects the textile fibres and metals.
c) Oxides of carbon : –
i) Carbon monoxide (CO)
• CO is one of the most harmful air pollutants.
• CO gas is produced by the incomplete combustion of carbon (coal, firewood,
petrol etc.)
C(s) + 12O2 → C0(g)
(g)
• CO is mainly released into atmosphere by automobiles.

Adverse effects :
• It stops the transportation of oxygen to the organs and tissues.
• When it is inhaled by a human being it forms stable complex with haemoglobin
of blood. This complex is named as carboxy haemoglobin.
CO + Hb → CO – Hb
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• This reduces the oxygen transportation in body and results into headache, eye
problems, nerveous problems and heart problems.
ii) Carbondioxide :
• CO2 is entered into atmosphere mainly by respiration process.
• CO2 is also formed by the burning of fossil fuels.
C + O2 → CO2 + heat energy
• CO2 is formed by the decomposition of lime stone.
CaCO3 Cao + CO2

Effects :
• Due to deforestation and burning of fossil fuels increases CO2 release and the
balance O2 – CO2 in atmosphere disturbed.
• The increased level of CO2 causes global warming which causes several problems
like dengue, malaria etc.
• Due to global warming efficiency of photosynthesis decreases.
d) Hydrocarbons:
• These mainly constitutes hydrogen and carbon.
• These are formed by the incomplete combustion of fuel used in auto mobiles.
Adverse Effects:
• These cause cancer.
• These are harmful to plants causing ageing, break down of tissues, flowers and
leaves are shedded.
Question 4.
What is green house effect ? and how is it caused ?
Answer:
a) Global Warming : The Earth is heated by sunlight and some of the heat that is
absorbed by the Earth is radiated back into space. But some gases like CO2, CFCs, O3,
NO and water vapour present in the lower atmosphere do not allow the Earth to re-
radiate the heat into space. A part of the heat so trapped in these atmospheric gases is
re-emitted to the earth’s surface. This phenomenon is called the “Green house effect”
(or) Global Warming.
The gases which are responsible for Green house effect are CO2, CFC’s, O3, NO,
CH4 water vapour etc. and they are termed as Green house gases. The effect of increase
in CO2 causes global warming.
b) Effects of global warming :
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1. If there is a 1° C increase in the temperature, the ice caps of the polar region melt
and level of the sea water increases by 90 cm. Due to this, so many coastal
countries will be submerged.
2. Due to global warming, the rate of evaporation of water from the seas, rivers,
ponds will increase. This leads to ultimately rains, cyclones and hurricanes.
3. Agriculture sector will be badly affected due to the fast evaporation of surface
water. There will be a shortage in the supply of water for agricultural purpose.
4. Unseasonal rains.
5. Increase the infectious diseases like dengue, malaria, yellow fever, sleeping
sickness etc.
Prevention : To reduce the level of CO2 on the earth’s atmosphere, one must increase
the number of sinks to absorb CO2. Plants absorb a major portion of the CO2. Therefore,
more plants, trees, forests should be grown. The blue green algae present in the sea
also gets extinct, due to water pollution. This should be prevented stopping the
production of CFC etc.
Question 5.
Explain, with Chemical equations involved, the formation of acid rain.
Answer:
Acid rains are due to oxides of N, S and C (NO2, SO2 and CO2).
• These oxides dissolve in rain water and formed as acids (HNO3, H2SO4 and H2CO3).
• These come down to earth as rain and deposited on the earth’s surface.
• Acid – rain is more in industrial areas.
Chemical equations involved
NO2 + NO3 → N2O5
N2O5 + H2O + 2HNO3
CO2 + H2O → H2CO3
SO3 + H2O → H2SO4
The pH of acid rain is less than 5.6.
Question 6.
Explain in detail the adverse effects caused by the acid rain.
Answer:
Acid rains are harmful because
1. The life of old buildings will be considerable reduced.
2. The pH of the soil changes affecting its fertility.
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3. Ammonium salts formed by acid rains can be seen as atmospheric haze.
4. Ammonium salts in rain drops result in wet decomposition.
5. Acid rains are harmful to agriculture, trees, plants etc.
6. Due to acid rains aquatic life disturbed.
7. Due to acid rains the historical monuments like Tajmahal are damaged.
Question 7.
How is Photochemical Smog formed ? What are its ill effects ?
Answer:
• When unsaturated hydrocarbons and nitrogen oxides produced from auto
mobiles, factories reacts with sunlight and forms photo chemical smog.
• This occurs in warm, dry and hot climate.
• This has high concentration of oxidising agents. Hence it is called as photo
chemical smog.
Formation :
• Fossil fuels are burnt, many pollutants are entered into troposphere.
• Out of these many pollutants two pollutants are main constituents of photo
chemical smog. These are hydrocarbons and nitric oxide.
• These pollutants interacts with sun light and following reaction takes place.
2NO(g) + O2 → 2NO2 (g) (g)
NO2 → NO(g) + O(g)

(g)
• This oxygen atoms formed in the above reaction combine with O2 to produce
ozone.
O(g) + O2 ⇌ O3
(g) (g)
NO(g) + O3 → NO2 + O2
(g) (g) (g)
• O3 is poisonous gas and both NO2 and O3 are strong oxidising agents.
• These react with unburnt hydro carbons in the polluted air to produce organic
substances like HCHO, PAN etc.
• The common components of photo chemical smog are ozone, NO, acrolein, form
aldehyde and PAN.
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Question 8.
How is Ozone layer depleted in the atmosphere and what are the harmful effects
caused by Ozone layer depletion ? [T.S. Mar. 16] [A.P. Mar. 15]
Answer:
• Ozone layer is present in stratosphere of the atmosphere.
• Ozone in the stratosphere is due to the following reactions.
• But due to industrialisation, certain chemical substances enter into stratosphere

and destroy the ozone.
• The following are the major substances that causes depletion of ozone layer.
1. CFCs (Chloro fluoro carbons (or) freons)
2. NO
3. Cl2 (Chlorine)
• CFCs are colourless, odourless, lighter, non flammable, non toxic organic
molecules which are used in refrigeratos, air conditioners, in the manufacturing of
plastic foam and for cleaning computer parts.
• These CFCs enter in the stratosphere and deplete the ozone as follows.
• Chlorine radicals (Cl*) are continuously generated and decompose O3.

• NO released by super sonic jet planes and that formed by burning fossil fuels
enters into stratosphere and decompose ozone.
• Cl2 decompose into Cl* radicals and these Cl* deplete O3 by chain reactions.
Effects of depletion of the ozone layer (ozone hole): Due to depletion of ozone more
U.V. enters into troposphere. This UV radiation leads to
1. ageing of skin
2. cataracts
3. skin burns
4. skin cancer
5. damage to fish production
6. killing many phytoplanktons
7. effect plant proteins leading to the harmful mutation of cells
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8. evaporate surface water through the stomata of the leaves.
9. decrease moisture content of the soil.
10.damage paints, fibres, by fading them faster.
11.effect on photo synthesis etc.
Question 9.
List out the industrial wastes that cause water pollution and what are the international
standards fixed for drinking water ?
Answer:
Industrial wastes from food processing plants and paper and pulp mills are oxygen –
demanding wastes. So they cause depletion of D.0 from the water.
Salts, trace of elements like Copper, Zinc, Arsenic etc., metals coming out of chromium
plating Industry pollute water. They effect the human health and aquatic animals.
In Japan, at Minimata, water was polluted with mercury released from industry.
The mercury enter the fish and the people who consumed the fish are adversely
effected.
Mining and Nuclear power plant pollute the water with radioactive substances.
International standards for drinking water
Fluoride concentration:
• The drinking water sample is tested for fluoride ion concentration. Its
deficiency causes diseases like tooth decay etc.
• The permissible level of concentration of fluoride in water is up to 1 ppm.
• Fluoride concentration above 2 ppm causes brown mottling of teeth.
• Fluoride concentration greater than 10 ppm causes harmful effects to bones
and teeth.
Lead :
• The prescribed upper limit of concentration limit of lead in drinking water is
about 50 ppm.
• Lead can damage kidney, liver, reproductive system etc.
Sulphate :
• Sulphate concentration greater than 500 ppm in drinking water causes
laxative effect.
Nitrate :
• Nitrate concentration maximum limit in drinking water is about 50 ppm.
• Excess of nitrate in drinking causes disease such as methemoglobinemia.
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Metals :
Maximum prescribed concentration of some common metals recommended in
drinking water given in the following table.
Maximum prescribed concentration of Some Metals in Drinking Water.
Question 10.
Explain in detail the strategies adopted in Green Chemistry to avoid environment
pollution.
Answer:
The ways of using the knowledge and the principles of chemistry and other
sciences to develop methods to reduce as far as possible the pollution of the
environment are known as green chemistry.
Ex : In the dry cleaning of clothes, earlier (CCl2 = CCl2) tetrachloroethane was used.
This com-pound contaminates the ground water and is a suspected carcinogen.
Therefore, using this compound is replaced by a process in which liquefied carbon
dioxide with a suitable detergent is used. This would not pollute ground water
much. Now-a-days hydrogen peroxide is used for bleaching clothes in laundries.
This gives better results and decreases the consumption of water.
Ex : Synthesis of ethanol is now commercially prepared by one step by the
oxidation of ethane in presence of catalyst.
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Question 1.
What is environmental pollution ? How many types of pollution are encountered ?
Answer:
Environmental pollution is defined as the addition of any external material like
organic, Inorganic biological, radio logical (or) any change in nature which may
harm (or) affect badly the living organism directly (or) indirectly, immediately (or)
slowly.
The types of pollution encountered are the following :
1. Air pollution
2. Water pollution
3. Soil pollution
4. Oil pollution
5. Noise pollution etc.
Question 2.
Explain the following in detail.
a) Global warming
b) Ozone depletion
c) Acid rain
d) Eutrophication.
Answer:
a) Global Warming : The Earth is heated by sunlight and some of the heat that is
absorbed by the Earth is radiated back into space. But some gases like CO2, CFC’s,
O3, NO and water vapour present in the lower atmosphere do not allow the Earth
to re-radiate the heat into space. A part of the heat so trapped in these
atmospheric gases is re-emitted to the earth’s surface. This phenomenon is called
the “Green house effect” (or) Global warming.
The gases which are responsible for Green house effect are CO2, CFC’s, O3, NO,
CH4 water vapour etc. and they are termed as Green house gases. The effect of
increase in CO2 causes global warming.
b) Effects of depletion of the ozone layer (ozone hole) : Due to depletion of ozone
more U.V. enters into troposphere. This UV radiation leads to
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1. ageing of skin
2. cataracts
3. skin burns
4. skin cancer
5. damage to fish production
6. killing many phytoplanktons
7. effect plant proteins leading to the harmful mutation of cells
8. evaporate surface water through the stomata of the leaves.
9. decrease moisture content of the soil.
10.damage paints, fibres, by fading them faster.
11.effect on photo synthesis etc.
c) Acid rain :
• Acid rains are due to oxides of N, S and C.(NO2, SO2 and CO2)
• These oxides dissolve in rain water and formed as acids. (HNO 3, H2SO4 and
H2CO3)
• These come down to earth as rain and deposited on the earth’s surface.
• Acid – rain is more in industrial areas.
Chemical equations involved:-
NO2 + NO3 → N2O5
N2O5 + H2O + 2HNO3
CO2 + H2O→ H2CO3
SO3 + H2O → H2SO4
The pH of acid rain is lessthan 5.6.
Acid rains are harmful because
1. The life of old buildings will be considerable reduced.
2. The pH of the soil changes affecting its fertility.
3. Ammonium salts formed by acid rains can be seen as atmospheric haze.
4. Ammonium salts in rain drops result in wet decomposition.
5. Acid rains are harmful to agriculture, trees, plants etc.
6. Due to acid rains aquatic life disturbed.
7. Due to acid rains the historical monuments like Tajmahal are damaged.
d) Eutrophication : Water present in ponds and lakes becomes over nutritious
when organic sub-stances from agriculture and industry are thrown into it. It can
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support the luxuriant growth of algae and thus the lakes and ponds become
marshy. This phenomenon is called Eutrophication.
Question 3.
Green Chemistry is to avoid environmental pollution. Explain.
Answer:
The ways of using the knowledge and the principles of chemistry and other
sciences to develop methods to reduce as far as possible the pollution of the
environment are known as green chemistry.
Ex : In the dry cleaning of clothes, earlier (CCl2 = CCl2) tetrachloroethane was used.
This com-pound contaminates the ground water and is a suspected carcinogen.
Therefore, using this com-pound is replaced by a process in which liquefied carbon
dioxide with a suitable detergent is used. This would not pollute ground water
much. Now-a-days hydrogen peroxide is used for bleaching clothes in laundries.
This gives better results and decreases the consumption of water.
Ex : Synthesis of ethanol is now commercially prepared by one step by the
oxidation of ethane in presence of catalyst.
Thus green chemistry is a cost effective approach and it involves reduction in

material, energy consumption and waste greneration.
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Question 1.
Write the reagents required for conversion of benzene to methyl benzene.
Answer:
Benzene reacts with methyl chloride in presence of anhydrous AlCl3 to form methyl
benzene.
This reaction is called as Friedal craft’s alkylation.
Question 2.
How is nitrobenzene prepared.
Answer:
Benzene undergoes nitration with nitration mixture (cone. HNO3 + Cone H2SO4) at less
than 60° C to form nitrobenzene.
485
Question 3.
Write the conformations of ethane.
Answer:
Question 4.
How do you prepare ethyl chloride from ethylene?
Answer:
Ethylene reacts with hydrogen chloride to form Ethyl chloride in presence of anhydrous
AlCl3 catalyst.
Question 5.
Write the IUPAC names of :
a) CH3 – CH2 – CH2 – CH = CH3
b)
c)
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Answer:
Question 6.
Write the structures of Trichloroethanoic acid, Neopentane, P – nitro benzaldehyde.
[Mar. ’13]
Answer:
Trichloro ethanoic acid – CCl3 – COOH
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Question 7.
Discuss Lassaigne’s test.
Answer:
Lassaigne’s Test: –
• A small dry sodium piece is taken in a fusion tube and heated gently till the
sodium melts.
• To this molten sodium a small amount of organic compound is added and
heated until it changes red hot.
• This red hot tube is plunged in a china dish containing water and this content is
boiled, cooled and filtered.
• The obtained filtrate is known as Lassaigne’s extract.
• This test is used to detect the elements Nitrogen, Sulphur, halogens etc.,
Detection of Nitrogen : –
The Lassaigne’s extract is made alkaline by adding few drops of dil. NaOH. to this
freshly prepared FeSO4 solution is added and warmed then few drops of FeCl3 are
added followed by acidification with Cone. HQ (or) H2SO4. A bluish green colouration
indicates the nitrogen.
Na + C + N → NaCN
2NaCN + FeSO4 → Na2SO4 + Fe (CN)2
Fe(CN)2 + 4NaCN → Na4 [Fe(CN)6]
3Na4 [Fe(CN)6] 4- 4FeCl3 → Fe4 [Fe(CN)6]3 + 12 NaCl (Prussian blue colouration)
Question 8.
Explain the principle of chromatography.
Answer:
Chromatography has been developed as a method of separation components of a
mixture generally between the stationary phase and a mobile phase.
Chromatography involves the three steps given below :
a) Adsorption and retention of a mixture of substances on the stationary phase and
separation of adsorbed substances by the mobile phase to different distances on the
stationary phase.
b) Recovery of the substances separated by a continuous flow of the mobile phase
(known as elution) and
c) Qualitative and quantitative analysis of the eluted substances.
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Question 9.
Explain why an organic liquid vaporizes at a temperature below it’s boiling point in it’s
steam distillation.
Answer:
In steam distillation, the liquid boils when the sum of vapour pressures due to the
organic liquid (P1) and that due to water (P2) becomes equal to the atmospheric
pressure (P) i.e., P = P1 + P2.
∴ P1 is lower than P the organic liquid vaporises at lower temperature than it’s boiling
point.
Question 10.
a) Crystallisation
b) Distillation
Answer:
a) Crystallisation:
• This technique is used for the purification of solid organic compounds.
• This method is based on the difference in the solubilities of the compound and
the impurities in a suitable solvent.
• The impure compound is dissolved in a solvent in which it is partially soluble at
room temperature and appreciably soluble at higher temperature.
• The solution is concentrated to get a nearly saturated solution on cooling the
solution pure compound crystallises.
• On repeating this process finally gets the very pure compound.
b) Distillation :
This method is used to separate
1. Volatile liquids from non volatile impurities and
2. The liquids having enough difference in their boiling points.
2. Liquids having different boiling points vapourises at different temperatures.
3. These vapours are cooled and the liquids formed are collected separately.
Eg : CHCl3 (b.pt. 334 K) and C6H5NH2 (b.pt. 457 K) are easily separated by
distillation technique.
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Question 1.
Complete the following reaction and name the products A, B and C. [T.S. Mar. ’15] [A.P.
Mar. 16]
Answer:
CaC2 + 2H2O → Ca(OH)2 + C2H2
Acetylene (= A)
A = C2H2 (Acetylene)
B = C6H6 (Benzene)
C = C6H5CH3 (Methyl benzene)
Question 2.
Name the products A, B and C formed in the following reactions. Give the equations for
the reactions.
Answer:
A = 1, 2- dibromo ethane
B = Acetylene
C = 1, 1, 2, 2 – tetra bromo ethane
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Question 3.
How does acetylene react with : a) Bromine b) Hydrogen ? Write the balanced
equations for the above reactions. Name the products.
Answer:
a) Addition of Br2: Acetylene reacts with bromine to form finally 1, 1, 2, 2 – tetra bromo
ethane.
b) Addition of hydrogen : Acetylene undergoes addition reaction with hydrogen in the

presence of Ni catalyst and gives ethylene and ethane.
Question 4.
What is substitution reaction ? Explain any two substitutuin reactions of benzene.
Answer:
Substitution : When an atom or a group in molecule is substituted by another atom or
group then the reaction is called electrophillic substitution reaction.
e.g. : 1) Friedal craft’s alkylation : C6H6 reacts with chlorine in the presence of AlCl3 and
form chloro benzene.
e.g. : 2) Nitration : C6H6 when heated with a mixture of cone. HNO3 and cone. H2SO4,
below 60° C, to give nitrobenzene.
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Question 5.
What is dehydrohalogenation ? Write the equation for the formation of alkene from
alkyl halide.
Answer:
Removal of hydrogen and halogen from the adjacent carbon atoms is called
dehydrohalogenation.
Alkene from alkyl halide : When ethyl chloride is heated with alcoholic KOH, ethylene is
formed due to dehydrohalogenation
Question 6.
Which type of compounds react with Ozone ? Explain with one example.
Answer:
1) Unsaturated hydrocarbons react with ozone and form addition compound called
ozonide. On hydrolysis the ozonide gives carbonyl compound. This is called ozonolysis.
2) Unsaturated hydrocarbons usually react with ozone. Ozonolysis is used for the
location of the double bond in unsaturated compounds like alkene, alkyne and
benzene.
Example : Ethylene undergoes addition reaction with ozone and form ozonide. If, on
hydrolysis, in presence of Zn dust, gives formaldehyde and H2O2.
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Question 7.
Give two examples each for position and functional isomerism. [A.P. Mar. ’16] [Mar. ’13]
Answer:
Position isomerism : This type of isomerism arises due to the difference in the position
of substituent group or in the position of multiple bond.
e.g.:
e.g.: 2. CH3 – CH2 – C = CH 1 – butyne

CH3 – C = C – CH3 2 – butyne
Functional group isomerism : This type of isomerism arises in carbon compounds
having the same molecular formula but with different functional groups.
e.g.: 1. CH3 – CH2 – CH2 – OH 1 – proparal (C3H3O)
CH3 – CH2 – O – CH3 methoxy ethane (C3H8O)
e.g.: 2. CH3 – CH2 – OH Ethanol
CH3 – O – CH3 methoxy methane
Question 8.
Explain the mechanism of halogenations of methane.
Answer:
Methane undergoes halogenation (with Cl2) to form finally tetrachloro methane. This is
a substitution reaction and takes place in presence of light.
Mechanism:
Halogenation process involves the free radical chain mechanism
This mechanism involves 3 steps
i) Initiation
ii) Propagation
iii) Termination
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i) Initiation : The reaction initiated by the cleavage of chlorine molecule in presence of
light. Cl – Cl bond is weaker than the C – C and C – H bonds
ii) Propagation : Chlorine free radical attacks the CH4 molecule and generates methyl
free radical.
The methyl radical formed attacks the 2nd molecule of chlorine to form another chlorine
free radical.
Propagation takes place in several steps as follows.
iii) Termination : The reaction terminated after sometime due to consumption of

reactants. The following are the possible chain terminating steps
Question 9.
How is ethylene prepared from ethyl alcohol ? Write the equation.
Answer:
Ethylalcohol reacts with Conc.H2SO4 at 170°C to form Ethylene.
The above reaction is dehydration reaction. (H2O removal takes place)
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Question 10.
Explain the reactions of acetylene with : a) Na in NH3 b) chromic acid. Write the
equations and name the products.
Answer:
a) With Na in NH3 : Acetylene reacts with Na in liquid NH3 to give monosodium
acetylide and disodium acetylide.
b) Chromic acid : Acetylene is oxidised to acetic acid by chromic acid.
Question 11.
Explain crystallisation and sublimation phenomenon which are used in the purification
of organic compounds.
Answer:
Crystallisation: The principle used here is that the impurities are insoluble or soluble in
the given solvent at any temperature, but the substance to be purified is sparingly
soluble at room temperature but highly soluble at highest temp. (i.e.,) almost near the
boiling temp. of the solvent.
This method is useful to purify solid compounds.
Sublimation : Some solid substances when heated pass directly into vapour state
without melting. Those vapour on cooling form directly solid with out condensing to
liquid. This phenomenon is called sublimation.
Impure compound is taken in a beaker covered with a watch glass and heated on an
electric plate. The compound sublimates and solidifies on the lower surface of the
watch glass. Impurities settle in the beaker. Pure compounds in separated by scratching
the watch glass.
This is also a purification method of solids.
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Question 12.
Describe solvent extraction method to purify a compound.
Answer:
Solvent extractiân : Suppose an organic compound ‘A’ is more soluble in an organic
solvent that in water but present in aq. solution. The aq. solution is shoken with the
organic solvent. ‘A’ goes into the organic solvent which is immiscible with water. The
organic layer is separated and distilled to remove the liquid solvent. The compound
remains with distillation flask.
Question 13.
Explain the estimation of phosphorus and sulphur in the given organic compounds.
Answer:
Estimation of phosphorus : Known mass of organic compound (‘a’ gm) is heated with
fuming HNO3 in a carius tube. ‘P’ is oxidised to H3PO4 acid. This acid is precipitated as
ammonium phosphomolybdate (‘b’ gm) by adding ammonia and ammonium
molybdate solutions.
% g of phosphorus = 100a × b1877 × 31 gm
Molecular mass of (NH4)3 PO4. 12 MO O3 (ammonium phosphomolybdate) = 1877
Estimation of sulphur : Known mass of organic compound (‘a’ gm) is heated with
sodium peroxide in a carius tube. If sulphur is present it is oxidised to sulphuric acid.
The acid is precipitated as barium sulphate (big) by adding excess of aq. BaCl2 solution.
The ppt. is filtered, washed, dried and weighed.
% g of sulphur = 100a × b×32233 g
Molecular mass of BaSO4 = 233
Question 14.
Explain addition of HBr to propene with the ionic mechanism.
Answer:
Electrophilic addition mechanism : (Ionic Mechanism)

Step (i) ; Formation of carbonium ion
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Step (ii) : Stable carbonium ion is attacked by Br⊖
Question 15.
What is the product formed when sodium propionoate is heated with soda lime, (imp)
Answer:
Sodium propionate is heated with sodalime to form ethane. This reaction is
decarboxylation reaction. NaOH + CaO is called as Decarboxylating agent.
Question 1.
Explain the classification of hydrocarbons.
Answer:
Classification of hydrocarbons : Hydrocarbons are classified as aliphatic hydrocarbons
and aromatic hydrocarbons. Aliphatic hydrocarbons are again classified as open chain
hydrocarbons and closed chain hydrocarbons i.e., cyclohydrocarbons. Both open chain
and closed chain hydrocarbons are again classified as hydrocarbons containing C – C
single bonds. > C = C < compounds, – C = C – hydrocarbons. Aromatic compounds are
497
called benzenoids as they are related to benzene.
Question 2.
Write IUPAC names of the following compounds :
a)
b) CH2 = CH – C C – CH3
c) CH3 – CH = C (CH3)2
d) CH2 – CH2 – CH = CH2

e)
Answer:
a) 1, 3 – Buta diene
b) CH2 = CH – C ≡ C – CH3
Pent, 1 -ene 3 – yne
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c) CH3 – CH = C (CH3)2
2 – Methyl 2 – Butene
d)
e)
4 – ethyl Dec 1, 5, 8 – Triene
Question 3.
Describe two methods of preparation of ethane. Give any three reactions of ethane.
Answer:
Methods of preparation of ethane:
1. Decarboxylation:
Ethane is prepared by heating sodium propionate with sodalime.
2. Kolbe’s electrolysis:
Ethane is obtained by the electrolysis of potassium acetate solution.
H2 gas evolves at cathode.

Ethane and CO2 are formed at anode.
Chemical properties of ethane :
1. Halogenation:
Ethane reacts with chlorine in the presence of sunlight. Hydrogen atoms are
substituted by halogen atoms successively. The final product is Hexachloro ethane.
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2. Nitration:
Ethane reacts with nitric acid at 400° C and gives nitro ethane.
3. Pyrolysis:
When ethane is heated in the absence of oxygen it decomposes giving ethylene and
hydrogen.
Question 4.
Write the structural formulas and IUPAC names for all possible isomers having the
number of double (or) triple bond as indicated :
a) C4H8 (one double bond)
b) C5H8 (one triple bond)
c) C5H12 (No multiple bonds).
Answer:
a) The possible Isomers of C4H8 (one double bond)
b) The possible Isomers of C5H8 (one triple bond)
c) The possible Isomers of C5H12 (No multiple bonds)
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Question 5.
Write chemical equations for combustion reaction of the following hydrocarbons.
a) Butane
b) Pentene
c) Hexyne.
Answer:
a) Combustion of Butane :
C4H10 + 132 O2 → 4CO2 + 5H2O + Energy
b) Combustion of Pentene:
C5H10 + 152 O2 → 5CO2 + 5H2O + Energy
c) Combustion of Hexyne:
C6H10 + 172 O2 → 6CO2 + 5H2O + Energy
Question 6.
Addition HBr to propene yields 2 – bromopropane, while in the presence of benzoyl
peroxide, the same reaction yields 1 – bromo propane. Explain and give mechanism.
Answer:
• Addition of HBr to propene yields 2 – Bromopropene. Here the reaction mechanism is
electrophillic. addition mechanism.
• Addition of HBr to propene in presence of benzoyl peroxide the reaction proceeds
through free radical mechanism.
Electrophilic addition mechanism : (Ionic Mechanism)

Step (i) : Formation of carbonium ion
HBr → H+ + Br⊖
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Question 7.
Describe two methods of preparation of ethylene. Give equation for the reactions
of ethylene with the following,
a) Ozone
b) Hypohalous acid
c) Cold and dil. alkKMno4
d) Heated with O2 at high pressure
Answer:
Preparation of ethylene:
1. Dehydrohalogenation of alkyl halide: When ethylbromide is heated with
alcoholic KOH, ethylene is formed.
2. Dehydration of ethanol: When ethanol is heated with cone. H2SO4 at 170°C,

ethylene is obtained.
a) With O3: Ethylene undergoes addition reaction with ozone and gives a cyclic
compound called ozonide. It undergoes hydrolysis in the presence of zinc dust to
give formaldehyde.
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b) With HOCl : Ethylene reacts with hypochlorous acid and gives ethylene
chlorohydrin.
c) Cold and dil. alk. KMnO4: Pink coloured cold and dil. alkaline KMn04 solution is
Bayer’s reagent. Ethylene decolourises Bayers reagent to give ethylene glycol. This
is test for unsaturation.
d) Polymerisation : When Ethylene is heated in the presence of 02 at a

temperature of 200° C and high pressure of 1500 – 2000 atmospheres gives
polyethene.
Question 8.
How does ethylene react with the following reagents ? Give the chemical
equations and names of the products formed in the reactions,
a) Hydrogen halide
b) Hydrogen
c) Bromine
d) Water
e) Oxygen in presence of Ag at 200° C.
Answer:
(a) Reaction with hydrogen halide : Ethylene reacts with Hydrogen halides to give
ethyl halides.
H2C = CH2 + HX → CH3 – CH2 X
e.g.: H2C – CH2 + HCl → C2H5Cl Ethyl chloride
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(b) With Hydrogen : Ethylene reacts with H2 in presence of Ni, Pt or Pd to give
ethane.
(c) With Bromine : Ethylene decolourises red coloured Br2 in CCl4 to give 1,2-
dibromo ethane.
(d) With water : Ethylene reacts with dil. H2SO4 to give ethyl alcohol.
(e)With Sulphur monochloride : Ethylene reacts with S2Cl2 to give musturd gas.
(f) With O2 at presence of Ag: Air oxidises ethylene to ethylene oxide known as
epoxide in presence of Ag catalyst at 200 – 400°C.
Question 9.
An alkene ‘A’ on ozonolysis gives a mixture of ethanal and pentan 3-one. Write the
reaction, structure of the products and alkene – A. Give the IUPAC name of alkene
– A.
Answer:
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Question 10.
An alkene ‘A1 contains three C – C, eight C – H bonds and one C = C bond. ‘A’ on
ozonolysis gives two moles of an aldehyde of molar mass 44o . Write IUPAC name
of ‘A’.
Answer:
IUPAC name of ‘A’ is 2 – Butene
Question 11.
Give two methods of preparation of acetylene. How does it react with water and
Ozone ?
Answer:
Preparation of acetylene :
1. Dehydrohalogenation : Acetylene is obtained when dibromo ethane is heated
with alcoholic KOH.
2. Acetylene is obtained by heating iodoform with silver powder.
3. Addition of water : Acetylene undergoes addition reaction with water in the

presence of mercuric sulphate and sulphuric acid. Vinyl alcohol formed in the
reaction undergoes rearrangement and gives acetaldehyde . [Mar. 06, June 04]
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4. Reaction with ozone : Acetylene reacts with ozone to form an ozonide which on
hydrolysis in presence of Zn forms glyoxal. [June 04]
Question 12.
How does acetylene react with the following reagents ? Give the corresponding
equations and name the products formed in the reactions
a) Acetic acid
b) Water
c) Hydrogen
d) Halogens
e) Hydrogen halide
f) Ammonical AgNO3 and Cl2Cl2
Answer:
(a) Reaction with Acetic acid : Acetylene on treatment with acetic acid gives vinyl
acetate in the 1st step and then gives ethylidene acetate. Hg2+ ions act as catalyst.
(b) Addition of water: Acetylene undergoes addition reaction with water in the
presence of mercuric sulphate and sulphuric acid. Vinyl alcohol formed in the
reaction undergoes rearrangement gives acetaldehyde.
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(c) Addition of hydrogen : Acetylene undergoes addition reaction with hydrogen in
the presence of Ni catalyst and gives ethylene and ethane.
(d) Addition of halogens : Acetylene undergoes addition reaction with halogens to

give 1, 1, 2, 2 tetra haloethane. Dihalo alkene is formed in the first step which then
adds on another molecule of halogen to give tetra halo ethane.
(e) With Hydrogen halide : Acetylene on addition with HCl gives Vinyl chloride and
finally 1, 1 – dichloroethane.
(f) With Ammonical AgNO3 solution : Acetylene gas is passed through ammonical
AgNO3 solution to form a white precipitate of silver acetylide. .
With Ammonical Cu2Cl2 solution : Acetylene gas is passed through Ammonical

cuprous chloride solution to give a red precipitate of cuprous acetylide.
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Question 13.
Describe any two methods of preparation of benzene with corresponding
equations. Benzene does not behave like an alkenes why ? How do we get methyl
benzene from benzene ?
Answer:
Preparation of Benzene:
1. When sodium benzoate distilled with sodalime. Benzene is formed.
2. Polymerisation of Acetylene : When Acetylene gas is passed through red hot Cu

or Fe tubes, it polymerises and gives Benzene.
Constitution of Benzene : Benzene molecule cannot be represented by a single

structure. It has the following Resonance structures.
The resonance energy of Benzene is 150.48 KJ/mole. Thus, it has more stability.
Hence does not undergo addition reactions like alkenes. Benzene is an aromatic
molecule.
Benzene to toluene (Friedal Craft’s Alkylation) :
Benzene reacts with methyl chloride in presence of AlCl3 and forms methyl
benzene (Toluene).
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Question 14.
How do we get benzene from acetylene ? Give the corresponding equation.
Explain the halogenations, alkylation, acylation, nitration and Sulphonation of
benzene.
Answer:
Preparation of Benzene from acetylene: On passing acetylene gas through red hot
iron tubes, it trimerises to give benzene.
Chemical Properties:
(1) Halogenation : Benzene reacts with chlorine in the presence of FeCl3 or AlCl3 to
give chioro-benzene.
(2) Friedel – Craft’s Alkylation : Benzene reacts with alkyl halides in the presence of
AlCl3 to give alkyl benzene.
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(3) Friedel – Craft’s Acylation : Benzene reacts with acetyl chloride in the presence
of AlCl3 to give acetophenone.
(4) Nitration : Benzene when heated with a mixture of cone. H2SO4 and cone.
HNO3 below 60°C to give Nitrobenzene.
(5) Sulphonation : With fuming H2SO4, benzene, reacts to form benzene sulphonic
acid.
Question 15.
Explain the differences between structural isomers and stereo isomers.
Answer:
Structural isomerism : When the isomerism is due to difference in the
arrangement of atoms within the molecule, without any reference to space, the
phenomenon is known as Structural isomerism. In this type of isomerism, the
isomers possess the same molecular formula, but different structural formula.
Structural isomerism is further classified into different types :
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Stereoisomerism : The stereoisomers have the same molecular and structural
formula, but differ in the arrangement of atoms or groups in space. Thus the
phenomenon exhibited by two or more compounds with the same molecular and
structural formulae, but different spatial arrangement of atoms or groups. The
spatial arrangement of atoms or groups is also referred to as configuration of the
molecule. It is further classified into three types.
Question 16.
What is the differences between conformation and configuration in open chain
molecules.
Answer:
Configurational Isomerism : (Optical and geometrical isomerism): These are the
stereo – isomers which are discrete, stable and isolable substances. They cannot
be inter-converted into one another without making and breaking of new bonds.
These isomers cannot be superimposed on each other.
These isomers are further classified as enantiomers, diastereomers and
geometrical isomers.
Conformational Isomers : These are the stereo – isomers that easily convert into
one another by the rotation around “C – C” bonds. These are in dynamic
equilibrium with one another and cannot be separated under ordinary conditions.
This type of isomerism is in alkanes such as n – butane.
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Question 17.
What do you understand about geometrical isomerism ? Explain the geometrical
isomers of 2 – butene.
Answer:
Geometrical isomerism (Cis – trans isomerism): The isomers which possess the
same structural formula but differ in spatial arrangement of the groups around the
double bond are called geometrical isomers and the phenomenon is known as
geometrical isomerism.
When the same groups lie on the same side of double bond, it is Cis – isomer,
while when the same groups lie on opposite side of double bond, the isomer is
trans.
Question 18.
Explain the method of writing E – Z configurations for geometrical isomers taking
CHCl = CFBr as your example.
Answer:
E – Z configurations for geometrical isomers : The following procedure is followed
in specifying the configurations of compounds.
i) Arrange the atoms / groups attached to each doubly bonded carbon in the order
of their atomic numbers.
ii) Choose the atom/group higher priority on each doubly bonded carbon. If the
atoms/groups of higher priority on each carbon are on the same side of the
molecule, the letter “Z” is used to denote the configuration of such isomer. When
the atoms/groups of higher priority on each carbon are on the opposite sides of
the molecule, the letter ‘E’ is prefixed before the name to indicate configuration.
Example : CHCl = CFBr
Among H and Cl, 17Cl gets more priority than 1H
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Among H and Br, 35Br gets more priority than 9F
Question 19.
If an alkene contains on carbons at double bond Cl. Br and – CH2 – CH2 – OH – CH
(CH3)2, Write the E and Z configurations of it.
Answer:
From the given data, the structural formulae of the molecule is
Question 20.
Write a note on :
a) Distillation
b) Fractional distillation
c) Distillation under reduced pressure
d) Steam distillation.
Answer:
a) Distillation : This process is useful for the purification of liquids contaminated
with nonvolatile impurities. The impure liquid is boiled in a distillation flask and
the vapours are condensed and collected in a receiver. This method can also be
used to separate liquids if only their boiling points differ by above 40°C. However,
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in the case of liquids that have boiling point difference less than 40°C fractional
distillation method is used.
b) Fractional distillation : Fractional distillation for liquids that have B.Pt difference
less than 40°C. The technique here is that vapours of liquid mixture. When pass
through long fractionating column vapours of the liquid with high B.Pt condense
and those with low B.Pt pass over through the condenser get condensed and
collected in the receiver.
Here, long tubes having different shapes and designs to fit for particular
requirements are used.
These are called fractionating columns. The liquid mixture is taken in a distillation
flask i.e., fitted with a fractionating column at its mouth. At the upper end of the
column, there is a provision to connect it to the water condenser.
c) Distillation under reduced pressure : This method is useful to purify liquids that
have very high boiling points and those which decompose at or below their boiling
points. If the external pressure is reduced the liquid boils at lower temperature
than its normal boiling point without decomposition.
d) Steam distillation : Here liquids which are immiscrible in water passes high
boiling point and steam volatile are purified. In this method steam is passed into
the hot liquid that is to be purified. The mixture of steam and vapour of volatile
organic compound come out. This is because of the sum of the vapour pressures of
steam and the liquid to be purified become equal to the atmospheric pressure.
They are passed through the condenser and condensed and finally collected in the
receiver. The water layer and the organic liquid layer are separated using a
separating funnel.
Question 21.
Write a brief note on chromatography.
a) Column chromatography
b) Thin layer chromatography
c) Partion chromatography.
Answer:
Chromatography has been developed as a method of separation components of a
mixture generally between the stationary phase and a mobile phase.
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Chromatography involves the three steps given below :
a) Adsorption and retention of a mixture of substances on the stationary phase
and separation of adsorbed substances by the mobile phase to different distances
on the stationary phase.
b) Recovery of the substances separated by a continuous flow of the mobile phase
(known as elution) and
c) Qualitative and quantitative analysis of the eluted substances.
Classification :
Two general chromatography techniques are discussed below. They are :
1. adsorption chromatography
2. partition chromatography.
Adsorption chromatography is based on the adsorption of different compounds on
an adsorbent to different degrees. Generally used adsorbents are silica gel and
alumina. A mobile phase is allowed to move over a stationary phase, the
adsorbent. The components of the mixture move to different distances over the
stationary phase.
Differential adsorption principle is used in
a) column chromatography and
b) thin layer chromatography.
Column chromatography : In the column chromatography the components of a
mixture are separated by a column of adsorbent packed in a glass tube. The
column is fitted with a stopcock at its lower end. The mixture to be adsorbed on
the adsorbent is placed at the top of the stationary phase. A suitable eluant, either
a single solvent or a mixture of solvents is allowed to flow down the column
slowly. Depending on the degree to which the compounds are adsorbed the
components are separated. The most readily absorbed substances are retained
near the top and other come down accordingly to various distances.
Thin layer chromatography (TLC): This also involves adsorption differences. Here
the adsorbent, say silica gel or alumina is coated over a glass plate of suitable size
in thin layer. The plate is called TLC plate or chromoplate. The solution of the
mixture to be separated is applied as a small spot at about 2 cm from the bottom
of the plate. The plate is then kept in a closed jar containing the eluant. As the
eluant rises up the plate, the components of the mixture move up along with the
eluant to various distances depending on their degree of adsorption.
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The relative adsorption of a component of the mixture is expressed in terms of its
RETARDATION FACTOR (Rf) value.
Rf = Distance moved by the subs tance from base line (X) Dis tance moved by the
solvent from base line (Y)
Partition chromatography : This is based on continuous differential partitioning of
components of a mixture between the Stationary phase and the mobile phase. In
paper chromatography, for example, a special paper called chromatography paper
contains water trapped in it which acts as the stationary phase. The
chromatography paper spotted with the solution of the mixture at the base is
suspended in a suitable solvent or a mixture of solvents.
This solvent acts as the mobile phase. The solvent rises up the paper by capillary
action and moves over the spot. The paper selectively retains different
components as per their differing partition in mobile and stationary phase. The
paper strip so developed is known as chromatogram. The spots of the separated
coloured compounds are detected and for colourless compounds other methods
like spraying suitable reagent, are used.
Question 22.
Explain the estimation of nitrogen of an organic compound by
a) Duma’s method
b) Kjeldahl’s method.
(or)
Describe Duma’s and Kjeldahl’s method for the estimation of Nitrogen.
Answer:
Estimation of nitrogen : There are two methods to estimate nitrogen in the given
organic compound known as
i) Duma’s method and
ii) Kjeldahed’s method.
i) Duma’s method : In this method a known weight of organic compound is heated
strongly with coarse cupric oxide. Carbon and hydrogen get oxidised to carbon
dioxide and water vapour respectively. Nitrogen if present is converted to nitrogen
gas. Even if some nitrogen is converted to its oxides. They are reduced by hot
copper gauze to nitrogen. The product gases are collected over a solution of
potassium hydroxide. CO2 is absorbed by KOH solution. Nitrogen is collected over
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potassium hydroxide solution and its volume is found out.
Suppose that ‘a’ g of organic compound gives V1 ml of N2 at room temperature TK.

If atmosphere pressure is P and aqueous tension at TK is P, then the pressure of
nitrogen gas at TK is (P – p). Let (P – p) = P1 Reduce the volume of nitrogen to
standard temperature 273 K and standard pressure 760 mm.
Volume of nitrogen at STP is v = P1 V1 T1×273760
28 g of nitrogen at STP occupies 22400 ml
? g. of nitrogen at STP occupies Vml. of nitrogen.
28 × V22400g
‘a’ g. of organic compound 28×V22400 g of nitrogen.
100 g organic compound has ? of nitrogen = 100a×28×V22400 g
ii) Kjeldah’s method : This is another method to estimate nitrogen. In this method,
the compound is heated with concentrated sulphuric acid in the presence of small
amount of CuSO4.
Nitrogen is quantitatively converted into ammonium sulphate. The contents of the
flask are transferred to another flask and heated with excess of sodium hydroxide
solution to liberate ammonia gas. Ammonia gas so liberated is passed and
absorbed in a known volume of known concentrated sulphuric acid that is
relatively more in amount than that is required to neutralise NH3 gas. Now, the
excess of acid remained after the neutralisation by NH3 is titrated against a
standard solution of alkali. From the above, the amount of H2SO4 used to
neutralise NH3 is calculated. From this, the mass of ammonia formed is calculated
and from that percentage of nitrogen is calculated.
Organic compound + H2SO4 →(NH4)2 SO4
(NH4)2SO4 + 2 NaOH → Na2SO4 + 2 H2O + 2 NH3
2 NH3 + H2SO4 → (NH4)2SO4
Calculation :
Let the mass of organic compound taken be ‘a’ g.
Let the volume of H2SO4 initially taken be ‘Vml‘ and its molarity M.
After passing the NH3 gas into the above acid, if the remaining acid is titrated with
M molar NaOH and it consumes V1 ml. of NaOH for complete neutralisation, then
from the formula
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MV1n1 (NaOH) = MV2n2 (H2SO4)
From the stoichiometric equation
2 NaOH + H2SO4 → Na2SO4 + 2H2O
n1 = number of moles of NaOH = 2; n2 = number of moles of H2SO4 = 1
MV12 = MV21 or V2 = V12 ml
Therefore, the volume of H2SO4 neutralised by NH3 is [V – V12] ml
(or) it is equal to 2 [V – V12] ml. of M molar NH3 solution.
1000 ml. of 1M NH3 solution contains 17g. of NH3 or 14g. of N2
2[V – V12] ml ml. of ‘M’ NH3 solution contains
14×M×2[V−V12]1000 g. of nitrogen.
Percentage of nitrogen = 14×M×2[V−V12]1000×100a
Question 23.
Explain inductive effect with a suitable example.
Answer:
Inductive effect: The electron donating or electron with drawing effect of a groups
an atom that is transmitted by the polarisation of electrons in σ bonds is called
inductive effect.
Illustration : Consider the molecule CH3 – CH2 – CH2 – Cl. There is a ‘σ’ covalent
bond between carbon atom and chlorine atom. The electron pair between them is
not equally shared. The more electronegative chlorine atom tends to attract the
shared pair more towards itself. Due to this, the electron density tends to be
greater nearer chlorine atom than carbon atom. It is generally represented
as But, carbon atom bonded to chlorine atom is itself
attached to other carbon atoms. Therefore, the effect can be transitted
further
“Inductive effect is defined as the polarisation of a bond caused by the polarization
of adjacent σ bond”.
(-I) effect i.e., electron with drawing effect is in the order
+NH > NO > CN > SO H > CHO > CO > COOH > COCl > COOR > CONH > F > G > Br >
3 2 3 2
I > OH > OR > NH2 > C6H5 > H.
+ I effect is – N¯R > – O¯¯¯¯ ; – Se > S > -O ; – C(CH3)3 > – CH(CH3)2 > – CH2CH3 > –
CH3.
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Question 24.
Write a note on mesomeric effect.
Answer:
Mesomeric effect:
“The electron pair displacement caused by an atom or group along a chain by a
conjugative mechanism is called the mesomeric effect of that atom or group”.
Salient features of the mesomeric effect:
i) Permanent effect operating in the ground state of the molecule.
ii) Lone pairs and n electrons are involved and operate through conjugative
mechanism of electron displacement.
iii) It influences the physical properties, reaction rates etc.
Groups which tend to increase the electron density of the rest of the molecule are
said to have (+M) effect. Such groups tend to posses lone pairs of electrons.
e.g. :
Groups that decrease the electron density of the rest of the molecule are said to
have (-M) effect. Unsaturated groups having polar character have – M effect.
. Here C = O group decreases the electron density of the remaining
molecule. It has – M effect.
+ M effect is – F > – Cl > – Br > – I;
-NR2 > OR > F;
– NH2 > – OH > – F;
– OR > – SR > SeR
– O > – OR
– M effect is = O > = NR > = CR2
= NR2< =NR ≡ N > ≡ CR
Question 25.
Describe resonance effect with one example.
Answer:
Resonance effect: It is the polarity produced in a molecule by the interactions of
two n bonds or between a π bond and a lone pair of electrons present on adjacent
atoms. This effect is transmitted through the chain.
If the transfer of electron is away from the atoms or substituent group attached to
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the conjugated system, then the molecule gets some of its positions high electron
density as in aniline and it is given (+ R). If the shift of electrons are towards the
atom or substituent group it is (- R) as in nitrobenzene.
Groups showing (+ R) are X, – OH, – OR, – COOR, – NH2, – NHR, – NR2, – NHCOR
etc.
(- R) effect are – COOH, CHO, > C = O, – CN, – NO2.
Question 26.
Explain how many types of organic reactions are possible.
Answer:
Organic reactions are mainly classified into four types known as
i) Addition rections.
ii) Substitution reactions
iii) Elimination reactions
iv) Molecular rearrangements.
i) Addition reactions : In these reactions the reagent and the substract combine
together to give a single product.
e.g.:
Depending on the reagent added in the slow rate determining step, addition
reactions are again a) Electrophilic classified addition reactions, b) Nucleophilic
addition reactions c) Free radical addition reactions.
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ii) Substitution reactions : In these reactions on atom or a group of the substrate
species is replaced by another atom or group. These are again classified as a)
Electrophilic substitution b) Nucleophilic substitution and c) Free radical
substitution reactions on the basis of the reagent involved in the rate determining
step.
e.g.-: O¯¯¯¯H(aq) + R – X → HO – R + X(aq)
iii) Elimination reactions : In these reactions two or more atoms or groups of an
organic substrate are removed to form multiple bonds.
iv) Molecular rearrangements : Here one organic species (generally less stable)
rearranges to other species (generally more stable). For example. Fries
rearrangement.
Question 27.
Write the possible conformations of ethane and explain which is more stable.
Answer:
Conformation of ethane : The conformational isomers of a given alkane are
obtained by rotation about C – C bond and they are represented by Newman
projections or line – Wedge or Sawhorse projections. Newman projections and
energy diagrams for the various conformations of ethane are given below.
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Staggered (S) occurs at Dihedral angle 60°, 180°, 300°
Rotation about the carbon – carbon bond in ethane is though very rapid, not
completely free. Two conformations of ethane known as staggered conformation
(S) and the eclipsed conformation (E) are very important though infinite number of
confomation are possible.
The C – H bonds in the staggered conformation are arranged so that each one
bisects the angle defined by two C – H bonds on adjacent carbon. In the eclipsed
conformation each C – H bond is aligned with a C – H bond on adjacent carbon.
In the staggered one the distance between the hydrogen nuclei is 2.55 A° but in
eclipsed 2.29 A°. The staggered and elipsed conformations are interconvertible by
rotation of one carbon with respect to the other around the a bond that connects
them. Different conformations of the same molecule are also called conformers or
rotamers.
Stability :
Staggered (S) form is more stable than eclipsed. Because in case of eclipsed form
electronic repulsions are high and in case of staggered form electronic repulsions
are minimum.
Question 28.
Explain aromatic electrophillic substitution reactions of benzene.
Answer:
1) Halogenation : Benzene reacts with bromine or chlorine in the presence of
Lewis acids like FeCl3, AlCl3 etc., to give corresponding halobenzene.
e.g. :
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Similarly with bromine, bromobenzene is formed.
2) Nitration : Benzene undergoes nitration when heated with a mixture of 1 : 1 (by

volume) concentrated nitric acid and concentrated sulphuric acid (nitration
mixture) at a temperature below 60° C.
3) Benzene reacts with fuming sulphuric acid (oleum) and gives benzene sulphonic
acid.
4) Friedel – Craft’s alkylation and acylation : Benzene reacts with alkyl halides and
acylh in the presence of Lewis acids (AlCl3, FeCl3) and gives alkyl benzenes and acyl
benzenes.
Benzene reacts with acetyl chloride in the presence of anhydrous aluminium,
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chloride and acetophenone.
General Mechanisms : Electrophilic substitution reaction (SE) proceeds in two steps

as
I. Generation of electrophile
II. a) Formation of carbocation intermediate
b) Removal of proton from carbocation intermediate.
I. Generation of electrophile E+: In the reactions halogenation, alkylation and

acylatio benzene, anhydrous AlCl3, the Lewis acid produces electrophile X+ say Cl+,
R+ and RCO+ by reacting the reagent chlorine, alkyl halide and acylhalide
respectively.
II. a) Formation of carbocation : Electrophile generated above attacks one of the

benz carbons to change it to sp3 hybridised. The carbocation (Arrhenium ion) is
stabilised through resonal.
Sigma complex loses aromatic character due to delocalisation of electrons

stopping at sp3 carb
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b) Losing of proton : To regain aromatic character the C+ loses one proton to
sp3 carbon on attack
of (AlCl4)– in case of halogenation, alkylation and acylation and HSO4– in case of
nitration.
Question 29.
Explain electrophilic addition reactions of ethylene with mechanism.
Answer:
Electrophilic addition reactions of ethylene :
1. Addition of Hydrogen : Ethylene react with hydrozen in the presence of Pt, Pd or
Ni catalyst to form ethane.
2. Addition of halogens : Halogens (Cl2 or Br2) react with ethylene in the presence
of an inert solvent like CCl4 to form dihalo derivative
Mechanism :
3. Addition of hydrogen halides : Ethylene reacts with HBr to form ethyl bromide
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4. Addition of water : In presence of few drops of cone. H2SO4, water adds to
ethylene to form alcohol.
Question 30.
With the help of mechanism explain free radical halogenations of alkanes.
Answer:
Methane undergoes halogenation (with Cl2) to form finally tetrachloro methane.
This is a substitution reaction and takes place in presence of light.
Mechanism :
• Halogenation process involves the free radical chain mechanism
• This mechanism involves 3 steps
i) Initiation
ii) Propagation
iii) Termination
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i) Initiation : The reaction initiated by the cleavage of chlorine molecule in
presence of light. Cl – Cl bond is weaker than the C – C and C – H bonds
ii) Propagation : Chlorine free radical attacks the CH4 molecule and generates
methyl free radical.
The methyl radical formed attacks the 2nd molecule of chlorine to form another
chlorine free radical.
iii) Termination : The reaction terminated after sometime due to consumption of

reactants.
The following are the possible chain terminating steps
Question 31.
Discuss Markownikov’s rule and Kharash effect.
Answer:
Statement of Markownikoff’s rule : The rule states that when an unsymmetrical
reagent adds to a double bond, the positive part of the adding reagent attaches
itself to a carbon of the double bond so as to yield the more stable carbocation as
an intermediate.
Mechanism : A pair of electrons from the double bond attacks the electrophilic HX
to produce an achiral trigonal planar carbocation intermediate. Thehalideion X
then adds to either face of the positively charged carbon forming alkyl halide
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product.
Anti Mark Kownikoffs addition or peroxide effect or Kharasch effect : In the

presence of peroxide (R – O – O – R) the addition of HBr to unsymmetrical alkene
like propene takes place against Markowni- koff’s rule. As per Anti Markownkoff’s
rule, the addition of HBr to an unsymmetrical alkene like propene takes place in
such a way that the hydrogen atom becomes attached to the carbon atom with
the fewer hydrogen atoms.
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The 2° free radical is more stable than 1°. Therefore. 1 – bromopropane is major
product.
Question 32.
How would you convert benzene in to following compounds ?
a) Chioro benzene
b) Toluene
c) p – nitrotoluene.
Answer:
a) Benzene reacts with chlorine inpresence of FeCl3 to form chlorobenzene.
b) Benzene reacts with methyl chloride in presence of AlCl3 to form toluene

(Friedal Craft’s alkylation)
c) From benzene p – nitro Toluene is obtained as follows.
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Question 33.
Why is wurtz reaction not preferred for the preparation of alkanes containing odd
number of carbon atoms ? Illustrate with one example.
Answer:
Wurtz reaction Alkyl halides reacts with sodium metal in presence of dry ether to
form higher alkanes.
R – X + 2Na + R – X R – R + 2NaX
• Wurtz reaction is preferred to prepare even no.of Carbons containing alkanes
but not for odd no.of Carbons containing Alkanes.
• For getting odd no.of Carbons containing alkanes we have to consider two
different alkyl halides.
The products obtained are in mixture form, So the percentage of the desired
hydrocarbon is less, i.e., yield of the desired product is low.
Methane can not be prepared by this reaction.
Question 34.
Write the equations involved in the detection of Nitrogen, Halogens and sulphur in
organic compounds.
Answer:
Lassaigne’s Test : –
• A small dry sodium piece is taken in a fusion tube and heated gently till the
sodium melts.
• To this molten sodium a small amount of organic compound is added and
heated until it changes red hot.
• This red hot tube is plunged in a china dish containing water and this content
is boiled, cooled and filtered.
• The obtained filtrate is known as Lassaigne’s extract.
• This test is used to detect the elements Nitrogen, Sulphur, halogens etc..
Detection of Nitrogen : –
The Lassaigne’s extract is made alkaline by adding few drops of dol. NaOH. to this
freshly prepared FeSO4 solution is added and warmed then few drops of FeCl3 are
added followed by acidification with Cone. HCl (or) H2SO4. A bluish green
colouration indicates the nitrogen.
Na + C + N →NaCN
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2NaCN + FeSO4 → Na2SO4 + Fe (CN)2
Fe(CN)2 + 4NaCN → Na4 [Fe(CN)6]
3Na4 [Fe(CN)6] + 4FeCl3 → Fe4 [Fe(CN)6]3 + 12 NaCl (Prussian blue colouration)
b) Detection of Halogens : The sodium fusion extract is acidified with HNO3 and is
treated with AgNO3 solution.
Ag + X → AgX
Θ
• White PPt indicates Cl ion
Θ
• Pale yellow PPt indicates Br ion
Θ
• Yellow PPt indicates I ion
c) Detection of Sulphur : To the sodium extract freshly prepared sodium
nitroprusside solution. A deep violet colouration takes place.
S-2 + [Fe(CN)5NO]2+ → [Fe(CN)5 NOS]4- Violet
Question 35.
Explain how carbon and Hydrogen are quantitatively determined in an organic
compound.
Answer:
Estimation of carbon and hydrogen : Both the elements are estimated in the same
experiment simultaneously. A known weight of the organic substance is taken and
completely burnt in excess of air and copper (II) oxide carbon changes to CO2 and
Hydrogen to H2O.
CxHy + (x + y4)O2 → x CO2 + (y2) H2O
CO2 and H2O SO obtained are passed through already weighed ‘U‘ – tubes
containing anhy, CaCl2 and caustic potash respectively. The increased weigh is of
these two tubes give the weigh of H2O formed and weight of CO2 formed.
Suppose ‘a’ g of organic compound on combustion gives ‘b’ grams of water vapour
and. ‘C g of CO2. Then
% g of Carbon = 1244 × 100a × C g
% g of Hydrogen = 218 × 100a × b g
531
Question 36.
How do you determine sulphur, phosphorous and Oxygen are determined
quantitatively in an organic compound ?
Answer:
Estimation of phosphorus : Known mass of organic compound (‘a’ gm) is heated
with fuming HNO3 in a carius tube. ‘P’ is oxidised to H3PO4 acid. This acid is
precipitated as ammonium phosphomolybdate (‘b’ gm) by adding ammonia and
ammonium molybdate solutions.
% g of phosphorus = 100a × b1877 × 31 gm
Molecular mass of (NH4)3 PO4. 12 MO O3 (ammonium phosphomoly bdate) = 1877
Estimation of sulphur : Known mass of organic compound (‘a’ gm) is heated with
sodium peroxide in a carius tube. If sulphur is present it is oxidised to sulphuric
acid. The acid is precipitated as barium sulphate (big) by adding excess of aq.
BaCl2 solution. The ppt. is filtered, washed, dried and weighed.
%g of sulphur = 100a × b×32233 × g
Molecular mass of BaSO4 = 233
Estimation of Oxygen : The percentage of oxygen in an organic compound is
usually found by difference between the total percentage composition (100) and
the sum of the percentages of all other elements. However, oxygen can also be
estimated directly as follows :
A definite mass of an organic compound is decomposed by heating in a stream of
nitrogen gas. The mixture of gaseous products containing oxygen is passed over
red-hot coke when all the oxygen is converted to carbon monoxide. This mixture is
passed through warm iodine pentoxide (I2O5) when carbon monoxide is oxidised to
carbon dioxide producing iodine.
On making the amount of CO produced in equation (A) equal to the amount of CO

used in equation (B) by multiplying the equations (A) and (B) by 5 and 2
respectively; we find that each mole of oxygen liberated from the compound will
produce two moles of carbondioxide.
Thus 88 g carbon dioxide is obtained if 32 g oxygen is liberated.
Let the mass of organic compound taken be mg
532
Mass of carbon dioxide produced be m1 g
∴ m1 g carbon dioxide is obtained from 32×m188 g O2
∴ Percentage of oxygen = 32×m1×10088×m%
Question 37.
Explain Carius method for the determination of Halogens quantitatively in an
organic compound.
Answer:
Estimation of halogens : (Carius method) Known mass of organic compound is
heated with framing nitric acid in the presence of AgNO3 in a hard glass tube called
carius tube. Carbon and hydrogen of the compound are oxidised to CO2 and H2O.
Halogens forms silver halide. So obtained silver halide (Agx) is filtered, washed,
dried and weighed.
% g of halogen = 100×b× atomic mass of ‘ x ‘ a× molecular mass of Agx
Where, a = mass of organic compound, b = mass of Agx formed
x = halogen atom.
Question 38.
What is carcinogenicity ? Explain with two examples.
Answer:
Benzene and several polynuclear hydrocarbons like 1, 3 – benzanthracene, 3 –
methyl cholanthrene, 1, 2- benzpyrene etc., are toxic and said to carcinogenic
(cancer producing).
Most of these are formed due to incomplete combustion of tobacco, coal,
petroleum etc.
They undergo various chemical changes in human body and finally damage DNAto
cause cancer.
533
Solved Problems
Question 1.
How many a and it bonds are present in each of the following molecules?
(a) HC ≡ CCH = CHCH3
(b) CH2 = C = CHCH3
Solution:
(a) σC-C : 4; σC-H : 6; πC=C: 1 ; π C ≡ C : 2
(b) σC-C : 3; σC-H : 6; πC=C : 2.
Question 2.
What is the type of hybridisation of each carbon in the following compounds?
(a) CH3Cl
(b) (CH3)2CO
(c) CH3CN,
(d) HCONH2
(e) CH3CH = CHCN
Solution:
(a) sp3,
(b) sp3, sp2,
(c) sp3, sp,
(d) sp2,
(e) sp3, sp2, sp2, sp
Question 3.
Write the state of hybridisation of carbon in the following compounds and shapes
of each of the molecules.
(a)H2C = O,
(b) CH3F,
(c) HC ≡ N.
Solution:
(a) sp2 hybridised carbon, trigonal planar;
(b) sp3 hybridised carbon, tetrahedral;
(c) sp hvbridised carbon, linear.
534
Question 4.
Expand each of the following condensed formulas into their complete structural
formulas.
(a)CH3CH2COCH2CH3
(b) CH3CH = CH(CH2)3CH3
Solution:
Question 5.
For each of the following compounds, write a condensed formula and also their
bond – line formula.
(a) HOCH3CH2CH2CH(CH3)CH(CH3)CH3
(b)
Solution:
Condensed formula:
(a) HO(CH2)3CH(CH3)CH(CH3)2
(b) HOCH(CN)2
Bond-line formula :
535
Question 6.
Expand each of the following bond-line formulas to show all the atoms including
carbon and hydrogen.
Solution:
536
Question 7.
Structures and IUPAC names of some hydrocarbons are given below. Explain why
the names given in the parentheses are incorrect.
Solution:
(a) Lowest locant number, 2, 5, 6 is lower than 3, 5, 7,
(b) substituents are in equivalent position; lower number is given to the one that
comes first in the name according to alphabetical order.
Question 8.
Write the IUPAC names of the compounds i-iv from their given structures.
Solution:
• The functional group present is an alcohol (OH). Hence the suffix is ‘-01’.
• The longest chain containing – OH has eight carbon atoms. Hence the
corresponding saturated hydrocarbon is octane.
The – OH is on carbon atom 3. In addition, a methyl group is attached at 6th
carbon. Hence, the systematic name of this compound is 6-Methyloctan-3-ol.
i)
Solution:
537
The functional group present is ketone (>C = 0), hence suffix ‘-one’. Presence of
two keto groups is indicated by ‘di’, hence suffix becomes ‘dione’. The two keto
groups are at carbons 2 and 4. The longest chain contains 6 carbon atoms, hence,
parent hydrocarbon is hexane. Thus, the systematic name is Hexane – 2, 4 – dione.
ii)
Solution:
Here, two functional groups namely ketone and carboxylic acid are present. The
principal functional group is the cat ooxyuc acid group; hence the parent chain will
be suffixed with ‘oic’ acid. Numbering of the chain starts from carbon of – COOH
functional group. The keto group in the chain at carbon 5 is indicated by ‘oxo’. The
longest chain including the principal functional group has 6 carbon- atoms; hence
the parent hydrocarbon is hexane. The compound is, therefore, named as 5 Oxo-
hexanoic acid.
iii)
Solution:
The two C=C functional groups are present at carbon atoms 1 and 3, while the C =
C functional group is present at carbon 5. These groups are indicated by suffixes
‘diene’ and ‘yne’ respectively. The longest chain containing the functional groups
has 6 carbon atoms; hence the parent hydrocarbon is hexane. The name of
compound, therefore, is Hexa-1, 3-dien-5-yne.
Question 9.
Derive the structure of
(i) 2-Chlorohex- ane,
(ii) Pent-4-en-2-ol,
(iii) 3- Nitro-cydohexerte,
(iv) Cyclohex-2-en-l-ol,
538
(v) 6-Hydroxy-heptanal.
Solution:
(i) ‘hexane’ indicates the presence of 6 carbon atoms in the chain The functional
group chloro is present at carbon 2. Hence, the structure of the compound is
CH3CH2CH2CH2CH(Cl)CH3.
(ii) ‘pent’ indicates that parent hydrocarbon contains 5 carbon atoms in the chain,
‘en’ and ‘ol’ correspond to the functional groups C=C and -OH at carbon atoms 4
and 2 respectively. Thus, the structure is CH2 = CHCH2CH (OH)CH3.
(iii) Six membered ring containing a carbon- carbon double bond is implied by
cyclo-hexene, which is numbered as shown in (I). The prefix 3-nitro means that a
nitro group is present on C-3. Thus, complete structural formula of the compound
is (II). Double bond is suffixed functional group whereas -NO2 is prefixed functional
group therefore double bond gets preference over -NO2 group:
(iv) ‘1 -0l’ means that a -OH group is present at C-1. OH is suffixed functional,
group and gets preference over C = C bond. Thus the structure is as shown in (II) :
(v) ‘heptanal’ indicates the compound to be an aldehyde containing 7 carbon

atoms in the parent chain. The ‘6-hydroxy’ indicates that -OH group is present at
carbon 6. Thus, the structural formula of the compound is :
CH3CH(OH)CH2CH2CH2CH2CHO. Carbon atom of – CHO group is included while
numbering the carbon chain.
539
Question 10.
Write the structural formula of :
(a) o-Ethylanisole
(b)p-Nitroaniline,
(c) 2,3 – Dibromo -1 – phenylpentane,
(d) 4-Ethyl – 1 – fluoro-2-nitrobenzene.
Solution:
Question 11.
Using curved-arrow notation, show the formation of reactive intermediates when
the following covalent bonds undergo heterolytic cleavage.
(a) CH3 – SCH3,
(b) CH3 – CN,
(c) CH3 – Cu
Solution:
540
Question 12.
Giving justification, categorise the fol-lowing molecules/ions as nucleophile or
electrophile :
HS–, BF3, C2H5O–, (CH3)3 N :,
Solution:
Nucleophiles: HS–, C2H5O–, (CH3)3 N:, H2N– These species have unshared pair of
electrons, which can be donated and shared with an electrophile.
Electrophiles:
Reactive sites have only six valence electrons; can accept electron pair from a
nucleophile.
Question 13.
Identify electrophilic centre in the fol-lowing: CH3CH = O, CH3CN, CH3I.
Solution:
Among , the starred carbon atoms are electrophilic
centers as they will have partial positive charge due to polarity of the bond.
Question 14.
Which bond is more polar in the following pairs of molecules:
(a) H3C – H, H3C – Br
(b) H3C – NH2, H3C – OH
(c) H3C – OH, H3C – SH
Solution:
(a) C – Br, since Br is more electronegative than H, (b) C – O, (c) C – O
Question 15.
In which C – C bond of CH3CH2CH2Br, the inductive effect is expected to be the
least ?
Solution:
Magnitude of inductive effect diminishes as the number of intervening bonds
increases. Hence, the effect is least in the bond between . carbon-3 and hydrogen.
541
Question 16.
Write resonance structures of CH3COO– and show the movement of electrons by
curved arrows.
Solution:
First, write the structure and put unshared pairs of valence electrons on
appropriate atoms. Then draw the arrows one at a time moving the electrons to
get the other structures.
Question 17.
Write resonance structures of CH2 = CH – CHO. Indicate relative stability of the
contributing structures.
Solution:
[I: Most stable, more number of covalent
bonds, each carbon and oxygen atom has an octet and no separation of opposite
charge II: negative charge on more electronegative atom and positive charge on
more electropositive atom; III: does not contribute as oxygen has positive charge
and carbon has negative charge, hence least stable].
542
Question 18.
Explain why the following two structures, I and 11 cannot be the major
contributors to the real structure of CH3COOCH3.
Solution:
The two structures are less important contributors as they involve charge
separation. Additionally, structure I contains a carbon atom with an incomplete
octet.
Question 19.
Explain why is more stable than and is the least stable cation.
Solution:
HyperconjugatiOn interaction in is greater than in as the has
nine C – H bonds. In , vacant p orbital is perpendicular to the plane in which C –
H bonds lie; hence cannot overlap with it. Thus, laoks hyper conjugative
stability.
Question 20.
On complete combustion, 0.246 g of an organic compound gave 0.1989/ of carbon
dioxide and 0.10149 of water. Determine the percentage composition of carbon
and hydrogen in the compound.
Solution:
Percentage of carbon = 12×0.198×10044×0.246
= 21 .95%
Percentage of hydrogen = 2×0.1014×10018×0.246
= 4.58%
543
Question 21.
In Dumas’ method for estimation of nitrogen, 0.3g of an organic compound gave
5OmL of nitrogen collected at 300K temperature and 715mm pressure. Calculate
the percentage composition of nitrogen in the compound. (Aqueous tension at
300K = 15 mm)
Solution:
Volume of nitrogen collected at 300K and 715mm pressure is 50 mL
Actual pressure = 715 – 15 = 700 mm
Volume of nitrogen at STP = 273×700×50300×760
= 41.9 ML
22,400 ml of N2 at STP weighs = 28 g
41.9 mL of nitrogen weighs = 28×41.922400 g
Percentage of nitrogen = 28×41.9×10022400×0.3
= 17.46%
Question 22.
During estimation of nitrogen present in an organic compound by Kjeldahl’s
method, the ammonia evolved from 0.5 g of the compound in Kjeldahl’s
estimation of nitrogen, neutralized 10 mL of 1 M H2SO4. Find out the percentage of
nitrogen in the compound?
Solution:
1 M of 10 mL H2SO4 = 1 M of 20 mL NH3 1000 mL of 1 M ammonia contains 14 g
nitrogen
20 ml of 1 M ammonia contains 14×201000 g nitrogen
Percentage of nitrogen = 14×20×1001000×0.5
= 56.0%
Question 23.
In Canus method of estimation of halogen1 0.15 g of an organic compound gave
0.12 g of AgBr. Find out the percentage of bromine in the compound.
Solution:
Molar mass of AgBr = 108 + 80
= 188 g mol-1
188 g AgBr contains 80 g bromine
544
0.12 g AgBr contains 80×0.12188 g bromine
Percentage of bromine = 80×0.12×100188×0.15
= 34.04%
Question 24.
In sulphur estimation, 0.157 g of an organic compound gave 0.4813 g of barium
sulphate. What is the percentage of sulphur in the compound ?
Solution:
Molecular mass of BaSO4 = 137 + 32 + 64
= 233g
233 g BaSO4 contains 32 g sulphur
0.4813 g BaSO4 contains 32×0.4813233 g sulphur
Percentage of sulphur = 32×0.4813×100233×0.157
= 42.10%
Question 25.
Write structures of different chain isomers of alkanes corresponding to the
molecular formula C6H14. Also write their IUPAC names.
Solution:
545
Question 26.
Write structures of different isomeric alkyl groups corresponding to the molecular
formula C5H11. Write IUPAC names of alcohols obtained by attachment of -OH
groups at different carbons of the chain.
Solution:
546
Question 27.
Write IUPAC names of the following compounds :
1. (CH3)3 C CH2C(CH3)3
2. (CH3)2 C(C2H5)2
3. tetra – tert-butylmethane
Solution:
1. 2, 2, 4, 4-Tetramethylpentane
2. 3 3-Dimethylpentane
3. 3, 3-Di-tert-butyl -2, 2, 4, 4 – tetramethylpentane
Question 28.
Write structural formulas of the following compounds:
(i) 3, 4, 4, 5-Tetramethylheptane
(ii) 2, 5-Dimethyhexane
Solution:
Question 29.
Write structures for each of the following compounds. Why are the given names
incorrect? Write correct IUPAC names.
(i) 2-Ethylpentane
(ii) 5-Ethyl – 3-methylheptane
Solution:
Longest chain is of six carbon atoms and not that of five. Hence, correct name is 3-
Methyl- hexane.
547
Numbering is to be started from the end which gives lower number to ethyl group.
Hence, correct name is 3-ethyl-5-methyl-heptane.
Question 30.
Sodium salt of which acid will be needed for the preparation of propane? Write
chemical equation for the reaction.
Solution:
Butanoic acid,
Question 31.
Write IUPAC names of the following compounds:
Solution:
(i) 2, 8 – Dimethyl – 3, 6 – decadiene;
(ii) 1, 3, 5, 7 Octatetraene;
(iii) 2 – n – Propylpent – 1 – ene;
(iv) 4 – Ethyl – 2, 6 – dimethyl – dec – 4 – ene;
548
Question 32.
Calculate number of sigma (σ) and pi (π) bonds in the above structures (i-iv).
Solution:
σ bonds : 33, π bonds : 2
σ bonds: 17, π bonds:4
σ bonds : 23, π bond : 1
σ bonds: 41, π bond : 1
Question 33.
Write structures and IUPAC names of different structural isomers of alkenes
corresponding to C2H10.
Solution:
549
Question 34.
Draw cis and trans isomers of the following compounds. Also write their IUPAC
names:
(i) CHCl = CHCl
(ii) C2H5CCH3 = CCH3C2H5
Solution:
Question 35.
Which of the following compounds will show cis-trans isomerism ?
(i) (CH3)2C = CH – C2H5
(ii) CH2 = CBr2
(iii) C6H5CH = CH – CH3
(iv) CH3CH = CCl CH3
Solution:
(iii) and (iv). In structures (i) and (ii), two identical groups are attached to one of
the doubly bonded carbon atom.
550
Question 36.
Write IUPAC names of the products obtained by addition reactions of HBr to hex-
1-ene
(i) in the absence of peroxide and
(ii) in the presence of peroxide.
Solution:
Question 37.
Write structures of different isomers corresponding to the 5th member of alkyne
series. Also write IUPAC names of all the isomers. What type of isomerism is
exhibited by different pairs of isomers ?
Solution:
5th member of alkyne has the molecular formula C6H10. The possible isomers are :
551
Position and chain isomerism shown by different pairs.
Question 38.
How will you convert ethanoci acid into benzene?
Solution:
552
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553
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COLLEGE CODE: CEVP

CHAITANYA ENGINEERING COLLEGE

APPROVED BY AFFILIATED ACCREDITED BY

STUDY MATERIAL COUNSELLING CODE:

2 CLASSIFICATION OF ELEMENTS AND PERIODICITYN IN 53 – 95

4 STATE OF MATTER : GASES AND LIQUIDS 136 – 182

5 STOICHIOMETRY 183 – 238

6 THERMODYNAMICS 239 – 284

7 CHEMICAL EQUILIBRIUM AND ACIDS BASES 285 – 376

8 HYDROGEN AND ITS COMPOUNDS 377 – 395

9 THE S – BLOCK ELEMNETS 396 – 425

11 THE P – BLOCK ELEMENTS (GROUP – 14 ) 443 – 467

12 ENVIRONMENTAL CHEMISTRY 468 – 484

14 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND 485 - 552

Additional Answer Questions

1. the number of protons and

⇒ n2 = 3 (i.e.,) original energy level of electron is 3.

• In case of absorption spectrum nf > ni → energy is absorbed (+ve) energy is

3) Magnetic quantum number: It was proposed by Lande. It shows the orientation of

In terms of wave numbers

∴ The increasing order of energy

2) Newland’s law of octaves : According to Newlands, the elements arranged in the

• Nitrogen has electronic configuration 1s2 2s2 2p3

has more negative electron gain enthalpy than that of

has more negative electron gain enthalpy than that of

• Electronic configuration is 1s2 2s2 2p3 (3 unpaired 2p electrons)

where v = frequency, Z = atomic number a, b = constants

• Due to presence of incompletely filled p – orbitals in Boron, its IE value is less.

How do you explain this deviation from the general trend ?

Illustration : Following table shows a comparison of the properties predicted by’Mendeleeff’

→ In 3rd period from Na to Cl atomic radius decreases.

Electronic configuration — 1s2 2s2 2p6 3s2 3p4

Electronic configuration of s-2 is 1s2 2s2 2p6 3s2 3p6

C2H4 contains 5 – sigma bonds and 1-pi bond.

b) Change in hybridised states N and B during [H3N → BF3] formation :

has four electrons.

5. Isomerism : Ionic bond is non-directional.

• Central atoms possessing more than 8 electrons which istermed as expanded

1. The electronic configuration of ‘B’ in the ground state is

In boron trichloride there are three ‘σ’ bonds.

Sigma bond (σ)

• In ethylene two carbons undergo sp2 hybridisation.

Formation of triple bond between the carbon atoms of C2H2 : –

• In acetylene two carbons undergoes sp hybridisation.

2) Phosphorus undergoes sp3d – hybridisation by intermixing of one s-orbital [3s], three

3) Hydronium ion (H3O+)

Properties of co-ordinate covalent bond :

Carbon – (1) – undergoes sp2 hyrbidisation

Carbon (1) and (2) both undergo ‘sp3‘ hybridisation.

2) Intramolecular hydrogen bond:

Abnormal behaviour due to hydrogen bond:

• Bond order = 6−42 = 22 = 1

→ Bond Order = 10−42 = 62 = 3

In ClF3 No.of bond pairs present are ‘3’

Long Answer Questions

2) Cl (Z = 17). The electronic configuration is = 1s2 2s2 2p6 3s2 3p5

In the formation of sodium chloride the 3s electron of sodium atom is transferred to

The electronic configuration of Chlorine atom is It has one half

The electronic configuration of oxygen atom is It has two half filled

2. On excitation the configuration is Now there are three half filled

1. Be atom has electronic configuration.

sequence is valid for oxygen and other heavier elements.

This sequence is valid for lighter elements like B.CandN.

Hence methane gas diffuses 2 times faster than SO2.