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Chemistry 5 Chapters Active Site

The document outlines the structure of the atom, detailing fundamental particles such as electrons, protons, and neutrons, along with their properties and discoveries. It discusses the limitations of Dalton's atomic theory and presents classical models of the atom, including Thomson's and Rutherford's models, highlighting their observations and conclusions. Additionally, it explains concepts like atomic number, mass number, isotopes, isobars, and isotones.

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0% found this document useful (0 votes)
187 views359 pages

Chemistry 5 Chapters Active Site

The document outlines the structure of the atom, detailing fundamental particles such as electrons, protons, and neutrons, along with their properties and discoveries. It discusses the limitations of Dalton's atomic theory and presents classical models of the atom, including Thomson's and Rutherford's models, highlighting their observations and conclusions. Additionally, it explains concepts like atomic number, mass number, isotopes, isobars, and isotones.

Uploaded by

Rahul verma
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 359

STRUCTURE OF

ATOM
THEORY

NCERT SOLUTIONS

NCERT EXEMPLAR, WORK


SHEETS

FIND ALL YOUR QUESTIONS HERE, BEFORE GETTING THEM

IN YOUR EXAM ……...


STRUCTURE OF ATOM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

STRUCTURE OF ATOM
John Dalton coined the term atom. The atom is the fundamental particle of matter and
considered to be indivisible and indestructible.
In fact, the atom as the whole is electrically neutral as
number of protons in it is equal to number of electrons.

How small is an atom?


Atoms are very small – they are about 0.00000001 cm wide.
Think about the thickness of a crisp. The number of atoms
you would need to stack up to make the thickness of a crisp, is
approximately the same number of crisps you would need to
stack up to make the height of Mount Everest!
That’s roughly 7 million crisps!
Electron, proton, neutron are the main fundamental particles of an atom.

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STRUCTURE OF ATOM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

Limitations of Dalton’s Theory


• It fails to explain why atoms of different kinds should differ in mass and valency etc.
• The discovery of isotopes and isobars showed that atoms of same elements may have
different atomic masses (isotopes) and atoms of different kinds may have same atomic
masses (isobars).
• The discovery of various sub-aomic particles like X-rays, electrons, protons etc. during
late 19th century lead to the idea that the atom was no longer an indivisible and smallest
particle of the matter.

DISCOVERY OF FUNDAMENTAL PARTICLES


The atom consists of several sub-atomic particles like electron, proton, neutron, positron,
neutrino etc. Out of these particles, the electron, proton and the neutron are called
fundamental subatomic particles.

Discovery of electron – study of Cathode rays:


J.J. Thomson observed that, when a high voltage is applied between the electrodes fitted
in discharge tube, at a very low pressure, some invisible radiations are emitted from the
cathode. At this stage wall of the discharge tube near cathode starts glowing.

Glowing is due to the bombardment of glass wall by the cathode rays. It may be noted that
when the gas pressure in the tube is 1 atm, no electric current flows through the tube. This
is because the gases are poor conductor of electricity.
Origin of Cathode rays:
Cathode rays are first produced in cathode due to bombardment of the gas molecules by the
high-speed electrons emitted first from the cathode.

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Properties of Cathode rays


i. They travel in straight lines with high speed.
Because they cast the shadow of an object on the
ZnS screen placed in its path.

ii. They are made up of material particles having both


mass and velocity. Because, they rotate a light
paddle wheel placed in its path.

iii. They carry negative charge, the negatively charged


material particles constituting the cathode rays are called
electrons.
Cathode rays get deflected when they placed in an
electric field & magnetic field. Direction of deflection
shows that they are negatively charged.

iv. They produce heating effect.

v. They cause ionization of the gas through which they pass.

vi. They produce X-rays when they strike against the surface

of hard metals like tungsten, molybdenum etc.

vii. They produce green fluorescence on the glass walls of the discharge tube exp: ZnS.

viii. They affect the photographic plates.

ix. They possess penetrating effect (i.e., they can easily pass-through thin foils of metals).

x. The nature of the cathode rays does not depend upon the nature of the gas, taken in

the discharge tube and the nature of cathode material.

xi. For each cathode rays, the ratio of charge (e) to mass (m) is constant

Discovery of proton – study of Anode rays:


Goldstein discovered the presence of positive rays. He performed discharge tube
experiment in which he took perforated cathode and a gas at low pressure was kept inside a
discharge tube.
On applying high voltage between electrodes, new rays were coming from the side of anode
and passing through the hole in the cathode gives fluorescence on the opposite glass wall
coated with zinc sulphide.
These rays were called anode rays or canal rays or positive rays.

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Origin of anode or positive rays:


In the discharge tube the atoms of gas lose negatively charged electrons. These atoms,
thus, acquire a positive charge. The positively charged particle produced from hydrogen gas
was called the proton.
H → H+(proton) + e-

Properties of Anode rays:


i) They travel in straight lines. However, their speed is much less than that of the
cathode rays.
ii) They are made up of material particles.
iii) They are positively charged, hence they called as canal rays or anode rays.’
iv) The nature of anode rays depends on the gas taken in the discharge tube.
v) For different gases taken in discharge tube the charge to mass ratio (e/m) of the
positive particles constituting the positive rays is different.

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STRUCTURE OF ATOM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

Fundamental particles:
1) Electron: Electron is a universal constituent discovered by the J.J. Thomson.
 Charge: It was determined by Mullikan by oil drop experiment as -1.602x10-19coulombs
or 4.803x10-10 e.s.u.
 Mass:9.11x10-28g (nearly equal to 1/1837th of mass of hydrogen atom).
 Specific charge:e/m ratio is called specific charge & is equal to 1.76x108 coulombs/gm.
 Mass of one mole of electrons: It is 0.55 mg.
 Charge on one mole of electron is 96500 coulombs or 1 faraday.
 Density: 2.17x1017 g/cc.

2. Proton: (+1p0 or 1H1)


 It was discovered by Goldstein.
 Charge:It carries positive charge i.e.1.602 x 10-19coulombs or 4.803x10-10 esu.
 Mass:1.672x10-24g or 1.672x10-27kg.It is 1837 times heavier than an electron.
 Specific charge (e/m):9.58x104coulomb/gm.

3. Neutron (0n1)
* It was discovered by Chadwick by bombarding Be atom with high speed -particles.
𝟒𝐁𝐞𝟗 + 𝟐 𝐇𝐞𝟒 → 𝟔𝐂
𝟏𝟐
+𝟎 𝐧 𝟏
* Charge: Charge less or neutral particle.
* Mass:1.675x10-24 g or 1.675x10-27 kg.
* Density:1.5x1014 g/cm3 and is heavier than proton by 0.18%.
* Specific charge: It is zero.
* Among all the elementary particles neutron is the heaviest and least stable.

Properties of Electron, Proton and Neutron

Properties Electron Proton Neutron


Discovery J.J.Thomson Goldstein Chadwick
Charge -1.6022x10-19C 1.6022x10-19 C Zero
Mass 9.109x10-31 kg 1.672x10-27 kg 1.675x10-27 kg
Spin ½ ½ ½
Charge -1 +1 0
Location Outside the nucleus In the nucleus In the nucleus

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Classical Models of Atom:


1) Thomson’s Atomic Model
According to Thomson, an atom is a sphere of positive charge having a number of
embedded electrons in it and sufficient enough to neutralize the positive charge. This
model is compared with a water melon in which seeds are embedded or pudding in which
raisins are embedded. Therefore, this model, sometime called watermelon model or raisin
or plum pudding model.

Important Features
• It shows the electrical neutrality of the atom.
• The mass of the atom is assumed to be uniformly distributed over the atom.
The model was rejected as it was not consistent with the results of the alpha
scattering experiment.
Limitation: It is failed explain the results of scattering experiment of Rutherford and the
stability of atom.

2) Rutherford’s Atomic Model:


Rutherford, performed -ray scattering experiment in which he bombarded thin foils of
metals like gold, silver, platinum or copper with a beam of fast-moving radioactive particles
originated from a lead block. The presence of 𝛼 particles at any point around the thin foil of
gold after striking it was detected with the help of a circular zinc sulphide screen. The
point at which a𝛼 particle strikes this screen; a flash of light is given out.

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Observations and Conclusions

i. Most of the -particles passed through the gold foil without any deflection from their
original path.
Bcz atom has largely empty space as most of the -particles passed through the foil
undeflected.
ii. A few of the alpha particles are deflected fairly at large angles while some are
deflected through small angles.
Bcz there is heavy positive charge at the center of the atom which causes repulsions.
The entire mass of the atom is concentrated in the nucleus.
iii. A very few -particles are deflected back along their path.
According to Rutherford,
1. Atom is spherical & mostly hollow with lot of empty space in it.
2. It has a small +ly charged part at its center known as nucleus.
3. The nucleus is surrounded by electrons. Electrons revolve round
the nucleus with very high speeds in circular paths called orbits.
4. The number of extra nuclear electrons is equal to the number of
units of positive charge in the nucleus. Therefore, the atom is electrically neutral.
Electrons and the nucleus are held together by electrostatic forces of attraction.
5. Rutherford’s model has resemblances with solar system. Hence, it’s also known as
planetary model of the atom.
6. There is an empty space around the nucleus called extra nuclear part. In this part
electrons are present. As the nucleus of the atom is responsible for the mass of the
atom, the extra nuclear part is responsible for its volume.
Drawbacks:
1. According to the electromagnetic theory of Maxwell, when a charged
particle moves under the influence of attractive force it loses energy
continuously in the form of electromagnetic radiation. Therefore, an
electron in an orbit will emit radiation.
As a result of this, the electron should lose energy at every turn and
move closer and closer to the nucleus following a spiral path. Ultimate result is that it
will fall into the nucleus thereby making the atom unstable.
i.e., Rutherford’s model cannot explain the stability of the atom.

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2. If the electrons lose energy continuously, the spectrum is


expected to be continuous but the actual observed
spectrum consists of well-defined lines of definite
frequencies. Here the loss of energy by the electrons is
not continuous in an atom.

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STRUCTURE OF ATOM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

Atomic number(Z): Atomic number denotes the number of protons or the number of
electrons in the neutral atom.
Atomic number (Z) = Number of protons in the nucleus of an atom or ion
= Number of electrons in a neutral atom.
Each element has a different atomic number.
A The atomic number of sulfur (S) is 16.
B The atomic number of iron (Fe) is 26.
C The atomic number of silver (Ag) is 47.

Each element has a definite and fixed number of protons.


If the number of protons changes, then the atom becomes a different
element.
Changes in the number of particles in the nucleus (protons or neutrons) are
very rare. They only take place in nuclear processes such as:
⚫ radioactive decay
⚫ nuclear bombs
⚫ nuclear reactors.
Remember!
In an atom… APE!
A= P= E
Atomic number = number of protons = number of electrons

Mass number (A): The mass number is the total number of protons and neutrons
present in the nucleus of an atom of an element and indicated as A.
Protons and neutrons present in the nucleus of an atom are collectively known as nucleons.
Therefore, the mass number is also known as nucleon number.
Mass number (A) = Number of protons (Z) + Number of neutrons (n)
The number of neutrons (n) in an atom is equal to the difference between the mass
number and the atomic number. n = A – Z

Mass Number

Atomic Number
A
Z X OR
Z XA

Symbol of Element

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A tomic number = Protons= Electrons


M ass number = Atomic number+number ofNeutrons

Isotopes, Isobars and Isotones:


Isotopes: The atoms of the same element which have the same atomic number but
different mass numbers are called isotopes.
Exp- 6 C12 , 6C13 , 6C14 , 8 O16 , 8 O17 , 8 O18 , 17 Cl35 , 17 Cl37

hydrogen deuterium tritium

1 proton 1 proton 1 proton

0 neutrons 1 neutrons 2 neutrons

1 electron 1 electron
1 electron

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Isotopes of an element differ in the number of neutrons present in the nucleus. But they
have the same number of protons and electrons.
Because of same number of electrons, they show same chemical properties. They,
have different number of neutrons, so they will have different masses and hence
different physical properties.

Isobars: The atoms of different elements which have the same mass number but
different atomic numbers are called isobars.
Exp: 18 Ar 40 , 19 K 40 , 20 Ca40

They have same number of nucleons. But they are differed chemically because the chemical
characteristics depend upon the number of electrons which is determined by the atomic
number.

Isotones: Isotones are the atoms of different elements which have the same number of
neutrons.
Eg: 6 C14 , 7 N15 , 8 O16 (n = 8)
14 Si30 , 15 P31, 16 S32 (n = 16)
Isotones show different physical and chemical properties.

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Nature of Light (Electromagnetic Radiation):


Electromagnetic radiation does not need any medium for propagation e.g visible, ultra violet,
infrared, x-rays, -rays, radio waves, radiant energy etc.
Two theories were proposed to explain the nature and the propagation of light
i. Corpuscular theory: This theory was proposed by Newton. According to this theory light
is propagated in the form of invisible small particles. i.e. light has particle nature.
The particle nature of light explained some of the experimental facts such as reflection
and refraction of light but it failed to explain the phenomenon of interference and
diffraction. Therefore, was discarded and ignored.
ii. Wave theory of light (electromagnetic wave theory): was explained by James Clark
Maxwell in 1864 to explain & understand the nature of electromagnetic radiation.

Features of this theory are:


a) The light is a form of electromagnetic radiations.
b) Light radiations consist of electric & magnetic fields oscillating
perpendicular to each other.
c) Vertical component of wave, ‘E’ indicates the
change in the strength of the electric field
and the horizontal component of the wave ‘H’
indicates the change in the strength of the magnetic field.
d) These radiations do not require any medium for propagation.
e) The radiations possess wave character and travel with the velocity of light
i.e. 3x108 m/sec because of the above characteristics, the radiation is called electromagnetic
radiations or waves.
Electromagnetic radiation is explained by following characteristics:

1. Wave length:

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The distance between two successive crests, troughs or between any two consecutive
identical points in the same phase of a wave is called wave length. It is denoted by the
letter (lambda).
The wave length is measured in terms of meters (m), centimeters (cm), angstrom units
(A0) nanometers (nm), picometers (pm) and also in millimicrons (m).
The S.I. unit of wavelength is meter, m
0 –10 –8
1A = 10 m or 10 cm
–9 –7
1nm = 10 m or 10 cm = 10A0
–12 –10
1pm = 10 m or 10 cm =10−2 A0

2.Frequency:
The number of waves that pass-through a given point in one second is known as
frequency of radiation. It is denoted by the ‘v’ (nue).
Crest  Crest

a
a 
Trough Trough

SI unit of frequency is per second(s–1) or Hertz (Hz). A cycle is said to be completed when
a wave consisting of a crest and a trough passes through a point.

3.Velocity:
Distance travelled by the wave in one second is called velocity or speed of the wave (C).

SI unit is meters per second (ms–1).


C of electromagnetic radiation in vaccum is a constant commonly called the speed of light
and is denoted by ‘c’.It is equal to 3 × 108ms–1.
4.Wave number:
Number of waves that can be present at any time in unit length is called wave number.
It is denoted by  (nue bar).
It is the reciprocal of wave length.
1
Wave number =  =

It is expressed in per centimeter (cm–1) or per meter (m–1).


The SI unit of wave number is m–1.

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Wave length, wave number𝝂̅ , frequency 𝝂 and velocity c are related as follows
.
⇒ 𝑪 = 𝜐𝜆

5.Amplitude:
The height of the crest or the depth of the trough of the wave is called amplitude of
the wave. It is denoted by A.
The amplitude determines the strength or intensity or brightness of radiation.

6.Time period:
It is the time taken by the wave for one complete cycle or vibrations. It is denoted by
T. It is expressed in second per cycle.
1 1
T= ( where  = frequency)
𝑉 

Electromagnetic spectrum:
The arrangement of different types of electromagnetic radiations in the order of
increasing wavelengths or decreasing frequencies is known as electromagnetic spectrum.

Limitations of Electromagnetic Wave Theory:


Electromagnetic wave theory was successful in explaining the properties of light such as
interference, diffraction etc.
But it could not explain the following:
(i) The phenomenon of black body radiation.

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(ii) The photoelectric effect.


(iii) The change heat capacity of solids as a function of T.
(iv) The line spectra of atoms with special reference to hydrogen.
These phenomena could be explained only if electromagnetic waves are supposed to have
particle nature.

Black body radiation:


When a radiant energy falls on the surface of a body, a part of it is absorbed, a part of it is
reflected and the remaining energy is transmitted.
An ideal body is expected to absorb completely the radiant energy falling on it is known as a
black body. A black body is not only a perfect absorber but also a perfect emitter of
radiant energy.
A hollow sphere coated inside with a platinum black, which has a small hole in its wall can act
as a near black body.

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The radiation emitted by a black body kept


at high temperature is called black body
radiation. A black body radiation is the
visible glow that the solid object gives off
when heated.
A graph is obtained by plotting the
intensity of radiation against wave length
gives the following details.
1. The nature of radiation depends upon the T of the black body.
2. If the energy emitted is continuous the curve should be as shown by the dotted lines.
3. At a given temperature the intensity of radiation increases with the wave length,
reaches maximum and then decreases.
4. The intensity of radiation is greatest at the medium wave lengths and least at highest
and lowest wave lengths.
5. As the temperature increases the peak of maximum intensity shifts towards the shorter
wave lengths.

Planck’s quantum theory:


In order to explain black body radiation, Max Planck proposed quantum theory of radiation.
Postulates
1. Emission of radiation from a body is due to vibrations of the charged particles in the body.

2. Energy is emitted or absorbed by a body discontinuously in the form of small packets of


energy called quanta.

3. Energy of each quantum of light is directly proportional to the frequency of the radiation.
E   or E = h 
Where ‘h’ is known as Planck’s constant.
The value of ‘h’, 6.6256 × 10–34 Jsec- or 6.6256 × 10–27ergs sec-
4. In case of light, the quantum of energy is called a photon.
Total amount of energy emitted or absorbed by a body is some whole number multiple of
quantum,
E = nh  , where n is an integer such as 1,2,3 . . . . .
This means that a body can emit or absorb energy equal to hv, 2hv, 3hv . . . . . Or any other
integral multiple of h. This is called quantization of energy.

5. The emitted radiant energy is propagated in the form of waves.

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Photoelectric Effect:
When radiations with certain minimum frequency (ν0 ) strike the surface of a metal, the
electrons are ejected from the surface of the metal. It is called photoelectric effect,
electrons emitted are called photoelectron.

For each metal a certain minimum frequency is needed to eject the electrons called as

threshold frequency (  ) which differs from metal to metal.


o
K.E. of photoelectron
K.E. of photoelectron

K.E. constant

o

Frequency of absorbed photon Intensity of Incident radiation

K.E. as a function of frequency K.E. as a function of intensity

It was explained by Einstein. When light of suitable frequency falls on a metal surface, the
light photon gives its energy to the electron of metal atom and the electron is ejected from
metal surface by absorbing this energy. The minimum energy of a photon required to
eject an electron from a metal is called work function () of the metal. The remaining part
of the energy (h  - ) of photon is used to increase the kinetic energy of the ejected
electron. If o is the threshold frequency and  , the frequency of incident light then

Work function,  = h o .

 According to Einstein, E = h 

 Kinetic energy of photo electron Ek = E -  = h − ho

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ATOMIC SPECTRA
Spectrum is the impression produced on a screen when radiations of a particular
wavelengths are analyzed through a prism or diffraction grating. Spectra are broadly
classified into two types.
1. Emission Spectrum: When the radiation emitted from some source, e.g., from the sun or
by-passing electric discharge through a gas at low pressure or by heating some substance to
high temperature etc. is passed directly through the prism and then received on the
photographic plate, the spectrum obtained is called ‘Emission spectrum’.
Spectrum of radiation emitted by a substance in its excited state is an emission spectrum.
Emission Spectrum is of two types:
a. Continuous Spectrum: When white light from any source such as sun, a bulb or any hot
glowing body is analyzed by passing through a prism, it is observed that it splits up into
seven different colors from violet to red, (like rainbow), as shown in fig.

These colors are so continuous that each of them merges into the next. Hence, the spectrum
is called continuous spectrum.
It may be noted that on passing through the prism, red colour with the longest wavelength is
dedicated least while violet colour with shortest wavelength is deviated the most.

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b. Discontinuous Spectrum: When gases or vapours of a chemical substance are heated in


an electric Arc or in a Bunsen flame, light is emitted. If the ray of this light is passed
through a prism, a line spectrum is produced.
• A discontinuous spectrum consisting of distinct and well-defined lines with dark areas in
between is called line spectrum. It is also called atomic spectrum.
• The emission spectrum consisting of a series of very closely spaced lines is called band
spectrum.

Band spectrum is the characteristic of molecules. Hence it is also known as molecular


spectrum. The band spectrum is due to vibrations and rotations of atoms present in a
molecule.

Differences between line and band spectrum


Line spectrum Band spectrum

1. The line spectrum has sharp, distinct well- 1. The band spectrum has many closed lines.
defined lines.
2. The line spectrum is the characteristic of 2. The band spectrum is characteristic of
atoms and is also called atomic spectrum. molecules and is also called molecular
spectrum.
3. The line spectrum is due to transition of 3. The band spectrum is due to vibrations and
electrons in an atom. rotations of atoms in a molecule

4. The line spectrum is given by inert gases, 4. The band spectrum is given by hot metals
metal vapors and atomized nonmetals. and molecular nonmetals.

2. Absorption spectra: When white light from any source is first passed through the solution
or vapours of a chemical substance and then analyzed by the spectroscope, it is observed that
some dark lines are obtained. Further, it is observed that the dark lines are at the same place
where coloured lines are obtained in the emission spectra for the same substance.

Difference between emission spectra and absorption spectra


EMISSION SPECTRA ABSORPTION SPECTRA

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1. Emission spectrum is obtained when the 1. Absorption spectrum is obtained when


radiation from the source are directly the white light is first passed through
analyses in the spectroscope. the substance and the transmitted light
is analyzed in the spectroscope.
2. It consists of bright coloured lines 2. It consists of dark lines in the
separated by dark spaces. otherwise continuous spectrum.
3. Emission spectrum can be continuous 3. Absorption spectrum is always
spectrum (if source emits white light) discontinuous spectrum of dark lines.
or discontinuous, i.e., line spectrum if
source emits some coloured radiation.

Emission Spectrum of Hydrogen:


When hydrogen gas at low pressure is taken in the discharge tube and the light emitted on
passing electric discharge is examined with a spectroscope, the spectrum obtained is called
the emission spectrum of hydrogen which contain large number of lines which are grouped
into different 5 different series,
• Lyman series,
• Balmer series
• Paschen series
• Brackett series
• Pfund series.
• Humphrey series

Wave numbers of all the lines in all the series can be calculated by the Rydberg equation.
1 1 1
ν̅ = = RZ2 ( 2 − 2 )
λ n1 n2

Where n1 and n2 are whole numbers, n2> n1.

For one electron species like He+, Li2+ and Be3+, the value of R is 109677 cm–1× Z2, where Z
is the atomic number of the species.

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n=7 Humphrey series


n=6
n1=5, n2=6,7,8----
n=5 Pfund series
n1=4, n2=5,6,7,8---- Infra-red region
n=4
Brakett series
n1=3, n2=4,5,6----
n=3
Paschen series

ELECTRONIC TRANSITIONS
n1=2, n2=3,4,5,6----
υ
n=2 Near
Balmer series Visible region
Infra-red region

n1=1, n2=2,3,4,5----
n=1 Lyman series U.V region

Different series of spectral lines in hydrogen emission spectrum

Name of the series n1 n2 Spectral region


Lyman series 1 2,3,4,5,6,7….. Ultraviolet
Balmer series 2 3,4,5,6,7… Visible
Paschen series 3 4,5,6,7…… Near infrared
Brackett series 4 5,6,7…. Infrared
Pfund series 5 6,7…. Far infrared
The wave number for any single electron species like He+, Li2+ and Be3+ can be calculated
1 1
from the equation ν̅ = Z 2 R H ( − )
n21 n22

Bohr’s and Sommerfeld’s Atomic models

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To overcome the objections of Rutherford model and to explain the hydrogen spectrum,
Bohr proposed a quantum mechanical model.

POSTULATES OF BOHR’S THEORY


• The electrons revolve round the nucleus with definite velocity in
certain fixed closed circular paths called orbits (or) shells (or)
stationary state. These shells are numbered as 1, 2, 3, 4 or
termed as K, L, M, N from the nucleus.
• Each orbit is associated with a definite amount of energy. As long as an
electron is revolving in an orbit it neither loses nor gains energy. Hence these orbits are
called stationary states or stable orbits.

• The centrifugal force of the revolving electron in a stationary orbit is balanced by the
electrostatic attraction between the electron and the nucleus.
• Electron can revolve only in orbits whose angular momentum are an integral multiple of the
factor h/2 π.
nh
mvr = 2π
Where m = mass of electron,
v = velocity of electron,
r = radius of the orbit and
‘n’ is the integral number like, 1, 2, 3, 4 . . . , is called principal quantum number and h =
Planck’s constant
• The energy of an electron changes only when it moves from one orbit to another. Outer
orbits have higher energies while inner orbits have lower energies.
The energy is absorbed when an electron moves from inner orbit to outer orbit. The
energy is emitted when the electron jumps from outer orbit to inner orbit.
• The energy emitted or absorbed in a transition is equal to the difference between the
energies of the two orbits (E2 – E1). Energy emitted or absorbed is in the form of quanta.
E=E2 – E1 = hv
Here E1 and E2 are the lower and higher allowed energy states.

• Expressions for radius of orbit:

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Consider an electron of mass ‘m’ and charge ‘e–’ revolving round the nucleus of charge ‘Ze’ in a
circular orbit of radius ‘r’.

Let ‘v’ be the tangential velocity of the electron. As per coulomb’s law, the electrostatic
force of attraction between the moving electron andthenucleus is –Ze2/r.

For the atom to be stable an equal centrifugal force must act away
from the nucleus. This centrifugal force is equal to –mv2/r, where
‘m’ is the mass of electron and ‘r’ is the radius of the orbit.

In a stationary orbit
–Ze2 −mv2 Ze2
= or = mv2
r2 r r
𝑛ℎ
As per Bohr’s quantum condition, mvr = 2𝜋

nh 𝑛2 ℎ 2
∴v= 2πmror v2= 4𝜋2𝑚2 𝑟 2

Substituting the value of v2, we get


Ze2 mn2 h2 n2 h2
or = 4π2 m2r2 or r =
r 4π2 mZe2

Radius for ‘nth’ orbit, rn =


n2 h2
4π2 mZe2

Substituting the standard values, of h, , m and e, we get radius of nth orbit rn =


0.529×n2

Z

For hydrogen, Z=l and n=1 for first orbit,

The radius of the first orbit of hydrogen is 0.529 A0 or 0.0529 nm or 52.9 pm. This value
is known as Bohr’s radius. As the value of n increases, the radius of the orbit will increase.
n2 h2
In S.I units, rn = 4π2mKZe2
1
Where,K = 4π∈ (ϵ0 = permitivity of air = 8.854 × 10−12 Farad Metre)
0

• Expression for Energy of electron:


The total energy of electron is the sum of kinetic and potential energies.Kinetic energy due
to motion of electron is mv2, where m is the mass of electron and v is its velocity.
1
2

Ze2 Ze2
K.E = 2mv2 =
1
∵ mv 2 =
2r 2r
−Ze2
P.E of electron = 𝑟

Total energy of electron, En = K.E + P.E

Ze2 Ze2 1 Ze2


En= − =−
2r r 2 r

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Substituting the value of r, we get energy of electron in nth orbit,


−Ze2 4π2 mZe2 −2π2 mZ2 e4
En = or En=
2n2 h2 n2 h2

Substituting the values of m, e, h and𝜋 in the equation, we get


−13.6 ×𝑍2
En = eV per atom
𝑛2

−313.6×𝑍 2
or En = k cal mol–1
𝑛2

−1312×Z2 –1
or En = kJ mol
n2

−2.18×10−11 𝑍 2
or En = erg per atom
𝑛2

−2.18×10−18 𝑍 2
orEn = j/atom
𝑛2

2π2 mK2 Z2 e4
In S.I units: En = − n 2 h2
–1
WhereK = 4𝜋𝜖 and 𝜀𝑜 beingpermittivity of air and is equal to 8.854 × 10–12 Farad metre
1
0

• Derivation of Rydberg equation:


When a gas is subjected to electric discharge or heated by a flame, the electrons in the
ground state of the atom absorb energy and they are promoted to higher quantum states.
As theyare not stable in these states, they emit energy and return to ground state or any
other lower energy states.If E2 is the energy of the higher energy state, E1 is the energy of
the lower energy state and 𝜈 is the frequency of emitted radiation E2 – E1 = h𝜈

If the numbers of the higher and lower energy states are n2 and n1 respectively, En2 =
−2π2 mZe4 1
. n2
h2 2
−2π2 mZe4 1
En1 = . n2
h2 1
−2π2 mZe4 1 1
En2 − E n1 = [n2 − n2 ]
h2 1 2

En2 − En1
But En2 − En1 = hcν̅ and ν̅ = ch

1 −2π2 mZe4 1 1
ν̅ = λ = [n2 − n2 ]
ch2 1 2

1 1 1
This equation is similar to Rydberg equation. [ν̅ = λ = R × (n2 − n2)]
1 2

2π2 mZ e4
Rydberg constant R should be equal to R = ch3

Substituting the values, we get RH= 1,09,681cm-1.This value is almost equal to Rydberg’s
constant 1,09,677 cm–1.

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The frequencies of the spectral lines in the hydrogen spectrum calculated by using Bohr’s
equation are in excellent agreement with the experimental values. This is a concrete
proof of the validity of Bohr’s theory of hydrogen atom.

• Expression for velocity of electron:


As per Bohr’s quantum conditions,
nh nh
mvr = 2π or v = 2πmr
n2 h2
∵ r = 4π2 m Ze2
nh 4π2 m Ze2
∴ v = 2πm × n2 h2

2πZe2
v= cms −1
n

Substituting the values of 𝜋, e and h in the above expression


2.18×108 ×𝑍 –1
vn= cm s
𝑛
8
Thus the velocity of electron in the first orbit of hydrogen atom is 2.18 ×10 cm s–1. As
the number of the orbit increases, the velocity of the electron decreases.

Explanation of Hydrogen Spectrum by Bohr’s Theory:


Bohr’s theory successfully explains the origin of lines in hydrogen emission spectrum.
Hydrogen atom has only one electron. It is present in K shell of the atom (n = 1). When
hydrogen gas is subjected to electric discharge, energy is supplied. The molecules absorb
energy and split into atoms. The electrons in different atoms absorb different amounts of
energies. By the absorption of energy, the electrons are excited to different higher energy
levels.
Atoms in the excited state are unstable. Therefore, the electrons jump back into different
lower energy states in one or several steps. In each step the energy is emitted in the form
of radiation and is indicated by a line.
Each line has a definite frequency and thus the emission spectrum of hydrogen has many
spectral lines.
• Lyman series are obtained in UV region, when electron returns to the ground state from
higher energy levels 2, 3, 4, 5 ......... and so on.
• Balmer series are obtained in visible region when electron returns to second energy level
from higher energy levels 3, 4, 5, 6 and so on.
• Paschen series are obtained in near infrared region, when electron returns to third energy
level from higher energy levels 4, 5, 6.... And so on.
• Brackett series are obtained in mid infrared region when electron returns to fourth energy
level from higher energy levels 5, 6, 7 . . . and so on.

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• Pfund series are obtained in far infrared region when electron returns to the fifth energy
level from higher energy levels 6, 7…….
The maximum number of lines produced when electrons jumps from nth level to ground level
𝑛(𝑛−1)
is equal to, Or ∑(𝑛2 − 𝑛1 )
2

Where, n2 = higher energy level.

n1 = lower energy level.

n = difference in the two energy levels.

Merits and demerits of Bohr’s Atomic model:


1. Bohr’s model explains the stability of the atom. The electron revolving in a stationary
orbit does not lose energy and hence it remains in the orbit forever.

2. Bohr’s theory successfully explains the atomic spectrum of hydrogen.

3. This theory not only explains hydrogen spectrum but also explains the spectra of one
2+ 3+
electron species such as He+, Li and Be etc.

4. The experimentally determined frequencies of spectral lines are in close agreement with
those calculated by Bohr’s theory.

5. The value of Rydberg constant for hydrogen calculated from Bohr’s equation tallies with
the value determined experimentally.

Limitations of Bohr’s model:


1. Bohr’s theory applicable for single electron species and fails to explain the spectra of
multielectron atoms.
2. It could not explain the fine structure of atomic spectrum.
3. It does not explain the splitting of spectral lines into a group of finer lines under the
influence of magnetic field (Zeeman Effect) and electric field (Stark effect).
4. Bohr’s theory predicts definite orbits for revolving electron. It is against the wave
nature of electron.
5. Bohr’s theory is not in agreement with Heisenberg’s uncertainty principle.
6. He couldn't give a theoretical reason for most of his assumption, for example, he
couldn't justify why angular momentum of the electron should be quantized.
7. Spectrum of isotopes of hydrogen were expected to be same according to the Bohr's
model but found different experimentally.

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Sommerfeld’s Atomic Model:


It is an extension of Bohr’s model. In this model, the electrons Radial Velocity
Tar velocity
in an atom revolve around the nuclei in elliptical orbit. The •
Avg Velocity
circular path is a special case of ellipse. Association of elliptical • major axis
orbits with circular orbits explains the fine line spectrum of
focus

atoms. Minor axis

The main postulates are:


n=4,k=4
n=4,k=3
i) The motion of electron in closed circular orbits is
n=4,k=2

influenced by its own nucleus and is set up into closed


elliptical paths of definite energy levels. • n=4, k

ii) The nucleus is one of the foci for all these orbits.
iii) The angular momentum of electron in closed elliptical
paths is also quantized i.e. k (h/2), where k is another integer except zero.
n length of major axis
iv) The ratio = length of suggests for the possible number of subshells in a shell.
k min or axis

Possible values of k for n = 4 are 1, 2, 3, 4 respectively. For any given value of n, k cannot be
zero as in that case, the ellipse would degenerate into a straight line passing through the
nucleus. When n = k, path becomes circular.

DUAL NATURE OF MATTER (de-BROGLIE’S WAVE THEORY)


Light exhibits different properties such as diffraction, interference, photoelectric
effect, Compton effect, reflection and refraction. The phenomenon of diffraction and
interference can be explained by the wave nature of the light. But the phenomenon of
photoelectric effect and Compton Effect can be explained by the particle nature of the
light. Thus light has dual nature. De-Broglie proposed that matter like radiation, should also
exhibit dual behavior.

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hc
Einstein’s generalization of Planck’s theory is given as, E = hν = λ
2
Einstein’s mass energy relationship is E = mc
hc 2 h h
Equating above two equations, we get, = mc or = mc or λ = mc
λ λ
h
Where ‘c’ is the velocity of light. If the velocity of micro particle is ‘v’ then, λ = mV
This is de Broglie’s equation,
Where ‘λ’ is the de Broglie’s wave length, ‘m’ is the mass of the moving particle and ‘h’ is
Planck’s constant.
h
P = mv or λ = P
Here 𝜆 signifies wave nature and P signifies particle nature.
It is applicable to microparticles like electron, proton, etc., and not applicable for macro-
bodies like cricket ball, bullet etc.
The electron moving with high speed possesses both the particle nature and the wave nature.
The waves associated with material particles are known as matter waves or particle waves.

The Heisenberg’s uncertainty principle:

“It is impossible to determine simultaneously and accurately the exact position and
momentum or velocity of a sub-atomic particle like electron in an atom”.
One can determine the position of a particle very accurately, and then the determination of
its velocity becomes less accurate. Similarly, one can determine the velocity of a particle
very accurately, and then the determination of its position becomes less accurate. The
certainty in one factor introduces the uncertainty in another factor.
If the uncertainty in the determination of the position of a small particle is given by Δx and
uncertainty in its momentum is Δp, then

(Δx) (Δp) ≥ 𝑛𝜋, Where n = 1,2,3,4.........
For an electron revolving around the nucleus in an atom the value of n is nearly 4.
Thus Heisenberg’s principle can also be stated as the product of uncertainty in position and
momentum of an electron like micro particle moving with high speed cannot be less than h/4.

Heisenberg’s equation can also be written as, (Δx) (Δv) ≥ 4𝜋𝑚

Where m is the mass of the particle and Δv is uncertainty in velocity.

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If the position of the particle is known exactly (Δx = 0), Δv becomes infinity (∞) and vice
versa. Heisenberg's uncertainty principle is not applicable to those objects which cannot
change their position by themselves when a light falls on them. It is applicable for micro
particles like electrons.

Significance of Heisenberg’s uncertainty principle:


Like de Broglie equation, although Heisenberg’s uncertainty principle holds good for all
objects but it is significance only for microscopic particles. The reason for this is quite
obvious. The energy of the photon is insufficient to change the position and velocity of
bigger bodies when it collides with them. For example, the light from a torch falling on a
running rat in a dark room, neither change the speed of the rat nor its direction, i.e.,
position.
This may be further illustrated with the following examples:
For a particle of mass 1 mg, we have
ℎ 6.625×10−34 𝑘𝑔𝑚2 𝑠−1
Δx.Δ𝜐 = = = 10−28 𝑚2 𝑠 −1
4𝜋𝑚 4×3.1416×(10−6 𝑘𝑔)

Thus, the product of Δx and Δ𝜐 is extremely small. For particles of mass greater than 1 mg,
the product will still smaller. Hence, these values are negligible.
For a microscopic particle like an electron, we have
ℎ 6.625×10−34 𝑘𝑔𝑚2 𝑠−1
Δx.Δ𝜐 = 4𝜋𝑚 = 4×3.1416×(9×10−31 𝑘𝑔) ≈ 10−4 𝑚2 𝑠 −1

Classical mechanics, based on Newton’s laws of motion, was successful in explaining the
motion of macroscopic bodies like falling stones or motion of planets around the sun etc. But
it failed when applied to microscopic particles like electrons, atoms, molecules etc. Hence,
new branch introduced called as ‘Quantum mechanics.

Schrodinger Wave Equation:


Quantum mechanics, as developed by Erwin Schrodinger is based on the wave motion
associated with the particles. The Schrodinger differential wave equation is given by
∂2 ψ ∂2 ψ ∂2 ψ 8π2 m
+ + + (E − V)ψ
∂x2 ∂z2 ∂y2 h2

Here x, y, z are Cartesian coordinates of the electron


m = mass of electron
h = Planck’s constant
E = total energy of the electron (KE + PE)
V = potential energy of the electron (PE)
ψ= wave function of the electron.
Significance of ψ: ψ is the wave function. It gives the amplitude of the electron wave.

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The intensity of light is proportional to the square of amplitude (ψ2). Just as 𝛙2 indicates
the density of photons in space, 𝛙2 in case of electron wave denotes the probability of
finding an electron in the space or probability of finding the electron is also maximum.

QUANTUM NUMBERS
The behavior of an electron in an atom is described mathematically by a wave function or
orbital. They are principal quantum number, azimuthal quantum number, magnetic quantum
number and spin quantum number.
‘Set of numbers used to describe energy, size, shape of orbitals in an atom’ called as
quantum numbers.
1.Principal quantum number(n):
• ‘n’ can be any whole number value such as 1,2,3,4, etc. The energy shells corresponding to
these numbers are K, L, M, N, etc.
• Principal Quantum no. indicates the main energy level to which the electron belongs. It also
indicates the average distance of an electron from nucleus and also the speed of the
atomic electron.
• As the ‘n’ value increases the distance of electron from the nucleus increases and its energy
also increases.

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• The maximum no. of electrons that can be present in an orbit is given by 2𝑛2 . The maximum
no. of electron in K, L, M, and N shells are 2,8,18 and 32 respectively.
0.529×𝑛2
• The radius of the orbit is given by the expression: rn = Ao.
𝑍
• The energy of the electron/orbit is given by the expression.
−13.6×𝑍 2
En= cm/sec
𝑛
2.18×108 ×𝑍
• The velocity of the electron is given by the expression. Vn= cm /sec.
𝑛

2. Azimuthal Quantum Number:


• Azimuthal Quantum number was introduced by Sommerfeld’s to explain the fine spectrum.
• It is also called as secondary quantum no. or orbital angular momentum quantum number or
subsidiary quantum number.
• It is denoted by l.
• ‘l’ can have the values from 0 to (n-1), a total of ‘n’ values. ‘l’ values 0,1,2,3 indicates s,p,d,f.
s,p,d and f are spectroscope terms which indicates sharp. Principle, diffuse and fundamental
respectively.
• Azimuthal Quantum number indicates the sub-shell to which the electron belongs. It also
determines the shapes of the orbital in which the electron is present.
• Each main energy shell can have ‘n’ number of sub-shells.
n l
1 0 (1s)

2 0 (2s), 1 (2p)

3 0 (3s), 1 (3p), 2(3d)


4 0 (4s), 1(4p), 2(4d), 3(4f)

• The orbital angular momentum (L) of an electron is given by the expression:



L = √𝑙(𝑙 + 1) 2𝜋

3. Magnetic Quantum number:


• Magnetic quantum number was introduced by Lande to explain Zeeman Effect.
• It is denoted by m or ml.
• This quantum number refers to different orientations of electron could in a particular
subshell. These orientations are called the orbitals.
• An electron due to its orbital motion around the nucleus generates an electric .This electric
field in turn produces a magnetic field which can interact with the external magnetic field.
Thus, under the influence of the external magnetic field, the electrons of a subshell can
orient themselves in certain preferred regions of space around the nucleus called orbitals.
The magnetic quantum number determines the number of preferred orientations of the
electron present in a subshell.

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Since each orientation corresponds to an orbital, therefore, the magnetic quantum


number determines the number of orbitals present in any subshell.
• ‘m’ can have values from – 𝑙 to +𝑙 including zero, a total (2 𝑙+1) values.
Subshell 𝒍 m values No. of orientations (Orbitals)
s 0 0 1
p 1 -1, 0, +1 3
d 2 -2, -1, 0, +1, +2 5
F 3 -3, -2, -1, 0, +1, +2, +3 7
• When l = 0, m has only one value, m = 0. The sub-level‘s’ has one orbital called s orbital.
• When l =1, m can have 3 values m = –1, 0, +1. The sub-level ‘p’ has three space orientations
or three orbitals. The three orbitals are designated as px, py and pz.
• When l = 2, m can have 5 values m = –2,–1, 0, +1, +2. The sub-level ‘d’ has five space
orientations or five orbitals. The five orbitals are designated as d xy, dyz, dzx,
dx2 −y2 and dz2 .
• When l = 3, m can have 7 values m = –3,–2,–1,0,+1,+2,+3. The sub-level ‘f’ has seven space
orientations or seven orbitals.
The magnetic quantum number gives orientation of orbitals in space. All the orbitals
present in a sublevel have same energy and shape. They are called ‘degenerate
orbitals’, which differ in their spatial orientation.

• Each value of ‘m’ constitutes an orbital in the sublevel.


• Maximum no. of electrons in subshell : 2(2𝑙+1) or (4 𝑙+2).

4. Spin Quantum Number:


• Spin Quantum number was proposed by Uhlenbeck and Goudsmith.
• It is denoted by ‘s’ or ‘ms’.
• It indicates the direction of spinning of electron present in any orbital.
• Since the electron in an orbital can spin either in the clockwise direction or in anti-clockwise
direction, hence for a given value of m, s can have only two values, i.e., +1/2 and -1/2 or
these are very often represented by two arrows pointing in the opposite direction,
i.e.,↑and ↓.
If an orbital contains 2 electrons, the two magnetic moments oppose and cancel each other.

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Thus, in an atom, if all the orbitals are fully


filled, net magnetic moment is zero and the
substance is diamagnetic (i.e., repelled by the
external magnetic field). However, if some half-
filled orbitals are present, the substance has a
net magnetic moment and is paramagnetic (i.e.,
attracted by the external magnetic field).

• The spin angular momentum (𝜇 s) of an electron


is given by
h
μs = √s(s + 1) 2π

Atomic Orbital:

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The three-dimensional space around the nucleus where the probability of finding the
electron is maximum is called an atomic orbital.

Differences between orbit and orbital:


Orbit Orbital
1. n orbit is a well-defined circular 1. An orbital is the region of space around
path 1. An orbital is the region of the around the nucleus where the
space around the probability of finding the electron is
around the nucleus in which the maximum (95%)
electron revolves.
2. An orbit represents the movement of 2. An orbital represents the movement of
electron in one plane. electron in three dimensional spaces.
3. An orbit means the position as well as 3. In an orbital it is not possible to find
the velocity of the electron can be the position as well as velocity of the
known with Certainty. electron can be known with certainty.
4. Orbits are circular or elliptical shaped. 4. They have different shapes like
spherical, dumbbell etc
Orbitals have different shapes.
s-orbital is Spherical and p orbital is
dumb bell shaped.
5. Orbits do not have directional 5. Except ‘s’ orbitals, all other orbitals
characteristics. have directional characteristics
6. An orbit can have a maximum number 6. An orbital can accommodate a
2
of2n electrons. maximum of only two electrons.

Node- The three-dimensional space around the nucleus where the probability of
finding the electron is minimum or zero.

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Types of Nodes:
Nodes are of two types: a) Radial Node b) Angular Node
A radial node is the spherical region around then nucleus, where the probability if finding
the electron is zero (Ψ2 = 0).

Similarly, nodal plane(angular plane) have zero probability of finding electron.

Calculation of no. of nodes:


No. of Radial nodes = n−𝑙 − 1
No. of angular nodes = 𝑙
Total no. of nodes = n-1
Ex: In a 3p -orbital
No. of Radial nodes = 3-1-1 = 1
No. of angular nodes = 1
Total no. of nodes = 2.

Shapes of Orbitals:
• s –Orbitals: s- Orbital can accommodate electrons with l = 0 and these orbitals are
present in every orbit starting from 1st orbit.

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Orbital in which e-s with n=1 , l = 0 are present is called 1s - orbital.


All s-orbitals are spherical in shape and the size of sphere increases with ‘n’ value. s -
Orbitals are spherically symmetrical because the probability of finding the electron around
the nucleus is same in all directions.

• p – Orbitals:
p- Sublevel begins from 2nd orbit. For p -
sublevel l = 1, indicates that each p - sub
level contains three orbitals with ‘m’
values –1, 0, +1. These are designated as
px, py and pz, depending on the axis in
which electron density is present.
In px-orbital, electron density is concentrated along the x-axis.
p-Orbitals have dumb-bell shape. Each p -orbital has two lobes separated by one nodal plane.
The probability density function is zero on the plane where the two lobes touch each other.
The nodal planes for px, py and pz - orbitals are YZ, ZX and XY - planes respectively.
The three orbitals present in a given p - sublevel will have same shape, size and energy but
different orientations (differ in m value). These three orbitals are perpendicular to each
other and the angle between any two p - orbitals is 90o.
• d - Orbitals:begins from 3rd orbit (n = 3). For d- sub level l= 2, indicates that each d -
sublevel contains five orbitals with ‘m’ values –2, –1, 0, +1, +2. These are designated as
dxy,dyz,dzx, 𝑑𝑥 2 −𝑦 2 and d𝑧 2 .
All the d-orbitals (except d𝑧 2 ) have double dumb-bell shape. Each d-orbital has four lobes
separated by two nodal planes.
In case of dxy, dyz and dzxorbitals, lobes are present in between the corresponding axes.
i.e., between x and y axis in case of dxy orbital. Where as in d𝑥 2−𝑦 2 and d𝑧 2 orbitals lobes are
present along the axes. dxy Orbital contains yz and zx as nodal planes. dyz and dzx contain
(xy, zx) and (xy, yz) planes respectively. d𝑥 2−𝑦 2 orbital contains two nodal planes perpendicular

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to each other and which make an angle of 45o with respect to x and y axes. 𝑑𝑧 2 orbital does
not contain nodal planes.
5d orbitals present in a given d- sublevel will have same energy in the ground state.

ENERGY OF ORBITALS
The energy of an electron in a hydrogen atom is determined only by the principal quantum
number. Within a shell, all hydrogen orbitals have the same energy, independent of the other
quantum numbers.
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
Although the shapes of 2s and 2p orbitals are different, an electron has the same energy
when it is in 2s orbital or 2p orbital. The energy of an electron in a multielectron atom
depends, not only on its principal quantum number, but also on its azimuthal quantum number.
The s, p, d and f orbitals within a given shell have slightly different energies in a multi
electron atom.

Electronic configuration of multi electron atoms:


The distribution and arrangement of electrons in the main shells, subshells and orbitals
of an atom is called electronic configuration of the element.
• Aufbau Principle:
“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 relative energy of an orbital is given by
(n + l ) rule or Bohr-Burry rule. As (n + l) value increases, the energy of orbital increases.
• The orbital with the lowest (n + l) value is filled first.

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• When two or more orbitals have the same


(n +l) value, the one with the lowest ‘n’ value
(or) highest l value is preferred in filling.
Exp- Consider two orbitals 3d and 4s.
n+l value of 3d = 3 + 2 = 5 and of 4s = 4 + 0 = 4.
Since 4s has lowest(n +l) value, it is filled first
before filling taking place in 3d.

Consider the orbitals 3d, 4p and 5s

The (n + l) value of 3d = 3 + 2 = 5

The (n +l) value of 4p = 4 + 1 = 5

The (n +l) value of 5s = 5 + 0 = 5

These three values are same. Since the ‘n’ value is


lower to 3d orbitals, the electrons prefer to enter in 3d, then 4p and 5s.

The order of increasing energy of atomic orbitals is:

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s and so on.

The sequence in which the electrons occupy various orbitals can be easily remembered with
the help of Moeller’s diagram as shown in above Fig

• Pauli’s Exclusion principle:stated as “No two electrons in an atom can have the same
set of values for all the four quantum numbers”. This means that two electrons in an
orbital may have the same n, same l and same m but differ in spin quantum number. In an
orbital if one electron has clockwise spin, the other has anticlockwise spin. It follows that
an orbital can hold a maximum of two electrons with opposite spins.
Exp- helium atom has two electrons in its 1s orbital. Quantum numbers for first electron are
n =1, l = 0, m = 0 and s = +1/2. Quantum numbers for second electron are:

n =1, l = 0, m =0, s = –1/2.

The two electrons have the same value for n, same value for l and same value for m but
differ in s.

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• Hund’s rule of maximum multiplicity:


According to this rule, when electrons are filled in degenerate orbitals of a subshell,
pairing of an electron takes place only when each orbital of the subshell is filled with
one electron each. It can be also stated that, in ground state of an atom, the
configuration which has more number of unpaired electrons is most stable.

Thus in s, p, d and f subshells, pairing starts from 2nd, 4th, 6th and 8th electrons respectively.

Ex: Electronic configuration of N (7) is 1s2 2s2 2p3.

The electrons in 2p subshell are occupied sing ally. i.e., 1s2 2s2 2𝑝𝑥1 2𝑝𝑦1 2𝑝𝑧1

Electronic configuration of elements from 1 to 30


1 H 1s1 1s1
2 He 1s2 1s2
3 Li 1s2 2s1 [He] 2s1
4 Be 1s2 2s2 [He] 2s2
5 B 1s2 2s2 2p1 [He] 2s2 2p1
6 C 1s2 2s2 2p2 [He] 2s2 2p2
7 N 1s2 2s2 2p3 [He] 2s2 2p3
8 O 1s2 2s2 2p4 [He] 2s2 2p4
9 F 1s2 2s2 2p5 [He] 2s2 2p5
10 Ne 1s2 2s2 2p6 [He] 2s2 2p6
11 Na 1s2 2s2 2p6 3s1 [Ne] 3s1
12 Mg 1s2 2s2 2p6 3s2 [Ne] 3s2
13 Al 1s2 2s2 2p6 3s2 3p1 [Ne] 3s2 3p1
14 Si 1s2 2s2 2p6 3s2 3p2 [Ne] 3s2 3p2
15 P 1s2 2s2 2p6 3s2 3p3 [Ne] 3s2 3p3
16 S 1s2 2s2 2p6 3s2 3p4 [Ne]3s2 3p4
17 Cl 1s2 2s2 2p6 3s2 3p5 [Ne] 3s2 3p5
18 Ar 1s2 2s2 2p6 3s2 3p6 [Ne] 3s2 3p6
19 K 1s2 2s2 2p6 3s2 3p6 4s1 [Ar] 4s1
20 Ca 1s2 2s2 2p6 3s2 3p6 4s2 [Ar] 4s2
21 Sc 1s2 2s2 2p6 3s2 3p6 3d1 4s2 [Ar] 3d1 4s2

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22 Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2 [Ar] 3d2 4s2
23 V 1s2 2s2 2p6 3s2 3p6 3d3 4s2 [Ar] 3d3 4s2
24 Cr 1s2 2s2 2p6 3s2 3p6 3d5 4s1 [Ar] 3d5 4s1
25 Mn 1s2 2s2 2p6 3s2 3p6 3d5 4s2 [Ar] 3d5 4s2
26 Fe 1s2 2s2 2p6 3s2 3p6 3d6 4s2 [Ar] 3d6 4s2
27 Co 1s2 2s2 2p6 3s2 3p6 3d7 4s2 [Ar] 3d7 4s2
28 Ni 1s2 2s2 2p6 3s2 3p6 3d8 4s2 [Ar] 3d8 4s2
29 Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1 [Ar] 3d10 4s1
30 Zn 1s2 2s2 2p6 3s2 3p6 3d10 4s2 [Ar] 3d10 4s2

Stability of atoms
Extra stability is associated with atoms in which degenerate orbitals are either half-filled
or completely filled due to
(1) Symmetrical distribution of electrons

(2) Exchange energy. Greater the exchange energy greater is the stability.
The presence of half-filled and completely filled degenerate orbitals gives greater
stability to atoms.

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1
It is for this reason the electronic configurations of Cr and Cu are represented as [Ar] 4s
5 1 10
3d and [Ar] 4s 3d respectively.

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NCERT SOLUTIONS
Q. 1.
(i) Calculate the number of electrons which will together weigh one gram.
(ii) Calculate the mass and charge of one mole of electrons.
Ans. (i) Mass of one electron = 9.10939 × 10 –31 kg
Number of electrons that weigh 9.10939 × 10 –31 kg = 1
1
Number of electrons that will weigh 1 g = (1 × 10 –3 kg) = 9.10939×10−31 𝑘𝑔 × (1 × 10−3 𝑘𝑔)
= 0.1098 × 10 –3 + 31 = 0.1098 × 10 28 = 1.098 × 10 27
(ii) Mass of one electron = 9.10939 × 10 –31 kg
Mass of one mole of electron = (6.022 × 10 23) × (9.10939 ×10 –31 kg) = 5.48 × 10 –7 kg
Charge on one electron = 1.6022 × 10 –19 coulomb
Charge on one mole of electron = (1.6022 × 10 –19 C) (6.022 × 1023) = 9.65 × 10 4 C
Q. 2.
(i) Calculate the total number of electrons present in one mole of methane.
(ii) Find (a) the total number and (b) the total mass of neutrons in 7 mg of 14C. (Assume that mass of
a neutron = 1.675 × 10 –27 kg).
(iii) Find (a) the total number and (b) the total mass of protons in 34 mg of NH 3 at STP.
Will the answer change if the temperature and pressure are changed?
Ans.
(i) Number of electrons present in 1 molecule of methane (CH4)
{1(6) + 4(1)} = 10
Number of electrons present in 1 mole i.e., 6.023 × 10 23 molecules of methane
= 6.022 × 10 23 × 10 = 6.022 × 10 24
(ii) (a) Number of atoms of 14C in 1 mole= 6.023 × 1023
Since 1 atom of 14C contains (14 – 6) i.e., 8 neutrons, the number of neutrons in 14 g of 14C is (6.023 ×
1023) ×8.
Or, 14 g of 14C contains (6.022 × 10 23 × 8) neutrons.
6.023 × 1023 × 8 × 7mg
Number of neutrons in 7 mg: = = 2.4092 × 10 21
1400mg
(b) Mass of one neutron = 1.67493 × 10 –27 kg
Mass of total neutrons in 7 g of 14C
= (2.4092 × 10 21) (1.67493 × 10 –27 kg)
= 4.0352 × 10 –6 kg
(iii) (a) 1 mole of NH3 = {1(14) + 3(1)} g of NH 3
= 17 g of NH3
= 6.022× 10 23 molecules of NH 3
Total number of protons present in 1 molecule of NH 3
= {1(7) + 3(1)} = 10
Number of protons in 6.023 × 10 23 molecules of NH 3
= (6.023 × 10 23) (10)
= 6.023 × 10 24
⇒ 17 g of NH3 contains (6.023 × 10 24) protons.
6.022 × 1024 × 34mg
Number of protons in 34 mg of NH 3 = = 1.2046 × 1022
17000mg
(b) Mass of one proton = 1.67493 × 10 –27 kg
Total mass of protons in 34 mg of NH 3

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= (1.67493 × 10 –27 kg) (1.2046 × 10 22) = 2.0176 × 10 –5 kg


The number of protons, electrons, and neutrons in an atom is independent of temperature and
pressure conditions. Hence, the obtained values will remain unchanged if the temperature and
pressure is changed.
Q.3. How many neutrons and protons are there in the following nuclei?
13 16 24 56 88
6𝐶 , 8𝑂 , 12𝑀𝑔 , 26𝐹𝑒 , 38𝑆𝑟
Ans.
1. 136𝐶 , Atomic mass = 13
Atomic number = Number of protons = 6
Number of neutrons = (Atomic mass) – (Atomic number)
= 13 – 6 = 7
2. 168𝑂,
Atomic mass = 16
Atomic number = 8
Number of protons = 8
Number of neutrons = (Atomic mass) – (Atomic number)
= 16 – 8 = 8
3. 24
12𝑀𝑔,
Atomic mass = 24
Atomic number = Number of protons = 12
Number of neutrons = (Atomic mass) – (Atomic number)
= 24 – 12 = 12
4. 56
26𝐹𝑒
Atomic mass = 56
Atomic number = Number of protons = 26
Number of neutrons = (Atomic mass) – (Atomic number)
= 56 – 26 = 30
5. 88
38𝑆𝑟
Atomic mass = 88
Atomic number = Number of protons = 38
Number of neutrons = (Atomic mass) – (Atomic number)
= 88 – 38 = 50
Q. 4. Write the complete symbol for the atom with the given atomic number(Z) & Atomic mass(A).
(i) Z = 17, A = 35
(ii) Z = 92, A = 233
(iii) Z = 4, A = 9
Ans. (i) 35 17Cl (ii) 233
92U (iii) 49Be
Q.5. Yellow light emitted from a sodium lamp has a wavelength (λ) of 580 nm. Calculate the
frequency (ν) and wave number (𝜈 ̅ ) of the yellow light.
𝑐
Ans. From the expression, 𝜆 = 𝜈
𝑐
We get, 𝜈 = …….. (i)
𝜆
Where, ν = frequency of yellow light
c = velocity of light in vacuum = 3 × 10 8 m/s
λ = wavelength of yellow light = 580 nm = 580 × 10 –9 m

Substituting the values in expression (i):

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Thus, frequency of yellow light emitted from the sodium lamp = 5.17 × 10 14 s–1

Wave number of yellow light,

Q.6. Find energy of each of the photons which


(i) correspond to light of frequency 3× 10 15 Hz.
(ii) have wavelength of 0.50 Å.
Ans.
(i) Energy (E) of a photon is given by the expression, E =
Where, h = Planck’s constant = 6.626 × 10 –34 Js
ν = frequency of light = 3 × 10 15 Hz
Substituting the values in the given expression of E:
E = (6.626 × 10 –34) (3 × 10 15)
E = 1.988 × 10 –18 J
(ii) Energy (E) of a photon having wavelength (λ) is given by the expression,

h = Planck’s constant = 6.626 × 10 –34 Js


c = velocity of light in vacuum = 3 × 10 8 m/s
Substituting the values in the given expression of E:

Q.7. Calculate the wavelength,frequency & wave number of a light wave whose period is 2.0×10 –10s.
1
Ans. Frequency (ν) of light =
𝑝𝑒𝑟𝑖𝑜𝑑

𝑐
Wavelength (λ) of light =
𝑣
Where, c = velocity of light in vacuum = 3×10 8 m/s
Substituting the value in the given expression of λ:

Wave number of light

Q.8. What is the number of photons of light with a wavelength of 4000 pm that p rovide 1 J of
energy?
Ans. Energy (E) of a photon = hν
Energy (En) of ‘n’ photons = nhν

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Where,
λ = wavelength of light = 4000 pm = 4000 ×10 –12 m
c = velocity of light in vacuum = 3 × 10 8 m/s
h = Planck’s constant = 6.626 × 10 –34 Js
Substituting the values in the given expression of n:

Hence, the number of photons with a wavelength of 4000 pm and energy of 1 J are 2.012 × 10 16.

Q.9. A photon of wavelength 4 × 10 –7 m strikes on metal surface, the work function of the metal
being 2.13 eV. Calculate
(i) the energy of the photon (eV),
(ii) the kinetic energy of the emission, and
(iii) the velocity of the photo electron (1 eV= 1.6020 × 10 –19 J).
Ans.
(i) Energy (E) of a photon = hν = hc/λ
Where,
h = Planck’s constant = 6.626 × 10 –34 Js
c = velocity of light in vacuum = 3 × 10 8 m/s
λ = wavelength of photon = 4 × 10 –7 m
Substituting the values in the given expression of E:

Hence, the energy of the photon is 4.97 × 10 –19 J.


(ii) The kinetic energy of emission Ek is given by

= (3.1020 – 2.13) eV = 0.9720 eV


Hence, the kinetic energy of emission is 0.97 eV.
(iii) The velocity of a photo electron (ν) can be calculated by the expression,

Where, is the kinetic energy of emission in Joules and ‘m’ is the mass of the photoelectron.
Substituting the values in the given expression of v:

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v = 5.84 × 10 5 ms–1
Hence, the velocity of the photoelectron is 5.84 × 10 5 ms–1.
Q.10. Electromagnetic radiation of wavelength 242 nm is just sufficient to
ionise the sodium atom. Calculate the ionisation energy of sodium in kJ mol –1.
𝑁𝐴 ℎ𝑐
Ans. Energy of sodium (E)=
𝜆

= 4.947 × 10 5 J mol–1
= 494.7 × 10 3 J mol–1 = 494 kJ mol –1

Q.11. A 25watt bulb emits monochromatic yellow light of wavelength of 0.57μm. Calculate the rate
of emission of quanta per second.
Ans. Power of bulb, P = 25 Watt = 25 Js –1
Energy of one photon, E = hν = hc/λ
Substituting the values in the given expression of E:

E = 34.87 × 10 –20 J
Rate of emission of quanta per second

Q.12. Electrons are emitted with zero velocity from a metal surface when it is exposed to radiation
of wavelength 6800 Å. Calculate threshold frequency (𝒗𝟎 ) and work function (W0) of the metal.
Ans. Threshold wavelength of radian = 6800 × 10 –10 m
Threshold frequency(𝒗𝟎 )of the metal

= 4.41 × 10 14 s–1
Thus, the threshold frequency of the metal is 4.41 × 1014 s–1.
Hence, work function (W0) of the metal = hν0
= (6.626 × 10 –34 Js) (4.41 × 1014 s–1)
= 2.922 × 10 –19 J
Q.13. What is the wavelength of light emitted when the electron in a hydrogen atom undergoes
transition from an energy level with n = 4 to an energy level with n = 2?
Ans. The ni = 4 to nf = 2 transition will give rise to a spectral line of the Balmer series. The energy
involved in the transition is given by the relation,

Substituting the values in the given expression of E:

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E = – (4.0875 × 10–19 J)
The negative sign indicates the energy of emission.

Wavelength of light emitted

Substituting the values in the given expression of λ:

Q.14. How much energy is required to ionise a H atom if the electron occupies n = 5 orbit? Compare
your answer with the ionization enthalpy of H atom (energy required to remove the electron from n
= 1 orbit).
Ans. The expression of energy is given by,

Where,
Z = atomic number of the atom
n = principal quantum number
For ionization from n1 = 5 to ,

Hence, the energy required for ionization from n = 5 to n = is 8.72 × 10 –20 J.


Energy required for n1 = 1 to n = ,

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Hence, less energy is required to ionize an electron in the 5 th orbital of hydrogen atom as compared
to that in the ground state.
Q.15. What is the maximum number of emission lines when the excited electron of an H atom in n =
6 drops to the ground state?
Ans. When the excited electron of an H atom in n = 6 drops to the ground state, the following
transitions are possible:

Hence, a total number of (5 4 3 2 1) 15 lines will be obtained in the emission spectrum.


The number of spectral lines produced when an electron in the nth level drops down to the ground
state is given by n(n-1)/2
Given, n = 6
Number of spectral lines = 6(6-1)/2 = 15.
Q.16
(i) The energy associated with the first orbit in the hydrogen atom is –2.18 × 10 –18 J atom–1. What is
the energy associated with the fifth orbit?
(ii) Calculate the radius of Bohr’s fifth orbit for hydrogen atom.
Ans.
(i) Energy associated with the fifth orbit of hydrogen atom is calculated as:

E5 = –8.72 × 10 –20 J
(ii) Radius of Bohr’s nth orbit for hydrogen atom is given by,
rn = (0.0529 nm) n2
For, n = 5
r5 = (0.0529 nm) (5) 2
r5 = 1.3225 nm
Q.17. Calculate the wave number for the longest wavelength transition in the Balmer series of
atomic hydrogen.
Ans. For the Balmer series, ni = 2. Thus, the expression of wave number is given by,

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Wave number is inversely proportional to wavelength of transition. Hence, for the longest
wavelength transition, has to be the smallest.
For to be minimum, nf should be minimum. For the Balmer series, a transition from ni = 2 to nf = 3 is
allowed. Hence, taking nf = 3, we get:

Q.18. What is the energy in joules, required to shift the electron of the hydrogen atom from the
first Bohr orbit to the fifth Bohr orbit and what is the wavelength of the light emitted when the
electron returns to the ground state? The ground state electron energy is –2.18 × 10 –11 ergs.
Ans. Energy (E) of the nth Bohr orbit of an atom is given by,

Where,
Z = atomic number of the atom
Ground state energy = – 2.18 × 10 –11 ergs
= –2.18 × 10 –11 × 10–7 J
= – 2.18 × 10 –18 J
Energy required to shift the electron from n = 1 to n = 5 is given as: ΔE = E5 – E1

Q.19. The electron energy in hydrogen atom is given by E n = (–2.18 × 10 –18)/n2 J. Calculate the
energy required to remove an electron completely from the n = 2 orbit. What is the longest

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wavelength of light in cm that can be used to cause this transition?


Ans. Given,

Energy required for ionization from n = 2 is given by,

ΔE = 0.545 × 10 –18 J
= 5.45 × 10 –19 J

Here, λ is the longest wavelength causing the transition.

= 3647 × 10 –10 m
= 3647 Å
Q.20. Calculate the wavelength of an electron moving with a velocity of 2.05 × 10 7 ms–1.
Ans. According to de Broglie’s equation,

Where,
λ = wavelength of moving particle
m = mass of particle
v = velocity of particle
h = Planck’s constant
Substituting the values in the expression of λ:

Hence, the wavelength of the electron moving with a velocity of 2.05 ×


107 ms–1 is 3.548 × 10 –11 m.

Q.21. The mass of an electron is 9.1 × 10 –31 kg. If its K.E. is 3.0 × 10 –25 J, calculate its wavelength.
Ans. From De Broglie’s equation,
λ = h/mv
Given,
Kinetic energy (K.E) of the electron = 3.0 × 10 –25 J

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Substituting the value in the expression of λ:

Hence, the wavelength of the electron is 8.9625 × 10 –7 m.

Q.22. Which of the following are isoelectronic species i.e., those having the same number of
electrons?
Na+ , K+ , Mg2+ , Ca2+ , S2–, Ar
Ans. Isoelectronic species have the same number of electrons.
Number of electrons in sodium (Na +) = 11
Number of electrons in (Na + ) = 10
A positive charge denotes the loss of an electron.
Similarly,
Number of electrons in K + = 18
Number of electrons in Mg 2+ = 10
Number of electrons in Ca 2+ = 18
A negative charge denotes the gain of an electron by a species.
Number of electrons in sulphur (S) = 16
∴ Number of electrons in S 2- = 18
Number of electrons in argon (Ar) = 18
Hence, the following are isoelectronic species:
1) Na+ and Mg2+ (10 electrons each)
2) K+ , Ca2+ , S2– and Ar (18 electrons each)

Q.23
(i) Write the electronic configurations of the following ions:
(a) H–
(b) Na+
(c) O2–
(d) F–
(ii) What are the atomic numbers of elements whose outermost electrons are represented by:
(a) 3s1
(b) 2p3
(c) 3p5?
(iii) Which atoms are indicated by the following configurations?
(a) [He] 2s1

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(b) [Ne] 3s2 3p3


(c) [Ar] 4s2 3d1.
Ans.
(i) (a) H– ion
The electronic configuration of H atom is 1s1.
A negative charge on the species indicates the gain of an electron by it.
∴ Electronic configuration of H – = 1s2
(b) Na+ ion
The electronic configuration of Na atom is 1s2 2s2 2p6 3s1.
A positive charge on the species indicates the loss of an electron by it.
∴ Electronic configuration of Na = 1s2 2s2 2p6 3s0 or 1s2 2s2 2p6
(c) O2– ion
The electronic configuration of 0 atom is 1s2 2s2 2p4.
A dinegative charge on the species indicates that two electrons are gained by it.
∴ Electronic configuration of O 2– ion = 1s2 2s2 p6
(d) F– ion
The electronic configuration of F atom is 1s2 2s2 2p5.
A negative charge on the species indicates the gain of an electron by it.
∴ Electron configuration of F – ion = 1s2 2s2 2p6
(ii) (a) 3s1
Completing the electron configuration of the element as
1s2 2s2 2p6 3s1.
∴ Number of electrons present in the atom of the element
= 2 + 2 + 6 + 1 = 11
∴ Atomic number of the element = 11
(b) 2p3
Completing the electron configuration of the element as
1s2 2s2 2p3.
∴ Number of electrons present in the atom of the element = 2 + 2 + 3 = 7
∴ Atomic number of the element = 7
(c) 3p5
Completing the electron configuration of the element as
1s2 2s2 2p5.
∴ Number of electrons present in the atom of the element = 2 + 2 + 5 = 9
∴ Atomic number of the element = 9
(iii) (a) [He] 2s1
The electronic configuration of the element is [He] 2s1 = 1s2 2s1.
∴ Atomic number of the element = 3
Hence, the element with the electronic configuration [He] 2s1 is lithium (Li).
(b) [Ne] 3s2 3p3
The electronic configuration of the element is [Ne] 3s2 3p3= 1s2 2s2 2p6 3s2 3p3.
∴ Atomic number of the element = 15
Hence, the element with the electronic configuration [Ne] 3s2 3p3 is phosphorus (P).
(c) [Ar] 4s2 3d1
The electronic configuration of the element is [Ar] 4s2 3d1= 1s2 2s2 2p6 3s2 3p6 4s2 3d1.
∴ Atomic number of the element = 21
Hence, the element with the electronic configuration [Ar] 4s2 3d1 is scandium (Sc).

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Q.24. What is the lowest value of n that allows g orbitals to exist?


Ans. For g-orbitals, l = 4.
As for any value ‘n’ of principal quantum number, the Azimuthal quantum number (l) can have a value
from zero to (n – 1).
∴ For l = 4, minimum value of n = 5
Q.25. An electron is in one of the 3d orbitals. Give the possible values of n, l and ml for this
electron.
Ans. For the 3d orbital:
Principal quantum number (n) = 3
Azimuthal quantum number (l) = 2
Magnetic quantum number (ml) = – 2, – 1, 0, 1, 2
Q.26: An atom of an element contains 29 electrons and 35 neutrons. Deduce
(i) the number of protons and
(ii) the electronic configuration of the element.
Ans:-
(i) For an atom to be neutral, the number of protons is equal to the number of electrons.
∴ Number of protons in the atom of the given element = 29
(ii) The electronic configuration of the atom is
1s2 2s2 2p6 3s2 3p6 4s2 3d10.
Q.27: Give the number of electrons in the species , H2 and
Ans:-
: Number of electrons present in hydrogen molecule (H2) = 1 + 1 = 2
∴ Number of electrons in =2–1=1
H2: Number of electrons in H 2 = 1 + 1 = 2
: Number of electrons present in oxygen molecule (O 2) = 8 + 8 = 16
∴ Number of electrons in = 16 – 1 = 15
Q. 28: (i) An atomic orbital has n = 3. What are the possible values of l and ml ?
(ii) List the quantum numbers (ml and l) of electrons for 3d orbital.
(iii) Which of the following orbitals are possible?
1p, 2s, 2p and 3f
Ans:-
(i) n = 3 (Given)
For a given value of n, l can have values from 0 to (n – 1).
∴ For n = 3
l = 0, 1, 2
For a given value of l, ml can have (2l 1) values.
For l = 0, m = 0
l = 1, m = – 1, 0, 1
l = 2, m = – 2, – 1, 0, 1, 2
∴ For n = 3
l = 0, 1, 2
m0 = 0
m1 = – 1, 0, 1
m2 = – 2, – 1, 0, 1, 2
(ii) For 3d orbital, l = 2.

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For a given value of l, mlcan have (2l 1) values i.e., 5 values.


∴ For l = 2
m2 = – 2, – 1, 0, 1, 2
(iii) Among the given orbitals only 2s and 2p are possible. 1p and 3f cannot exist.
For p-orbital, l = 1.
For a given value of n, l can have values from zero to (n – 1).
∴ For l is equal to 1, the minimum value of n is 2.
Similarly,
For f-orbital, l = 4.
For l = 4, the minimum value of n is 5.
Hence, 1p and 3f do not exist.
Q.29: Using s, p, d notations, describe the orbital with the following quantum numbers.
(a) n = 1, l = 0,
(b) n = 3; l =1,
(c) n = 4; l = 2,
(d) n = 4; l =3.
Ans:- (a) n = 1, l = 0 (Given)
The orbital is 1s.
(b) For n = 3 and l = 1
The orbital is 3p.
(c) For n = 4 and l = 2
The orbital is 4d.
(d) For n = 4 and l = 3
The orbital is 4f.
Q.30: Explain, giving reasons, which of the following sets of quantum numbers are not possible.

(a) n = 0, l = 0, ml = 0,
(b) n = 1, l = 0, ml = 0,

(c) n = 1, l = 1, ml = 0,

(d) n = 2, l = 1, ml = 0,

(e) n = 3, l = 3, ml = – 3,

(f) n = 3, l = 1, ml = 0,
Ans:-
(a) The given set of quantum numbers is not possible because the value of the principal quantum
number (n) cannot be zero.
(b) The given set of quantum numbers is possible.
(c) The given set of quantum numbers is not possible.
For a given value of n, ‘l’ can have values from zero to (n – 1).
For n = 1, l = 0 and not 1.
(d) The given set of quantum numbers is possible.
(e) The given set of quantum numbers is not possible.
For n = 3,

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l = 0 to (3 – 1)
l = 0 to 2 i.e., 0, 1, 2
(f) The given set of quantum numbers is possible.
Q.31: How many electrons in an atom may have the following quantum numbers?

(a) n = 4,
(b) n = 3, l = 0
Ans:-
(a) Total number of electrons in an atom for a value of n = 2n2
∴ For n = 4,
Total number of electrons = 2 (4) 2 = 32
The given element has a fully filled orbital as
1s2 2s2 2p6 3s2 3p6 4s2 3d10.
Hence, all the electrons are paired.

∴ Number of electrons (having n = 4 and ) = 16


(b) n = 3, l = 0 indicates that the electrons are present in the 3s orbital. Therefore, the number of
electrons having n = 3 and l = 0 is 2.
Q.32: 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.
Ans:- Since a hydrogen atom has only one electron, according to Bohr’s postulate, the angular
momentum of that electron is given by:

Where, n = 1, 2, 3, …
According to de Broglie’s equation:

Substituting the value of ‘mv’ from expression (2) in expression (1):

Since ‘2πr’ represents the circumference of the Bohr orbit (r), it is proved by equation (3) that the
circumference of the Bohr orbit of the hydrogen atom is an integral multiple of de Broglie’s
wavelength associated with the electron revolving around the orbit.

Q.33: What transition in the hydrogen spectrum would have the same wavelength as the Balmer
transition n = 4 to n = 2 of He spectrum?
Ans:- For He+ ion, the wave number associated with the Balmer transition, n = 4 to n = 2 is given by:

Where,
n1 = 2, n2 = 4

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Z = atomic number of helium

According to the question, the desired transition for hydrogen will have the same wavelength as that
of He+ .

By hit and trail method, the equality given by equation (1) is true only when n1 = 1and n2 = 2.
∴ The transition for n2 = 2 to n = 1 in hydrogen spectrum would have the same wavelength as Balmer
transition n = 4 to n = 2 of He + spectrum.

Q.34: Calculate the energy required for the process He+(g)→ He+(g) + e- The ionization energy for
the H atom in the ground state is 2.18 ×10 –18 J atom–1
Ans:- Energy associated with hydrogen-like species is given by,

For the given process,

An electron is removed from n = 1 to n = ∞.

∴ The energy required for the process


Q.35: If the diameter of a carbon atom is 0.15 nm, calculate the number of carbon atoms which can
be placed side by side in a straight line across length of scale of length 20 cm long.
Ans:- 1 m = 100 cm
1 cm = 10 –2 m
Length of the scale = 20 cm
= 20 × 10 –2 m
Diameter of a carbon atom = 0.15 nm
= 0.15 × 10 –9 m
One carbon atom occupies 0.15 × 10 –9 m.
∴ Number of carbon atoms that can be placed in a straight line

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Q.36: 2 × 10 8 atoms of carbon are arranged side by side. Calculate the radius of carbon atom if the
length of this arrangement is 2.4 cm.
Ans:- Length of the given arrangement = 2.4 cm
Number of carbon atoms present = 2 × 10 8
∴ Diameter of carbon atom

Q.37: The diameter of zinc atom is .Calculate (a) radius of zinc atom in pm and (b) number of
atoms present in a length of 1.6 cm if the zinc atoms are arranged side by side lengthwise.
Ans:- (a) Radius of zinc atom = diameter/2

(b) Length of the arrangement = 1.6 cm


= 1.6 × 10 –2 m
Diameter of zinc atom = 2.6 × 10 –10 m
∴ Number of zinc atoms present in the arrangement

Q.38: A certain particle carries 2.5 × 10 –16C of static electric charge. Calculate the number of
electrons present in it.
Ans:- Charge on one electron = 1.6022 × 10–19 C
⇒ 1.6022 × 10 –19C charge is carried by 1 electron.
∴ Number of electrons carrying a charge of 2.5 × 10 –16 C

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Q.39: In Milikan’s experiment, static electric charge on the oil drops has been obtained by shining
X-rays. If the static electric charge on the oil drop is –1.282 × 10 –18C, calculate the number of
electrons present on it.
Ans:- Charge on the oil drop = 1.282 ×10 –18C
Charge on one electron = 1.6022 × 10–19C
∴Number of electrons present on the oil drop

Q.40: In Rutherford’s experiment, generally the thin foil of heavy atoms, like gold, platinum etc.
have been used to be bombarded by the α-particles. If the thin foil of light atoms like aluminium
etc. is used, what difference would be observed from the above results?
Ans:- A thin foil of lighter atoms will not give the same results as given with the foil of heavier atoms.
Lighter atoms would be able to carry very little positive charge. Hence, they will not cause enough
deflection of α-particles (positively charged).
Q.41: Symbols 𝟕𝟗 79 𝟑𝟓 35
𝟑𝟓𝑩𝒓 and Br can be written, whereas symbols 𝟕𝟗𝑩𝒓 and Br are not acceptable.
Answer briefly.
Ans:- The general convention of representing an element along with its atomic mass (A) and atomic
number (Z) is
Hence, is acceptable but is not acceptable.
can be written but cannot be written because the atomic number of an element is constant,
but the atomic mass of an element depends upon the relative abundance of its isotopes. Hence, it is
necessary to mention the atomic mass of an element
Q.42: An element with mass number 81 contains 31.7% more neutrons as compared to protons.
Assign the atomic symbol.
Ans:- Let the number of protons in the element be x.
∴ Number of neutrons in the element
= x + 31.7% of x
= x + 0.317 x
= 1.317 x
According to the question,
Mass number of the element = 81
∴ (Number of protons number of neutrons) = 81

Hence, the number of protons in the element i.e., x is 35.


Since the atomic number of an atom is defined as the number of protons present in its nucleus, the
atomic number of the given element is 35.
∴ The atomic symbol of the element is .

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Q.43: An ion with mass number 37 possesses one unit of negative charge. If the ion contains 11.1%
more neutrons than the electrons, find the symbol of the ion.
Ans:- Let the number of electrons in the ion carrying a negative charge be x.
Then, Number of neutrons present = x + 11.1% of x
= x + 0.111 x
= 1.111 x
Number of electrons in the neutral atom = (x – 1)
(When an ion carries a negative charge, it carries an extra electron)
∴ Number of protons in the neutral atom = x – 1
Given, Mass number of the ion = 37
∴ (x – 1) + 1.111x = 37
2.111x = 38
x = 18
∴The symbol of the ion is

Q.44: An ion with mass number 56 contains 3 units of positive charge and 30.4% more neutrons
than electrons. Assign the symbol to this ion.
Ans:- Let the number of electrons present in ion
∴ Number of neutrons in it = x + 30.4% of x = 1.304 x
Since the ion is tri-positive,
⇒ Number of electrons in neutral atom = x + 3
∴ Number of protons in neutral atom = x + 3
Given, Mass number of the ion = 56

∴ Number of protons = x + 3 = 23 + 3 = 26
∴ The symbol of the ion
Q.45: Arrange the following type of radiations in increasing order of frequency:
(a) radiation from microwave oven
(b) amber light from traffic signal
(c) radiation from FM radio
(d) cosmic rays from outer space and
(e) X-rays.
Ans:- The increasing order of frequency is as follows:
Radiation from FM radio < amber light < radiation from microwave oven < X- rays < cosmic rays
The increasing order of wavelength is as follows:
Cosmic rays < X-rays < radiation from microwave ovens < amber light < radiation of FM radio
Q.46: Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of photons
emitted is 5.6 × 10 24, calculate the power of this laser.
Ans:- Power of laser = Energy with which it emits photons

Power

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Where,
N = number of photons emitted
h = Planck’s constant
c = velocity of radiation
λ = wavelength of radiation
Substituting the values in the given expression of Energy (E):

E = 0.3302 × 107 J
= 3.33 × 106 J
Hence, the power of the laser is 3.33 × 10 6 J.
Q.47: Neon gas is generally used in the sign boards. If it emits strongly at 616 nm, calculate
(a) the frequency of emission,
(b) distance traveled by this radiation in 30 s
(c) energy of quantum and
(d) number of quanta present if it produces 2 J of energy.
Ans:- Wavelength of radiation emitted = 616 nm
= 616 × 10 –9 m (Given)
(a) Frequency of emission

Where,
c = velocity of radiation
λ = wavelength of radiation
Substituting the values in the given expression of :

= 4.87 × 10 8 × 109 × 10–3 s–1


ν = 4.87 × 10 14 s–1
Frequency of emission (ν) = 4.87 × 10 14 s–1
(b) Velocity of radiation, (c) = 3.0 × 10 8 ms–1
Distance travelled by this radiation in 30 s
= (3.0 × 10 8 ms–1) (30 s)
= 9.0 × 10 9 m
(c) Energy of quantum (E) = hν
(6.626 × 10 –34 Js) (4.87 × 10 14 s–1)
Energy of quantum (E) = 32.27 × 10 –20 J
(d) Energy of one photon (quantum) = 32.27 × 10 –20 J
Therefore, 32.27 × 10 –20 J of energy is present in 1 quantum.
Number of quanta in 2 J of energy

= 6.19 ×10 18
= 6.2 ×1018

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Q.48: In astronomical observations, signals observed from the distant stars are generally weak. If
the photon detector receives a total of 3.15 × 10 –18 J from the radiations of 600 nm, calculate the
number of photons received by the detector.
Ans:- From the expression of energy of one photon (E),
E = hc / λ
Where,
λ = wavelength of radiation
h = Planck’s constant
c = velocity of radiation
Substituting the values in the given expression of E:

E
E = 3.313 × 10 –19 J
Energy of one photon = 3.313 × 10 –19 J
Number of photons received with 3.15 × 10 –18 J energy

= 9.5 ≈ 10
Q.49: Lifetimes of the molecules in the excited states are often measured by using pulsed radiation
source of duration nearly in the nano second range. If the radiation source has the duration of 2 ns
and the number of photons emitted during the pulse source is 2.5 × 10 15, calculate the energy of the
source.
Ans:- Frequency of radiation (ν),

ν = 5.0 × 108 s–1


Energy (E) of source = Nhν
Where,
N = number of photons emitted
h = Planck’s constant
ν = frequency of radiation
Substituting the values in the given expression of (E):
E = (2.5 × 1015) (6.626 × 10–34 Js) (5.0 × 108 s–1)
E = 8.282 × 10–10 J
Hence, the energy of the source (E) is 8.282 × 10–10 J.
Q. 50: The longest wavelength doublet absorption transition is observed at 589 and 589.6 nm.
Calculate the frequency of each transition and energy difference between two excited states.
Ans:-
For λ1 = 589 nm
Frequency of transition
Frequency of transition (ν1) = c / λ1

= 5.093 × 10 14 s–1
Similarly, for λ2 = 589.6 nm
Frequency of transition

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Frequency of transition (ν2) = c / λ2

=5.088 × 10 14 s–1
Energy difference (ΔE) between excited states = E1 – E2
Where,
E2 = energy associated with λ2
E1 = energy associated with λ1
ΔE = hν1 – hν2
= h(ν1 – ν2)
= (6.626 × 10 –34 Js) (5.093 × 10 14 – 5.088 × 1014)s–1
= (6.626 × 10 –34 J) (5.0 × 10 –3 × 1014)
ΔE = 3.31 × 10 –22 J.
Q.51: The work function for caesium atom is 1.9 eV. Calculate
(a) the threshold wavelength and
(b) the threshold frequency of the radiation. If the caesium element is irradiated with a wavelength
500 nm, calculate the kinetic energy and the velocity of the ejected photoelectron .
Ans:- It is given that the work function (W 0) for caesium atom is 1.9 eV.

(a) From the expression, , we get:

Where,
λ0 = threshold wavelength
h = Planck’s constant
c = velocity of radiation
Substituting the values in the given expression of (λ0):

6.53 × 10 –7 m
Hence, the threshold wavelength is 653 nm.
(b) From the expression, , we get:
Vo = W0/h
Where, ν0 = threshold frequency
h = Planck’s constant
Substituting the values in the given expression of ν0:

(1 eV = 1.602 × 10 –19 J)
ν0 = 4.593 × 10 14 s–1
Hence, the threshold frequency of radiation (ν0) is 4.593 × 10 14 s–1.
(c) According to the question:
Wavelength used in irradiation (λ) = 500 nm
Kinetic energy = h (ν – ν0)

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= 9.3149 × 10 –20 J
Kinetic energy of the ejected photoelectron = 9.3149 × 10 –20J

Since K.E

= 4.52 × 10 5 ms–1
Hence, the velocity of the ejected photoelectron (v) is 4.52 × 10 5 ms–1.
Q.52: Following results are observed when sodium metal is irradiated with different wavelengths.
Calculate (a) threshold wavelength and, (b) Planck’s constant.

Ans:- (a) Assuming the threshold wavelength to be , the kinetic energy of the
radiation is given as:

Three different equalities can be formed by the given value as:

Similarly,

Dividing equation (3) by equation (1):

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Threshold wavelength = 540 nm


Note: part (b) of the question is not done due to the incorrect values of velocity given in the
question.

Q.53 The ejection of the photoelectron from the silver metal in the photoelectric effect experiment
can be stopped by applying the voltage of 0.35 V when the radiation 256.7 nm is used. Calculate the
work function for silver metal.
Ans. From the principle of conservation of energy, the energy of an incident photon ( E) is equal to the
sum of the work function (W 0) of radiation and its kinetic energy (K.E) i.e.,
E = W0 K.E

⇒ W0 = E – K.E
Energy of incident photon (E)
Where,
c = velocity of radiation
h = Planck’s constant
λ = wavelength of radiation
Substituting the values in the given expression of E:

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E = 4.83 eV
The potential applied to silver metal changes to kinetic energy (K.E) of the photoelectron. Hence,
K.E = 0.35 V
K.E= 0.35 eV
Work function, W 0 = E – K.E
= 4.83 eV – 0.35 eV
= 4.48 eV

Q.54 If the photon of the wavelength 150 pm strikes an atom and one of its inner bound electrons is
ejected out with a velocity of 1.5 × 10 7 ms–1, calculate the energy with which it is bound to the
nucleus.
Ans. Energy of incident photon (E) is given by,
E = hc / λ

Energy of the electron ejected (K.E)

= 10.2480 × 10 –17 J = 1.025 × 10 –16J


Hence, the energy with which the electron is bound to the nucleus can be obtained as:
E – K.E = 13.252 × 10 –16 J – 1.025 × 10 –16 J
= 12.227 × 10 –16 J

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Q.55 Emission transitions in the Paschen series end at orbit n = 3 and start from orbit n and can be
represented as v = 3.29 × 10 15 (Hz) [1/32 – 1/n2] . Calculate the value of n if the transition is
observed at 1285 nm. Find the region of the spectrum.
Ans. Wavelength of transition = 1285 nm
= 1285 × 10–9 m (Given)

(Given)
Since v = c/λ

ν = 2.33 × 1014 s–1


Substituting the value of ν in the given expression,

n = 4.98 ≈ 5
Hence, for the transition to be observed at 1285 nm, n = 5.
The spectrum lies in the infra-red region.
Q.56 Calculate the wavelength for the emission transition if it starts from the orbit having radius
1.3225 nm & ends at 211.6 pm. Name the series to which this transition belongs & the region of the
spectrum.
Ans. The radius of the nth orbit of hydrogen-like particles is given by,

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For radius (r1) = 1.3225 nm


= 1.32225 × 10 –9 m
= 1322.25 × 10 –12 m
= 1322.25 pm

Thus, the transition is from the 5 th orbit to the 2 nd orbit. It belongs to the Balmer series.
Wave number for the transition is given by,

1.097 × 10 7 m–1

= 2.303 × 10 6 m–1
Wavelength (λ) associated with the emission transition is given by,

= 0.434 ×10 –6 m
λ = 434 nm
Q.57 Dual behaviour of matter proposed by de Broglie led to the discovery of electron microscope
often used for the highly magnified images of biological molecules & other type of material. If the
velocity of the electron in this microscope is 1.6×10 6 ms–1, calculate de Broglie wavelength
associated with this electron.
Ans. From de Broglie’s equation,

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= 4.55 × 10 –10 m = 455 pm


de Broglie’s wavelength associated with the electron is 455 pm.
Q.58 Similar to electron diffraction, neutron diffraction microscope is also used for the
determination of the structure of molecules. If the wavelength used here is 800 pm, calculate the
characteristic velocity associated with the neutron.
Ans. From de Broglie’s equation,

Where,
v = velocity of particle (neutron)
h = Planck’s constant
m = mass of particle (neutron)
λ = wavelength
Substituting the values in the expression of velocity (v),

= 4.94 × 10 2 ms–1
v = 494 ms–1
Velocity associated with the neutron = 494 ms –1
Q.59 If the velocity of the electron in Bohr’s first orbit is 2.19 × 10 6 ms–1, calculate the de Broglie
wavelength associated with it.
Ans. According to de Broglie’s equation,

Where,
λ = wavelength associated with the electron
h = Planck’s constant
m = mass of electron
v = velocity of electron
Substituting the values in the expression of λ:

λ = 332 pm
Wavelength associated with the electron = 332 pm

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Q.60 The velocity associated with a proton moving in a potential difference of 1000 V is 4.37 ×
105 ms–1. If the hockey ball of mass 0.1 kg is moving with this velocity, calculate the wavelength
associated with this velocity.
Ans. According to De Broglie’s expression,
λ = h/mv
Substituting the values in the expression,

Q.61 If the position of the electron is measured within an accuracy of 0.002 nm, calculate the
uncertainty in the momentum of the electron. Suppose the momentum of the electron is h/4π m ×
0.05 nm, is there any problem in defining this value.
Ans. From Heisenberg’s uncertainty principle,

Where,
Δx = uncertainty in position of the electron
Δp = uncertainty in momentum of the electron
Substituting the values in the expression of Δp:

= 2.637 × 10–23 Jsm–1


Δp = 2.637 × 10–23 kgms–1 (1 J = 1 kgms2s–1)
Uncertainty in the momentum of the electron = 2.637 × 10 –23 kgms–1.

Actual momentum =

= 1.055 × 10–24 kgms–1


Since the magnitude of the actual momentum is smaller than the uncertainty, the value cannot be
defined.
Q.62 The quantum numbers of six electrons are given below. Arrange them in order of increasing
energies. If any of these combination(s) has/have the same energy lists:
(1). n = 4, l = 2, ml = –2 , ms = –1/2
(2). n = 3, l = 2, ml= 1 , ms = 1/2
(3). n = 4, l = 1, ml = 0 , ms = 1/2
(4). n = 3, l = 2, ml = –2 , ms = –1/2
(5). n = 3, l = 1, ml = –1 , ms= 1/2
(6). n = 4, l = 1, ml = 0 , ms = 1/2
Ans. For n = 4 and l = 2, the orbital occupied is 4d.
For n = 3 and l = 2, the orbital occupied is 3d.
For n = 4 and l = 1, the orbital occupied is 4p.

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Hence, the six electrons i.e., 1, 2, 3, 4, 5, and 6 are present in the 4d, 3d, 4p, 3d, 3p, and 4p orbitals
respectively.
Therefore, the increasing order of energies is 5(3p) < 2(3d) = 4(3d) < 3(4p) = 6(4p) < 1 (4d).
Q.63 The bromine atom possesses 35 electrons.It contains 6 electrons in 2p orbital,6 electrons in
3p orbital & 5 electrons in 4p orbital. Which of these electron experiences the lowest effective
nuclear charge?
Ans. Nuclear charge experienced by an electron (present in a multi-electron atom) is dependant upon
the distance between the nucleus and the orbital, in which the electron is present. As the distance
increases, the effective nuclear charge also decreases.
Among p-orbitals, 4p orbitals are farthest from the nucleus of bromine atom with ( 35) charge. Hence,
the electrons in the 4p orbital will experience the lowest effective nuclear charge. These electrons are
shielded by electrons present in the 2p and 3p orbitals along with the s-orbitals. Therefore, they will
experience the lowest nuclear charge.
Q.64 Among the following pairs of orbitals which orbital will experience the larger effective nuclear
charge?
(i) 2s and 3s,
(ii) 4d and 4f,
(iii) 3d and 3p
Ans. Nuclear charge is defined as the net positive charge experienced by an electron in the orbital of
a multi-electron atom. The closer the orbital, the greater is the nuclear charge experienced by the
electron (s) in it.
(i) The electron(s) present in the 2s orbital will experience greater nuclear charge (being closer to the
nucleus) than the electron(s) in the 3s orbital.
(ii) 4d will experience greater nuclear charge than 4f since 4d is closer to the nucleus.
(iii) 3p will experience greater nuclear charge since it is closer to the nucleus than 3f.
Q.65 The unpaired electrons in Al and Si are present in 3p orbital. Which electrons will experience
more effective nuclear charge from the nucleus?
Ans. Nuclear charge is defined as the net positive charge experienced by an electron in a multi-electron
atom.The higher the atomic number,the higher is the nuclear charge. Silicon has 14 protons while
aluminium has 13 protons. Hence, silicon has a larger nuclear charge of ( 14) than aluminium, which has
a nuclear charge of ( 13) Thus, the electrons in the 3p orbital of silicon will experience a more effective
nuclear charge than aluminium.
Q.66 Indicate the number of unpaired electrons in:
(a) P,
(b) Si,
(c) Cr,
(d) Fe
(e) Kr.
Ans. (a) Phosphorus (P):
Atomic number = 15
The electronic configuration of P is:
1s2 2s2 2p6 3s2 3p3
The orbital picture of P can be represented as:

From the orbital picture, phosphorus has three unpaired electrons.


(b) Silicon (Si):
Atomic number = 14

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The electronic configuration of Si is:


1s2 2s2 2p6 3s2 3p2
The orbital picture of Si can be represented as:

From the orbital picture, silicon has two unpaired electrons.


(c) Chromium (Cr):
Atomic number = 24
The electronic configuration of Cr is:
1s2 2s2 2p6 3s2 3p6 4s1 3d5
The orbital picture of chromium is:

From the orbital picture, chromium has six unpaired electrons.


(d) Iron (Fe):
Atomic number = 26
The electronic configuration is:
1s2 2s2 2p6 3s2 3p6 4s2 3d6
The orbital picture of chromium is:

From the orbital picture, iron has four unpaired electrons.


(e) Krypton (Kr):
Atomic number = 36
The electronic configuration is:
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6
The orbital picture of krypton is:

Since all orbitals are fully occupied, there are no unpaired electrons in krypton.
Q.67
(a) How many sub-shells are associated with n = 4?
(b) How many electrons will be present in the sub-shells having ms value of –1/2 for n = 4?
Ans. (a) n = 4 (Given)
For a given value of ‘n’, ‘l’ can have values from zero to (n – 1).
∴ l = 0, 1, 2, 3
Thus, four sub-shells are associated with n = 4, which are s, p, d and f.
(b) Number of orbitals in the nth shell = n2
For n = 4
Number of orbitals = 16
If each orbital is taken fully, then it will have 1 electron with ms value of - ½.
∴ Number of electrons with ms value of (- ½ ) is 16.

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EXEMPLER PROBLEMS

Q1. Which of the following conclusions could not be derived from Rutherford’s α-
particle scattering experiment?
(a) Most of the space in the atom is empty.
(b) The radius of the atom is about 10 -10 m while that of nucleus is 10 -15
(c) Electrons move in a circular path of fixed energy called orbits.
(d) Electrons and the nucleus are held together by electrostatic forces of attraction.
Sol: (c) The concept of circular paths of fixed energy was proposed by Bohr and not derived
from Rutherford’s scattering experiment.

Q2. Which of the following options does not represent ground state electronic
configuration of an atom?
(i) 1s2 2s2 2p6 3s2 3p6 3d8 4s2
(ii) 1s2 2s2 2p6 3s2 3p6 3d9 4s2
(iii) 1s2 2s2 2p6 3s2 3p6 3d10 4s1
(iv) 1s2 2s2 2p6 3s2 3p6 3d5 4s1
Sol: (b) Correct configuration in ground state should be 1 s2 2s2 2p6 3s2 3pb3d104s1

Q3. The probability density plots of Is and 2s orbitals are given in the following
figures.

The density of dots in a region represents the probability density of finding electrons in
the region. On the basis of the above diagram, which of the following statements is
incorrect?
(a) 1s and 2s orbitals are spherical in shape.
(b) The probability of finding the electron is maximum near the nucleus.
(c) The probability of finding the electron at a given distance is equal in all directions.
(d) The probability density of electrons for 2s orbital decreases uniformly as distance
from the nucleus increases.
Sol: (d) The probability density of electrons for 2s orbital first increases then decreases
and after that it begins to increase again.

Q4. Which of the following statements is not correct about the characteristics of
cathode rays?
(a) They start from the cathode and move towards the anode.
(b) They travel in straight line in the absence of an external electrical or magnetic
field.
(c) Characteristics of cathode rays do not depend upon the material of electrodes in

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cathode ray tube.


(d) Characteristics of cathode rays depend upon the nature of gas present in the
cathode ray tube.
Sol:(d) Cathode rays consist of negatively charged material particles called electron. They
were discovered by William Crookes. The characteristics of cathode rays do not depend upon
the material of electrodes and the nature of the gas present in the cathode ray tube.

Q5. Which of the following statements about the electron is incorrect?


(a) It is a negatively charged particle.
(b) The mass of electron is equal to the mass of neutron.
(c) It is a basic constituent of all atoms.
(d) It is a constituent of cathode rays.
Sol: (b) The mass of electron is very small as compared to the mass of the neutron. Mass of
electron = 9.1 x 10-31 kg Mass of neutron = 1.674 x 10-27 kg

Q6. Which of the following properties of atom could be explained correctly by Thomson
Model of atom?
(a) Overall neutrality of atom.
(b) Spectra of hydrogen atom.
(c) Position of electrons, protons and neutrons in atom.
(d) Stability of atom.
Sol: (a) According to Thomson model of atom, the mass of the atom is assumed to be
uniformly distributed over the atom. This model was able to explain the overall neutrality of
the atom.

Q7. Two atoms are said to be isobars if


(a) they have same atomic number but different mass number.
(b) they have same number of electrons but different number of neutrons.
(c) they are same number of neutrons but different number of electrons.
(d) Sum of the number of protons and neutrons is same but the number of protons is
different.
Sol: (d) Isobars have different atomic number, i.e., number of protons but same mass
number, i.e., sum of number of protons and neutrons.

Q8. The number of radial nodes for 3p orbital is .


(a) 3 (b) 4 (c) 2 (d) 1
Sol: (d) Number of radial nodes = n-1 – 1
For 3p orbital, n = 3 – 1 – 1 = 1
Number of radial nodes = 3 – 1 – 1 = 1

Q9. Number of angular nodes for 4d orbital is __________ .


(a) 4 (b) 3 (c) 2 (d) 1
Sol: (c) Number of angular nodes in 4d orbital = l = 2

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Q10. Which of the following is responsible to rule out the existence of definite paths
or trajectories of electrons?
(a) Pauli’s exclusion principle
(b) Heisenberg’s uncertainty principle
(c) Hund’s rule of maximum multiplicity
(d) Aufbau principle
Sol: (b) According to Heisenberg’s uncertainty principle, the position and velocity of an
electron cannot be determined simultaneously with accuracy which rules out the existence of
fixed paths.

Q11. Total number of orbitals associated with third shell will be _______.
(a) 2 (b) 4 (c) 9 (d) 3
Sol: (c) No of orbitals in 3 shell (n = 3) = n2 = 32 = 9.
rd

Q12. Orbital angular momentum depends on


(a) l (b) n and l (c) n and m (d) m and s
𝒉
Sol. (a) Orbital angular momentum= √𝒍(𝑖 + 1) 𝟐𝝅. Hence, it depends only on l

Q13. Cl exists in two isotopic forms, Cl-37 and Cl-35, but its atomic mass is 35.5.
This indicates the ratio of Cl-37 and Cl-35 is approximately
(a) 1 : 2 (b) 1 : 1 (c) 1:3 (d) 3:1

Q14. The pair of ions having same electronic configuration is _______


(i) Cr3+, Fe3+ (ii) Fe3+, Mn2+ (iii) Fe3+, Co3+ (iv) Sc3+, Cr3+

Q15. For the electrons of oxygen atom, which of the following statements is correct?
(a) Zeff for an electron in a 2s orbital is the same as Zeff for an electron in a 2p
(b) An electron in the 2s orbital has the same energy as an electron in the 2p
(c) Zeff for an electron in Is orbital is the same as Zeff for an electron in a 2s orbital.
(d) The two electrons present in the? s orbital have spin quantum numbers ms but of
opposite sign.

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Q16. If traveling at same speeds, which of the following matter waves have the
shortest wavelength?
(a) Electron
(b) Alpha particle (He2- )
(c) Neutron
(d) Proton

More than One Correct Answer Type


Q17. Identify the pairs which are not of isotopes?

Q18. Out of the following pairs of electrons, identify the pairs of electrons present in
degenerate orbitals:
(a) (i) n = 3, l = 2, ml = -2, ms = -1/2, (ii) n = 3, l= 2, ml = -1, ms = -1/2
(b) (i) n = 3, l = 1, ml = 1, ms = +1/2, (ii) n = 3, l = 2, ml = 1, ms = +1/2
(c) (i) n = 4, l = 1, ml = 1, ms = +1/2 (ii) n = 3, l = 2, ml = 1, ms = +1/2
(d) (i) n = 3, l = 2, ml = +2, ms = -1/2 (ii)n = 3, l = 2, ml = +2, ms = +1/2
Sol: (a, d) Degenerate orbitals mean the orbitals of the same sub-shell of the same main shell,
i.e., their n and l values are the same. Other two pairs have different values of n and l
hence, cannot be having the same energy.
Q19. Which of the following sets of quantum numbers are correct?

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Sol: (b, c) If n = 1, l ≠ 1. Hence, (a) is wrong.


If n = 2, l= 0, 1. For l = 1, m = -1, 0, +1. Hence (b) is correct.
If n = 3, l= 0, 1,2. For l = 2, m = -2, -1, 0, +1, +2. Hence (c) is correct.
If n = 3, l ≠4. Hence, (d) is wrong.

Q20. In which of the following pairs, the ions are isoelectronic?


(i) Na+, Mg2+ (ii) Al3+, O– (iii) Na+, O2- (iv) N3–, Cl–

Q21. Which of the following statements concerning the quantum numbers are correct?
(a) Angular quantum number determines the three dimensional shape of the orbital.
(b) The principal quantum number determines the orientation and energy of the orbital.
(c) Magnetic quantum number determines the size of the orbital.
(d) Spin quantum number of an electron determines the orientation of the spin of
electron relative to the chosen axis.
Sol: (a, d)
(a) Azimuthal quantum number l is also known as orbital angular momentum or subsidiary
quantum number. It determines three-dimensional shape of the orbital.
(b) The principal quantum number determines the size of the orbit.
(c) Magnetic quantum number determines the orientation of the electron cloud in a subshell.
(d) An electron spins around its own’ axis, much in a similar way as earth spins around its own
axis while revolving around the sun. In other words, an electron has, besides charge and
mass, intrinsic spin angular quantum number.

Short Answer Type Questions


Q22. Arrange s, p and d sub-shells of a shell in the increasing order of effective nuclear
charge (Zeff) experienced by the electron present in them
Sol: .s-orbitals shield the electrons from the nucleus more effectively than p-orbitals which
in turn shield more effectively than d-orbitals. Hence, the arrangement of subshells in the
increasing order of effective nuclear charge is: d < p < s

Q23. Show the distribution of electrons in oxygen atom (atomic number 8)


using orbital diagram.

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Q24. Show the distribution of electrons in oxygen atom (atomic number 8) using orbital
diagram.
Sol: Ni (28): ls2 2s2 2p6 Is2 3p6 3d8 4s2
Ni2+ (26): Is2 2s2 2p6 3s2 3p6 3d8
Hence, to form Ni2+ ion, it will lose 2 electrons from 4s orbital.

Q25. Which of the following orbitals are degenerate?


3dxy, 4dxv, 3dyz, 3dz2:, 4dyz., 4dz2:
Sol: Degenerate orbitals are the orbitals of the same subshell of the same main shell. Hence,
these are
(3dxy, 3d z2, 3dyz) and (4dxy, 4dxz, 4d z2).

Q26. Calculate the total number of angular nodes and radial nodes present in 3p
orbital.
Sol: For 3p orbital, n = 3,l= 1
Number of angular nodes = 1=1
Number of radial nodes = n — l —1 = 3—1 — 1 = 1
Q27. The arrangement of orbitals on the basis of energy is based upon their (n +l)
value. Lower the value of (n + l), lower is the energy. For orbitals having the same
values of (n + I), the orbital with lower value of n will have lower energy.
I. Based upon the above information, arrange the following orbitals in the increasing
order of energy.
(a) 1s, 2s, 3s, 2p (b) 4s, 3s , 3p, 4d
(c) 5p, 4d, 5d, 4f, 6s (d) 5f, 6d , 7s , 7p
II. Based upon the above information, solve the questions given below:
(a) Which of the following orbitals has the lowest energy?
4d, 4f, 5s, 5p
(b) Which of the following orbitals has the highest energy?
5p, 5d, 5f 6s, 6p

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Q28. Which of the following will not show deflection from the path on passing through
an electric field?
Proton, cathode rays, electron, neutron.
Sol: Neutron, since it is neutral and cannot be deflected by an electric field.

Q29. An atom having atomic mass number 13 has 7 neutrons. What is the atomic
number of the atom?
Sol: Atomic mass number = A = 13. n = 7
As A = n + p p = A — n= 13 —7 = 6
Hence Z = p = 6

Q30. Wavelengths of different radiations are given below:

Q31. The electronic configuration of valence shell of Cu is 3d10 4s 1 and not 3d94s2. How
is this configuration explained?
Sol: Configuration with completely filled and half-filled orbitals have extra stability. In
3d104s1, d-orbitals are completely filled and s-orbital is half- filled. Hence, it is a more stable
configuration.

Q32. The Balmer series in the hydrogen spectrum corresponds to the transition from
n1 = 2 to n2 = 3, 4,……… This series lies in the visible region. Calculate the wave number
of line associated with the transition in Balmer series when the electron moves to n = 4
orbit. (RH = 109677 cm-1).

Q33. According to de Broglie, matter should exhibit dual behaviour, that is both
particle and wave like properties. However, a cricket ball of mass 100 g does not move
like a wave when it is thrown by a bowler at a speed of 100 km/h. Calculate the
wavelength of the ball and explain why it does not show wave nature.

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Since the wavelength is very small, the wave nature cannot be detected.

IMPORTANT QUESTIONS

1 Marks Questions
Question 1. How many total electrons are present in nitrate ion?
Answer:
No. of electrons in NO3– ion
= No. of electrons on N + No. of electrons on 3 oxygen atom + one ē = 7 + 3 × 8 + 1 = 32 e-

Question 2. The nucleus of the atom of an element does not contain a neutron. Name the
element and what does its nucleus consists of.
Answer:
The nucleus of hydrogen. It contains only one proton.

Question 3. What are nucleons?


Answer:
The neutrons and protons present in the nucleus of an atom are collectively called nucleons.

Question 4. Write electronic configurations of Chromium (At. Np. = 24).


Answer:
Cr = 24 = 1s2, 2s2 2p6, 3s2 3p6 3d5, 4s1.

Question 5. Which of the following has the smallest de-Broglie wavelength? O2, H2, a proton,
an electron.
Answer:
According to the de-Broglie equation λ = hm×v for same value of velocity λ ∝1m
∴ O2 molecule has shortest wavelength.

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Question 6. How many unpaired electrons are there is a carbon atom in the ground state?
Answer:
C = 6 = 1s2, 2s2, 2p1x 2p1y. There are only two unpaired electrons.
Question 7. What type of spectrum is obtained when light emitted from the discharge tube
containing hydrogen gas is analyzed?
Answer:
Emission line spectrum.

Question 8. What is the maximum number of e-s in an atom having n = 3, l = 1 and s = + 12?
Answer:
Three electrons (one each in 3px’ 3py’, 3pz’ ).
Question 9. Name the spectral line in the spectrum of H-atom obtained when an electron
jumps from n = 4 to n = 2.
Answer:
Balmer Series.
Question 10. Give some examples of electromagnetic radiation.
Answer:
Y-rays, X-rays, UV-rays, visible rays, radio waves, etc.
Question 11. State two properties of electromagnetic radiation.
Answer:
Electromagnetic radiation shows the phenomenon of:
1. Interference,
2. Diffraction.
Question 12. What is meant by the quantization of electron energy?
Answer:
It means that an electron in an atom has a certain, specific, discrete amount of energy.
Question 13. What does a principal quantity number denote?
Answer:
It denotes a specific stationary state.
Question 14. Why Bohr’s orbits are also called ‘energy levels’?
Answer:
Because they are associated with a certain definite amount of energy.
Question 15. How many spherical nodal surfaces are there in a 3s- sub-shell?
Answer:
Two.
Question 16. Out of 6s and 4f orbitals, which has higher energy and why?
Answer:
4forbital has higher energy, ((n + l) value of 4f is 7 while that of 6s is 6). The higher the (n +
l) value of an orbital higher is the energy.
Question 17. List the value/values of quantum numbers n and l for 4f electrons.
Answer:
n = 4, l = 3.

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Question 18. Out of 4s and 3d orbitals, which will have higher energy and why?
Answer:
3d orbital has higher energy as it has a higher value of (n + l).
Question 19. Which of the following orbitals are not possible?
1p, 2p, 2d, 3f, 4f?
Answer:
1p, 2d, 3f is not possible.
Question 20. Which orbital does not have directional characteristics?
Answer:
s-orbital.
Question 21. An electron is in 3p-orbital. What are the permitted values of n, l, and m?
Answer:
n = 3, l = 1, m = – 1, 0, + 1.
Question 22. Write designation of an orbital having n = 5,1 = 3.
Answer:
5f -orbital.
Question 23. Consider the electronic configuration 1s° 2s° 2p° 3s1.
Name the element having this configuration. Is it in an excited state or ground state?
Answer:
It is the configuration of the H-atom. It is in an excited state.
Question 24. Which quantum number determines the
(i) size, Principal
(ii) orientation, Magnetic
(in) the shape of orbital, Azimuthal quantum number.
Question 25. Which energy level does not have a p-orbital?
Answer:
First energy level (i.e., n – 1, K-shell).
Question 26. Name an element that has only one d-electron.
Answer:
Scandium (atomic no. = 21).
Question 27. Given an isotone of C-13 atom.
Answer:
Isotones are the atoms of different elements which have the same number of neutrons. N-
14 is an isotone of a C-13 atom.
Question 28. Which of the following orbitals does not make sense? 5s, 4f, 3p, 2d.
Answer:
2d orbital does not exist and thus makes no sense.
Question 29. Name the famous experiment which showed for the first time that an atom has
a nucleus.
Answer:
Rutherford experiment of scattering of a-particles.

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Question 30. Write the value of four quantum numbers for the valence electron of the
sodium atom.
Answer:
Na atom has 11 electrons and its valence electron is 3s1 (as configuration is 1s2, 2s2p6, 3s1)
∴ The value are: n = 3, l = 0, m = 0, s = + 12
Question 31. What is the relationship between velocity, wavelength, and frequency of
radiation?
Answer: These three characteristics of wave motion are related to each other as frequency
= Velocity Wavelength
In terms of symbols v = cλ.
Question 32. How wave number (v⃗ ) and wave length (λ) are related?
Answer:
v⃗ = 1λ . Wave number is the reciprocal of wavelength.
Question 33.Which series of hydrogen spectrum lies in the visible spectrum?
Answer:
Balmer series.
Question 34.How do you distinguish the two electrons present in the same orbital?
Answer:
By their spin quantum no. s which has + 12 and – 12 values.
Question 35. Name the principle which establishes that two electrons cannot have the same
values for all the 4 quantum numbers.
Answer:
Pauli exclusion principle.
Question 36. Write down the electronic configuration of Cu (= 29) in the ground state.
Answer:
Cu = 29 = 1s2, 2s2 2p6, 3s2 3p6, 3d10 4s1.
Question 37. What is the lowest value of n that allows g orbitals to exists?
Answer:
n = 5.
Question 38. Why do an atom M and its ion M2+ have the same mass?
Answer:
Both have the same no. of neutrons and protons which are responsible for the mass of an
atom.
Question 39. The nucleus of an atom has 6 protons and 8 neutrons. What are its atomic
number and mass number? What is this element1?
Answer:
At. No. = 6; Mass No. = 6 + 8 = 14; Element is Carbon.
Question 40. What is the number of electrons having l = 0 in an atom with an atomic number
29?
Answer:
7. [1s2, 2s2, 3s2, 4s1, i.e., 2 + 2 + 1 = 7]

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Question 41. Express s, p, d, f for a shell in increasing order of energy.


Answer: s < p < d < f. .
Question 42. For n = 5; what are the possible values of l?
Answer: When n = 5; l = 0,1, 2, 3, 4.
Question 43. For l = 3, what are the possible values of m?
Answer: m = – 3, – 2, – 1, 0, + 1, + 2, + 3.
Question 44. The ionization potential of an atom is 13.6 V. How much energy is required to
ionize it?
Answer: 13.6 eV.
Question 45. The threshold wavelength for a metal surface is λ0. How is it related to the
work function of the metal?
Answer: W0 = hcλ0
Question 46.Write the energy E of a photon in terms of frequency.
Answer: E = hv where h is called Planck’ constant.
Question 47. How much energy is required for the removal of the only electron present in
the hydrogen atom?
Answer:
ΔE = E∞ – E1 = 0 – (- 1312 kJ mol-1) – 1312 kJ mol-1.
Question 48. Which quantum number determines the
(a) shape, Azimuthal
(b) orientation, Magnetic
(c) size of the orbital, Principal.
Question 49. Write down the values of n, l, m, s of the last electron in potassium (Z = 19)?
Answer:
The last electron in potassium is present in 4s.
Its n = 4; l = 0; m = 0, s = + 12 or – 12.
Question 50.What is the sequence of energies of 3s, 3p, and 3d orbitals in
(i) H-atom
Answer:
H-atom: 3s = 3p = 3d
(ii) a multi-electron atom?
Answer:
3s < 3p < 3d.
Question 51. Name the cations which do not have any electrons.
Answer:
H+, He2+.
Question 52. How many quantum numbers are required to specify an orbital? Name them.
Answer: Three quantum numbers.
These are 1. Principal quantum no. (n)
2. Azimuthal quantum No. (l)
3. Magnetic quantum no. (m).

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Question 53. What is observed when an opaque object is placed in the path of cathode rays?
Answer:
A shadow of an opaque object is observed on the wall opposite to cathode.
Question 54. What happens when a very light paddle wheel is placed? in the path of cathode
rays?
Answer:
It begins to undergo a rotatory motion.
Question 55. What name was given to the particles which constitute cathode rays?
Answer:
Electron.
Question 56. Arrange the following orbitals in the order in which electrons may be normally
expected to fill them.
3s, 2p, 3p, 2s, 3d, 4s.
Answer: According to the Aufbau principle, the given orbitals will be filled in the order: 2s,
2p, 3s, 3p, 4s, 3d.
Question 57. Which fundamental property of an atom is not understood if we assume that an
atom consists of a nucleus containing protons only and an extranuclear part containing an
equal number of electrons?
Answer:
The mass number of atoms and stability of the nucleus cannot be explained.
Question 58. The following ions are isoelectronic: F–, Mg2+, O2-. Write the common electronic
configuration.
Answer: Each given ion contains 10 electrons. The common configuration is that of the Neon
atom, i.e., 1s2, 2s2 p6.
Question 59. What is the atomic number of an element whose mass number is 23 and
contains 12 neutrons in its nucleus? What is the symbol of an element?
Answer:
Atomic number = No. of protons in the nucleus
= Mass no. – No. of neutrons
= 23 – 12 = 11
The element is sodium and its symbol is Na.
Question 60. An atom has 2 K, 8 L, and 5 M electrons. Write the electronic configuration of
the atom. How many unpaired electrons are there in the atom?
Answer:
Electronic configuration of atom is: 1s2, 2s2p6, 3s2, 3p1x, 3p1y, 3p1z. It has three unpaired
electrons.
Question 61. Write the various possible quantum numbers for unpaired electron of Aluminium
atom?
Answer:
Al = 13 = 1s2, 2s2 2p6 3s2 3p1x
n = 3; l = 1; m = – 1, 0, + 1; s = 12 or – 12 .

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Question 62. Give the values of quantum numbers for the electron with the highest energy in
sodium atom.
Answer:
n = 3; l = 0; m = 0; s = + 12 or – 12 .
Question 63. What do you observe in the spectrum of NaCl?
Answer:
Two yellow lines with a wavelength of 5890 Å and 5896 Å
Question 64. What do you mean by saying that the energy of the electron is quantized?
Answer:
This means that the electrons in an atom have only definite values of energy.
Question 65. Why are Bohr’s orbits called stationary states?
Answer:
This is because the energies of the orbits in which the electrons revolve are fixed.
Question 66. What is the difference between a quantum and a photon?
Answer:
The smallest packet of energy of any radiation is called a quantum whereas that of light is
called a photon.
Question 67. Which quantum number does not follow from the solution of the Schrodinger
wave equation?
Answer:
Spin quantum number.
Question 68. How many orbitals will be possible in a g-subshell?
Answer:
For g-subsheil l = 4; m = 2l + 1; – 4, – 3, – 2, – 1, 0, + 1, + 2, + 3, + 4; 9 orbitals.

2 Marks Questions
Question 1. Enumerate the important characteristics of anode-rays (or positive rays). How
this study led to the discovery of proton?
1) The mass of positive particles which constitute these rays depend upon the nature of
the gas in the tube.
2) The charge/mass (e/m) ratio of anode-rays is not constant but depends upon the
nature of gas in the tube. The value of e/m is greatest for the lightest gas, hydrogen
the electric charge on a lightest positively charged particle from hydrogen gas was
found to be exactly equal in magnitude but opposite in sign to that of the electron.
This lightest positively charged particle from hydrogen gas was named the proton. The
mass of a proton is almost 1836 times that of the electron.
Question 2. What are anode-rays? Illustrate their formation by a diagram.
Answer: Anode-rays. If a perforated cathode is used in the discharge tube experiment, it is
found that a certain type of radiation also travels from anode to cathode. These are called
anode rays or positive rays.

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Question 3. Describe the important properties of cathode-rays. What is concluded about the
nature of these rays?
Answer: The cathode rays possess the following properties:
1) Travel in straight lines perpendicular to the surface of the cathode.
2) Consists of material particles.
3) Have got the heating effect.
4) Consists of negatively charged particles.
5) Produce X-rays when they strike against hard metals like copper, tungsten, platinum,
etc.
6) Produce fluorescence when they strike glass or certain other materials like zinc
sulfide.
7) Penetrate through thin aluminum foils and other metals.
8) Affect the photographic plates.
Question 4. What are the main features of Rutherford’s model of an atom?
Answer: The main features of this model are:
1) Atom is spherical and consists of two parts: Nucleus and extra-nuclear part.
2) The entire mass and entire positive charge are concentrated in a very small region at
the center known as the nucleus.
3) The space surrounding the nucleus known as the extra-nuclear part is negatively
charged so an atom as a whole is neutral.
4) Most of the extra-nuclear part is empty.
5) The electrons are not stationary but are revolving around the nucleus at very high
speeds like planets revolving around the Sun.
Question 5. What is meant by the dual nature of radiation?
Answer: The fact that light energy is carried in terms of packets of energy (i.e., photons) as
suggested by Planck’s theory means that light has a particle character. At the same time,
the fact light has a wave character. These experimental facts led Einstein to suggest that
light has a dual character, i.e., it behaves both like a wave and like a particle.
Question 6. Describe the drawback to Rutherford’s model of the atom.
Answer: The main drawback is that it could not explain the stability of an atom. Maxwell has
shown that when electric charge is subjected to acceleration, it emits energy in the form of
radiations. In Rutherford’s model of the atom, electrons are orbiting the nucleus and hence
the direction of their velocity is constantly changing, i.e., electrons are accelerating.
This will cause the electrons will have lesser and lesser energy and will
get closer and closer to the nucleus until at last, it spirals into the
nucleus and thus does not provide a stable model of the atom.

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Question 7. What is the value of (i) charge to mass ratio (e/m) of electrons,
Answer: J. Thomson determined the value of e/m for electron by the study of deflection of
electron beam under the simultaneous influence of electric and magnetic field perpendicular
to each other, the e/m value is 1.76 × 108 coulomb per gram of electrons.
(ii) charge of electrons,
Answer: The charge of electrons was measured by Millikan in 1909 by his famous ‘oil drop’
experiment. It was found to be 1.60 × 10-19 coulombs.
(iii) mass of an electron?
Answer: The mass of electrons is 9.1 × 10-28 g.
Question 8. How is it concluded that electrons are a universal constituent of all matter?
Answer: The charge/mass (e/m) ratio for the particles in the cathode rays (i.e., electron) is
found to be the same irrespective of the nature of the cathode or the nature of the gas
taken in the discharge tube. This shows that electrons are universal constituents of all
matter.
Question 9. Distinguish between an Emission spectrum and an Absorption spectrum.
Answer: The important differences between the emission and absorption spectra are given in
the following table:
Emission Spectrum Absorption Spectrum

1. Absorption spectrum is obtained when the white


1. Emission spectrum is obtained when
light is first passed through the substance (in a
radiations emitted by the excited substance
gaseous state or in solution) and the transmitted
are analyzed in a spectroscope.
light is analyzed in a spectroscope.

2. Emission spectrum consists of bright 2. Absorption spectrum consists of dark lines in an


colored lines separated by dark spaces. otherwise continuous spectrum.

Question 10. What are the shortcomings of Bohr’s atomic model?


1) It couldn’t explain the spectra of multi-electron atoms.
2) It fails to explain the splitting of spectral lines when subjected to the electrostatic
or magnetic fields (Stark or Zeeman’s effect).
3) It does not account for the fine splitting of spectral lines.
4) It affords a two-dimensional picture of the revolution of electrons while actually
electron revolves around the nucleus in three dimensions.
5) It does not account for the shapes of molecules.
According to it, this is possible to determine simultaneously both the position and momentum
of the electron accurately. But this is contrary to Heisenberg’s Uncertainty Principle.
Question 11. Account for the stability of the atom with the help of Bohr’s theory.
Answer: According to Bohr’s theory, an electron revolves around the nucleus only in a
definite orbit and cannot lose energy continuously. It can lose energy only if it jumps from a
higher orbit to a lower orbit but this is possible only if the electron has already acquired a
higher energy level by absorbing a certain amount of energy. If no lower level is available,

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the electron cannot lose energy at all, i.e., an atom does not collapse. In other words, it is
quite stable.
Question 12.What are the main achievements of Bohr’s theory of the atom?
Answer:The main achievements of Bohr’s theory of atom are:
1) It can explain the stability of the atom.
2) It successfully explains the line spectrum of hydrogen.
3) It explains the line spectra of single-electron ions like He+ and Li2+.
Question 13.Write a short note on de-Broglie relation (or de-Borglie) equation.
Answer: A moving material particle, like an electron, proton, etc. having mass m and velocity v
is associated with wavelength X related by:
λ = hmv=hp
where p stands for the momentum of the particle and h is Planck’s constant. This relation is
known as a de-Broglie equation.
Question 14. Do atomic orbitals have sharp boundaries? Explain why or why not?
Or
Why don’t we draw a boundary surface diagram within the probability of finding the electron
is 100%?
Answer: No, atomic orbitals do not have sharp boundaries because the probability of finding
the electron even at large distances may become very small, but not equal to zero.
Question 15. What is the difference between the angular momentum of an electron present
in 3p and that present in 4p?
Answer: No difference, because angular momentum is given by = h2πl(l+1)−−−−−−√, i.e., it
depends only on the value of l and not the principal quantum no. n.
Question 16. Why splitting of spectral lines takes place when the source giving the spectrum
is placed in a magnetic field?
Answer: In the presence of a magnetic field, the orbitals present in a subshell (which were
degenerate) take up different orientations.
Question 17. How many electrons in Sulphur (Z = 16) can have n + l = 3?
Answer: 16S = 1s2, 2s2 2p6 3s2 3p4
• For 1s2, n + l = l+ 0 = l
• For 1s2, n + l = 2 + 0 = 2
• For 2p6, n + 1 = 2 + 1= 3
• For 3s2, n + l = 3 + 0 = 3
• For 3p4, n + l = 3 + l = 4.
Thus n + l = 3 for 2p6 and 3s2 electrons, i.e. for 8 electrons.
Question 18. Why Pauli Exclusion principle is called the exclusion principle?
Answer: This is because according to the principle, if one electron in an atom has some
particular values for the four quantum numbers, then all the other electrons in that atom are
excluded from having the same set of values.
Question 19. Why Hund’s rule is called the rule of maximum multiplicity?
Answer: This is because out of the various possible electronic configurations, only that
Configuration is correct for which the total spin value is maximum.

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Question 20. How many orbitals are present in the M-shell?


Answer:

3 Marks Questions
Question 1. How many nucleons are present in an atom Nobelium, No? How many electrons are
present in the atom? How many nucleons may be considered neutrons?
Answer: Nucleons = 254, electrons = 102 and neutrons 254 – 102 = 152.
Question 2. Complete the following table:

Answer:

Question 3. Complete the following table:

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Answer:

Question 4. Find the number of protons, electrons an-d neutrons in


(a) 1327A3+
Answer:
p = 13, ē = 10, n = 14
(b) 815O2-
Answer:
p = 8, ē = 10, n = 7.
Question 5. Name the element whose atomic nucleus does not contain any neutrons.
Answer:The nucleus of the hydrogen atom does not contain any neutron.
Question 6. Calculate the total no. of electrons present in one mole of methane.
Answer: 1 Molecule of methane (CH4) contains electrons = 6 + 4 = 10
1 Mole, i.e., 6.022 × 1023 molecules will contain electrons = 6.022 × 1024
Question 7. Find (a) the total number and
(b) the total mass of neutrons in 7 mg of 14C
(Assume that the mass of a neutron = 1.675 × 10-27 kg).
Answer: 1 mol of 14C = 6,022 × 1023 atoms
i. e. 14 g of 14C = 6.022 × 1023 atoms
∴ 14 g of it = 6.022 × 1023 × 0.008 neutrons [∵ one atom ofuC contains = 14 – 6 = 8 neutrons]
and now 0.007 g of it will have
= 6.022 × 1023 × 8 × 0.007/13 = 2.409 × 1021 neutrons .
(b) Mass of 1 neutrons = 1.675 × 10-27 kg
∴ Mass of 2.409 × 1021 neutrons = 4.035 × 10-6 kg.
Question 8. A particular radio station broadcasts at a frequency of 1120 kHz (kilohertz).
Another radio station broadcasts at a frequency of 98.7 MHz (megahertz). What are the
wavelengths of the radiations from each station?

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Question 9. Calculate the wave number of radiations having a frequency of 4 × 1014 Hz.
Answer:
v = 4 × 1014 Hz = 4 × 1014 sec-1
Wave lemgth v̅ = 1λ=vc
= 4×1014sec−13×108msec−1
= 1.33 × 106 m-1
= 1.33 × 104 cm-1.
Question 10. A photon of wave length 4 × 10-7 m strikes on metal surface, the work function
of the metal being 2.13 eV. Calculate
(i) the energy of the photon (eV)
Answer: Energy of the photon = E = hv

(ii) the kinetic energy of the emission and


Answer:
Kinetic energy of emission = 12 mv2 = hv – hv0 = 3.10 – 2.13 = 0.97 eV
(iii) the velocity of the photoelectron [leV = 1.602 × 10-19 J].
Answer:

Question 11. Electromagnetic radiation of wavelength 242 nm is just sufficient to ionize the
sodium atom. Calculate the Ionisation energy of solution in kJ mol-1

Question 12. The wavelength of the first line in the Balmer Series is 656 nm. Calculate the
wavelength of the second line and limiting line in the Balmer series.
Answer: According to Rydberg’s formula

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For the Balmer series n1 = 2 and for the first line n2 = 3

Divide (i) by (ii)

Question 13. Calculate the wavelength of the spherical line in the Lyman series corresponding
to n2 = 3.
Answer: For the Lyman series n1 = 1
∴ v̅ = R[112−132]
= 109577 × 89 = 97490.7 m-1
λ = 1v=197490.7 cm-1
= 102.6 × 10-7cm
= 102.6 nm
Question 14. Calculate the velocity of electrons in the first Bohr orbit of the hydrogen atom.
Given that Bohr’s radius = 0,529 A. Planck’s constant h = 6.626 × 10-34 Js mass of electron =
9.11 × 10-31 kg and 1 J = 1 kg m2 s-1.

Question 15. The electron energy in a hydrogen atom is given by EH = (- 2.18 × 10-18)/n2 J.
Calculate the energy required to, remove the electron completely from n = 2 orbit. What is

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the longest wavelength of light in cm that can be used to cause this transition?

Question 16. Give the values of the quantum numbers for the electron with the highest
energy in the sodium atom.
Answer: Electronic configuration of riNa = 1s2, 2s22p6 3s1
The electron with the highest energy is 3s1 for which n = 3 and l = 0
Question 17. Find the number of unpaired electrons in Fe2+ and Fe3+. At.No. of Fe = 26.
Answer: Electronic configuration of 26Fe = 1s2, 2s22p6, 3s2 3p6 3d6 4s2
Fe2+ = 1s2, 2s2 2p6, 3s2 3p6 3d6 It has 4 unpaired electrons
Fe3+ = 1s2, 1s2 2p6, 3s2 3p6 3d5 It has 5 unpaired electrons.
Question 18. What atoms are indicated by the following electronic cofigurations?
(i) 1s2, 2s22p1,
Answer: Total no. of electrons = 2 + 2 + 1 = 5
∴ At. no. of element is 5.
Hence the element is Boron (B).
(ii) [Ar] 4s2 3d1
Answer: Total no. of electrons in [Ar] 4s2 3d1 = 18 + 2 + 1 = 21
∴ At. no. of element is 21.
Hence the element is Scandium (Sc).
Question 19. Give the electronic configuration of N-3, K+, P-3, O2-.
• N = 7 = 1s2,2s2 2p3
• N3- = 10e = 1s2, 2s2 2p6
• K = 19 = 1s2, 2s2 2p6, 3s2 3p6 4s1
• K+ = 18e = 1s2, 2s2 2p6, 3s2 3p6
• P = 15 = 1s2, 2s2 2p6, 3s2 3p3
• p3- = 18e– = 1s2, 2s2 2p6, 3s2 3p6
• O = 8 = 1s2, 2s2 2p4
• O2- = 10e– = 1s2, 2s2 2p6
Question 20. Which out of Cu2+, Fe2+, Cr3+ has the highest paramagnetism and why?
Answer: Paramagnetism is a property of unpaired electrons. More the no. of unpaired
electrons, more the paramagnetism.
Cu2+ = 1s2, 2s2 2p6, 3s2 3p6 3d9
∴ It has only one unpaired electron.
Fe2+ = 1s2, 2s2 2p6, 3s2 3p6 3d6

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STRUCTURE OF ATOM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

∴ It has 4 unpaired electrons.


Cr3+ = 1s2, 2s2 2p6, 3s2 3p6 3d3
∴ It has 3 unpaired electrons.
Hence Fe2+ with 4 unpaired electrons is having the highest paramagnetism.
Question 24. Find the velocity (in ms-1) of the electron in the first Bohr orbit of radius a0.
Also, find the de Broglie wavelength in m. Find the orbital angular momentum of 2p orbital of
hydrogen in units of h2π
Answer: For H-like particle, velocity in the nth orbit
Vn = 2.188 × 106 × Zn ms-1
For H-atom, Z = 1; For 1st orbit n = 1
∴ v = 2.188 × 106 ms-1
∴ de Broglie wavelength λ = hmv
= 6.626×10−349.1×10−31×2.188×106 m
= 3.33 × 10-10 m
∴ Orbital angular momentum = l(l+1)−−−−−−√h2π
For 2p orbital, l = 1
∴ Orbital angular momentum = l(l+1)−−−−−−√h2π = –2–√h2π .

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XI Chemistry Worksheet
Time: 30 min Ch#2 : Structure of Atom-02 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 -Find the wavelength of radiation emitted when an electron from infinity falls to stationary state 1 in
a hydrogen atom. (RH = 1.09 x 107 m-1)    

                                        
(3 Marks)
Q2 - Explain Hund’s rule with the help of example of nitrogen.
(3 Marks)

Q3 - Derive de Broglie’s relationship. What is its significance?


(5 Marks)

Q4 - The frequency of a radiation is 6 x 1014 cycles / sec. Find out the wavelength of radiation in
nanometer.
(2 Marks)

Q5 - An isotope of atomic mass 27 has 14 neutrons in the nucleus. What is the atomic number, name
and symbol of element.

(2 Marks)

Q6 - Write the designation for orbitals with following quantum numbers-


         (a)   n = 3, l = 1         (b)            n = 5, l = 2
(2 Marks)

Q7 - Who discovered neutrons?


(1 Mark)
Q8 - Which element does not have any neutron in it?
(1 Mark)
Q9 - Give two examples from everyday life where cathode ray tubes are used?
(1 Mark)
XI Chemistry Worksheet
Time: 30 min Ch#2 : Structure of Atom-03 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 - The uncertainty in momentum of an electron is 1.0 x 10-5 Kg ms-1 . What is the uncertainty in its
position?

(2 Marks)
Q2 - Find the de Broglie wavelength in Å of a particle with mass 1g and velocity 100m/s.
(2 Marks)

Q3 - Find wavelength of photon having energy 3.03 x 10-19 J.

(2 Marks)

Q4 - What will be the uncertainty in velocity of an electron (mass of electron = 9.1 x 10-28 g) moving
with a velocity of 3.0 x 104 ms-1 accurate up to 0.011%?

Q5 -Write the electronic configuration of following atoms/ions -


                                  F–, Cr, Mg2+, O–, Ca
(Atomic number of F = 9, Cr = 24, Mg = 12 ,O = 8, Ca = 20)
(5 Marks)

Q6 - Which of the following species are isoelectronic?


Na+, O2-, F-, Ca2+, K+
(2 Marks)

Q7 - (i) Write values of n and l for 4f orbital.   


(ii) Write all possible values of l and m for n = 2.
(2 Marks)
Q8 - Write one isobar of
(1 Mark)
Q9 -  Which series of lines of the hydrogen spectrum lie in the visible region?
(1 Mark)
Q10 -  What do you mean that energy of the electron is quantized?
(1 Mark)
XI Chemistry Worksheet
Time: 30 min Ch#2 : Structure of Atom-01 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 - What were the discrepancies observed in Bohr’s model?


(5 Marks)

Q2 - How many protons and neutron are in the following nuclei?

(3 Marks)

Q3 - Which of the following orbitals are not possible -


   2d, 4f, 6d, 3g   
(2 Marks)

Q4 - If the largest value of m for an electron is +2, then the electron may be present in what type of sub
shell?
(2 Marks)

Q5 - Point out the differences and similarities in the orbitals represented by following sets of quantum
numbers-
                                n             l              m
           (i)                3             2             +2
         (ii)                3             2             –1
(2 Marks)

Q6 - The work function of a metal is 4.2 eV. If radiations of 2000 A0 fall on the metal , then find the
kinetic energy of fastest photon electron.    
(3 Marks)

Q7 -  What is the value of Plank’s constant in S.I. Units?


(1 Mark)
Q8 -  When a ball is hit with a hockey stick by a player, it does not make a wave. Why?
(1 Mark)
Q9 -  Which series are produced when electrons from the outer orbits jumps to 3rd orbit?
(1 Mark)
BASIC CONCEPTS IN
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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

SOME BASIC CONCEPTS OF


CHEMISTRY

Chemistry is the branch of Science which deals with the study of composition of matter,
its properties and structure. It also deals with the relation between changes in composition
and changes in energy.

But now chemistry is a science, not an Art. Chemistry is an experimental science which
concerns itself with the study of matter. Due to its abnormal development, chemistry has been
divided into a number of branches. Important branches of chemistry are:

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

CLASSIFICATION OF MATTER:
Anything that has mass and occupies space is called matter.

It exists in three physical states, e.g., Solid, Liquid and Gas. It also has two others, states
namely Bose-Eistein condensite and Plasma

Matter can be classified in two ways:

(A) Physical classification of matter: Depending upon the physical state of matter, it can be
classified into solid, liquid and gaseous state.

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

(B) Chemical classification of matter: Based on chemical composition, matter classified into
three types: elements, compounds and mixtures

• Element: is a pure substance made up of same kind of atoms is called element.


Ex: hydrogen, oxygen, nitrogen, sulphur etc.

Gold is an element
made up of only gold
atoms.

Carbon is an element
made up of only carbon
atoms.

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

• Compound: They are formed by the chemical combination of atoms of different


elements in a definite ratio. Elements lose their properties in the formation of during
compound formation from their elements.

The properties of the compound are totally different from the elements from which these are
formed: A compound can be organic or inorganic.

• Mixture: A combination of two or more elements or compounds in any proportion so that


the components do not lose their identity is called mixture. Mixtures are of two types.

(a) Homogeneous mixtures: have same composition throughout the sample.

Ex:air, alloys, gasoline, etc

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

(b) Heterogeneous mixtures: These consist of two or more phases which have different
compositions.

Ex: a mixture of sand and salt.

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

PHYSICAL QUANTITIES AND THEIR S.I. UNITS:


Chemists describe the behavior of chemical substances on the basis of physical and chemical
properties. The measurements of chemical properties involve chemical reactions, whereas
the measurement of physical properties does not involve any chemical reactions.
The common physical properties are mass, length, time, volumes,
temperature, density, etc., among these mass, lengths and
time are fundamental physical quantities.

(1) Mass tells us about the quantity of matter. Mass is measured


with the help of analytical balance. Massof a substance is the
amount of matter present in it while weight is the force exerted by
gravity on an object.
The mass of a substance is constant whereas its weight may vary from
one place to another due to change in gravity.
SI unit of mass is kg.
(2) Size of the object is measured in terms of length, area and
volume. Length refers to one dimension, area to two dimensions and volume to three
dimensions of space.
(3) Time helps us to know how long it takes for a process to occur.
Seven basic units of measurement namely mass length, time, temperature, electric current,
luminous intensity and amount of substance are taken as fundamental basic units. All the
other units can be derived from them are called derivedunitslikearea, volume, force, work,
density, velocity, energy, etc., are all derived units.
(4) Temperature
9
– Fahrenheit (°F), TF = ( )TC + 32
5
5
– Celsius (°C), TC = ( )(TF - 32)
9
– Kelvin (K), TK = TC + 273.15

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

S.I. UNITS AND DERIVED UNITS

The 11th general conference of weights and measures in 1960 recommended the use of
international system of units. Abbreviated as SI Units (after the French expression La
System International de units).

SI OR BASE QUANTITY DERIVED QUANTITY

S.I OR BASE UNITS has seven basic units from which all other units are derived.

Physical quantity Name of unit Abbreviation


Mass Kilogram Kg
Length Meter M
Temperature Kelvin K
Amount of substance Mole Mol
Time Second S
Electric current Ampere A
Luminous intensity Candela Cd

DERIVED UNITS: -Units of different physical quantities can be derived from the seven
basic units are called derived units because these are derived from the basic units.

For deriving these units, we can multiply or divide the symbols for units as if they are algebraic
quantities.

• Volume = Length x Breadth x Height.


3
If units of length are m, then V = m x m x m = m

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

2
• Area = Length x Breadth = mx m = m
Mass 𝐊𝐠
• Density= =
Volume 𝐦𝟑

Velocity m.s−1 -2
• Acceleration= = = m.s
Time s
-2
• Force = Mass x acceleration = Kg. m.s
Kg.m.s−2 -1 -2
• Pressure=
Force
= =Kg.m .s
Area m2
-2 2 -2
• Energy, work = Force x distance = Kg.m.s x m = Kg.m .s = Joule
• Electric charge = current x time = A. S = Coulomb
Energy kg.m2 .s−2 -1 -1
• Electric potential= = = Joule. A .s = Volt
Charge A.S

Quantity with Symbol Unit (S.I.) Symbol

Velocity,v Meter per sec ms−1

Area,A Square meter m2

Volume, V Cubic meter m3

Density,  Kilogram m−3 Kg m−3

Energy, E Joule (J) Kg m2s−2

Force, F Newton (N) Kg ms−2

Frequency,  Hertz Cycle per sec

Pressure, P Pascal (Pa) Nm−2

Electrical charge Coulomb (C) A-s (ampere –sec)

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

PREFIXES: The SI units of some of the physical quantities are either too small or too large.
To change the order of magnitude, these are expressed by using prefixes before the names
of the basic units.

UNITS AND DIMENSIONAL ANALYSIS


Convertion of Units:It is used to convert one set of units to another in calculations. In
order to use this method, we write the units with every number and carry the units through
the calculations, treating them as algebraic quantities.
60 sec 1 min
For interconversion of the units of time, we know that, 1= 1 min or 1=60 sec

These equalities are called unit conversion factor or conversion factor or simply unit factor.

Examples

• To find the number the seconds in 5 min.


60 sec
5min = 5min 1 min =300sec

• To convert 0.74 A° into picometre.


-10 10−10 m
1A°= 10 m or 1= 1 Ao

10−10 m -10
0.74A° = 0.74A°x = 0.74 x 10 m
1 Ao

-12 1 pm
1pm = 10 m or 1 =10−12 m

∴ 0.74 × 10−10 m = 0.74 × 10−10 mx = 0.74 × 102 pm = 74pm∴

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

• Conversion of liter - atmosphere to joule


-3 3 10−3 m3
1L = 10 m or 1 = 1L

10−3 m3 -3 3
1L atm = 1 L atm x = 10 m atm
1L
101,325 pa
1atm = 101, 325 Pa or 1 = 1 atm

3 -3 3 3
10-3m atm=10 m atmx =101, 325Pa10-3m3= 101.325Pa.m
101,325 pa
1 atm
N
But, Pa =m2

3 3N
101.325Pa.m =101.325.m =101.325N.m = 101.325 J (Q 1 J = N.m)
m2

Precision and Accuracy:


To express the results of different scientific measurements two terms accuracy and precision
are commonly used.

• It is a measure of the difference between the experimental value and the true value.
Small difference between the experimental value and the true value, larger is the accuracy.
Accuracy expresses the correctness of measurement.
• Precision is the difference between a measured value and the arithmetic mean value for
a series of measurements.
Precision refers for the closeness of the set of values obtained from identical measurement
of a quantity.

Example: Three students were asked to determine the mass of piece of metal where mass is
known to be0.520g. Data obtained by each student are recorded as follows.

Measurements(g) Average(g)
(1) (2) (3)
Student A 0.521 0.515 0.509 0.515
Student B 0.516 0.515 0.514 0.515
Student C 0.521 0.520 0.520 0.520
Data of student A are neither very precise nor accurate. The individual values differ widely
from one another and the average value is not accurate.

Student B was able to determine the mass more precisely. The values deviate, but little from
one another. However, the average mass is still not accurate. The data for student C is both
precise and accurate.

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

SCIENTIFIC NOTATION (OR) EXPONENTIAL NOTATION


In scientific notation, the large or small numbers are expressed in N×10n formator a number
between 1.000 and 9.999 multiplied or divided by 10, an appropriate no. of times.
Where, N is a no between1.000 and 9.999 and n is exponent.

The distance from the sun to


the Earth is approximately
150,000,000 kilometers.

X-ray The wavelength of x-rays is


0.000000000023 meter.

Example, 1) 138.42 = 1.3842×10×10 = 1.3842×102

2) 0.00013842 = 1.3842×10-4
1.To transform a number larger than 9.999... to scientific rotation, the decimal point there
is only one non-zero digit before the decimal point. If the decimal point is moved x
places to the left, then exponent n = x

Ex: 138.42 = 1.3842×102

1395.2 = 1.3952×103

21.654 = 2.1654×101
2.To transform a number smaller than 1 to scientific notation, the decimal point is moved to
the right until there is one nonzero digit before the decimal point. If the decimal point is
moved ‘y’ places to the right, the exponent, n = -y

Ex: 0.00013482 = 1.3482×10-4

0.00549 = 5.49×10-3

0.1641 = 1.641×10-1

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

SIGNIFICANT FIGURES
To express the results in an accurate way, we express generally those digits which are known
with certainty. This is done is terms of significant figures.

The significant figures in a number are all the certain digits plus one doubtful digit. The
digits in a properly recorded measurement are knows as significant figures.

The greater the number of significant figures in a reported result, smaller is the uncertainty
and greater than precision.

Rules for determining number of significant figures:


1. All non-zero digits are significant.

Ex: The number of significant figures in 1.887 = 4

The number of significant figures in 12.612 = 5


The number of significant figures in 1.23 = 3

2. When a number is greater than 1, all the zeros to the right of the decimal point are
significant

Ex: The number of significant figures in 3.0 = 2


The number of significant figures in 91.070 = 5

The number of significant figures in 42.000 = 5

3. For a number less than 1, only zeros to the right of the first significant digit at
significant. But the zeros to the left of the first significant digit are not significant
Ex: The number of significant figures in 0.4960 = 4
The number of significant figures in 0.0013 = 2

The number of significant figures in 0.0002 = 1


The number of significant figures in 0.030 = 2

4. A zero becomes significant if it comes in between two non - zero digits

Ex: The number of significant figures in 3.01 = 3


The number of significant figures in 6.023 = 4
The number of significant figures in 3.0023 = 5

5. When adding or subtracting, the number of decimal places in the answer should be equal
to the number of decimal places in the number with the least number of decimal places.

Ex: 3.21(3 significant figures 2 decimal places)

1.5(2 significant figures 1 decimal places)

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

21.402 (5 significant figures 3 decimal places)

Since the term 1.5 involved in addition, has only one decimal place, the overall answer of
26.112 should be reported as 26.1.

6. In multiplication and division, the number of significant figures in the answer should be
same as that in the number with least number of significant figures.

Ex:Since the term3.376 has 4 and1.25 has3 significant figures, the multiplied answer
should be 4.22

7. When a number is rounded off the number of significant figures is reduced.


• If digit to be dropped is greater than 5, the lost retaining digit is increased by 1.
Exp- 12.6 is rounded to 13
• If digit to be dropped is less than 5, the lost retaining digit is left as it is.
Exp- 12.4is rounded to 12
• If digit to be dropped is 5, the lost remaining digit is increased by 1,if it is odd but left
as it is if even. Exp- 11.5 is rounded to 12 and 12.5 is rounded to 12
• last digit retained is increased by 1, only if the following digit is 5, and is left as such if
the following digit is 4.

Ex: 12.696,18.35 and 13.93 are reported as 12.7, 18.4, 13.9 respectively when rounded off
to three significant figures

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

LAWS OF CHEMICAL COMBINATION

1) Law of conservation of mass: It states that “matter is neither created nor destroyed
during any physical or chemical change”

This law is also called the Law of indestructibility of matter.

Thus, Total mass of reactants = Total mass of products


(Before reaction) (After the chemical reaction)

Chemical combination is a must for the validity of this law.

• When matter undergoes a physical change: A piece of ice (solid water) is taken in a
small conical flask. It is well corked and weighed. The flask is now heated gently to melt
Heat
the ice (solid) into water (liquid).Ice → Water

The flask is again weighed. It is found that there is no change in the Weight though a
physical change has taken place.

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

• When matter undergoes a chemical change: The following chemical changes illustrate
the law.

Ex: Decomposition of Mercuric oxide:100g of mercuric oxide when heated in a closed


tube, decomposed to produce 92.6g of mercury and 7.4g of oxygen gas,

i.e. total mass of products = 100 g:


1
HgO(s) → Hg(l) + 2 o2 (g)

100g 92.6g 7.4 g

Thus, inabove decomposition reaction, matter is neither gained nor lost.

Ex. 1-5.2g of CaCO3heated produced 1.99g of Carbon dioxide and the residue (CaO)
left behind weighs 3.2g. Show that these results illustrate the law of
conservation of mass.

Solution: Weight of CaCO3taken = 5.2g

Total weight of the products (CaO +CO )= 3.20+1.99 =5.19 g


2

Difference between the wt. of the reactant and the total wt. of the products is

= 5.20 – 5.19 =0.01 g.

This small difference may be due to experimental error.

Thus, law of conservation of mass holds good within experimental errors.

Ex. 2: When 20g of NaHCO3 is heated, 12.62g of Na2CO3 and 5.24g of CO2 is
produced. How many grams of H2O is produced?

Solution: Total mass of NaHCO3 heated= 20 gms;

Total mass Na2CO3 produced = 12.62 gms

Total mass of CO2 produced = 5.24 gms

 Mass of H2O produced = 20–12.62 –5.24 = 2.14 gms

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

2) Law of definite proportion (Law of constant proportion)states that “Any pure compound
however made contains the same elements in the fixed ratio of their weights”, or
‘A pure chemical compound always contains the same elements combined together
in the fixed ratio of their weights whatever its methods of preparation may be’.

Ex.1:Pure water contains 2gm of hydrogen and 16gm of oxygen i.e., the ratio of hydrogen and
oxygen in pure water is 1: 8.

Ex.2: A sample of CO2 may be prepared in the laboratory by (a) heating lime stone (CaCO3),
(b) by burning coal in air, (c) by the action of dilute hydrochloric acid on marble, (d) by heating
sodium bicarbonate. In each case, it is found that CO2 is made up of the same elements. i.e.,
carbon and oxygen, combined together in the same fixed ratio of 12: 32 or 3: 8 by mass.

Limitations of Law of Constant Composition:

It is not applicable if an element exists in different isotopes which may

be involved in the formation of the compound.

For example, in theformation of the compound CO2, if C-12isotope combines, the ratio of C:O
is 12: 32, but if C-14 isotopes combines, the ratio ofC:O is 14 : 32.

Problem 1.6.488g of lead combine directly with 1.002g of oxygen to form lead peroxide
(PbO2).Itis also produced by heating lead nitrate and it was found that the percentage of
oxygen present in lead peroxide is 13.38 percent. Use these data to illustrate the law of
constant composition.
Solution: Step1. To calculate the percentage of oxygen in first experiment.
Mass of peroxide formed = 6.488 + 1.002 = 7.490g.

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7.490g of lead peroxide contain 1.002g of oxygen


1.002
∴ 100g of lead peroxide will contain oxygen,= × 100 = 13.38g,
7.490

i.e. oxygen present = 13.38%


Step2. To compare the percentage of oxygen in both the experiments.
Percentage of oxygen in PbO2 in the first experiment = 13.38
Percentage of oxygen in PbO2 in the second experiment = 13.38
Since the percentage composition of oxygen in both the samples of PbO 2 is identical, the
above data illustrate the law of constant composition.

Problem 2. Ammonia contains 82.65% N 2 and 17.65% H2. If the law of constant proportions
is true, then the mass of zinc required to give 10g Ammonia will be:

Solution: The mass of zinc required to give 10g ammonia will be


40×22.65
= = 9.06gm
100

Problem 3. Irrespective of the source, pure sample of water always yields 88.89% mass of
oxygen and 11.11% mass of hydrogen. This is explained by the law of:

(A) conservation of mass (B) constant composition

(C) multiple proportion (D) constant volume


Hydrogen 2
Solution: As in water, = 16 ⇒ H: O = 1: 8 by mass
Oxygen

8
So, oxygen = 8+1 × 100 = 88.89%
1
Hydrogen = 8+1 × 100 = 11.11%

Both values always constant. Obey law of constant composition.

Hence (B) is correct.

Problem 4. Copper oxide was prepared by the following methods:

(a) In one case, 1.75g of the metal were dissolved in nitric acid and igniting the residual copper
nitrate yielded 2.19g of copper oxide.

(b)In the second case, 1.14g of metal dissolved in nitric acid was precipitated as copper
hydroxide by adding caustic alkali solution. The precipitated copper hydroxide after washing,
drying and heating yielded 1.43g of copper oxide.

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(c)In the third case, 1.45g of copper when strongly heated in a current of air yielded 1.83g of
copper oxide. Show that the given data illustrate the law of constant composition.

Solution: Step 1: In the first experiment.

2.19g of copper oxide contained 1.75g of Cu.


1.75
 100g of copper oxide contained = 2.19 × 100 = 79.91g

Step 2: In the second experiment.

1.43g of copper oxide contained 1.14g of copper.


1.14
 100g of copper oxide contained= 1.43 × 100 = 79.72g.

Step 3:In the third experiment.

1.83g of copper oxide contained 1.46g of copper


1.46
 100g of copper oxide contained = 1.83 × 100 = 79.78g

Thus the percentage of copper in copper oxide derived from all the three experiments is nearly
the same. Hence, the above data illustrate the law of constant composition.

3) Law of multiple proportions:‘When two elements combine to form two or more


compounds, in which fixed weight of one element combines with different weights of
the other, will be in a simple numerical ratio’.
Ex: Weight of Oxygen that will combine with 12gm of carbon in CO and CO2 is in ratio of 1: 2

Ex: The weight of Oxygen that will combine with 32gm of sulphur in SO2 and SO3 is the
ratio of 2: 3

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Problem 2. Carbon is found to form two oxides, which contain 42.9% and 27.3% carbon
respectively. Show that these figures illustrate the law of multiple proportions.

Solution: Step1. To calculate the percentage composition of carbon and oxygen in each of the
two oxides

First oxide Second oxide

Carbon 42.9% 27.3%

Oxygen 57.1 % 72.7%

Step2. To calculate the masses of carbon which combine with a fixed mass, i.e., one part
by mass of oxygen in each of the two oxides:

In1SToxide,57.1parts by mass of oxygen combine with carbon=42.9 parts.


42.9
1 part by mass of oxygen will combine with carbon= 57.1 = 0.751

In 2ND, 72.7parts by mass of oxygen combine with carbon =27.3parts.


27.3
1part by mass of oxygen will combine with carbon= 72.7 = 0.376

Step3. To compare the masses of carbon which combine with the same mass of oxygen in
both the oxides:

The ratio of the masses of carbon that combine with the same mass of oxygen (1 part) is
0.751: 0.376 or2: 1

Since this is a simple whole number ratio, of the above data illustrate the law of multiple
proportions.

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4) Law of Reciprocal Proportions:

The ratio of the masses of two elements A and B which combine separately with a fixed
mass of the third element C is either the same or some simple multiple of the ratio of the
masses in which A and B combine directly with each other.

“when two elements combine separately with fixed mass of third element then ratio of
their masses in which they do so is either the same or some whole number multiple of the
ratio in which they combine with each other”.

This law may be illustrated with the help of the following examples:

(1) Elements C and O combine separately with the third element H to form CH4 and H2O
and they combine directly with each other to form CO2, as shown below
O
CO2 H2O
C H
CH4

In CH4,12parts by mass of C combine with 4parts by mass of hydrogen.

In CO2, 12parts by mass of C combine with 32 parts by mass of hydrogen.

In H2O, 2 parts by mass of H combine with 16parts by masses of oxygen. Thus, the masses of
C and O which combine with fixed mass of hydrogen(say 4parts by mass) are 12 and 32,

i.e., they are in the ratio 12 : 32 or 3 : 8.Now, in CO2, 12parts by mass of carbon combine
directly with 32parts by mass of oxygen, i.e. they combine directly in the ratio 12: 32 or 3:
8 which is the same as the first ratio.
(2) The elements H and O combine separately with the third
element S to form H2S and SO2 and they combine directly with
each other to from H2O, the masses of H and O which combine
with the fixed mass of S, viz, 32parts are 2 and 32,

i.e. they are in the ratio 2: 32 or 1: 16.When H and O combine


directly to form H2O, the ratio of their combining masses is 2: 16 or 1:8
1 1
The two ratios are related to each other as : i.e., they are simple multiple of each other.
16 8

Problem 3. NH3 contains 82.35% of nitrogen and 17.65% of hydrogen. Water


contains 88.90% of oxygen and 11.10% of hydrogen. Nitrogen trioxide contains
63.15% of oxygen and 36.85% of nitrogen. Show that these data illustrate
the law of reciprocal proportions.
Solution: In NH3. 17.65g of H combine with N = 82.35g
82.35
∴1 g of H combines with N= 17.65 g = 4.67g

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88.90
In H2O, 11.10gof H combine with O=88.90g 1g of H combine withO =11.10 g = 8.01g

∴ Ratio of the masses of NandO which combine with fixed mass (=1g) of H =4.67:8.01=1: 1.72

In N2O3, ratio of masses of N and O which combine with each other = 36.85: 63.15 = 1: 1.71

Here two ratios are the same.Soit illustratesthe law of reciprocalproportions.

4) Gay - Lussac’s law of combining volumes: Under same conditions of temperature and
pressure, whenever gases react together, the volumes of the reacting gases as well
as products are in a simple whole number ratio.

‘at the same temperature and pressure, the volumes of gaseous reactants reacted and
the volumes of gaseous products formed bear a simple ratio.’

Ex: H2+ H2 + O2→ 2H2O (Volume ratio is 2:1:2)


2Vol 1Vol 2Vol

Ex: N2 + 3H2→ 2NH3(Volume ratio 1: 3:2)

1Vol 3Vol 2Vol

5) Avogadro’s Law: Equal volumes of all gases under similar conditions of temperature
and pressure contains equal number of molecules

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Applications of Avogadro’s law

(i) Provides a method to determine the atomic weight of gaseous elements.


(ii) Provides a relationship between vapour density (V.D.) and molecular masses of substances.
Molecular mass = 2 × vapour density
Volume of definite amount of Gas
Vapour density = Volume of same amount of Hydrogen

Weight of n molecules of Gas


or Vapour density = Weight of n molecules of Hydrogen

Weight of one molecule of Gas


or Vapour density =
Weight of one atom of hydrogen×2

Molecular weight
or Vapour density = 2

(iii) It helps in the determination of mass of fixed volume or molar volume of a gas.
Mass of 1 ml gas = V.D. 0.0000897gm.

 V.D. (i.e., molecular mass) gm has volume = V.D. × 0.0000897 ml = 22400ml


1 × 2 × V.D.
2

 Molar mass of a gas or its 1 mole occupies 22.4 L volume at S.T.P.


(v) It helps in determination of molecular formulae of gases and is very useful in gas analysis.
By knowing the molecular volumes of reactants and products of reaction, molecular
composition can be determined easily.

DALTON’S ATOMIC THEORY:


The main postulates of this theory are:
• Matter is made up of extremely small individual particles called atoms.
• Atoms of the same element are identical in all respects.
• Atoms of the different elements are different in all respects and have different masses
and chemical properties.
• Atom is the smallest unit that takes part in chemical combinations.
• Atoms of two or more element combine in a simple whole number ratio to form compound
atoms.
• Atoms can neither be created nor destroyed during any physical and chemical change.
• Chemical reactions involve only combination, separation or rearrangement of atoms.

Limitations The main failures of Dalton’s atomic theory are:

• Atom was no more indivisible. It is made up of various sub−atomic particles like


electrons, proton and neutron etc.
• It failed to explain how atoms of different elements differ from each other.

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• It failed to explain how and why atoms of elements combine with each other to form
compound atoms or molecules.
• It failed to explain the nature of forces that bind together different atoms in
molecules.
• It failed to explain Gay Lussac’s law of combining volumes.
• It did not make any distinction between ultimate particle of an element that takes part
in reaction (atoms) and the ultimate particle that has independent existence (molecules).

Atom: The smallest particles of an element that can take part in chemical
bonding but generallyCannot exist freely as such.

Molecule:The smallest particle of a substance (element or compound)


which has independent existence.

• Atomic Mass: The number which indicates how many times the mass
1 th 12 1 th
of one atom of the element a heavier than12 of the mass of C mass of an atom of
12
12
C is knows as atomic mass unit (amu).

It is equal to 1.66 x 10-24 gm.


Weight of 1 atom of the element
Atomic weight of an element =
Weight of 1 atom of hydrogen

When equivalent weight scale was altered from H =1 to O =16 the definition of atomic weight
changes to
Weight of 1 atom of the element
Atomic weight of an element = 1
×weight of 1 atom of oxygen
16

Modern reference standard for atomic weights is carbon isotope of mass number 12.
Weight of 1 atom of the element
Atomic weight of an element = 1
×weight of 1C12
12

1
Unit of atomic weight: The modern unit of atomic weight is of the mass of one atom of C–
12
12. Unit of atomic weight representation as a.m.u.
1
1a.m.u. =12× mass of C—12 atom.

Mass of one atom of C–12 has been determined as 1.9924 × 10–23gram.


1.9924×10−23
∴ 1𝑎. 𝑚. 𝑢 = 23
= 1.66 × 10−24 gram.

1.66 × 10–24 gram is referred to as the gram-equivalent of a.m.u.

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Gram atomic mass: The atomic mass of an element expressed in grams is called its gram
atomic mass.Itis also called gram atom.

Ex: The atomic mass of Oxygen = 16amu

The gram atomic mass of Oxygen = 16gm

AVERAGE ATOMIC MASS- Elements are found in different isotopic forms (atoms of same
elements having different atomic mass), so the atomic mass of any element is the average of
all the isotopic mass within a given sample.

Mass of first isotope(a) × Its%(p) + Mass of 2nd isotope(b) × Its%(q)


Average atomic mass =
%of first isotope + %of 2nd isotope
a×p+b×q
Or Average atomic mass = p+q

Exp- 1 Use the date given in the following table to calculate the molar mass of naturally
occurring argon.
Isotope Isotopic molar mass Abundance
36 −1
Ar 35.96755 g mol 7.1%
38
Ar 37.96272gmol−1 16.3%
40 −1
Ar 39.9624 g mol 76.6%
Solution: Molar mass of Ar
= 35.96755  0.071 + 37.96272  0.163 + 39.96924  0.766
= 39.352gmol−1

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Exp-2 Carbon occurs in nature as a mixture of carbon 12 and carbon 13. The average atomic
mass of carbon is 12.011. What is the percentage abundance of carbon 12 in nature?
∑ %abundance×atomicmass
Solution: Average atomic mass= 100
𝑥×12+(100−𝑥)13
i.e.12.011 = 100
1201.1 = 12x + 1300 – 13x
x = 1300 – 1201.1 = 98.9%

• Molecular Mass: is number which indicates how many times the mass of one molecule of
1 th
a substance is heavier than12 part of mass of C12.
weight of one molecule of a substance
Molecular weight = 1
×weight of one atom of C–12
12

Molecular weight of a substance is an additive property. It can be calculated by adding the


atomic weights of atoms present in one molecule by multiplying the atomic mass of each
element by the number of its atoms and adding them together.
Exp- Molecular mass of methane, CH4= (12.011) + 4 (1.008) = 16.043
Similarly, H2O=2 × atomic mass of hydrogen + 1 × atomic mass of oxygen
= 2 (1.008) + 16.00 = 18.016
For instance, the molecular weight of CaCO3 is = 40 + 12 + 3 × 16
= 40 + 12 + 48 = 100

Gram molecular mass or Gram molecule: The molecular mass of an element or compound
expressed in grams is called its gram molecular mass.
Ex:The molecular mass of Oxygen = 32amu
The gram molecular mass of Oxygen = 32gm
One-gram molecule of Oxygen = 32gm of Oxygen
Calculation of Molecular Mass:

Ex.1 H2SO4: (2 x 1) + (1 x32) + (4 x 16) = 98

Ex.2. Glucose (C6H12O6): (6 x 12) + (12 x 1) + (6 x 16) = 180

Ex.3 Oxalic acid (H2C2O4.2H2O) : (2 x 1)+(2 x 12)+(4 x 16)+2(18)= 126

Molar volume-Volume occupied by one mole of any gas at STP is called Gram molar volume.
The value of gram molar volume is 22.4litres. Volume of 1mole of any gas at STP = 22.4litres

• Equivalent mass: The number of parts by mass of a substance that combines with or
displaces 1.008parts by mass of hydrogen or 8.0parts of oxygen or 35.5parts of chlorine
is called equivalent mass (EM). On the other hand, quantity of a substance in grams

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numerically equal to its equivalent mass is called its gram equivalent mass (GEM) or gram
equivalent.
Mass of the substance in grams
Number of GEM =
GEM of the substance
Expressions for equivalent mass (EM)
Atomic mass
(i) EM of an element = Valency
Molecular mass
(ii)EM of an acid = Basicity

(Basicity of acid is the number of replaceable H- atoms in one molecule of the acid).
Molecular mass
(iii)EM of a base= Acidity

(Acidity of a base is the number of replaceable–OHgroups in one molecule of the base).


Formula mass
(iv) EM of a salt =Total positive or negative charge
Formula mass
(v) EM ofoxidising agent = Number of electrons gained per molecule or Total change in O.N.

Equivalent mass of common oxidising agent changes with the medium of the reaction.

MOLE CONCEPT
Mole: The amount of substance that contains the same number of chemical
entities (atoms, molecules, ions), as the number of atoms present in 12gm of
12
C isotope.

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Avogadro number: The number of atoms present in one-gram atom of an element or the
number of molecules present in one-gram molecule (1mole) of a substance is
called Avogadro number. It is equal to 6.023 x 1023. Thus, a mole contains
6.023x1023 units. These units can be atoms, molecules, ions, electron or
anything else.
1mole of hydrogen atoms means 6.023x1023 hydrogen atoms.
1mole of H2molecules means 6.023x1023 hydrogen molecules
1mole of potassium ions means 6.023x1023 potassium ions
1mole of electron ions means 6.023x1023 electrons.

How much does one mole weigh?


That depends on the nature of particles (units). The mass of one mole atoms of any element is
exactly equal to the atomic mass in grams (gram atomic mass or gram atom) of that element.
Exp-the atomic mass of Al is 27amu. One amu is equal to 1.66x 10-27g. One mole of aluminium
contains 6.023x1023aluminium atoms

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Mass of one atom aluminium = 27 x 1.66 x 10-24 g


Mass of one mole aluminium = 27x1.66x10-24x6.023x1023 = 27g
This is the atomic mass of aluminium in grams or it is one-gram atomic mass or one gram atom
of aluminium.
Similarly, the mass of 6.023x1023 molecules(1mole) of a substance is equal to its molecular
mass in grams or gram molecular mass or gram molecule
Exp-molecular mass of water is 18amu.
Thus, mass of one mole of water = 18x1.66x10-24x6.023x 1023 = 18 g
This is the molecular mass of water 1grams or one-gram molecular mass or one gram molecule
A mole of any substance is related to:

(a) Number of particles(b) mass of a substance

(c) Volume of the gaseous substance

(a) Mole-Particle Relationship

A mole is a collection of6.023 × 1023 particles, ions, atoms etc.

Avogadro Number (NA). The number of carbon atoms present in one gram-atom (1 mole
atom) of C–12 isotope.
One gram-atom (12grams) of C–12 contains 6.02 × 1023atoms. Thus the numerical value
of Avogadro’s number (NA) is 6.02 × 1023 per mol. It should be noted that
th of mass of a C12 atom
1
1 a.m.u.=
12
i.e. (i)6.023 × 1023 atoms of Na constitute one mole atom of Na.
(ii) 6.023×1023molecules of oxygen constitutes 1mole of oxygen molecules.
(iii) 6.023 × 1023 electrons constitute one mole of electrons.
Number of particles
(iv) No. of moles = 6.023×1023

(b) Mole-Weight Relationship


One mole of every substance weighs equal to the gram atomic weight of the substance
or to the gram molecular weight of the substance.
e.g. (i)1mole of sodium weighs 23g of Na.
(ii)1mole of CaCO3 weighs 100g.
Mass of substan ce in grams
Number of moles =
Molecular weight in grams

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(c) Mole-Volume Relationship


One mole of every gas occupies 22.4lit. of volume at STP.
i.e. 1mole of O2 occupies 22400 ml of volume at STP.
1mole of He occupies 22400 ml of volume at STP.
′V′ of gas in litres at STP
Number of moles =
22.4

FORMULA SHEET FOR MOLE CALCULATIONS:


S. No. Items Formula
Wt. in gm
1. Molecules
Molecular mass
Wt. in gm
2. Atom
Atomic mass
Volume at STP
3. Gases
Standard molar Volume at STP
Number of particles
4. Any Particle
Avogardro number
5. Moles of A in AxBy x
For Gases at any P(in atm), V(in PV
6. n= where R=0.0821 lit-atm/mol K
litres) & T(in K) RT

Standard Temperature and Pressure (STP OR NTP): The temperature of 273K and a
pressure of 1atm are taken as STP conditions

Formula weight: The formula weight of a substance is the total mass of all atoms present in
the chemical formula of the substance.

Molar Mass: The mass of one mole of a substance is called its molar mass. The units of
molar mass are gm/mole or Kg/mole.

Therefore, molar mass is equal to atomic mass or molecular mass expressed in grams depends
on whether the substance contains atoms or molecules.

• 1mole atom = 6.02x1023atoms =Gram Atomic weight =22.4litres at STP (only for
gas) (or 1 gram atom)
23
Ex:1mole He =6.02x10 atoms = 4gram = 22.4 litres at STP
23
• 1mole molecule=6.02x10 molecules=Gram Molecular weight=22.4 lit at STP (Only
for gas)

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Sample Problem 1: Calculate the number of molecules present


(i)in 34.20grams of cane sugar (C12H22O11)
(ii)in one litre of water assuming that the density of water 1g/cm3.
(iii) In one drop of water having mass 0.05g.
Solution:
(i)1mole of C12H22O11= 342g
Molecular mass of cane sugar(C12H22O11)=12× 12 + 22 × 1 + 11 × 16 = 342amu
=6.022x1023, molecules
Now, 342g of cane sugar contain 6.022x1023 molecules
6.022×1023
∴34.2gcane sugar will contain 342
34.2=6.022× 1022 molecules

(ii)1mole of water = 18g = 6.022x1023 molecules


Mass of 1lit of water=Volume x density = 1000 mL x 1gmL-1= 1000g
Now, 18g of water contains = 6.022x1023 molecules
6.022×1023 ×1000
1000g of water contain = 3.346 × 1025 molecules
18

(iii)1mole of H2O = 18g = 6.022x1023 molecules


Mass of 1drop of water = 0.05g
Now, 18g of H2O contain = 6.022x1023 molecules
6.022×1023
0.05g of H2O will contain= × 0.05 = 1.673 × 1021 molecules.
18

Problem 2: Calculate the number of atoms of the constituent elements in 53g of Na2CO3.
Solution: By mole concept.
1mole of Na2CO3=Gram formula mass of Na2CO3=2x23+12+16x3=106 g
Now, 106g of Na2CO3=1mole
53g of Na2CO3= 0.5mole of Na2CO3
But 1mole Na2CO3 contains 2moles of Na+ ion or 2x6.022x1023 Na+ ions.
0.5mole of Na2CO3 contain 2x6.022x1023x0.5Na+ ions=6.022x1023Na+ ions
Again, 1mole Na2CO3 contains 1mole of carbon atoms=6.022x1023Na+ ions
23 23
∴0.5mole of Na2CO3contain=6.022x10 x0.5 carbon atoms=3.011x 10 carbon atoms.
Further, 1mole Na2CO3 contains 3moles of oxygen atoms
or 3x6.022x 1023oxygen atoms.
23 23
∴0.5 mole of Na2CO3 will contain = 3 x 6.022 x 10 x 0.5 oxygen atoms = 9.033 x 10 oxygen
atoms.

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Sample Problem 3: Calculate the number of molecules present in 350cm3 of NH3 gas at
273Kand 2atmosphere pressures.

Solution: First of all, we have to determine the volume of the gas at STP.

Given conditions At STP

V1 = 350cm3 V2=?

T1 = 273K T2 = 273K

P1 = 2atmospheres P2 = 1atm
𝑃1 𝑉1 𝑃2 𝑉2
Applying gas equation: =
𝑇1 𝑇2
350×2 1×𝑉2 350×2 273
Weget = orV2 = × = 700𝑐𝑚3
273 273 273 1

By mole concept, 1mole of NH3=6.022x1023 molecules=22400cm3 at STP

Thus, 22400cm3 of NH3 at STP contain 6.022x1023molecules


3 3 6.022×1023
∴700cm of NH will contain 22400
× 700 = 1.882 × 1022 molecules

Sample Problem 4:(i) Assuming the density of water to be 1g/cm3, calculate the volume
occupied by one molecule of water.

(ii)Assuming the water molecule to be spherical, calculate the diameter of the water molecule.
Approximately the diameter of the oxygen atom.

Solution: (i)1mole of H2O =18g =18cm3=6.022x1023 molecules of H2O

Thus,6.022x1023 molecules of H2O have volume =18cm3(densityH2O =1g/cm3)


18
1molecule of H2O will have volume = 6.022 ×1023 cm3 = 2.989 x 10-23 cm3

(ii)As water molecules is assumed to be spherical. If R is its radius, then its volume will
4
be πR3 = 2.989 × 10−23 cm3 orR3 = 7.1336 x 10-24 or R = (7.133) 1/3
x 10-8= 1.925 x 10-8 cm
3
1 1
Take n=(7.133)1/3logn= 3 log 7.122 =3 × 0.8533 = 0.2844

N = Antilog 0.2844 = 1.925


-8 -8
∴Diameter of water molecule = 2x1.925x10 cm = 3.85x10 cm

(iii)As oxygen atom occupies half of the volume occupied by water molecule, hence if r is
4
theradius of oxygen atom, then 3 πr 3 = 2.989 × 10−23 cm3 or

r3= 3.566 x 10-24 which gives r = 1.528 x 10-8 cm


-8 -8
∴Diameter of oxygen atom = 2x1.528x10 cm = 3.056 x 10 cm.

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1. From 200mg of CO2, 1021molecules are removed. How many moles of CO2 are left?
Mass in gram 0.2
Solution: Total no. of moles of CO2 = = = 0.00454
Gram molecular mass 44

1021
No. of moles removed = = 0.00166
6.022×1023

No. of moles of CO2 left= 0.00454 – 0.00166=0.00288

2. How manymoles of glucose are present in 540g of glucose?


Mass in gram 540
Solution: Number of moles = Gram molecular mass = = 3moles
180

3. Calculate the number of moles of H, S and O in 5moles of H2SO4.


Solution: 1 molecule of H2SO4 contain 2Hatoms, 1 atom of S and 4 atoms of oxygen.

1 mole of H2SO4 contains 2 moles of H.

 5 moles of H2SO4 contains 10 moles of H.

1 mole of H2SO4 contains 1 mole of S.

or 5 moles of H2SO4 contains 5 moles of S.

Similarly 1 mole of H2SO4 contains 4 moles of O.

or 5 moles of H2SO4 contains 20 moles of O.

4. Calculate the total number of electrons present in 1.6g of CH4.


1.6
Solution: No. of moles of CH4 = 16 = 0.1

No. of molecules in 1.6g of CH4=moles  NA

= 0.1  6.022  1023molecules = 6.022  1022 molecules

1 molecule of CH4 has 10 electrons.

 6.022  1022 molecules of CH4 has electrons.

= 10  6.022  1022 = 6.022  1023(electrons).

5. How many atoms are there in 100amu of He?


1
Solution:1amu = 12 × mass of one C atom

or mass of one C – 12 atom=12 amu=Atomic mass of C

Similarly, the atomic mass/weight of He= 4.

Mass of one He atom=4 amu


100
Thus, number of atoms in 100amu of He = = 25.
4

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6. Calculate the number of molecules in 11.2lit SO2 gas at NTP.


Volume at NTP(in litre)
Solution: No. of moles of SO2= Std.molar volume in litre

11.2 1
=22.4 = 2 = 0.5

No. of molecules of SO2= No. of moles  NA


=0.5 x 6.022 x 1023

=3.011  1023

7. Calculate the mass of 0.1mole of sodium carbonate.


Solution: Molecular mass of Na2CO3 =106 g

 mass of Na2CO3 in gram=No. of moles  Gram molecular mass.

=0.1 106 = 10.6 g

8. Calculate the mass of 12.044  1023 atoms of carbon.


12.044×1023
Solution: No. of moles of C = =2
6.022×1023

Mass of carbon atoms = no. of moles  gram at. mass

= 2 12 = 24g.

9. Calculate mass of 6.0221023molecules of CaCO3(CaCO3= 100)


6.022×1023
Solution: Number of moles of CaCO3 = 6.022×1023 = 1

 Mass of CaCO3 = Number of moles  molecular mass

= 1  100 = 100

PERCENTAGE COMPOSITIONS-of any element or constituent in a compound is the number


of parts by mass of that element or constituent present in 100parts by mass of the compound.

It can be calculated by the following two steps:

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Step1. Calculate the molecular mass of the compound from its formula its formula by adding
the atomic masses of the elements present.

Step2.Calculate the percentage of the element or the constituent by supplying the following
relation:
𝑁𝑜. 𝑜𝑓𝑝𝑎𝑟𝑡𝑠𝑏𝑦𝑚𝑎𝑠𝑠𝑜𝑓𝑡ℎ𝑒𝑒𝑙𝑒𝑚𝑒𝑛𝑡𝑠𝑜𝑟𝑐𝑜𝑛𝑠𝑡𝑖𝑡𝑢𝑒𝑛𝑡
% of the element = × 100
𝑀𝑜𝑙.𝑚𝑎𝑠𝑠𝑜𝑓𝑡ℎ𝑒𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

Sample Problem 1: Calculate the percentage compositions of the various elements in MgSO4.

Solution: Mol. mass of MgSO4= 24 + 32 + 4 x 16 = 120


No.of parts by mass of Mg 24
% of Mg = × 100 = 120 ×100=20%
Mol.mass of MgSO4
No.of parts by mass of S 32
% ofS = × 100 = 120 ×100=26.67%
Mol.mass of MgSO4
𝑁𝑜.𝑜𝑓𝑝𝑎𝑟𝑡𝑠𝑏𝑦𝑚𝑎𝑠𝑠𝑜𝑓𝑂 64
% of O = × 100 = 120 ×100=53.33%
𝑀𝑜𝑙.𝑚𝑎𝑠𝑠𝑜𝑓𝑀𝑔𝑆𝑂4

Sample Problem 2: Calculate the percentage of water of crystallisation in the sample of blue
vitriol (CuSO4.5H2O).

Solution: Mol. mass of CuSO4.5H2O = 6.3 + 32 + 4 x16 + 5 x 18 = 249.5

No. of parts by mass of H2O = 5 x 18 = 90


90
∴ % of H2O = 249.5 × 100 = 36.07%

EMPIRICAL FORMULA AND MOLECULAR FORMULA


The formula which gives the actual number of atoms of various elements present in one
molecule of the compound is called molecular formula.

The formula which gives the relative number of atoms of various elements in one molecule
of the compound is called empirical formula.

Ex: Molecular formula of benzene is C6H6. It means that one molecule of benzene has six
carbon atoms and six hydrogen atoms.

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Empirical formula of benzene is CH. It means that carbon and hydrogen are present in the
ratio of 1:1 in benzene.

Relation between emperical formula and molecular formula

Molecular Formula = Emperical Formula x n


Molecular mass
n =Emperical formula mass

Note: Molecular mass =2 xVapour Density

DETERMINATION OF THE EMPERICAL FORMULA OF A COMPOUND


• Divide the percentage of each element by its atomic mass.
• Divide the result obtained in the above step by the smallest value among them to get
the simplest ratio of various atoms.
• If any number obtained above is not a whole number, then multiply all the numbers by a
suitable integer to get whole number ratio. This ratio is the simplest whole number
ratio. The empirical formula of the compound written the help of this ratio.

1. Compound contains C = 71.23%, H = 12.95% and O = 15.81%. What is the empirical formula
of the compound?
Element Atomic Weight % in Relative no, of atom Simplest atomic Empirical
mass compound ratio formula

C 12 71.93 71.93 5.936


= 5.936 =6
12 0.988
H 1 12.95 12.95 12.95
= 12.95 = 13 C6H13O
1 0.988
O 16 15.81 15.81 0.988
= 0.988 =1
16 0.988

2. The simplest formula of a compound containing 50% of element X (Atomic mass=10) and
50% of the element Y (Atomic mass=20) is
(A) XY (B)X2Y (C) XY2 (D)X2Y3

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Element Atomic Weight % in Relative number of Simplest atomic Empirical


mass compound atom ratio formula
X 10 50 50/10 = 5 5/2.5 = 2
X2Y
Y 20 50 50/20 = 2.5 2.5/2.5 = 1

3. A compound of carbon, hydrogen and nitrogen contains these elements in the ratio
9:1:3.5. Calculate the empirical formula. If its molecular mass is 108, what is the
molecular formula?
Element Element ratio Atomic mass Relative number of atoms Simplest ratio
C 9 12 9 0.75
= 0.75 =3
12 0.25
H 1 1 1 1
=1 =4
1 0.25
N 3.5 14 3.5 0.25
= 0.25 =1
14 0.25
Empirical formula = C3H4N
Empirical formula mass = (3  12) + (4  1) + 14 = 54
mol. mass 108
n= = =2
Emp. mass 54
Thus, molecular formula of the compound = 2 empirical formula
= 2  C3H4N = C6H8N2

4. 2.38 gm of uranium was heated strongly in a current of air. The resulting oxide weighed
2.806g. Determine the empirical formula of the oxide. (At. mass U =238; O=16).
Step1: To calculate the percentage of uranium and oxygen in the oxide.

2.806g of the oxide contain uranium =2.38g


2.38
 Percentage of uranium = 2.806 × 100 = 84.82

Hence, the percentage of oxygen in the oxide= 100.00–84.82=15.18

Step 2:To calculate the empirical formula

Relative no. of
no.
At. mass of

atomic ratio

atomic ratio
of elements
Percentage

atoms
elements
Element

Simplest
Simplest

Percentage
=
whole

At. mass

Uranium 84.82 238 84.82


= 0.3562
0.3562
=1 3
238 0.3562
Oxygen 15.18 16 15.18
= 0.94875
0.94875 8
16 0.3562
= 2.666
Hence the empirical formula of the oxide is U3O8.

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5. 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.
Step 1: Percentage of the elements present

Carbon Hydrogen Chlorine


10.06 0.84 89.10
Step 2: Dividing the percentage compositions by the respective atomic weights of the
elements
10.06 0.84 89.10
12 1 35.5
0.84 0.84 2.51
Step 3: Dividing each value in step 2 by the smallest number among them to get simple
atomic ratio
0.84 0.84 2.51
0.84 0.84 0.84

Step 4: Ratio of the atoms present in the molecule C : H : Cl 1 : 1 : 3

 The empirical formula of the compound𝐶1 𝐻1 𝐶𝑙3 or 𝐶𝐻𝐶𝑙3 .

6. The empirical formula of a compound is𝐶𝐻2 𝑂. Its molecular weight is 90. Calculate the
molecular formula of the compound.
(Atomic weights C=12, H=1, O=16)
Solution: Empirical formula = CH2 O
Empirical formula weight = (12 + 2 + 16) = 30
molecular weight 90
n = empirical formula weight ∴ n = 30 = 3

The molecular formula (CH2 O)3 = C3 H6 O3

7. A substance, on analysis, gave the following percentage composition: Na= 43. 4%,
C= 11.3%, O= 45.3%. Calculate its empirical formula. {Na= 23, C= 12,O= 16]
Simple ratio of Simplest whole no.
SYMBOL % age Atomic Mass Relative number of moles
moles ratio
43 .4 1.88
Na 43.4 23 = 1.88 =2 2
23 0.94
11 .3 0.94
C 11.3 12 = 0.94 =1 1
12 0.94
45 .3 2.83
O 45.3 16 = 2.83 =3 3
16 0.94
Therefore, the empirical formula is Na2CO3.

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8. A compound has the following composition: Mg = 9.76%, S = 13.01%, O =


26.01%, H2O = 51.22%. What is its empirical formula?[Mg = 24, S = 32, O =
16, H = 1]
Atomic Relative number of Simple ratioof SimplestWhole
Symbol % age
Mass moles moles no.ratio

9.76 0.406
Mg 9.76 24 = 0.406 =1 1
24 0.406
13 .01 0.406
S 13.01 32 = 0.406 =1 1
32 0.406
26 .01 1.625
O 26.01 16 = 1.625 =4 4
16 0.406
51 .22 2.846
H2O 51.22 18 = 2.846 =7 7
18 0.406

Hence, the empirical formula is MgSO4. 7H2O.

9. What is the simplest formula of the compound which has the following percentage
composition. Carbon 80%, Hydrogen 20%. If the molecular mass is 30, calculate
its molecular formula.
Relative number of Simple ratio of Simples whole
Element % age At. Mass
moles moles no.ratio
80 6.66
C 80 12 = 6.66 =1 1
12 6.66
20 20
H 20 1 = 20 =3 3
1 6.66
 Empirical formula is CH3

Molecular mass 30
 Empirical mass = 12  1 + 1  3 = 15 n = = =2
Emprical formula mass 15

Molecular formula = Empirical formula  2 = CH3 2 = C2H6

10. A compound on analysis gave the following percentage composition: C = 54.54%,


H = 9.09%, O = 36.36%. The vapour density of the compound was found to be
44. Find out the molecular formula of the compound.
Relative number of Simple ratio of Simplest whole no.
Element % age At. Mass
moles mole ratio
54 .54 4.53
C 54.54 12 = 4.53 =2 2
12 2.27
9.09 9.09
H 9.09 1 = 9.09 =4 4
1 2.27
36 .36 2.27
O 36.36 16 = 2.27 =1 1
16 2.27
 Empirical formula is C2H4O. Calculation of molecular formula:

Empirical formula mass = 12 2+14+161 = 44

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Molecular mass = 2  Vapour density = 2 44 = 88

Molecular mass 88
n= = =2
Empirical formula mass 44

Molecular formula = Empirical formula  n = C2H4O  2= C4H8O2.

11. An organic compound on analysis gave the following data: C = 57.82%, H = 3.6%,
and the rest is oxygen. Its vapour density is 83. Find its empirical and molecular
formula.
Simple ratio of Simplest whole no.
Element % age At. Mass Relative number of moles
moles ratio
57 .82 4 .8
C 57.82 12 = 4.80 =2 4
12 2 .4
3.60 3 .6
H 3.60 1 = 3.60 = 1 .5 3
1 2 .3
38 .58 2 .4
O 38.58 16 = 2.40 =1 2
16 2 .4

 Empirical formula is C4H3O2.

Empirical formula mass = 124+ 13 + 2  16 = 83

Molecular mass = 2  V.D. = 2  83 = 166

Molecular mass 166


n= = =2
Emprical formula mass 83

Molecular formula = Empirical formula  n = C4H3O2 2 = C8H6O4

12. 2.746 gm of a compound gave on analysis 1.94 gm of silver, 0.268 gm of sulphur


and0.538 gm of oxygen. Find the empirical formula of the compound. (At masses:
Ag = 108, S = 32, O = 16)
Solution: To calculate percentage composition.Percentage composition of the compound is
calculated as under:

1.94
Silver =  100 = 70.65%
2.746

0.268
Sulphur =  100 = 9.75 %
2.746

0.538
Oxygen =  100 = 19.6%
2.746

To calculate empirical formula:

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Relative number Simplest ratio of Simplest whole


Element % age At. Mass
of moles moles no.ratio
70.65 0.654
Ag 70.65 108 = 0.654 =2 2
108 0.305

9.75 0.305
S 9.75 32 = 0.305 =1 1
32 0.305
19 .6 1.22
O 19.6 16 = 1.22 =4 4
16 0.305

 Empirical formula is Ag2SO4

STOICHIOMETRY OF CHEMICAL REACTIONS


A General Approach: One of the most important aspects
of a chemical equation is that when it is written in the
balanced form, it gives quantitative relationships between
the various reactants and products in terms of moles,
masses, molecules and volumes. This is called stoichiometry
(Greek word, meaning ‘to measure an element’). The
coefficients of the balanced chemical equation are called
stoichiometric coefficients.
For example, a balanced chemical equation along with the quantitative information conveyed by
it is given below:
Let us consider the combustion of methane. A balanced equation for this reaction is as given
below:
CH4 (g) + 2O2 (g) → CO2 (g) + 2 H2O(g)

The above balance reaction gives the following information:

• For every 1mole of CH4, 2mole of O2 will be required to produce


1mole of CO2 and 2 moles of H2O. this signifies Mole – Mole relation

• For every 16gms of CH4 , 64gms of O2 will be required to produce 44gms of CO2 and 36gms
of H2O this signifies Mass – Mass relation
• Ratio of moles of CO2 : H2O at any time = 1 : 2

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• There will be no change in total mass of all reactants and products at any time for any
chemical reaction.
The quantitative information conveyed by a chemical equation helps in a number of calculations.
The problems involving these calculations may be classified into the following different types:

(1)Mass-Mass Relationships, i.e., mass of one of the reactants or products is given and the
mass of some other reactant or product is to be calculated.

(2)Mass-Volume Relationship, i.e, mass/volume of one of the reactants or products is given


andthe volume/mass of the other is to be calculated.

(3)Volume-Volume Relationship, i.e, volume of one of the reactants or the products is given and
the volume of the other is to be calculated.

The general method of calculations for all the problems of the above types consists of the
following steps:

(i) Write down the balanced chemical equation


(ii) Write the relative number of moles or the relative masses (gram atomic or molecular
masses) of the reactants and the products below their formulae.
(iii) In case of a gaseous substance, write down 22.4litres at STP below the formula in place
of 1mole.

Sample Problem 1: Calculate the mass of iron which will be converted into its oxide (Fe3O4)by
the action of 18g of steam on it.

Solution:The chemical equation representing the reaction is:

3Fe+ 4H2O → Fe3O4+ 4H2

3×56 =168g 4×18=72g

Thus, 72g of steam reacts with 168g of iron


168
∴18g of steam will react with 72 × 18 = 42g of iron

∴Mass of iron required = 42g.

Sample Problem 2: What mass of slaked lime would be required to decompose completely
4grams of ammonium chloride and what would be the mass of each product?
Solution: The equation representing the decomposition of NH4CI by slaked lime, i.e.Ca (OH)2is:
Ca(OH)2+ 2NH4Cl → CaCl2 + 2NH3 + 2H2O
40+2(1+16) 2(14+4+35.5) 40+2×35.5 2(14+3×1) 2(2×1+16)
=74g =107g =111g =34g =36g

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(i)To calculate mass of Ca(OH)2 required to decompose 4g of NH4Cl.


From the above equation,107g of NH4Cldecomposed by 74g of Ca (OH)2
74
∴4g of NH4Cl will be decomposed by Ca (OH)2= 107 × 4 = 2.766𝑔
Thus, the mass of slaked lime required = 2.766g.
(ii)To calculate the mass of CaCl2 formed.
107g of NH4Cl when reacted with Ca(OH)2 produce 111g of CaCl2.
∴4g of NH4Cl when reacted with Ca(OH)2 will produce CaCl2
111
= × 4 = 4.15𝑔
107
Hence the mass of CaCl2 produced = 4.15g.
(iii) To calculate the mass of NH3 produced.
107gofNH4 Cl react to form 34g of NH3
34
∴ 4g ofNH4 Cl react to form = 4 × 107 = 1.271 g

(iv)To calculate the mass of H2O formed


107g of NH4Cl react with Ca (OH)2 to yield 36g of H2O
36
∴ 4g of NH4Cl when reacted with= 107 × 4 = 1.345g
So, the mass of H2O formed = 1.3458g.

Sample Problem 3:1.5g of an impure sample of sodium sulphate dissolvedin water was treated
with excess of barium chloride solution when 1.74 g of BaSO4was obtained as dry
precipitate. Calculate the percentage purity of the sample.
Solution: The chemical equation representing the reaction is:

Na2SO4+BaCl2→BaSO4+ 2NaCl
2×23+32+4×16=142g 137+32+4×16=233g
Step1.To calculates the mass of Na2SO4which produces 1.74g of BaSO4? From the chemical
equation, 233g of BaSO4 are produced from Na2SO4=142g
142
∴1.74g of it would be obtained from NaSO4= 233 × 1.74 = 1.06g
This is the mass of pure Na2SO4 present in 1.5g of impure sample.
Step2. To calculate the percentage purity of impure sample.
1.5g impure sample contains pure Na2SO4= 1.06g
1.06
∴100g of impure sample will contain pure Na2SO4= 1.5
× 100 = 70.67 g

Thus, percentage purity of impure sample = 70.67

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Sample Problem 4: Current market prices of Al, Zn and Fe scraps per kg are Rs.20, Rs.16 and
Rs.3 respectively. If H2 is to be prepared by the reaction of one of these metals with
H2SO4, which would be the cheapest metal to use? Which would most expensive?
Solution: The various chemical reactions involved are given below:
(i) 2Al + 3H2SO4→ Al2(SO4)3 + 3H2
2×27=57g 3×2=6g
(ii) Zn + H2SO4→ ZnSO4 +H2
65g 2g
(iii) Fe + H2SO4→ FeSO4 +H2
56g 2g
Let us suppose that the amount of hydrogen to be prepared = 100g.
Step1. To calculate the cost of preparation of 100g of H2 from Al

6g of H2 is prepared from Al= 54g


54
∴100g of H2 will be obtained from Al = 6 × 100
20
Cost of 1000g of Al = Rs.20cost of 900g of Al=1000 × 900 = Rs. 18

Step 2. To calculate the cost of preparation of 100g of H2 from Zn.

2g of H2produced from Zn=65g


65
∴100g of H2 will obtained from Zn = 2 × 100 = 3250 g
16
Cost of 1000g Zn=Rs.16/-∴cost of 3250g of Zn=1000 × 3250 = Rs. 52

Step3.To calculate the cost of preparation of 100g of H2 from Fe.

2g of H2 produced from Fe=56g ∴100g of H2 will be obtained from


56
Fe = × 100 = 2800 g
2

Cost of 1000g of Fe = Rs.3/-


3
∴ Cost of 2800g of Fe = 1000
× 2800 = 8.40

Thus, Fe is the cheapest and Zn is the most expensive metal to use of the preparation of H2.

Sample Problem5: Calculate the amount of lime, Ca(OH)2, required to remove hardness of
50,000litres of well water which has been found to contain 1.62g of calcium bicarbonate
per 10litre.
(i)Calculation of total Ca(HCO3)2 present.

10L of water contain Ca(HCO3)2= 1.62g

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1.62
50,000L of water will contain Ca(HCO3)2= 10 × 50000g = 8100 g

(ii)Calculation of lime required. The balanced equation for the reaction involved is:

Ca (HCO3)2 + Ca (OH)2 → 2CaCO3 + 2 H 2O

1 mole 1 mole

162g Ca (HCO3)2 require lime = 74g


74
∴8100g Ca (HCO3)2 will require lime =162 × 8100 𝑔 = 3700 g = 3.7kg

Sample Problem 6:1.0g of a mixture of carbonates of calcium and magnesium gave 240cm3 of
CO2 at STP. Calculate the percentage composition of the mixture.

Solution: Mass of mixture of carbonates of Ca and Mg taken = 1.0g


Suppose the mass of CaCO3 = x g Mass of MgCO3 = (1-x) g

The chemical equations involved are:

CaCO3 → CaO + CO2


40+12+3×16=100g 22400cm3 at STP

MgCO3 →MgO+CO2

24+12+3×16=84g 22400cm3 at STP

Step1.To calculatevolume of CO2 evolved at STP from x g of CaCO3.

100g of CaCO3 evolve CO2 at STP = 22400cm3


22400
∴x g of CaCO3 will evolve CO2 at STP = ×xcm3= 224xcm3
100

Step2.Calculate, volume of CO2 evolved at STP from, (1–x) g of MgCO3.


22400 800
84g of MgCO3evolves CO2 at STP = × (1 − x)cm3 = (1 − x)cm3
84 3

Step3. To calculate the value of x


800
Total volume of CO2 evolved at STP = 224 x+ × (1 − x)cm3
3

But total volume of CO2 evolved at STP = 240cm3 (Given)


800 5
∴224 x+ 3
× (1 − 𝑥) = 240 or 672 x + 800 – 800x = 720 or 128x = 80 ∴𝑥 = 8

Step4. To calculate the percentage composition of the mixture.


5
∴Percentage of CaCO3=8×1 × 100 = 62.5

∴Percentage of MgCO3=100–62.5=37.5

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

Limiting Reagent
In single-reactant reactions, the calculations are carried out with only that amount of the
reactant which has converted to the product. This is done in all the methods mentioned above.

• Reactions proceed until one of the reactants is used up and one is left in excess.
• The limiting reactant limits the extent of the reaction and, thereby, determines the
amount of product formed.
• The excess reactants are all the leftover unused reactants.
• Determining the limiting reactant is important because the amount of the product
formed depends on this reactant.

In the reactions where more than one reactant is involved, one has to first identify the limiting
reactant, i.e., the reactant which is completely consumed or runs out first. All calculations
are to be carried out with the amount of the limiting reactant only. Now the question is how
to identify the limiting reactant? The procedure is simple analogy as illustrated below:
(1) Syrup is a limiting Reagent

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(2) Initially… 5moles 12moles 0 moles

A + 2B → 4C

If A is the limiting reactant; moles of C produced = 20

If B is the limiting reactant: moles of C produced = 24

The reactant producing the least number of moles of the product is the limiting
reactant and hence A is the limiting reactant.

Experimental Conditions
Reactants Products

Before reaction
2 molecules N2 3 molecules H2 0 molecules NH3

After reaction
1 molecule N2 0 molecules H2 2 molecules NH3

N 2 + 3H 2 ⎯⎯
→ 2NH 3
Initial mole 5 12 −

If N2 is the limiting reactant moles of NH3 produced =10. If H2 is the limiting


3
reactant moles of NH3 produced =  12 = 8 . The reactant producing the least number of
2
moles of the product is the limiting reactant, hence H2 is the limiting reactant.

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Ex.1: How much magnesium sulphide can be obtained from 2.00 g of magnesium and
2.00 g of sulphur by the reaction Mg + S⎯⎯→MgS? Which is the limiting reagent?
Calculate the amount of the reactants which remains unreacted.

Solution: First of all, each of these masses are converted into moles:
2.00
2.00 g of Mg = = 0.0824 moles of Mg
24 .3
2.00
2.00 g of S = = 0.0624 moles of S
32 .1

From the equation, Mg + S ⎯⎯→MgS, it follows that one mole of Mg reacts with one mole of
S. We are given more moles of Mg than of S. Therefore, Mg is in excess and some of it will
remain unreacted when the reaction is over. S is the limiting reagent and will control the
amount of product. From the equation we note that one mole of S gives one mole of MgS, so
0.0624 mole of S will react with 0.0624 mole of Mg to form 0.0624 mole of MgS.

Molar mass of MgS = 56.4 g

 Mass of MgS formed = 0.0624  56.4 g = 3.52 g of MgS

Moles of Mg left unreacted = 0.0824 –0.0624 moles of Mg

= 0.0200 moles of Mg

Mass of Mg left unreacted = moles of Mg  molar mass of Mg

= 0.0200  24.3 g of Mg = 0.486 g of Mg

Ex.2: 4 mole of MgCO3 is reacted with 6 moles of HCl solution. Find the volume of
CO 2 gas produced at STP. The reaction is MgCO3 + 2HCl → MgCl2 + CO2 + H 2O
Solution: From the reaction MgCO3 + 2HCl → MgCl2 + CO2 + H 2O
Given moles 4 mole 6 mole
Given mole ratio 2 : 3
Stoichiometric
Coefficient ratio 1 : 2
There should be one limiting reagent.
To find the limiting reagent, divide the given moles by stoichiometric coefficient.
MgCO3 HCl
4 6
=4 =3
1 2
HCl is limiting reagent.
moles of HCl moles of CO2 produced
Q =
2 1
 moles of CO 2 produced = 3 moles
 volumes of CO 2 produced at S.T.P, = 3 22.4 = 67.2L

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Ex. 3: What weight of AgCl will be precipitated when a solution containing 4.77 g NaCl
is added to a solution of 5.77g of AgNO3 ?
Solution: AgNO3 + NaCl ⎯⎯→ AgCl + NaNO3
5.77 4.77
moles. Mixed =  1000  1000
170 58.5
= 33.94 = 81.54 0 0
moles. left 0 47.60 33.94 33.94
w
 moles of AgCl formed = 33.94,  1000 = 33.94 WAgCl = 4.87g
143.5

Information Contained in a Balanced Equation

Viewed in Reactants Products



Terms of C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g)

Molecules 1 molecule C3H8 + 5 molecules O2 → 3 molecules CO2 + 4 molecules H2O

Amount (mol) 1 mol C3H8 + 5 mol O2 → 3 mol CO2 + 4 mol H2O

Mass (amu) 44.09 amu C3H8 + 160.00 amu O2 → 132.03 amu CO2 + 72.06 amu H2O

Mass (g) 44.09 g C3H8 + 160.00 g O2 → 132.03 g CO2 + 72.06 g H2O

Total mass (g) 204.09 g → 204.09 g

• EQUIVALENT WEIGHT OF ELEMENT


It is the weight of element that combines with or displaces 8parts by weight of oxygen,
35.5parts by weight of chlorine or 1part by weight of hydrogen.
Atomic mass
Equivalent mass of an element =
Valency
55.84
e.g.1: equivalent mass of iron in ferrous compounds = = 27.92
2
e.g.2: equivalent mass of iron in ferric compounds =
55.84
= 18.613
3

Eg.3: Mg + Cl2 → Mg Cl2

1mole 1mole
24gram 71grams
71-gram Cl2 → 24gram Mg

35.5gram Cl2 → 12gram Mg


24 A.w
E.W. of Mg=12= =
2 Valency

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Eg.4: 4A l + 3O2 → 2Al2O3

4 mole 3 mole
4 x 27gram 3 x 32 gram
3 x 32gram O2 → 4 x 27gram Al
4×27
8gram O2 → x8 = 9gram Al
3×32
27 𝐴.𝑤
E.W. of Al = 9 = =
3 𝑉𝑎𝑙𝑒𝑛𝑐𝑦

• Equivalent weight of acid:


It is the weight of acid that gives one mole H+ ions
Molecular mass
Equivalent mass of an acid =
Basicity(H + )
Basicity: is the number of hydrogen (H) atoms in a molecule of the acid, which can be
displaced by metal ion.
+
Eg.1: H2SO4 → 2H + SO2−
4

1mole 2mole
98gram

2mole H+ → 98gram H2SO4


+ 98
1mole H → 2 = 49gram H2SO4
98 M.W
E.W. of H2SO4 = 49 = =
2 Basicity

Eg.2: H3PO4 → 3H+ + 𝑃𝑂43−

1 mole 3 mole 98gram

3mole H+ → 98gram H3PO4

1mole H+
98
→ = 32.66
3
98 𝑀.𝑊
E.W. of H3PO4= 32.66 = = 𝐵𝑎𝑠𝑖𝑐𝑖𝑡𝑦
3

• Equivalent weight of base:It is the weight of base that gives one mole OH − . or reacts
with 1mole H+
Molecular mass
Equivalent mass of a base =
Acidity(OH − )
Acidity: The number of hydroxyl groups present in a molecule of the base “is known as
acidity of the base.
Eg. Ca (OH) 2
→ Ca2+ + 2OH-
1 mole 2 mole
74gram

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2mole OH → 74gram Ca(OH)2

1mole OH → = 37gram Ca(OH)2


𝑀.𝑊 74
E.W. of base =𝐴𝑐𝑖𝑑𝑖𝑡𝑦 = = 37
2

• Equivalent weight of ion:


It is the weight of ion that contains 1mole charge
2- 2-
Eq.1: SO4 1 mole SO4 →2mole charge →96gram
96
1mole charge → 2 = 48gram
2- 96 Formula weight
E.W of SO4 = 48 = 2 = charge

Eq.2:P𝑂43− 1 moleP𝑂43− → 3mole charge → 95grams


95
1mole charge → 3 =31.66 gram
95 Formula weight
E.W of P𝑂43− = 31.66 = =
3 charge
𝐹𝑜𝑟𝑚𝑢𝑙𝑎𝑤𝑒𝑖𝑔ℎ𝑡𝑜𝑓𝑖𝑜𝑛𝑠
E.W. of ions = 𝑐ℎ𝑎𝑟𝑔𝑒𝑜𝑛𝑖𝑜𝑛

• Equivalent weight of ionic compounds:


It is the weight of compound that contains 1mole positive and 1mole negative charge
3+
Ex. AlCl3 → Al + 3Cl-

1mole
133.5gram
133.5gram AlCl3→3mole positive & 3mole negative charge

1mole charge→ = 44.5g AlCl3


133.5
E.W. of AlCl3= 44.5 = 3
𝐹𝑜𝑟𝑚𝑢𝑙𝑎𝑤𝑒𝑖𝑔ℎ𝑡𝑜𝑓𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
E.W. of ionic compound = 𝑡𝑜𝑡𝑎𝑙+𝑣𝑒𝑜𝑟 −𝑣𝑒𝑐ℎ𝑎𝑟𝑔𝑒

• Gram equivalent weight: When equivalent weight is expressed in grams, it is called gram
equivalent weight.
𝑤𝑒𝑖𝑔ℎ𝑡𝑜𝑓𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
Number of gram equivalents = 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑤𝑒𝑖𝑔ℎ𝑡

Relation between number of moles and equivalent:


𝑊𝑒𝑖𝑔ℎ𝑡𝑖𝑛𝑔𝑟𝑎𝑚
No. of Moles = 𝐺.𝑀.𝑊
𝑤𝑡.𝑖𝑛𝑔𝑟𝑎𝑚 𝑤𝑡.𝑖𝑛𝑔𝑟𝑎𝑚
No. of Equivalents = =
𝐺.𝐸.𝑊 𝐺.𝑀.𝑊/𝑥

x→ Valency, Acidity, Basicity

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𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑤 𝐺.𝑀.𝑊
=𝐺.𝑀.𝑊/𝑥 × =𝑥
𝑀𝑜𝑙𝑒𝑠 𝑤

No. of Equivalents =No. of Moles ×x

Determination of equivalent mass:


(i) Hydrogen displacement method: Calculate the mass of the metal which displaces
1.008parts bymass of hydrogen.
mass of element mass of element
Eq.mass=mass of hydrogen × 1.008 =Vol(ml)of H × 11200
2 displaced at STP

(ii) Oxide formation or reduction of the oxide method: Calculate the mass of metal
which combines with or displaces 8parts by mass of oxygen.
mass of element mass of element
Eq.mass = × 8 = Vol(ml)of O × 5600
mass of oxygen 2 displaced at STP

(iii) Chloride formation method: Calculate the mass of the element which combines with
or displaces 35.5parts by mass of chlorine
mass of element
Eq.mass = mass of chlorine × 35.5

(iv)Metal displacement method: When a more electropositive metal is added to displace a less
electropositive metal from its salt
(e.g Zn +CuSO4→ZnSO4+Cu)
Mass of metal added Eq.Mass of metal added
=
Mass of metal displaced Eq.Mass of metal displaced

(iv) Double decomposition method: For a reaction of the type


AB+CD→AD↓+BC (e.g, AgNO3+NaCl→ AgCl↓+NaNO3)
Mass of AB taken Eq. Mass of AB Eq. mass of A + Eq. mass of B
= =
Mass of AD formed Eq. Mass of AD Eq. mass of A + Eq. mass of D
(v) Electrolytic method: (Faraday’s second law). When the same quantity of electricity
flows through solutions of different electrolytes,
Mass of X deposited Eq. mass of X
=
Mass of Y deposited Eq . mass of Y
(vi) Neutralization method: To calculate the equivalent mass of an acid, calculate the
mass of the acid neutralized by 1000cc of 1N base solution (which contains 1g eq).
Like-wise equivalent mass of a base can be calculated.
(vii)Silver salt method (for organic acids only):A known mass of silver salt of the organic
Eq.Mass of RCOOAg Mass of silver salt
acid is ignited to give a residue of Ag, then =
Eq.Mass of Ag(108) mass of silver

Eq. mass of acid (RCOOH) = Eq. mass of RCOOAg – Eq. mass of Ag+ Eq. mass of H
= Eq. mass of RCOOAg – 107

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Methods of expressing Concentration of solutions.


A solution is a homogeneous mixture of two or more chemically non reacting substance whose
composition can be varied within certain limits.

Solution made up of; two components are called binary solutions, three components are
ternary solutions, four components are quaternary solutions.

Components of binary solutions are solute and solvent.

The componet which is major ingredient and whose physical state is the same as that of
solution is called solvent.

METHODS OF EXPRESSING THE CONCENTRATION OF A SOLUTION

CONCENTRATION TERMS

• A solution is a homogeneous mixture of two or more substance, the composition of


which may vary within limits.
• A solution is a special kind of mixture in which substances are intermixed so intimately
that they cannot be observed as separated components.
• The substance which is to be dissolved is called solute while the medium in which the
solute is dissovled to get a homogeneous mixture is called the solvent.
• A solution is termed as binary and ternary if it consists of two and three components
respectively.

• The concentration of a solution is defined as the amount of solute present in the given
quantity of the solution (or solvent).
• Solutions containing relatively high concentration of solute are called concentrated
solutions, while those of relatively low concentrations of solute are called dilute
solutions

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Concentration of a solution can be expressed in different ways as follows,

• Mass Percentage: It is the amount of solute in grams present in 100grams of the


solution
mass of solute
Mass percentage=mass of solution × 100

• Volume Percentage:isthe volume of the solute present per 100 parts by volume of
solution.
volume of solute
Volume percentage= volume of solution × 100

6
• Parts per million (ppm): It is the amount of the solute in grams present in 10 grams
of the solution.
𝑚𝑎𝑠𝑠𝑜𝑓𝑥
ppm of ‘x’=𝑚𝑎𝑠𝑠𝑜𝑓𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 × 106

• Molarity: Molarity is the number of moles of the solute present in one litre of the
solution. It is denoted by ‘M’. The units of molarity are moles/litre.
When one mole of the solute is dissolved in 1litre solution, the solution is called one
molar(or 1M) solution.

Mathematical Relations:
𝑛𝑜.𝑜𝑓𝑚𝑜𝑙𝑒𝑠𝑜𝑓𝑠𝑜𝑙𝑢𝑡𝑒 wt.of solute 1
• Molarity = = ×
𝑣𝑜𝑙𝑢𝑚𝑒𝑜𝑓𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑙𝑖𝑡𝑟𝑒𝑠) G.M.W. volume of solution (litres)

wt. of solute 1000


= ×
G. M. W. volume of solution (ml)

• No. of moles = M.V.(litres)


No. of millimoles = M.V.(ml)
10×%
• Calculation of molarity, when % mass of solution is given, M = GMW
• Calculation of molarity, when % mass of solution and density are given (only for
10 × % ×density
competitive exams), M= GMW
• When a solution of molarity M1 and volume V1 is diluted with a solvent to get a solution
of molarity M2 and volume V2, then
M1V1 = M2V2

• Calculation of resultant molarity, when two or more solutions of the same substance are
mixed.

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𝐌𝟏 𝐕𝟏 + 𝐌𝟐 𝐕𝟐 + 𝐌𝟑 𝐕𝟑 + … … … .
𝐌=
𝐕𝐟𝐢𝐧𝐚𝐥

M1 and V1, M2 and V2, M3 and V3 are the molarities and volumes of the individual solutions.

• When two solutions of different substance are mixed together (titrated against each
other), then
M1V1 M2V2
=
n1 n2

M1, V1, and M2, V2, are molarities and volumes of the two solutions n1 and n2 are the no. of
moles of the two substances involved.

Note: Semi molar: molarity is 0.5; Deci molar: molarity is 0.1

Centimolar: molarity is 0.01; Millimolar: molarity is 0.001


Molarity changes with temp because volume of solution changes with temp.

Ex.1 :149 gm of potassium chloride (KCl) is dissolved in 10 Lt of an aqueous solution.


Determine the molarity of the solution (K = 39, Cl = 35.5)

Solution: Molecular mass of KCl = 39 + 35.5 = 74.5 gm

149gm
 Moles of KCl = =2
74.5gm

2
Molarity of the solution = = 0.2M
10

Ex.2: What volume of a 3.0 M HCl solution be mixed with 500 mL of a 7 M HCl
solution to prepare a HCl solution whose molarity will be 4.0?

Solution:Let V mL of 3.0 M HCl solution is taken, then


3 V + 500 × 7 = 4 × ( 500 + V )  V = 1500 mL

Ex.3: Determine molarity of a solution obtained by mixing 50 mL of a 0.26 M H 2SO4


solution with another 150 mL 0.48 M H 4SO4 solution.

Solution: It is a case of mixing of two solutions of different molarities. Applying the


mixing formula:

M1V1 + M 2 V2 50  0.26 + 150  0.48


 M3 = = = 0.425 M
V3 50 + 150

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BASIC CONCEPTS IN CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

Ex. 4: What volume of a 5.00 M H 2SO4 solution should be added to a 150 mL 1.0 M
H 2SO4 solution to obtain a solution of sulphuric acid of molarity 2.5?

Solution: It is again a case of mixing of two solutions. Let us assume that V mL of the
stock solution of H 2SO4 is added.

 5V + 150 × 1.0 = 2.5 × (150 + V )

 2.5 V = 225

225
 V= = 90 mL
2.5

Ex.5: A 150 mL 0.25 M NaCl solution, 250 mL 0.45 M CaCl2 solution and a 100 mL
0.60 M AlCl3 solution are mixed together and diluted to a final volume of 750
mL by adding enough water. Determine molarity of chloride ion Cl− ( ) in solution
assuming that all three salts are completely soluble as well as completely
dissociated.

Solution: First we need to calculate total mmoles of Cl from the three salt solutions:

mmoles of Cl ion from NaCl = 37.5

mmoles of Cl ion from CaCl2 = 2 × mmoles of CaCl2

= 2 × 112.5 = 225

mmoles of Cl ion from AlCl3 = 3 × mmoles of AlCl3

= 3 60 = 180

 Total mmoles of Cl in final solution

= 37.5 + 225 + 180 = 442.5

mmoles of Cl – 442.5
 Molarity of Cl – = = = 0.59 M
mL of solution 750

Normality: It is the number of gram equivalents of the solute present in one litre of the
solution. It is denoted by ‘N’. The units of normality are gram equivalents/litre. When one gram
equivalent weight of a solute is dissolved in 1litre solution, the solution is called one normal
(1N) solution.

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Mathematical Relations:
no.of moles of solute
Normality =
volume of solution (litres)

𝑤𝑡.𝑜𝑓𝑠𝑜𝑙𝑢𝑡𝑒 1 wt.of solute 1000


= × = ×
G.E.W. volume of solution (litres) G.E.W. volume of solution (ml)

• No. of equivalents = N.V.(litres)


No. of milliequivalents = N.V.(ml)
𝟏𝟎×%
• Calculation of molarity, when % mass of solution is given, 𝐍 = 𝐆𝐄𝐖
• Calculation of Normality, when % mass of solution and density are given (only for
competitive exams)
10 × % ×density
N= GEW

• When a solution of Normality N1 and volume V1 is diluted with a solvent to get a solution
of Normality N2 and volume V2, then, N1V1 = N2V2
• Calculation of resultant Normality, when two or more solutions of the same substance
are mixed.
N1 V1 + N2 V2 + N3 V3 + ……….
N= Vfinal

• When two solutions of different substance are mixed together (titrated against each
wt
other), then, N1V1 = N2V2 (or)G.E.W = N. V. (lit)

i.e. no. of equivalents of both the substance should be equal.


• Calculation of resultant normality when two solutions of different substances are mixed
together. Let Na and Va be the normality and volume of acid, Nb and Vb be the normality
and volume of base.
Na Va −Nb Vb
(i) If NaVa>NbVb acidic (pH < 7), Nresultant = Vfinal
Nb Vb −Na Va
(ii)If NbVb>NaVa basic (pH > 7), Nresultant = Vfinal

(iii) If NaVa = NbVb neutral


• Relation between Normality and Molarity
wt 1 wt 1
Normality = × Molarity = ×
G. E. W. V(L) G. M. W. V(L)
Normality G.M.W. G.M.W.
= × G.M.W./x−factor
Molarity G.E.W.

 Normality = Molarity × x -factor

x -factor is basicity for acids, acidity for bases, total +ve or –ve charges for salts, change
in oxidation no. for oxidant & reductant.

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• Molality: It is defined as the number of moles of the solute present in 1 kg of the


solvent. It is denoted by ‘m’.
The units of molality are moles/kg. When one mole of a solute is dissolved in 1 kg of the
solvent, the solution is called 1 molal or 1m solution.
no.of moles of solute
Molality, m = weight of solvent kg

weight of solute 1000


∴ m= GMW of solute × weight of solvent in gm

Ex.1:255 gm of an aqueous solution contains 5 gm of urea.


What is the concentration of the solution in terms of molality? (Mol. wt. of urea =
60)

Solution: Mass of urea = 5 gm

Molecular mass of urea = 60

5
Number of moles of urea = = 0.083
60

Mass of solvent = (255 – 5) = 250 gm

Number of moles of solute 0.083


 Molality of the solution = × 1000 = 1000 = 0.333
Mass of solvent in gram 250

Ex.2: The molarity and molality of a solution are M and m respectively. If the
molecular weight of the solute is M  , calculate the density of the solution in
terms of M, m and M  .
Sol: Let weight of solute be w g and weight of solvent is W g and volume of solution is V mL.
w 1000
 M= … (1)
M  V

w  1000
m= … (2)
M  W
w+W
D= … (3)
V
MMV
By Eq. (1) w = … (4)
1000

w 1000 MMV 1000


By Eq. (2) W = = by Eq. (4)
M  m 1000  M  m

MV
W= … (5)
m

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MV MMV
+ M 
1
 By Eq. (3) D = m 1000 D = M +
V  m 1000 

• Mole Fraction: It is defined as the ratio of number of moles of one component to


the total number of moles of the solution. Mole fraction is denoted by ‘x’
Consider a solution containing two components A and B. If xA and xB are mole fractions of
A and B respectively and nA and nB are the number of moles of A and B respectively. Then
wA
nA
xA =
MA
= wA wB
nA +nB +
MA MB
wB
nB
xB =
MB
= wA wB
nA +nB +
MA MB

Where, wA and wB are the weights of A and B in grams respectively and MA and MB are the
molecular masses of A and B respectively.
The sum of the mole fractions of the components of a solution is equal to unity. In a binary
solution, mole fraction of solute + mole fraction of solvent = 1
• Formality: It is the number of formula masses in grams of the solute dissolved per litre
of the solution. It is denoted by ‘F’. It is used for ionic compounds in which there is no
existence of molecule.
Number of gram formula units of solute
Formality(F) =
Volume of solution in litres
Mass of ionic solute (g)
Formality(F) =
gram formula unit mass of solute × Volume of solution (l)

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NCERT SOLUTIONS

Question 1.1: Calculate the molecular mass of the following:


(a) H2O, (b) CO2, (c) CH4
(a) H2O
The molecular mass of water, H 2O:
= (2 × Atomic mass of hydrogen) + (1 × Atomic mass of oxygen)
= [2(1.0084) + 1(16.00 u)]
= 2.016 u + 16.00 u
= 18.016
= 18.02 u
(b) CO2
The molecular mass of carbon dioxide, CO 2:
= (1 × Atomic mass of carbon) + (2 × Atomic mass of oxygen)
= [1(12.011 u) + 2 (16.00 u)]
= 12.011 u + 32.00 u
= 44.01 u

(c) CH4
The molecular mass of methane, CH 4:
= (1 × Atomic mass of carbon) + (4 × Atomic mass of hydrogen)
= [1(12.011 u) + 4 (1.008 u)]
= 12.011 u + 4.032 u = 16.043 u

Question 1.2: Calculate the mass per cent of different elements present in sodium
sulphate (Na2SO4).
The molecular formula of sodium sulphate is Na 2SO4
Molar mass of Na2SO4 = [(2 × 23.0) + (32.066) + 4 (16.00)] = 142.066 g
𝑚𝑎𝑠𝑠 𝑖𝑓 𝑡ℎ𝑎𝑡 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
Mass percent of an element = × 100
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
46.0𝑔
∴ Mass percent of sodium: = × 100 = 32.379 = 32.4%
142.066𝑔
32.066𝑔
Mass percent of sulphur:= × 100 = 22.57 = 22.6 %
142.066𝑔
64.0𝑔
Mass percent of oxygen: = × 100 = 45.049 = 45.05%
142.066𝑔

Question 1.3: Determine the empirical formula of an oxide of iron that has 69.9%
iron & 30.1% dioxygen by mass.
Given:
% of iron by mass = 69.9 %
% of oxygen by mass = 30.1 %
𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑖𝑟𝑜𝑛 𝑏𝑦 𝑚𝑎𝑠𝑠 69.9
Relative moles of iron in iron oxide: = = = 1.25
𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖𝑟𝑜𝑛 55.85
𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛 𝑏𝑦 𝑚𝑎𝑠𝑠 30.1
Relative moles of oxygen in iron oxide: = = = 1.88
𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖𝑟𝑜𝑛 16.0

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The simplest molar ratio of iron to oxygen: = 1.25: 1.88 = 1:1.5 = 2:3
∴ The empirical formula of the iron oxide is Fe2O3.

Question 1.4: Calculate the amount of carbon dioxide that could be produced when
(a) 1 mole of carbon is burnt in the air.
(b) 1 mole of carbon is burnt in 16 g of dioxygen.
(c) 2 moles of carbon are burnt in 16 g of dioxygen.

The balanced reaction of combustion of carbon can be written as:

(a) As per the balanced equation, 1 mole of carbon burns in 1 mole of dioxygen (air) to
produce 1 mole of carbon dioxide.
(b) According to the question, only 16 g (0.5 mol) of dioxygen is available. Hence, it will
react with 0.5 moles of carbon to give 22 g of carbon dioxide. Hence, it is a limiting
reactant.
(c) Since oxygen is the limiting reactant here, the 16g (0.5 mol) of O 2 will react with 6 g of
carbon (0.5 mol) to form 22 g of carbon dioxide. The remaining 18 g of carbon (1.5 mol) will
not undergo combustion.

Question 1.5: Calculate the mass of sodium acetate (CH 3COONa) required to make
500 mL of 0.375 molars aqueous solution. The molar mass of sodium acetate is
82.0245 g mol–1.
0.375 M aqueous solution of sodium acetate ≡ 1000 mL of a solution containing 0.375 moles
of sodium acetate.
∴ A number of moles of sodium acetate in 500 mL. = 0.375/1000 x 500 = 0.1875 mole
Molar mass of sodium acetate = 82.0245 g mol–1 (Given)
∴ Required mass of sodium acetate = (82.0245 g mol –1) (0.1875 mole) = 15.38 g

Question 1.6: Calculate the concentration of nitric acid in moles per litre in a
sample that has a density, 1.41 g mL –1, and the mass percent of nitric acid in it
being 69%.
The mass percent of nitric acid in the sample = 69 % (Given)
Thus, 100 g of nitric acid contains 69 g of nitric acid by mass.
Molar mass of nitric acid (HNO 3): = [1 +14 + 3(16)] g mol–1 = 1 +14 + 48 = 63 g mol–1
69𝑔
∴ Number of moles in 69 g of HNO 3 = = 1.095 mol
63𝑔𝑚𝑜𝑙 −1
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 100𝑔
The volume of 100 g of nitric acid solution = =
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1.41𝑔𝑚𝑜𝑙−1
= 70.92 mL ≡ 70.92 x 10-3 L

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1.095 𝑚𝑜𝑙𝑒
The concentration of nitric acid:= 𝐿 = 15.44 mol/L
70.92 × 10−3
∴ Concentration of nitric acid = 15.44 mol/L

Question 1.7: How much copper can be obtained from 100 g of copper sulphate
(CuSO4)?
1 mole of CuSO4 contains 1 mole of copper.
Molar mass of CuSO4 = (63.5) + (32.00) + 4(16.00) = 63.5 +32.00 + 64.00 = 159.5 g
159.5 g of CuSO4 contains 63.5 g of copper.
63.5 ×100𝑔
⇒ 100 g of CuSO4 will contain of copper.
159.5
63.5 ×100𝑔
∴ Amount of copper that can be obtained from 100 g CuSO 4 = = 39.81
159.5

Question 1.8: Determine the molecular formula of an oxide of iron in which the mass
per cent of iron and oxygen are 69.9 and 30.1, respectively. Given that the molar
mass of the oxide is 159.69 g mol –1.
► Mass percent of iron (Fe) = 69.9% (Given)
► Mass percent of oxygen (O) = 30.1% (Given)
► Number of moles of iron present in the oxide = 69.90/55.85 = 1.25
► Number of moles of oxygen present in the oxide = 30.1/16.0 = 1.88
► The ratio of iron to oxygen in the oxide: 1.25 : 1.88
1.25 1.88
= ∶ = 1: 15 = 2 ∶ 3
1.25 1.25
The empirical formula of the oxide is Fe 2O3.
Empirical formula mass of Fe 2O3 = [2(55.85) + 3(16.00)] g
Molar mass of Fe2O3 = 159.69 g
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 159.69𝑔
So, 𝑛 = 𝑒𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑚𝑎𝑠𝑠 = = 0.999 = 1(𝑎𝑝𝑝𝑟𝑜𝑥)
159.7𝑔
Molecular formula of a compound is obtained by multiplying the empirical formula with n.
Thus, the empirical formula of the given oxide is Fe 2O3 and n is 1.
Hence, the molecular formula of the oxide is Fe 2O3.

Question 1.9: Calculate the atomic mass (average) of chlorine using the
following data:
% Natural Abundance Molar Mass

35
Cl 75.77 34.9689

37
Cl 24.23 36.9659

75.77 ×34.9689𝑢 +24.23 ×36.9659𝑢 2649.59𝑢+895.68𝑢


The average atomic mass of chlorine: = = = 35.45𝑢
75.77+24.23 100
The average atomic mass of chlorine = 35.4527 u

Question 1.10: In three moles of ethane (C 2H6), calculate the following:

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(a) Number of moles of carbon atoms.


(b) Number of moles of hydrogen atoms.
(c) Number of molecules of ethane.
(a) 1 mole of C2H6 contains 2 moles of carbon atoms.
Number of moles of carbon atoms in 3 moles of C 2H6 = 2 × 3 = 6
(b) 1 mole of C2H6 contains 6 moles of hydrogen atoms.
Number of moles of carbon atoms in 3 moles of C 2H6 = 3 × 6 = 18
(c) 1 mole of C2H6 contains 6.023 × 1023 molecules of ethane.
Number of molecules in 3 moles of C 2H6 = 3 × 6.023 × 1023 = 18.069 × 10 2

Question 1.11: What is the concentration of sugar (C 12H22O11) in mol L–1 if its 20 g
are dissolved in enough water to make a final volume up to 2 L?
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑢𝑔𝑎𝑟/𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑢𝑔𝑎𝑟
Molarity (M) of a solution is given by: = =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒𝑠 2𝐿

20𝑔/[(12×12)+(1×22)+(11×16)]𝑔 20𝑔/342𝑔 0.0585𝑚𝑜𝑙


= = = = 0.02925 mol L–1
2𝐿 2𝐿 2𝐿
The molar concentration of sugar = 0.02925 mol L –1

Question 1.12: If the density of methanol is 0.793 kg L –1 , what is its volume


needed for making 2.5 L of its 0.25 M solution?
Molar mass of methanol (CH 3OH) = (1 × 12) + (4 × 1) + (1 × 16) = 32 g mol–1 = 0.032 kg mol–1
0.793𝑘𝑔 𝐿−1
Molarity of methanol solution ≔ 0.032 𝑘𝑔 𝑚𝑜𝑙−1 = 24.78 𝑚𝑜𝑙 𝐿−1
(Since density is mass per unit volume)
Applying, M1V1 = M2 V2
(Given solution) = (Solution to be prepared)
(24.78 mol L–1) V1 = (2.5 L) (0.25 mol L–1)
V1 = 0.0252 L = 25.22 mL

Question 1.13: The pressure is determined as force per unit area of the surface.
an SI unit of pressure, Pascal is as shown below:
• 1 Pa = 1 N m –2
If the mass of air at sea level is 1034 g cm –2, calculate the pressure in Pascals.
The pressure is defined as a force acting per unit area of the surface.
P = F/A
1034𝑔×9.8 𝑚𝑠−1 1𝐾𝑔 (100)2 𝑐𝑚2
= × 1000𝑔 × = 1.01332 × 105 kg m-1 s-2
𝑐𝑚2 1𝑚2
We know, 1 N = 1 kg ms–2
Then,
1 Pa = 1 N m–2 = 1 kg m–2s–2
1 Pa = 1 kg m1–s2–

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∴ Pressure = 1.01332 × 10 5 Pa.

Question 1.14: What is the SI unit of mass? How is it defined?


The SI unit of mass is the kilogram (kg).
• 1 Kg is defined as the mass equal to the mass of the international prototype of the k g.
Question 1.15: Match the following prefixes with their multiples
Prefixes Multiples
(i) micro 106
(ii) deca 109
(iii) mega 10–6
(iv) giga 10–15
(v) femto 10
Question 1.16: What do you mean by significant figures?
Significant figures are those meaningful digits that are known with certainty. They indicate
uncertainty in an experiment or calculated value.
Example: If 15.6 mL is the result of an experiment, then 15 is certain while 6 is uncertain,
and the total number of significant figures is 3.
Hence, significant figures are defined as the total number of digits in a number, including
the last digit that represents the uncertainty of the result.

Question 1.17: A sample of drinking water was found to be severely contaminated


with chloroform, CHCl 3, supposed to be carcinogenic in nature. The level of
contamination was 15 ppm (by mass).
(a) Express this in per cent by mass.
(b) Determine the molality of chloroform in the water sample.
(a) 1 ppm is equivalent to 1 part out of 1 million (10 6) parts.
The mass percent of 15 ppm chloroform in water = 15/106 × 100 ≈ 1.5 x 10-3 %
(b) 100 g of the sample contains 1.5 × 10 –3 g of CHCl3.
⇒ 1000 g of the sample contains 1.5 × 10–2 g of CHCl3.
1.5×102 𝑔
The molality of chloroform in water:
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶𝐻𝐶𝑙3
Molar mass of CHCl3 = 12.00 + 1.00 + 3(35.5) = 119.5 g mol–1
Molality of chloroform in water = 0.0125 × 10 –2 m = 1.25 × 10–4 m

Question 1.18: Express the following in the scientific notation:


(a) 0.0048
(b) 234,000
(c) 8008
(d) 500.0
(e) 6.0012
(a) 0.0048 = 4.8× 10–3
(b) 234, 000 = 2.34 ×105

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(c) 8008 = 8.008 ×103


(d) 500.0 = 5.000 × 102
(e) 6.0012 = 6.0012

Question 1.19: How many significant figures are present in the following?
(a) 0.0025
(b) 208
(c) 5005
(d) 126,000
(e) 500.0
(f) 2.0034
(a) 0.0025, there are 2 significant figures.
(b) 208, there are 3 significant figures.
(c) 5005, there are 4 significant figures.
(d) 126,000, there are 3 significant figures.
(e) 500.0, there are 4 significant figures.
(f) 2.0034, there are 5 significant figures.

Question 1.20: Round up the following up to three significant figures:


(a) 34.216
(b) 10.4107
(c) 0.04597
(d) 2808
(a) 34.2
(b) 10.4
(c) 0.0460
(d) 2810

Question 1.21: The following data are obtained when dinitrogen and dioxygen react
together to form different compounds:
Mass of dinitrogen Mass of dioxygen
(i) 14 g 16 g
(ii) 14 g 32 g
(iii) 28 g 32 g
(iv) 28 g 80 g
(a) Which law of chemical combination is obeyed by the above experimental data?
Give its statement.
(b) Fill in the blanks in the following conversions:
(i) 1 km = ........... mm = ........... pm
(ii) 1 mg = ........... kg = ........... ng
(iii) 1 ml = ........... l = ........... dm3

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(a) If we fix the mass of dinitrogen at 28 g, then the masses of dioxygen that will combine
with the fixed mass of dinitrogen are 32 g, 64 g, 32 g, and 80 g.
The masses of dioxygen bear a whole number ratio of 1:2:2:5. Hence, the given
experimental data obeys the law of multiple proportions.
The law states that if two elements combine to form more than one compound, then the
masses of one element that combines with the fixed mass of another element are in the
ratio of small whole numbers.
(b) (i) 1 km = 1 km × 1000 m/1 km × 100 cm/1m × 10 mm/1cm
⇒ 1 km = 106 mm
⇒ 1 km = 1 km × 1000 m/1 km × 1 pm/10-12 m
⇒ 1 km = 1015 pm
Hence, 1 km = 106 mm = 1015 pm
(ii) 1 mg = 1 mg × 1 g/1000 mg × 1 kg/1000 g
⇒ 1 mg = 10-6 kg
⇒ 1 mg = 1 mg × 1 g/ 1000 mg × 1 mg/ 10-9 g 1
⇒ 1 mg = 106 ng
Hence, 1 mg = 10–6 kg = 106 ng
(iii) 1 mL = 1 mL × 1 L/1000 mL
⇒ 1 mL = 10–3 L
⇒ 1 mL = 1 cm3
1𝑑𝑚 × 1𝑑𝑚 × 1𝑑𝑚
= 1𝑐𝑚3 × = 1𝑚𝑙 = 10−3 𝑑𝑚3
10𝑐𝑚 × 10𝑐𝑚 × 10𝑐𝑚
= 1𝑚𝑙 = 10−3 𝐿 = 10−3 𝑑𝑚3

Question 1.22: If the speed of light is 3.0 × 10 8 ms-1, calculate the distance
covered by light in 2.00 ns.
According to the question:
Time taken to cover the distance = 2.00 ns = 2.00 × 10 –9 s
Speed of light = 3.0 × 10 8 ms–1
Distance travelled by light in 2.00 ns:
= Speed of light × Time taken
= (3.0 × 108 ms –1) (2.00 × 10–9 s)
= 6.00 × 10–1 m = 0.600 m

Question 1.23: In a reaction A + B 2 → AB2


Identify the limiting reagent, if any, in the following reaction mixtures.
(a) 300 atoms of A + 200 molecules of B 2
(b) 2 mol A + 3 mol B 2
(c) 100 atoms of A + 100 molecules of B 2

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(d) 5 mol A + 2.5 mol B


(e) 2.5 mol A + 5 mol B
A limiting reagent determines the extent of a reaction. It is the reactant which is the first
to get consumed during a reaction, thereby causing the reaction to stop and limiting the
number of products formed.
(a) According to the given reaction, 1 atom of A reacts with 1 molecule of B. Thus, 200
molecules of B will react with 200 atoms of A, thereby leaving 100 atoms of A unused.
Hence, B is the limiting reagent.
(b) According to the reaction, 1 mol of A reacts with 1 mol of B. Thus, 2 mol of A will react
with only 2 mol of B. As a result, 1 mol of A will not be consumed. Hence, A is the limiting
reagent.
(c) According to the given reaction, 1 atom of A combines with 1 molecule of B. Thus, all
100 atoms of A will combine with all 100 molecules of B. Hence, the mixture is
stoichiometric where no limiting reagent is present.
(d) 1 mol of atom A combines with 1 mol of molecule B. Thus, 2.5 mol of B will combine with
only 2.5 mol of A. As a result, 2.5 mol of A will be left as such. Hence, B is the limiting
reagent.
(e) According to the reaction, 1 mol of atom A combines with 1 mol of molecule B. Thus, 2.5
mol of A will combine with only 2.5 mol of B and the remaining 2.5 mol of B will be left as
such. Hence, A is the limiting reagent.

Question 1.24: Dinitrogen and dihydrogen react with each other to produce ammonia
according to the following chemical equation:
N2(g) + H2(g) → 2NH3(g)
(a) Calculate the mass of ammonia produced if 2.00 × 10 3 g dinitrogen reacts with
1.00 × 103 g of dihydrogen.
(b) Will any of the two reactants remain unreacted?
(c) If yes, which one and what would be its mass?
(a) Balancing the given chemical equation, N2(g) + H2(g) → 2NH3(g)
From the equation, 1 mole (28 g) of dinitrogen reacts with 3 mole (6 g) of dihydrogen to
give 2 mole (34 g) of ammonia.
⇒ 2.00 × 103 g of dinitrogen will react with 6 g/28 g × 2.00 x 103 g dihydrogen i.e., 2.00 ×
103 g of dinitrogen will react with 428.6 g of dihydrogen.
Given,
Amount of dihydrogen = 1.00 × 10 3 g
Hence, N2 is the limiting reagent. 28 g of N 2 produces 34 g of NH3.
Hence, mass of ammonia produced by: 2000 g of N2 = 34 g/28 g × 2000g = 2428.57 g
(b) N2 is the limiting reagent and H 2 is the excess reagent. Hence, H 2 will remain
unreacted.

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(c) Mass of dihydrogen left unreacted = 1.00 × 10 3 g – 428.6 g = 571.4 g

Question 1.25: How are 0.50 mol Na 2CO3 and 0.50 M Na 2CO3 different?
Molar mass of Na2CO3 = (2 × 23) +12.00 + (3 × 16) = 106 g mol –1
Now, 1 mole of Na2CO3 means 106 g of Na2CO3.
106𝑔
⇒ 0.5 mol of Na2CO3 = × 0.5 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑁𝑎2 𝐶𝑂3 = 53 g Na2CO3
1 𝑚𝑜𝑙𝑒
⇒ 0.50 M of Na2CO3 = 0.50 mol/L Na2CO3
Hence, 0.50 mol of Na2CO3 is present in 1 L of water or 53 g of Na 2CO3 is present in 1 L of
water.

Question 1.26: If ten volumes of dihydrogen gas react with five volumes of dioxygen
gas, how many volumes of water vapour would be produced?
Reaction of dihydrogen with dioxygen can be written as: 2H2(g) + O2(g) → 2H2O(g)
Now, two volumes of dihydrogen react with one volume of dihydrogen to produce two
volumes of water vapour.
Hence, ten volumes of dihydrogen will react with five volumes of dioxygen to produce ten
volumes of water vapour.

Question 1.27: Convert the following into basic units:


(a) 28.7 pm
(b) 15.15 pm
(c) 25365 mg
(a) 28.7 pm
1 pm = 10–12 m
28.7 pm = 28.7 × 10–12 m = 2.87 × 10–11 m
(b) 15.15 pm
1 pm = 10–12 m
15.15 pm = 15.15 × 10–12 m = 1.515 × 10–11 m
(c) 25365 mg
1 mg = 10–3 g
25365 mg = 2.5365 × 104 × 10–3 g
Since, 1 g = 10–3 kg
2.5365 × 101 g = 2.5365 × 10–1 × 10–3 kg
25365 mg = 2.5365 × 10–2 kg.

Question 1.28: Which one of the following will have largest number of atoms?
(a) 1 g Au (s)
(b) 1 g Na (s)
(c) 1 g Li (s)
(d) 1 g of Cl2(g)

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(a) 1 g of Au (s) = 1/197 mol of Au (s) = 6.022 × 1023/197


atoms of Au (s) = 3.06 × 10 21 atoms of Au (s)
(b) 1 g of Na (s) = 1/23 mol of Na (s)
= 6.022 × 1023/23 atoms of Na (s)
= 0.262 × 1023 atoms of Na (s)
= 26.2 × 1021 atoms of Na (s)
(c) 1 g of Li (s) = 1/7 mol of Li (s)
= 6.022 × 1023/7 atoms of Li (s)
= 0.86 × 1023 atoms of Li (s)
= 86.0 × 1021 atoms of Li (s)
(d) 1 g of Cl2 (g) = 1/71 mol of Cl2 (g)
(Molar mass of Cl2 molecule = 35.5 × 2 = 71 g mol –1) = 6.022 x 1023/71
= 0.0848 × 1023 molecules of Cl2 (g)
= 8.48 × 1021 molecules of Cl2 (g)
As one molecule of Cl2 contains two atoms of Cl.
Number of atoms of Cl = 2 × 8.48 × 10 21 = 16.96 × 1021 atoms of Cl
Hence, 1 g of Li (s) will have the largest number of atoms.

Question 1.29: 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).
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶 𝐻 𝑂𝐻
Mole fraction of C2H5OH = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
2 5

𝐶𝐶2𝐻5 𝑂𝐻
0.040 = … … … … … … . . (1)
𝑛𝐶2𝐻5 𝑂𝐻 + 𝑛𝐻2 𝑂
1000𝑔
Number of moles present in 1 L water:𝑛𝐻2 𝑂 = 18𝑔 𝑚𝑜𝑙−1 = 55.55 𝑚𝑜𝑙
Substituting the value of 𝑛𝐻2 𝑂 in equation (1)
𝑛𝐶2𝐻5 𝑂𝐻
= 0.040
𝑛𝐶2 𝐻5 𝑂𝐻 + 55.55

𝑛𝐶2 𝐻5 𝑂𝐻 = 0.040𝑛𝐶2𝐻5 𝑂𝐻 + (0.040)(55.55)

0.96𝑛𝐶2𝐻5 𝑂𝐻 = 2.222𝑚𝑜𝑙

2.222
𝑛𝐶2 𝐻5 𝑂𝐻 = 𝑚𝑜𝑙 = 2.314𝑚𝑜𝑙
0.96
2.314𝑚𝑜𝑙
∴ 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = = 2.214𝑀
1𝐿
Question 1.30: What will be the mass of one 12C atom in g?
1 mole of carbon atoms = 6.023 × 10 23 atoms of carbon = 12 g of carbon
Mass of one 12C atom = 12 g/6.022 × 10 23 = 1.993 × 10–23 g.

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Question 1.31: How many significant figures should be present in the of the
following calculations?
𝟎.𝟎𝟐𝟖𝟓𝟔×𝟐𝟗𝟖.𝟏𝟓×𝟎.𝟏𝟏𝟐
(a)
𝟎.𝟓𝟕𝟖𝟓
(b) 5 × 5.364
(c) 0.0125 + 0.7864 + 0.0215
𝟎.𝟎𝟐𝟖𝟓𝟔×𝟐𝟗𝟖.𝟏𝟓×𝟎.𝟏𝟏𝟐
(a)
𝟎.𝟓𝟕𝟖𝟓
Least precise number of calculations = 0.112
Number of significant figures in the Ans = Number of significant figures in the least
precise number = 3
(b) 5 × 5.364
Least precise number of calculations = 5.364
Number of significant figures in the Ans = Number of significant figures in 5.364 = 4
(c) 0.0125 + 0.7864 + 0.0215
Since the least number of decimal places in each term is four, the number of significant
figures in the Ans: is also 4.

Question 1.32: Use the data given in the following table to calculate the molar mass
of naturally occurring argon isotopes:
Isotope Isotopic molar mass Abundance
36
Ar 35.96755 gmol–1 0.337%
38
Ar 37.96272 gmol–1 0.063%
40
Ar 39.9624 gmol–1 99.600%
0.337 0.063 90.60
Molar mass of argon: = [(35.96755 × ) + (37.96272 × ) + (39.9624 × )]
100 100 100
= [0.121 + 0.024 + 39.802] 𝑔𝑚𝑜𝑙 −1 = 39.947 g mol–1

Question 1.33: Calculate the number of atoms in each of the following:


(a) 52 moles of Ar
(b) 52 u of He
(c) 52 g of He
(a) 1 mole of Ar = 6.022 × 1023 atoms of Ar
52 mol of Ar = 52 × 6.022 × 10 23 atoms of Ar
= 3.131 × 1025 atoms of Ar
(b) 1 atom of He = 4 u of He
Or,
4 u of He = 1 atom of He
1 u of He= 1/4 atom of He
52 u of He = 52 /4 atoms of He
= 13 atoms of He
(c) 4 g of He = 6.022 × 1023 atoms of He

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6.022×1023 ×52
52𝑔 𝑜𝑓 𝐻𝑒 = 𝑎𝑡𝑜𝑚𝑠 𝑜𝑓 𝐻𝑒 = 7.8286 × 1024 atoms of He.
4

Question 1.34: 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:
(a) Empirical formula
(b) Molar mass of the gas
(c) Molecular formula
a) 1 mole (44 g) of CO2 contains 12 g of carbon.
3.38 g of CO2 will contain carbon = 12 g/44 g × 3.38 g = 0.9217 g
18 g of water contains 2 g of hydrogen. = 2 g/18 g × 0.690
0.690 g of water will contain hydrogen = 0.0767 g
Since carbon and hydrogen are the only constituents of the compound, the total mass of
the compound is: = 0.9217 g + 0.0767 g = 0.9984 g
Percent of C in the compound = 0.9217 g/0.9984 × 100 = 92.32%
Percent of H in the compound = 0.0767 g/0.9984 × 100 = 7.68%
Moles of carbon in the compound = 92.32/12.00 = 7.69
Moles of hydrogen in the compound = 7.68
∴ Ratio of carbon to hydrogen in the compound = 7.69 : 7.68 = 1: 1
Hence, the empirical formula of the gas is CH.
(b) Given,
Weight of 10.0 L of the gas (at S.T.P) = 11.6 g
11.6𝑔
∴ Weight of 22.4 L of gas at STP = × 22.4𝐿 = 25.984 g≈ 26 g.
10.0𝐿
Hence, the molar mass of the gas is 26 g.
(c) Empirical formula mass of CH = 12 + 1 = 13 g
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑔𝑎𝑠
𝑛 = 𝑒𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑔𝑎𝑠 = 26 g/13 gn = 2
Molecular formula of gas = (CH) = C 2H2

Question 1.35: Calcium carbonate reacts with aqueous HCl to give CaCl 2 and
CO2 according to the reaction,
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)
What mass of CaCO3 is required to react completely with 25 mL of 0.75 M HCl?
0.75 M of HCl ≡ 0.75 mol of HCl are present in 1 L of water
≡ [(0.75 mol) × (36.5 g mol–1)] HCl is present in 1 L of water
≡ 27.375 g of HCl is present in 1 L of water
Thus, 1000 mL of solution contains 27.375 g of HCl.
Amount of HCl present in 25 mL of solution = 27.375 g/1000 mL × 25 mL = 0.6844 g

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From the given chemical equation,


CaCO3(g) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)
2 mol of HCl (2 × 36.5 = 73 g) react with 1 mol of CaCO 3 (100 g).
∴ Amount of CaCO3 that will react with 0.6844 g = (100/73) × 0.6844
= 0.9375 g

Question 1.36: 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?
1 mol [55 + 2 × 16 = 87 g] MnO 2 reacts completely with 4 mol [4 × 36.5 = 146 g] of HCl.
5.0 g of MnO2 will react with
= 146 g/87 g × 5.0 g of HCl = 8.4 g of HCl
Hence, 8.4 g of HCl will react completely with 5.0 g of manganese dioxide.

EXEMPLER PROBLEMS

Multiple Choice Questions (Type-I)


1. Two students performed the same experiment separately and each one of them
recorded two readings of mass which are given below. Correct reading of mass is 3.0 g.
On the basis of given data, mark the correct option out of the following statements.

(i) Results of both the students are neither accurate nor precise.
(ii) Results of student A are both precise and accurate.
(iii) Results of student B are neither precise nor accurate.
(iv) Results of student B are both precise and accurate.
Solution:

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For both the students, average value is close to the correct value. Hence, readings of both
are accurate. But readings of student A are also close to each other (differ only by 0.02)
and also close to the average value, hence readings of A are also precise. But readings of B
are not close to each other (differ by 0.1) and hence are not precise. Thus, results of
student A are both precise and accurate.

2. A measured temperature on Fahrenheit scale is 200 °F. What will this reading be on
Celsius scale?
(i) 40 °C (ii) 94 °C (iii) 93.3 °C (iv) 30 °C
Solution:

3. What will be the molarity of a solution, which contains 5.85 g of NaCl(s) per 500 mL?
(i) 4 mol L–1
(ii) 20 mol L–1
(iii) 0.2 mol L–1
(iv) 2 mol L–1
Solution:

4. If 500 mL of a 5M solution is diluted to 1500


mL, what will be the molarity of the solution
obtained?
(i) 1.5 M
(ii) 1.66 M
(iii) 0.017 M
(iv) 1.59 M

5. The number of atoms present in one mole of an element is equal to Avogadro number.
Which of the following element contains the greatest number of atoms?
(i) 4g He (ii) 46g Na (iii) 0.40g Ca (iv) 12g He

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Sol: (d) As we know that

Hence, 12 g of He contains the greatest number of atoms.


6. If the concentration of glucose (C6H12O6) in blood is 0.9 g L–1 , what will be the
molarity of glucose in blood?
(i) 5 M
(ii) 50 M
(iii) 0.005 M
(iv) 0.5 M

7. What will be the molality of the solution containing 18.25 g of HCl gas in 500 g of
water?
(i) 0.1 m
(ii) 1 M
(iii) 0.5 m
(iv) 1 m

8. One mole of any substance contains 6.022 × 1023 atoms/molecules. Number of


molecules of H2SO4 present in 100 mL of 0.02M H2SO4 solution is ______.
(i) 12.044 × 1020 molecules
(ii) 6.022 × 1023 molecules
(iii) 1 × 1023 molecules
(iv) 12.044 ×1023 molecules

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9. What is the mass percent of carbon in carbon dioxide?


(i) 0.034%
(ii) 27.27%
(iii) 3.4%
(iv) 28.7%
Sol: b) Molecular mass of C02 =1×12 + 2×16 = 44 g
1 g molecule of C02 contains 1 g atom of carbon
44 g of C02 contains C = 12 g of carbon
% of C in CO2 = 12/44 x 100 =27.27%
Hence, the mass per cent of carbon in C02 is 27.27%.
10. The empirical formula and molecular mass of a compound are CH2O and 180 g
respectively. What will be the molecular formula of the compound?
(i) C9H18O9
(ii) CH2O
(iii) C6H12O6
(iv) C2H4O2
Sol: (c) Empirical formula mass = 12 + 2+ 16 = 30

11. If the density of a solution is 3.12 g mL-1, the mass of 1.5 mL solution in significant
figures is _______.
(i) 4.7g
(ii) 4680 × 10-3 g
(iii) 4.680g
(iv) 46.80g
Sol: (a) Density of solution = 3.12 g mL-1
Volume of solution =1.5 mL
Mass of solution = Volume x Density
= 1.5 mL x 3.12 g mL-1 = 4.68 g = 4.7 g (up to 2 significant figures)

12. Which of the following statements about a compound is incorrect?


(i) A molecule of a compound has atoms of different elements.
(ii) A compound cannot be separated into its constituent elements by physical methods
of separation.

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(iii) A compound retains the physical properties of its constituent elements.


(iv) The ratio of atoms of different elements in a compound is fixed.
Sol: (c) A compound does not retain the physical or chemical properties of its
constituent elements.
13. Which of the following statements is correct about the reaction given below:
4Fe(s) + 3O2 (g) → 2Fe2O3(g)
(i) Total mass of iron and oxygen in reactants = total mass of iron and oxygen in
product therefore it follows law of conservation of mass.
(ii) Total mass of reactants = total mass of product; therefore, law of multiple
proportions is followed.
(iii) Amount of Fe 2 O 3 can be increased by taking any one of the reactants (iron or
oxygen) in excess.
(iv) Amount of Fe 2 O 3 produced will decrease if the amount of any one of the
reactants (iron or oxygen) is taken in excess.
Sol: (a) 4Fe + 302 —> 2Fe203 follows law of conservation of mass since mass of
reactants is equal to mass of products.
14. Which of the following reactions is not correct according to the law of conservation
of mass.
(i) 2Mg(s) + O2(g) → 2MgO(s)
(ii) C3H8(g) + O2(g) → CO2(g) + H2O(g)
(iii) P4(s) + 5O2(g) → P4O10(s)
(iv) CH4(g) + 2O2(g) → CO2(g) + 2H2O (g)
Sol: (b) C3H8 + 02 → C02 + H20
Since the reaction is not balanced, hence, mass of reactants and products are different. It
is against the law of conservation of mass.
15. Which of the following statements indicates that law of multiple proportion is being
followed.
(i) Sample of carbon dioxide taken from any source will always have carbon and oxygen
in the ratio 1:2.
(ii) Carbon forms two oxides namely CO2 and CO, where masses of oxygen which
combine with fixed mass of carbon are in the simple ratio 2:1.
(iii) When magnesium burns in oxygen, the amount of magnesium taken for the reaction
is equal to the amount of magnesium in magnesium oxide formed.
(iv) At constant temperature and pressure 200 mL of hydrogen will combine with 100
mL oxygen to produce 200 mL of water vapour.
Sol: (b) The element, carbon, combines with oxygen to form two compounds, namely,
carbon dioxide and carbon monoxide. In C02, 12 parts by mass of carbon combine with
32 parts by mass of oxygen while in CO, 12 parts by mass of carbon combine with 16
parts by mass of oxygen.
Therefore, the masses of oxygen combine with a fixed mass of carbon (12 parts) in
C02 and CO are 32 and 16 respectively. These masses of oxygen bear a simple ratio of

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32 : 16 or 2 : 1 to each other.
This is an example of law of multiple proportion.

Multiple Choice Questions (Type-II)


In the following questions two or more options may be correct.
1. One mole of oxygen gas at STP is equal to _______.
(i) 6.022 × 1023 molecules of oxygen
(ii) 6.022 × 1023 atoms of oxygen
(iii) 16 g of oxygen
(iv) 32 g of oxygen
Sol:(a,d) 1 mole of 02 gas at STP = 6.022 x 1023 molecules of 02 (Avogadro number) = 32
g of 02. Hence, 1 mole of oxygen gas is equal to molecular weight of oxygen as well as
Avogadro number.
2. Sulphuric acid reacts with sodium hydroxide as follows :
H2SO4 + 2NaOH → Na2SO4 + 2H2O
When 1L of 0.1M sulphuric acid solution is allowed to react with 1L of 0.1M sodium
hydroxide solution, the amount of sodium sulphate formed and its molarity in the
solution obtained is
(i) 0.1 mol L-1
(ii) 7.10 g
(iii) 0.025 mol L-1
(iv) 3.55 g
Sol: (b, c) Moles of H2S04 taken = 0.1 moles
Moles of NaOH taken = 0.1 moles
As H2S04 and NaOH react in ratio 1:2, so 0.1 moles of H2S04 reacts with 0.2 mole of
NaOH which we don’t have.
0.1 mole of NaOH reacts with 0.05 mole of H2S04, so NaOH is Limiting reactant.
Product is calculated w.r.t limiting reactant so Number of moles of Na2S04 formed will
also be equal to 0.05.
Mass of Na2S04 = 0.05 x 142 = 7.1 g

3. Which of the following pairs have the same number of atoms?


(i) 16 g of O2 (g) and 4 g of H2(g)
(ii) 16 g of O2 and 44 g of CO2
(iii) 28 g of N2 and 32 g of O2
(iv) 12 g of C(s) and 23 g of Na(s)

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4. Which of the following solutions have the same concentration?


(i) 20 g of NaOH in 200 mL of solution
(ii) 0.5 mol of KCl in 200 mL of solution
(iii) 40 g of NaOH in 100 mL of solution
(iv) 20 g of KOH in 200 mL of solution

5. 16 g of oxygen has same number of molecules as in


(i) 16 g of CO
(ii) 28 g of N2
(iii) 14 g of N2
(iv) 1.0 g of H2

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6. Which of the following terms are unitless?


(i) Molality
(ii) Molarity
(iii) Mole fraction
(iv) Mass percent

7. One of the statements of Dalton’s atomic theory is given below:


“Compounds are formed when atoms of different elements combine in a fixed ratio”
Which of the following laws is not related to this statement?
(i) Law of conservation of mass
(ii) Law of definite proportions
(iii) Law of multiple proportions
(iv) Avogadro law
Sol:(a, d) The statement is related to law of definite proportions and law of multiple
proportions.

Short Answer Type Questions


1. What will be the mass of one atom of C-12 in grams?
Sol: 1 mole of carbon atoms = 12 g = 6.022 x 1023 atoms. 6.022 x 1023 atoms of carbon-
12 have mass = 12 g

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2. How many significant figures should be present in the answer of the following
2.5×1.25×3.5
calculations?
2.01

involving multiplication and division, the number of significant figures will be 2.


Since the least number of significant figures from the given figures is 2 (in 2.5 and
3.5) the result should not have more than two significant figures.
3. What is the symbol for SI unit of mole? How is the mole defined?
Sol: Symbol for SI unit of mole is mol. A mole is defined as the amount of substance
that contains as-many entities as there are atoms in 12 g of carbon – in C-12 isotope.
4. What is the difference between molality and molarity?
Sol: Molality is the number of moles of solute present in 1 kg of solvent, whereas
molarity is the number of moles of solute dissolved in 1 litre of a solution. Molality is
independent of temperature, whereas molarity depends on temperature.
5. Calculate the mass percent of calcium, phosphorus and oxygen in calcium phosphate
Ca3(PO4)2.

6. 45.4 L of dinitrogen reacted with 22.7 L of dioxygen and 45.4 L of nitrous oxide was
formed. The reaction is given below:
2N2(g) + O2(g) → 2N2O(g)
Which law is being obeyed in this experiment? Write the statement of the law?
Sol: Gases are reacting together to form gaseous products. Ratio of volumes of gases:
N2: 02: N20 = 45.4 : 22.7 : 45.4 =2:1:2
Which is a simple whole number ratio. Hence the experiment proves Gay- Lussac’s law
of gaseous volumes. This law states that gases combine or are produced in a chemical
reaction in a simple whole number ratio by volume provided that all gases are at the
same temperature and pressure.
7. If two elements can combine to form more than one compound, the masses of one
element that combine with a fixed mass of the other element, are in whole number
ratio.

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(a) Is this statement true?


(b) If yes, according to which law?
(c) Give one example related to this law.
Sol: (a) Yes, the statement is true.
(b) According to law of multiple proportions.
(c) Hydrogen and oxygen react to produce two compounds, water and hydrogen
peroxide. Masses of oxygen which combine with fixed mass of hydrogen are in simple
ratio.

Masses of oxygen (16 and 32) which combine with fixed mass of hydrogen (2) are in
the ratio of 16 : 32 or 1 : 2
8. Calculate the average atomic mass of hydrogen using the following data:

9. Hydrogen gas is prepared in the laboratory by reacting dilute HCl with granulated zinc.
Following reaction takes place.
Zn + 2HCl → ZnCl2 + H2
Calculate the volume of hydrogen gas liberated at STP when 32.65 g of zinc reacts
with HCl. 1 mol of a gas occupies 22.7 L volume at STP; atomic mass of Zn = 65.3 u.
Sol: Given that, mass of Zn = 32.65 g
1 mole of gas occupies = 22.7 L volume at STP Atomic mass of Zn = 65.3u
The given equation is

10. Density of 3 molal solution of NaOH is 1.110 g mL-1. Calculate the molarity of solution.
Sol: 3 molal solution of NaOH means 3 moles of NaOH is dissolved in 1000 g of water.
But 3 moles of NaOH = 3 x 40 g = 120 g

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120 g = 1120 g

11. Volume of a solution changes with change in temperature, then, will the molality of
the solution be affected by temperature? Give reason for your answer.
Sol: No, molality of a solution does not change with temperature since mass remains
unaffected by temperature.

12. If 4 g of NaOH dissolves in 36 g of H2O, calculate the mole fraction of each


component in the solution. Also, determine the molarity of solution (specific gravity of
solution is 1g mL-1).

13. The reactant which is entirely consumed in reaction is known as limiting reagent. In
the reaction 2A + 4B → 3C + 4D, when 5 moles of A react with 6 moles of B, then
(i) which is the limiting reagent?
(ii) calculate the amount of C formed?

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Matching Type Questions


1. Match the following:
Column I Column II

A. 88 g of C02 a. 0.25 mol

B. 6.022 x 1023 molecules of H20 b. 2 mol

C. 5.6 litres of 02 at STP c. 1 mol

D. 96 g of 02 d. 6.022 x 1023 molecules

E. 1 mole of any gas e. 3 mol

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2. Match the following physical quantities with units


Column I (Physical) Column II (Unit)
(i) Molarity a. g mL-1
(ii) Mole fraction b. mol
(iii) Mole c. Pascal
(iv) Molality d. Unitless
(v) Pressure e. mol L-1
(vi) Luminous intensity f. Candela
(vii) Density . g. mol kg-1
(viii) Mass h. N m-[1]
i. kg
Sol: (i →e), (ii → d), (iii → b), (iv →g), (v —> c), (vi —» f), (vii → a), (viii → i)
(i) Molarity = mol L-1
(ii) Mole fraction = no units
(iii) Mole = mol
(iv) Molality = mol kg 3
(v) Pressure = Pascal or N m 2
(vi)Luminous intensity = Candela
(vii) Density = g mL-1
(viii) Mass = kg

Assertion and Reason Type Questions


In the following questions a statement of Assertion (A) followed by a statement of
Reason (R) is given. Choose the correct option out of the choices given below each
question.
1. Assertion (A) : The empirical mass of ethene is half of its molecular mass.
Reason (R) : The empirical formula represents the simplest whole number ratio of
various atoms present in a compound.
(i) Both A and R are true and R is the correct explanation of A.
(ii) A is true but R is false.
(iii) A is false but R is true.
(iv) Both A and R are false.
Sol: (a) Empirical formula of ethene = CH2
Empirical formula mass of ethene =14 amu
= 1/2 — x molecular mass of ethene .
Empirical formula shows that ethene has (C : H):: 1 : 2

2. Assertion (A) : One atomic mass unit is defined as one twelfth of the mass of one
carbon-12 atom.
Reason (R) : Carbon-12 isotope is the most abundunt isotope of carbon and has been

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chosen as standard.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.
Sol: (b) 1 amu = —1/12 Mass of one C12 atom
C12 isotope is considered as standard for defining the atomic and molecular mass.

3. Assertion (A) : Significant figures for 0.200 is 3 whereas for 200 it is 1.


Reason (R) : Zero at the end or right of a number are significant provided they are not
on the right side of the decimal point.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not a correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.
Sol: (c) Significant figures for 0.200 = 3
Significant figure for 200 = 1
Zeros at the end of a number without decimal- point, may or may not be significant
depending on the accuracy of measurement.

4. Assertion (A) : Combustion of 16 g of methane gives 18 g of water.


Reason (R) : In the combustion of methane, water is one of the products.
(i) Both A and R are true but R is not the correct explanation of A.
(ii) A is true but R is false.
(iii) A is false but R is true.
(iv) Both A and R are false.
Sol: (c) CH4(g) + 202(g) → C02(g) + 2H20(g)
16 g of CH4 on complete combustion will give 36 g of water

Long Answer Type Questions


1. A vessel contains 1.6 g of dioxygen at STP (273.15K, 1 atm pressure). The gas is now
transferred to another vessel at constant temperature, where pressure becomes half
of the original pressure. Calculate
(i) volume of the new vessel.
(ii) number of molecules of dioxygen.

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2. Calcium carbonate reacts with aqueous HCl to give CaCl2 and CO2 according to the
reaction given below:
CaCO3 (s) + 2HCl (aq) → CaCl2(aq) + CO2(g) + H2O(l)
What mass of CaCl2 will be formed when 250 mL of 0.76 M HCl reacts with 1000 g of
CaCO3 ? Name the limiting reagent. Calculate the number of moles of CaCl2 formed in
the reaction.

Since HCl on complete consumption gives lesser amount of product hence HC1 will be
limiting reagent and the number of moles of CaCl2 formed will be 0.095 mol.
3. Define the law of multiple proportions. Explain it with two examples. How does this law
point to the existence of atoms?
Sol: Law of multiple proportions: When two elements combine to form two or more
chemical compounds, then the masses of one of the elements which combine with a
fixed mass of the other, bear a simple ratio to one another, e.g., carbon combines with
oxygen to form two compounds, namely, carbon dioxide and carbon monoxide.

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The masses of oxygen which combine with a fixed mass of carbon in C02 and CO are 32
and 16 respectively. These masses of oxygen bear a simple ratio of 32 : 16 or 2 : 1 to
each other. For example, sulphur combines with oxygen to form two compounds,
namely, sulphur trioxide and sulphur dioxide.
The masses of oxygen which combine with a fixed mass of sulphur in S03 and S02 are
48 and 32 respectively. These masses of oxygen bear a simple ratio of 48 : 32 or 3 : 2
to each other. This law shows that there are constituents which combine in a definite
proportion. These constituents may be atoms. Thus, the law of multiple proportions
shows the existence of atoms which combine to form molecules.

4. A box contains some identical red coloured balls, labelled as A, each weighing 2 grams.
Another box contains identical blue coloured balls, labelled as B, each weighing 5
grams. Consider the combinations AB, AB2, A2B and A2B3 and show that law of multiple
proportions is applicable.
Sol:
Combination of A and B AB ab2 A, B A2B3
Mass of A (in g) 2 2 4 4
Mass of B (in g) 5 10 5 15

Short & Long answer Questions

Q.1. When do zeros present in a number become insignificant?


Ans. The zeros written to the left of the first non-zero digit in a number are
insignificant. For example, in the number 0.014, both the zeros are insignificant.

Q.2. Is velocity a basic or derived quantity according to S.I. system?


Ans. Velocity is a derived quantity and it depends upon two basic quantities i.e. distance
and time. The SI units of velocity are: Velocity = Distance/Time = ms −1
Q.3. Which is more precise measurement of the length of a thread
(i) 10.0 cm (ii) 10.00 cm?
Ans. The measurement 10.0 cm represents a length between 9.9 cm and
10.1 cm while the measurement 10.00 cm is between 9.99 cm and 10.010
cm. This means that the measurement 10.00 cm is the most precise
representation.

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Q.4. Why do we regard the gaseous state of water as vapours while that of
ammonia as gas?
Ans. Only the gaseous states of those substances are regarded as vapours which are
liquid at room temperature. Since water is a liquid, its gaseous state is called vapours.
However, the gaseous state of ammonia is called gas because it is not a liquid at room
temperature.

Q.5. Why is distilled water a compound while tap water a mixture?


Ans. Distilled water contains only H 2O molecules since it is free from impurities. It is
therefore, a compound. Since some impurities such as dust particles etc. are normally
mixed with tap water, it is, therefore, a mixture.

Q.6. Mixture of salt & water is a solution while that of oil & water is not. Explain.
Ans. Solution is a homogeneous mixture of two or more components. The mixture of salt
and water is generally homogeneous. Therefore, it is a solution. Oil and water on the
other hand, form a heterogeneous or immiscible mixture. Therefore, it is not a solution.

Q.7. When is the law of definite proportions not obeyed?


Ans. The law of definite proportions is not obeyed when the element exists in isotopic
forms. For example, in HCl the elements H and Cl may be in the ratio of 1 : 35 and 1 : 37
by mass in case 35Cl and 37Cl isotopes are considered.

Q.8. Which law co-relates the mass and volume of a gas?


Ans. It is the Avogadro's Law and states that equal volumes of all gases under similar
conditions of temperature and pressure contain equal number of moles (or molecules).

Q.9. Atomic mass of oxygen is 16 u. What does its indicate?


Ans. It indicates that the mass of an oxygen atom is 16 times more than 1/12th of the
mass of carbon atom (C-12).

Q.10. An element has fractional atomic mass. What does it indicate?


Ans. It indicates that the element exists in the form of isotopes and its atomic mass is
an average atomic mass.

Q.11. What is the difference between the mass of a molecule and molecular mass?
Ans. Mass of a molecule is that of a single molecule also known as its actual mass. But
molecular mass is the mass of Avogadro's number (6.022 × 10 23) of molecules.

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Q.12. Where do we use the words mole and mol?


Ans. In the text part, we use the word mole while as a unit, we call it mol.

Q.13. Does one gram mole of a gas occupy 22.4 L under all conditions of
temperature and pressure?
Ans. No, one gram mole of a gas occupies 22.4 L only under N.T.P. or S.T.P. conditions,
i.e. at 273 K temperature and under 760 mm pressure. If these conditions are not used,
then the volume is not 22.4 L.

Q.14. What is the basic difference between empirical and molecular formulae?
Ans. Empirical formula gives the simplest ratio of the atoms of different elements in
the molecule of a substance but the molecular formula gives their actual ratio.

Q.15. The percentages of all the elements present in a compound are 92. What
does it indicate?
Ans. This indicates that the compound contains in it oxygen also and its percentage is
(100 - 92) = 8.

Q.16. Why is it necessary to balance a chemical equation?


Ans. A chemical equation has to be balanced in order to satisfy the law of conservation
of mass. According to the law, there is no change in mass when the reactants change into
the products. Therefore, the chemical equation has to be balanced.

Q.17. In the combustion of methane, why is methane regarded as the limiting


reactant?
Ans. Methane (CH 4) is regarded as the limiting reactant because air or oxygen is always
present in excess. The amounts of CO 2 and H2O formed in the reaction depend upon the
amount of methane only. Therefore, it is regarded as the limiting reactant.

Q.18. What is the difference between molarity and molality?


Ans. By definition, molarity (M) of a solution is the number of moles of the solute
dissolved per litre of the solution and molality (m) is the number of moles of the solute
dissolved per kilogram of the solvent. Therefore, in molarity, volume of the solution is
considered while in molality, mass of the solvent is taken into consideration.

Q.19. Classify the following substances into elements, compounds and mixtures : (i)
Milk (ii) 22-carat gold (iii) Iodized table salt (iv) Diamond (v) Smoke (vi) Steel (vii)
Brass (viii) Dry ice (ix) Mercury (x) Air (xi) Aerated drinks (xii) Glucose (xiii)
Petrol/Diesel/Kerosene oil (xiv) Steam (xv) Cloud.

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Ans. Elements - (iv), (ix) Compounds - (viii), (xii), (xiv), (xv) Mixtures - (i), (ii), (iii), (v),
(vi), (vii), (x), (xi), (xiii).

Q.20. Why is air sometimes considered as a heterogeneous mixture?


Ans. This is due to the presence of dust particles which form a separate phase.

Q.21. What physical quantities are represented by the following units and what are
their most common names?
(i) kgms −2
(ii) kgm 2s−2
(iii) dm 3
Ans.
(i) Force (newton)
(ii) Work (joule)
(iii) Volume (no special name).

Q.22. Rewrite the following after necessary corrections:


(i) The length of a rod is 10 cms.
(ii) The work done by a system is 10 Joules.
Ans.
(i) The length of a rod is 10 cm (s is not used).
(ii) The work done by a system is 10 joules (small letter is used in place of capital letter).

Q.23. Given that density of water is 1gmL −1. What is its density in kgm −3?
Ans.

= 1000 kg m -3
Q.24. What is the difference between the following?
(i) 2⋅5 × 103 g and 2⋅50 × 103g
(ii) 160 cm and 160.0 cm.
Ans.
(i) 2⋅5 × 103g has two significant figures while 2⋅50 × 103g has three significant figures.
Hence, 2⋅50×103g represents greater accuracy than 2⋅5×103.
(ii) 160 has three significant figures while 160.0 has four significant figures. Hence,
160.0 represents greater accuracy.

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Q.25. Why Law of conservation of mass should better be called as Law of


conservation of mass and energy?
Ans. In nuclear reactions, it is observed that the mass of the products is less than the
mass of the reactants. The difference of mass, called the mass defect, is converted into
energy according to Einstein equation, E = Δmc 2. Hence, we better call it as a law of
conservation of mass and energy.

Q.26. Is the law of constant composition true for all types of compounds? Explain
why or why not.
Ans. No, law of constant composition is not true for all types of compounds. It is true
only for the compounds obtained from one isotope. For example, carbon exists in two
common isotopes, 12C and 14C. When it forms CO 2 from 12C, the ratio of masses is 12 : 32
= 3 : 8 but from 14C, the ratio will be 14 : 32 = 7 : 16 which is not same as in the first
case.

Q.27. 1 L of a gas at S.T.P. weighs 1.97 g. What is the vapour density of the
gas?
Ans. 22.4 L of the gas at S.T.P. will weigh = 1.97 × 22.4g = 44.1 g , i.e., molecular mass =
44.1. Hence, vapour density = 44.1/2 = 22.05.

Q.28. What is the difference in the molar volume of a gas if S.T.P. conditions are
(i) 1 atm,0 ∘ C
(ii)1 bar,0 ∘ C?
Ans.
(i) If S.T.P. conditions are 1 atm, 0 ∘C molar volume = 22400 cm 3
(ii) If S.T.P. conditions are 1 bar, 0 ∘C, molar volume = 22700 cm 3

Q.29. Why atomic masses are the average values?


Ans. Most of the elements exist in different isotopes, i.e., atoms with different masses,
Example: Cl has two isotopes with mass numbers 35 and 37 existing in die ratio 3 : 1.
Hence, average value is taken.

Q.30. Why are the atomic masses of most of the elements fractional?
Ans. This is because atomic masses are the relative masses of atoms as compared with
an atom of C-12 isotope taken as 12.

Q.31. What is die difference between the mass of a molecule and gram molecular
mass?
Ans. Mass of a molecule is the actual mass of a single molecule expressed in grams

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whereas gram molecular mass is the mass in gram of Avogadro's number of molecules.

Q.32. Why molality is preferred over molarity in expressing the concentration of a


solution?
Ans. Molality is the number of moles of the solute present in 1 kg of the solvent whereas
molarity is the number of moles of the solute present per litre of the solution. Thus,
molality involves only masses which do not change with temperature whereas molarity
involves volume which changes with temperature. Hence, molality is preferred over
molarity.

Q.33. Write the formulae and names of three compounds containing same
percentage composition of C, H and O.
Ans. Compounds with the same percentage composition of C, H and O will have the same
empirical formula. The compounds with the empirical formula CH 2O can be

Q.34. Determine the equivalent weight of each of the following compounds assuming
the formula weights of these compounds are x, y and z respectively.
(i) Na 2SO4
(ii) Na 3PO4.12H2O
(iii) Ca 3(PO4)2
Ans.
Eq wt = Mol. wt/Total positive valency of metal atoms
(i) x/2
(ii) y/3
(iii) z/6

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XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -02 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 - Express the results of following calculations to appropriate number of significant digits


816 + 0.02456 + 215.36
(2 Marks)

Q2 - Calculate the molar volume of water at 273 K (density of water = 1.00 g/cm3).
(1 Mark)

Q3 -How many moles of methane are required to produce 22 g CO?

(5 Marks)

Q4 - A solution is prepared by dissolving 5.85g of NaCl in 90g of H2O. Find mole fraction of NaCl and
H2O.
(3 Marks)

Q5 - Find the molarity of solution prepared by dissolving 7.1g of Na2SO4 in 100ml of aqueous solution.
(3 Marks)

Q6 - What is one atomic mass unit (amu) or Unified mass (U)?


(1 Mark)
-3
Q7 - Find the number of significant figures in 3.248x10 .
(1 Mark)
Q8 - Write the S.I. unit of molality.
(1 Mark)
Q9 - What is the value of Avogadro constant?
(1 Mark)
Q10 - Empirical formula of an organic compound is C2H3O2. Its molecular weight is 118. Write its
molecular formula.

(2 Marks)
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -03 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 -Express the following in SI units-


(i)  Speed of ball 90 miles per hour
(ii)  Carbon - carbon bond length 1.33 Å
(2 Marks)
Q2 - Solve the following and state the answer in proper number of significant digits.
                          108/8.2                                         

(2 Marks)

Q3 - On complete combustion 0.858 g of compound (x) gives 2.63 g of CO2 and 1.27g of H2O. Calculate
the empirical formula of the compound.
(5 Marks)

Q4 -Density of mercury is 13.6 g/cc.  Its density in Kg m–3 is


(1 Mark)

13
Q5 - Solve the following and express the answer in standard exponential form (2.0 x 10 ) +
(1.5 x 10 14).

(1 Mark)
Q6 - (i) How many moles of sulphur will be produced when 2 moles of H2S reacts with 11.2L of SO2 at
NTP.
(ii) Name the limiting reagent in the above reaction.
(2 Marks)

Q7 - Define limiting reagent.

(1 Mark)
Q8 -A car consumes 30 moles per gallon of gasoline and drives 12000 miles per year. Calculate the
amount of oxygen required to run the car for  one year.
[Assume that octane (C8H18) is the main component of the gasoline.]

(3 Marks)

Q9 -The mass of an empty beaker is 50.55g. The mass of a same beaker when filled completely with a
liquid is 150.457g. If the volume of the empty glass is 100.2ml, calculate the density of the liquid.
Express the answer in appropriate significant figures.

(3 Marks)
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -03 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 -Express the following in SI units-


(i)  Speed of ball 90 miles per hour
(ii)  Carbon - carbon bond length 1.33 Å
(2 Marks)
Q2 - Solve the following and state the answer in proper number of significant digits.
                          108/8.2                                         

(2 Marks)

Q3 - On complete combustion 0.858 g of compound (x) gives 2.63 g of CO2 and 1.27g of H2O. Calculate
the empirical formula of the compound.
(5 Marks)

Q4 -Density of mercury is 13.6 g/cc.  Its density in Kg m–3 is


(1 Mark)

13
Q5 - Solve the following and express the answer in standard exponential form (2.0 x 10 ) +
(1.5 x 10 14).

(1 Mark)
Q6 - (i) How many moles of sulphur will be produced when 2 moles of H2S reacts with 11.2L of SO2 at
NTP.
(ii) Name the limiting reagent in the above reaction.
(2 Marks)

Q7 - Define limiting reagent.

(1 Mark)
Q8 -A car consumes 30 moles per gallon of gasoline and drives 12000 miles per year. Calculate the
amount of oxygen required to run the car for  one year.
[Assume that octane (C8H18) is the main component of the gasoline.]

(3 Marks)

Q9 -The mass of an empty beaker is 50.55g. The mass of a same beaker when filled completely with a
liquid is 150.457g. If the volume of the empty glass is 100.2ml, calculate the density of the liquid.
Express the answer in appropriate significant figures.

(3 Marks)
2011-2012

Subject : Chemistry Std.- XI / Sec.: Worksheet :1

……………………………………………………………………………………………………..

CHAPTER : SOME BASIC CONCEPTS OF CHEMISTRY

Q1. How is atmosphere related to kilopascal ? 1M

Q2. What is the difference between 5 g and 5.0 g ? 1M

Q3. What is the length in centimeters of a glass rod 7.82 inches long ? 1M

Q4. Calculate the mass of 3 g molecules of nitric acid. 1M

Q5. Differentiate between molecular mass and formula mass. 1M

Q6. What will be the mass of one 12C atom in g ? 2M

Q7. Calculate the total number of electrons present in 1.6 g of methane. 1M

Q8. How is empirical formula related to its molecular formula ? 1M

Q9. What is the mass in grams of one molecule of caffeine (C8H10N4O2) ? 1M

Q10. Explain precision and accuracy with suitable examples. 2M

Q11. Carbon and oxygen are known to form two compounds. The carbon content in
one of these is 42.9% while in the other it is 27.3%. Show that this data is in

agreement with the law of multiple proportions. 2M

Q12. A fluoride of oxygen was prepared by mixing oxygen and fluorine in the proper

ratio at 60K. This compound contains 32.1 % F and 67.9 % O. What is the

empirical formula of the compound ? 2M

Q13. Calculate the percentage of water of crystallization in CuSO4.5H2O. 2M

Q14. Calculate the molarity of a solution of ethanol in water in which the mole

Fraction of ethanol is 0.040. 2M

Q15. Define the following (i) Molarity (ii) Molality (iii) Molefraction 3M

Q16. State and explain the following laws:

(i) Law of multiple proportions (iii) Avogadro’s law

(ii) Gay Lussac’s law of combining Volumes 3M

Q17. (a) How many significant figures are there in (i) 202.50 (ii) 9.78 x 10-24

(iii) 29.6 ?

(b) Round off the following into three significant figures:

(i) 5.685 (ii) 0.9865 (iii) 8.5236

Q18. Calculate (i) the molality of the solution (ii) the mole fraction of sugar. 3M

(ii) Calculate the number of atoms in each of the following:

(a) 3.2 g of sulphur (b) 0.5 mole atoms of nitrogen.


2M
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -01 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 - What is the mass of 3 gram atoms of calcium?


(1 Mark)

Q2 -Calculate the mass of CaCO3 which is required to react with 25 ml of 0.75 M HCl.
(5 Marks)

Q3 - During preparation of ammonia by Haber’s process 30 L of H2 and 30 L of N2 are mixed. The yield
of NH3was 50%. Find the composition of gaseous mixtures.

(3 Marks)

Q4 -Potassium bromide (KBr) contains 32.9% potassium by mass. If 6.40 g of Br2 is made to react with
3.60 g of potassium, find the actual mass of potassium which reacts with bromine.
(2 Marks)

-22
Q5 - One atom of an element weighs 1.8 x 10 g . What is the atomic mass of element?

(1 Mark)
Q6 -Chlorophyll contains 2.7% of Magnesium by mass.The number of magnesium atoms present in
4.00g of chlorophyll is
(3 Marks)

Q7 - How much water is required to dilute 10 ml of 10 N hydrochloric acid to make it exactly


decinormal?
(2 Marks)

Q8 - Find the molarity of solution prepared by dissolving 4g of NaOH in 3L of solution.


(2 Marks)

Q9 - How many molecules are present in 1 kg mole?

(1 Mark)
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -01 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 - What is the mass of 3 gram atoms of calcium?


(1 Mark)

Q2 -Calculate the mass of CaCO3 which is required to react with 25 ml of 0.75 M HCl.
(5 Marks)

Q3 - During preparation of ammonia by Haber’s process 30 L of H2 and 30 L of N2 are mixed. The yield
of NH3was 50%. Find the composition of gaseous mixtures.

(3 Marks)

Q4 -Potassium bromide (KBr) contains 32.9% potassium by mass. If 6.40 g of Br2 is made to react with
3.60 g of potassium, find the actual mass of potassium which reacts with bromine.
(2 Marks)

-22
Q5 - One atom of an element weighs 1.8 x 10 g . What is the atomic mass of element?

(1 Mark)
Q6 -Chlorophyll contains 2.7% of Magnesium by mass.The number of magnesium atoms present in
4.00g of chlorophyll is
(3 Marks)

Q7 - How much water is required to dilute 10 ml of 10 N hydrochloric acid to make it exactly


decinormal?
(2 Marks)

Q8 - Find the molarity of solution prepared by dissolving 4g of NaOH in 3L of solution.


(2 Marks)

Q9 - How many molecules are present in 1 kg mole?

(1 Mark)
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -02 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.

Q1 - Express the results of following calculations to appropriate number of significant digits


816 + 0.02456 + 215.36
(2 Marks)

Q2 - Calculate the molar volume of water at 273 K (density of water = 1.00 g/cm3).
(1 Mark)

Q3 -How many moles of methane are required to produce 22 g CO?

(5 Marks)

Q4 - A solution is prepared by dissolving 5.85g of NaCl in 90g of H2O. Find mole fraction of NaCl and
H2O.
(3 Marks)

Q5 - Find the molarity of solution prepared by dissolving 7.1g of Na2SO4 in 100ml of aqueous solution.
(3 Marks)

Q6 - What is one atomic mass unit (amu) or Unified mass (U)?


(1 Mark)
-3
Q7 - Find the number of significant figures in 3.248x10 .
(1 Mark)
Q8 - Write the S.I. unit of molality.
(1 Mark)
Q9 - What is the value of Avogadro constant?
(1 Mark)
Q10 - Empirical formula of an organic compound is C2H3O2. Its molecular weight is 118. Write its
molecular formula.

(2 Marks)
CHEMICAL EQUILIBRIUM

INTRODUCTION:
Equilibrium is a state in which there are no observable changes as time goes by.
When a chemical reaction has reached the equilibrium state, the concentrations of
reactants and products remain constant over time and there are no visible changes
in the system.However, there is much activity at the
molecular level because reactant molecules continue to from
product molecules while product molecules react to yield
reactant molecules. This dynamic situation is the subject of this chapter.
Some examples for equilibrium systems are
N2 + 3H2 2NH3 + 23 k cal
2SO2 + O2 2SO3 + 45 k cal
N2 + O2 + 43.2 k cal 2NO
PCl5 + 10 k cal PCl3 + Cl2
2HI + 5 k cal H2 + I2

Types of chemical reactions

1. Irreversible Reactions:
The chemical reactions in which the products formed do not combine to give back the
reactants are known as irreversible reaction.
Properties of irreversible reactions
• Reactions in which reactant react to form product only.
• Reactions proceed in one single direction.
• Always proceed to completion.
• In this type of reactions, if product is gaseous in state, then they can escape
from reacting site and if they are solid in state they will precipitate.
• Reaction in which one of product is a gas,
e.g.2 H+ (aq) + Mg (s) ⎯→ Mg2+ (aq) + H2 (g)
• Reaction in which one of product is a precipitate,
CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
e.g.Ag+ (aq) + Cl− (aq) ⎯→ AgCl (s)
• Reaction in which one of the product is a weak electrolyte,
e.g.H+ (aq) + OH− (aq) ⎯→ H2O (l)
• Reaction in which a large amount of energy is released,
e.g. CH4 (g) + 2 O2 (g) ⎯→ CO2 (g) + 2 H2O (l)

Examples:
a. Thermal decomposition in open vessel. 2KClO3 ⟶ 2KCl + 3O2
b. All the neutralization reaction of strong acid and strong base.
NaOH + HCl ⟶ NaCl + H2 O
c. Ionic precipitation reaction. AgNO3 + NaCl ⟶ AgCl + NaNO3
d. Oxidation-reduction reactionSnCl2 + 2FeCl2 ⟶ SnCl4 + 2FeCl2

2. Reversible Reactions:
The reactions in which the products can react with one another to give back the
reactants again under suitable conditions called as reversible reaction.
R1 + R2 P1 + P2
Re ac tan ts Pr oducts

Properties of reversible reactions


• In these types of reactions, reactant reacts to form product and product further
react to form reactant.
• Reactions proceed in both directions.
• These types of reactions never complete in nature.
• Products neither escape nor precipitate.
Examples
a. Thermal dissociation in closed vessel.
𝐶𝑎𝐶𝑂3 ⇌ 𝐶𝑎𝑂 + 𝐶𝑂2
PCl5 ⇌ PCl3 + Cl2
b. Salt hydrolysis except strong acid and strong base
NH4 Cl + H2 O ⇌ NH4 OH + HCl
c. All normal gaseous reactions in closed vessel.
N2 + O2 ⇌ 2NO
H2 + I2 ⇌ 2HI
N2 + 3H2 ⇌ 2NH3 2SO3 ⇌ 2SO2 + O2
d. All the reactions of organic hydrolysis.
CH3COOCH2CH3 + H2O⇌CH3COOH + CH3CH2OH

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
Reversible reactions are also of two types:
I. Homogenous Reversible Reactions:
If in a reversible reactions physical state of reactant and product are same it is
called as homogenous reversible reaction.
N2 (g) + O2 (g) ⇌ 2NO(g)
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
CH3 COOC2 H5 (l) + H2 O(l) ⇌ CH3 COOH(l) + C2 H5 OH(l)
Graphite (s) ⇌ Diamond (s)
SRh (s) ⇌ Smono (s)
Irreversible reaction Reversible reaction
1 The reaction which proceeds in one direction (forward 1 The reaction which proceed in both the direction under the same
direction) only. set of experimental conditions.
2 Reactants are almost completely converted into products. 2 Reactants form products and products also react to form reactants
Products do not react to form reactants again. in backward direction. These are possible in closed vessels .

3 Do not attain equilibrium state. 3 Attain the equilibrium state and never go to completion.
4 Such reactions are represented by single arrow {→} 4 Represented by double arrow ( ) or ( )
5 Examples – 5 Examples :–
(a) Precipitation reactions e.g. (a) Homogeneous reactions- only one phase is present
NaCl(aq) + AgNO3(aq) → NaNO3(aq) + AgCl  (i) Gaseous phase–
(b) Neutralization reactions e.g H2(g) + I2(g) 2HI(g)
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O N2(g) + O2(g) 2NO(g) [Birkland eyde process (HNO3)]
(c) 2KClO3 (s) ⎯⎯→  2KCl(s) + 3O2(g) N2(g) + 3H2(g) 2NH3(g) (Haber’s process)
(d) Reactions in open vessel :– (ii) Liquid phase
Even a reversible reaction will become irreversible if it is CH3 COOH(l) + C2H5OH(l) CH3COOC2H5(l)+ H2O(l)
carried out in open vessel. Ex. Heterogeneous reactions– More than one phases are present
CaCO3(s) CaO(s) + CO2(g) Open CaCO 3 (s) CaO(s) + CO 2 (g)
NH4HS(s) NH3(g) + H2S(g) vessel (b) NH4HS(s) NH3(g) + H2S(g) Closed
vessel

II. Heterogeneous Reversible Reactions:


If in a reversible reaction physical state of reactant and product are different it is
called as heterogeneous reversible reaction.
CaCO3 (s) ⇌ CaO(s) + CO2 (g)
FeO(s) + CO(g) ⇌ Fe(s) + CO2 (g)
3Fe(s) + 4H2 O(g) ⇌ Fe3 O4 (s) + 4H2 (g)

State of Equilibrium
In general, reactions (physical and chemical) do not proceed to completion when they
are carried out in a closed container. Consider vaporization of water, in closed
vessel
𝐋𝐢𝐪𝐮𝐢𝐝 𝐰𝐚𝐭𝐞𝐫 ⇌ 𝐖𝐚𝐭𝐞𝐫 𝐯𝐚𝐩𝐨𝐮𝐫
• At any temperature, vaporization of water takes place, initially the concentration
of water is much greater than the concentration of vapour, but with the progress
of time, concentration of vapour increases whereas that of water remains constant

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
and after a certain interval of time, there is no change in concentration of vapour
this state is known as state of physical equilibrium.
• Similarly, in chemical reactions, for exp, when PCl5(g) is heated in a closed container,
its dissociation starts with the formation of PCl3(g) and Cl2 (g). Initially, only
PCl5(g) was taken, but with the progress of reaction, PCl3(g) and Cl2(g) are formed due
to dissociation of PCl5(g) . After a certain interval of time, the concentration
of PCl5(g) , PCl3(g) andCl2(g) each becomes
constant.
It does not mean that at this point of
time, dissociation of PCl5(g) and its
formation from PCl3(g)and Cl2(g) has been
stopped. Actually, the rate of dissociation
of PCl5 and the rate of formation of
PCl5(g) becomes equal. This state is called
the state of chemical equilibrium. So, the
state of chemical equilibrium is dynamic.
exp: PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
This can be shown graphically.

or

So, state of chemical equilibrium in a reversible reaction at which both forward and
backward reactions occur of the same speed.

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

Classification of equilibrium:
A. Equilibrium in Physical Process:
1. Solid Liquid equilibrium: Some amount of ice& water are taken in a thermo flask.
Exp- H2 O(s) ⇌ H2 O(L)
When temperature remains constant, the mass of ice & water remains constant.
Some liquid molecules adhere to ice and simultaneously some molecules of ice enter
into liquid. The no. of molecules of water forming ice &no. of molecules of ice
forming water are same i.e., equilibrium is attained.So, no change in mass of ice &
water.
The temperature at which the solid & the liquid phase are at equilibrium at
atmospheric pressure is called freezing point.
2. Liquid Vapour equilibrium:-Liquid water is taken in closed vessel at room temp, it
starts evaporating.

Exp- H2 O(l) ⇌ H2 O(g)

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
As process continuous, more water molecules escape& pressure increases later,
condensation takes place. Finally, rate of evaporation becomes equal to rate of
condensation.
The pressure exerted by the vapour over the liquid when it is in equilibrium with it
is called vapor pressure of the liquid.
The temperature at which the Vapour Pressure of liquid is equal to atmospheric
Pressure, is called Boiling Point.
Different liquids have different vapour pressure. At the same temperature, the
liquid which has a higher Vapour Pressure is more volatile or boils at a lower
temperature.

3. Solid Vapour equilibrium:- This exists when solid sublimes to vapour.


𝐈𝟐(𝐬) ⇌ 𝐈𝟐(𝐠)
When we heat some I2 in a closed vessel, it sublimes & vessel filled with violet
vapours.
After sometime, intensity of violet colour remains constant. At this state
equilibrium is attained i.e., Rate of sublimation of solid I2 to form vapour is equal to
rate of condensation of I2 vapour to give solid I2 .

4. Solid – Solution equilibrium: Sugar (in solution) ⇌ Sugar(Solid)


When more and more amount of sugar is added into a fixed volume of water at
room temperature, after sometime no more sugar dissolves and settles at the
bottom. The solution is now said to be saturated and the concentration of sugar in
the solution remains constant.
This indicates that a state of equilibrium has been reached between the
undissolved sugar & dissolved sugar.

5. Gas Solution equilibrium: In carbonated drinks, CO2(g) ⇌ CO2 (in solution)


At a given temperature, a liquid can dissolve only a certain definite mass of the
gas. This suggests that a state of equilibrium exists between the molecules in the
gaseous state and the molecules dissolved in the liquid.
Solubility of a gas in liquid depends on the pressure. It is explained by Henry’s law.
i.e., the mass of a gas dissolved in a given mass of solvent at a particular temp is
directly proportional to the pressure of the gas above the solvent.
m ∝ p ⟹ m = kp

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

gas volume is reduced;


pressure (concentration!)
increases; more collisions
occur with liquid surface

B. Equilibrium in Chemical Process:


Ex 1. Decomposition of 𝐂𝐚𝐂𝐎𝟑 :
When CaCO3 is heated in a closed vessel at 8000 C, it decomposes into CaO & CO2 .Due
to production of CO2 , pressurewill increases in the vessel. After sometime, it is
observed that pressure becomes constant at constant temperature,even though
some CaCO3 is still present. This constancy confirms that equilibrium has been
reached.
CaCO3 (s) ⇌ CaO(s) + CO2 (g)

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
Ex 2. Reaction between 𝐇𝟐 &𝐈𝟐 :
When H2 & I2 are heated in a closed vessel, HI is formed. At the beginning the
reaction mixture is deep violet in colour due to presence of I2 . As the reaction
proceeds the intensity of the colour decreases due to decrease in concentration of
I2 and increase in concentration of HI. After some time, the intensity of colour
remains constant. This confirms that equilibrium has been attained.
H2 + I2 ⇌ 2HI

Characteristics of Chemical Equilibrium:


1. Equilibrium is attained for reversible reactions only in a closed vessel.
2. At equilibrium, the rate of forward reaction is equal to rate of backward
reaction.
3. For a reversible reaction, the equilibrium constant for the forward reaction is
inverse of the equilibrium constant for the backward reaction.
1
In general, K forward reaction = K′
backward reaction

4. At Equilibrium, all observable or measurable properties such as pressure,


concentration, colour and density etc remains constant
5. It is dynamic in nature. i.e. reaction takes place in both the directions at same
speed although appears to be stopped.
6. At equilibrium, concentration of reactants and products remains constant.
7. Catalyst has no effect on the position of chemical equilibrium, but it helps to
attain the Equilibrium state rapidly.
A catalyst has the same effect on both forward and backward reactions.
8. Change in pressure, temperature or concentration favours either forward or
backward reaction and thus shifts the equilibrium point in one direction.
9. Change in free energy is equal to zero at equilibrium.
10. Equilibrium can be homogeneous or heterogeneous.
11. Equilibrium can be attained in either direction. The value of anequilibrium
constant tells the extent to which a reaction proceeds in the forward or
reverse direction.

Rate or Velocity of a reaction– is the change in molar concentration of the


reactants or products in unit time.
𝐝𝐱
It is denoted by , where dx is the change in concentration of the reactants or
𝐝𝐭
products in a given time dt.

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
For a reaction R ⟶ P
−𝐝𝐑
Rate = ,where -dR indicates the decrease in the concentration of reactants.
𝐝𝐭
𝐝𝐏
For product, Rate = , +dP indicates the increase in concentration of products.
𝐝𝐭
Unit of the rate of reaction is mol L-1 s-1

Active Mass- is also known asmolar concentration, shown by square brackets [ ].


Number of g molecules present in unit volume (say 1 litre) is called active mass.
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑔
g molecule =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡
𝑔𝑟𝑎𝑚 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑔
Active mass = or
𝑣𝑜𝑙𝑢𝑚𝑒 𝑖𝑛 𝑙 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡×𝑣𝑜𝑙𝑢𝑚𝑒
The unit of active mass is g molecule/Litre
Active mass or partial pressure of solids and excess of pure liquid is regarded as
unity because molecules are closely packed in solids

Equilibrium Constant(K)
aA + bB cC + dD
we have
rf = Rate of forward reaction  [A]a [B]b
rb = Rate of backward reaction  [C]c [D]d.
Let k f be the rate constant for the forward reaction and kb be that for the
backwardreaction. Then,
rf = k f [A]a [B]b; rb = kb [C]c [D]d.
At equilibrium, rf = rb
k
 K = f =
Cc Dd .
kb A a Bb
This expression is the law of chemical equilibrium.
kf
K = , is the equilibrium constant.
kb
When the active masses of reactants & products are expressed in molar
concentration, the equilibrium constant is represented as Kc. On other hand, when
the active masses are expressed as partial pressures, it is represented as Kp.

Example: What should be the respective active masses in g mole/litre when 4g of


H2 and 128g of HI are present in a two-litre container
4𝑔
Solution : (a) Active mass of H2 = = 1 gm mol/lit
2×2
(Molecular weight of H2 = 2)

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
128
(b) Active mass of HI = = 0.5g mole/litre
128×2
(Molecular weight of HI = 1 + 127 = 128)
Remember -
1 g molecule H2 = 2g
1 g molecule O2 = 32g
1 g molecule N2 = 28g
1 g molecule NH3 = 17g
1 g molecule I2 = 254g

Example: If 4g molecule of H2 is present in a two-litre container, the active mass


will be
𝑔 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 4
Solution: Active mass = = = 2 g mole/litre
𝑣𝑜𝑙𝑢𝑚𝑒 2

LAW OF MASS ACTION


Guldberg and Waagein 1807 gave this law and according to this law,“At constant
temperature,the rate of a reaction is directly proportional to the product of active
masses(molarconcentrations) of the reactants”.
For a reaction, A ⟶ Product
𝐝𝐱
Rate, = K[A] where K is Rate constant.
𝐝𝐭
For a reaction, A + B ⟶ Product
Rate = K [A] [ B]
For a reaction, 2A + 3B ⟶ Product
Rate = K [A] [A] [ B] [B] [B]
Rate = K [A]2 [ B]3
For a reaction, aA + bB ⟶ Product
Rate = K [ A]a [ B]b
EX.1: 8.5grams of ammonia are dissolved to form 4L aqueous solution. Calculate
the active mass.
𝒘𝒆𝒊𝒈𝒉𝒕 𝟖.𝟓
Sol.𝒏 = 𝒈𝒓𝒂𝒎 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒘𝒆𝒊𝒈𝒉𝒕 = = 𝟎. 𝟓
𝟏𝟕
𝑛 0.5 -1
Active mass = = = 0.125 molL
𝑉 4
EX.2: What is the active mass of one litre of Nitrogen gas at NTP?
Sol. At STP, active mass of Nitrogen = 1 atm
At STP,22.4 litres of Nitrogen= 1 mole
𝑛 1 -1
Active mass= 𝑉 = 22.4 = 0.0446molL

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EX.3: Determine the active mass of NaOH in a solution containing 4gm of NaOH in
500ml.
no.of moles 4 1
Solution-Active mass = Vol.of solution inL = 40 × 0.5 = 0.2mL−1

EX.4:Calculate the active masses of ethanol and carbon tetrachloride taking their
densities to be 0.8and 1.58g per ml respectively.

Solution - Active mass = Molar conc. = No. of Moles Litres –1.


(i) Active mass of ethanol
1litre of ethanol = 1000ml of ethanol= 1000 × 0.8m of ethanol.
–1
[ density of C2H5OH = 0.8gl ]= 800gm of ethanol.
800
No. of moles/ litre of ethanol = = 17.39 [ Mol wt. of C2H5OH=46]
46
Hence active mass of ethanol = 17.39moles/litre.
(ii) Calculation of active mass of CCl4
–1
1 litre of CCl4 = 1000ml of CCl4= 1000 × 1.58g[ density of CCl4=1.58 gl ]
= 1580g of CCl4
1580
No. of moles/litre = = 10.26 [ Mol wt. of CCl4 = 154]
154
Hence active mass of CCl4 = 10.26moles/litre

Equilibrium Constant Kc in terms of concentration:


Consider the following reversible reaction
aA + bB ⇌ cC + dD
Rate of forward reaction, R f ∝ [A]a [B]b
R f = k f [A]a [B]b --------(i)
Where k f =rate constant of forward reaction
Rate of reverse reaction, R b ∝ [C]c [D]d
R b = k b [C]c [D]d --------(ii)
Wherek b =rate constant of reverse reaction
At equilibrium, Rate of forward reaction = Rate of reverse reaction. i.e.R f = R b
So, from equations (i) and (ii) we get
k [C]c [D]d
k f [A]a [B]b = k b [C]c [D]d or,k f = [A]a [B]b
b
kf [C]c [D]d
= Kc =
kb [A]a [B]b
Where, 𝐊 𝐜 is the equilibrium constant in terms of molar concentration.

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The equilibrium constant, at a given temperature, is the ratio of rate constant of
forward and backward reactions. Or
𝐊 𝐜 is defined asthe ratio of the product of molar concentration of the products and
to the product of the molar concentration of the reactants in which concentration
terms raised to the power of respective stoichiometric coefficient in a balanced
chemical equation at constant T.

Problem.1: When alcohol and acetic acid are mixed together in equimolecular
proportions, 66.5% areconverted into ester. Calculate the equilibrium constant of
the reaction.
Solution- The concerned reaction is, CH3COOH + C2H5OH ⇌ CH3COOC2H5 + H2O

Let initial conc. of alcohol = 100moles


initial conc. of acid = 100moles
conc. of ester at equb. = 66.5moles
conc. of water at equb. = 66.5moles
conc. of alcohol at equb. = 100 – 66.5moles = 33.5moles
[CH COOC H ][H2 O] 66.5×66.5
K = [CH 3COOH][C
2 5
= 33.5×33.5 ≈ 4
3 2 5 OH]
H

Problem.2: 1.1mol of A is mixed with 2.2mol of B and the mixture is kept in a one
litre flask till theequilibrium,A + 2B ⇌ 2C + Dis reached. At equilibrium 0.2mol of C
is formed. Calculate the equilibrium constant for the above reaction.

Solution

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At start 1.1 mol 2.2 mol 0 0
A + 2B 2C + D
At equb (1.1 − 0.1) mol (2.2 − 0.2) mol 0.2 mol 0.1 mol
= 1 mol = 2mol
0.2 0.1 1 2
Thus, [C] = mL−1 ; [D] = mL−1 [A] = mL−1 ; [B] = mL−1
1 1 1 1
[C2 ] [D] (0.2)2  0.1 0.2  0.2  0.1
KC = = = = 1  10 −3
[A] [B] 2
1 2 2
1 2  2
Problem. 3. What should be the relationship between K2 and K1, if the equilibrium constant
of the reaction given below are K1 and K2 respectively ?
1
2SO (g) + O (g)
2 2
2SO (g)3
SO (g) +
2
O (g)
2
SO (g)
3
2
Ans. 2SO2(g) + O2(g) 2SO3(g) + O2(g) SO3(g)
2
[SO3 ] [SO3 ]
K1 = K2 = , Therefore, K2 = √𝐾1
[SO 2 ]2 [O 2 ] [SO2 ][O2 ]
Problem.4. In a reaction A (g) + B (g) C (g)+ D(g) , A, B, are mixed in a vessel at
temperature T. Initial concentration of A was twice the initial concentration of B. After the
equilibrium is reached, concentration of C was thrice the concentration of B Calculate KC.
Sol.Let concentration of B initially is ‘a’ mole/litre
A + B C + D  Dn = 0
at t = 0 2a a 0 0
at t = teq 2a – x a – x x x
3 [C] [D]
Given that, x = 3 (a – x)  x = a KC =
4 [A] [B]
2
 3a 
 4 
x. x   9
Kc =  Kc = Þ Kc = = 1.8
(2a − x)(a − x)  3a   3a  5
 2a − 4   a − 4 
   

Expressions of Keq for some reactions


[ NH 3 ] 2 p 2NH 3
1. N2(g) + 3H2 (g) 2NH3(g), K c = ; Kp =
[ N 2 ][H 2 ]3 p N 2 . p 3H 2
[HI] 2 p HI
2. H2(g) + I2(g) 2HI (g), K c = ; KP =
[H 2 ][I 2 ] p H2 . p I2
2
[SO 3 ] 2 p SO
3. 2SO2(g) + O2(g) 2SO3(g), K c = ; Kp = 3

[SO 2 ] 2 [O 2 ] 2
p SO 2
. p O2
[PCl 3 ][Cl 2 ] p PCl3 . p Cl2
4. PCl5(g) PCl3(g) + Cl2(g), K c = ; Kp =
[PCl 5 ] p PCl5
[ NO] 2 p 2NO
5. N2(g) + O2(g) 2NO(g), K c = ; Kp =
[ N 2 ] [O 2 ] p N2 . p O2

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Equilibrium Constant (𝐊 𝐩 )in terms of Partial Pressures:
Consider the same general reaction taking place at constant temperature,
aA(g) + bB(g) ⇌ cC(g) + dD(g)
[C]c [D]d
From law of mass action,K c = [A]a [B]b ------- (1)
n
From ideal gas equation, PV = nRT or,P = V RT
𝐧
At constant temperature, 𝐏 ∝ 𝐕
In a mixture of gases, Partial pressure of any component (say A),PA ∝ [A]
Similarly, PB ∝ [B], Pc ∝ [C], PD ∝ [D]
Pcc ×Pd
D
So, equation (1) can be rewritten as, K p =
PaA ×Pb
B

Relationshipbetween KP&KC
aA(g) + bB(g) ⇌ cC(g) + dD(g)
[C]c [D]d PcC ×Pd
D
K c = [A]a [B]b and Kp =
PaA ×Pb
B
n
From the ideal gas equation,PV = nRT, P = V RT
So, PA = [A]RT ; PB = [B]RT; PC = [C]RT ; PD = [D]RT
Substituting the values of PA, PB, PC and PD, we get,
[C]c (RT)c ×[D]d (RT)d [C]c [D]d (RT)(c+d)
K p = [A]a(RT)a OrK p = × (RT)(a+b)OrK p = K c (RT)Δn
×[B]b (RT) b [A]a [B]b
Where,Δn = (c + d) − (a + b)
i.e.,Δn=no of moles of gaseous products - no. of moles of gaseous reactants.
Case (i):If Δn = O; K c = K p , Ex:H2 (g) + I2 (g) ⇌ 2HI(g)
Case (ii):If Δnis positive;K p > K c Ex:PCl5 (g) ⇌ PCl3 (g) + Cl2 (g),Δn = 2 − 1 = 1 ∴ K p = K c (RT)
Case (iii):If Δnis negative; K p < K c
Ex: N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
Δn = 2 − 4 = −2
K p = K c (RT)−2

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Example 1. The value of KP for the reaction 2H2 O(g) + 2Cl2 (g) ⇌ 4HCl(g) + O2 (g) is
0.035atm at 400oC, when the partial pressures are expressed in atmosphere.
1
Calculate KC for the reaction2 O2 (g) + 2HCl(g) ⇌ Cl2 (g) + H2 O(g)
Solution: K P = K C (RT)Δn
Δn = Moles of product – moles of reactance = 5 − 4 = 1
R = 0.082Latm/molK, T = 400 + 273 = 673K
∴ 0.035 = K C (0.082 × 673)
K C = 6.342 × 10−4 moll−1
1
for the reverse reaction would be K .
∴ K′C
C
1
∴ K′C = = 1576.8(moll−1 )−1 .
6.342 × 10−4
When a reaction is multiplied by any number n (integer or a fraction) the K′C or K′P
becomes(K C )n or (K P )nof the original reaction.
1
∴ KC for O2 (g) + 2HCl(g) ⇌ Cl2 (g) + H2 O(g) is √1576.8 = 39.7(mol. l−1 )−½
2
Problem 2. KP for the equilibrium,FeO(s) + CO(g) ⇌ Fe(s) + CO2 (g)at 1000°Cis 0.4.
IfCO(g) at a pressure of 1atm and excess FeO(s)are placed in container at 1000oC,
what are pressures of CO(g) and CO2 (g)when equilibrium is attained?
Solution:Acc, to ideal gas equn, partial pressures are proportional to the no. of
moles present. Since moles of CO2 formed equals moles of CO consumed, the drop in
partial of CO will equal the partial pressure of CO2 produced. Let the partial
pressure of CO2 at equilibrium be ′x′ atm. Then, partial pressure of CO will be (1 −
x)atm.
PCO2 x
Since K p = = 1−x = 0.4 ⇒ x = 0.286
PCO

Hence PCO = 1 − x = 𝟎. 𝟕𝟏𝟒𝐚𝐭𝐦


Problem 3. At temperature T, a compound AB2 (g)dissociates according to the reaction:
2AB2 (g) ⇌ 2AB(g) + B2 (g) with a degree of dissociation ′x′which is small compared to unity.
Deduce the expression for ′x′in terms of the equilibrium constant K Pand the total pressure
P.
Solution 2AB2 (g) ⇌ 2AB(g) + B2 (g)
Mole before dissociation 1 0 0
𝑥
Mole after dissociation (1 − x)x
2
x x
Total mole at equilibrium (∑n) = 1 − x + x + 2 = 1 + 2
nB2 ×(nAB )2 P Δn
Now, K p = (nAB2 )
× [∑n]
x
,(x)2 1
P 𝑥3 x 3 2K
KP = 2
(1−x)2
×[ x ] = [ x is small, 1 − x  1 and 1 +  1 ]or x = √ P
1+ 2 2 P
2

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Problem 4. In which case does the reaction go farthest to completion:


K = 1;K = 1010 ; K = 10−1 and why?
[Product]
Solution, The ratio is maximum when K = 1010 and thus reaction goes farthest
[Reactant]

to completion when K = 1010 .


Problem 5. The K C for A2 (g) + B2 (g) ⇌ 2AB(g)at 100°C is 50. If one litre flask
containing one mole of A2 is connected with a two litre flask containing 2mole of B2 .
how many mole of AB will be formed at 100°C?
Solution A2 (g) + B2 (g) ⇌ AB2

Initial mole 1 2 0

Final mole at equilibrium(1 − x) (2 − x) 2x

Total volume of both containers on joining becomes 3 litre.


1−x 2−x 2x
At equilibrium,[A2 ] = 3
; [B2 ] = 3
; [AB] = 3
[AB]2 4x2 4x2
K C = [A = 1−x 2−x = (2−3x+x2 )
= 50
2 ][B2 ] 9( )( )
3 3

 4𝑥 2 = 100 − 150𝑥 + 50𝑥 2


or 46x 2 − 150x + 100 = 0

x = 0.93 mol and 2.326which is not valid since x | 2

Mole of AB = 2x = 2(0.93) = 𝟏. 𝟖𝟔

Problem 6. NH3 is heated at 15atm from 27°C to 247°C assuming volume constant.
The new pressure becomes 50atm at equilibrium of the reaction 2NH3 ⇌ N2 + 3NH2 .
Calculate % of mole of NH3 actually decomposed.
Solution 2NH3 ⇌ N2 + 3H2
Initial mole a 0 0
Mole at equilibrium (a − 2x) x 3x
Initial pressure of a mole of NH3 of NH3 = P atm at 347°C
15 P
300 = 620P = 31atm
At constant volume and at 347°C mole  pressure

a ∝ 31(Before equilibrium)

a + 2x ∝ 50(After equilibrium)
𝑎+2𝑥 50 19
 𝑎
= 31  x = 62 a
2x 2×19a
 % of NH 3 decomposed = a
× 100 = 62×a
× 100 = 𝟔𝟏. 𝟑%

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Characteristics of Equilibrium Constant:
The value of equilibrium constant is independent of the following factors:
1. Initial concentrations of the reactants involved
2. The presence of a catalyst
3. The direction from which the equilibrium has been attained
4. The presence of inert materials

Factors determining the value of equilibrium constant:


The value of equilibrium constant depends in the following factors:
• The mode of representation of the reaction:
A+B ⇌ C+D
The equilibrium constant for the reaction,
[C][D]
K c = [A][B]…(i)

Now, for backward reaction,


C+D⇌A+B
The equilibrium constant for the reaction is
[A][B]
K ′c = … … … … . (ii)
[C][D]
1
The equilibrium constant, K ′c is the reciprocal of K c i.e.,K ′c =
Kc

• Stoichiometry of the chemical equation:


1
Example 1 :2NO2 ⇌ N2 + 2O2 … (i)OrNO2 ⇌ 2 N2 + O2 ….(ii)
[N2 ][O2 ]2
For equation (i), the value of Kc = [NO2 ]2
1
[N2 ]2 [O2 ]
For equation (ii), the value ofK ′c = [NO2 ]

Thus, the two constants are related as𝐊 ′𝐜 = √𝐊 𝐜


In general, when a given reversible system is divided by n, the numerical value of
equilibrium constant is obtained by taking n√k of the original system.
1 1
Example 2:2 H2 + 2 I2 ⇌ HI… (i) H2 + I2 ⇌ 2HI…(ii)
1 1
[H2 ]2 [I2 ]2
For equation (i), the value of Kc = [HI]
[H2 ][I2 ]
For equation (ii), the value of K ′c = [HI]2

Thus, the two constants are related to each other,𝐊 ′𝐜 = 𝐊 𝟐𝐜


In general, when a balanced equation having equilibrium constantK c , is
multiplied by a certain value n, the equilibrium constant for the new equation
will be equal to (K c )n .

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• Use of partial pressures instead of concentrations:
When the reactants and products are in gaseous state, the partial pressures can
be used instead of concentrations at a definite temperature, as the partial
pressure of a substance is proportional to its concentration in the gas phase.
K p = K c (RT)Δn
K p can be equal or less or greater than Kc, depending upon the chemical reaction.
E
• Temperature: According to Arrhenius equation, K = A. e−RT …(i)
Where, k = rate constant,
E = activation energy,
R= gas constant.
T = absolute temperature ande = exponential constant.
k −E 1 1
log k2 = 2303R [T − T ] …. (ii)
1 2 1
When,T2 > T1
k E 1 1
For forward reaction,log (kf 2) = − 2.303R
f
[T − T ] … . (iii)
f1 2 1
kb 2 Eb 1 1
For backward reaction,log (k ) = − 2.303R [T − T ] … … … . . (iv)
b1 2 1
Kf
2
Kb (Ef −Eb ) 1 1
Subtracting eq. (iii) from eq. (iv), we get, log ( kf
2
)=− [T − T ]
1 2.303R 2 1
kb
1
k2 ΔH 1 1
log ( )=− [ − ] … … . (v)
k1 2.303R T2 T1
Where,ΔHis the heat of reaction at constant volume and K1 and K 2 are the
equilibrium constants of a reaction at temperatures T1 and T2 (T2 > T1 )
The effect of temperatures can be studied in the following three cases
First Case:-ΔH = 0, i.e. neither heat is evolved, not absorbed.
k2 ΔH 1 1
log ( ) = − [ − ]
k1 2.303R T2 T1
So, log K 2 − log K1 = 0 Or log k 2 = log k1 Or K 2 = K1
Thus, equilibrium constant remains the same at all temperatures.
Second case:-When,ΔH = +ve, i.e., heat is absorbedendothermic reaction. The
temperature T2 is higher than T1 .
k2 ΔH 1 1
log ( ) = − [ − ]
k1 2.303R T2 T1
1 1
Thus,(𝑇 − 𝑇 )is negative,
2 1

So, logK 2 − logK1 = +veOrlogK 2 > 𝑙𝑜𝑔K1 Or K 2 > K1


The value of equilibrium constant increases with increase intemperature in the case
of endothermic reactions.

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Third case:-When ΔH = −ve, i.e, heat is evolved in exothermic reaction. The


temperature T2 is higher than T1 (T2> T1)
k2 ΔH 1 1
log ( ) = − [ − ]
k1 2.303R T2 T1
1 1
Thus (𝑇 − 𝑇 )is positive,
2 1

So, log K 2 − logK1 = −veOrlog K1 > log K 2 OrK1 > K 2


The value of equilibrium constant decreases with increase intemperature in the case
of exothermic reactions.
Problem 1. At 10650C, Kp = 0.0118atm for the reaction, 2H2S(g) 2H2(g)+ S2(g)
The enthalpy of the reaction is 177.3kJ/mol. Calculate the equilibrium constant at
12000C. (Given R = 8.314J)
Solution: Effect of temperature over the equilibrium constant is given by, Van’t Hoff
equation:
K 11
p ΔH T −T
log = [ 2 1]
2.303R T1 T2
K 1p
K 1p and K 11
p are the equilibrium constants at temperatures T 1 and T2
1
T1 = 1065 + 273 = 1338K and K p = 0.0118
11
T2 = 1200 + 272 = 1473K and K p = ?
K 11 177.3 1473 − 1338
=
p
log
K 1
p 2.303  8.314  10  1473 1338
−3 

177 .3  135
=
2.303  8.314  1473  1338  10 − 3
177 .3  135  10 3
= = 0.6342
2.303  8.314  1473  1338
K11
p
= 4.307
K1p
p =4.307 K p = 4.307  0.0118atm = 0.0508atm
K 11 1

Problem 2. For the reaction N2(g)+3H2(g) 2NH3(g) at 773K, the equilibrium constant
Kp=1.40410-5Pa-2. Calculate the value of Kc for this equilibrium with concentration
units of mol/L and mol/m3. [R = 8.134J/k/mol]
Solution:N2(g) + 3H2(g) 2NH3(g)
n= - 2.0
Kp = 1.404  10-5Pa-2 = 1.404  10-5(N/m2)2
Kp = Kc.(RT)-2
−2 2
 N   8.314 
Kc = Kp. (RT)2 = 1.404  10-5     (773 K )2
 m2   K.mol 

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=
1.404  10 − 5 m 4

(8.314 )2  N 2 m 2 (773 K )2
N2 K 2 .mol 2
5.798  10 −10 m 6 5.798  10 −8
= =
mol 2 mol 2 / m 6
= 5.79810-8C-2 where C = conc. in mol/m3

Units of Equilibrium Constant- The units of equilibrium constant vary in case of


different reactions.
• ‘K’ has no units for a reaction in which total number of moles of reactants
and products are the same.
For exp , for dissociation of nitric oxide, Kc has no units.
2NO ⇌ N2 + O2
[N2 ][O2 ]
Kc =
[NO]2
• 𝐊 𝐜 will have units for a reaction in which the total number of moles of
reactants and products are different.
For exp, for decomposition of PCl5, the Kc has mol/litre units.
[PCl3 ][Cl2 ]
PCl5 ⇌ PCl3 + Cl2 , Kc = [PCl5 ]

In the formation of ammonia,N2 + 3H2 ⟶ 2NH3


[NH3 ]2
K c = [N 3
K c has𝐥𝐢𝐭𝐫𝐞𝟐 𝐦𝐨𝐥−𝟐 units
2 ][H2 ]

In general; unit of K c = [M]ΔnWhere, M = mol litr −1


Δn =no, of gaseous moles of products – no, of gaseous moles of reactants.
Note: (i) The above relation can be used in homogeneous liquid system.
(ii) Similarly, the unit of K p = [atm]Δn
• If K c > 103 , products predominate over reactants. If K c is very large, the
reaction proceeds almost all the way to completion.
• If K c < 10−3 , reactants predominate over products. If K c is very small, the
reaction proceeds hardly at all.
• If K c is in the range 10−3 to 103 , appreaciable concentration of both
reactants and products are present.
Kc

Reaction proceeds hardly Reaction proceeds to


at all
10–3 103 completion
Both reactants and products
are present at equilibrium

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CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
Reaction Quotient OR Mass Action Ratio
Let us consider a reaction:A + B⇌ C + D
[C][D]
Q=
[A][B]
Q is denoted as Qc or Qp depending upon whether the concentration is taken in terms
of moles per litre or partial pressures respectively.
With the help of mass action ratio we can determine whether the reaction is at
equilibrium or not.
I. When, 𝐐𝐜 = 𝐊 𝐜 𝐨𝐫 𝐐𝐩 = 𝐊 𝐩 , then the reversible reaction is at equilibrium,
i.e, the rate of forward and backward reaction becomes equal.
II. When, 𝐐𝐜 < 𝐊 𝐜 𝐨𝐫 𝐐𝐩 < 𝐊 𝐩 . The reaction will be fast in forward direction, i.e,
reaction has tendency to form product/products.
Rate of forward reaction >Rate of backward reaction.
III. When, 𝐐𝐜 > 𝐊 𝐜 𝐨𝐫 𝐐𝐩 > 𝐊 𝐩 . The reaction will be fast in backward direction, i.e,
have a tendency to formreactants.
Rate of forward reaction < Rate of backward reaction.

Problem 1. For the reaction,A(g) + B(g) 2C(g) at 25°C, in a 2litre vessel


contains 1, 2, 3 moles of respectively. Predict the direction of the reaction if
(a)Kc for the reaction is 3
(b)Kc for the reaction is 6
(c)Kc for the reaction is 4.5
Solution: A(g) + B(g) 2C(g)
3 2
[C]2 ( ) 9
2
Reaction quotient Q = = 1 2 = 2 = 4.5
[A][B] ×
2 2

(a)∴ Q > K c , therefore, backward reaction will be followed


(b) ∵ Q < K c ∵The forward reaction is followed
(c) Q = Kc The reaction is at equilibrium

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Problem 2. For the reaction: A(aq)+ B(aq)⇌C(aq)+D(aq) , the net rate of consumption
of B at 25C and at any time 't' is as given below,
𝑑[𝐵]
− = {410-4[A] [B] – 1.3310-5 [C] [D]} mol L-1 min-1.
𝑑𝑡
Predict whether the reaction will be spontaneous in the direction as written in
reaction mixture in which each A, B, C & D is having a concentration of 1mol L-1?
K1 4×10−4
Solution: K = = 1.33×10−5 = 30
K2
[C][D] 1×1
Q = [A][B]
= 1×1= 1 < K
Since Q < K, so the above reaction is spontaneous in the forward direction.

APPLICATIONS OF LAW OF MASS ACTION


1. Synthesis of Hydrogen Iodide:
Suppose ‘a’ moles ofH2 and ‘b’ moles of I2 are heated at 444°𝐶in aclosedcontainerof
volume ‘V’ liter and at equilibrium, 2x moles of HI are formed.
H2(g) + I2(g) ⇄ 2HI(g)
Initial moles a b o
Initial concentration a b 0
(mol L−1 ) V V
Equilibrium moles a− x b− x 2x
Equilibrium concentration a−x b−x 2X
(mol L−1 ) V V v

[HI]2
Kc =
[H2 ][I2 ]
Substituting the equilibrium concentrations ofH2 , I2 and HIin above equation, we get
2x 2
(V) 4x 2
Kc = a−x b−x
=
( V )( V ) (a − x)(b − x)
P 2 HI
Kp =
PH2 , PI2
Total no. of moles at equilibrium = (a – x) + ( b – x) + 2x = ( a + b)
a−x
PH2 = P × xH2 = P ×
a+b
P×(b−x)
Similarly, PI2 = (a+b)

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P × 2x
PHI =
(a + b)
2x 2
(P × a+b)
Kp = a−x b−x
P × a+b × P × a+b
4x2
∴ K p = (a−x)(b−x) ----------(iv)
From equations (iii) and (iv), that,K p = K c
This is so, because n = 0 for the synthesis of HI from H2 and I2

2. Thermal dissociation of PhosphorusPentachloride


PCl5(g) dissociates thermally according to the reaction,PCl5(g) ⇄ PCl3(g) + Cl2 (g)
Let us consider that ‘a’ mole of PCl5 has been taken in a container of volume V litre
and atequilibrium x moles of PCl5(g) dissociates. ThusPCl3(g) + Cl2(g)
PCl5(g) ⇄ PCl3(g) + Cl2(g)
Initial moles a 0 0
Initial concentration (mol L−1 ) a 0 0
v
Equilibrium moles (a – x) x x
Equilibrium concentration a−x x x
(mol L−1 ) V V V

According to law of mass action, at constant temperature,


[PCl3 ][Cl2 ]
Kc = ..............(i)
[PCl5 ]
PpCl3 ×PCl2
And K p = .............(ii)
PPCl5

Substituting the values of equilibrium concentration, in equation (1), we have


x x
×
V V x2
Kc = α−x or K c = V(a−x)
V

Now, total number of moles at equilibrium = a − x + x + x = a + x


a
Mole fraction of PCl3 = Mole fraction of Cl2 = a+x . P
a−x
and mole fraction of PCl5 = .P
a+x
Suppose total pressure at equilibrium is P, then we have from equation (2),
x x 2
× P x2 P
a+x a+x
Kp = a−x or K p = (a−x)2
P
a+x

3. Thermal dissociation of solid ammonium chloride:


The thermal dissociation of NH4 Cl(s) takes place in aclosed container according to the
equation:NH4 Cl(s) ⇌ NH3(g) + HCl(g)
Let us consider a mole of NH4 Cl(s) is kept in a closed container of volume ‘V’ litre at
temperature TK and if x mole of NH4 Cldissociates at equilibrium, then

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𝑁𝐻4 𝐶𝑙(𝑠) ⇄ 𝑁𝐻3(𝑔) + 𝐻𝐶𝑙(𝑔)
Initial moles a 0 0
Initial concentration 𝑎 0 0
(𝑚𝑜𝑙𝐿−1 ) 𝑣
Equilibrium moles (𝑎 – 𝑥) x x
Equilibrium concentration 𝑎−𝑥 𝑥 𝑥
(𝑚𝑜𝑙𝐿−1 ) 𝑉 𝑉 𝑉
[𝑁𝐻3 ][𝐻𝐶𝑙]
Applying law of mass action, 𝐾𝑐 = [𝑁𝐻4 𝐶𝑙]

As NH4 Clis a pure solid, so there is no appreciable change in its concentration.


Thus,K c = [NH3 ][HCl] and K p = PNH3 × PHCl
4. Decomposition of 𝐂𝐚𝐂𝐎𝟑 :CaCO3(s)⟶Cao(s) + CO2(g)
K c = [CO2 ] or K p = PCO2
When CaCO3 is heated in a closed vessel at a definite temperature, the pressure or
concentration of CO2 produced becomes constant irrespective of the amount of
CaCO3 taken.
5. Reaction of steam on heated iron:3Fe(s) + 4H2 O(g) ⇌ Fe3 O4 (s) + 4H2 (g)
[H2 ]4 ′
PH42
Kc = or K p = = 4√K p
[H2 O]4 PH42O
6. Reaction of steam on heated carbon:C(s) + H2 O(g) ⇌ CO(g) + H2 (g)
[𝐶𝑂][𝐻2 ] 𝑃𝐶𝑂 ×𝑃𝐻2
𝐾𝑐 = [𝐻2 𝑂]
or𝐾𝑝 = 𝑃𝐻2

7. Dissociation of ammonium carbonate:NH2 COCNH4 (s) ⇌ 2NH3 (g) + CO2 (g)


2
K c = [NH3 ]2 [CO2 ] ; K p = [PNH3 ] × [PCO2 ]
NOTE:- Relation between degree of dissociation (α) density of a gaseous system.
D−d
α=
d(n − 1)
D = initial vapour density
d = vapour density at equilibrium
n = no. of molecules formed on dissociation

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LE CHATELIER’S PRINCIPLE

Three main factors which can change the state of equilibrium in a reversible system
i.e., concentration, pressure and temperature.
Le Chatelier explained the effect of change in concentration, pressure and
temperature on any reversible system whether physical or chemical.

According to him, if a system at equilibrium is subjected to a change of


concentration, pressure or temperature, the equilibrium shifts in the direction that
tends to undo the effect of the change,
(OR)
If a system at equilibrium is subjected to a change in concentration, pressure or
temperature, the system adjusts itself in such a way as to nullifies the effect of
that change.

• Effect of Change in concentration: If an additional amount ofreactant or product


is added to the system, the stress is relieved as the reaction that consumes the
added substance occurs more rapidly than its reverse reaction,
i.e., in general, increasing the concentrations of the reactants results in shifting the
equilibrium towards products while increasing concentrations of the products results
in shifting the equilibrium towards reactants.
Note : The addition of any solid component does not affect the equilibrium.

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• Change of pressure: At equilibrium, when medium consists of gases, then the


concentrations of all the components can be altered by changing the pressure. When
the pressure on the system is increased, the volume decreases proportionately.

i.e., If pressure is increased, then process will move in that direction where number
of moles of gaseous species are fewer and vice versa.
• Change in temperature: In a reversible chemical reaction, if one reaction is
endothermic, other will be exothermic in nature.

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When heat energy is added by raising temperature, the system can relieve itself
from the stress if the reaction which absorbs heat moves faster, i.e, endothermic
reaction is always favoured with increase of temperature.

Exothermic process- increase in temperature favours backward reaction, vice versa.


Endothermic process- increase in temperature favours forward reaction, vice versa.

• Addition of an inert gas: When inert gas addedto a system at equilibrium, inert
gas neither reacts with reactants nor with products.
Case I: Addition of inert gas at constant pressure process will move in that
direction where number of moles of gaseous species are greater.
Addition of inert gas will increase the total volume at equilibrium. Now
• When Δn = 0e.g.,2HI ⇌ H2 + I2
x2
For this equilibrium K c = K p = 4(1−x)2 ; where x is the degree of dissociation
The equation is independent of P and V terms and thus there is no effect of
addition of inert gas to this type of equilibrium.
• When Δn > 0;eg.,PCl5 ⇌ PCl3 + Cl2
Moles at t = 0 1 0 0
Moles at equilibrium (1–x) xx
x2
Kc =
V(1 − x)
Where x is the degree of dissociation
Since V increases and thus to keep 𝐾𝑐 constant, ‘x’ must increase i.e., degree
of dissociation of PCl5 increases or [PCl3 ] and [Cl2 ]increases at equilibrium and the
[PCl5 ]decreases at equilibrium

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Case II:Addition of inert gasesat constant volume to an equilibrium will increase the
pressure at equilibrium. Now
• Δn = 0, 2HI ⇌ H2 + I2
x2
For the equilibrium K c = K p = 4(1−x2)
Where x is the degree of dissociation.
Since the equation is independent of P and V terms and thus no effect of
addition of inert gas to this type of equilibrium.
• Δn = 0 PCl5 ⇌ PCl3 + Cl2
x2
For this equilibrium K c = V(1−x)

Where ‘x’ is the degree of dissociation.


Since volume remains constant during the change and the addition of inert
gas at constant volume will also have no influence on the equilibrium
concentration for this type of equilibrium.
Conclusions:
1. Increase in concen., of any substance favours the reaction in which it is used up.
2. High pressure is favourable for the reaction in which there is decrease in volume.
3. A rise in temperature favours the endothermic reaction.
4. Effect of inert gas addition:
Condition Effect
ΔV = 0, V = ConstantΔn Δn No effect
≠ 0, = 0, +ve or − ve No effect
= Constant Δn = 0 Forward shift
ΔV ≠ 0, V ≠ ConstantΔV Δn > 0 Backward shift
≠ 0, V Δn < 0
≠ Constant
5. Effect of temperature and pressure:
Nature of reaction Effect of increased 𝛥𝑛; side with fewer mole Effect of increase in P
temperature of gas
1. Exothermic backward shift 0; No shift
2. Exothermic backward shift -ve; right forward shift
3. Endothermic forward shift -ve; right forward shift
4. Endothermic forward shift +ve; left backward shift
5. Exothermic backward shift +ve; left backward shift
6. Exothermic backward shift -ve tight forward shift
7. Endothermic forward shift +ve left backward shift
8. Endothermic forward shift +ve left backward shift

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Applications of LeChatelier’s Principle:
a. Formation of HI: H2 (g) + I2 (g) ⇌ 2HI(g) + 3000cal
• Effect of concentration: When concentration of H2 & I2 is increased at equilibrium,
the system moves in a direction which decreases the concentration, i.e., the rate
of forward reaction increases.
• Effect of pressure: As there is no change in the number of moles in the
reaction, the equilibrium state remains unaffected by change of pressure.
• Effect of temperature: By increasing temperature, the equilibrium state shifts
towards the reaction which moves with absorption of heat. The formation of HI is
an exothermic reaction. Thus, the backward reaction moves faster when
temperature is increased.
In short, we can say that the favorable conditions for greater yield of HI are:
(i) High concentrations of H2 and I2 and
(ii) Low temperature

b. Formation of Nitric Oxide: N2 (g) + O2 (g) ⇌ 2NO(g) − 43200cal


• Effect of concentration: When concentration of N2 or O2 is increased, the
system moves in a forward reaction thereby increasing the concentration of NO.
• Effect of pressure: In the formation of nitric oxide, the number of moles
remains the same, i.e, no change in volume occurs. Consequently, the equilibrium
state is not affected by any change in pressure.
• Effect of temperature: The formation of NO is endothermic in nature. If the
temperature is raised, the equilibrium shifts in the direction in which heat is
absorbed. The concentration of NO will, therefore, be higher at higher
temperature.
Thus, favourable conditions for greater yield of nitric oxide are
(i) High concentrations ofN2 or O2 or both.
(ii) High temperature

c. Dissociation of PCl5: PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) − 15000cal


• Effect of concentration: When concentration of PCl5is increased, the rate of
forward reaction increases as to decrease the added concentration. Thus, more
of PCl5 & Cl2are formed.

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• Effect of pressure: The volume increases in the dissociation of PCl 5. When


pressure is increased, the system moves in the direction in which there is
decrease in volume. Thus, high pressure does not favors dissociation of PCl 5.
• Effect of temperature: The dissociation of PCl5is an endothermic reaction. Thus,
increase of temperature favours the dissociation.
Thus, favorable conditions for dissociation of PCl5are
(i) High concentration of PCl5.
(ii) Low pressure and
(iii) High temperature
Fe
d. Formation of Ammonia: N2 (g) + 3H2 (g) → 2NH3 (g); ΔH = −22.4 kcal/mol

• At high pressure reaction will shift in forward direction to form more product
• When concentration of N2 and H2 is raised or concentration of NH3 is lowered,
thenequilibrium shifts in forward direction to from more amonmia.
• The reaction shifts in forward direction at low temperature.
But at very low temperature the rate of reaction becomes very low; thus moderate
temperature is favourable for this reaction.

Example 1. At what conditions will the following reaction go in the forward direction?
1. N2 (g) + 3H2 (g) ⇌ 2NH3 (g) + 23kcal.
2. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g) + 45kcal
3. N2 (g) + O2 (g) ⇌ 2NO(g) − 43.2kcal
4. 2NO(g) + O2 (g) ⇌ 2NO2 (g) + 27.8kcal
5. C(s) + H2 O(g) ⇌ CO2 (g) + H2 (g) + Xkcal
6. PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) − Xkcal
7. N2 O4 (g) ⇌ 2NO2 (g) − 14kcal

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Solution: 1. Low T, High P, excess of N 2 and H 2
2. Low T, High P, excess of SO2 and O2
3. High T, any P, excess of N 2 and O2
4. Low T, High P, excess of NO and O2
5. Low T, Low P, excess of C and H 2O
6. High T, Low P, excess of PCl5
7. High T, Low P, excess of N 2O4

Applications of Le-Chateleirs Principle to Physical Equilibria:


1. Vapour pressure of a liquid: Consider the equilibrium, Liquid ⇌ Vapour
Change of a liquid into its vapour is done by absorption of heat whereas the
conversion of vapour into liquid state is done by evolution of heat.
Therefore, addition of heat to such a system will shift the equilibrium towards the
right. On raising the temperature of the system, liquid will evaporate. This will raise
the vapour pressure of the system. Thus, the vapour-pressure of a liquid increases
with rise in temperature.
2. Effect of pressure on the boiling point of a liquid:
If pressure on the system is increased, some of the vapours will change into liquid
so as to lower the pressure. Thus, the application of pressure on the system tends
to condense the vapour into liquid state at a given temperature. In order to
counteract it, a higher temperature is needed. This explains the rise of boiling point
of a liquid on the application of pressure.
3. Effect of temperature on solubility:
In most cases, when a solute passes into solution, heat is absorbed, i.e., cooling
results. When heat is applied to a saturated solution in contact with solute, the
change will take place in that direction which absorbed heat (i.e., which tends to
produce cooling). Therefore, some more of the solute will dissolve.
i.e., the solubility of the substance increases with rise in temperature.

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GENERAL ORGANIC
CHEMISTRY
THEORY

NCERT SOLUTIONS

NCERT EXEMPLAR, WORK


SHEETS

FIND ALL YOUR QUESTIONS HERE, BEFORE GETTING THEM

IN YOUR EXAM ……...


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BASIC PRINCIPLES & TECHNIQUES IN


ORGANIC CHEMISTRY (GOC)

Introduction
‘The branch of chemistry dealing with these compounds, which are widely distributed in
nature and play an important role in our daily lives’, is called organic chemistry.

In earlier period of development of chemistry, compounds were classified as follows


1. Organic compounds derived from ‘living matter’ (plants and animals).
2. Inorganic compounds prepared from ‘non-living matter’ (mineral sources).
Berzelius, a Swedish chemist proposed the mistaken notion that a ‘vital force’ present in
living matter was essential for the synthesis of organic compounds. However, the synthesis
of urea an organic compound present in urine, from ammonium cyanate, an inorganic
compound by Frederic Wohler in 1828 effectively destroyed the myth of organic compounds
being associated with a ‘vital force’.

Soon afterwards the pioneering work of Herman Kolbe who synthesized acetic acid and of
Berthelot who synthesized methane showed conclusively that organic compounds are
essentially the compounds formed by carbon with itself and other elements and that they
can be synthesized in a laboratory as easily as inorganic compounds.

CH 3 − CHO ⎯[⎯→
O]
CH 3 − COOH
Acetic acid
Acetaldehyde
(First organic compound synthesized from its elements)

The chemistry of hydrocarbons and their derivatives constitutes organic chemistry.


The number of organic compounds available today is more compare to total inorganic
compounds of all elements except carbon. This is due to unique catenation property of
Carbon.

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Some properties of Carbon


• Catenation: is the property of an element where a large
number of its own atoms join together through covalent
bonds. Due to which it forms single as well as multiple
covalent bonds with other carbon atoms. It is further
supplemented by the fact that it also forms covalent bonds
with atoms of other elements like hydrogen, oxygen,
nitrogen, Sulphur, phosphorus and halogens in a variety of
ways (i.e., single and multiple bonds).
This property gives a scope for the Chemists to synthesize new compounds.
• Tetravalency of carbon atom
The atomic number of carbon is 6 and it has four electrons in its valence shell. In order to
acquire a stable noble gas configuration, it can share its 4 electrons with the electrons of its
atom or electrons of other atoms to form four covalent bonds. The bonds can be sigma(σ) or
pi(π).

2s2 2p2 2s1 2p3


energy

Ground state Excited state


Alkanes → CnH2n+2 Alkenes→CnH2n Alkynes→CnH2n–2

As per Lewis theory, Carbon can easily form tetra-bonds with other carbon atoms & other atoms. C-C,
C=C, C≡C exists in nature but not Carbon-Carbon tetrabonds.
Carbon can form single, double or triple bond (covalent). When a single bond is formed between carbon
atoms (or any atoms), energy is released. Changing the molecule's electron arrangement to make a
double bond releases more energy, but not as much as when the first bond was made. Making a triple
bond again releases energy, but again to a lesser degree. However, when a fourth bond is attempted,
the overcrowded electrons between the atoms resist the change so strongly that it releases little, if
any, energy. This arrangement is therefore unstable, so a quadruple bond will be essentially impossible.
• Hybridization in carbon compounds
Hybridization is defined as intermixing of degenerate orbitals (orbitals at nearly same
energy) to produce entirely equivalent number of new orbitals of same energy, identical
shapes and symmetrically disposed in planes. The orbitals formed are called hybrid
orbitals.

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➢ The orbitals of an isolated atom can undergo hybridization.
➢ Numbers of hybrid orbitals generated are equal to number of contributing atomic orbitals.
➢ The hybrid orbitals orient in the space providing definite geometry to molecule or ion.
➢ Like atomic orbital, a hybrid orbital cannot have more than two electrons of opposite spins.
In diamond carbon is sp3 hybridized and in graphite carbon is sp 2 hybridized.
There are three types of hybridization,
(i) sp3 hybridization (contain saturated organic compounds with only single covalent bonds)
(ii) sp2 hybridization (here organic compounds having carbon atoms linked by double bonds)
(iii) sp hybridization (here organic compounds having carbon atoms linked by a triple bonds).
Type of hybridization sp3 sp2 sp

Number of orbitals used 1s and 3p 1s and 2p 1s and 1p

Number of unused p-orbitals Nil One Two

Bond Four - Three -, One - Two -, Two -

Bond angle 109.5 120 180

Geometry Tetrahedral Trigonal planar Linear

% s-character 25 or 1/4 33.33 or 1/3 50 or 1/2

Prediction of hybridization- It can be done by two methods,


(i) First Method: In this method hybridization can be known by the number of  − bonds
present on that particular atom.
Number of – bond/s 0 1 2
3 2
Type of hybridization sp sp sp
O (ii)
(i) || CH 2 = C = CH 2
CH3 − CH = CH −C − CH 3   
    
sp 2 sp sp
2
2
sp3 sp sp 2 sp 2 sp3

(iii) (iv) HC  C − CH = CH 2
CH 3 − CH = CH − CH 2 − C  N
         
sp3 sp
2
sp 2 sp3 sp sp sp sp sp 2 sp 2

(ii) Second Method (Electron pair method): The hybridized state of an atom of a molecule
or an ion or radical can be predicted by calculating number of orbitals or electron pairs
involved in hybridization (H) which is evaluated as follows.
H = (number of  bonds formed with adjected atom/s + number of lone pairs of electrons
ep = bp + lp;
where, ep = electron pair present in hybrid orbitals,
bp = bond pair present in hybrid orbitals
Number of bp = Number of atoms attached to the central atom of the species (do not include  electron pairs).

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Value of H 2 3 4
Hybridization sp sp2 sp3
Structure linear trigonal planar tetrahedral
Central atom
First atom H
H
C=C
Second atom H H
bp = 3
Third atom
Central atom
1 2
H − C  C− H 2
1
H

bp = 2
3
bp = 3

Number of lp’s can be determined as follows,


(a) If C has  - bonds or positive charge or odd electron, than lp on C will be zero.
(b) If carbon has negative charge, then lp will be equal to one.
Example:
   • 
CH 2 = CH CH  C CH 2 = CH CH 2 = C − CH 3 CH3 − CH − CH3
   | 
bp = 2 bp=1 bp = 2 bp=3
lp = 1 CH 3 lp = 1
lp = 0 lp = 1
ep = 2,sp bp = 3 ep = 4,sp3
ep = 2,sp ep = 3,sp 2 lp = 0
ep = 3,sp 2

Pitfall - It may be noted that, the hybridized state of a heteroatom containing lone
pair electrons or carbanion or free radical bonded in conjugation with multiple bond/s is
sp2. For example, hybridized state of allylic or benzylic carbanions or free radicals or
atoms of aromatic ring is sp2.

Problem 1: How many sigma () and pi () bonds are present in each of the following
molecules? a) CH2 = C = CH2 b) CH3 – CH = CH – C  C – CH3
Solution: Every single bond is a  bond; every double bond contains one −bond and one
−bond while every triple bond consists of one − and two −bonds. Thus
a) C−C : 2, C−H : 4, C−C : 2 b) C−C : 5, C−H : 8, C−C : 3
Problem 2: Predict the shape of each of the following molecules.
a) HC  CH b) CH3Cl c) H2C = O
Solution: sp hybridization can always be correlated to tetrahedral shape, sp2 to trigonal
3

planar and sp to linear. Thus,


a) sp hybridized carbon atoms, linear
b) sp3 hybridized carbon, tetrahedral
c) sp2 hybridized carbon, trigonal planar

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Applications of hybridization
(i) Size of the hybrid orbitals: Since s- orbitals are closer to the nucleus than p-orbitals, it
is reasonable to expect that greater the s-character of an orbital the smaller it is. Thus, the
decreasing order of the size of the three hybrid orbitals is opposite to that of the decreasing
order of s orbital character in the three hybrid orbitals. sp3  sp 2  sp
(ii) Electro negativity of different orbitals
(a) Electro negativity of s-orbital is maximum.
(b) Electro negativity of hybrid orbital  % s-character in hybrid orbitals
Orbital sp sp 2 sp3
% s -character 50 33.33 25
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
s-character in decreasing order and electronegativity in decreasing order
Thus sp-hybrid carbon is always electronegative in character and sp3-hybrid carbon is
electropositive in character. sp 2 -hybrid carbon can behave as electropositive (in carbocation)
as well as electronegative (in carbanion) in character.
 
CH3 − CH 2 CH 2 = CH

sp 2 sp

Electropositive carbon Electronegative carbon


having positive charge

(c) Electro negativities of hybrid & unhybrid orbitals in decreasing order is as follows
2 3
s  sp  sp  sp  p
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
% s-character and electronegativity in decreasing order.
(iii) Bond length in hydrocarbons,% of s orbital character  1

1
C − C bond length C − H bond length
Bond type (C – H) Bond length Bond type (C – C) Bond length
sp − s (alkanes)
3
1.112Å sp − sp (alkanes)
3 3
1.54 Å
sp − s (alkenes)
2
1.103Å sp − sp (alkenes)
2 2
1.34Å
sp − s (alkynes) 1.08Å sp − sp (alkynes) 1.20Å

(iv) Bond strength in hydrocarbons: The shorter is the bond length, the greater is the
compression between atomic nuclei and hence greater is the strength of that bond.
Bond type(C – H) Bond energy (kcal/mole) Bond type (C – C) Bond energy (kcal/mole)
3 3 3
sp -s (in alkanes) 104 sp -sp (in alkanes) 80 – 90
sp2-s (in alkene) 106 sp2-sp2 (in alkenes) 122 – 164

sp-sp (in alkynes) 121 sp-sp (in alkynes) 123 – 199

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Structural representation of Organic Compounds


Structural formula (structure) is the sequence in which different atoms constituting the
molecule are bonded to one ano0ther. Structures of molecules of organic compounds can be
described in various ways. The most common types of representations are:
1) Lewis structure (or electron dot structure) Here dots are used to represent all of the
valence electrons of all the bonded atoms in the molecule:
H H H
H C H H C C H H C C H
H Ethene Ethyne
Writing dot structure is tedious and time–consuming. The other representations are more
convenient and are, therefore, more often used.
2) Dash structural formula The Lewis structure can be simplified by representing a shared
electron pair by a ‘stick’ (dash, −) between the bonded atoms. When there is one dash
between two atoms, the atoms are said to be bonded by a single covalent bond. A double
covalent bond, in which two pairs of electrons are shared, is shown by two dashes between
the atoms. A triple bond is represented by three dashes between the atoms.
The valence electrons that are not included in covalent bonds are called nonbonding
electrons (lone pairs). These are assigned to specific atoms and are represented by dots
drawn next to the symbols for these atoms.
Lone pair of electrons on hetero atoms (e.g. oxygen, nitrogen, sulphur, phosphorus, halogens)
may or may not be shown. Such structural formulae which focus only on the valence
electrons involved in bond formation are called complete structural formulae.

H H H H
| | | |
H − C− C− H H − C = C− H H−C  C −H
| |
H H
Ethane Ethene Ethyne
H H H H
| | | |
H − C− Cl or H − C− Cl H − C− O− H or H − C− O − H
| | | |
H H H H
Methyl chloride Methyl alcohol
chloromethane methanol

3) Condensed structural formula Complete structural formulae can be shortened by leaving


out some or all of the covalent bonds and by denoting the number of identical groups
attached to an atom by a subscript. The resulting description of the molecule is called a
condensed structural formula. Thus,
CH3CH3 H2C = CH2 HC  CH CH3CH2Cl
or or or or
C2H6 C2H4 C2H2 C2H5Cl
Ethane Ethene Ethyne Ethyl Chloride

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CH3CH2CH2OH CH3CH2CH2CH2CO2H
or or
CH3(CH2)2OH CH3(CH2)3CO2H
Methanol Pentanoic acid
Condensed structural formulae are easier to write than dash formulae. In condensed formulae
all of the hydrogen atoms that are attached to a particular carbon are usually written
immediately after the carbon. In fully condensed formulae, all of the atoms that are attached
to the carbon are usually written immediately after that carbon, listing hydrogens first.
For example, the condensed formula for isopropyl alcohol can be written in four different
ways:
CH3 CHCH3 CH3CH ( OH) CH3 CH3 CHOHCH3 or(CH3 )2 CHOH

|
condensedformulae
OH

4) Bond-line structural formula: For further simplification only lines are used to represent
the structures of organic molecules. Here carbon and hydrogen atoms are not shown. The
lines denoting the carbon – carbon bonds are drawn in a zig – zag fashion. The only atoms
especially written are the hetero atoms (oxygen, nitrogen etc). They are neither carbon nor
hydrogen bonded to carbon. The termini describe methyl (CH3 − ) groups (unless denoted
otherwise by a functional group). The line junctions indicate carbon atoms bonded to
suitable number of hydrogens needed to satisfy the covalency of the carbon atoms: Thus
The bond-line representation is the quickest of all to write because it shows only the carbon
skeleton.
CH3

a) CH3CH2CH2CH(CH3)CH2CH2CH2CH3 ⎯⎯⎯
step 1
⎯→ CH2 CH CH2 CH3

CH3 CH2 CH2 CH2

Step 2

Line junctions denote carbon atoms

Terminals describe methyl groups

Cl

CH CH2

b) CH3CHClCH2CH2CH3 ⎯⎯⎯→
step1
CH3 CH2 CH3
step 2

Cl

CH2 CH2 CH2 CO2H

c) CH3(CH2)6CO2H ⎯⎯⎯→ step1


CH3 CH2 CH2 CH2
Step 2

OH

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Ring or cyclic compounds - An organic compound in which carbon atoms are not bonded in
chain but are bonded in closed structures called rings are known as cyclic compounds. Such a
compound containing one or more rings is represented by drawing the suitable ring (polygon)
without indicating the carbon and hydrogen atoms. The corner of the polygon denotes a
carbon atom and its sides represent a carbon – carbon bond. An atom or a group of atoms
(other than hydrogen) bonded to the carbon is however shown in the structure.
Bond–line formulae of some cyclic compounds are:
CH2
CH2 H2C CH2
H2C CH2

H2C CH2 H2C CH2 H2C CH2


Cyclopropane Cyclobutane Cyclopentane
OH CO2 H
OH CO2 H
CH CH

H2C CH2 H2 C CH2

H2C CH2 H2 C CH2

CH2 CH2
Cyclohexanol Cyclohexane carboxylic acid

Multiple bonds are also indicated in bond-line formulae.


For example:
H3 C CH CH3
C H2 C

CH3
CH2 CH CH 2 OH .

OH
Exp 1: Convert each of the following Lewis structures into complete structural formulae:
O H
a) H C O H b) H C N c) H C Cl
H
Solution: Use the dash to represent the shared electron pair.

H H
O O | |
a) || || b) H – C  N: or H – C  N c) H − C − Cl or H − C− Cl
H − C − O − H or H − C− O − H | |
H H
Exp2: Convert each of the complete structural formulae into condensed formulae.
H H H H H H H
a) | |
H − O − C− C− N− H
b) | | | | |
H − C− C  C − C − C − C − C − H
| | | | | | | |
H H H H H H H H
H O H H H H H
c) H − C| − C|| − C| − H d) H − C| − C| − C| − C| − N = O
| | | | | | 
H H H H H H O
Solution: Omitting some or all of the dashes and indicating the number of identical groups by
a subscript we get
a) HO(CH2)2NH2 b) CH3C  C(CH2)3CH3 c) H3CCOCH3 d) CH3(CH2)3NO2

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Exp 3: Write the condensed structural formulae for the compound that follows in different
ways.
H H H H

H C C C C H

H H H
H C H

Solution: CH3− CH CH2CH3 or CH3CH ( CH3 ) CH2CH3 or CH3 CH2 CHCH3


| |
CH3 CH3
or ( CH3 )2 CHCH2CH3 or CH3 CH2CH ( CH3 )2

Exp 4: Write the bond–line formula for H3C− CH−CH2− CH2− CH2− OH
|
CH3
Solution: First, outline the carbon skeleton, including the OH group as follows:
H3C CH2 CH2 C C
C
C C OH
CH CH2 OH
C
CH3
Thus, the bond–line formula is .
OH

.
Exp 5: For following condensed formulae write the corresponding bond-line formula.
a) (CH3)2CH(CH2)2CH2OH b) CH3(CH2)4CHICH2CHO
c) (CH3)2CHCH3CH(CH2)3NO2 d) (CN)2CHCH2COCl
Solution: In bond-line formula carbon and hydrogen atoms except those that are part of the
functional groups are not shown. We show only the carbon skeleton. The number of hydrogen
atoms necessary to fulfill the carbon atoms’ valences is assumed to be present, but we do not
write them in. Other atoms (e.g., Cl, O, N) are written in. Each intersection of two or more
lines and the end of a line represent a carbon atom unless some other atom is written in.
CH3

a) (CH3)2 CH (CH2)2CH2OH ⎯⎯⎯→ step1


CH CH2 OH

CH3 CH2 CH2


Step 2

OH

I
b) CH3(CH2)4CHICH2CHO ⎯⎯⎯→
step1
CH2 CH2 CH CHO
CH3 CH2 CH2 CH2

step 2

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.

. NO 2
c) (CH3)2CHCH3CH(CH2)3NO2 ⎯⎯⎯
step 2
⎯→

.
CH2 Cl
NC
CH C
d) (CN)2CHCH2COCl ⎯⎯⎯→ step1

CN O
step 2

Cl
NC
C

CN O

Exp 6: Draw all possible bond-line formulae for a cyclic compound, C5H10.
Solution: Start with the maximum number of carbon atoms in the ring and move towards the
ring of 3 carbon atoms. Explore all sorts of possibilities on this route:

Three-dimensional representation of organic molecules


None of the formulae that we have described so far conveys any information about how the
atoms of a molecule are arranged in space. Shape or the three-dimensional (3-D) structure
of organic molecules can be described on a paper (two-dimensional) by exploring certain
conventions. For instance, by using solid and dashed wedge formula the 3–D
image of an organic molecule can be perceived on a two-dimensional paper.
In solid-wedge and dashed-wedge description the solid-wedge denotes a bond projecting
out of the plane of the paper towards the viewer. The dashed-wedge depicts the bond
projecting behind the plane of the paper and going away from the viewer. Both the wedges
are drawn in such a way that the broad end of the wedge is near the viewer. The other two
bonds lying in the plane of the paper are shown by using a normal line ( ⎯ ).
Let’s consider the wedge- and dashed-wedge representation of methane (CH4) molecule:
H H

H or H
H H H
H

The two carbon-hydrogen bonds represented by normal lines are in the plane of paper,
whereas the carbon-hydrogen bond represented with a solid wedge is aimed to be in front of
the plane of paper. The hydrogen bonded to carbon by dashed wedge is intended to be
behind the plane of paper. Note that the carbon atom is lying in the plane of paper.
Wedge and dashed-wedge formulae are an important tool for clearly showing three
dimensions.

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Classification of organic compounds

The compounds with C and H are called hydrocarbons. Organic compounds are considered as
the derivatives of hydrocarbons obtained by replacing H-atoms by other atoms or groups.
Based on C - skeleton, organic compounds divided as below,
1. Acyclic compounds - The open chain organic compounds are called acyclic compounds.
The carbon chains may be linear or branched.
The open chain compounds are classified into two groups.
a. Saturated compounds: Open chain compounds in which carbon atoms of parent chain are
bonded with single bonds are called saturated acyclic compounds.
Example:
CH3CH2CH2CH3 O CH3
CH − CH − CH || |
n–Butane 3 3
H − C− H
| CH3 −C− OH
CH3 |
Formaldehyde CH3
Isobutane
tert-Butyl alcohol
b. Unsaturated compounds: The open chain organic compounds in which parent chain contains
one or more carbon-carbon double bonds or triple bonds are called unsaturated acyclic
compounds.
CH3 CH3
CH2 CH2 CH3CH CH2 CH3CH CHCH3 CH3C CHCH3 CH3 CH C CH
ethylene propene 2-butene 2-methyl-2-butene 2-methyl-1-butyne

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2. Cyclic Compounds – Here carbon atoms are linked by covalent bonds to form ring
structures are called cyclic compounds. Depending upon the constituents of ring, these
compounds are further classified into two groups.
A. Carbocyclic compounds (Homocyclic compounds): The cyclic compounds containing only
carbon atoms in their ring are called carbocyclic compounds. They are further divided into
two groups.
➢ Alicyclic compounds: The carbocyclic compounds which resemble with aliphatic
compounds in most of their properties are called alicyclic compounds.
H2
C H2 C CH2
or or
H2 C CH2 H2 C CH2
cyclopropane cyclobutane

H2 H2
C C
H2 C CH2 H2 C CH2
or or
H2 C CH2 H2 C CH2
C
cyclopentane H2 cyclohexane

Aromatic compounds: Benzene is the parent aromatic hydrocarbon. The organic compounds
containing one or more isolated or fused benzene rings and their functionalized derivatives
are called aromatic compounds or benzenoid compound.
CH3
OH CHO

benzene naphthalene diphenyl toluene phenol benzaldehyde


The aromatic compounds which resemble benzene in most of their properties are called non-
benzenoid aromatic compounds.

O
azulene tropolone

➢ Heterocyclic compounds: The cyclic compounds containing one or more heteroatoms


(atom other than C it may be O, N, S, etc.,) in their ring are called heterocyclic
compounds. Depending upon their chemical behaviors, they are further classified into
two groups.
i. Alicyclic heterocyclic compounds: The aliphatic cyclic compounds containing one or more
hetero atoms in their ring are called alicyclic heterocyclic compounds.
O O H2C CH2
or or
CH2 N
H2 C CH2 H2C
O O H
oxirane (ethylene oxide) tetrahydrofuran (THF) pyrrolidine
or epoxide

ii. Aromatic heterocyclic compounds: The aromatic cyclic compounds containing one or
more hetero atoms in their molecules are called aromatic heterocyclic compounds.

O N N S
furan pyrrole pyridine thiophene
H

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Organic Compound

Open chain/Acyclic/Aliphatic Closed chain/Cyclic/Aliphatic

Hydrocarbon Containing
functional Homocyclic/ Heterocyclic
group Carbocyclic [Ring having at least one
[Ring having only hetero Atom][N, O, S]
Saturated C atoms]
Unsaturated
Ex :- Alkane
CnH2n+2
Alicyclic Aromatic
Alicyclic Aromatic
Ex :- CH2–CH2
Alkene Alkyne Alkenyne Containing O
CnH2n CnH2n–2 CnH2n–4 Alternate O
– and = Bond Oxirane
[C=C] [C  C] [C=C–CC] Cyclo Cyclo Furan
CH2–CH2
Propane Butane Ex :-
Cl
CH2–CH2
O NH
Benzene Tetra hydrofuran Pyrrole
Cyclo Cyclo Chloro (THF)
Pentane Hexane benzene CH2–CH2
S
CH2–CH2
Thiophene
Nephthalene NH
Pyrrolidine
N

Anthracene Pyridine

Functional groups: is defined as “an atom or group of atoms present in a molecule which
decides the chemical properties of the organic compounds”.
Double and triple bonds are also considered as functional groups.
The organic compounds are further classified into different classes depending upon the
nature of functional group. Classification of organic compounds based on functional group is
summarized in the table.

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Homologous Series
A series of structurally related organic compounds with same functional group can be
represented by a general formula and differ by -CH2 group is called homologous series.
The individual members of such series are called homologue and this phenomenon is known
as homology.

Characteristics of a homologous series are as follows.


• Each homologues series can be represented by general molecular formula.
Exp - General molecular formula of alkane is CnH2n+2. Molecular formula CnH2nO2
represents alkanoic acids (carboxylic acids) and alkyl-alkanoates (esters).
• All members of a given homologous series (homologues) possess the same functional group.
• The successive members of a homologous series differ by a -CH2- group or by mass units.
• Homologues of a homologous series can be prepared by general methods.
• The physical properties such as boiling point, melting point, density, etc., of the members
of a homologues series show a regular gradation with increase in molecular mass.

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• Chemical properties of the members of a homologous series are similar though the first
homologue may vary considerably from the rest of the homologues.

Nomenclature of Organic Compounds


The nomenclature deals with the naming of millions of organic compounds. The following
systems are employed.
1. Trivial system (common system)
It is the oldest system of naming organic compounds. In the early stages of the development
of organic chemistry, organic compounds were named after the source from which they were
first isolated. Generally, the names chosen had Latin or Greek roots. The following illustrations
justify the statement.

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2. IUPAC System - Saturated hydrocarbons are the parent compounds and other organic
compounds as their derivatives obtained by substituting one or more hydrogen atoms
with functional groups. IUPAC name of any organic compound may consist of three parts.
“prefix-root word-suffix”.
IUPAC system for naming is something that is very similar to addressing a person with his
complete designation.

a. Root word – is assigned to organic molecule based on the number of carbon atoms
present in the main parent chain
No. of C atoms Root word Molecular formula Molecular structure IUPAC name
1 Meth CH4 CH4 Methane
2 Eth C2H6 CH3CH3 Ethane
3 Prop C3H8 CH3CH2CH3 Propane
4 But C4H10 CH3(CH2)2CH3 Butane
5 Pent C5H12 CH3(CH2)3CH3 Pentane
6 Hex C6H14 CH3(CH2)4CH3 Hexane
7 Hept C7H16 CH3(CH2)5CH3 Heptane
8 Oct C8H18 CH3(CH2)6CH3 Octane
9 Non C9H20 CH3(CH2)7CH3 Nonane
10 dec C10H22 CH3(CH2)8CH3 Decane
11 Undec
12 dodec

b. Suffix – is based on the nature of bonds and functional group present in the molecules.
It is of 2 types,
• Primary suffix: A primary suffix is added next to the root word to indicate whether the
parent chain is saturated or unsaturated.

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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Type of carbon chain root word primary suffix generic name

Saturated (C-C single bonds) alk ane alkane

Unsaturated [C=C bond] alk ene alkene

Unsaturated [−CC−] alk yne alkyne

Note: A carbon-carbon double bond or triple bond must be included in parent chain even if it
contains less number of carbon atoms.
• Secondary suffix added next to the primary suffix to indicate the presence of a functional
group in organic compounds which determines the class of organic compounds.
Secondary suffix of a few functional groups are given.
Functional group Structure Secondary suffix Class of organic compounds

Hydroxyl –OH - ol Alcohols

Aldehydic O
- al Aldehydes
C H

Ketonic C O - one Ketones

Carboxy O
-oic acid Carboxylic acids
C OH

Ester O
alkylalkanote Esters
C OR

Amino –NH2 - amine Amines

Note - While adding the secondary suffix, the letter ‘e’ of the primary suffix (i.e., ane, ene
and yne) is dropped if the secondary suffix begins with a vowel (a, e, i, o or u). It is retained
if secondary suffix begins with a consonant.
c. Prefix (substituent)
All the groups which are not names in parent chain and functional groups are called as
substituents. Its name placed before the root word.
Exp – Alkyl group, halo atoms, nitro group
Substituents group Prefix
-CH3 Methyl
-C2H5 Ethyl
-NO2 Nitro
-Cl Chloro
-OR Alkoxy
–C–C– Epoxy
O
-NO Nitroso

Alkyl groups – derived from an alkane, by removing a hydrogen atom bonded to carbon.
These groups are named simply by dropping –ane from the name of the corresponding alkane
and replacing it by –yl. R is a general symbol, general formula for an alkyl group is CnH2n+1,
because it contains one less hydrogen atom than the parent alkane, CnH2n+2.

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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Alkane Alkyl group Abbreviation
Methane, CH4 Methyl, CH3− Me−
Ethane, CH3CH3 Ethyl, CH3CH2− or C2H5− Et −
n – propyl, CH3CH2CH2−
Propane, CH3CH2CH3 Isopropyl, CH3CHCH3 n-Pr – or Pr – i-Pr−
|
n-Butyl, CH3CH2CH2CH2−
n-Bu– or Bu–
n-Butane, CH3CH2CH2CH3 sec – Butyl, CH3 CH2CHCH3
| s-Bu–

Isobutyl, CH3CHCH2
|
CH3 i-Bu–
Isobutane, CH3CHCH3
| CH3
CH3 |
tert–Butyl, CH3−C−
| t-Bu−
CH3

Among the alkyl groups we encounter the problem of isomerism.


• While only one alkyl group can be derived from methane (the methyl, CH3−)
• Ethane (the ethyl, CH3CH2−)
• Two or more alkyl groups can be derived from higher alkanes.
Exp – (1) From propane (C3H8), two alkyl groups can be derived. Removal of one of the
hydrogens from one of the end carbon atoms gives an alkyl group that is called the propyl
group or n-propyl group.
→ CH3 CH2CH2 − or n − Propyl
−H
CH3 CH2CH3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯
fromendcarbon
Propane Propyl
Removal of one of the hydrogens from the middle carbon atom gives an alkyl group that is
called the isopropyl group.
−H
CH3CH2CH3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → CH3CHCH3
Propane frommiddlecarbon |
Isopropyl

Both these alkyl groups contain the propane chain, but differ in the point of attachment of
the group to the rest of the molecule.
(2) There are four butyl groups, two derived from the straight–chain n-butane, and two
derived from the branched–chain isobutane. These are given the designations: n− (normal),
sec– (secondary), iso– and tert– (tertiary) as shown below:
−H
−H
CH3−CH 2CH 2CH 2 − from a terminal CH 3−CHCH 2−
from a terminal carbon |
n-Butyl group
carbon CH 3
Isobutyl group
CH3CHCH3
CH3CH2CH2CH3 |
n-Butane CH3
−H |
−H CH 3−C− CH 3
CH 3CH 2C HCH 3 from the central |
from the | carbon CH 3
non-terminal carbon sec− Butyl group tert-Butyl group

CH3 CH3

CH3 CH2 CH2 CH2 CH3 CH3 CH CH2 CH3 CH3 C CH3
n-pentane iso-pentane CH3
neo-pentane

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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An alkyl group is described as,
❖ primary if the carbon at the point of attachment is bonded to only one other carbon,
❖ as secondary if bonded to two other carbons,
❖ tertiary if bonded to three other carbons. Thus, if R is any hydrocarbon radical, the
different kinds of alkyl groups are
RCH2− R2CH− R3C−
Primary Secondary Tertiary

Problem 1: Classify each of the following alkyl groups as primary, secondary or tertiary:
Butyl, Isopropyl, Isobutyl, sec-Butyl and tert-Butyl.
Solution: Primary alkyl group is RCH2 −
CH3CH2CH2CH2− CH3CHCH2−
Butyl |
CH3
Isobutyl
Secondary alkyl group is
CH3CH2
CH3
R CH − CH −
CH − CH3 H3C
R Isopropyl sec - Butyl

R
R C

Tertiary alkyl group is


CH3
(tert-Butyl)
R
|
CH3 −C−
|
CH3

 Prefix n-(normal) is used for those alkanes in which all the carbon atoms form a
continuous chain with no branching.
CH 3 CH 2CH 2CH 3 ; CH 3 CH 2 CH 2 CH 2 CH 3
n − Butane n − Pentane

 Prefix iso is used for those alkanes in which one methyl group is attached to the next-to-
end carbon atom (second last) of the continuous chain.
CH 3 − CHCH 3 CH 3 − CH − CH 2 CH 3 CH 3 − CHCH 2 CH 2 CH 3
| | |
CH 3 CH 3 CH 3
Isobutane Isopentane Isohexane

 Prefix neo is used for those alkanes which have two methyl groups attached to the second
last carbon atom of the continuous chain.
CH 3 CH 3
| |
CH 3 − C − CH 3 CH 3 − C − CH 2 − CH 3
| |
CH 3 CH 3
Neopentane Neohexane

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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Rules for naming of open chain Organic compound.


Rule 1 - Longest chain rule (root word rule)
The continuous carbon chain containing maximum carbon atoms including the function group
is selected. It is called the parent chain. For one to four carbon atoms of the parent chain,
special root words are used but for chains of five or more carbon atoms Greek number roots
are employed.
The generic root word for any parent chain is ‘alk’.
Priority order: Functional group > Multiple bond (= or ) > Substituent
Substituents
CH 3
|
Parent chain
CH 3 − CH − CH 2 − CH 2 − C − CH 2 − CH 3
| |
CH 3 CH 3
CH3
| Substituents
CH3 CH2
| |
CH3 − CH − CH − CH3 - substituted pentane
Similarly, the following hydrocarbon will be regarded as a substituted hexane because the
longest continuous carbon chain (parent chain/ root chain) contains six carbon atoms.
CH3 − CH2 − CH2 − CH2 − CH − CH3 Substituted hexane
|
CH3

CH3 ( CH2 )3CHCH3CH2CH3 → CH3 − CH2 − CH2 − CH2 − CH − CH3 Substituted heptane
|
CH2
|
CH3

CH2CH3 CH2CH2CH2CH3
| |
CH3CH2CHCH3 ( CH2 )2 CHC2H5 ( CH2 )3 CH3 → H3C −CH− CH2 − CH2 − CH− CH2CH3
substituted decane

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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Note:
• If two different chains of equal length are possible, the chain with maximum number
of side chains or alkyl groups is selected.
• Number used to specify the position of the substituents is called locant.

Rule 2 - Lowest sum rule (rule of locant)


Parent carbon chain is numbered using Arabic numerals 1, 2, 3, 4, 5..... in such a way that
functional group or substituents containing carbon receive least number.
CH3
| 1 2 3 4 5 6 7 3
5
CH3 − CH − CH 2 − CH 3 6 5 4 3 2 1 2 6 4 4 6 2
1 3 4 8
2 CH 3CH 2 CH 2 CH 2 CH CH 3
1 3 5 7 1 
4 3 |
2 1
CH 3
8 

1 2 3 4 5 5 CH 3 1
7 6 5 4 3 |
CH 3CH 2CH 2CH 2− CH−CH 3 CH34 CH 2 2
| | | 9 8 7 6 5 4 3 2 1
2CH 2 6 CH3 − CH − CH − CH3 1 2 3 4 5 6 7 8 9
1 2 3 CH3CHCH 2CH2CH2CHCH 2CH2CH3
|
5 4 3
1CH 3 7 CH3 CH2CH3

 When the parent chain contains two or more substituents, the numbering is done from the
end where the sum of the locants is least.
CH3
6 5 4 3 2 1 (2 + 5 + 5 = 12, wrong)
CH3 C2 CH2 CH2 CH CH3
1 2 3 4 5 6
CH3 CH3 (2 + 2 + 5 = 9, correct)

 Parent chain with one substituent: Prefix the name of the substituent to the root word
of parent chain and indicate its position. The name of the substituent is separated from its
locant by a hyphen (-). Name of the organic compound is written as one word.
1 2 3 4 1 2 3 4 5 6
1 2 3
CH3 CH CH3 CH3 CH CH2 CH3 CH3CH2 CH CH2CH2CH3

CH3 CH3 CH2CH3


2-methylpropane 2-methylbutane 3-ethylhexane
 Naming of different substituents: When two or more different substituents are
present on the parent chain, they are named in alphabetical order along with their
appropriate locants.
1 2 3 4 5 6 7 1 2 3 4 5 6 7 8
CH3 CH CH2 CH CH2CH2CH3 CH3 CH CH2CH2CHCH2CH2CH3
CH3 CH2CH3 Cl CH3
4-ethyl-2-methylheptane 2-chloro-5-methyloctane
 Numbering of different substituents at equivalent positions: If two different alkyl or
halo groups are present at equivalent positions, the numbering of the parent chain is done in
such a way that the substituent which comes first in the alphabetical order gets the lower
number.

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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CH2 CH3
6 5 4 3 2 1 correct numbering
CH3 CH2 CH CH CH2CH3
1 2 3 4 5 6
incorrect numbering
CH3

3-ethyl-4-methylhexane (NOT 3-methyl-4-ethylhexane)


Br
1 2 3 4 correct
CH3 CH CH CH3
4 3 2 1 incorrect
Cl
2-bromo-3-chlorobutane (NOT 3 - chloro-2-bromobutane)
 Presence of the same substituent more than once: If the same substituent occurs
more than once, the prefixes di, tri, tetra are prefixed to the name of the substituent. It
may be noted that the position and name of the substituent are separated by a hyphen (-)
whereas the numerals representing the positions of the substituents are separated by
commas.
CH3 CH2CH3 CH3

CH3 CH CH CH3 CH3 CH CH CH C CH3

CH3 CH3 CH3


2, 3-dimethylbutane 4-ethyl-2,2,5-trimethylhexane
 Naming a complex substituent: In case the substituent on the parent chain is complex
(i.e., it has a branched chain), it is named as a substituted alkyl group by numbering the
carbon atom of this group attached to the parent chain as 1. Name of complex substituent is
enclosed in bracket to avoid confusion with the numbers of parent chain.
CH3
1 2
CH3 CH CH3 CH3 CH CH CH3
1 2 3
CH3 CH2 CH2 CH CH2 CH2 CH3 CH3CH2CH2CH2CHCH2CH2CH2CH3
1 2 3 4 5 6 7 1 2 3 4 5 6 7 8 9

4-(1-methylethyl)heptane 5-(1, 2-dimethylpropyl)nonane


If same complex substituent occurs more than once on the parent chain, prefixes bis, tris,
tetrakis, etc., are used before the name of the complex substituent.
The application of IUPAC rules to the structure of a molecule to arrive at IUPAC name
is illustrated as follows.
CH2 CH3
CH3 CH CH CH CH3
5 4 3 2 1
CH3 Br

• Parent chain has 5 carbon atoms, and it has more number of substituents. The root word is
‘pent’.
• Primary suffix is ‘ane’
• Sum of locants is 9, the substituent which comes first in alphabetical order gets the lower
number.
• Prefixes to the rootword are bromo, ethyl and methyl. Hence, IUPAC name is
• “2-bromo-3-ethyl-4-methylpentane”

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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A few examples are given below:
CH3 Br CH3
CH3 C CH2 CH CH3 CH3 CH CH CH CH2 CH3
1 2 3 4 5 1 2 3 4 5 6
CH3 CH3 CH2 CH3

2,2,4-trimethylpentane 2-bromo-3-ethyl-4-methylhexane
1 2 3 4 5 6 1 2 3 4 5 6 7 8 9
CH3CHCH 2CH2CH2CH3 C H 3C H C H 2C H 2C H 2C H C H 2C H 2C H 3
| |
CH3
CH 3 CH 2CH 3
2−Methylhexane 6–Ethyl–2−methylnonane
CH3
1 2 3 4 5 6 7 1 2 3 4 5 6 7
CH3CH2CHCH2CH2CH2CH3 CH3 CH 2 C CH 2CH2CH2CH3
|
CH3 CH2
CH3
3−Methylheptane 3–Ethyl–3–methylheptane
1 2 3 4 5 6
C H 3C H −C H 2CHCH2C H 3
| |
4–Ethyl–2–methylhexane
CH 3 CH 2
|
CH 3
not
2–Methyl–4−ethylhexane because ethyl comes before methyl alphabetically

1 2 3 CH 3 CH3 CH3
C H 3− C H− C H − CH 3 2 |3 4
| | 1 5 1| 3 4| 5
2

CH 3 4 CH 2
C H 3C H C HCH−CH 3 C H3−C − CH2− C− C H 3
| | | |
| CH3 CH3
5
CH 3
CH 3 CH 3

2, 3 – Dimethylpentane 2, 3, 4 – Trimethylpentane 2, 2, 4, 4 – Tetramethylpentane


CH 3CH 2 CH 3 CH 3
1 2 | 3 |4 5 6 7
8 7 6 5 4 3 2| 1
C H 3C H 2CH − C − C H 2C H 2CH 3 CH 3CHC H 2CH 2− CHCH 2− C − CH 3
| | | |
CH 3 CH 3 CH2CH3 CH 3
3 – Ethyl – 4, 4 – dimethylheptane 4 – Ethyl – 2, 2, 7− trimethyloctane

8 10 7 5 3 1
2 3 4 5 6
1 7 9 4 2
6
8

4,5–Diethyl–3, 6-dimethyldecane 5-Ethyl–2, 2–dimethyloctane


(“di” not considered in alphabetical ordering)
CH3

1 CH CH 3
1 2 3 4 5 6 7 8 9 10
7 6 5 4 3 2 CH3CH2CH2 CH CH CH 2CH2CH2CH2CH3
8
H3C CH CH 2 CH 3
5–(1, 1-Dimethylethyl)−3−ethyl-6-methyloctane 5–sec–Butyl– 4−isopropyldecane
(“di” is being part of substituent name)

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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1 2 3 4 5 6 7 8 9
2 CH3CH2CH2CH2 CH CH 2CHCH 2CH3
CH3
1CH
1 2
CH3 CH
1 2 3 4 5 6 7 2
CH3 C CH3
CH3CH2CH2CHCH 2CH2CH3
3 CH
3
4 – Isopropylheptane 5-(2, 2–Dimethylpropyl)nonane
or
4–(1–Methylethyl)heptane
CH2CH3
10 9 8 7 6 5 1 2 3 4
CH3CH2CH2CH2CH2 CH CH 2 CH CH 2CH3

4 CH2

H3C C CH 3
3
CH2 CH 3
2 1
5–(2–Ethylbutyl)–3, 3–dimethyldecane
N.B. Longest chain selected has maximum number of side chains.
Naming of organic compounds containing a functional group
Prefix and suffix names of a few common functional groups and their decreasing order of
priority are given in the table.

Group Prefix name Suffix name Class of organic compounds

−COOH − -oic acid Carboxylic acids

−COOR − alkyl....oate Esters

−COX − -oyl halide Acid halides

−CONH2 carbamoyl -amide Amides

−CHO formyl -al Aldehydes

−CO oxo -one Ketones

−OH hydroxyl -ol Alcohols

−NH2 amino -amine Amines

− -ene Alkenes
C C

−CC− − -yne Alkynes

−X (halogen) halo − Alkyl halides

−NO2 nitro − Nitroalkanes

−OR alkoxy − Ethers

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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It may be noted that the groups -R, -OR, -NO2, -X, etc. are considered as substituents
and are indicated as prefixes.
1. Longest chain- The parent chain is the one which has functional group directly attached
to it, even if it violates the longest chain rule.
2. Numbering of parent chain-The numbering should be done in such a way that the carbon
linking to the functional group gets the lowest number even if it violates the lowest sum
rule or locant rule.
When the functional group itself contains carbon atom, then that carbon atom is assigned as
number 1.
3. Naming of compounds with polyfunctional group- If there is more than one functional
group present in a compound, then one of the functional group is chosen as the principal
functional group (secondary suffix) and the remaining functional groups are treated as
(substituents) subordinate functional groups.
The functional group with higher priority in the sequence given below is termed as principal
functional group.

1. Write the correct IUPAC names of the following bond line formula:
Me

O
C
O
(i) (ii) (iii) (iv)
Cl H3CO
O OMe
Me Me OH Me Et

H OH Me Me Me
HO H Me Me
(v) Me (vi) (vi) H H (vii) Me COOH

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
- 2022)

O
Me
N CHO

(ix) O (x) (xi) (xii)


Me Me

O
(xiii) H H (xiv) O
Answers
(i) 2-Methylpropanoyl chloride (ii) Methyl propanoate
(iii) Methyl 2-ethylbutanoate (iv) 5-Ethyl-4, 6-dimethyloct-1-ene
(v) Butane-2,3-diol (vi) 5,6-Diethyl-3-methylundec-4-ene
(vii) 3-Methyl cyclopentam-1-ol (viii) 7-Ethyl-6-methylundec-6-cnoic acid
(ix) Ethyl propanoate (x) N-Ethyl-N-methyl propan-1-amine
(xi) Hex-3-yne (xii) 3-Ethyl-4-methylpentanal
(xiii) 2,3-Dimethyloxirane (xiv) Tetrahydrofuran

2. Write the IUPAC names of the following compounds:


(i) HOH2C –CH = CH – CH2OH (ii) H2C = C –CH2–CH2–OH
CH3

(iii) HC = C–CH2–CH2–CH–CHO (iv) CH3COCOOH


Cl
O
(v) CH2–CH – CHO (vi) CH3–CH – C – CH – OCH3
OH Cl CH3 CH3

–CH–CCl3
(vii) (viii) C H –CH = CH – COOH
6 5

O
(ix) CH3–CH – C – CH – OCH2CH3 (x) CH2–CH–CH2
OCH3 CH3 OH OH OH
O CH3
(xii) –O–C–CH–CH3 (xiii) [(CH3)2CH]3COH

CH3
(xiv) (CH3)3COH (xv) CH3–CH2 – CH – C – CH2Cl
Br Br
NO2
(xvi) CH3CH2CH(CHO)CH2COOH (xvii)
H2N NO2

3. Write correct IUPAC names of the following polyfunctional compounds:


(i) CH2 = CH–CH2Cl (ii) CH3CH CHCH2OH
CH3
CH–C(OCH3)CHO CH3–CH–COOH
CH3
CH3 CH2CHO
(iii) (iv)

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
- 2022)
O O
(v) CH3–C–CH2CH3 (vi) CH3–C–C–OCH2CH3
CH2OH
OO O O
(vii) CH3–C–C–OCH2OCH3 (viii)
H–C–C–OH
O
(ix) CH3CH2N–C–H (x) CH3CH2CHCH2CN
Cl
4. Write IUPAC names of the following compounds:
(i) CH3OCH2CH2CH2OC2H5 (ii) HOCH2CHCHO
NH2
O
(iii) CH3–C–N–CH2CH3 (iv) HC=C–CH=CH–CH3
H
OH
(v) CH3–C–COOH
H
Answers
1. (i) –C = N> –C– > –OH (ii) –SO3H > –COCl > –CHO
(i) –COOR > –CONH2 > –CHO
2. (i) But-2-ene-1, 4-diol (ii) 3-Methyl-but-3-en-l-ol
(iii) 2-Chlorohex-5-yn-l-al (iv) 2-Ketopropanoic acid
(v) 2-Chloro-3-hydroxypropanal (vi) 2-Methoxy-4-methylpentan-3-one
(vii) 1,1,1-Trichloro-2,2-diphenylethane (viii) 3-Phenylprop-2-en-l-oic acid
(ix) 2-Ethoxy-4-methoxypentan-3-one (x) Propane 1,2,3-triol
(xi) 2-Methoxybenezoic acid (xii) Phenyl 2-methylpropanoate
(xiii) 2,4-Dimethyl-3-(1-nethylethyl) pentan-3-ol (xiv) 2-Methylpropan-2-ol
(xv) 2,3-Dibromo-1-chloro-2-methylpentane (xvi) 3-Formylpentanoic acid
(xvii) 2,4-Dinitro benezamine
3. (i) 3-chloroprop-1-ene (ii) butane-1,2,3-triol
(iii) 2-Methoxy-2,3-dimethylbutanal (iv) 3-Formyl-2-methylproanoic acid
(v) 2-Ethyl-3-hydroxy-2-methyl propanal (vi) Ethyl-(2-oxo) propanoate
(vii) 1-Methoxy-2-3,-butanedione (viii) Formylmethanoic acid
(ix) N-Chloro-N-ethyl methanamide (x) 2-Ethyl-butane-1,4-dinitrile
4. (i) 1-Ethoxy-3-methoxypropane (ii) 2-Amino-3-hydroxypropanal
(iii) N-Ethyl ethanamide (iv) Pent-3-en-1-yne
(v) 2-Hydroxypropanoic acid

Nomenclature of substituted benzene compounds


Benzene is a six membered cyclic compound with alternate single and double bonds. It is
represented in any one of the following ways:

or
(i) Naming of monosubstituted benzene
It is derived by adding the name of the substituent with the word benzene.

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GENERAL ORGANIC CHEMISTRY (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021
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Substituent + benzene → substituted benzene
CH3 Br NO2

Example:
methylbenzene bromobenzene nitrobenzene
Special names of some monosubstituted benzene compounds
Molecular formula Structural formula IUPAC name Special name
CH3
C6H5CH3 methylbenzene Toluene

NH2
C6H5NH2 benzenamine Aniline

OH
C6H5OH phenol Phenol

C6H5CHO CHO Benzene Benzaldehyde


Carbaldehyde

C6H5COOH Benzene Benzoic acid


COOH
Carboxylic acid

C6H5OCH3 OCH3 methoxybenzene Anisole

If the functional group is attached to the carbon chain connected to benzene ring, then
benzene ring is considered as substituent and is prefixed before the root word as phenyl.
Example: CH CH CHO CH CH Cl
2 2 2 2

3-phenylpropanal 2-phenylchloroethane
(ii) Naming of disubstituted benzene
(a) If the substituents are same: In such case, the relative position of the substituents
must be indicated by adding the symbols o − (1, 2) ; m − (1, 3) ; p − (1, 4).
X o-ortho : positions 2, 6
1 m-meta : positions 3, 5
6 2
p-para : positions 1, 4
5 3
4
In the trivial system of nomenclature, the terms ortho(o), meta(m) and para(p) are used as
prefixes to indicate the relative positions 1, 2-; 1, 3 and 1, 4-respectively.

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Cl NO2 SO3 H
Cl

Example: NO2
SO3 H
1,2-dichlorobenzene 1,3-dinitrobenzene 1,4-benzenedisulphonic acid
(or) o-dichlorobenzene (or) m-dinitrobenzene (p-benzenedisulphonic acid)
(b) If the two substituents are different, they are named in the alphabetical order.
I Cl

NO2
Br
1-bromo-4-iodobenzene 1-chloro-3-nitrobenzene
(or) p-bromoiodobenzene (or) m-chloronitrobenzene
(c) If there are more than two substituents: The numbering is done in such a way that it
satisfies the lowest sum rule.
Cl 1 COOH
3

CH3 2
1
2 Cl 4 3
Br NO2
1-bromo-3-chloro-2-methylbenzene 4-chloro-3-nitrobenzoic acid

Nomenclature of Bicyclo compounds


(i) Bicyclo compounds contain two fused rings with the help of a bridge. We use the name of
the alkane corresponding to the total number of carbon atoms as the base name. The
carbon atoms common to both the rings are called bridge heads, and each bond or chain
of atoms connecting the bridgehead atoms called a bridge.
(ii) While naming the bi-cycloalkane we write an expression between the word bicyclo and
alkane (in square bracket), that denotes the number of carbon atoms in each bridge. The
numerals are written in descending order and the numbers are separated by a point.
(iii) If substituents are present, we number the bridged ring system beginning at one bridge
head, proceeding first along the longest bridge to the other bridge head, then along the
second next longest bridge back to first bridge head. The shortest bridge is numbered in
the last.
Example:
Bridge head
One carbon bridge
CH2 1
CH2 CH2
(1) Two carbon bridge { CH CH2
CH
}Two carbon bridge 2

3
7
6

5
Bicyclo [2, 2, 1] heptane
It's common name is norborane
2 2
CH 4

Bridge head

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7
(4)
(2) (3) 4 6

1 5
3
2
Biyclo [4.1.0] heptane Bicyclo [2.2.1] hept-2-ene Bicyclo [3.2.2] nonane
1 7 1 2

7
2 (6) CH2 CH CH2
6 3
(5) CH2
5 8 CH3 8CH
3
4
CH2 CH CH2
6 5 4
Bicyclo [2.2.2] octa-2,6-dione 8-Methylbicyclo [3.2.1] octane

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Isomerism
The existence of two or more compounds with the same molecular formula but different
physical and chemical properties is known as isomerism and the molecules themselves called
as isomers.
The term was given by Berzelius. The difference
in properties of the two isomers is due to
difference in the arrangement of atoms within
their molecules.

Isomerism is mainly classified into structural isomerism and stereoisomerism.


1. Structural isomerism
It is due to the differences in structures of the isomers. Structural isomerism is further
classified into 5 types.
(i) Chain isomerism (nuclear isomerism)
Compounds with same molecular formula but differ in the arrangement and number of
carbon atoms within the molecule are called chain isomers and the phenomenon as chain
isomerism.

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DIFFERENCES BETWEEN CHAIN ISOMERS


Chemical properties- Isomers show similar chemical properties because the same
functional group is present.
Physical Properties- such as density and boiling point show trends according to the of
the degree of branching
Boiling Point of straight chain isomers have higher values than branched ones the
greater the degree of branching the lower the boiling point branching decreases the
effectiveness of intermolecular forces less energy has to be put in to separate the
molecules

For example,
(i) Butane (C4H10) has two isomers – normal butane and isobutene. One isomer has a straight
chain and the other has a branched chain.
CH3−CH2−CH2−CH3 CH3−CH−CH3
|
n−butane CH3
isobutane
(ii) cyclohexane and methylcyclopentane are nuclear isomers.
CH3
CH2 |
CH
CH2 CH2
CH2 CH2
CH2 CH2
CH2 CH2 CH2

cyclohexane methylcyclopentane
(iii) C5H12 has three chain isomers.
CH3
CH3CH2CH2CH2CH3 CH3CH2 − CH − CH3 CH3 − C − CH3
CH3 CH3
n−pentane Isopentane neopentane

(iv) C4H9NH2 also shows two chain isomers.


CH3
CH3CH2CH2CH2NH CH3 C − NH2
2 CH3

n−butylamine tert.butylamine

Solve 1- How many chain isomers does butane have?


CH3−−CH 2CH 2 = CH 2 CH3−−C = CH 2
CH 3
n − Butylene (1 − Butene ) CH 3
Isobutylene ( 2-Methylpropene ) CH 2 CH 2 CH3 CH−−CH 3

Solve 2 - How many chain isomers does propyl benzene have?

n − Propylbenzene Isopropylbenzene

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(ii) Functional isomerism


Compounds with same molecular formula but differ in functional groups are called functional
isomers and the phenomenon is known as functional isomerism.
For example

• Diethyl ether butyl alcohol both has the molecular formation C4 H6 O, but contains different
functional groups.
C2 H5 − O − C2 H 5 C4 H9 − OH
diethyl ether butyl alcohol
Thus, functional group in diethyl ether is ( −O − ) , while is butyl alcohol it is ( −OH ) .

• Acetone and propionaldehyde both with the molecular formula C3 H 6 O are functional isomers.
CH3 − CO − CH3 CH3 − CH 2 − CHO
acetone acetaldehyde
In acetone the functional group is ( −CO − ) , while in acetaldehyde it is ( −CHO )

• Cyanides are isomeric with isocyanides;


RCN RNC
Alkyl cyanide Alkyl isocyanide

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• Carboxylic acids are isomeric with esters.


CH3CH 2COOH CH3COOCH3
Propanoic acid Methyl ethnoate
• Nitroalkanes are isomeric with alkyl nitrites:
O
R−− N R−−O −−N = O
O Alkyl nitrite
Nitroalkane

• Sometimes a double bond containing compound may be isomeric with a triple bond containing
compound. This also is called as functional isomerism. Thus, butyne is isomeric with butadiene
(molecular formula C 4 H 6 ).
CH3 − CH 2C  CH CH 2 = CH − CH = CH 2
1 – Butyne 1, 3 – Butadiene
• Unsaturated alcohols are isomeric with aldehydes. Thus,
CH 2 = CH − OH CH3CHO
Vinyl alcohol Acetaldehyde
• Unsaturated alcohols containing three or more carbon atoms are isomeric to aldehydes as well
as ketones:
CH 2 = CH − CH 2OH CH3CH 2CHO CH3COCH3
Allyl alcohol Propionaldehyde Acetone
• Aromatic alcohols may be isomeric with phenols
CH 2 OH CH 3
OH

Benzyl alcohol o − Cresol


• Primary, secondary and tertiary amines of same molecular formula are also the functional
isomers.
CH3−− N−−CH3
CH3CH 2CH 2 NH 2 CH3 − NH − C2 H5
n-propylamine (1o) Ethylmethyla min (2o) CH 3
Trimethylamine ( 3)
• Alkenes are isomeric with cycloalkanes:

CH3CH 2CH = CH 2 CH 3
Butene
Cyclobutane
Methycyclopropane
• Such isomers in which one is cyclic and other is open chain are called ring-chain isomers. Alkynes
and alkadienes are isomeric with cycloalkanes.
CH3CH 2C  CH CH 2 = CH −−CH = CH 2
1 − Butyne 1,3 − Butadinene

Cyclobutene

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(iii) Position isomerism
Compounds which have the same structure (arrangement) of carbon chain (carbon
skeleton) but differ in the position of the multiple bond or the functional group are
called position isomers and the phenomenon is known as position isomerism.
Thus the following compounds can exhibit position isomerism:
(a) Alkenes (b) Alkynes (c) Arenes d) Alkyl halides
(e) Aryl halides (f) Alcohols (g) Amines and h) Nitro compounds
a) Alkenes containing four or more carbon atoms can exhibit position isomerism due to the difference in the
position of double bond on the same carbon skeleton, For example:

i) CH3CH2CH = CH2 CH3CH = CHCH3


But-1-ene But-2-ene
ii) CH3CH2CH2CH = CH2 CH3CH2CH = CHCH3
Pent-1-ene Pent-2-ene
iii) CH3CH2CH2CH = CH2 CH3CH2CH2CH = CHCH3
Hex-1-ene Hex-2-ene
CH3CH2CH = CHCH2CH3
Hex-3-ene
b) Alkynes containing four or more carbon atoms can exhibit position isomerism due to the difference in the
position of triple bond on the same carbon skeleton. For example:
i) CH3CH2 C  CH CH3C  CCH3
But-1-yne But-2-yne
ii) CH3CH2CH2C  CH CH3CH2C  CCH3
Pent-1-yne Pent-2-yne
c) Arenes containing eight or more carbon atoms exhibit position isomerism due to the difference in the
position of alkyl groups on the benzene ring. For example:
i)
CH3 CH
3 CH 3

CH3

CH 3

CH 3

o – Xylene m – Xylene p - Xylene


ii)
CH3 CH3 CH3

CH3 CH3

H3 C CH3
CH3
CH3

1, 2, 3 – Trimethyl benzene 1,2,4– Trimethylbenzene 1, 3, 5 – Trimethylbenzene


(hemimellitene) (pseudocumene) (mesitylene)

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d) Alkyl halides containing three or more carbon atoms can exhibit position isomerism due to the difference in
the position of halogen atom on the same carbon skeleton. For example
i) C3H7Cl has two position isomers:
CH3CH2CH2Cl CH3 − CH− CH3
|
1 – Chloropropane Cl
2 – Chloropropane
ii) n – Pentane on monochlorination gives three isomeric chloropentanes:
CH3CH2CH2CHCH3 CH3CH2 CHCH2CH3
CH3CH2CH2CH2CH2Cl | |
Cl Cl
1 – Chloropentane 2 – Chloropentane 3 – Chloropentane
Polyhalogen derivatives containing two or more carbon atoms can also exhibit position isomerism. For example:
CH3CHCl2 1, 1 – Dichloroethane ClCH2CH2Cl 1, 2 – Dichloroethane
e) Aryl halides containing two or more benzene rings can exhibit position isomerism due to the difference in
the position of halogen atom. For example:
Cl
Cl

1 – Chloronaphthalene 2 – Chloronaphthalene
Polyhalogen compounds containing just one benzene ring can also exhibit position isomerism. For example:
Br
Br
Br

Br Br
Br
1, 2 – Dibromobenzene 1, 3 – Dibromobenzene 1, 4 – Dibromobenzene

f) Alcohols containing three or more carbon atoms exhibit position isomerism due to the difference in the
position of functional group ( −OH). For example :
i) The molecular formula C3H8O represents two isomeric alcohols:
CH3CH2CH2OH CH3CHCH3
|
OH
Propan-1-ol Propan-2-ol
ii) Four monohydric alcohols differing in the position of – OH group can be derived from isopentane:
OH
CH3CH− CH2CH2− OH |
| CH3CH− CHCH3
CH3 |
CH3
3 – Methylbutan-1-ol 3 – Methylbutan-2-ol
OH
| HO − CH2− CHCH2CH3
CHCCH |
3 2CH3
| CH3
CH3
2 – Methylbutan-2-ol 2 – Methylbutan-1-ol
g) Primary amines (RNH2) containing three or more carbon atoms can exhibit position isomerism due to the
difference in the position of amino group on the same carbon skeleton. For example:
NH2
|
CH3CH2CH2NH2 CH3 − CH − CH3
1 – Aminopropane 2 – Aminopropane

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h) Nitro compounds (RNO2) containing three or more carbon atoms can exhibit position isomerism due to the
difference in the position of nitro group on the same carbon skeleton. For example:
CH3 CHCH2CH3
|
CH3CH2CH2CH2NO2 NO2
1-Nitrobutane 2-Nitrobutane

(iv) Metamerism
Here two or more different compounds having the same molecular formula but different number and
arrangement of carbon atoms on either side of the functional group is called metamerism. Such
compounds are known as metamers.
Metamerism is never possible in compounds possessing the univalent functional group.
Metamerism is due to the difference in the nature of alkyl groups attached to the same polyvalent
functional group such as −C−, −Ö̤ −, −S̤̈ −, −N̈H−, −N̈ −and − C− O − .
|| |
O
||
O

Metamerism is exhibited by compounds of the same homologous series.


a) Ethers, R–O–R, exhibit metamerism due to difference in the nature of the alkyl groups
attached to the oxygen atom. Thus, the molecular formula, C4H10O, represents the following
metamers:
CH3CH2 − O − CH2CH3 CH3 − O − CH − CH3 CH3 − O − CH2CH2CH3
|
CH3
O
||
b) Ketones, R − C − R , exhibit metamerism due to the difference in the nature of the alkyl groups
attached to the carbonyl group. Thus, the molecular formula, C5H10O, represents the following
metamers:
O O O
|| || ||
CH3 − C − CH2CH2CH3 , CH3 − C − CHCH3 , CH3 − CH2 − C− CH2 − CH3
|
CH3

c) Thioethers, R–S–R, exhibit metamerism due to the difference in the nature of the alkyl groups
attached to the sulphur atom. Thus, the molecular formula, C4H10S, represents the following
metamers:
CH3 − S − CH2CH2CH3 CH3 − CH2 − S − CH2 − CH3 CH3 − S − CH − CH3
|
CH3

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d) Secondary and tertiary amines exhibit metamerism due to the difference in the nature
|
of the alkyl groups attached to the – NH – group and the − N− atom respectively. Thus
the molecular formula, C4H11N, represents the following metamers:
CH3CH2 − NH − CH2CH3 CH3 − NH − CH2CH2CH3 CH3 − NH − CH − CH3
|
CH3
O
||
e) Esters, R − C − O − R , exhibit metamerism due to the difference in the nature of the alkyl
O
||
groups attached to the − C− O − group. Thus, the following esters are metamers:
O O
|| ||
CH3CH2 − C− O − CH3 CH3 − C− O − CH2CH3
Note- If same polyvalent functional group is present in two or more organic compounds, then
instead of chain or position isomerism, treat the phenomenon as metamerism.
(i) Pentan – 2- one and pentan – 3- one are metamers and not position isomers. They can be
included in position isomerism, if metamerism is not mentioned.
(ii) Similarly, pentan – 2- one and 3 – methylbutan-2-one are metamers and not chain isomers.
Metamers may be considered as position isomers. For instance, pentan – 2- one and penta-3-
one may be regarded as position isomers as well as metamers.

(v) Tautomerism
Here a single compound exists in two readily interconvertible structures that differ in
position of hydrogen atom. Tautomer exhibits dynamic equilibrium with each other.
A very common form of tautomerism is that between a carbonyl compound containing an  -
hydrogen and its enol form. This type of isomerism is also known as keto−enol isomerism.
R' R' O OH
H O
R − C − C − R'' R − C = C − R" O H
H CH3 C CH3 CH3 C CH2
H O O−H
keto form enol form
Keto form Enol form
The percentage of enol form increases in the order simple aldehydes and ketones <
−keto esters < −diketones < −diketones having phenyl group < phenols. This
increase in the enol content is due to the fact that the enol form of the above type of
compounds is increasingly stabilized by resonance and hydrogen bonding than the
corresponding keto form.

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(vi) Ring – chain isomerism


The phenomenon of existence of two or more compounds having the same molecular formula
but possessing open chain and closed chain (cyclic structure) is called ring – chain isomerism.
This type of isomerism arises due to different modes of linking of carbon atoms. Thus ring-
chain isomers possess open chain or closed chain structures as illustrated by the following
examples:
i) Two ring-chain isomers are possible corresponding to the molecular formula C3H6:

CH3CH = CH2 and

Propene Cyclopropane
ii) Six pairs of ring-chain isomers are possible for the molecular formula C4H8:
CH3CH2CH = CH2 and
Me
CH3CH2CH = CH2 and

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CH3CH = CHCH3 and


CH 3
CH3CH = CHCH3 and

CH3 − CH = CH2
| and
CH3
CH3 − CH = CH2 CH 3
| and
CH3
iii) The molecular formula C3H4 represents the two ring – chain isomers:

and
CH3 – C  CH
Ring chain isomerism, can be included in functional isomerism, if not considered separately.

Concepts in organic reaction mechanism


The organic reactions involve the breaking of covalent bonds in the reacting molecules and
formation of new bonds to give product molecules
The organic molecule which reacts with attacking reagent is called substrate. In multistep
organic reactions, substrate react with reagent and leads to the formation of one or more
reaction intermediates. The general reaction path involving the formation of one reaction
intermediate is depicted as follows.

Organic molecule + attacking reagent [reaction intermediate] product(s) + byproduct (s)


(substrate)
Substrate + Reagent ⎯⎯→ Intermediate ⎯⎯→ Products
(Transition state)

Fission or Cleavage of covalent bond


The fission of covalent bond can take place in two ways depending on the nature of covalent
bond, nature of attacking reagent and conditions of the reaction.
Like other chemical reactions, organic reactions are also a process of bond breaking and bond
making. A covalent bond between two atoms can be broken in essentially the following ways:
R. .
X
R:X R : X
-

R :X-
1) Homolytic cleavage (Homolytic fission)
“In this type of fission bond breaks symmetrically and each fragment formed gets an odd
electron from the shared bond pair electrons”.
This cleavage results in the formation of
specie(s) with unshared electron called free
radicals. It is also known as free radical cleavage
or non-polar bond fission. The homolytic fission of a sigma () bond is shown as follows.
A – B ⎯⎯→ A• + B•

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Cl Cl 2 Cl
Cl Cl
sunlight
2 Cl
. free radical
chlorine
chlorine free radical
heat or light
R
. +
.
R X X
heat or light .
alkylRradical +
.
R X X
halogen radical
alkyl radical halogen radical
The free radicals contain unpaired electron (with odd number of electrons), electrically
neutral and paramagnetic.

The conditions favorable for homolytic cleavage are


• The difference in electro negativity between A and B is less or zero.
• Homolysis takes place in gaseous phase or in the presence of non polar
solvents(CCl4, CS4), peroxide, UV light, high temperature (≥5000C),
electricity and free radical.

2) Heterolytic cleavage (Heterolytic fission)


In this type of cleavage, covalent bond breaks asymmetrically & one of the two species
gets both the electrons and other loses resulting in the formation of ions. Heterolytic
cleavage results in formation of electron deficient and electron rich fragments.
It is also known as ionic cleavage or polar bond or ionic fission.
The electron deficient fragment is called electrophile
while electron rich fragment is known as nucleophile.
In case of organic compounds, if positive charge is
present on the carbon then cation is termed as
carbocation. If negative charge is present on the
carbon then anion is termed as carbanion. The
heterolytic fission is shown below
[Electronegativity of A is greater than B]
_
A - B ⎯⎯
→ A : + B+
[Electronegativity of B is greater than A]
_
A - B ⎯⎯
→ A+ + B :

H Br H
+
+
..
Br
electrophile nucleophile

CH3 Br
+
CH3 + Br
..
electrophile nucleophile
Both electrophile and nucelophile contain even number of electrons, influenced by strong
electrical field as they possess positive or negative charge and they are diamagnetic.
• The factor which favors heterolysis is greater difference of electro
negativities between A and B.
• The energy required for heterolysis is always greater than that for
homolysis due to electrostatic forces of attraction between ions.
• Low temperature
• Polar nature of substrate and attacking reagent
• Presence of acid or base catalyst

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Reaction intermediates
Highly reactive, short lived and energetic intermediate formed in multistep organic
reactions by the action of reagent on substrate and readily transformed into product(s)
is called reaction intermediate.
The important reaction intermediates are free radicals, carbocations, carbanions, carbenes,
benzyne and nitrenes.
(i) Carbocations or Carbonium ions
A reaction intermediate formed by heterolytic fission of a covalent bond which contains
one positively charged carbon with three bond pair electrons (sextext of electrons) is
called carbocation.
For example,
CH 3+ ,CH 3 CH 2+ ,(CH 3 CH 2 )2 CH + ,(CH 3 )3 C + et c.
+ –
C X C +X

Formation of carbocations:
(i) (CH3)3CCl ⎯⎯→ (CH3)3C+ + Cl− (Heterolytic fission)
+
(ii) CH3 – OH ⎯⎯→
H
CH3 – OH2+ (Protonation)
_
H 3C Br ⎯⎯⎯
FeBr3

→ CH 3+ + F eBr 4 (Abstraction of halide ion by Lewis acid)

+
H 3C N (Removal of N2 from diazonium cation)
⎯⎯→ CH 3+ + N 2
N

The carbocations are classified into different groups depending upon the nature of carbon
bearing the positive charge. Alkyl carbocations may be primary (1), secondary (2) or
tertiary (3) carbocations.
+ + + +
CH3 CH3 CH2 CH3 CH CH3 CH3 C CH3
methyl ethyl iso propyl CH3 tertiary butyl
carbocation carbocation carbocation carbocation
(1o ) (1o ) (2o ) (3o )
+
CH2
+ +
CH2 CH CH2 CH CH2
vinyl carbocation allyl carbocation beznyl carbocation
Structure of carbocation: The carbocations are electron deficient and contain six electrons
(three bond pair electrons). In strong electrical field, carbocations move towards cathode.
The carbocations have trigonal planar structure and the positively charged carbon in sp2
hybridized.
Rate of formation of carbocations:
More stable carbocation forms at faster rate as compared to less stable carbocation.
For example,
(i) R – CH2 – Cl ⎯⎯→ R – CH2+ + Cl−
(ii) R3C – Cl ⎯⎯→ R3C+ + Cl−
A tertiary carbocation is more stable, the transition state of tertiary carbocation is lower in
energy than transition state of primary carbocation. As a result, a tertiary carbocation will
form more rapidly than primary carbocation.

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Stability of carbocations:
➢ Electron deficient carbocations are stabilized by electron releasing group. Participation
of empty p-orbital in lateral overlap with completely filled orbital is the major
contributing factor for stability to stability in which positive charge is delocalized.
Alkyl group directly bonded to the positively charged carbon stabilize the carbocations
due to inductive and hyperconjugation effects. The dispersal of the positive charge due to
hyperconjugation stabilize the carbocation. The observed order of carbocation stability is
(C6H5 )3 C+  (C6H5 )2 CH+  C6H5 CH2+  CH2 = CH − CH2+  3  2  1  CH3+
+ + + +
CH3 C CH3 > CH3 CH CH3 > CH3 CH2 > CH3
CH3 o
2o 1
3o
➢ The reaction intermediates are highly reactive, usually order of reactivity of such
intermediates is reverse that of its stability. Therefore, order of reactivity of
+
carbocations follows the sequence: CH3  1  2  3
➢ Electron attractors (−I effect) increases the postive charge on carbon atom and thus
reduces the stability of carbocation, e.g.𝑂2 𝑁 − 𝐶𝐻2 − 𝐶𝐻2+ , 𝐶𝑙 − 𝐶𝐻2 − 𝐶𝐻2+ .]
➢ Carbocation are sp2 hybridized and have trigonal planar structure, so the attacking
species can approach both from top and bottom.
➢ Hybridized state of carbon:
Higher the s-character, lesser the stability. The order of stability is
+
+ + +
CH3 CH2 > CH2 CH < > CH C

➢ Resonance: The greater the delocalization of positive charge of carbocations, higher is


the stability. The stability of benzyl carbocation is comparable with allyl carbocation as
resonance energies is nearly the same
+
CH2
> +

➢ Carbocations, undergo rearrangement forming more stable carbocations.

H
..
H shift +
+

(ii) Carbanions
A reaction intermediate formed by heterolytic fission of a covalent bond which results
negatively charged carbon with eight electrons in its valence shell is called carbanion.
The heterolytic cleavage of a covalent bond as indicated inC the
X following
C – +X reactions gives +

carbanions.
O H O H

– + OH –
C X C +X H C C H H C C + H2O
H H

For example, CH ,CH3 CH ,(CH3 )2 CH ,CH CHO etc.



3

2
− −
2
O H O H
Formation of carbanion: OH –

H
H C −C base H C C +HO
(i) CH3 – CHO + OH ⎯⎯⎯ → CH2− − CHO + H2O
2

H H
(ii) C2H5O− + CH3 − COOC2H5 ⎯⎯→CH2− − COOC2H5 + C2H5OH

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The carbanions are classified as primary (1), secondary (2) and tertiary (3) depending upon
the nature of carbon bearing negative charge.
.. .. ..
CH3 C CH3 CH2 CH
CH3
o o phenyl carbanion
tertiarybutyl carbanion (3 ) vinyl carbanion (1 )
Structure of carbanion: The carbanions are electron rich with complete octate configuration.
Shape of alkyl carbanion is usually pyramidal like ammonia when carbon atom carrying the
negative charge is sp3 hybridised.
In contrast, carbnions which are stabilised by resonance are planar and carbon atom carrying
negative charge is sp2 hybridised. The vinyl carbanion, phenyl carbanion and cyclopentadiene
carbanion are sp2 hybridised where as acetylide carbanion is sp hybridised.
sp3
sp 2
H 2C C HC C
C
H
H H
H
P yr a m ida l P la n a r Lin ea r
(I) (II) (III)

St a bilit y order III  II  I

Stability of carbanions:
➢ Alkyl group bonded to negatively charged carbon increases the intensity of negative
charge due to +I effect and destabilize the carbanion. The order of stability of alkyl
carbanions is:
.. .. .. >
..
CH3 > CH3 CH2 > CH3 CH CH3 CH3 C CH3
CH3
methyl
carbanion 1° 2° 3°
➢ The order of reactivity of carbanions is reverse that of its stability. Therefore, order
..
of reactivity of carbanions follows the sequence: 3o > 2o > 1o > CH3
➢ Higher the s character greater the stability of carbanion. Order of stability is
.. .. .. ..
HC C > > CH2 CH > CH3 CH2

➢ Resonance: Greater the delocalisation of negative charge by resonance, higher the


stability. The stability of benzyl carbanion is comparable with allyl carbanions.
CH2
..
> CH2 CH2 CH2

(iii) Free radicals


A reaction intermediate formed by the homolytic cleavage of a covalent bond which
contains an unpaired electron is called free radical.
The homolytic cleavage is favored for nonpolar covalent bond. Such cleavage for bond is
initiated by the action of heat, light or a reagent.
For example, CH•3 ,CH 3 CH•2 ,(CH 3 )2 CH• ,CH 2 = CH - CH •2 ,C 6 H 5CH •2 et c.

Cl Cl
light
2 Cl
.
homolysis
chlorine radical

. light .
CH3 H + Cl CH3 + HCl
methane homolysis
reagent
methyl radical

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Depending upon nature of carbon atom carrying the unpaired electron, free radicals are also
classified as primary (1), secondary (2) and tertiary (3) free radicals.
. . .
CH3 CH3 CH2 CH3 CH CH3

methyl radical (1o ) ethyl radical (1o ) iso propyl radical (2o )
.
. . CH2
CH3 C CH3 CH2 CH CH2
CH3
tertiary butyl radical (3o ) allyl radical (1o ) benzyl radical (1o )

Structure of free radical: The free radicals are electron deficient since they contain seven
electrons on carbon atom. They are electrically neutral and paramagnetic. The structure of
alkyl radical is not known with certainty. For alkyl radicals two possible structures have been
proposed. The first is a planar sp2 hybridised radical similar to a carbocation. The second one
is a pyramidal sp3 hybridised radical similar to a carbanion.
• Resonance stabilised free radicals such as allyl radicals and benzyl radicals are planar sp2
hybridised.
• The bridge head free radicals are pyramidal (sp3-hybridised) because they cannot assume
planar geometry due to angle strain. Further, the free radicals in which carbon is bonded
to highly electronegative atoms are pyramidal.
.
. CF3
.
bridge head radical (sp3-hybridised) trifluoromethyl radical
(sp3-hybridised)
Stability of free radicals: The relative stability of alkyl free radicals is explained on the
basis of hyperconjugation and inductive effects. Greater the number of alkyl groups attached
to the carbon atom carrying unpaired electron, higher the delocalisation and hence more stable
is the alkyl radical. The order of stability of a few alkyl radicals is given below
. . . .
CH3 C CH3 CH3 CH CH3 CH3 CH2 CH3
CH3
t-butyl radical (3o) iso propyl radical (2o) ethyl radical (1o) methyl radical (1o)
The order of stability of free radicals on the basis of resonance inductive effect is as follows:
(C 6 H 5 )3 C• > (C 6 H 5 )2 CH• > C 6 H 5• > CH 2 = CH CH •2 > 3° > 2° >1° > CH •3

Like carbocations and carbanions, free radicals are highly reactive and short-lived
intermediates because of the strong tendency of the carbon atom carrying the unpaired
electron to acquire one more electron from an atom or a group to complete its octate. The

reactivity of alkyl radical is reverse the order of stability CH3  1  2  3
The allyl and benzyl radicals are stabilised by resonance. The stability of allyl and benzyl
radicals is comparable.
.
CH2 .
> CH2 CH CH2

The allyl or benzyl radicals are more stable than alkyl radicals.

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The reactions involving free radicals are
(i) catalysed by light, heat etc.
(ii) proceed in vapour phase or in non polar solvents.
(iii) autocatalytic.

(iv) Carbenes
They are neutral and highly reactive species generally obtained by successive elimination of an
electrophile and a nucleophile from the same carbon atom (-elimination). The carbon atom of
carbene has six electrons in valence shell, out of which two constitute unshared electrons and
two bond pair electrons. So they are divalent carbon species containing two unshared electrons
and electrically neutral.
Carbenes exist in two possible forms
(i) Singlet
(ii) Triplet
(i ) Sin glet (ii ) Tr iplet
H
C
H C H
H
sp 2 h ybr idized sp h ybridized
Two elect r on s a r e Two elect r on s a r e in
in sa m e or bit a l t wo differ en t or bit a ls
(spin pa ir ed ) (spin fr ee)

O
. . . . .
H C. H R C. H Cl C
. H R C C. H Cl C. Cl
carbene alkyl carbene chloro carbene acyl carbene dichloro carbene

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Attacking Reagents
The organic reactions proceed by the attack of highly reactive reagents on the substrate molecule.
These reagents are called attacking reagents which may be electron deficient or electron rich. They
are classified into two groups.
Electrophiles
The electron deficient molecules or positively charged ions which are capable of accepting an
electron pair from substrate molecule are called electrophiles.
These species act as Lewis acids and attack the electron rich centre of the organic molecules.

C..
+
+ E C E
substrate electrophile
They are of following types,
(i) Positively charged: The species having a positive charge, e.g.
H+ ,CH3+ ,NO2+ ,H3O + ,NO + ,Br + ,CH3CO + etc .
(ii) Neutral: The molecules containing electron deficient atom (i.e. Lewis acids) e.g. :CH2, AlCl3,
BF3, ZnCl2, FeCl3, SO3, etc.
(ii) Ambident: Molecules with 2 electrons deficient centers,
e.g. , -unsaturated carbonyl compounds.
It may be noted that all the positively charged species do not act as electrophiles. The positively
charged species which can accept an electron pair can act as electrophiles. The positively charged ions
+ + + 2+
such as H3 O, N H4 , Na, C a , etc. do not act as electrophile as they cannot accept electron pair, since all
the ions have an octet configuration.

Nucleophiles
The molecules or negatively charge ions which are capable of donating an electron pair
to electron deficient centre of the substrate are called nucleophiles.
These species act as Lewis bases & attack on electron deficient centre of organic molecule.
..
C+ + Nu C Nu

substrate nucleophile

The common examples of nucleophiles are given below:


(i) Negatively charged: The species having a negative charge, e.g. Cl−, Br−, OH−, CN−, NO2− etc.
(ii) Neutral: The molecules having an unshared pair of electrons (i.e. Lewis base),
.. .. .. .. ..
e.g. 𝑁𝐻3 , 𝑅 − 𝑁𝐻2 , 𝑅2 − 𝑁𝐻, 𝐻2 𝑂, 𝑅 − 𝑂 − 𝐻 𝑒𝑡𝑐.
.. ..
.. .. .. .. ..
(iii) Ambident: The molecule with two electron rich centres, e.g. − C  N,N
.. = O, O  N− O etc.
Comparison between Nucleophiles and electrophiles
Nucleophiles Electrophiles
• Electron rich, donate electron pair, generally • Electron deficient, accept electron pair, generally
anions. cations
• Act as Lewis bases • Act as Lewis acids
• Attack an region of low electron density of • Attack on region of high electron density of
substrate substrate
..
• They are represented by a general symbol ( Nu ) • They can be represented by a general symbol (E+)

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Electron Displacement Effects in Covalent Bonds


The electron pair displacement in organic molecules takes place under the influence of a
hetero atom/group or by the attacking reagent. The displacement or shift of electron pair in
the organic molecule under the influence of substituent makes the molecule permanently
polar.

(i) Inductive effect (I effect)


The inductive effect is defined as “the permanent displacement of sigma (σ) bond pair of
electrons towards more electronegative atom or group and as a result molecule becomes
permanently polar”.
Larger the displacement of σ bond pair electrons greater the polarity. Consider the carbon
chain in which terminal carbon is bonded to a chlorine atom. Since chlorine is more
electronegative bond pair of electrons are displaced towards chlorine.
𝐂 − 𝐂 − 𝐂 − 𝐂 is non polar
+ + + + −
C  C  C  C X

− − − − +
C  C  C  C Y

+3 +2 +1 −


C C C Cl order of intensity of I effect +3  +2   +

There are two types of Inductive effect,


a. Positive inductive effect (+I effect)
Here substituent (Y) releases electron pair away from itself. In other words,  bond pair
of electrons are displaced away from the substituent towards the C-chain.
When less electronegative atom is attached to carbon atom (i.e. electron donating group),
the inductive effect is called + I effect.

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electron releasing substituent

 +
C Y
− −− − +
+ I effect C3 C2 C1 Z
Electronegativity of Y or Z is less than carbon atom, so the Y or Z group releases electron and
gets a partial positive charge (i.e. +) and induces a partial negative charge (i.e. −) on C1. As we
move along the chain from C1 to C3, the partial negative charge decreases.
The examples of electron donating group are (CH3)3C, (CH3)2CH, CH3CH2, CH3 etc.
The order of electron releasing or releasing ability of substituent is given below.
O
.. .. o
C6 H5 O > C O > (CH3)3C > (CH3)2CH > CH3 CH2 > CH3 > D > H
phenate ion carboxylate ion 3oalkyl 2oalkyl 1oalkyl
+ I power in decreasing order with respect to the reference H

b. Negative inductive effect (−I effect)


Here, the sigma bond pair of electrons are displaced towards electron withdrawing
substituent (X) or away from the carbon chain.
More electronegative atom is attached to carbon atom (i.e. electron withdrawing group), the
inductive effect is called – I effect.
+
The examples of electron withdrawing group 𝑁𝑅3 , 𝑁𝑂2 , 𝐹, 𝐶𝑙, 𝐼, 𝑂𝐻 𝑒𝑡𝑐.
electron withdrawing substituent
+

C X
+ + + −
C3 C2 C1 Z I effect
Order of electron withdrawing ability (−I effect) of a few substituents is given below.

𝑵𝑯𝟑 > 𝑵𝑶𝟐 > 𝑪𝑵 > 𝑺𝑶𝟑 𝑯 > 𝑪𝑯𝑶 > 𝑪𝑶 > 𝑪𝑶𝑶𝑯 > 𝑪𝑶𝑪𝒍 > 𝑪𝑶𝑶𝑹 > 𝑪𝑶𝑵𝑯𝟐 > 𝑭 > 𝑪𝒍 > 𝑩𝒓 > 𝑰 > 𝑶𝑯 > 𝑶𝑹 > 𝑵𝑯𝟐 > 𝑪𝟔 𝑯𝟓 > 𝑯
–I power of groups in decreasing order with respect to the reference H

Applications of inductive effect:


(i) Magnitude of +ve and -ve charges: can be compared by + I or – I groups present in it.
• Magnitude of +ve charge 
1
 −I power of the group.
+ I power of the group

• Magnitude of −ve charge 


1
 +I power of the group.
− I power of the group

(ii) Reactivity of alkyl halide: + I effect of methyl group enhances – I effect of the halogen
atom by repelling the electron towards tertiary carbon atom.
CH 3 CH 3
H 3C C X  H3C CH X  CH 3 CH 2 X  CH 3 X
CH 3
Tertiary > Secondary > Primary > Methyl
(iii) Relative strength of the acids:
(a) Any group or atom showing +I effect decreases the acid strength as it increases the
negative charge on the carboxylate ion which holds the hydrogen firmly. Alkyl groups have + I
effect. Thus, acidic nature is, HCOOH  CH 3 COOH  C2 H 5 COOH  C3 H7 COOH  C4 H 9 COOH
+I effect increases, so acid strength decreases
Formic acid, having no alkyl group, is the most acidic among these acids.

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(b) The group or atom having – I effect increases the acid strength as it decreases the
negative charge on the carboxylate ion. Greater is the number of such atoms or groups (having
– I effect), greater is the acid strength.
Thus, acidic nature is, CCl3 COOH  CHCl 2 COOH  CH 2 ClCOOH  CH 3 COOH
Trichloro Dichloro Monochloro Acetic acid
acetic acid acetic acid acetic acid

(– Inductive effect increases, so acid strength increases)


(c) Strength of aliphatic carboxylic acids and benzoic acid
R COOH C6 H 5 COOH
 
+ I group − I group

Hence benzoic acid is stronger acid than aliphatic carboxylic acids but exception is formic
acid. Thus, HCOOH > C6 H 5 COOH > RCOOH
Acid strength in decreasing order
As compared to water, phenol is more acidic (–I effect) but methyl alcohol is less acidic (+I
effect).
OH  H − OH > CH 3 OH
Phenol Water Methyl alcohol

(vi) Relative strength of the bases (Basic nature of −𝑵𝑯𝟐 )


The difference in base strength in various amines can be explained on the basis of
inductive effect. The +I effect increases the electron density while –I effect decreases it.
The amines are stronger bases than NH 3 as the alkyl groups increase electron density on
nitrogen due to + I effect while ClNH2 is less basic due to –I effect. “So more is the tendency
to donate electron pair for coordination with proton, the more is basic nature, i.e., more is the
negative charge on nitrogen atom (due to +I effect of alkyl group), the more is basic nature”.
Thus, the basic nature decreases in the order; (C 2 H 5 )2 NH  CH 3 CH 2 NH 2  CH 3 NH 2  NH 3  ClNH2
Diethyl Ethyl Methyl Ammonia Chloro
amine amine amine amine

The order of basicity is as given below;


Alkyl groups (R–) Relative base strength
CH3 R 2 NH > RNH2 > R 3 N > NH3
C2 H5 R 2 NH > RNH2 > NH3 > R 3 N
(CH3 )2 CH RNH2 > NH3 > R 2 NH > R 3 N
(CH3 )3 C NH3 > RNH2 > R 2 NH > R 3 N
(vii) Basicity of alcohols: The decreasing order of base strength in alcohols is due to +I effect
of alkyl groups. (CH 3 )3 COH  (CH 3 )2 CHOH  CH 3 CH 2 OH  CH 3 OH
(3 o ) (2 o ) (1 o )

(viii) Stability of carbonium ion: +I effect tends to decrease the (+ve) charge and –I effect
tends to increases the +ve charge on carbocation.
(CH 3 )3 C   (CH 3 )2 CH   CH 3 CH 2  CH 3

(ix) Stability of carbanion: Stability of carbanion increases with increasing – I effect.


CH 3−  CH 3 CH 2−  (CH 3 )2 CH −  (CH 3 )3 C −

(x). Dipole moment: Inductive effect produces dipole moment in a molecule. As this effect
increases (electronegativity difference increases) the dipole moment also increases.
CH3 − I  CH3 − Br  CH3 − Cl
1.648 D 1.79 D 1.83 D

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(ii) Resonance effect (R−effect) or Mesomeric effect


“The permanent polarity produced in the molecule by the shift of pi() or lone pair
electrons in the conjugate system creating electron deficient and electron rich centres
called resonance effect (R−effect).
The conditions required for M or R effect:
1. Molecule should be unsaturated with conjugated system (presence of alternate single and
double bond or heteroatom containing one or more lone pair electrons linked to multiple
bonded atom) of double bond.
1,3-butadiene, aniline, phenol, nitrobenzene, etc. In such systems,  or lone pair electrons are
delocalised and the molecule develops polarity.
2. Negative charge is in conjugation with double (or multiple) bond.
3. Lone pair of electrons in conjugation with double bond.
The reactivity of compounds is affected by the presence of groups like
NO2 , C  N, O , Cl, NH 2 etc.

The movement of  electrons from one end to the other end of the chain through a conjugated
system of double bond is observed in resonance effect. It is a permanent effect.
Depending upon the direction of shift of electron pair in conjugate system, R−effect is
classified into two types.
a. Positive resonance effect (+R effect / +M effect): In this effect, of electron pair
( or lone pair) moves away from the substituent or towards the conjugate system.
The +R effect in aniline as shown below.

.. ..
Substituents exert only +R effect as follows, −𝐂𝐥, −𝐁𝐫, −𝐈, −𝐍𝐇𝟐 , −𝐍𝐑𝟐 , −𝐎𝐇, −𝐎𝐑, −𝐒𝐇, −𝐎𝐂𝐇𝟑 , −𝐒𝐑
..
The substituent which exerts +R effect are called electron releasing groups.
The resonance effect in which resonance structure violates the octate rule should not be
considered. For example, structure (II) cannot be considered as resonance structure since it
violates the octate rule because oxygen has 10 electrons in the valence shell.
.. + ..
CH2 CH ..OCH3 X CH2 CH ..OCH3
I II
b. Negative resonance effect (−R effect / −M effect): isthe shift of  or lone pair
electrons is towards the substituent attached to the conjugate system. The electron
displacement depicted in nitrobenzene represents −R effect.
.. .. .. .. .. .. .. ..
O + O O + O +
O N O +
O N O +
O N O
N N

+ +

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𝑶
||
Substituents, which exert −R effect are given below. −𝑵𝑶𝟐 , −𝑪 ≡ 𝑵, −𝑪−, −𝑪𝑯𝑶, −𝑪𝑶𝑶𝑯, −𝑺𝑶𝟑𝑯, −𝑪𝑶𝑶𝑹
The substituent which exert −R effect is called electron withdrawn group. Resonance effect
provides explanation to least reactivity of haloalkenes and aryl halides towards nucleophilic
substitution reactions, acidic nature of phenols and carboxylic acids, mechanism of
electrophilic substitution reactions of benzene.
..
Substituents like N O , (phenyl) etc. exert both +R and −R effects.
➢ Resonance
• Delocalization of p-electrons in conjugation is known as resonance.
• When one structure is not sufficient to explain each and every property (chemical &
physical) then, a different structure has been drawn which is known as Resonating
Structure (canonical structure).
• All these structures contribute to the formation of a Real structure, known as
Resonating Hybrid.

or
(Actual Structure)
(resonating structures) (Resonance hybrid)
Condition for showing resonance:
(i) Molecule should be planar, nearly planar or a part of it is planar
(ii) Molecule should possess conjugated system.

Note:
They are not resonating structures rather they are tautomers.
➢ Resonating Structure
• Hypothetical structure existing on paper.
• The energy difference b/w different resonating structure is very small.
• All R.S. contribute towards the formation of resonance hybrid (Their contribution
may be different).
• A single R.S. can't explain each & every property of that particular compound.

Q. Draw the resonating structures:

Sol. (i)

(ii)

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•Resonance hybrid: It is a real structure that explains all the properties of a
compound formed by the contribution of different R.S.
It has got maximum stability as compared to any R.S.
• Resonance Energy: It is the difference b/w theoretical value of H.O.H &
experimental value. Or it can be defined as the difference b/w more stable R.S. &
R. H.
The more resonance energy, the more stable will be the molecule.
Resonance energy is an absolute term.
Note: Cyclohexane is thermodynamically more stable than benzene, even though the
resonance energy of benzene is more.
Contribution of different R. S. towards resonance hybrid:
• Non-polar R.S. contributes more than polar R.S.
Example: (a) CH2 = CH - CH = CH2 (b) CH2-CH = CH - CH2 (c) CH2 - CH = CH - CH2
Order of stability of given R.S. ⇒ a > b = c
• Polar R. S. with complete octet will contribute more as compared with the one with an
incomplete octet
CH3 - CH - OCH3 (Incomplete octet) CH3 - CH = :O - CH3 (Complete octet)
• In polar R. S. the -ve charge should be on more electro - ve atom & +ve charge should
be on more electro +ve atom.
Example:

(a) (more stable)

(b) (less stable)


• Compound with more covalent bonds will contribute more.
• Unlike charges should be closer to each other whereas like charges should be isolated.
• Extended conjugation contributes more than cross conjugation.

Example: < (Cross conjugation < Extended conjugation)

➢ Fries Rule:
• Compounds with more benzenoid structures are more stable.
• As the Resonance energy is greater than those in which lesser no. of benzenoid
structures are present.

• R. E. is <
• If a double bond is participating in resonance then it will acquire a partial single
bond character as a result of which bond length increases & bond strength
decreases.
• If a single bond is involved in resonance then it will acquire partial double bond
character. As a result of which bond length decreases & bond strength increase.

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Q. Find the order of Stability in the following:

(i)

(ii) (a) (b) (c) (d)

(iii)

(iv) (a) (b) CH2 - CH = F


Sol. (i) a = e > b = d > c
(ii) a > b > c > d, c and are in complete
(iii) +CCl3 < +CF3, due to back bonding in +CF3
(iv) a > b (stability)

Note:
When lone pair, as well as a double bond, is present in some atom then only p bond will be
participating in resonance. Whereas lone pair remains sp2 hybridized orbital. When an atom
has two or more than two lone pairs then only one lone pair will participate in resonance and
the other one remains in sp 2 hybridized orbital.

(iii) Hyperconjugation (No bond resonance)


The phenomenon of hyperconjugation is also known as Baker-Nathan effect as it was proposed
by Baker and Nathan. The hyperconjugation effect is much weaker compared to resonance
effect, yet it is quite useful is explaining relative stability, physical and chemical properties
of organic molecules.
This effect is extension of resonance in which C–H sigma () bond pair electrons are involved
in delocalization. It is a permanent effect in which electron releasing alkyl group bonded
to unsaturated system in which delocalization of electrons takes place through overlap
between C–H sigma () orbital and Pi() bond orbital or vacant p-orbital is known as
hyperconjugation.
The hyperconjugation is a stabilizing interaction. The delocalization of electrons by
hyperconjugation in propene molecule is depicted as in figure

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H (  conjugation) hyperconjugation

 bond orbital
H
C C
H C H
H
H

 bond
Orbital diagram showing hyperconjugation in propene
Propene molecule may be regarded as the resonance hybrid of the following hyperconjugative
structures (I – IV).
+
H H H H
.. + .. ..
H C CH CH2 H C CH CH2 H C CH CH2 H C CH CH2
+
H H H H
(I) (II) (III) (IV)
Since there is no bond between carbon and hydrogen atoms in these structures (II –IV),
hyperconjugation is also called no bond resonance. It may be noted that although a free proton
(H+) has been shown in the above structures, it is still bound firmly to the - cloud and hence
is not free to move.
Hyperconjugation effect in carbocations, let us take an example of ethyl carbocation
+
(CH3 − CH 2 ) , in which the positively charged carbon atom has an empty p orbital. One of the C–
H  bond orbital of methyl group align in the plane of empty p orbital and this bond pair
electrons delocalise into the empty p-orbital as shown in figure.
(  conjugation) hyperconjugation
H
sp3 s
 bond
H
+
C C
H H
H empty p-orbital
Orbital diagram showing hyperconjugation in ethylcarbocation
The overlap of completely filled C–H  bond orbital with empty p-orbital of carbocation
causes dispersion of positive charge and stabilize the carbocation. The ethyl carbocation is
resonance hybrid of following contributing structures.
+
H H H H
+ +
H C CH2 H C CH2 H C CH2 H C CH2
+
H H H H
(I) (II) (III) (IV)

In general, larger the number of -hydrogen atoms of alkyl groups attached to a


positively charged carbon atom greater the stability of carbocations.

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Applications of hyperconjugation effect:
1. Stability of alkenes: Larger the number of hyperconjugative structures higher the
delocalization of electron pairs and greater the stability of alkene. Number of
hyperconjugative structures is equal to number of -hydrogen atoms plus one.
More number of methyl groups attached to double bonded carbon atom more would be the
stability of alkene.
CH2 = CH2 < CH3 – CH = CH2 < (CH3)2 C = CH2
No hyperconjugation 3 hyperconjugation 6 hyperconjugation
structures structures structures
This order of stability is because of greater number of hyperconjugative contributing
structures causing larger delocalisation of -electrons solve and hence accounts for higher
stability of alkene.
CH 3 − CH = CH 2  CH 3 − CH 2 − CH = CH 2  CH 3 − CH − CH = CH 2
|
CH 3
Stability in decreasing order
2. Stability of carbonium ions: More, number of hyperconjugation structures of the
carbocation more will be its stability.
tert–butyl > isopropyl > ethyl
9 hyperconjugation 6 hyperconjugative 3 hyperconjugation
structures structures structures
3. Bond lengths: The bond length in a molecule change if there is hyperconjugation. In

C3H3 − C2H = C1H2 , the C1−C2 bond length is found to be more than 1.34 A (normal C = C bond

length) while the C2−C3 bond distance is less than 1.54 A (normal C – C bond length).
4. Directive influence of the group: +M effect of methyl group in toluene is due to
hyperconjugation.
H
H H H H H H
+ + +
H H H H H

Due to hyperconjugation, there are nine different structures having negative charge at ortho
and para positions. Hence, + M effect of alkyl group attached to benzene ring follows the
order: 𝐦𝐞𝐭𝐡𝐲𝐥 > 𝐞𝐭𝐡𝐲𝐥 > 𝐢𝐬𝐨𝐩𝐫𝐨𝐩𝐲𝐥 > 𝐭𝐞𝐫𝐭 − 𝐛𝐮𝐭𝐲𝐥.
In the same way, the meta directing influence and deactivating effect of –CCl3 group in
benzotrichloride can be explained on the basis of hyperconjugation as follows,
Cl
Cl Cl Cl Cl Cl Cl
- - -
Cl Cl Cl Cl Cl

Due to low electron density at ortho and para positions, the meta position becomes point
of high electron density, hence electrophilic substitution takes place in meta position.

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(iv) Electromeric effect (E effect)


The complete transfer or shift of  electron pair of a multiple bond to one of the bonded
atoms during the attack of positively or negativity attacking agents. As soon as the reagent is
removed, the molecule reverts back to original position.
𝐄 ⊕ −
𝐀=𝐁 → 𝐀 − 𝐁:
Reagent

Temporary polarization of the substrate molecule at the site of multiple bonds, by


complete shift of an  electron pair from one atom to the other under the influence of
attacking reagents.
H H H H
⎯⎯⎯⎯⎯⎯⎯
Reagent added
⎯⎯⎯⎯⎯⎯ →

+
C C
Re agent removed

H H H H
Depending upon the direction of displacement, E effect is also of two types.
• −E effect: An attacking reagent is said to have −E effect when the direction of 
electron pair transfer of multiple bond is away from the attacking reagent.
CH3 H
.. ..
C O + CN CH3 C O
H
CN
acetaldehyde; (-E effect)
The −E effect operates during nucleophilic addition reaction of aldehydes and ketones.
• +E effect: An attacking reagent is said to have +E effect when the direction of 
electron pair transfer of a multiple bond is towards the attacking reagent.
+ +
CH3CH CH2 + H CH3CHCH3
Propene ; (+E effect) isopropyl carbocation
The +E effect is observed during electrophilic addition reaction of alkenes and alkynes
.. +
CH3 MgI CH3 + MgI

.. ..
HO + H CH2 CHO CH2 CHO + H2O
ethanal ethanal carbanion

.. ..
H2N + H C CH C CH + NH3
amide acetylide ion
Steric Hindrance or Steric Strain
When two atoms are closer to each other than the sum of their van der Waal’s radii
they repel each other due to spatial crowding. Steric hindrance or steric strain refers
to non-bonded repulsive interactions between atoms which arise when the atoms come
too close due to the shape of the molecule. The repulsion arises due to nuclear-nuclear
and electron-electron repulsive forces which start dominating the attractive forces.
Molecules with steric strain are relatively less stable than those having no strain or
less strain.

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For example, in cis-but-2-ene steric hindrance is present because the two methyl
groups are quite close to each other wheras in trans-but-2-ene no steric hindrance is
there because the two methyl groups on the opposite sides.
Steric hindrance NoSteric hindrance

CH3 H
C=C C=C
H H H CH3
cis-But-2-ene trans-But-2-ene
(Sterically hindered (No Steric hindrance,
molecule, less stable) more stable)

Steric factors have great influence on orientation and reactivity of organic molecules
in various reactions.

Types of Organic Reactions


I. Substitution reaction
The reactions in which an atom or a group in a molecule is replaced by another are called
substitution reactions. The incoming group gets attached to the same carbon atom to which
leaving group was attached. The substituting species may be a nucleophile, an electrophile or
a free radical.
A – B + X – Y ⎯⎯⎯→ A – X + B – Y
(i) Nucleophilic substitution (SN) reactions
The substitution reactions which are brought about by the attack of nucleophile (Nu)..
are called nucleophilic substitution reactions.
R// R//
.. ..
[ Nu = attacking reagent; L = leaving group]
Nu + R/ C L Nu C R/ + L
R R
The common examples of S N reactions are as follows.
R−CH2−X + NaOH ⎯⎯⎯→ aqueous
R−CH2−OH + X− (X = Cl, Br, I)
R−CH2−X + KCN ⎯⎯⎯→ R−CH2CN + X−
alcohol

R−CH2OH + SOCl2 ⎯⎯ → R−CH2Cl + HCl + SO2


(ii) Electrophilic substitution (SE) reactions
The substitution reactions which are brought about by the attack of an electrophile are
called electrophilic substitution reactions. The substitution reactions of aromatic
compound such as chlorination, nitration of benzene are representatives of S E reactions.
• Chlorination: Cl2 + FeCl3 → FeCl −4 + Cl+
H + H
+ slow FeCl4 Cl
+ Cl Cl + FeCl3 + HCl
heat

(iii) Free radical substitution


The substitution reactions which are brought about by the attack of free radical are
called free radical substitution reactions. The chlorination of aliphatic hydrocarbons in
presence of diffused sunlight is common example of free radical substitution.

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sunlight
CH4 + Cl2 CH3Cl + HCl

O
h/CCl4
+ N Br + HBr
heat
Br
O
N-bromosuccinamide(NBS)

h
Br
+ Br2 + HBr

II. Addition reaction


“An addition reaction is defined as one in which an unsaturated molecule combines with
reagent (addendum) to give a single saturated or nearly saturated compound”. If one  bond
is broken then two  bonds are formed. A few examples for different types of addition
reactions are given below
A = B + X–Y ⎯⎯→ X–A–B–Y
(i) Electrophilic addition reactions
The addition of common reagents like X 2 (X = Cl, Br or I) , HX, H2O, HOCl, etc to alkenes and
alkynes are common examples of electrophilic addition reaction. The addition of
unsymmetrical molecules like HX, H2O, HOCl, etc. to unsymmetrical alkenes or alkynes takes
place according to Markownikoffs’ rule.
R CH CH2 + HX R CH CH3
X

R CH CH2 + HOCl R CH CH2Cl


OH
(ii) Nucleophilic Addition Reactions
The electron deficient carbonyl group of aldehydes or ketones is easily attacked by
nucleophile which can supply an electron pair. Thus the addition reactions of carbonyl
compounds initiated by nucleophile and known as nucleophilic addition reactions.
R R R
.. .. H CN ..
C O + CN R/ C O R/ C OH + CN
Addition of hydrogen cyanide R/ CN CN

R′=H or alkyl (−CH3, −CH2CH3, etc.) or aryl (C6H5−) or aralkyl (C6H5CH2−)

R + R
R .. + H3O
C O + R// Mg.X R/ C O . MgX R/ C OH

Addition to Grignard reagent R/ R// R//

R/
R
C O + NaHSO3 R/ C OH
SO3Na (white solid)
Addition of sodium bisulphite R/

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III. Elimination reactions
The loss of atoms or group from adjacent carbon atoms (one in the form of a nucleophile and
other in the form of an electrophile) resulting in the formation of an unsaturated compound is
known as elimination reaction.
CH 3 CH 3 H 3C CH 3
H 3C CH 3 ⎯⎯→ + H+ + X−
H X H 3C CH 3

[Note: If these two groups or atoms are removed from adjacent carbon atoms, then it is known
as  elimination reaction.]
R
R
⎯⎯⎯⎯
con c.
H SO
→ + H 2O
H OH 2 4 CH 2
The elimination reactions are two types, -elimination reactions and -elimination reactions
(i) -elimination reactions
This type of reaction involves loss of two atoms or groups from vicinal (adjacent) carbon
atoms resulting in the formation of a  bond. Thus, it is the reverse of addition reactions.
The most familiar example of
-elimination reactions are dehydrohalogenation reactions of alkylhalides, dehalogenation of
dihaloalkanes, dehydration of alcohols, pyrolysis of esters, Hofmann elimination of
quaternary ammonium hydroxide.
Dehydrohalogenation
When alkylhalides are treated with alcoholic potassium hydroxide solution or sodamide the
corresponding alkenes are formed with the elimination of hydrogen halide.
  alcohol
R CH CH R/ + KOH R CH CH R/ + KX + H2O
alkene
H X

-elimination
R   H
C heat H + NaX + NH3
C + NaNH2 R C C
H X alkyne
-elimination
(i) Sodamide (NaNH2) is stronger dehydrohalogenating agent.
(ii) An example of 1,4-elimination (-elimination) is

R CH CH CH CH2 + KOH R CH CH CH CH2 + KX + H2O


H X 1,3-alkadiene
1,4-elimination

Dehalogenation
The dehalogenation involves the removal of halogen molecule (X2) from vicinal dihalide by
heating with zinc dust in alcoholic medium.
ethanol
R CH CH R/ + Zn R CH CH R/ + ZnBr2
Br Br
 -elimination

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Dehydration of alcohols
When alcohols are heated with dehydrating agent like concentrated sulphuric acid, the
corresponding alkenes are formed with the elimination of water (-elimination). The reaction
is called dehydration of alcohols.
 
170o C
CH2 CH2 CH2 CH2 + H2O

H OH
170o C
CH3 CH CH2 CH3 CH CH2 + H2O
H OH

100o C
CH3 CH CH2 CH3 CH CH2 + H2 O

OH H

(ii) -elimination: It involves loss of two atoms from same atom resulting in the formation of
reaction intermediates like carbine
H
H
H C H + alc.KOH C : + KCl + H2O
H
H
IV. Rearrangement reactions
The reactions which proceed by a rearrangement or reshuffling of atoms or groups in the
molecule to produce a structural isomer of the original substance are called rearrangement
reactions.
A B A B

X Y Y X
H H
OH O+ H
H+ +
–H2O Rearrangement –H+
CH3
+

OH
HN NH2

⎯⎯

OH
P h en yl h ydroxyla m in e p − a m in oph en ol
(i)
H3C N N
H3C C
(ii) O
O
acetyl nitrene methyl isocyanate

CH3
+ +
H3C CH H3C C
CH3
CH3
CH3
(iii) sec − ca rboca t ion t ert − ca rboca t ion

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Purification and Characteristics of Organic Compounds


The study of organic compounds starts with the characterization of the compound and the
determination of its molecular structure. The procedure generally employed for this purpose
consists of the following steps:
(1) Purification of organic compounds
(2) Qualitative analysis of organic compounds
(3) Quantitative analysis of organic compounds
(4) Determination of molecular mass of organic compounds
(5) Calculation of Empirical formula and Molecular formula of organic compounds

(1) Purification of organic compounds: A large number of methods are available for the
purification of substances. The choice of method, however, depends upon the nature of
substance (whether solid or liquid) and the type of impurities present in it. Following methods
are commonly used for this purpose,
(i) Filtration
The process of filtration is used to separate insoluble
solid component of a mixture from the soluble
components in a given solvent.
Exp- It is used to separate a mixture of Naphthalene
and Urea using a water as solvent. Urea dissolves in
water while Naphthalene remains insoluble. Upon
filtration, naphthalene remains on the filter paper
while urea is recovered from the filtrate by
evaporating water.
Filtration is very slow and takes along time. In
such cases, filtration is carried out under reduced
pressure using a Buchner funnel and water suction pump.

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(ii) Crystallization
The method is based on the difference in
the solubilities of the compound and the
impurities in a suitable solvent. Pure
compound crystallises out from the
solution and highly soluble impurities
remain in the solution. Impure organic
compounds like glucose, urea, cinnamic
acid, etc are purified. Fractional
crystallisation is used for the separation
of a mixture of two compounds which are
soluble in the same solvent but to a
different extent.
Ex: Separation of sugar and salt.

(ii) Sublimation is the process of direct conversion of a solid into the gaseous state on
heating without passing through the intervening liquid state and vice versa on cooling.
Heat
Solid Vapour
Cool

Only those substances whose vapour pressure becomes equal to the atmospheric pressure
much before their respective melting points are capable of undergoing sublimation.
There exists an equilibrium between the solid and its vapours.

Camphor, naphthalene, anthracene, iodine, benzoic acid, salicylic acid, NH4Cl, HgCl2, etc are
purified by sublimation.

(iii) Distillation- Distillation is a method used to separate constituents of a liquid mixture


which differ in their boiling points.
Distillation is a process which involves two steps:
Vapourisation: Liquid is converted into vapours.
Condensation: Vapours are condensed again into liquid.
Depending upon the difference in the boiling points of the constituent liquids, different types
of distillation methods are employed.

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• Simple distillation: Simple distillation is applied only for volatile liquids which boil without
decomposition at atmospheric pressure and contain non-volatile impurities.

This method can also be used for separating liquids having sufficient difference in their boiling
points. For example,
(i) benzene (boiling point 353 K) and aniline (boiling point 475 K)
(ii) chloroform (boiling point 334 K) and aniline (boiling point 457 K)
(iii) ether (boiling point 308 K) and toluene (boiling point 383 K)
Nitrobenzene prepared in the laboratory can also be purified by distillation.
• Fractional distillation: This method is used for the separation of two or more volatile
liquids from a liquid mixture which has boiling points close to each other. Liquids forming a
constant boiling mixture (azeotropic mixture) such as rectified spirit cannot be separated
by this method.

Fractional distillation is used these days in industries, especially, in the distillation of


petroleum, coal tar and crude alcohol. A mixture of methanol (boiling point 338 K) and
propanone (boiling point 330 K) or a mixture of benzene and toluene may be separated by
fractional distillation.

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• Distillation under reduced pressure (Vacuum distillation): The compounds, which


decompose at a temperature below their normal boiling points, cannot be purified by
distillation under ordinary atmospheric pressure.

Glycerin is one such compound which decomposes at its boiling point. The pressure is reduced
by suction pump and the distillation is carried out at lower temperature as glycerine can be
distilled at 453 K (normal boiling point 563 K) under a pressure of 10-12 mm. Cane juice can
also be concentrated by this method. This technique can be used to separate glycerol from
spent lye in soap industry.

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• Steam distillation: This method is used to purify the organic compounds which
❖ Are volatile in steam but are immiscible with water.
❖ Possess high vapour pressure at the boiling point of water.
❖ Contain nonvolatile impurities.

The compound to be purified is distilled with steam and impurities being nonvolatile remains in
mother liquor. For example, o- nitrophenol (volatile) and p-nitrophenol (non volatile) are
separated by this method.

(iv) Differential extraction (or solvent extraction): The process


of separation of an organic compound (solid or liquid) from its
aqueous solution by shaking with a suitable
organic solvent is termed as solvent extraction. This method is
employed for non-volatile compounds. For example, benzoic acid is
extracted from its aqueous solution using benzene as solvent.

(v) Chromatography
Chromatography is the technique of separating the components of mixture in which the
separation is achieved by the differential movement of individual components through a
stationary phase under the influence of a mobile phase.

jar adsorbent coated solvent


front
on glass plate
spot
sample dot
base line y
solvent x
base line
Thin layer chrom atography
chromatogram being developed Developed chromatogram
Dis tance moved by the substance formbaseline ( x )
Rf = Dis tance moved by the solvent from base line ( y)
Depending upon the nature of the stationary phase (either a solid or a liquid tightly bound on
a solid support) and the nature of the mobile phase (either a liquid or a gas), different types
of chromatographic techniques are followed.

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Chromatography

Adsorption Chrom. Partition Chrom.

Column chromatography
Paper Chrom.
High Performance Liquid Chrom. (HPLC)
Ascending Decending Radial
Thin Layer Chrom. (TLC)

Gas-Liquid Chrom. (GLC)


Type of chromatography Stationary phase Mobile phase Application
Column/adsorption Solid Liquid Large scale separation
Thin layer chromatography (TLC Solid Liquid Qualitative analysis
High performance liquid Qualitative analysis and also
Solid Liquid
chromatography (HPLC) for separation
Qualitative analysis and also
Gas liquid chromatography(GLC Liquid Gas
for separation
Qualitative analysis and also
Proper chromatography Liquid Liquid
for separation
The various components on the developed TLC plate are identified through their retardation
factor, i.e., Rf values.
distance moved by the substance from base line
Rf =
distance moved by the solvent from base line
A component with highest value of Rf elute first. A component with greater tendency to adsorb
on solid has lesser the Rf value.

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2. Qualitative Analysis (Detection of Elements)


The qualitative analysis of an organic compound involves the detection of all the elements
present in it. Carbon and hydrogen are generally present in all organic compounds. Other
elements which may be present in organic compounds are oxygen, nitrogen, sulphur, halogens,
phosphorus, etc. These elements are detected by the following tests.

Detection of Carbon and Hydrogen by Copper oxide test


Principle Organic compounds undergo oxidation in the presence of a suitable oxidizing agent. In
this process, carbon is oxidized to CO2 and hydrogen is oxidized to water.

Procedure The compound is intimately mixed with dry cupric oxide. The mixture is strongly
heated in a hard glass test tube fitted with a cork and a delivery tube. The liberated gases
are passed into lime water.

Organic compound + CuO CO2 + H2O +Cu


Carbon Water Copper
dioxide

Passed into
lime water
Ca(OH) 2 Passed into
anhydrous
CuSO4

lime water
turns milky
Copper sulphate
turns blue

Carbon (C) present


in organic compound Hydrogen (H) present
in organic compound
ℎ𝑒𝑎𝑡
[𝐶] + 2𝐶𝑢𝑂 → 𝐶𝑂2 + 2𝐶𝑢
𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
CO 2 + Ca(OH) 2 ⎯⎯
→ CaCO3 + H 2O
lime water (milky)
ℎ𝑒𝑎𝑡
[2𝐻] + 𝐶𝑢𝑂 → 𝐻2 𝑂 + 𝐶𝑢
𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

𝐶𝑢𝑆𝑂4 + 5𝐻2 𝑂 → 𝐶𝑢𝑆𝑂4 . 5𝐻2 𝑂


(𝑤ℎ𝑖𝑡𝑒) (𝑏𝑙𝑢𝑒)

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Detection of Nitrogen, Halogen and Sulphur by Lassaigne’s test
Principle This is the most reliable test for the detection of nitrogen, sulphur, halogens etc. In
this method sodium fusion extract of organic compound is prepared. In this fusion process,
carbon and nitrogen present in the organic compounds get converted into cyanide ion (CN –),
sulphur (S) into sulphide ion S2– and halogens (X) into halide ion (X–). By testing for radicles,
presence of these elements can be find.
Preparation of Sodium fusion extract
A piece of Na metal taken in a fusion tube and heated. Na melts to form shining globule.
Organic compound added to it and heated to red hot. Red hot tube is now dropped into water
taken in a porcelain dish. The contents are heated to concentrate the solution. Solution is then
filtered. The filtrate is called sodium fusion extract.
Test for nitrogen
Ferrous sulphate are added to the sodium fusion extract. The mixture is boiled and cooled. It
is acidified with hydrochloric acid and a few drops of ferric chloride solution are added.
Sodium cyanide in the filtrate reacts with ferrous sulphate to give sodium ferrocyanide. It
further reacts with ferric chloride to give a blue coloured solution of ferric ferrocyanide.
𝑓𝑢𝑠𝑒
[𝐶, 𝑁] + 𝑁𝑎 → 𝑁𝑎𝐶𝑁
𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

𝐹𝑒𝑆𝑂4 + 2𝑁𝑎𝐶𝑁 → 𝐹𝑒(𝐶𝑁)2 + 𝑁𝑎2 𝑆𝑂4

𝐹𝑒(𝐶𝑁)2 + 4𝑁𝑎𝐶𝑁 → 𝑁𝑎4 [𝐹𝑒(𝐶𝑁)6 ]


𝑠𝑜𝑑𝑖𝑢𝑚𝑓𝑒𝑟𝑟𝑜𝑐𝑦𝑎𝑛𝑖𝑑𝑒

3𝑁𝑎4 [𝐹𝑒(𝐶𝑁)6 ] + 4𝐹𝑒𝐶𝑙3 → 𝐹𝑒4 [𝐹𝑒(𝐶𝑁)6 ]3 + 12𝑁𝑎𝐶𝑙


𝑓𝑒𝑟𝑟𝑖𝑓𝑒𝑟𝑟𝑜𝑐𝑦𝑎𝑛𝑖𝑑𝑒(𝑷𝒓𝒖𝒔𝒔𝒊𝒂𝒏 𝒃𝒍𝒖𝒆)

Few drops of NaOH


Organic compound Lassaignes’s extract Na4 Fe(CN)
Fused with sodium (has NaCN) and freshly prepared FeSO 6
4 Sodium ferrocyanide

Excess of HCl
and FeCl 3

𝑭𝒆𝟒 [𝑭𝒆(𝑪𝑵)𝟔 ]𝟑
𝒇𝒆𝒓𝒓𝒊𝒇𝒆𝒓𝒓𝒐𝒄𝒚𝒂𝒏𝒊𝒅𝒆(𝑷𝒓𝒖𝒔𝒔𝒊𝒂𝒏 𝒃𝒍𝒖𝒆)

Note- If organic compound contains N and S, sodium thiocyanate is formed in sodium extract
which gives blood red colouration with FeCl3 due to the formation of ferric thiocyanate.
𝒇𝒖𝒔𝒆
[𝑪, 𝑵, 𝑺] + 𝑵𝒂 → 𝑵𝒂𝑪𝑵𝑺
𝒐𝒓𝒈𝒂𝒏𝒊𝒄𝒄𝒐𝒎𝒑𝒐𝒖𝒏𝒅

𝑵𝒂𝑪𝑵𝑺 + 𝑭𝒆𝑪𝒍𝟑 → 𝑭𝒆(𝑪𝑵𝑺)𝑪𝒍𝟐 + 𝑵𝒂𝑪𝒍


𝒇𝒆𝒓𝒓𝒊𝒄 𝒔𝒖𝒍𝒑𝒉𝒐 𝒄𝒚𝒂𝒏𝒊𝒅𝒆(𝑷𝒓𝒖𝒔𝒔𝒊𝒂𝒏 𝒃𝒍𝒖𝒆)

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Test for Sulphur
Lead acetate test: Second part of the filtrate is treated with excess of acetic acid and
lead acetate solution. A black precipitate of lead sulphide is formed.
𝑓𝑢𝑠𝑒
[𝑆] + 2𝑁𝑎 → 𝑁𝑎2 𝑆
(𝑜𝑓𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑)

𝑁𝑎2 𝑆 + 𝑃𝑏(𝐶𝐻3 𝐶𝑂𝑂)2 → 2𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 + 𝑃𝑏𝑆 ↓


𝑏𝑙𝑎𝑐𝑘𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
Sodium nitroprusside test: To the sodium fusion extract, a few drops of sodium nitroprusside
are added. The appearance of violet or purple colour indicates the presence of sulphur.
𝑁𝑎2 𝑆 + 𝑁𝑎2 [𝐹𝑒(𝐶𝑁)5 𝑁𝑂] → 𝑁𝑎4 [𝐹𝑒(𝐶𝑁)5 𝑁𝑂. 𝑆] or 𝑁𝑎3 [𝐹𝑒(𝑂𝑁𝑆𝑁𝑎)(𝐶𝑁)5 ]
Sodium nitroprusside 𝑠𝑜𝑑𝑖𝑢𝑚 𝑠𝑢𝑙𝑝ℎ𝑜 𝑛𝑖𝑡𝑟𝑜 𝑝𝑟𝑢𝑠𝑠𝑖𝑑𝑒 Sodium thionitroprusside
(Purple) (Violet)

Organic compound Lassaignes's extract Divide the extract in two parts
Fused with sodium (has Na2S
sodium shulphide)

To one portion add acetic acid To other portion add


(CH3COOH) and lead acetate freshly
[Pb(CH3COO)2] prepared sodium
nitroprusside
Na2[Fe(CN)5(NO)]

Black ppt. of lead sulphide


Violet colouration
(PbS) confirms the presence
of Na4[Fe(CN)5NOS]
of sulphur in organic compound
confirms the presence
of sulphur in organic
compound
Test for Halogens
Silver nitrate test A portion of the stock solution is boiled with dil. HNO3, cooled and silver
nitrate is added.
A white precipitate soluble in ammonium hydroxide shows the presence of chlorine. A pale
yellow precipitate slightly soluble in ammonium hydroxide shows the presence of bromine. A
yellow precipitate insoluble in ammonium hydroxide shows the presence of iodine.
𝐻𝑁𝑂3
𝑁𝑎𝑋 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝑋 ↓
𝑝𝑝𝑡

𝑁𝑎𝐶𝑙 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐶𝑙 ↓ + 𝑁𝑎𝑁𝑂3


𝑤ℎ𝑖𝑡𝑒 𝑝𝑝𝑡

𝑁𝑎𝐵𝑟 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐵𝑟 ↓ + 𝑁𝑎𝑁𝑂3


𝑝𝑎𝑙𝑒 𝑦𝑒𝑙𝑙𝑜𝑤 𝑝𝑝𝑡

𝑁𝑎𝐼 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐼 ↓ + 𝑁𝑎𝑁𝑂3


𝑦𝑒𝑙𝑙𝑜𝑤 𝑝𝑝𝑡
Note: During the detection of halogens, the sodium fusion extract is boiled with nitric acid in
order to expel the N and S as HCN and H2S.
When AgNO3 added cyanide gives white ppt, sulphide gives black ppt and interfere with
observation.

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 dil. HNO3
Organic compound Lassaignes extract
and AgNO3
Fused with sodium (has NaX
(has covalent bonds sodium halide)
with carbon and halogens)
White ppt of Pale yellow ppt Yellow ppt of
silver chloride of silver iodide
(AgCl) soluble in silver bromide (Agl)
ammonia confirms (AgBr) sparingly insoluble
the presence of soluble in in ammonia
chlorine in ammonia confirms the
organic compound confirms the presence of
persence of iodine in
bromine in organic
organic compound
compound

Note: Beilstein’s test: Beilstein’s test is used to detect the halogen in an organic compound.
A copper wire is heated in a Bunsen flame till no colour is imparted to the flame. The copper
wire is dipped in the given organic compound and exposed to the non-luminous zone of the
Bunsen flame. A bluish green coloured flame indicates the presence of halogen.

Test for Phosphorus


Organic compound containing phosphrous is fused with sodium peroxide. The phosphorus of
the compound is oxidised to phosphate. The fused mass is extracted with water and filtered.
The filtrate containing sodium phosphate is boiled with nitric acid and then treated with
ammonium molybdate. A yellow solution or precipitate indicates the presence of phosphorus.
Na + P + O → Na3PO4
Na3PO4 + 3HNO3 → H3PO4 + 3NaNO3
H 3PO 4 + 12(NH 4 ) 2 MoO 4 + 2HNO 3 → (NH 4 ) 3 PO 4 12MoO 3 + 21NH 4 NO 3 + 12H 2O
ammonium molyblate ammonium phosp hom olybdate


Phosphorus present in organic compound
Organic compound
With Na2O change to phosphate (Na
3PO4)

(sodium peroxide)
boiled with nitric acid
(HNO3) and added
ammonium molybdate
[(NH4)2MoO4]

Yellow ppt of
ammonium
phosphomolybdate
[(NH4)3PO4.12MoO3]
confirms the presence
of phosphorus in
organic compound

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(3) Quantitative analysis The quantitative analysis deals with the determination of
percentage of various elements. The following methods are employed for the determination
of percentage composition of elements present in the organic compounds.
Estimation of carbon and hydrogen by Liebig’s combustion method
Principle: A known mass of organic compound is oxidized with cupric oxide in C02 free
atmosphere. C gets oxidized to C02, H to H2O. Water formed is absorbed in weighed anhydrous
CaCl2 U bulbs and carbon dioxide absorbed in weighed KOH bulbs. Increase in mass of CaCl2
and KOH bulbs are determined. Difference in mass corresponds to the mass of H2O and C02
respectively.
Knowing the increase in mass, the percentage of C and H in the organic compound can be
calculated.
𝒚 𝜟 𝒚
𝑪𝒙 𝑯𝒚 + ቀ𝒙 + ቁ 𝑶𝟐 → 𝒙𝑪𝑶𝟐 + 𝑯𝟐 𝑶
𝟒 𝟐

Calculations
• Let the mass of organic compound taken = m g
• Mass of water formed = m1 g
(increase in CaCl2 U-tube)
• Mass of carbon dioxide formed = m2 g
(increase in potash tubes)
(a) Percentage of Carbon
We know that 1 mole of carbondioxide (44 g) contains 1 gram atom of carbon (12g).
44 g of CO2 contain C = 12g
12
m2 g of CO2 contains C = × m2 g
44
12m2
Hence Percentage of carbon = × 100
44×m
(b) Percentage of Hydrogen
We know that one mole of water (18g) contains 2gram atom of hydrogen (2g)
H2O = 2H
18g of H2O contain H = 2g
2
m1 g of H2O contains H = × m1 g
18
2m1
Percentage of hydrogen = × 100
18×m

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Estimation of nitrogen by Kjeldahl’s method

Principle: Kjeldahl’s method is based on the quantitative conversion of nitrogen of the


organic compound to ammonium sulphate by sulphuric acid. The reaction product is treated
with an alkali and the ammonia released is determined. From this the amount of nitrogen in
the organic compound is calculated.
𝑐𝑜𝑛𝑐.𝐻2 𝑆𝑂4
[𝐶, 𝐻, 𝑁, 𝑆] → 𝐶𝑂2 + 𝐻2 𝑂 + 𝑆𝑂2 + (𝑁𝐻4 )2 𝑆𝑂4
𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 ℎ𝑒𝑎𝑡
ℎ𝑒𝑎𝑡
(𝑁𝐻4 )2 𝑆𝑂4 + 2𝑁𝑎𝑂𝐻 → 𝑁𝑎2 𝑆𝑂4 + 2𝐻2 𝑂 + 2𝑁𝐻3
2𝑁𝐻3 + 𝐻2 𝑆𝑂4 → (𝑁𝐻4 )2 𝑆𝑂4
This method is simple, convenient and largely used for the estimation of nitrogen in food
stuffs, drugs, fertilizers and many other organic compounds. However, this method cannot
be employed for the estimation of nitrogen in following types of organic compounds.
• Organic compound containing nitrogen in aromatic ring such as pyridine, quinoline, etc.,
• Organic compounds containing nitro (−NO2) and diazo (− N = N −) groups.

Calculations
Let the mass of organic compound = w g
Volume of standard acid taken = V cm3
Normality of acid = N1
Let vol. of standard alkali used for neutralisation of unused acid = V2 cm3
Normality of standard alkali = N2
𝑁
⏟ 1 𝑉1 =𝑁
⏟2 𝑉2
𝑎𝑙𝑘𝑎𝑙𝑖 𝑎𝑐𝑖𝑑
Let this volume of v cm3
Vol. of acid used for neutralisation of ammonia = (V – v) cm3 of N1 normality
Ammonia liberated = (V – v) cm3 of N1 solution
Now, 1000 cm3 of 1N NH3 solution contains nitrogen = 14 g
(V – v) cm3 of N1 NH3 solution contains
14(V − v)x N1
nitrogen = g
1000
Mass of nitrogen
Percentage of nitrogen = × 100
Mass of organic compound

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14(V − v)xN1 100 1.4(V − v)x N1
= × =
1000 w w
volume of the acid (cm3 ) × normality of the acid × 1.4
Percentage of nitrogen in the compoun =
mass of organic compound in g

Estimation of Nitrogen by Duma’s method


Principle: The organic compound containing nitrogen when heated with excess of copper oxide
in the atmosphere of carbon dioxide, yields nitrogen in addition to carbon dioxide and water.
𝑪 + 𝟐𝑯 + 𝟑𝑪𝒖𝑶 → 𝑪𝑶𝟐 + 𝑯𝟐 𝑶 + 𝟑𝑪𝒖
𝟐𝑵 + 𝟐𝑪𝒖𝑶 → 𝑵𝟐 +oxide of nitrogen
or
𝑦 𝑦 𝑦 𝑧
[𝐶𝑥 𝐻𝑦 𝑁𝑧 ] + ቀ2𝑥 + ቁ 𝐶𝑢𝑂 → ቀ2𝑥 + ቁ 𝐶𝑢 + 𝑥𝐶𝑂2 + 𝐻2 𝑂 + 𝑁2
𝑂𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 2 2 2 2
Traces of nitrogen oxides formed during combustion of organic compound are reduced to
nitrogen by passing the gaseous mixture over a heated copper gauze. The percentage of
nitrogen present in a given organic compound is calculated from the volume of nitrogen
collected over potassium hydroxide solution from a known mass of organic compound.

Calculations
Let the mass of organic compound = wg
The volume of nitrogen collected = Vcm3
Atmospheric pressure from barometer) = P mm of Hg
0
Room temperature = t C
0
Aqueous tension at t C = a mm of Hg
Pressure of dry nitrogen = (P – a) mm of Hg
Let us first convert the volume of nitrogen to volume at S.T.P.
Experimental conditions S.T.P. conditions
P1 = (P – a)mmHg P2 = 760 mm
T1 = (273 + t)K T2 = 273
V1 = V cm3 V2 = ?

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P1 V1 𝑃2 𝑉2
Applying gas equation =
T1 𝑇2
= x cm3 (say)
𝑃1 𝑉1 𝑇2 (𝑃−𝑎)𝑥𝑉𝑥273
V2 = =
𝑃2 𝑇1 760(273+𝑡)
Now 22400 cm3 of N2 at S.T.P. weight = 28 g
x cm3 of N2 at S.T.P. will weigh = ×
28
xg
22400
𝑀𝑎𝑠𝑠𝑜𝑓𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 28x𝑥100
Percentage of nitrogen = x 100 =
𝑀𝑎𝑠𝑠𝑜𝑓𝑜𝑟𝑔𝑎𝑛𝑖𝑐𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 22400𝑥𝑤
28 𝑉
% of N = × × 100
22400 𝑊
Where, V= volume of 𝑁2 in nitrometer (in ml) at NTP,
1.4×N×𝑉
W= Weight of substance taken; % of 𝑁 =
𝑊

Estimation of Halogen by Carius method

Principle: A known mass of an organic compound is heated with fuming nitric acid and a few
crystals of silver nitrate in a sealed tube called Carius tube. The Carbon, hydrogen or sulphur
present in the compound will be oxidised to CO2, H2O and H2SO4 respectively. Halogen is
precipitated to give silver halide.
[C H X] + [O] ⎯⎯⎯⎯⎯
fuming HNO3
→ CO 2 + H 2O + HX
heat
Organic compound

HX + AgNO3 → AgX + HNO3


Precipitate

• This method does not give satisfactory results in the estimation of iodine as AgI is slightly
soluble in nitric acid and iodide may oxidise to iodine to some extent.
• The results of this method is not very accurate in case of polyhalogenated aromatic
compounds
• Estimation of fluorine can not be carried out as AgF is soluble in water.
Calculations:
Let the mass of organic compound be w g
Mass of silver halide formed = a g
Now, AgX = X
108 + X parts by weight of silver halide contains X parts by weight of halogen (X is its atomic mass)
(108 + X) g of silver halide give halogen = X
𝑋
a g of silver halide will give halogen = (108+𝑋) × ag

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atomic mass of X mass of silver halide in grams
Percentage of halogen =  100
molecular mass of AgX mass of organic compound in grams Xxa 100
= ×
(108+ X) w
Here X is the atomic mass of halogen, e.g. Cl = 35.5 , Br = 80 (79.9 exact), I = 127 (126.9 exact)
35.5 mass of silver chloride in grams
Percentage of chlorine =  100
(108 + 35.5) mass of organic compound in grams
80.0 mass of silver bromide in grams
Percentage of bromine =  100
(108 + 80) mass of organic compound in grams

127 mass of silver iodide in grams


Percentage of iodine =  100
(108 +127) mass of organic compound in grams

Estimation of sulphur by Carius method


Principle: An organic compound is digested with fuming nitric acid in a sealed tube. The sulphur
present in the compound is quantitatively oxidised into sulphuric acid. Sulphuric acid so formed
is precipitated as barium sulphate by adding excess of barium chloride.
The main reactions are : S + H2O + 3O ⎯HNO
⎯⎯3 → H2SO4
H2SO4 + BaCl2 ⎯→ BaSO4
ppt.
Calculations :
Let the mass of organic compound = w g
Mass of BaSO4 formed = ag
BaSO4 137 + 32 + 64 = 32 = 233
233 g of BaSO4 contain sulphur = 32 g
32 x a
ag of BaSO4 will contain sulphur = g
233
Mass ofsulphur 32𝑎 100
Percentage of sulphur = × 100 = ×
Massoforganiccompound 233 𝑤
32 mass of barium sulphate in grams
Percentage of sulphur =  100
233 mass of organic compounds in grams

Estimation of phosphrous by Carius method


Principle: The phosphorus present in the organic compound is oxidised to orthophosphoric acid
by heating with fuming nitric acid. The phosphoric acid so obtained is precipitated as
MgNH4PO4 which on ignition is converted into Mg2P2O7.
[C, H, P] + [O] ⎯⎯⎯
fuming
→ H3PO4 + H 2O + CO2
Organic compound nitric acid

H 3PO 4 + [NH 4Cl + NH 4OH + MgCl 2 ] → MgNH 4PO 4


magnesia mixture white precipitate

2MgNH 4 PO4 ⎯⎯⎯


ignite
→ Mg P O
2 2 7 + H 2O + 2NH3
magnesium pyrophoshate

62 mass of Mg 2 P2O 7 in grams


Percentage of phosphorus = 222  mass of organic compound in grams 100

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Estimation of oxygen
There is no direct method for the estimation of oxygen present in the organic compound. The
percentage of oxygen in the compound is generally estimated by difference.
Percentage of oxygen = 100 − [sum of percentage of all other elements present in it]
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.
Compound ⎯⎯ ⎯
heat
→ O2 + other gaseous products
2C + O2 ⎯⎯⎯→ 2CO]  5 … (A)
1373 K

I2O5 + 5CO ⎯⎯ → I2 + 5CO2 ]  2 … (B)


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 carbon dioxide.
Thus 88 g carbon dioxide is obtained if 32 g oxygen is liberated.
Let the mass of organic compound taken be mg
Mass of carbon dioxide produced be m1g
32  m1
 m1g carbon dioxide is obtained from g O2
88
32  m1  100
 Percentage of oxygen = %
88  m
The percentage of oxygen can be derived from the amount of iodine produced also.
Presently, the estimation of elements in an organic compound is carried out by using
microquantities of substances and automatic experimental techniques. The elements, carbon,
hydrogen and nitrogen present in a compound are determined by an apparatus known as CHN
elemental analyser. The analyser requires only a very small amount of the substance (1-3 mg)
and displays the values on a screen within a short time. A detailed discussion of such methods
is beyond the scope of this book.

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115
HALOALKANES AND
HALOARENES

THEORY

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HALOALKANES AND HALOARENES (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)

HALOALKANES AND
HALOARENES
Introduction:
Compounds derived from hydrocarbons by the replacement of one or more hydrogen atoms
by the corresponding number of halogen atoms are termed as halogen derivatives.
They are the compounds which have the general formula ‘RX’ , where
‘R’ is an alkyl or substituted alkyl group & ‘X’ is the halogen (F, Cl, Br, I). Likewise, haloarenes
or aryl halides are the compounds containing halogen attached directly to an aromatic ring.
They have the general formula ‘ArX’ (where ‘Ar’ is phenyl or substituted phenyl).
R–X Ar – X
An alkyl halide An aryl halide
(Haloalkane) (Haloarene)
R = Alkyl or substituted alkyl Ar = Phenyl or substituted phenyl
X = F, Cl, Br, I X = F, Cl, Br, I
Halogen containing organic compounds occur in nature & some of these are medicinally useful.
For exp, the chlorine containing antibiotic chloromycetin or chloramphenicol, produced by soil
microorganism, is very effective for the treatment of typhoid fever.

Our body produces an iodine containing hormone called thyroxine, the deficiency of which
causes the disease goiter.

Some synthetic halogen containing compounds are very useful in health–care and medicine.
For example, chloroquine is used for the treatment of malaria fever.

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Classification:
Halogen derivation of hydrocarbons broadly classified in to two types:
A. Aliphatic halogen compounds:
These are obtained by replacement of one or more hydrogen atoms of an aliphatic
hydrocarbon by an equal number of halogen atoms. Depending upon the nature of the
aliphatic hydrocarbon, whether alkane, alkene, alkyne aliphatic halogen compounds are of the
following three types:
a) Haloalkanes: are the halogen derivatives of alkanes. They derived from alkanes by the
replacement of one or more hydrogen atoms by the corresponding number of halogen
atoms (fluorine, chlorine, bromine, or iodine) are called as halo–alkanes.
These are named as fluro, chloro, bromo or iodo compounds according to the type of halogen
present in them.
CH3 Cl C2 H5 I C3 H7 Br
Ex:
Methyl chloride Ethyl Iodide Propyl Bromide
Depending on the number of halogen of atoms present in the halogen derivative, these are
termed as mono-, di-, tri-and tetra halogen derivatives.
• Monohalogen derivatives are formed by the replacement of one hydrogen atom by one
halogen atom
CH3 Cl CH3 CH2 Cl
Methyl chloride Ethyl chloride
Monohalogen derivatives or alkyl halides are classified as primary (1°), secondary (2°) or
tertiary (3°) depending upon whether the halogen atom is attached to primary, secondary
or tertiary carbon atoms.
i] Primary (𝟏°) alkyl halide: When the carbon atom containing halogen atom is linked to only
one carbon atom (i.e., primary carbon atom).
e.g. CH3 – CH2 – Cl, CH3 – CH2 – CH2 – CH2 – Cl, CH3 – CH – CH2 – Cl
Chloroethane Chlorobutane CH3 or
1-chloro-2-methyl propane

ii] Secondary (𝟐°) alkyl haide


When the carbon atom having halogen atom is linked to two carbon atoms (i.e., secondary
carbon atom) H
e.g CH3 – CH – Cl CH3 – C – CH2 – CH3
CH3 Cl
2-chloropropane 2-chloro-3-methylbutane
iii] Tertiary (𝟑°) alkyl halide
When the carabon atom having halogen atom is killed to three carbon atoms (i.e.,tertiary
carbon atoms). Cl Cl
e.g or CH3 – CH – CH3 CH3 – CH – CH2 – CH3
CH3 CH3
2-chloro-2-methylpropane 2-chloro-2-methylbutane

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• Dihalogen derivatives: These are formed by the replacement of two hydrogen atoms by
two halogen atoms. The dihalogen derivatives are mainly three types.
a] Geminal or Gem-dihalides- Here both the halogen atoms are attached to the same
carbon atom. These are also called alkylidene halides
H Cl H H H
H–C–C–C–H H – C – C – Cl
H Cl H H Cl
(Isopropylidene chloride) (Ethylidene chloride)
(2,2-Dichloro propane) (1,1-Dichloro ethane)
b] Vicinal or vic-dihalides- Here both the halogen atoms are attached to adjacent carbon
atom. These are also called alkylene halides
Cl
Cl – CH2 – CH2 – Cl CH3 – CH – CH2 – Cl
(Ethylene chloride) (Propylene chloride)
(1,2-Dichloride ethane) (1,2-Dichloropropane)
c] 𝛂 − 𝛚 Halides (terminal dihalides)- Here both the halogen atoms are attached to
terminal carbon atoms. These are also called polymethylene halides.
Cl – CH2 – CH2 – CH2 – Cl
(1,3-Dichloropropane)
• Trihalogen derivatives- These are formed by the replacement of three hydrogen atoms
from three halogen atoms. These are also known as haloforms
Cl
Cl – C – H

Cl
1,1,1-trichloropropane(Chloroform)
• Tetrahalogen derivatives
These are formed by the replacement of four hydrogen atoms from four halogen atoms
CHCl3
Cl – C – H CCl4

CHCl3 Tetrachloromethane
1,1,2,2-tetrachloroethane
(b) Haloalkenes or Alkenyl halides are the halogen derivates of alkenes. The mono halogen
derivates of alkenes with formula is CnH2n–1X .
where X = F, Cl, Br or I and n = 2,3,4….., etc.

(c) Haloalkynes of Alkynyl halides are the halogen derivatives of alkynes. The monohalogen
derivatives of alkynes have the general formula CnH2n–3X,where X = F, Cl, Br or I and n = 2, 3,
4…., etc. For example,

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B) Aromatic Halogen Compounds- These are obtained by replacement of one or more


hydrogen atoms of an aromatic hydrocarbon by an equal number of halogen atoms.
These have been further classified into the following two major categories:
(i) Nuclear halogen derivatives (aryl halides). Halogen derivatives of aromatic hydrocarbons
in which the halogen atom (F, Cl, Br or I) is directly attached to an aromatic ring are
called aryl halides. Their general formula is Ar–X where Ar (short name for aryl)
represents a phenyl, a substituted phenyl or any other aryl group such as naphthyl, etc.
Some examples of aryl halides are:

(ii) Side chain halogen derivatives (aralkyl halide). Halogen derivatives of aromatic
hydrocarbons in which the halogen atom is linked to one of the carbon atoms of the
side chain carrying the aryl group are called aralkyl halides. For example,
Cl CH2 CH 2 Br

chlorobenzene (2-bromoethyl)benzene

Classification based on hybridization of the carbon atom linked to the halogen:

(A) A compound containing C–X bond, where carbon is sp3-hybridized.


i) Alkylhalides or Haloalkanes: In alkyl halides, the halogen atom is bonded to an alkyl group.
The homologous series is represented by CH2n+1X.
They are further classified as primary (1°), secondary (2°) tertiary (3°) halides depending
upon whether the halogen atom is attached to a primary, secondary and tertiary carbon atom.
Examples: H R2 R2
R –C–X
1
R –C–X
1
R –C–X
1

H H R3
(Primary haloalkane) (Secondary haloalkane) (Tertiary haloalkane)

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(ii) Allylic halides: In these halides, the halogen atom is attached to allylic carbon like
C = C – C* – X. i.e., carbon atom next to C=C.
Allylic halides may be primary secondary or tertiary.
CH2 = CH – CH2 – X X
(Allyl halide)
(3-Halo-1-propene)
(3-Halocyclohex-1-ene)
(iii) Benzylic halides: In these halides, the halogen atom is attached to a benzylic carbon
i.e.,the carbon atoms of the side chain carrying
,
the aryl group.
CH2X X R1
C–X
R2
(Benzyl halide) (1-Halo-1,2,3,4-tetra- (Dialkylbenzyle halide)
hydro naphthalene)
✓ NOTE :- Benzylic halides may be primary, secondary or tertiary.

(B) Compounds containing C–X bond, where carbon is sp2 hybridized


(i) Arylhalides: In these halides, the halogen atom is directly attached to the carbon
atom of an aromatic ring. These halides are also called haloarenes.
Cl I Br
CH 3

Chlorobenzene Iodobenzene 2-bromotoluene

(ii) Vinylic halides:In these halides, the halogen atom is attached to vinylic carbon
i.e., one of the carbon atoms of C= C.
CH2 = CH – X X
(Vinyl halide)
(1-Halocyclohex-1-ene)

Nomenclature of Halogen Compounds


Alkyl halides: In the common or trivial system, the monohalogen derivatives of alkanes are
called alkyl halides.
• Their individual names are derived by naming the alkyl group followed by the name of the
halogen as halide, i.e., fluoride, chloride, bromide or iodide. The complete name of any alkyl
halide is always written as two separate words.
• In the IUPAC system, the monohalogen derivatives of alkanes are named as haloalkanes.

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COMMON NAME STRUCTURE IUPAC NAME


Methyl chloride CH3 – Cl Chloromethane
n-propyl fluoride CH3 – CH2 – CH2 – F 1-Fluoropropane
Iso-propyl chloride CH3 – CH – Cl 2-chloropropane
CH3
n-Butyl chloride CH3 – CH2 – CH2 – CH2 – Cl 1-chlorobutne
Sec-butyl chloride CH3 – CH2 – CH – CH3 2-chlorobutane
Cl
Iso-butyl chloride CH3 – CH – CH2 – Cl 1-chloro-2-methyl propane
CH3
Tert-butyl chloride CH3
CH3 – C – CH3 2-Bromo-2-methyl propane
Br
Neo-pentyl bromide CH3
CH3 – C – CH2 – Br 1-Bromo-2,2-dimethyl propane
CH3
Iso-pentyl chloride CH3 – CH – CH2 – CH2 – Cl 1-Chloro-3-methyl butane
Vinyl chloride CH2 = CH – Cl Chloro ethane
Allyl bromide CH2 = CH – CH2 – Br 3-Bromoprop-1-ene
Methylene chloride CH2 – Cl2 Dichloromethane
Chloroform CHCl3 Trichloromethane
Carbon tertrachloride CCl4 Tetrachloromethane
O-chloro toluene CH3
Cl 2-chlorotoluene or,
1-chloro-2-methyl benzene

Benzyl chloride CH2 – Cl Chlorophenyl methane

Alkyl halides: CH3CH2CH2Br Benzylic halides:


(Propyl bromide) CH2Br
Cycloalkyl halides:
Memories

Br

Allylic halides: CH2 = CH – CH2 – Cl


Cyclohexyl bromide Aryl halides: Cl

Vinylic halides: CH2 = CH – Cl

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METHODS OF PREPARATION OF HALOALKANES


(1) From Alkanes: [Halogenation of Alkanes]
Alkanes react with halogen (Cl2, Br2) in presence of sunlight at ordinary temperature or by
heating at 400–500° or heating in presence of free radical initiators such as peroxides, TEL,
etc give RX.
𝑿𝟐
R-H → R-X + HX
𝒉𝝂
The reactivity of halogens decreases in the order: F2> Cl2> Br2> I2
This is a chain process and direct halogenation proceeds through free radical mechanism.
This is not a suitable laboratory methods since polyhalogen derivatives are formed along
with monohalogen derivatives.
For example, chlorination of methane gives four products,
𝐂𝐥𝟐 −𝐇𝐂𝐥 𝐂𝐥𝟐 −𝐇𝐂𝐥 𝐂𝐥𝟐 −𝐇𝐂𝐥 𝐂𝐥𝟐 −𝐇𝐂𝐥
i.e., 𝐂𝐇𝟒 → 𝐂𝐇𝟑 𝐂𝐥 → 𝐂𝐇𝟐 𝐂𝐥𝟐 → 𝐂𝐇𝐂𝐥𝟑 → 𝐂𝐂𝐥𝟒
Mechanism: Reaction proceeds via free radical formation.It takes place in the following steps:
• Initiation Step: The reaction is initiated by the breaking of chlorine molecule into
chlorine-free radicals in presence of UV light.
𝐇𝐨𝐦𝐨𝐥𝐲𝐭𝐢𝐜 𝐟𝐢𝐬𝐬𝐢𝐨𝐧
𝐂𝐥𝟐 → 𝐂𝐥• + 𝐂𝐥• (Chain initiation) … (i)
𝐡𝐯 𝐨𝐫 𝐡𝐞𝐚𝐭
• Propagation Step:The chlorine-free radicals attach methane molecule (𝐶𝑙 • is a substituent)
̇ 𝟑 + 𝐇𝐂𝐥 (Chain propagation) … (ii)
𝐂𝐇𝟒 + 𝐂𝐥• → •𝐂𝐇
Each methyl-free radicals, in turn, reacts with chlorine molecule to form methyl chloride and
at the same time chlorine-free radical is produced.
𝐂̇𝐇𝟑 + 𝐂𝐥𝟐 → 𝐂𝐇𝟑 𝐂𝐥 + 𝐂𝐥• (Chain propagation).
The chlorine-free radical can react with fresh methane molecule as in next step or methyl
chloride.This process may extend further till all the replaceable hydrogen atoms in the
methane have been substituted by chlorine atoms.
• Chain termination on step: The chain reaction is terminated when any two free radicals.
𝐂𝐥̇ + 𝐂𝐥̇ → 𝐂𝐥𝟐
𝐂̇𝐇𝟑 + 𝐂𝐥̇ → 𝐂𝐇𝟑 𝐂𝐥
𝐂̇𝐇𝟑 + 𝐂𝐇̇ 𝟑 → 𝐂𝐇𝟑 − 𝐂𝐇𝟑
Direct iodination is not possible as the reaction is slow, reversible, endothermic. Hence it
is done by heating alkane with I2 in presence of oxidising agents like conc. HIO3, HNO3, HgO.
𝐂𝐇𝟒 + 𝐈𝟐 ⇌ 𝐂𝐇𝟑 𝐈 + 𝐇𝐈
𝟓𝐇𝐈 + 𝐇𝐈𝐎𝟑 → 𝟑𝐈𝟐 + 𝟑𝐇𝟐 𝐎
𝟐𝐇𝐈 + 𝟐𝐇𝐍𝐎𝟑 → 𝐈𝟐 + 𝟐𝐇𝟐 𝐎 + 𝟐𝐍𝐎𝟐
𝟐𝐇𝐈 + 𝐇𝐠𝐎 → 𝐇𝐠𝐈𝟐 + 𝐇𝟐 𝐎
Fluorination of alkanes is highly exothermic or explosive hence it cannot be controlled under
ordinary conditions.
• In case of higher alkanes, even monohalogenation gives a mixture of all the possible
isomeric haloalkanes indicating the replacement of all the types of possible H atoms
present in a given alkane.

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Monohalogenation does not depend upon the type of carbon atoms present in given alkanes,
but on type of replaceable H atoms in the given structures.
The relative amounts of the isomeric haloalkanes depends upon the nature of halogen and the
number type of hydrogens (1°, 2°, 3°) being substituted. The ease of substitution of various
H atoms generally follows the order 3° > 2° > 1°, but their relative rate of abstraction varies
with the nature of halogens.

The abstraction of H is in the order: Benzylic  allylic > 3° > 2° > 1° > CH4> Vinylic = aryl
Chlorination of n–alkanes (C4 and above) gives a mixture of d– and l–optical isomers i.e., racemic
mixture (optically inactive)

Allylic substitution: When alkenes are heated with Cl2 or Br2 at high T, H atom of allylic
carbon is substituted with the halogen atom without breaking double bond and forms allyl
halide.
𝟓𝟎𝟎°𝐂 𝐂𝐥 − 𝐂𝐇𝟐 − 𝐂𝐇 = 𝐂𝐇𝟐
𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇𝟐 + 𝐂𝐥𝟐 → + 𝐇𝐂𝐥
𝐚𝐥𝐥𝐲𝐥 𝐜𝐡𝐥𝐨𝐫𝐢𝐝𝐞
Allylic substitution can also be carried out by heating the alkene with NBS or SO2Cl2 at 200°C
in presence of light and traces of organic peroxides.

(2) From Alkenes:


Halogen acids add over alkene readily to give RX. The addition of HX to alkene is electrophilic
addition forming carbocation as reactive intermediate.
𝐇𝐈
𝐑 − 𝐂𝐇 = 𝐂𝐇𝟐 → 𝐑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 𝐈
The unsymmetrical alkens follow Markownikoff’s rule during addition forming 2° or 3° RXs
predominantly through the formation of most stable carbocation.
‘In the addition reactions of unsymmetrical alkenes the −ve part attaches to the carbon
atom having lesser number of H-atoms’.

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𝐇𝐈
𝐂𝐇𝟐 = 𝐂𝐇𝟐 → 𝐂𝐇𝟑 − 𝐂𝐇𝟐 𝐈

 −
CH3−CH=CH2 ⎯⎯
⎯→ CH3−CH−CH3 ⎯⎯
HX
⎯→
X
CH3−CH−CH3
(2° carbocation)
X

[Resonance stabilized carbocation is major more stable than hyperconjugation carbocation]

In presence of peroxides such as benzoyl peroxide (C6H5CO–O–O–COC6H5), the addition


of HBr (but not of HCl or HI) to unsymmetrical alkenes takes place opposite to
Markovnikov’s rule. This is known as Peroxide effect or Kharash effect. Thus,
• •
CH3− CH = CH2 ⎯⎯⎯→ CH3− CH−CH2− Br ⎯⎯
HBr
⎯→ CH3− CH2− CH2Br +
H Br
Peroxide
(2° radical)
Br

Mechanism: The addition of HBr to alkenes in presence of peroxides occurs by a free radical
mechanism. It consists of the following three steps:

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a. Initiation

b. Propagation: During the first step, a Br adds to the double bond in such a way to give the
more stable free radical. In the second step, the free radical thus produced abstracts a
H from HBr to complete the addition.

c. Termination: It involves the following three steps:

Exceptional behaviour of HBr: Peroxide effect is effective only in the case of HBr,
because HF and HCl are held by strong electrostatic force hence they cannot be broken
into free radicals.
H–I also give corresponding halogen free radicals. I° free radical being larger in size is less
reactive towards C= C bond but readily combines with another I° to give I2 molecule.

(3) From Alcohols:


Alkyl halides are prepared from alcohols by replacing –OH group of alcohols by a halogen atom.
R–OH + H–X ⎯→ R–X + H2O
The replacement of –OH group can be done with HX, phosphorus halides and SOCl2.
a. By action of halogen acids (Groves process)
This reaction is carried out in presence of a dehydrating agent as ZnCl2 or conc. H2SO4.
The 1:1 ratio of of HCl and anhydrous ZnCl2 is known as Lucas’s reagent.

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𝐙𝐧𝐂𝐥𝟐
𝐑 − 𝐎𝐇 + 𝐇𝐂𝐥(𝐠)𝐨𝐫𝐇𝐂𝐥(𝐜𝐨𝐧𝐜. ) → 𝐑𝐂𝐥 + 𝐇𝟐 𝐎
𝐙𝐧𝐂𝐥𝟐
𝐂𝐇𝟑 𝐂𝐇𝟐 𝐎𝐇 + 𝐇𝐂𝐥 → 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐥 + 𝐇𝟐 𝐎
𝐞𝐭𝐡𝐲𝐥𝐜𝐡𝐥𝐨𝐫𝐢𝐝𝐞

The reactivity of halogen acids is in the order: HI > HBr > HCl.
The order of reactivity of alcohols for halogen acid is as: 3° > 2° > 1°.
Reason: This reaction is an example of a nucleophilic substitution reaction in which the
nucleophile i.e., halide ion attacks the protonated alcohol molecule with the expulsion of water–
a good leaving group.

H+ SN1 +X−
R −OH R−O−H R R−X + (Some rearranged
−H2O
product, if possible)
H
X− SN2

R − X + H2O
∵ the reaction of alcohol with HX proceeds via the formation of a carbocation, hence 𝐶𝑙 −
attacks the most stable carbocation.

Ex: and not


Because of the strong tendency of neopentyl cation to rearrange to the more stable 3°
carbocation, neopentyl chloride cannot be prepared by the action of HCl on neopentyl alcohol.
Instead 2–chloro–2–methylbutane is formed as shown below :
(b) By action of Phosphorus halides
Alkyl chlorides are formed by the action of PCl3 or PCl5 on alcohols.
R−OH + PCl5 ⎯⎯→ R−Cl + POCl3 + HCl
3R−OH + PCl3 ⎯
⎯→ 3R−Cl + H3PO3
In case of preparation of alkyl bromides and iodides, PBr3 or PI3 required for the reaction is
generally produced in sites by the action of red P ON Br2 or I2.
3R−OH + PBr3 ⎯
⎯→ 3R−Br + H3PO3
3R−OH + PI3 ⎯⎯→ 3R−I + H3PO3
This method gives a good yield of 𝟏° RX but poor yield of 2° and 3° alcohols on heating forms
alkenes. This method is used in preparation of lower RBr and RI in the lab.
(c) By action of SOCl2 [Darzen’s method]
Alkyl chlorides are prepared by refluxing alcohols with SOCl2 in presence of pyridine.
⎯→ R−Cl + SO2 + HCl
R−OH + SOCl2 ⎯⎯⎯
Pyridine

The best method of preparation of haloalkanes from alcohols is using SOCl 2. In this method,
both the by-products (SO2 & HCl) are gaseous. They escape, leaving behind the product. Hence,
the product, does not need purification.
Corresponding bromides and iodides cannot be obtained by this method because thionyl bromide
is unstable while thionyl iodide does not exist.

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4. By Hunsdieker reaction or Borodine – Hunsdiekar reaction


Alkyl chlorides or alkyl bromides are prepared by the action of Cl2 or Br2 in CCl4 on silver salt
of fatty acids.
RCOOAg + X2 ⎯⎯
⎯4 → R−X + AgX + CO2
CCl

(X2 = Cl2 or Br2)

This reaction gives the product with one carbon atom less than the fatty acid.
The yield of RX by this method is in the order: 1° > 2° > 3°.
5. By halide exchange method: This is a convenient method for the preparation of RI.
• The corresponding RBr or RCl are heated with a sol. of NaI in acetone or methanol. This is
called Finkelstein reaction.
𝑵𝒂𝑰
R−Cl → R−I + NaCl
𝑨𝒄𝒆𝒕𝒐𝒏𝒆
𝑵𝒂𝑰
R−Br → R−I + NaBr
𝑨𝒄𝒆𝒕𝒐𝒏𝒆

• Alkyl fluorides may also be obtained by treating an RCl or RBr with Hg2F2 or SbF3 or AgF.
This is called Swart’s reaction.
𝟐𝐂𝐇𝟑 𝐂𝐥 + 𝐇𝐠𝐅𝟐 → 𝟐𝐂𝐇𝟑 𝐅 + 𝐇𝐠𝐂𝐥𝟐
𝐂𝐇𝟑 𝐁𝐫 + 𝐀𝐠𝐅 → 𝐂𝐇𝟑 𝐅 + 𝐀𝐠𝐁𝐫
𝟑𝐂𝐇𝟑 𝐂𝐂𝐥𝟐 𝐂𝐇𝟑 + 𝟐𝐒𝐛𝐅𝟑 → 𝟑𝐂𝐇𝟑 𝐂𝐅𝟐 𝐂𝐇𝟑 + 𝟐𝐒𝐛𝐂𝐥𝟑

Physical Properties:
1. CH3F, CH3Cl, CH3Br and C2H5Cl are gases at room temperature, while CH3I is a liquid at room
temperature. Haloalkanes upto C18 are colourless liquids while higher members are
colourless solids.
2. RXs being polar in nature are water insoluble.
3. They burn on Cu wire with green edged flame (Beilstein test for halogens)
4. RBrs and RIs are heavier than water, RCls and RFs are lighter than water.
5. RIs become brown or violet in colour on exposure to light.
𝐥𝐢𝐠𝐡𝐭
𝟐𝐑𝐈 → 𝐑 − 𝐑 + 𝐈𝟐
The I2 thus liberated dissolves in RX to impart dark colour.
6. The B.Ps of RXs are in the order: RI > RBr > RCl > RF.
Greater the molecular mass, stronger the vanderwaal’s forces of attraction and hence higher
is the M.P and B.P. For a given halogen, the B.Ps of RXs increases with the increase of the size
of ‘R’ group.
In isomeric RXs, as branching increases, surface area is decreased and hence B.P is decreased.
This it is in the order: 1° > 2° > 3°.

7. Decreasing order of density among RXs is in the order: RI > RBr > RCl > RF.
High density is observed for CH3I. Thus, for RI, the decreasing order of density is as follows:
CH3I > CH3CH2I > CH3CH2CH2I >……

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8. Stability of C–X bond decreases as the strength of C–X bond decreases. Bond strength
of C–X bond decreases as the size of halogen atom increases.
∴ bond strength of C–X bond is in the order: CH3–F > CH3–Cl > CH3–Br > CH3–I
9. Dipole moment of RXs decreases as E.N. of halogen atom decreases from Cl to Br to I.
fluorides have lower ′𝜇′than chlorides due to very small size of F which out weights the
effect of greater E.N. The actual order is: CH3Cl > CH3F > CH3Br > CH3I

Chemical Properties:
Nature of C–X Bond
The high reactivity of RXs can be explained in terms of the nature of C–X bond which is highly
polarized covalent bond due to large difference in E.N of C and halogen atoms.

- or −𝐶 𝛿+ − 𝑋 𝛿−

This polarity gives rise to 2 types of reactions namely nucleophilic substitution reactions and
elimination reactions.

Such reactions in which a stronger nucleophile displaces a weaker nucleophile are called
nucleophilic substitution reactions and the atom or group (halide ion in the present case) which
departs with its bonding pair of electrons is called the leaving group. Better the leaving group,
more facile is the nucleophilic substitution reaction.
Mechanism of nucleophilic substation reactions:
2 types of nucleophilic substitution reaction namely sN2 and sN1 .
1] Substitution nucleophilic bimolecular reactions 𝐬𝐍 𝟐
If the rate of the reaction depends on the concentration of alkyl halide as well as
nucleophile, then the reaction is known as 𝑠N2 reaction.
Rate ∝ [alkyl halide] [nucleophile]
sN2 Reactions are occurred in one step. During the reaction the nu attacks from the back
side (opposite side) of the halogen atom, the carbon-halogen band starts breaking and a
new carbon–nu bond starts forming. These two processes take place simultaneously in a single
step and a transition state is formed.
In the transition state, the carbon atom is simultaneously bonded to the incoming
nucleophile and the outgoing leaving group. This is unstable state, it ultimately decomposes
to form the product (CH3OH) and the leaving group (Cl– ion).

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H H
HO C I H
-
H HO C I HO C I
H H
H H H
iodomethane transition state methanol

Since the nucleophile attacks from the back side, hence optical property is inversion of
configuration so 𝐬𝐍 𝟐 reaction also called as Walden inversion.
Note-Since nucleophile attacks from the back side hence most favorable substrate will be
primary alkyl halide because less no. of alkyl groups will hinder the approach of nucleophile to
the carbon atom C-X bond among the 𝟏° alkyl halide, the most favorable R – X is methyl halide
Thus, the overall order of reactivity of different alkyl halides towards 𝑠N2 reaction is:
Methyl halides > 𝟏°halides > 𝟐°halides > 𝟑°halides.

ii] Substitution nucleophilicuni molecular reaction 𝐬𝐍 𝟏 :


Here rate of reaction of depends on only the concentration of alkyl halide only, then the
reaction is known as sN1 reaction
Rate ∝ [alkyl halide]

𝐬𝐍𝟏 Reaction takes place in two steps


Step1: The formation of carbocation
The alkyl halide undergoes heterolytic cleavage forming a carbocation. This is slow and rate
determining step.

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CH3 CH3

H3C C Br H3C C + Br .....Slow

CH3 CH3
Carbocation

Step 2: The nucleophile can attack the planar carbocation from either side to give the
substituted product. This step is fast and hence does not affect the rate of the reaction

Thus, reactivity of different alkyl halides towards 𝑠𝑛1 reaction is:


𝟑°Alkyl halide>𝟐° Alkyl halide>𝟑° Alkyl halide > Methyl halide.
Stereochemistry of nucleophilic substitution reactions: As the reaction involves the
formation of a planar carbocation, it allows the attack of nucleophile from both sides and
leads to the formation of enantiomers. So optical property observed is racemization

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COMPARISON OF SN1 AND SN2


SN1 SN2
(a) Number of steps 2 steps : 1 step :
(i) R : L ⎯⎯⎯→ R+ + :L−
slow R : L + : Nu− → R:Nu + :L−
Or
(ii) R+ + :NuH ⎯⎯
⎯→ R:Nu + H+
fast

R : L + :NuH → R : N+uH +:L−

(b) Reaction rate & order Rate = k1[RL]; first order Rate = k1[RL] [:Nu−]; second order
(c) Molecularity Unimolecular Bimolecular
−
(d) TS of slow step + − Nu……C…… L− (with : Nu−)
R …… L ……HNu: +
HNu……C…. L− (with : HNu)
(e) Stereochemistry Inversion and retention (Partial racemization) Inversion of configuration (backside
attack)
(f) Reacting nucleophile Nucleophilic solvent; stable R+ may react with added Added nucleophile
nucleophile
(g) Structure of R 3° > 2° > 1° > Me Me > 1° > 2° > 3°
(h) Nature of Leaving group Weakest base is best leaving group, i.e. Weakest base is best leaving group,
I− > Br− > Cl− > F− i.e. I− > Br− > Cl− > F−
(i) Nature of nucleophile For HNu: (solvent), In protic solvents,
rate  basicity of HNu: (i) Within a periodic table group, rate
 polarizability of Nu
(ii) For same nucleophilic site, rate 
basicity of Nu
In polar aprotic solvents, rate
 basicity of Nu
(j) Solvent effect Rate  H−bonding ability and dielectric constant Depends on charge type. Polar aprotic
solvents leave “freest” most reactive
Nu.
(k) Determining factor Stability of R+ Steric hindrance
(l) Rearrangement Observed Not observed, except for allylic
(m) Catalysis Lewis and Bronsted acids: No specific catalyst
Ag+, AlCl3 , ZnCl2 etc.

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The nucleophilic substitution reactions of haloalkanes are discussed below.


1. Substitution by hydroxyl group :
Haloalkanes on treatment with boiling aqueous alkalies or moist 𝐀𝐠 𝟐 𝐎 undergo hydrolysis to
form alcohols.
(𝑏𝑜𝑖𝑙)
𝑅 − 𝑋 + 𝐻𝑂𝐻 → 𝑅 − 𝑂𝐻 + 𝑋 −
𝛥
𝑅 − 𝑋 + 𝐾𝑂𝐻(𝑎𝑞. ) → 𝑅 − 𝑂𝐻 + 𝐾𝐵𝑟
𝛥
𝑅 − 𝑋 + 𝐴𝑔2 𝑂(𝑚𝑜𝑖𝑠𝑡) → 𝑅 − 𝑂𝐻 + 𝐴𝑔𝐵𝑟
2. Substitution by alkoxy group:
Haloalkanes on treatment with sodium or potassium alkoxides or dry Ag 2 O from ethers. If the
attacking nucleophile is OR− , the reaction is called williamson’s ether synthesis.
Δ
R − X + NaOR′ → R − OR′ + NaX
Δ
2RX + Ag 2 O → R − O − R + 2Ag X
Δ
Ex: C2 H5 Br + NaOCH3 → C2 H5 OCH3 + NaBr
Δ
Ex: 2C2 H5 Br + Ag 2 O → C2 H5 OC2 H5 + 2AgBr
3] Substitution by hydro-sulphide group:
Haloalkanes on Heating with aqueous alcoholic sodium or potassium hydrogen Sulphide gives
thioalcohols.
C2 H5 OH / H2 O
RX + NaSH→ RSH + NaX
Δ
C2 H5 OH / H2 O
Ex: C2 H5 Br + NaSH → C2 H5 SH + NaBr
Δ
4] Substitution by cyano group :
Haloalkanes on heating with alcoholic solution of KCN (ionic natured) gives alkyl cyanides as
the major product along with a small amount of alkyl isocyanide.
alochol
RX + KCN → RCN + KX
Δ
alochol
EX- C2 H5 I + KCN→ C2 H5 CN + KI
Δ

5] Substitution by isocyanide group:


Alkyl halides on heating with aqueous ethanolic solution of AgCN(covalent natured),gives alkyl
isocyanides (carbylamines) as the major product along with a small amount of alkyl cyanide
alochol
RX + AgCN→ RNC + AgX
Δ
alochol
Ex: C2 H5 Cl + AgCN→ C2 H5 NC + AgCl
Δ

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Explanation: The formation of cyanides or isocyanides from alkyl halides involves nucleophilic
substitution reaction.
• Alkali metal cyanides (KCN or NaCN) are predominantly ionic. Therefore, both carbon and
nitrogen atoms are free to donate electron pair. Since C–C bond is relatively stronger than
C–N bond, therefore, in this case attack mostly occurs through the carbon atom of the
cyanide group and alkyl cyanides are the major product.
• Silver cyanide is predominantly covalent. Consequently, only nitrogen electron pair is available
for bond formation, and the attack mostly occurs through the nitrogen atom of cyanide group
giving alkyl isocyanides as the major product.
6] Substitution by nitrite group:
Alkyl halides react with aq, ethanolic solution of 𝐾𝑁𝑂2,alkyl nitrite major product formed along
with a small amount of nitro alkane.
alochol
RX + K + O− − N = 0→ R − O − N = O + KX
Δ
alochol
Ex: C2 H5 Cl + K + O− − N = O→ C2 H5 − O − N = O + KCl
Δ
7] Substitution by nitro group:
Haloalkanes react with aqueous ethanolic solution of AgNO2 gives nitro alkane as the major
product with a small amount of alkyl nitrite

alochol
Ex: C2 H5 Br + AgNO2 → C2 H5 − NO2 + AgBr
Δ
Explanation: Nitrite ion (–O–N=O) like cyanide ion is an ambident nucleophile since it has two
sites (oxygen and nitrogen) through which it can attack an alkyl halide. Whereas attack through
nitrogen gives nitro compounds, attack through oxygen gives nitrites.

Alkali metals nitrites are ionic compounds and hence have a negative charge on one of the
oxygen atoms. Hence, it gives alkyl nitrites.
In contrast, silver nitrite is a covalent compound and hence does not have a negative charge
on the oxygen atom, therefore, lone pair of electrons on the nitrogen atom is more easily
available for bond formation or nucleophilic attack occurs through nitrogen and hence silver
nitrite predominantly gives nitro compounds

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8] Substitution by carboxylate group: -


Alkyl halides on heating with ethanolic solution of silver salts of fatty acids give esters.
C2 H5 OH
R′ COOAg + RX→ R′ COOR + AgX
Δ
C2 H5 OH
Ex: CH3 COOAg + C2 H5 Br → CH3 COOC2 H5 + AgBr
Δ
9] Substitution by aminogroup:
Haloalkanes on heating with ethanolie solution of NH3 in a sealed tube at100°𝐶, gives a mixture
of 𝟏°, 𝟐°, 𝟑° amines and quaternary ammonium salts . This reaction is called Hoffmann
ammonolysis.
C2 H5 OH
Ex: C2 H5 Br + NH3→ C2 H5 NH2 + HBr
Δ
1° amine

C2 H5 OH
C2 H5 NH2 + C2 H5 Br → (C2 H5 )2 NH + HBr
Δ
2° amine
C2 H5 OH
(C2 H5 )2 NH + C2 H5 Br → (C2 H5 )3 N + HBr
Δ
3° amine
C2 H5 OH
(C2 H5 )3 N + C2 H5 Br → (C2 H5 )4 N+ Br −
Δ
4° ammonoium salt
10] Substitution of chlorine or bromine by iodine:
Alkyl chlorides or bromides on treating with NaI or KI in acetone give alkyl iodides. This
reaction is called finkelstein reaction.
acetone
C2 H5 Br + NaI → C2 H5 I + NaBr.

B] Elimination Reaction: (Dehydrohalogenation)


When alkyl halide boiled with conc.Alc KOH, they undergo dehydrohalogenation to give alkenes.
These reactions are called 𝜷- elimination reactions because the hydrogen atom of haloalkane
which is eliminated comes from a 𝛽 −carbon

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Orientation of dehydrohalogenation: If the halogen is present on the terminal C atom of


chain, dehydrohalogenation can occur only in one direction to give only the terminal alkene.
For example,1-chlorobutane on dehydrohalogenation gives but-1-ene

In the dehydrohalogenation of secondary and tertiary haloalkenes, when there is a possibility


of formation of two isomers, the hydrogen atoms is preferentially eliminated from the
adjacent carbon atom with lesser number of hydrogen atoms. This generalization is known as
Saytzeff’s rule, i.e., the more substituted alkene is more stable. For example,

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H 3C CH CH CH 3
CH 3 But- 2-ene
alc. KOH (Major ) (80%)
H 3C

H 3C CH 2 CH CH 2
Br
But- 1-ene
(Minor) (20%)

but-1-ene
(minor)

but-2-ene(Major)
can exist as cis and trans isomers

The ease of dehydrohalogenation is in the order :


Tertiary alkyl halide > Secondary alkyl halide > Primary alkyl halide.
C] Other reaction:
1] Reduction: Alkyl halides on reduction with ZN/HCL, No/alcohol, LiAlH4 or ZnCU
couple/alcohol gives corresponding alkanes.
Zn − Cu couple
RX + 2H→ R − H + HX
alcohol
Zn − Cu couple
Ex: C2 H5 CL + 2H→ C2 H6 + HCl
alcohol
2] Reaction with sodium (Wurtz reaction):
Alkyl halides react with metallic sodium in presence of dry ether to form symmetrical
alkanes containing double the number of carbon atoms present in the alkyl halide.
R – X + 2Na + X – R Dry ether R – R + 2NaX
(Alkane)
H5C2 – X + 2Na + X – C2H5 Dry ether CH3 CH2 CH2 CH3 + NaCl
(n-Butane)
3] Reaction with magnesium:
Alkyl halides form Grignard reagents when treated with dry magnesium powder in dry ether.
R–X + Mg Dry ether RMgX
(Alkyl halide) (Alkyl magnesium halide)
(Grignard reagent)
CH3 – CH2 – Br + Mg Dry ether CH3 – CH2 - MgBr
(Ethyl magnesium bromide)

Grignard reagents are used for making a very large


number of organic compounds.
Reactivity order is RI > RBr > RCl.

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4. Reaction with other metals: Organometallic compounds are formed.


• When heated with zinc powder in ether, alkyl halides form dialkyl zinc compounds. These
are called Frankland reagents.
Ether
2C2 H5 Br + 2Zn → (C2 H5 )2 Zn + ZnBr2
Heat
• When heated with lead–sodium alloy, ethyl bromide gives tetra ethyl lead (TEL) which is
used as antiknock compound in petrol.
dryether
4CH3 CH2 Br + 4Pb(Na) → (CH3 CH2 )4 Pb + 4NaBr + 3Pb

• Alkyl halides reacts with lithim dialkyl cuprate (R2CuLi) to form unsymmetrical alkanes
(Corey –House Synthesis).

+ KOH (aq.) + KNO2


R – OH + KX R – O – N = O + KX
(Alcohol) (Alkyl nitrite)
+ Na+OR- + AgNO2
R – O – R + NaX
1
R – NO2 + AgX
(Ether) (Nitroalkane)
+ KCN (alc.) + LiAlH4
R – CN + KX R–H
(Alkyl cyanide) R–X (Alkane)
ALKYL HALIDE
+ AgCN + NH3
R – NC + AgX R – NH2 + H – X
(Alkyl isocyanide) (Alkyl amine)
+ NaSH O
R – SH + NaX + R – C – O – Ag
1

(Thioalcohol)
+ Na+C-≡ CH O
R – C ≡ CH + NaX R – C – O – R1 + AgX
(Higher Alkyne) (Ester)

Dihalogen compounds
General methods of preparation of gem-dihalides
1] From aldehydes and ketones:
Aldehydes and ketones on treating with PCl5 gives gem-dehalides.
𝐶𝐻3 𝐶𝐻𝑂 + 𝑃𝐶𝑙5 → 𝐶𝐻3 𝐶𝐻𝐶𝑙2 + 𝑃𝑂𝐶𝑙3
Ethylidene chloride

𝐶𝐻3 𝐶𝑂𝐶𝐻3 + 𝑃𝐶𝑙5 → 𝐶𝐻3 𝐶𝐶𝑙2 𝐶𝐻3 + 𝑃𝑂𝐶𝑙3


Isopropylidene chloride

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2] From alkynes: Addition of halogen acids to alkynes gives gem-dihalides


𝐻𝐶𝑙
𝐶𝐻 ≡ 𝐶𝐻 + 𝐻𝐶𝑙 → 𝐶𝐻2 = 𝐶𝐻𝐶𝑙 → 𝐶𝐻3 − 𝐶𝐻𝐶𝑙2

General methods of preparation of vicinal dihalides:


1. From glycols : Glycols on reacting with halogen acids, PCl3 , PCl5 or SOCl2 gives Vic-
dihalides.

2. From alkenes: Addition of halogens to alkenes gives ric-dihalides.


𝐶𝐻2 = 𝐶𝐻2 + 𝐶𝑙2 → 𝐶𝐻2 𝐶𝑙 − 𝐶𝐻2 𝐶𝑙

Trihalogen derivatives
Chloroform(𝐶𝐻𝐶𝑙3): It was discovered by Liebig and named chloroform by Dumas. Earlier it
was extensively used as anesthesia for surgery. But now it is rarely used as it causes liver
damage.
Preparation of chloroform- By distillation of ethyl alcohol and bleaching powder:
Chloroform is prepared by the distillation of ethyl alcohol with bleaching powder and water.
The yield is about 40% the available chlorine from bleaching powder serves as oxidising agent
and chlorinating agent.
The reaction takes place in 4 steps.
a] Hydrolysis of bleaching powder, 𝐶𝑎𝑂𝐶𝑙2 + 𝐻2 𝑂 → 𝐶𝑎(𝑂𝐻)2 + 𝐶𝑙2
b] Oxidizing of ethyl alcohol to acetaldehyde by Cl2 , 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐶𝑙2 → 𝐶𝐻3 𝐶𝐻𝑂 + 2𝐻𝐶𝑙
c] Chlorination of acetaldehyde to chloral, 𝐶𝐻3 𝐶𝐻0 + 3𝐶𝑙2 → 𝐶𝐶𝑙3 𝐶𝐻𝑂 + 3𝐻𝐶𝑙
d] Hydrolysis of chloral with Ca(OH)2, 2𝐶𝐶𝑙3 𝐶𝐻𝑂 + 𝐶𝑎(𝑂𝐻)2 → (𝐻𝐶𝑂𝑂)2 𝐶𝑎 + 2𝐶𝐻𝐶𝑙3
Physical properties:
1] It is a colorless sweet-smelling liquid
2] It is a heavier than water. (d= 1.485 g/cc)
3] It is less soluble in water but more soluble in organic solvents
4] It is a non-inflammable liquid. But vapors burn with green flame
Chemical properties:
1] Oxidation: When chloroform is exposed to sunlight and air it is slowly oxidized to phosgene
a colourless poisonous gas.
1 ℎ𝜈
𝐶𝐻𝐶𝑙3 + 𝑂2 → 𝐶𝑂𝐶𝑙2 + 𝐻𝐶𝑙
2
The oxidation of chloroform is prevented by
a] Strong chloroform in dark brown-colored bottles filled up to the brim.
b] Adding 1% ethyl alcohol- Ethyl alcohol prevents the oxidation chloroform and converts
phosgene into harm less ethyl carbonate.
COCl2 + 2C2 H5 OH → (C2 H5 O)2 CO + 2HCl

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Phosgene is extremely poisonous gas. To use chloroform as an anesthetic agent, it is necessary


to prevent the above reaction. The following precautions are taken when chloroform is stored.
(a) It is stored in dark blue- or brown-colored bottles which are filled up to the brim.
(b) 1% ethyl alcohol is added. This retards the oxidation and converts the phosgene formed
into harmless ethyl carbonate.

Carbylamine reaction (isocyanide test): This reaction is actually a test of primary amines.
Chloroform, when heated with primary amine in presence of alcoholic potassium hydroxide
forms a derivative called isocyanide (carbylamines) which has a very offensive smell.

This reaction is also used for the test of chloroform.


Uses:
(i) It is used as a solvent for fats, waxes, rubber, resins, iodine, etc.
(ii) It is used for the preparation of chloretone (a drug) and chloropicrin (insecticide).
(iii) It is used in laboratory for the test of primary amines, iodides and bromides.
(iv) It can be used as anaesthtic but due to harmful effects it is not used these days for this
purpose. It causes liver damage when inhaled in excess (SO is CCl4).
(v) It may be used to prevent putrefaction of organic materials, i.e., in the preservation of
anatomical species.
Test of chloroform:
(i) It gives isocyanide test (carbylamines test).
(ii) It forms silver mirror with Tollen’s reagent.
(iii) Pure chloroform does not give white precipitate with silver nitrate.

Iodoform: Iodoform resembles chloroform in the methods of preparation and properties.


Iodoform reaction: Organic compounds having methyl ketone (CH3 – C O )
Or gives methyl ketone group on oxidation, when heated with I2 in presence of alkali gives
iodoform. Basic requirement for a compound to give iodoform reaction is presence of

(or) . Group. Compounds having group. undergo oxidation with

halogens to give group

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p - p - Dichloro diphenyl tri chloro ethane (DDT)


It is manufactured by condensation of chloro benzene with trichloro acetaldehyde (chloral) in
the presence of sulphuric acid.
Cl
Cl
Cl 1 2 Cl (Structure of DDT)
Cl H

Preparation of DDT:
Cl H Cl Cl Cl
Cl – C – CH O + H+ Cl – C – CH
Cl H Cl Cl Cl
DDT
Properties It is a white powder insoluble in water but soluble in oils.
Uses It is a powerful insecticide. However, it is highly stable & is not easily decomposed in the
environment. Therefore, its long-term effect could be potentially dangerous & its use
is banned in many countries

FREONS These are poly chlorofluoro derivative of alkane.

Preparation of freons :
CCl4 + HF ⎯SbCl
⎯⎯→ CCl3F + HCl
5

C2Cl6 + 2HF ⎯SbCl


⎯⎯→ C2F2Cl4 + 2HCl
5

hexachloro ethane freons–112


Properties & uses of freons :
(a) Freons are colourless, odourless, unreactive & non-combustible liquids.
(b) Having very low boiling points (e.g CF2Cl2= – 29.8ºC). They easily converted from gaseous
state to liquid state, therefore they are used as a coolant in A.C. & Refrigerator.
(c) Used as a aerosol propellant in aeroplane & rockets.
(d) Also used as a solvent.
Note: Main cause of Ozone layer decay (CFC – chlorofluoro car
Nomenclature of Freons:
• The common name of freons is F-cba, Where c = number of carbon atoms – 1
b = number of hydrogen atoms + 1
a = total number of atoms of fluorene
Example: CFCl3 : C – 1 ⇒ 1 – 1 = 0, H + 1 ⇒ 0 + 1 = 1, F = 1 ⇒ F-11
CF2Cl2 : C – 1 ⇒ 1 – 1 = 0, H + 1 ⇒ 0 + 1 = 1, F = 2 ⇒ F-12

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Haloarenes
Compounds in which halogen is directly attached to an aromatic ring are known as aryl halides
or haloarenes and are represented as Ar –X, where 𝐴𝑟 is phenyl, substituted phenyl or a group
derived from other aromatic system.
General methods of preparation:
1. By direct halogenation of aromatic hydrocarbons: This method is used for the
preparation of chloro and bromo derivatives. Halogens react with aromatic hydrocarbons in
presence of catalysts or halogen carriers such as iron, iodine or anhydrous ferric or
aluminium chloride (Lewis acid) at room temperature in absence of direct sunlight.
H
+ X2 Fe or FeX3 / dark + HX (X = Cl, Br)

H
+ I2 HIO3 or HNO3 + HX (X = Cl, Br)
Cl

AlCl3
+ Cl2 + HCl

Br
Fe or
Br 2 HBr
FeBr 3
(Bromobenzene)
CH 3 CH 3
CH 3
Cl
FeCl 3
Cl 2
dark
(o-chlorotoluene)
Cl
(p-chlorotoluene)

For further halogenation, more halogen is used,

The function of the Lewis acid is to carry the halogens to the aromatic hydrocarbon.
If toluene is used instead of benzene, a mixture of o–and p–chlorotoluenes is obtained since –
CH3 group is o, p–directing.
CH 3
CH 2Cl

Cl 2 338 K HCl
Sunlight
1-chloro-1-phenylmethane

(b) Side chain halogenation-Benzylic halogenation:


The most convenient method for the preparation of side chain substituted aryl halides or
aralkyl halides is by the direct halogenation of a suitable arene. For example, when Cl2 is passed

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through boiling toluene in presence of sunlight and absence of halogen carrier,


phenylchloromethane (benzyl chloride) is formed.
CH 3
CH 2Cl

Cl 2 338 K HCl
Sunlight
1-chloro-1-phenylmethane
If Cl2 is passed for a longer time, the initially formed benzyl chloride reacts further to form
first benzal dichloride and then benzo trichloride.

2. From diazonium salts


NH2 N+≡ 𝑁𝐶𝑙 −
H
NaNO2 /HCl (273-278K) + HX (X = Cl, Br)

CuCl/HCl Cl + N2

Sandmayer’s reaction
CuBr/HBr Br + N2
N+≡NC𝑙 −

(Benzene diazoniu + KI I + KCl + N2


chloride)

+ NaBH4 F + BF3 + NaCl + N2

(i) By Sandmeyer reaction:


NH 2
N2 Cl-

273-277 K
HNO 2 HCl 2H2 O

Aniline Benzenediazonium chloride

The diazonium compound is treated with CuCl and HCl or CuBr and HBr to give the
corresponding haloarene. This reaction is known as Sandmeyer reaction.
-
N2 Cl Cl

CuCl
N2

-
N2 Cl Br
CuBr
N2 CuCl

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(ii) By Gattermann reaction:


Haloarenes particularly chloro-and bromoarenes can also be prepared by Gattermann reaction.
It is a modification of the Sandmeyer reaction. In this reaction, a mixture of freshly
prepared copper powder in the presence of HCl or HBr is used. The yields are often around
40%. Thus,

• From silver salt or aromatic acids–Hunsdiecker reaction: Like alkyl bromides, aryl
bromides can also be prepared by refluxing the silver salt of aromatic acids with bromine
in boiling carbon tetrachloride.
C6H 5COOAg X 2 ⎯⎯⎯⎯⎯
CCl4 / Xylene
→ C6H 5 X CO 2 AgX
(Cl 2 or Br 2)

Chemical properties of haloarenes:- Aryl halides are less reactive than that of alkyl halides
towards nucleophilic substitution reactions.
This can be explained as follows:
(i) Resonance Effect: In haloarenes (e.g., chlorobenzene), the lone pairs of electrons on the
halogen atom are delocalized on the benzene ring as shown below:

+ + +
X X X X X

CANONICAL FORM
𝛿+ X
𝛿− 𝛿−

𝛿−
As a result, C–Cl acquires some double bond character. On the other hand, in case of alkyl
halides (say methyl chloride) carbon is attached to chlorine by a pure single bond.
Consequently, C–X bond in aryl halides is little stronger than in alkyl halides, and hence cannot
be easily broken.
(ii) Bond energies due to difference in hybridization:
In alkyl halides, the carbon holding halogen is 𝑠𝑝3 −hybridised. In aryl halides, carbon is
𝑆𝑃2 −hybridized; the carbon −halogen bond is shorter and stronger, and the molecule is more
stable.

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(iii) Polarity (or Nature) of the carbon halogen bond: Another reason for the low reactivity
of aryl/vinyl halides over alkyl halides is their lesser polar character.

The sp2–hybrid carbon due to greater s–character is more electronegative than a sp3–hybrid
carbon. Therefore, the sp2–hybrid carbon of C–X bond in aryl halides or vinyl halides has less
tendency to release electrons to the halogen than a sp3–hybrid carbon in alkyl halides. As a
result, the C–X bond in aryl halides or vinyl halides is less polar than in alkyl halides. This is
supported by the observation that the dipole moment of chlorobenzenes just1.69D as
compared to the dipole moment of methyl chloride i.e., 1.86 D. Consequently, the halogen atom
present in aryl halides cannot be easily displaced by nucleophiles.
1] Substitution reactions: Nucleophilic substitution reactions of chlorobenzene given below
(a) Replacemet of –Cl by –OH: When chlorobenzene is heated at 350°C under high pressure
with caustic soda, phenol is formed (Dow process).
Cl ONa OH

623 K, 300 atm H


NaOH Na

(b) Replacement by methoxy group: Ether is formed when chlorobenzene is heated with
sodium methoxide at 200°C in presence of copper salts.
Cl OR

Cu salt (catalyst)
NaOR, High pressure, 573 K

Ether

(c) Replacement by amino group: When chlorobenzene is treated with aqueous ammonia at
200°C under a pressure of 60 atmospheres in presence of cuprous oxide or cuprous chloride,
aniline is formed.
475 K
2 Cl 2NH 3 Cu 2O 2 NH 2 2 CuCl H 2O
60 atm

(d) Replacement by –CN group: When chlorobenzene is treated with cuprous cyanide in
pyridine or DMF at 200°C, phenyl cyanide is formed.

DMF
Br CuCN CN CuBr
470 K
Phenyl cyanide

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2] Reaction with sodium: Alkyl halides when heated with sodium in presence of dry either
gives diaryls. This reaction is called fitting reaction.

2 Cl 2Na ether 2 NaCl

When a mixture of aryl halide and alkyl halide is heated with sodium in presence of dry ether
gives alkyl derivatives of benzene. This reaction is called Wurtz –fitting reaction.
Cl 2Na ether
CH 3Cl CH 3 2 NaCl

Toluene
3] Reaction with magnesium: Bromo–and iodoarenes from Grignard reagents when their
ethereal solution is treated with magnesium turnings. Chloroarenes from Grignard
reagents only if the reaction is carried out in dry tetrahydrofuran (THF) as solvent.
Br MgBr

ether
Mg

Phenyl magnesium bromide


THF
Cl Mg MgCl

Phenyl magnesium chloride


4] Reaction with lithium: Bromo– and iodoarenes also react with lithium metal in presence of
dry ether to form the corresponding organometallic compounds. For example,
Br 2Li dry ether Li LiBr
Phenyl lithium
5] Reduction: Chlorobenzene undergoes reduction with LiAlH4 or Ni–Al alloy in NaOH solution
or Na–Mg/H2O to give benzene.
Ni Al alloy
C6H 5Cl 2H C6H 5 HCl
NaOH
Benzene
6] Reactions of benzene ring:
–Cl group in chlorobenzene is o–, p–director and deactivating. However, because of steric
hindrance at the o–position, the p–product usually predominates over the o–product. The
benzene ring undergoes halogenation, nitration, sulphonation (Electrophilic substitution)
reactions.

+ + +
X X X X X

CANONICAL FORMATS
Due to resonance, the electron density increases more at ortho & para positions than at meta
position. Therefore, electrophilic substitution reaction take place at ortho & para position.

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(i) Halogenation
Cl Cl Cl
Cl
Fe or FeCl 3
Cl 2 or anh. AlCl
3

1,2-dichlor o benzene
Cl
1, 4-dichloro benzene
(ii) Nitration
Cl Cl Cl
NO 2

HNO 3 H 2SO4 
(conc.) (conc.)
l-chloro 2 nitro benzene
NO 2
l -chloro
benzene
(iv) Sulphonation
Cl Cl Cl
SO3H

H 2SO4 
(conc.)
2-chloro benzene
sulphonic acid SO3H
4-chloro benzene
sulphonic acid
(iv) Friedel–Crafts reaction
Cl Cl Cl
CH 3

anhy. AlCl 3
CH 3Cl

2-chlorotoluene
CH 3
4-chlorotoluene
Cl Cl Cl
COCH 3
anlcy AlCl 3
CH 3COCl

o-chloro acetophenone
COCH 3
(Minor)
p-chloro acetophenone
(Major)

(v) Reaction with chloral: When chlorobenzene is heated with chloral (trichloracetaldehyde)
in the presence of conc. H2SO4, a powerful insecticide, DDT (p, p'–
dichlorodiphenyltrichloroethane) is formed.

H Cl Cl
Conc. H 2SO4
CCl 3 CHO CCl 3 CH

H Cl - H 2O Cl

[l, l, l, trichloro- 2, 2-bis


(p-chlorophenyl) ethane

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BASIC STEREOCHEMICAL PRINCIPLES AND NOTATION


OPTICAL ISOMERISM Certain organic compounds, when their solutions are placed in the
path of a plane polarized lights have the remarkable property of rotating its plane through a
certain angle which may be either to the left or to the right. This property of a substance of
rotating the plane polarized light is called optical activity and the substance passing it is said
to be optically active.

CONDITIONS FOR OPTICAL ACTIVITY:


Asymmetric or Chiral carbon atom: A carbon atom is described as being asymmetric when four
different atoms or groups are bonded to it thus an asymmetric carbon in formulas is usually indicated
by on asterik (*) placed near it.
All organic compounds containing an asymmetric carbon atom are optically active.
OH CH3
| |
CH3–C*–COOH CH3–CH2–C*–CH2OH
| |
H H
lactic acid amyl alcohol
(optically active) (optically active)
Asymmetric or Dissymmetric molecules: Molecules which have asymmetric or dissymmetric molecular
structure in tetrahedral perspective, are called asymmetric molecules. The two features of such
structures are -
(i) No plane of symmetry : A 'Plane' of symmetry' is a plane which divides an object in such a way
that the part of it on one side of the plane is the mirror image of that on the other side for eg. a ball
is symmetrical while a hand is asymmetric

Plane of symmetry Plane of symmetry


(absent) (present)

Similarly, an organic molecule is asymmetric if there is no plane (or centre) of symmetry for example.
COOH C COOH
C
H OH H OH
H H F
OH H Br H
H HO
Br
COOH COOH

Symmetric symmetic asymmetic asymmetric

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(ii) Non superimposable on its mirror image:


An asymmetric object cannot be superimposed on its mirror image thus right hand produces a mirror
image which is identical with your left hand. The two hands are non-superimposable which is clearing
evident if your right and in the left-handed glove. On the other hand, asymmetric object like a ball can
be superimposed its mirror image which is another similar ball.

Mirror
Mirror
COOH COOH
Cl | |
| Cl
| C C
C
C H OH HO H
H F F H CH3 CH3
Br Br

Chirality: - This term has been recently used to describe such molecules as have no elements of
symmetry, thus symmetrical molecules are also called chiral molecules and optical activity is attributed
to certain chiral centres in them. An asymmetrical carbon is a chiral center.
Chirality is lost when the two atoms bonded to an asymmetric carbon become similar thus lactic acid
is optically active but propionic acid is inactive.

Chirality or molecular dissymmetry cause of optical Isomerism


• The necessary condition for a molecule to exhibit optical isomerism is dissymmetry or chirality .
Thus, all organic compounds which contain one asymmetric carbon are chiral and exist in two
tetrahedral forms.
• Although the two forms (I and II) shown in fig. (a) have the same structure, they have different
arrangements of groups a,b,d,e about the asymmetric carbon in fact, they represent asymmetric
molecules they do not have a plane of symmetry they are related to each other as an object to its
mirror image and are non-superimposable.
• The two models or structures (I and II) stand for dextro or (+) and laevo or (-) isomers. Since they
are related to each other as mirror images, they are commonly called Enantiomers (Gr, enantio =
opposite, morph - form) or enantiomers thus optical isomerism is now often reflected to as an
enantiomer.

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• It is obvious that optical isomers or enantiomers due to the presence of an asymmetric carbon atom
in a compound differ only in the arrangement or configuration of groups in tetrahedral perspective
this may be illustrated by taking a few examples of compounds which exist as (+) and (-) enantiomers.
COOH Mirror COOH H Mirror H
| | | |
C C C C
H OH H CH3 C6H5
HO C6H5 CH3
CH3 CH3 Cl Cl

(+) and (–)-Lactic acid (+) and (–)-1-Chloro-1-phenyl ethane


Number of optical isomers :
Case - 1 When the molecule is unsymmetrical. (It cannot be divided into two halves)
Number of d and  isomers = 2n
Number of meso form = 0 Where n is the number of chiral carbon atoms
Total number of optical isomers = 2n
e.g.
. Pentane-2, 3-diol
CH3
|
H––C*––OH Number of d and  isomers = 22 = 4
|
H––C*––OH Number of meso isomers = 0
|
C2H5
Case - 2 When the molecule is unsymmetrical and number of chiral carbon = even number
Number of d and  isomers =2(n – 1)
Number of meso isomers =2(n/2 – 1)
n 
 –1
Total number of optical isomers = 2 (n–1)
+ 2 2 

e.g. : Tartaric acid


COOH
| Number of d and  isomers = 2(2 – 1) =21 = 2
H––C*––OH
| Number of meso isomers = 2(2/2 – 1) =2º = 1
H––C*––OH Total optical isomers = 2 + 1 = 3
|
COOH
Case- 3. When the molecule is symmetrical number of chiral carbon = odd number
( n –1)
Number of d and  isomers = 2(n – 1) – 2 2

Number of meso isomers = 2


Total number of optical isomers = 2 n–1

e.g. Pentane – 2,3,4-triole


Number of d&  isomers = 22 – 21 = 4 – 2 = 2
* * *
CH3–CH–CH–CH–CH3  3 –1 
| | |  
OH OH OH Number of meso isomers = 2 2 
= 21 = 2
Total optical isomer = 23–1 = 22 = 4

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D, L- SYSTEM (RELATIVE CONFIGURATION) :


Optically inactive
(does not rotate plane polarised light)

Organic compound Laevorotatory [rotates the plane polarised


(𝑙 or –) light towards left]
Optically active + & – isomers of an
(rotate plane polarised light) organic compound
Dextrorotatory [rotates the plane polarised are optical isomers
(𝑑 or +) light towards right]

It is applicable for Fischer projection formula.


It represents relative configuration with respect to glyceraldehydes.
Following configuration of glyceraldehyde is considered as standard configuration.
CHO CHO

H * OH HO * H

CH2OH CH2OH

D- glyceraldehyde L- glyceraldehyde
(– OH is on R.H.S.) (– OH is on L.H.S.)
• All molecules which could be chemically relative to D-glyceraldehyde are assigned the D-
configuration and those related to L-glyceraldehyde are designated L-configuration as illustrated
below -
COOH COOH COOH COOH

H * OH HO * H H2N * H H 2N * H

CH3 CH2OH CH3 CH2OH

(D-form) (L-form)
(L-form) (D-form)
CH2OH
CHO
CHO COOH C=O
H * OH H * OH
H * OH H * NH2 HO * H H * OH
HO * H HO * H
H * OH HO * H
CH2OH CH3 H * OH
CH2OH
(L-form) (D-form)
CH2OH
(D-form) (L-form)
Special Point:
The method of separating a racemic mixture into its enantiomeric constituents is called as Resolution.
There is no direct relation between D, L– configuration with d, l or (+), (–) configuration.

ENANTIOMERS: The stereoisomers related to each other as non-superimposable mirror


images are called enantiomers.
PROPERTIES OF ENANTIOMERS :
(1) Enantiomers have chiral molecule (optically active)
(2) Enantiomers have identical physical properties like BP, MP, refractive index, density etc.
(3) They rotate PPL in opposite direction but to the equal extent.
(4) They have identical chemical properties, However their reactivity i.e. rate of reaction will be differ
if they combine with other optically active reagent.

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k3
k1
R + x ⎯⎯→ R + y ⎯⎯→ P
P active, then K3  K4
k2 inactive, then K1 = K2 k4
S + x ⎯⎯→ P S + y ⎯⎯→ P

(5) They have different biological properties i.e. (+) sugar play significant role in animal metabolism
while (–) sugar do not.

Meso compounds; These are the compounds containing the more than one asymmetric
carbon atom but due to the presence of plane of symmetry, do not show optical activity.
They are optically inactive compounds.

DIASTEROMERS: Such configurational isomers which are neither be mirror image nor be
superimpossible on each other, called as diastereoisomer.
e.g.
CH3 CH3
H OH H OH
HO H & H OH
CH3 CH3
CH3 CH3 CH3 H
C=C & C=C
H H H CH3

(cis) (trans)
Cis-trans isomer are geometrical isomer but they are not the mirror image thus, they are said to be
diastereomer
CHARACTERISTICS OF DIASTEREOMERS:
(1) They are generally optical active, however geometrical isomers are exception.
(2) They have different physical properties like MP, BP, density, solubilities & value of specific rotation.
(3) They are separated by fractional distillation, fractional crystallisation & chromatography etc.
(4) They exhibit similar

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