Vidya Mandir Classes Class 11 Chem

Vidyamandir Classes Atomic Structure
Atomic Structure
DALTON’S THEORY OF ATOM SECTION - 1A
John Dalton developed his famous theory of atom in 1803. The main postulates of his theory were :
 Atom was considered as a hard, dense and smallest indivisible particle of matter.
 Each element consists of a particular kind of atoms.
 The properties of elements differ because of differences in the kinds of atoms contained in them.
 This theory provides a satisfactory basis for the law of chemical combination.
 Atom is indestructible, i.e., it cannot be destroyed or created.
Drawbacks
 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-atomic 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 CATHODE RAYS & POSITIVE RAYS SECTION - 1B

Cathode Rays
Sir William Crooks studied various gases in a gas discharge tube (a glass tube with a very high potential
applied to its ends) at low pressures. If the pressure in the tube is lowered to about 104 atm, glass begins to
fluoresce (glow) faintly. It was established that the glow was due to bombardment of the glass by a certain
kind of rays emerging from cathode (negative electrode) which travel in a straight line until they strike the
anode (positive electrode). These rays were called as cathode rays.
Sir J. J. Thomson demonstrated that when cathode rays were deflected on to an electrometer, it acquired
negative charge. He also showed that the rays were deflected on application of an electric field. The
cathode ray beam was deflected away from the negatively charged plate. These results were found to be
identical, irrespective of the gas taken in the discharge tube. He concluded that the cathode rays were a
stream of fast moving negatively charged particles called electrons (named by Stoney). He also calculated
the velocity and specific charge for an electron. The specific charge is the ratio of charge to the mass of
an electron, denoted as e/m ratio. The e/m ratio was found to be same for all gases. This led to the
conclusion that the electron must be a fundamental or universal particle common to all kinds of the atoms.
The e/m ratio (for an electron) = 1.758 x 1011 C/Kg.
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Atomic Structure Vidyamandir Classes
Note : (i) J. Millikan determined the value of the charge on an electron with the help of famous Oil drop
experiment. The magnitude of the charge on an electron = 1.60206  1019 C and the mass of an
electron = 9.1  1031 kg.
(ii) You will be studying the details of Thomson’s calculations of e/m ratio and Millikan’s oil drop experiment
for the determination of electronic charge later in Modern Physics in the Module of Physics.
Positive Rays
Since the atom as a whole is neutral, it means that an equal amount of positive charged particle should also
be there in the atom. Goldstein, by carefully experimenting with the discharge tube consisting of perforated
cathode, showed the presence of another type of rays. These rays emanating from anode passed through
the perforations in the cathode. These carried positive charge and were called as positive or anode rays.
It was established that these rays consist of positively charged particles called as protons. The magnitude
of charge on a proton is same as that on an electron, but its mass was found to be 1837 times the mass of
an electron. The mass of a proton = 1.6735  1027 kg.
Since the electron has negligible mass (as compared to the proton), so it was assumed that whole mass of
an atom is associated with the protons. Later in 1932, with the discovery of neutron as IIIrd fundamental
particle (Ist and IInd being electron and proton), it was established that the mass of an atom is the total
mass of protons and neutrons taken together.
MODELS OF ATOM SECTION - 2A
Thomson’s Model
Putting together all the facts known at that time, Thomson assumed that an atom is a sphere of positive
charges uniformly distributed, with the electrons scattered as points throughout the sphere. This was
known as plum-pudding model at that time. However this idea was dropped due to the success of
scattering experiments studied by Rutherford and Mardson.
Rutherford’s Model
Rutherford studied the scattering of  particles (doubly ionised Helium atom) by the thin metallic foils (of
gold, platinum etc.). A narrow pencil beam of fast moving  - particles were struck on a thin metal foil
( 104 atoms thick). The angular deflections of scattered  particles were studied with the help of a moving
microscope.
Observations of the Rutherford’s experiment :

 Most of the particles passed through the foil undeflected, i.e., went straight through the foil.
 Some of them were deflected, but only at small angles.
 A very few (1 in 20,000) were deflected at large angles (180 ).
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Conclusions :
 As most of the -particles passed undeflected, it was concluded by Rutherford that the atom must be
predominantly empty.
 -Particles are positively charged with appreciable mass (4 amu) and were moving high kinetic
energy. In order to produce deflections, there must be some enormous positively charged body inside
the atom.
 Only a few received large deflections. This led to the conclusion that enormous charge must be con-
fined to a very small region. This small region was given the name nucleus.
 Rutherford then proposed that an atom is composed of a dense positive nucleus, thinly surrounded by
the electrons. The mass and the positive charge of the nucleus are confined in a very small region of
space. The electrons are outside the nucleus, so that an atom is almost entirely empty space.
 From stability point of view, the electrons cannot be stationary otherwise they would be drawn into
the nucleus. So Rutherford assumed that electrons were moving in circles around the nucleus; the
necessary centripetal force being provided by the electrostatic attraction between nucleus and the
electrons. He gave no further justification for this assumption.
Note :  From experiments, it was confirmed that with in the nucleus, the distribution of positive charge is
uniform and atomic nuclei are spherical in shape.
 Later with the discovery of the neutrons (In 1932 by Chadwick), it was established that these also
occupy the place in the nucleus bonded along with the protons by a very complex type of forces
called as Nuclear Forces.
 Now the constituents of the nucleus, i.e., Protons and Neutrons are called as Nucleons and the
number of nucleons in a particular atom is called as Mass Number denoted by A. The number of
protons is known as Atomic Number denoted by Z.
 The order of the diameter of an atom is 1010 m or 1 Å (1 Å = 1010 m) and the order of the diameter
of the nucleus is 1015 m or 1 fm (fm is called as Fermi and 1 fm = 1015 m).
 Radius of the nucleus of an atom is proportional to the cube root of the mass number of an atom (i.e.,
the number of nucleons in the atom). If r0 denotes the radius of the nucleus then,
r0 = (1.2  1015) A1/3 m. (A = mass number)
Failure of Rutherford’s Model

According to Classical Theory of Electromagnetism, whenever a charge is subjected to acceleration
around an opposite charge, it emits radiation continuously. Hence the electron in Rutherford’s atom will
loose energy and will not be able to stay in a circular path around the nucleus and should ultimately go into
a spiral motion. Such an electron will fall into the nucleus. This, of course, does not happen for electrons in
an atom and the discrepancy could not be explained at that time.
Note : Later Niel Bohr, a student of Rutherford analysed atomic spectra of Hydrogen atom in terms of Quantum
Theory of Radiation and applied the results of Photoelectric Effect to it and developed a model of atom
which was widely accepted at that time.

NATURE OF CHARACTERISTICS OF RADIANT ENERGY SECTION - 2B
Newton was first person to comment on the nature of light in terms of Corpuscular Theory of Light.
According to this theory, light is a stream of particles commonly known as corpuscles of light. He was able
to explain reflection and refraction, the most common phenomenon of light. But the other phenomenon
like diffraction and interference could not be explained on the basis of this theory.
Maxwell, in 1870 proposed that radiant energy (light) has wave characteristics. Light according to him is
Electromagnetic Wave arising due to the disturbance created by electric and magnetic fields oscillating
perpendicular to each other in space. Like all other mechanical waves, it is characterised by velocity, c ;
frequency,  and wavelength,  which are related as :
c=  [value of c is constant and equal to 3  108 m/s]
Electromagnetic Spectrum
 Electromagnetic wave or radiation is not a single wavelength radiation, but a mixture of various wave
length or frequencies. All the frequencies have same speed (= c).
 If all the components of Electromagnetic Radiation (EMR) are arranged in order of decreasing or
increasing wavelengths or frequencies, the pattern obtained is known as Electromagnetic Spectrum.
The following table shows all the components of light.
Continuous Spectrum :
When sunlight (white light) is passed through a prism, it is dispersed or resolved into continuous spectra of
colours. It extends from Red (7600 Å) at one end to the Violet (3800 Å) at other end. In this region, all the
intermediate frequencies between red and violet are present. This type of spectrum is known as Continuous
Spectrum. Hence continuous spectrum is one, which contains radiation of all the frequencies.
Note : A similar spectrum is produced when a rainbow forms in the sky.
Discontinuous Spectrum :
Light emitted from atoms heated in a flame or excited electrically in gas discharge tube, does not contain a
continuous spread of wavelengths (or frequencies). It contains only certain well-defined wavelengths (or
frequencies). The spectrum pattern appears as a series of bright lines (separated by gaps of darkness) and
hence called as Line Spectrum.
One notable feature observed is, that each element emits a characteristic spectrum, suggesting that there is
direct relation between the spectrum characteristics and the internal atomic structure of an atom.

The Quantum Theory of Radiation

In 1901, Max Planck studied the distribution of the frequencies of radiations emitted from the hot bodies.
He proposed a bold hypothesis that the radiant energy such as heat or light, is not emitted continuously but
discontinuously in the form of small packets called as quanta. According to him, the energy of the
electromagnetic radiation is directly proportional to the frequency of the radiation. The proportionality
constant is called as Planck’s constant (h). If energy of the radiation is E, and the frequency of the radiation
is , then we have :
E=h (The value of h is 6.626  1034 Js)
If n is the number of quanta of a particular frequency and TE be the total energy, then :
TE = n (h)
Illustration - 1 Find the ratio of frequencies of violet light (1 = 4.10  105cm) to that of red light
(2 = 6.56  105 cm). Also determine the ratio of energies carried by them.
SOLUTION :
Using c =  
where c: speed of light;  : frequency; Now the energy associated with electromagnetic
 : wavelength radiation is given by E = h
E1 v1  2
ν1  2  E  v    1.6 :1
 [1 : violet and 2 : red] 2 2 1
ν2 1
Hence the ratio of energies is same as that of frequencies.
1 6.56  105
   1.6 : 1
2 4.10  105
Illustration - 2 A 100 W power source emits green light at a wavelength  = 5000 Å. How many photons
per minute are emitted by the source ?
SOLUTION :
Energy given out by the source per sec
Using P = 100 J/s,  = 5000  1010 m and t = 60 s
= Power (P)
 Energy given by source in t sec = P  t  Number of photons (n) :
As  = 5000 Å, the energy per photon of green
hc 

100  60  5000  1010   1.5  1022
light is given by : h 


Number of photons (n) emitted in time
 6.626  1034  3  108 
Pt Pt
t sec is given by : n 
 hc /   hc
Photoelectric Effect
It was observed by Hertz and Lenard around 1880 that when a clean metallic surface is irradiated by
monochromatic light of proper frequency, electrons are emitted from it. This phenomenon of ejection of the
electrons from metal surface was called as Photoelectric Effect.
 It was observed that if the frequency of incident radiation is below a certain minimum value (threshold
frequency), no emission takes place however high the intensity of light may be.
 Another important feature observed was that the kinetic energy of the electrons emitted was indepen-
dent of the intensity of the light. The kinetic energy of the electrons increase linearly with the frequency
of incident light radiation. This was highly contrary to the laws of Physics at that time i.e. the energy of
the electrons should have been proportional to the intensity of the light, not to the frequency.
These features could not be properly explained on the basis of Maxwell’s concept of light i.e.
light as electromagnetic wave.
In 1905, Einstein applied Planck’s quantum theory of light to account for the extraordinary features of the
photoelectric effect. He introduced a new concept that light shows dual nature. In phenomenon like
reflection, refraction and diffraction, it shows wave nature and in phenomenon like photoelectric
effects, it shows particle nature. According to the particle nature, the energy of the light is carried in
discrete units whose magnitude is proportional to the frequency of the light wave. These units were called as
photons (or quanta).
According to Einstein, when a quantum of light (photon) strikes a metal surface, it imparts its energy to the
electrons in the metal. In order for an electron to escape from the surface of the metal, it must overcome the
attractive force of the positive ions in the metal. So a part of the photon’s energy is absorbed by the metal
surface to release the electron, this is known as work function of the surface and is denoted by W0. The
remaining part of the energy of the photon goes into the kinetic energy of the electron emitted. If Ei is the
energy of the photon, KE is the kinetic energy of the electron and W0 be the work function of the metal then
we have ;
Ei = KE + W0 (This is known as Einstein’s photoelectric equation)
For each metal, there is a characteristic minimum frequency
known as the threshold frequency (0) below which the
photoelectric effect does not occur. Electrons are emitted only
after the frequency of light is equal to or above the threshold
frequency. The threshold frequency is proportional to the work
function of the metal. If 0 be the threshold frequency and  the
frequency of incident light, E is energy of incident light, then we
have :
W0 = h 0 and Ei = h 
 KE = Ei  W0 or KE = h   h 0 = h (  0)

Also, if m be the mass and v be the velocity of the electron ejected then
1
KE  mv 2  h  ν  ν 0 
2
Note :
 The Electromagnetic radiation (or wave) now emerges as an entity which
shows dual nature i.e. sometimes as Wave and sometimes as Particle
(quantum aspect).
 The energy of an individual photon depends only on its frequency and
not on the intensity of the light beam. The intensity of a light beam is a
measure of the number of photons in the beam and not of the energies
of those photons. A low-intensity beam of high-energy photons might
easily knock out electrons from a metal but a high intensity beam of low
energy photons might not be able to knock out a single electron.
 Sometimes, it is convenient to calcualte energy (in eV) of a photon in short form using:
hc 12400 1240
EP   eV  eV
λ λ  in Å  λ  in nm 
Illustration - 3
Illustration - 3 Calculate the velocity of electron ejected from platinum surface when radiation of 200 nm
19
falls on it. Work function of platinum is 5 eV. (1eV  1.6 10 J )
SOLUTION :
Using Einstein’s photoelectric equation :  KE = Ei  W0 = (6.2 – 5) eV = 1.2 eV
Ei = KE + W0 = 1.2 × 1.6 × 10–19 J = 1.94 × 10–19
where Ei : energy of incident radiation ; 1 2 2KE
Now, KE = mv  v =
KE : kinetic energy of ejected electron 2 m
W0 : work function of metal 2(1.94 1019 )
 v= = 6.52  105 m/s
1240 (9.11031 )
Ei  eV  6.2 eV; and W0  5 eV
200

Illustration - -4 4
Illustration A photon of light with  = 400 nm falls on a metal surface. As a result, photoelectrons are
ejected with a velocity of 6.4  105 m/s. Find :
(a) the kinetic energy of emitted photoelectrons, (b) the work function (in eV) of the metal surface.
SOLUTION :
1
(a) Kinetic energy of electron = mv 2 (b) From Einstein’s photoelectric equation :
2
Ei = KE + W0  W0 = Ei  KE
1
 KE = (9.1  1031) (6.4  105)2 1240
2  W0   KE  3.1  1.16  1.94eV
= 1.86  1019 J = 1.16 eV 400
 W0  1.94eV
NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK
ATOMIC SPECTRA OF HYDROGEN AND BOHR’S MODEL SECTION - 3
It is observed that the atoms of hydrogen in gas discharge tube emit radiations whose spectrum shows line
characteristics (line spectra). The line spectra of hydrogen lies in three regions of Electromagnetic Spectrum:
Infra-red, Visible and UV region. In all there are five sets of discrete lines.
The set of lines in the Visible region are known as Balmer Series, those in Ultra-Violet as Lyman series
and there are three sets of lines in Infra-red region : Paschen, Brackett and Pfund series. Balmer and
Rydberg gave an empirical relation to define the wavelength of the lines in each series in terms of a param-
eter called as Wave Number denoted by  . The wave number is defined as reciprocal of the wavelength
1 2
 1 1 
i.e.,   ;   RZ  2  2
 n m 

where n and m are whole numbers;  : wavelength of spectral line ;  : wave number of spectral line
R : Rydberg constant. The values of n and m for different spectral lines for each series are listed below.
Region Spectral line n m

UV Lyman Series 1 2, 3, 4, . . .
Visible Balmer Series 2 3, 4, 5, . . .
Infra-red Paschen Series 3 4, 5, 6, . . .
Infra-red Brackett Series 4 5, 6, . . . .
Infra-red Pfund Series 5 6, 7, . . . .
Humphry Series 6 8, 7, 8 . . .

In Hydrogen atom spectra :

 Intermediate frequencies were emitted i.e. only specific spectral lines are there in the spectrum
(Planck’s quantum theory).
 Lines observed were characteristic of Hydrogen atom only.
These observations led Bohr to conclude that electrons in an atom are not randomly distributed, but were
arranged in definite energy states. The energy of each state (or level) was fixed or quantised (from charac-
teristic nature of H-atom spectra). The complete theory developed by him is organised in his postulates.
Bohr’s Postulates
Bohr’s theory was based on the application of Planck’s Quantum theory on the atomic spectra of Hydrogen
atom. The fundamental postulates of his theory are discussed below :
 The electron in an atom has only certain definite stationary states of motion allowed to it, called as
energy levels. Each energy level has a definite energy associated with it. In each of these energy
levels, electrons move in circular orbit around the positive nucleus. The necessary centripetal force is
provided by the electrostatic attraction of the protons in the nucleus. As one moves away from the
nucleus, the energy of the states increases.
 These states of allowed electronic motion are those in which the angular momentum of an electron
h
is an integral multiple of or one can say that the angular momentum of an electron is quantised.
2
 h 
 Angular momentum = mvr  n   Angular momentum = moment of Inertia  angular velocity
 2 
v
= mr 2 × = mvr
r
where m is the mass of the electron, v is the velocity of the electron, r is the radius of the orbit, h is Planck’s
constant and n is a positive integer.
 When an atom is in one of these states, it does not radiate any energy but whenever there is a
transition from one state to other, energy is emitted or absorbed depending upon the nature of
transition.
When an electron jumps from higher energy state to the lower energy state, it emits radiations in form of
photons or quanta. However, when an electron moves from lower energy state to a higher state, energy is
absorbed, again in form of photons.
The energy of a photon emitted or absorbed is given by using Planck’s relation (E = h ). If E1 be the energy
of any lower energy state and E2 be the energy of any higher energy state, then the energy of the photon
(emitted or absorbed) is given as E (i.e., the difference in the energies of two states) :
c
E = E2  E1 = h  h

where h : Planck’s constant and  : frequency of radiation emitted or absorbed.

Additional Information :
Coulomb’s Law of Electrostatic force of attraction or repulsion (F) between two charges q1 & q2
K | q1 | | q 2 |
separated by a distance ‘r’ is given by : Force (F) 
r2
1
where K  = 9  109 Nm2 C–2
4 0
Note that charge on any particle can only be an integral multiple of charge on an electron (e).
Electrostatic Potential energy (E.P.E.) of a system of two charges separated by a distance ‘r’ is
given by :
Kq1q 2
E.P.E. 
r
Note : E.P.E. is +ve when charges are like and ve when charges are opposite.
Electrostatic force (F) is repulsive when both q1 and q2 are of same sign (i.e. either both are positive or both
are negative) and is attractive when q1 and q2 are of different signs.
Bohr Model :
Consider a species of atomic number (Z) containing single electron
revolving around its nucleus at a distance of ‘r’ as shown in the figure.
Note : Atomic number  Number of protons on the nucleus = Z

 Charge on the nucleus = + Ze
[As charge on each proton is +e and neutrons don’t have any charge]
Electrostatic force of attraction (F) between the nucleus of charge + Ze and electron (e) is given by :
K Ze  e K Ze2
F  . . . (i)
r2 r2
me v2
The centrifugal forces acting on the electron is . . . (ii)
r
[Assuming uniform circular motion]
This centrifugal force must be provided by the electrostatic force of attraction (F).
 From (i) and (ii), we have :
K Ze2 me v 2
 . . . (iii)
r2 r
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Also, according to Bohr’s postulate of quantization of angular momentum, we have :

nh
Angular momentum of electron about the nucleus = me vr  . . . (iv)
2
where ‘n’ is a positive integer
(n = 1, 2, 3, . . . . )
Solve (iii) and (iv) to get :
2  K Ze 2 n 2h2
v and r 
nh 4 2 K me e 2 Z
Put K = 9  109 Nm2C–2, e = 1.6  10–19 C and h = 6.626  10–34 Js in the above expressions to get :
Z
Velocity of an electron in nth Bohr orbit  vn  2.18  10
6
ms 1
n
and Radius of the nth Bohr orbit
n2 n2 n2
 rn  0.529  1010 m  0.529 Å  52.9 pm 1pm  1012 m 
Z Z Z
Now, the Total Energy of the electron moving in nth orbit  K.E.n + E.P.E.n
1 K  Ze   e   Kq1q 2 
T.E.n  mv n2    E.P.E.  r 
2 r  
1  KZe 2  K  Ze    e 
 T.E n    [Using (iii)]
2  rn  rn
 KZe2
 E n  T.E. n 
2rn
It can be shown from the above expressions that :
1 KZe2  KZe2  KZe2
K.E.n  , P.E.n  and En 
2 rn rn 2rn
or K.E.n =  En and E.P.E.n = 2En
Using the value of rn in the expression of En, we get :
2 2 K 2 m e e 4 Z2
En 
n2h 2
Z2 Z2
E n  2.18  1018 J / atom  13.6 eV / atom  1eV  1.6  1019 J 
n 2
n 2  

Z2 Z2
 2.18  1018  6.02  1023 J / mole  1312 kJ / mole
n2 n2
Note :  Bohr’s Model is applicable only to one-electron atoms like : He+, Li2+, Be3+ apart from H-atom.
Illustration - 5 Determine the frequency of revolution of the electron in 2nd Bohr’s orbit in hydrogen
atom.
SOLUTION :
The frequency of revolution of electron is given by : Calculate velocity (v2) and radius (r2) for electron in 2nd
Bohr orbit in H-atom (Z = 1)
1 Z = 1 for H-atom.
Frequency = time period
n2
Using rn  0.529 Å
Time period Z
Total distance covered in 1 revolution  22
 r2  0.529  1010 m  1.12  1010 m
velocity 1
vn = 2.18  106 (1/n) m/s

2 r

v
v2 = 2.18  106 (1/2) = 1.09  106 m/s
v
Hence frequency =
2 r
v2 1.09  106
Hence frequency  
2 r2 2(  )(2.12  1010 )
 = 8.18 × 1014 Hz.
2 r n3  n2 Z
Note : Frequency of revolution (f) = 1/T where T   r  and v  
v Z2  Z n
Z2
 f 
n3
What does the negative electron energy (En) means ?

The energy of the electron in a hydrogen atom has a negative sign for all possible orbits. What do this
negative sign convey ? This negative sign means that the energy of the electron in the atom is lower than the
energy of a free electron at rest. An electron in an atom is because of attractive force due to protons in the
nucleus. A free electron at rest is an electron that is infinitely far away from the nucleus and is assigned the
energy value of zero. Mathematically, this corresponds to setting n equal to infinity in the equation so that
E= 0. As electron gets closer to the nucleus, En becomes larger in absolute value and more and more nega-
tive. The most negative energy value is given by n = 1 which corresponds to the most stable orbit.

When an electron jumps from an outer orbit (higher energy) n2 to an inner orbit (lower energy) n1, then the
energy emitted in form of radiation is given by :
2 2 K 2 me 4 Z2  1 1   1 1 
E = E n 2  E n      E  2.18  1018  Z2   
1 h2  n 2 n2   n2 n 2 
 1 2  1 2
 1 1 
Also, E  13.6  Z2    eV/atom
 n2 n2 
 1 2
1 E 2 2 K 2 me4 Z2  1 1 
As we know that : E  h ;        
 hc c h3  n2 n 2 
 1 2
The above equation can be represented as :
 1 1  2 2 4
  RZ2    where R  2  K me
 n2 n2 
 1 2 c h3
R is known as Rydberg constant. Its value to be used is = 109677 cm–1 = 10967700 m–1
1
Note : (i) The value of  911.5 Å is sometimes useful.
R
(ii) This relation exactly matches with the empirical relation given by Balmer and Rydberg to account
for the spectral lines in H-atom spectra. In fact the value of Rydberg constant in the empirical
relation is approximately the same as calculated from the above relation (Bohr’s Theory). This
was the main success of Bohr’s Theory i.e. to account for the experimental observations by postu-
lating a theory.
(iii) The maximum number of lines that can be emitted when an electron in an excited state n = n2
(n 2  n1  1)(n 2  n1 )
de-excites to a state n = n1 (n2 > n1) is given by :
2
Illustration - 6 Determine the maximum number of lines that can be emitted when an electron in H atom
in n = 6 state drops to the ground sate. Also find the transitions corresponding to the lines emitted.
SOLUTION :
The maximum number of lines can be calculated by using the above formula with n2 = 6 and n1 = 1 are 15.
The distinct transitions corresponding to these lines are:
6 1
6 2, 2 1
6 3, 3 2, 3 1
6 4, 4 3, 4 2, 4 1
6 5, 5 4, 5 3, 5 2, 5 1

Note : Each line (in emission spectra) corresponds to a particular photon emitted. The photon with shortest
wavelength is corresponding to the largest energy difference (6  1) and with longest wave length is
corresponding to minimum energy difference (6  5).
ENERGY LEVELS OF HYDROGEN ATOM SECTION - 4
The spectrum of H-atom studied by Lyman, Balmer, Paschen, Brackett and Pfund can now be explained
on the basis of Bohr’s Model.
It is now clear that when an electron jumps from a higher energy state to a lower energy state, the radiation is
emitted in form of photons. The radiation emitted in such a transition corresponds to the spectral line in the
atomic spectra of H-atom.
Lyman Series
When an electron jumps from any of the higher states to the ground state or Ist state (n = 1), the series of
spectral lines emitted lies in ultra-violet region and are called as Lyman Series. The wavelength (or wave
number) of any line of the series can be given by using the relation :
1 1 
  R Z2    n2 = 2, 3, 4, 5, . . . .
 12 n 2 
 2
Note : For H-atom, Z = 1 ; He+ ion, Z = 2 and Li2+, Z = 3

Balmer Series
When an electron jumps from any of the higher states to the state with n = 2 (IInd state), the series of
spectral lines emitted lies in visible region and are called as Balmer Series. The wave number of any
spectral line can be given by using the relation :
 1 1 
  R Z2    n2 = 3, 4, 5, . . . .
 22 n 2 
 2
Paschen Series
When an electron jumps from any of the higher states to the state with n = 3 (IIIrd state), the series of
spectral lines emitted lies in near infra-red region and are called as Paschen Series. The wave number of
any spectral line can be given by using the relation :
 1 1 
  R Z2    n2 = 4, 5, 6. . . . .
 32 n 2 
 2
Brackett Series
When an electron jumps from any of the higher states to the state with n = 4 (IVth state), the series of
spectral lines emitted lies in far infra-red region and called as Brackett Series. The wave number of any
 1 1 
  R Z2    n2 = 5, 6, 7. . . .
 42 n 2 
 2
Pfund Series
When an electron jumps from any of the higher states to the state with n = 5 (Vth state), the series of
spectral lines emitted lies in far infra-red region and are called as Pfund Series. The wave number of any
 1 1 
  RZ2    n2 = 6, 7 . . . .
 52 n 2 
 2 
Note that Lyman series in UV region, Balmer series in visible region and Paschen, Brackett & Pfund series
in Infra-red region are only for H-atom (Z = 1).
Note : In a particular series, First [(n1 + 1)  n1], second [(n1 + 2)  n1], third [(n1 + 3)  n1] . . . . lines are called
as, , , . . . .lines respectively. For example line in Balmer series corresponds to (2 + 2)  2 i.e.,
4  2. In Lyman series :   line  2  1 ;   line  3  1 ;   line  4  1.
The energy required to remove the electron from the outermost orbit of the atom in gaseous phase is called
as Ionisation energy. Here, since we are considering only one electron species, Ionisation energy
(IE) = E1 = +13.6 Z2 eV.

Illustration - 7 The Lyman series of Hydrogen spectrum can be represented by the equation :
1 1  1
v  3.28  1015    s . Calculate the maximum and minimum frequency in this series.
12 n2 
SOLUTION :
Lyman frequency will be maximum corresponding to maximum energy transition. i.e. 1  
1 1  1
  max  3.28  1015   s = 3.28  1015 s1
2 2
1  
Note that corresponding wavelength will be shortest wavelength.
And Lyman frequency will be minimum corresponding to minimum energy transition. i.e. 1  2
1 1  1
  min  3.28  1015   s = 2.46  1015 s1
2 2
1 2 
Note that corresponding wavelength will be longest wavelength.
Illustration - 8 The wavelength of second line (also called as line) in Balmer series of hydrogen atom
is :
(A) 656.28 Å (B) 4872 Å (C) 6562.8 Å (D) 486.2 Å
SOLUTION :
The transition responsible for second Balmer (line) line is 4  2. In H-atom, n1 = 2 for Balmer series.
 1 1 
 E = 13.6 (1)2  2  2  = 2.55 eV
2 4 
hc 6.626  1034  3  108
Now   E 
2.55  1.6  1019
  = 4.872  107 m = 4872 Å

Hence correct option is (B).

Illustration - 9 A spectral line in the spectrum of H-atom has a wave number of 15222.22 cm1. The
transition responsible for this radiation is : (Rydberg constant R = 109677 cm1).
(A) 2 1 (B) 42 (C) 32 (D) 23
SOLUTION :
  1 / v  1 /15222.22  6.569  10 5 cm  6569 Å

Clearly, it lies in Visible region i.e, in Balmer series.
Hence n1 = 2
Using the relation for wave number for H-atom:
 1 1 
  1/   RZ2   
 n2 n2 
 1 2
 1 1 
15222.22  109677   
 22 n 2 
 2
 n2 = 3
 the required transition is 3  2
Hence (C) is correct.
Note : (D) is wrong, since 2  3 will absorb radiation.
Drawbacks of Bohr model :

Bohr’s model was successful in explaining the spectra and hence the structure of Hydrogen atom; still many
questions were not answered.
 His postulates combined two different concepts : one from classical physics and second from modern
theory of quantization.
 It could not explain the spectrum of atoms or ions having two or more electrons. It accounted only for
the spectra of H-atom, He+ ion and Li++ ion.
 There was no justification for the quantization of angular momentum of an electron, though this was a
correct assumption.
 His model could not provide a satisfactory picture of Chemical Bond.
 It also failed to account for the brightness of the spectral lines, splitting spectral lines in electric field
(Stark Effect) and in magnetic field (Zeeman Effect).

Illustration - 10 Calculate the wavelength of light radiation that would be emitted, when an electron in the
fourth Bohr’s orbit of He+ ion falls to the second Bohr’s orbit. To what transition does this light radiation
correspond in the H-atom ?
SOLUTION :
First calculate the energy difference (E) between 4th and 2nd Bohr orbit using :
 1 1 
E 4 2   13.6 Z2    eV
 n2 n 2 
 1 2
Substituting n1 = 2 and n2 = 4, Z = 2 we get ;
E = 10.2 eV
This energy difference (energy lost by the electron) will be equal to the energy of the emitted photon.
12400 12400
Using :   Å Å = 1215.7Å
E Photon  eV  10.2
Note : The emitted radiation is in UV region which implies that, in H-atom this transition would lie in Lyman
Series (n1 = 1). Hence our aim is now to find the transition : n2  1
1 1 
Use : E(n 2 1)  13.6  12    eV
 12 n 2 
 2
 1 
 10.2 = 13.6  1  2  eV
 n 
 2 
 n2 = 2
Hence the corresponding transition in H-atom is 2  1
Note : This concept can be applied only for H-atom.
Alternate Approach :
hc  1 1 
As discussed above : E(4  2) (in He  )   13.6  22     eV . . . .(i)
 Photon  22 42 
hc  1 1 
E (n 2  n1 ) (in H)   13.6  12   eV
 Photon 2 2 . . . .(ii)
n
 1 n 2
Try to convert equation (ii) in the form given in equation (i) and compare it with equation (i) as below :
hc 1 1 
 E(4  2) (in He  )   13.6  12     eV [22 shifted inside]
2
 Photon 1 22 
On comparing the above equation with equation (i), we get :
n1 = 1 and n2 = 2
Note : This concept can be applied for any H-like species.

Illustration - 11 Find the wavelength of radiation required to excite the electron in ground level of Li++
(Z = 3) to third energy level. Also find the ionisation energy of Li2+. (R = 109, 677 cm1)
SOLUTION :
Ground level : n = 1
1  1 1 
Use :  RZ2   
2
  n1 n 22 
Putting the values : n1 = 1, n2 = 3, Z = 3
1 2  1 1 
We get :   109677  3   2  2 
1 3 
1 1
  877416cm1   = 113.97 Å
 v
Ionisation energy is the energy required to remove the electron from ground state to infinity i.e. corresponding
transition responsible is 1  .
1 1 
i.e. E(1   )  13.6  32    eV
2
1 2 
Ionisation energy = E (1   )  122.4 eV  1.95  10 17 J  1eV  1.6  10 19 J 
Note : Ionisation Energy (IE) = –E1 = + 13.6 Z2 eV
Illustration - 12 Find the energy released (in ergs) when 2.0 gm atom of Hydrogen atoms undergo transi-
tion giving spectral line of lowest energy in visible region of its atomic spectra.
SOLUTION :
For Hatom, the spectral lines in visible region correspond to Balmer Lines (n1 = 2). Now for lowest energy
photon, the required transition will be from 3  2.
Using the relation for E :
 1 1 
E  2.18  1018 (1) 2    J / atom
 2 2
2 3 
19
= 3.03  10 J
Now for 2.0 gmatoms, the energy released will be
E  (2  6.023 1023 )  3.03 10 19 J

= 3.65  105 J  3.65  1012 [1J 107 ergs]

WAVE NATURE OF PARTICLES SECTION - 5
We have studied that light shows dual nature i.e. wave nature (Electromagnetic Radiation) and particle
nature (photons). In the following article we will see that not only light but matter also shows dual nature.
In 1923, de Broglie suggested that, since light is dualistic in nature: behaving in some aspects as waves and in
others like particles, the same might be true of matter. According to him, every form of matter (electron or
proton or any other particle) behaves like waves in some circumstances. These were called as matter waves
or de Broglie waves. de Broglie postulated that a particle of mass m moving with a velocity v should have a
wavelength  given by :
h h
  (p = linear momentum = mv)
p mv
Now we can think of a model of atom where moving electrons (obviously around the nucleus) should behave
like waves. The wave hypothesis of de Broglie was later developed by Heisenberg, Schrödinger, Fermi and
many others in modern atomic theory and is known as wave mechanics or quantum mechanics.
In new theory, electrons in an atom are visualised as diffused clouds surrounding the nucleus. The idea that the
electrons in an atom move in definite orbits (Bohr’s model) is now abandoned. The new theory assigns
definite energy states to an atom but discards a definite path for movement of an electron.
Due to wave nature of electron in an atom, it is now highly impossible to ascertain the exact whereabouts of an
electron. This idea is defined by Heisenberg’s Uncertainty Principle as :
“ It is impossible to specify at any given instant, both the momentum and the position of a sub-atomic
particle like electron.”
Whenever there is an attempt to specify the position of electron precisely, an uncertainty is introduced in its
momentum and vice-versa. If x is the uncertainty in position and p be the uncertainty in its momentum, then
according to Heisenberg, these quantities are related as follows :
h
x . p 
4
In other words, it can be defined as :
An expression of limits set by the wave nature of matter (electron) on finding the position and the state
of motion of moving body (momentum) such that the product of uncertainties in simultaneous mea-
surements of the position and momentum of a sub-atomic particle cannot be less than h/4 .
Hence, in new atomic theory, an electron can not be regarded as having a fixed (definite) path around the
nucleus, called orbits. It is a matter of probability that an electron is more likely to be found in one place or the
other. So we can now visualise a region in space (diffused cloud) surrounding the nucleus, where the probabil-
ity of finding the electron is maximum. Such a region is called as an orbital. It can be defined as :
“ The electron distribution described by a wave function and associated with a particular energy.”

 The new theory still defines a definite energy to an orbital in an atom

(a remarkable and accepted feature of Bohr’s model). The new theory
abandons the concept of sharply defined paths.
 If we consider an electron moving in a circular orbit around the nucleus, then
the wave train associated with the electron is shown in the figure.
If the two ends of the electron wave meet to give a regular series of crests and
troughs, the electron wave is said to be in phase.
n   2  r
where n is the number of waves made by an electron in that Bohr orbit
 The number of waves made by the electron
circumference of the orbit

=
wavelength
2 r 2 r  h 
Thus, n =


h / mv    mv 
2 2  nh nh 
  mvr      n 
 mvr  2  
h h  2 
Hence the number of waves ( n ) made by an electron in an orbit is equal to principal quantum number (n)
Illustrating the concept :

Find out the number of waves made by a Bohr electron in one complete revolution in its 3rd orbit.
Using the above result, the number of waves made by the electron in 3rd Bohr orbit is 3 (i.e. n = 3).
Illustration - 13 An electron is accelerated through a potential difference of V volts. Find the de Broglie
wavelength associated with the electron.
SOLUTION :
When the electron is accelerated through a po- And de Broglie wavelength ()
tential difference of V volts, it acquires a kinetic h h
= 
energy given by E = qV, where q is the charge on mv 2Em
the electron. Also, if m be its mass and v be the Note :The above result can be used directly, whenever
1 required.
velocity then, E  mv 2 In the given case, E = qV
2
2E h
 v  
m 2(q V) m

Illustration - 14 Calculate the uncertainty in position assuming uncertainty in momentum within 0.1 %
for :
(a) a tennis ball weighing 0.2 kg and moving with a velocity of 10 m/s.
(b) a electron moving in an atom with a velocity of 2 106 m/s.
SOLUTION :
Using Uncertainty Principle,
h
x . p =
4π
(a) p = mv = 0.2  10 = 2.0 Kg m/s
p = 0.1% of p = 2  103
h 6.626 1034
 x = 
4 p 4  3.14  2 103
= 2.63  1032 m.
(b) For an electron, p = m v

p = 9.1  1031  (2  106)
= 1.82  1024 Kg m/s
p = 0.1 % of p = 1.82  1027 Kg m/s
h 6.626 1034
x = 
4 p 4  3.14 1.82 1027
 x = 2.89  108 m
Note : This shows that for sub-atomic (microscopic) particles, Heisenberg’s Principle is highly meaningful, as x is
greater than their atomic radius.

CONCEPT OF QUANTUM NUMBERS SECTION - 6
Introduction to Quantum Mechanics

Macroscopic Objects :
Motion of these objects can be described/calculated using classical mechanics (based on Newton’s law
of motion).
Microsopic Objects
Motion of these objects can not be described/calculated using classical mechanics (based on Newton’s
law of motion).
(i) Dual nature of matter is not considered in classical mechanics, so there is a need for Quantum
Mechanics (takes into consideration the dual nature of matter).
(ii) Quatum mechanics can also be applied on macroscopic objects (we can ignore their wave like
properties) and still get the same results as Classical Mechanics.
Equation of Quantum Mechanics :

It defines the laws of motion that microscopic objects must obey.
Schrödinger equation is the governing equation of Quantum Mechanics. It is a complex equation and difficult
to understand and solve with the knowledge of mathematics in classes XI and XII.
Schrödinger equation is relatively easier to construct. For a H-atom, when this equation is solved, it gives
the energy levels for the electrons and corresponding wave function (  ) of the electron associated with
each energy level.
What is a wave function (  ) ?

 It is a mathematical function whose value depends upon the coordinates of the electron in the atom.
 It doesn’t have any physical significance.
 It is characterized (represented) by set of three quantum numbers (n : Principal quantum number,
 : Azimuthal quantum number and m: Magnetic quantum number).
Basically, it contains all the information about the electron.
Note :  Schrödinger equation can not be solved exactly for multi-electron atom (but can be solved
approximately).
 In case of single electron atom, energy of the orbital depends only on the principal quantum number
(n) but in case of multi-electron atom, it depends on ‘n’ as well as .

Designation of An Electron in an Orbital

An orbital is basically designated by three quantum numbers n,  and m as defined below :
(i) Principal Quantum Number (n) :

It is a positive integer with values of n = 1, 2, 3, . . . . . In other way, it can also be designated with
letters as K (n = 1), L (n = 2), M (n = 3), . . . . . . .
Significance :
(a) It determines the size and energy of the orbital.
Note : For H and H-like species, orbital size and energy depends only on ‘n’ but for multi electron species, orbital
energy depends on both ‘n’ and ‘’.
(b) It is also used to calculate the number of orbitals given by ‘n2’. Thus, the maximum number of elec-
trons in a shell (i.e. energy level as designated with letters as K, L, M etc.) are given by ‘2n2’, since
one orbital can at the maximum contains two electrons.
 As we have learnt in Bohr Model, increasing ‘n’ increases the energy of the electron, thus, energy of
the orbital increases.
 Also, we have learnt that size of the energy shells increases with increasing ‘n’. Thus, we can expect
the orbital size to increase with ‘n’.
(ii) Azimuthal Quantum Number () : It is an integer having all values between 0 and n – 1. It is also
also known as orbital angular momentum quantum number or subsidiary quantum number.
Significance :
(a) It is used to define the shape of an orbital.
(b) It is used to represent a subshell (Each shell has subshells equal to shell number). A subshell can be
thought of as sub-energy level inside an energy level.
For example : n = 1 (K shell) has only one subshell ( = 0)

n = 2 (L shell) has two subshells (= 0, 1)
And so on . . . . .
Each value of ‘’ can be designated with letters as s ( = 0), p ( = 1), d ( = 2), f ( = 3), g ( = 4)
and so on . . . . .
We can create the following notation :

n = 1,  = 0  1s
n = 2,  = 0, 1  2s, 2p
n = 3,  = 0, 1, 2  3s, 3p, 3d and so on . . . . .
(iii) Magnetic Quantum Number (m) :
It is an integer having values between – to + including zero.

Significance :
(a) It gives information about the orientation of an orbital with respect to coordinate axis.
 For example : ‘s’ orbital is spherical in shape. So, it can be oriented only in one way in
space, hence only one orbital is possible.
Note : Number of orbitals in a sub-shell  Number of possible orientations of an orbital.

 ‘p’ orbital has lobes above and below the plane as shown :
‘p’ subshell can be oriented in three ways (lobes can be along X, Y and Z axes).
Thus, three orbitals are possible in a p-subshell.
In general, number of orbitals in a sub-shell = 2 + 1
Thus, ‘s’ – subshell ( = 0) has 2 (0) + 1 = 1 orbital
‘p’ – subshell ( = 1) has 2 (1) + 1 = 3 orbital
Subshell  No. of orbitals Max. e’s per subshell Possible values of m
s 0 1 2 0
p 1 3 6 –1, 0, 1
d 2 5 10 –2, –1, 0, 2
f 3 7 14 –3, –2, –1, 0, 1, 2, 3
Note the conventions :

‘s’ – subshell ‘p’ – subshell ‘d’ – subshell
m  0
Note : n, , m are the solutions of Schrödinger equation. There is another quantum number known as spin quantum
number (ms) which has been obtained experimentally.

There is an orbital angular momentum associated with an electron in a subshell given by :

h h
L      1      1  (where   = reduced Planck’s constant)
2 2
Spin Quantum number (ms) : This quantum number accounts for the spin of electron about its axis
similar to earth’s motion about the sun as well as about its own axis.
An orbital can have a maximum of two electrons spinning in opposite directions leading to a spin angular
momentum (vector quantity).
Thus, for two electron in an orbital,
1
ms   (spin anticlockwise)  
2
1
ms   (spin clockwise)  
2
h
Magnitude of spin angular momentum is given by : s  s  1
2
3 h  1 
  s  for an electron 
2 2  2 
3  h 
     reduced planck's constant 
2  2 
1 1
Note :  ms  for any electron. In an orbital, ms   has been taken so as to distinguish the two
2 2
electrons in it.
 spin quantum number has no classical analogue.
Difference between Orbit and Orbital :

Orbit Orbital
1. It is circular path around the nucleus in which 1. It is a quantum mechanical concept and
an electron moves. refers to one electron wave.
2. It is characterized by n. 2. It is characterized by n, , m.
3. It has no real meaning. 3. It represents the probability of finding an
electron at any point (through  2 ).

Hydrogen atom and the Schrodinger Equation:

When Schrodinger equation is solved for hydrogen atom, the solution gives the possible energy levels the
electrons can occupy function(s)  ψ  of the electron associated with each energy level. These quantized
energy sates and corresponding wave functions which are characterized by a set of three quantum numbers
(principal quantum number n, azimuthal quantum number l and magnetic quantum number m1) arise as a
natural consequence in the solution of the Schrodinger equation. When an electron is in any energy state, the
wave function corresponding to that energy state contains all information about the electron. The wave
function is a mathematical function whose value depends upon the coordinates of the electron in the atom
and does not carry any physical meaning. Such wave functions of hydrogen or hydrogen like species with
one electron are called atomic orbitals. Such wave functions pertaining to one-electron species are called
one-electron system. The probability of finding an electron at a point within an atom is proportional to the
2
ψ at that point. The quantum mechanical results of the hydrogen atom successfully predict all aspects of
the hydrogen atom specturm including of the hydrogen atom spectrum including sum phenomena that could
not be explaoned by the Bohr model.
Application of Schrondinger equation of multi-electron atoms presents a difficulty: the Schrodinger equation
cannot be solved exactly for a multi-electron atom. This difficulty can be overcome by using approximate
methods. Such calculations with the aid of modern computers show that orbitals discussed above. The
principal difference lies in the consecuence of increased nuclear charge. Because of this all the orbitals are
somewhat contracted. Further, as you shall see later (in subsections 2.6.3 and 2.6.4), unlike orbitals of
hydrogen or hydrogen only on the quantum number n, the energies of the orbitals in multi-electron atoms
depends on quantum numbers n and l.
Shapes of Atomic Orbitals :

Graph of  for various orbitals as a function of 2 at any point, gives the probability density of
electron at that point.
r (the distance from the nucleus is as shown :
As we see from the above graph, 2 decreases and approaches to zero as r increases. Region where 2
reduces to zero is called nodal surface (nodes). A node is a region of space where probability of finding the
electron is zero. There also angular nodes (nodal plane) which represents plane passing through nucleus and
having probability density function as zero.

For a hydrogen like atom wave function, of principal quantum number n, there are
(i) (n – – 1) radial nodes (ii) angular nodes (iii) (n – 1) total nodes.
Thus :
 2s has one node. 3s has two nodes and so on.
 1s (n = 1,  = 0) subshell is without any node.
 2s (n = 2,  = 0) subshell will have only one radial node, while 2p (n = 2,  = 1) subshell will have
only one angular node.
 3s (n = 3,  = 0) subshell will have two radial nodes, 3p (n = 3,  = 1) subshell will have one radial
and one angular node while 3d (n = 3,  = 2) will have two angular nodes.
Boundary surface diagram : It is surface (contour) which represents a constant ||2. In general, it is the
region where the probability of finding the electron is 90%.
As mentioned earlier, the ‘s’ orbitals are spherical in shape which means that
the probability of finding the electron at a given distance is equal in all the
direction.
Also, the size of these orbitals increases as ‘n’ increases.
Boundary Surface Diagrams of p-orbitals are not spherical as shown :
As we can see, there are two lobes on either side of the plane passing through the nucleus having
probability of finding the electron as zero on it.
 All three orbital have same shapes and energy.
 Here also, energy of these orbitals increases with increasing ‘n’.
 No. of radial nodes (for p-orbitals) are given by n – 2
Boundary Surface Diagrams of d-orbitals are shown below. For d-subshells, there are 5 values of m. Thus,
d has 5 orbitals.

Energy of orbitals :
 For H-atom, energy of an orbital can be solely calculated by using ‘n’
Thus, 1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f < ……
Orbitals having same energy are called degenerate orbitals.
 For an atom containing multi electrons, energy of an electron depends on ‘n’ as well as ‘’.
In this case, each e– is attracted by the nucleus but is repelled by every other electron. The electrons in the
outer shell experiences less attractive force as there is a partial screening of positive change known as
shielding of the outer shell electrons from the nucleus.
 ‘s’ orbitals are more tightly bound to nucleus than p orbitals, p orbitals are more tightly bound to
nucleus than d orbitals and so no. Thus, energy of ‘s’ orbitals is more negative than p-orbitals.
Illustration - 15 In all, how many nodal planes are there in the atomic orbitals for the principal quantum
number n = 3.
SOLUTION :
Shell with n = 3 has 1 ‘s’ (3s), 3 ‘p’ (px, py, pz) and 5
‘d’ (dxy, dxz, dyz, d 2 2 and dz2) orbitals.
(x  y )
 ‘s’ has no nodal plane.
 Each of px, py, pz has one nodal plane, which means a total of 3 nodal planes.
 dz2 has no nodal plane.
Each of dxy, dxz, dyz, d 2 2 has 2 nodal planes, which means a total of 8 nodal planes.
(x  y )
Hence for n = 3, a total of 11 nodal planes are there.

ELECTRONIC CONFIGURATION OF ELEMENTS SECTION - 7
Quantum numbers can now characterise the electrons in an atom. To describe the arrangements and distribution
of electrons for different elements, following rules and selective principles are used. The distribution of electrons
in an atom is known as the electronic configuration of that element.
Aufbau Principle
An atom in its lowest state of energy is said to be in ground state. The ground state is the most stable state in
an atom. According to Aufbau principle:
“ electrons are added progressively to the various orbitals in their order of
increasing energy starting with the orbital of lowest energy.”
The order of increasing energy may be summed up as follows:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d,.....
As a working rule, a new electron enters an empty orbital

for which the value of (n + ) is minimum. If the value of
(n + ) is same for two or more orbitals, the new electron
enters an orbital having lower value of n.
Pauli Exclusion Principle

According to this principle :
“ no two electrons in an atom can have the same set of
all the quantum numbers. or one can say that no two
electrons can have the same quantised states.”
Consider an electronic arrangement in Ist energy level
(n = 1). For n = 1,  = 0, and m = 0. Now ms can have
two values corresponding to each value of m i.e.
ms = +1/2, 1/2. Hence the possible designation of an
electron in a state with n = 1 is (1, 0, 0, +1/2) and
(1, 0, 0, 1/2)  (n, , m, ms) i.e., two quantised states.
This implies that an orbital can accommodate (for n = 1,
m = 0, i.e., one orbital) maximum of two electrons having
opposite spins.
The maximum number of electrons in the different sub-shells
are :
s sub-shell = 2, p sub-shell = 6, d sub-shell = 10 and f sub-shell = 14.

Hund’s Rule Of Maximum Multiplicity

According to this rule : “ electrons never pair until no available empty degenerate orbitals are left to
them.”
This means an electron always occupies a vacant orbital in the same sub-shell (degenerate orbital) and pairing
starts only when all of the degenerate orbitals are filled up. This means that the pairing starts with 2nd electron
in s sub-shell, 4th electron in p sub-shell, 6th electron in d sub-shell and 8th electron in f sub-shell.
By doing this, the electrons stay as far away from each other as possible. This is highly reasonable if we
consider the electron-electron repulsion. Hence electrons obey Hund’s rule as it results in lower energy state
and hence more stability.
Extra Stability of Half And Fully Filled Orbitals

A particularly stable system is obtained when a set of equivalent orbitals (degenerate orbitals) is either fully
filled or half filled, i.e., each containing one or a pair of electrons. This effect is more dominant in d and f sub-
shells.
This means three or six electrons in p sub-shell, five or ten electrons in d sub-shell, and seven or fourteen
electrons in f sub-shell forms a stable arrangement. Note this effect when filling of electrons takes place in d
sub-shells (for atomic numbers Z = 24, 25 and 29, 30).
Electronic configuration of an element is represented by the notation n x :
n : principal quantum number  : denotes the sub-shell x : number of electrons present in an orbital
Illustration - 16 Write down the electronic configuration of following species. Also find the number of
unpaired electrons in each. (a) Fe, Fe2+, Fe3+ (Z of Fe = 26) , (b) Br, Br  (Z of Br = 35) ,
(c) V, V3+ (Z of Fe = 23)
SOLUTION :
Follow the order of increasing energy (Aufbau Rule) :
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d……..
(a) Fe(Z = 26): 1s2 2s2 2p6 3s2 3p6 4s2 3d6
Note that 3d orbital are not fully filled.
3d6 
Orbitals filled as per Hund’s Rule.
Clearly the number of unpaired electrons is 4.
 Fe2+ : (Z = 26) [No. of electrons = 24]

While writing electronic configuration (e.c.) of cations, first write e.c of neutral atom and then “remove desired
number of electrons from outermost orbital”.
In Fe2+, remove 2e from 4s2 since 4s orbital (through lower in energy then 3d) is the outermost. Hence e.c.
of Fe2+ is: 1s2 2s2 2p6 3s2 3p6 3d6 4s0
Note that number of unpaired electrons remains same as that in Fe, i.e. 4.
 Fe3+ (Z = 26) [No. of electrons = 23]
Now remove 2e from 4s2 and 1e from 3d6 to get e.c. as : 1s2 2s2 2p6 3s2 3p6 3d5 4s0

Note that, now all ‘d’ orbits have an odd electron (i.e. are half filled).
Hence number of unpaired electrons in Fe3+ = 5.

(b) Br (Z = 35) [No. of electrons = 35]
Following Aufbau rule, e.c. is : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p5
Clearly one of 4p5 orbitals contains unpaired electrons: 4p5 
Hence Br has only one unpaired electron.
 Br   Z  35  [No. of electrons = 36]
Since anion(s) is(are) formed by adding electron(s), so simply write e.c. as per total number of electrons
finally. For Z = 35, e.c. is : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6
Clearly there are no unpaired electrons.
(c) Following on pattern in (a), we can write e.c. for V as follows.
V(Z = 23) : 1s2 2s2 2p6 3s2 3p6 4s2 3d3
3d3 
 3 unpaired electrons.
 V3+ (Z = 23) [No. of electrons = 20]
Remove 3e  from outermost orbitals successively i.e.,‘2e  ’ from 4s 2 and 1e  from 3d 3 .
Hence e.c. of V3+ is :
1s2 2s2 2p6 3s2 3p6 4s0 3d2
3d 2 

 2 unpaired electrons.

Illustration - 17 A compound of Vanadium has a magnetic moment of 1.73 B.M. Work out the electronic
configuration of vanadium in the compound.
SOLUTION :
The magnitude of magnetic moment () of a compound/species/ion is given by :
  n  n  2 B M
(n = number of unpaired electrons ; BM : unit of magnetic moment in Bohr’s Magneton)
 1.73  n  n  2 
On solving for n, we get n = 1. This means that vanadium ion (Z = 23) in the compound has one unpaired
electron.
3d :
So its electronic configuration (e.c.) must be :
1s2 2s2 2p6 3s2 3p6 3d1
i.e., vanadium exists as V4+ ion in the compound since the ground state e.c. of 23V is :
1s2 2s2 2p6 3s2 3p6 3d3 4s2
3d : 4s :
Note : In these kind of questions, keep on removing e from the outermost orbitals till the required number of unpaired
e is achieved.
MISCELLANEOUS ILLUSTRATINS
Illustration - 18 Find the threshold wavelength for a copper plate, a sodium plate and cesium plate. The
work functions of these plates are : 4.5 eV, 2.3 eV & 1.9 eV respectivley.
SOLUTION :
hc
Use λ 0= E  stopping energy.
E
For copper λ 0 = 1242 ev – nm = 276 nm

4.5eV
1242 ev – nm
For Sodium λ0 = = 540 nm
4.5 eV
For caesium λ 0 = 1242 ev – nm = 654 nm

1.9 eV

Illustration - 19 A UV light of wavelength 280 nm is used an experiment on photoelectric effect with Li

(work function = 2.5 eV) as cathode. Find:
(a) the maximum KE of photoelectrons and (b) the stopping potential
SOLUTION :
(a) The maximum K.E is : (b) Stopping potential V is given by
hc
K max = 
λ K max
V  1.9 V
1242 e
  2.5  1.9 eV
280
Illustration - 20 (a) Find the wavelength of the radiation required to excite the electron in Li++ from
the first to the third Bohr orbit. (b) How many spectral lines are observed in the emission spectrum of the
above excite system ?
SOLUTION :
z2
(a) As we know E = 13.6 2 eV (b) There are three lines in the spectrum.
n
So  E = E3  E1 = 8×13.6 eV = 108eV.
1242 eV  nm
Use λ  108.8 eV
= 11.4 nm
Illustration - 21 A hydrogen sample is prepared in a particular excited state A. Photons of energy 2.55 eV
get absorbed into the sample to take some of the electrons to a further excited state B. Find the quantum
number of the states A and B.
SOLUTION :
Use the energy difference diagram and we can see that 2.55 eV can only be absorbed in transition
n = 2 to n = 4. Hence the quantum number are 2 and 4.

Illustration - 22 Find the wavelengths in a hydrogen spectrum between the range 500 nm to 700 nm.
SOLUTION :
First find energy of the photons having wave Thus the energy difference should be between
length 500 nm and 700 nm. 1.77 eV and 2.44 eV.
1242 eV  nm The desired transition is  2 for
Eλ 500   2.44 eV
500 nm  E = 1.9 eV.
1242 eV  nm hc 1242 eV  nm
Eλ  700   1.77 eV Hence λ  ΔE  1.9 eV
 654 nm
700 nm
Illustration - 23 A beam of ultraviolet radiation having wavelength between 100 nm and 200 nm is inci-
dent on a sample of atomic hydrogen gas. Assuming that the atoms are in ground state, which wavelengths
will have low intensity in the transmitted beam ? If the energy of a photon is equal to the difference between
the energies of an excited state and the ground state, it has large probability of being absorbed by an tom in
the ground state.
SOLUTION :
1242 eV  nm Thus 10.2 eV and 12.1 eV have larger
E λ=100 nm = = 12.42 eV probability.
100 nm
And that corresponding to 1 = 200 nm is 1242 eV  nm
 λ1 = = 122 nm
6.21 eV 10.2 eV
E 2  E1 = 10.2 eV and E3  E1 = 12.1eV 1242 eV  nm
and λ2 = = 103nm
E 4  E1 = 12.75eV 12.1eV
Illustration - 24 Light corresponding to the transition n = 4 to n = 2 in hydrogen atoms falls on cosium

metal (work function = 1.9 eV). Find the maximum kinetic energy of the photoelectriosn emitted.
SOLUTION :
The energy of photons emitted in transition
n = 4 to n = 2 is
 1 1 
hv  13.6 eV  2  2   2.55 eV
2 4 
K .Emax  2.55  1.9  0.65 eV

Illustration - 25 Calculate the smallest wavelength of radiation that may be emitted by

(a) hydrogen (b) He+ and (c) Li++
SOLUTION :
Smallest wavelength will be from   1 . 1 1 1  1
For He+ ion Z = 2 = R .Z2   ; λ=
λ  1 2 
2 4R
For H-atom
1 1 1  1
1 1 1  For Li2+; 2 = 3 = R .32  2  2  ; λ=
= RZ2  2  2  = R  1 = 911.5 Å λ 1   9R
λ 1  
Illustration - 26 Find the binding energy of a hydrogen atom in the state n = 2.

SOLUTION :
z2
Binding energy will be 13.6 2
n
12
For n = 2; B.E. = 13.6 2 = 3.4 eV
2
Illustration - 27 Find the radius and energy of a He+ ion in the states
(a) n=1 (b) n = 4 and (c) n = 10
SOLUTION :
n2
Radius = 52.9 pm
z
z = 2, n = 1
12
 r  52.9   26.45 pm
2
42 102
r4  52.9   423.2 pm rn 10  52.9   2645 pm
2 2
Illustration - 28 A positive ion having just one electron ejects it if a photon of wavelength 228 Å or
less is absorbed by it. Identify the ion.
SOLUTION :
First find  E corresponding to this wavelength
1242
E = = 54.47 eV
22.8
 54.47 = 13.6 z 2  z=2
Hence the ion is He+.

Illustration - 29 A hydrogen atom in state n = 6 makes two successive transitions and reaches the ground
state. In the first transition a photon of 1.13 eV is emitted.
(a) Find the energy of the photon emitted in the second transition.
(b) What is the value of n in the intermediate state ?
SOLUTION :
Use the energy diagram 1 1 1 
E6 = – 0.378 = R×12 ×  2  2 
λ 1 5 
E5 = – 0.544
E4 = – 0.85 1 8R
E3 = – 1.51 =
λ 9
By looking at the energy gap vale of 1.13 eV.
9 9
We can see that intumidiate state is 3rd . λ= = ×911.5Å = 1024.4Å
8R 8
Hence the second transition will be form 3  1.
Illustration - 30 A beam of light having wavelengths distributed uniformly between 450 nm to 550 nm
passes through a sample of hydrogen gas. Which wavelength will have the least intensity in the transmitted
beam ?
SOLUTION :
hc
E1 = = 2.76 eV;
450
1242
E2 = = 2.26 eV Observing from the energy diagram
550
Clearly, the intermediate wavelength absorbed will be corresponding to

energy = 2.55 eV
Hence corresponding wavelength will be 486 nm.
Illustration - 31 A hydrogen atom in ground state absorbs a photon of ultraviolet radiation of wavelength
50 nm. Assuming that the entire photon energy is taken up by the electron, with what kinetic energy will the
electron be ejected ?
SOLUTION :
Illustration - 31the given situation corresponding to a photoelectric effect.
Visualise
1242
Energy corresponding to 50 nm wavelength = = 24.84 eV
50
The ionization energy of hydrogen atom in ground state is 13.6 eV which is equivalent to work function of
hydrogen atom.
Hence, K.E. of electron ejected = 24.84  13.6 = 11.24 eV .

Electronic Configurations of the Elements

Element Z 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
H 1 1
He 2 2
Li 3 2 1
Be 4 2 2
B 5 2 2 1
C 6 2 2 2
N 7 2 2 3
O 8 2 2 4
F 9 2 2 5
Ne 10 2 2 6
Na 11 2 2 6 1
Mg 12 2 2 6 2
Al 13 2 2 6 2 1
Si 14 2 2 6 2 2
P 15 2 2 6 2 3
S 16 2 2 6 2 4
Cl 17 2 2 6 2 5
Ar 18 2 2 6 2 6
K 19 2 2 6 2 6 1
Ca 20 2 2 6 2 6 2
Sc 21 2 2 6 2 6 1 2
Ti 22 2 2 6 2 6 2 2
V 23 2 2 6 2 6 3 2
Cr* 24 2 2 6 2 6 5 1
Mn 25 2 2 6 2 6 5 2
Fe 26 2 2 6 2 6 6 2
Co 27 2 2 6 2 6 7 2
Ni 28 2 2 6 2 6 8 2
Cu* 29 2 2 6 2 6 10 1
Zn 30 2 2 6 2 6 10 2
Ga 31 2 2 6 2 6 10 2 1
Ge 32 2 2 6 2 6 10 2 2
As 33 2 2 6 2 6 10 2 3
Se 34 2 2 6 2 6 10 2 4
Br 35 2 2 6 2 6 10 2 5
Kr 36 2 2 6 2 6 10 2 6
Rb 37 2 2 6 2 6 10 2 6 1
Sr 38 2 2 6 2 6 10 2 6 2
Y 39 2 2 6 2 6 10 2 6 1 2
Zr 40 2 2 6 2 6 10 2 6 2 2
Nb* 41 2 2 6 2 6 10 2 6 4 1
Mo* 42 2 2 6 2 6 10 2 6 5 1
Tc 43 2 2 6 2 6 10 2 6 5 2
Ru* 44 2 2 6 2 6 10 2 6 7 1
Rh* 45 2 2 6 2 6 10 2 6 8 1
Pd* 46 2 2 6 2 6 10 2 6 10
Ag* 47 2 2 6 2 6 10 2 6 10 1
Cd 48 2 2 6 2 6 10 2 6 10 2
In 49 2 2 6 2 6 10 2 6 10 2 1
Sn 50 2 2 6 2 6 10 2 6 10 2 2
Sb 51 2 2 6 2 6 10 2 6 10 2 3
Te 52 2 2 6 2 6 10 2 6 10 2 4
I 53 2 2 6 2 6 10 2 6 10 2 5
Xe 54 2 2 6 2 6 10 2 6 10 2 6
*Elements with exceptional electronic configurations

SUBJECTIVE SOLVED EXAMPLES
Example - 1 Calculate the wavelength and wave number of the spectral line when an electron in H-atom
falls from higher energy state n = 3 to a state n = 2. Also determine the energy of a photon to ionize this atom
by removing the electron from 2nd Bohr’s orbit. Compare it with the energy of photon required to ionize the
atom by removing the electron from the ground state.
SOLUTION :
First calculate the energy (E) between the Bohr

orbits n = 3 and n = 2 using :
 1 1 
E = 13.6 Z  2  2
2  eV

 n1 n2 
 To ionize the atom from n = 2, the transition will
 1 1 
 be
E(3  2) = 13.6 (1)2  2  2  eV = 1.89 eV
2 3  n = 2  n = .
 1 1 
Now this energy difference is the energy of the E(2  ) = 13.6  12   2  2  eV
photon emitted. 2  
= 3.4 eV
12400  To ionize the atom from ground state (n = 1),
 E Photon  eV
  in Å  the transition is 1  .
12400 1 1 
   6560.3 Å E = 13.6 eV 12   2  2  = 13.6 eV
1.89 1  
1
and    1.52  106 m 1

Self Study Course for IITJEE with Online Support Subjective Solved Examples 39
Example - 2 A hydrogen atom in the ground state is hit by a photon exciting the electron to 3rd excited
state. The electron then drops to 2nd Bohr orbit. What is the frequency of radiation emitted and absorbed in
the process ?
SOLUTION :
18 1 1 
Energy is absorbed when electron moves from  E(1  4)  2.18  10  12    J
2
1 42 
ground state (n = 1) to 3rd excited state (n = 4).
 2.04  1018 J
First calculate the energy difference between This is the energy of the photon absorbed.
n = 1 and n = 4. Use : E Photon  h  2.04  10 18 J to get :
Use :  15
v  3.08  10 Hz
 1 1   Similarly, when electron jumps from n = 4 to
E (1  4)  2.18  1018  Z2   
2 ; ; n = 2, energy is emitted and is given by the
 n1 n 22 
same relation.
Put n1 = 2 and n2 = 4 in the expression of E,
to get
 1 1 
E(4  2)  2.18  1018  12    J
2
2 42 
 4.08  1019 J
This is the energy of the photon emitted.
Use : E Photon  h  4.08  10 19 J
Here Z = 1, n1 = 1, n2 = 4
   6.16  1014 Hz
Example - 3 A hydrogen like ion, He+ (Z = 2) is exposed to electromagnetic waves of 256.4 Å. The
excited electron gives out induced radiations. Find the wavelength of the induced radiations, when electron
de-excites back to the ground state. R = 109677 cm1.
SOLUTION :
He+ ion contains only one electron, so Bohr’s Substitute for  = 256.4 Å = 256.4  108 cm,
model is applicable here. It absorbs a photon of
R = 109677, Z = 2 for He+ ion, n1 = 1
wavelength  = 256.4 Å. Assume the electron to
be in ground state initially. Let it jumps to an ex- Now, Find n2 .
cited state n2. Use the relation, to find n2.
1
1  1 1  256.4  108
   R Z2   
  n2 n2  1
 1 2 1 
 109677 107  (2)2   
 12 n 2 
 1 2
40 Subjective Solved Examples Self Study Course for IITJEE with Online Support
 n2 = 3  (3  1) = 256.4 Å,  (3  2) = 1641.3 Å,
From n = 3, the electron can fall back to the  (2  1) = 303.9 Å
ground state in three possible ways (transitions) :
3  1, 3  2, 21
Hence three possible radiations are emitted. Find
the wavelengths corresponding to these transi-
tions.
The wavelength () for transition, 3  1 will be
same i.e., 256.4 Å. Find  for 3  2 and 2  1
using the same relation.
Example - 4 Hydrogen gas when subjected to photo-dissociation, yields one normal atom and one atom
possessing 1.97 eV more energy than normal atom. The bond dissociation energy of hydrogen molecule into
normal atoms is 103 kcals mol1. Compute the wave length of effective photon for photo dissociation of
hydrogen molecule in the given case.
SOLUTION :
H2  H + H* The extra energy possessed by excited atom is
*
where H is normal H-atom and H is excited 1.97 eV
H-atom. So the energy required to dissociate H2 in  1.97  1.6  1019 J = 3.15  1019 J
this manner will be greater than the usual bond E (absorbed) = 7.175  1019 + 3.15  1019 J
energy of H2 molecule. = 1.03  1018 J
E(absorbed) = dissociation energy of Now calculate the wavelength of photon
H2 + extra energy of excited atom corresponding to this energy.
hc
Energy required to dissociate in normal manner E photon   1.03  1018 J

= 103  103 cal per mol (given)   = 1930 Å
103  103  4.18

= = 7. 17  1019 J /molecule
23
6  10
Example - 5 An electron in the first excited state of H-atom absorbs a photon and is further excited.
The de Broglie wavelength of the electron in this state is found to 13.4 Å. Find the wavelength of photon
absorbed by the electron in Å. Also find the longest and shortest wavelength emitted when this electron de-
excites back to ground state.
SOLUTION :
Note : The energy state n = 1 is known as Ground State Using the relation :
The energy state n = 2 is known as First Excited  1 1 
State. E  13.6 Z2    eV
(2  4)  n2 n2 
The energy state n = 3 is known as Second  1 2
excited State and so on. = 2.55 eV [n1 = 2, n2 = 4, Z = 1]
The electron from n = 2 absorbs a photon and is 12400
 E  eV
further excited to a higher energy level (2  4)   in Å 
(let us say n). 12400

 =  Å  4863.1Å
The electron in this energy level (n) has a de 2.55
Broglie wavelength () = 13.4 Å.
The longest wavelength emitted when this
electron (from n = 4) falls back to the ground
state will corresponds to the minimum energy
transition.
The transition corresponding to minimum energy
will be 4  3.
h Note : The transition corresponding to maximum
e 
m e ve energy will be 4  1.
Z hc
and ve  2.18  106 ms 1 E (Energy diff .)  E Photon   h
n 
[ve is the velocity of e in nth Bohr orbit] 1
 E  or E  vPhoton
h  Photon
1
 ve   2.18  106  
m n Using the same relation :
6.626 1034  1
E (4  3)  13.6 Z2  
1 
eV
 2 2
13.4 1010   9.11031  n
 1 n 2
1
 2.18  106  [ n1 = 3, n2 = 4, Z = 2]
n
 n=4  E(4  3)  0.66 eV
Now find the wavelength of the photon respon- 12400

E  E Photon  eV
sible for the excitation from n = 2 to n = 4   in Å 
  = 18752.8 Å 12400
 E (4  1)  E Photon  eV
  in Å 
Shortest wavelength : 4 1
   973.2Å
1
2 1 
E(4  1)  13.6  1     eV
 12 42 
= 12.75 eV
Example - 6 A single electron orbits around a stationary nucleus of charge +Ze, where Z is a constant and
e is the magnitude of electronic charge. It requires 47.2 eV to excite the electron from second Bohr orbit to the
third Bohr. Find :
(a) the value of Z
(b) the energy required to excite the electron from n = 3 to n = 4
(c) the wavelength of radiation required to remove electron from 2nd Bohr’s orbit to infinity
(d) the kinetic energy, potential energy and angular momentum of the electron in the first orbit.
(e) the ionisation energy of above one electron system in eV.
SOLUTION :
Since the nucleus has a charge +Ze, the atomic   E = 16.53 eV
number of the ion is ‘Z’. (c) The required transition is n1 = 2  n2 =  by
(a) The transition is n1 = 2  n2 = 3 by absorbing absorbing a photon of energy E.
a photon of energy 47.2 eV. Find E by using the relation :
 E = 47.2 eV  1 1 
E  13.6 (5) 2   
 2
Using the relation : 2 2 
 1 1 
E  13.6 Z2     E = 85 eV
 n 2 n 2  eV
 1 2 Find  of radiation corresponding to energy
 1 85 eV.
1 
 47.2  13.6 Z2     Z = 5 12400
 22 32    Å = 146.16 Å
(b) The required transition is n1 = 3  n2 = 4 by 85
absorbing a photon of energy E. (d) If energy of electron be En, then KE = En and
Find E by using the relation : PE = 2En
 1 1  13.6 Z 2 13.6  52
E  13.6 Z2    En   = 340 eV
 n 2 n 2  eV n2 12
 1 2
KE = (340 ev) = 340 eV
 1 1 
E  13.6(5)2  
 2 2  eV PE = 2 (340 eV) = 680 eV
3 4 
 h  (e) The ionisation energy (IE) is the energy required

Angular momentum () = n  
 2  to remove the electron from ground state to infin-
 6.626  1034  ity. So the required transition is 1  .
  1  
 2  The ionisation energy
34
= 1.05 10 J-s
(IE) =  E1 = 13.6 (Z)2 eV
Note : Angular momentum of e is also equal to
 IE = +13.6  52 = 340 eV.
me v e r .
Example - 7 The hydrogen-like species Li 2 is in a spherically symmetric state S 1 with one radial node.
Upon absorbing light the ion undergoes transition to a state S 2 . The state S2 has one radial node. The ratio
of its energy in state S 1 to the ground state energy of the hydrogen atom.
(i) The state S 1 is : (A) 0.75 (B) 1.50
(A) 1s (B) 2s (C) 2.25 (D) 4.50
(C) 2p (D) 3s (iii) The orbital angular momentum quantum
(ii) Energy of the state S 1 in units of the number of the state S 2 is :
hydrogen atom ground state energy is: (A) 0 (B) 1
(C) 2 (D) 3
SOLUTION : (i)-(B) (ii)-(C) (iii)-(B)

Radial node = n    1 Energy of electron in S1
S 1 2s (As it is spherically symmetric and has
Z2 32
one radial node) = 13.6× eV = 13.6× eV
n2 22
S2  3p (As its energy is equal to ground state
Energy of hydrogen in ground state
energy of H-atom hence, its principal quantum
= 13.6 eV
number is 3 and it contains only 1 radial node)
Hence its Orbital angular momentum quantum  Energy of electron in S1 is 2.55 times the
number is 1. (1  3    1  1) energy hydrogen atom in ground state.
Example - 8 Find the energy required to excite 1.10 litre of hydrogen atoms gas at 1.0 atm and 298 K to
the first excited state of atomic hydrogen. The energy required for the dissociation of HH bond is 436
kJ/mol. Also calculate the minimum frequency of a photon to break this bond.
SOLUTION :
Let us, first find the number of moles of hydrogen The energy required to excite the given number
atoms. of Hatoms = 6.02  1022  1.635  10–18 J
= 98.43 kJ
PV 1 1.10
n H2    0.045 So the total energy required
RT 0.0821 298
= 19.62 + 98.43 = 118.05 kJ
Thus the energy required to break 0.045 moles
Now the energy required to break a single
of H2 (HH bond) = 0.045  436 = 19.62 kJ.
Now calculate the energy needed to excite the 436 103
H-H bond =
Hatoms to first excited state i.e., to n = 2 (First 6.023 1023
excited state is referred to n = 2).
 1  7.238  1019 J / atm
18 2 1 
E  2.18  10 (1)    J / atom
 12 22  = Energy supplied by the photon
= 1.635  1018 J/atom  7.238  1019 = h = 6.626  1034 ()
No. of H atoms = (No. of H2 molecules)  2   = 1.09  1015 Hz.
= (0.05  6.02  1023)  2 = 6.02  1022
Example - 9 Estimate the difference in energy between 1st and 2nd Bohr’s orbit for a Hatom. At what
minimum atomic number (Z), a transition from n = 2 to n = 1 energy level would result in the emission of
radiation with wavelength  = 3.0  108 m ? Which Hydrogen atom like species this atomic number corre-
sponds to ? How much ionisation potential is needed to ionise this species ? (R = 1.097  107 m1)
SOLUTION :
The difference in energy is given by E : Hence the Hlike atom is He+ ion.
18 2 1 1  To ionise, He+ ion, ionisation energy (IE)

E  2.18  10 (1)  2  2  J / atom = (E1)
1 2 
18 11
IE = (13.6  22) = + 54.4 eV
= 1.65  10 J  1.65  10 ergs  10.2 eV
The ionisation potential (IP) is the voltage dif-
8
For a Hlike atom,  = 3.0 10 m. ference required to generate this much energy.
 IE = qV = e (IP) = 54.4 eV
1 1 
 E  2.18  1018  Z2   2  2  J  IP (required) = 54.4 Volts
(2  1) 1 2 
hc
 E Photon   Z=2

Example - 10 Math the following :

List 1 List 2
(A) Orbital angular momentum of the electron in a hydrogen-like (p) principal quantum number
atomic orbital
(B) A hydrogen-like one-electron wave function obeying (q) Azimuthal quantum number
Pauli principle
(C) Shape, size and orientation of hydrogen-like atomic orbitals (r) Magnetic quantum number
(D) Probability density of electron at the nucleus in (s) Electron spin quantum number
hydrogen-like atom
SOLUTION : [A-q, r] [B-p, q, r, s] [C-p, q, r]
[D-p, q]
(A) Orbital angular momentum of the (C) Shape, size and orientation of hydrogen-like
electron in a hydrogen like atomic atomic orbital are indicated by , n, m .
orbital depends on type of atomic
(D) Probability density of electron at the nucleus in
orbital ( ) and its orientation (m ) . hydrogen-like atom is obtained by the square
(B) As per Pauli’s principle, every electron
of the wave functions. (ψ 2 ) and it depends on
is unique, hence all four quantum
numbers are required. n and 
Example - 11 A stationary He+ ion emits a photon corresponding to the first line (H) of Lyman series.
The photon thus emitted, strikes a Hatom in the ground state. Find the velocity of the photoelectron ejected
out of the hydrogen atom. The value of R = 1.097  107 m1.
SOLUTION :
1 2
The difference in energy (E) will be equal to the KE = Ei  Wo = m e ve [Ei = Incident energy]
2
energy of the photon emitted.
First line in Lyman series corresponds to the 2 (Ei  Wo )
 ve 
transition 2 1. me
1 1 
E  2.18  1018 (2)2  
12
22 
 J / atom
 ve 
2  6.54 1018  2.18 1018 
= 6.54  1018 J 9.11031
The photon of this much energy strikes a Hatom in  ve = 3.09  106 m/s
the ground state. Note that the ionisation energy of
We can also calculate the wavelength of electron
Hatom is +2.18  1018 J. This will be the work
function of Hatom. Using the Einstein’s photoelectric ejected out  2.36  1010 m  2.36 Å
equation :
h 6.626  1034
e   m  2.36 Å
me ve 9.1  1031  3.09  106
Example - 12 An electron in a hydrogen like species, makes a transition from nth Bohr orbit to next
outer Bohr (  n  1) . Find an approximate relation between the dependence of the frequency of the photon
absorbed as a function of ‘n’. Assume ‘n’ to be a large value (n >> 1).
SOLUTION :
 1 1 
E (energy difference)  h  2.18  1018  Z2   J
2 2
(n  n  1)  n (n  1) 
2n  1
 h  2.18  1018  Z2  
2 2 J
 n (n  1) 
Since n >> 1 (given)
 n + 1 ~ n ; 2n + 1  2n
2n
 h  2.18  1018 Z2  J
n4
   n 3
THINGS TO REMEMBER
1. Number of photons (n) emitted in time t sec from a source of radiation with power P is given by :
Pt Pt
n 
 hc /   hc
2. Einstein’s photoelectric equation : Ei = KE + W0 or KE = h   h0 = h (  0) or
1
KE  mv2  h  ν  ν 0 
2
3. Bohr model of Atom : Bohr’s Model is applicable only to one-electron atoms like : He+, Li2+, Be3+ apart
from H-atom.
6 Z
Velocity of an electron in nth Bohr orbit  vn  2.18  10 ms 1
n
Radius of the nth Bohr orbit
n2 n2 n2
 rn  0.529  1010 m  0.529 Å  52.9 pm 1pm  1012 m 
Z Z 2
Energy of electron in nth Bohr orbit
Z2 Z2
 E n  13.6 eV / atom  2.18  1018 J / atom 1eV  1.6  1019 J 
n 2
n 2  
K.E.n =  En and E.P.E.n = 2En
Self Study Course for IITJEE with Online Support Things To Remember 47
4. When an electron jumps from an outer orbit (higher energy) n2 to an inner orbit (lower energy) n1, then the
energy is emitted in form of photons, which is given by :
 1 1   1 1 
E  E n 2  E n1  2.18  1018  Z2    J/atom  13.6  Z2   
 n2 n2   n 2 n 2  eV/atom
 1 2  1 2
If an electron is to be moved from lower energy state (n1) to a higher energy state (n2), the same amount of
energy ( E) is needed to absorb in the form of photons
h h
5. de-Broglie wavelength is given as :    (p = linear momentum = mv)
p mv
48 Things To Remember Self Study Course for IITJEE with Online Support
Vidyamandir Classes
My Chapter Notes
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Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Periodic Properties of Elements
Classification of Elements & Periodicity in Properties

EARLIER ATTEMPTS OF PERIODIC CLASSIFICATION OF ELEMENTS Section - 1
Certain groups of elements have similar chemical properties; we classify elements as members of the same
chemical family. Such similarity in the properties of elements has led scientists to classify them in such a form
where one can study them in an organized manner. Such an arrangement is called as Periodic Table. Some of
significant earlier attempts are discussed below.
Dobereiner’s Triads
In 1829, J. Dobereiner made an important first step towards a systematic classification by arranging elements
into groups of three (triads). He observed that the atomic weight of the middle element of the group was
midway between the atomic weights of the other two. He also concluded that the same midpoint relation held
true for the physical properties of these elements.
Some of his triads were :
Li, Na, K Cl, Br, I Ca, Sr, Ba
Newland’s law of Octaves
In 1865, Newland proposed that if the elements are arranged according to the increasing atomic weights
(beginning with lightest element, excluding Hydrogen), the chemical and physical properties of a particular
element would be similar to those of the elements seven places before and seven places after it (like the eight
note in an octave of music). This led to the idea of periodicity for the first time in true sense.
For example, Li, the second element in Newland’s list, had properties similar to Na, the ninth element in the
list and K, the sixteenth element. Thus these were similar elements represented by numbers 2, 9, 16 that
show interval of seven.
Mendeleev’s Periodic law and Classification
In 1869, the Russian Chemist Mendeleev was successful in arranging the elements in the form a periodic
table, in such a way that the elements having similar properties were placed in same vertical columns, called
groups.
Mendeleev organized the elements according to a regular increase in the atomic weight. He thus obtained a
pattern where similar chemical properties for element recurred periodically. In fact his observations were
based on a periodic law stating :
“ The physical and chemical properties of the elements are periodic functions of their respective
Atomic weights.”
His proposal was even backed by the predictions for the undiscovered elements. He took a bold step to
leave the blank places for such elements. He in fact predicted the properties of these elements and called
some of them as eka-sillicon (Germanium), eka-aluminum (Gallium) and eka-boron (Scandium). Later on
when these elements were discovered, Mendeleev’s predictions were found to be amazingly accurate.

Periodic Properties of Elements Vidyamandir Classes
Modern Periodic Table

With the establishment of atomic theory in the first quarter of 20th century and work of physicist Henry
Moseley, the chemical behavior of an atom is known to be dependent on its electrical characteristic signified
by its Atomic number (Z). So Mendeleev’s periodic table was modified to include the later developments in
so called Long-form of periodic table. It is based on modern Periodic Law stated as :
“The physical and chemical properties of the elements are periodic functions of their respective Atomic
numbers”
In the long form of periodic, the elements having the same electronic configuration in their outer shell were
grouped together. The electrons in the outer shell are termed as valence electrons. Valence electrons determine
the properties and chemcial reactivity of the elements and participate in chemical bonding (discussed later in
the chapter).
Hence a major modification in the long form of periodic table, is the arrangement of elements in order of
increasing Atomic numbers rather than increasing Atomic weights.
MODERN PERIODIC TABLE Section - 2
In modern periodic table, elements are arranged in horizontal rows (periods) and vertical columns (groups). In
all there are seven periods and eighteen groups. The groups were divided into two categories according to old
convention. Now the groups are numbered from 1 to 18. In old convention group nos.were
IA, IIA, ......... VIIA, IB, IIB ......... VIIIB.
IA, IIA, IIIA,…………VIIIA ; now written as 1, 2, 13, 14, 15, 16, 17, 18
IIIB,…………VIIB ; now written as 3, 4, 5, 6, 7
VIIIB corresponds to 8, 9, 10 and IB, IIB correspond to 11, 12 respectively.
Periods :
Ist Period contains only two elements namely Hydrogen (H), Helium(He). It is called as shortest period.
IInd period starts with Lithium (Li) and contains eight elements.
Li, Be, B, C, N, O, F, Ne.
IIIrd period starts with Sodium (Na) and contains eight elements.
Na, Mg, Al, Si, P, S, Cl, Ar.
Note : II and III periods are called as short-periods.

IVth period contains eighteen elements starting with Potassium (K).
K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Kr.
Vth period contains eighteen elements starting from Rubidium (Rb).
Rb, ………….., Xe (Xenon).
Note : IVth and Vth periods are called as long-periods.


VI period consists of 32 elements, starting from Cesium (Cs) and ending with Radon (Rn). It is called as
longest period. Apart from the representative and transition elements this period also contains Inner
transition elements called as Lanthanides (Ce,………., Lu).
VII period is incomplete period and at present contains 19 elements starting form Fr (Francium). Upto
Uranium (U) all the elements are naturally occurring but rest are radioactive with very short half-lives. These
also include a part of inner transition elements, called as actinides (Th,…Lr).
Groups :
Group 1 consists of H (1s1), Li (2s1), Na (3s1),… The common outermost electronic configuration is ns1.
Elements belonging to this group are called as Alkali Metals.
Group 2 consists of Be (2s2), Mg (3s2), Ca (4s2),… The common electronic configuration is ns2. Elements
of this group are called as Alkaline Earth Metals.
Group 13 consists of B (2s2 2p1), Al (3s2 3p1),… The common electronic configuration is ns2 np1. Elements
of this group are called as Boron Family.
Group 14 contains C (2s2 2p2), Si (3s2 3p2),… The common electronic configuration is ns2 np2. This group
is known as Carbon Family.
Group 15 contains N (2s2 2p3), P (3s2 3p3),… The common electronic configuration is ns2np3. This group
is known as Nitrogen Family. The elements of this group are also called as PNICTOGENS (poisonous
compounds forming elements).
Group 16 contains O (2s2 2p4), S (3s2 3p4),… The common electronic configuration is ns2 np4. This group
is known as Oxygen Family. The elements of this group are also famous as CHALCOGENS (ore-forming
elements).
Group 17 contains F (2s2 2p5), Cl (3s2 3p5),… The common electronic configuration is ns2 np5. Elements of
this group are called as HALOGENS (salt forming elements).
Group 18 (or Zero group) contains He (1s2), Ne (2s2 2p6), Ar (3s2 3p6),… The common electronic
configuration is ns2 np6. Elements of this group are called as Inert Gases or Noble Gases.


Features of Groups 1, 2, 13 – 18
 Elements belonging to these groups are in general called as Representative Elements
 General Electronic Configuration for group 1, 2 can be written as: ns1-2 and ns2 nd 1-6, for group
13- 18.
n : here represents the number of period to which a particular elements belongs (principal quantum
number).
The total number of electrons i.e., number of electrons in s & p sub-shells gives the number of group
to which a particular elements belongs.
 Elements of 1 and 2 groups are also called as s-block elements, as final electron in these elements
(also called as differentiating electron) enters s sub-shell. Elements of 13 to 18 groups are called as p-
block elements, as differentiating electron in these elements enters p sub-shell.
Features of Groups 3 – 12
 Groups 3 to 12 are known as transition elements or d -block elements, as the differentiating
electron (last electron) in these elements enters d-sub-shell. General electronic configuration of
these elements can be written as (n – 1) d 1-10 n s0-2.
 Group 3 has a special feature in sense that, it contains elements in which the differentiating electron
enters the f sub-shell, hence these elements are also called as f-block elements apart from being
called as Inner transition elements. These are placed in two horizontal rows below the table and are
called as Lanthanides (also called as Lanthanoides) and Actinides (also called as Actinoids).
General electronic configuration of these elements is :
Lanthanoides : 4 f n 5d 0-1 6s2
Actinoids : 5 f n 6d 0-2 7s2.
Some other features of the periodic table are as follows :

Typical Elements
Elements of third period are also called as Typical Elements. These include Na, Mg, Al, Si, P, S, Cl. The
properties of all the elements belonging to a particular group resemble the properties of the corresponding
typical element of that group. For example, the general properties of Alkali Metal can be predicted from the
behaviour of Na, not Li, the first member of the family.
The typical elements (all having n = 3) can take up 18 electrons. Note that, for these elements 3d sub-shell is
available, but it is not filled i.e., these have vacant d sub-shell. This is not the case with second period elements,
hence they have somewhat different properties than the rest of the group or we can say that it is the typical
element, which in true sense represents a group.

Bridge Elements
Elements of second period are also called as Bridge Elements. The properties of these elements resemble
with the properties of elements belonging to third period placed diagonally. This is illustrated as follows.
Noble or Inert Gases

Elements of group 18 or zero group are called Inert or Noble Gases. They have completely filled (2 or 8
electrons in outermost shell) outermost shells, called as stable configuration. Their valency is zero. They are
almost inert in their chemical behaviour. They have weak intermolecular forces in them and hence are gases and
exist in monatomic states.
Classification of Elements based on their position is the periodic table

1. Metals
This is the largest class of the elements. This includes elements belonging to 1, 2, 3 to 12 (i.e. all
transition and inner-transition elements) and some elements of groups 13 to 15 lying near the bottom of
the table. The metals are characterized by their nature of readily giving up the electron apart from
shinning luster. The oxides of metals are basic in nature.
2. Non-metals
These do not give up electron, in fact like to take up the electron to form negative ion. These include 10
elements lying to the right side of the table. They are C, N, O, F (2nd period), P, S, Cl (3rd period),
Se, Br (4th period) and I (5th period). The oxides of non-metals are acidic in nature.
3. Metalloid
You can have very easily observed that metallic character has decreased when one moves to the right
of the table across a row. It is observed that some elements lying at the border of metallic and non-
metallic behaviour, exhibit both the metallic and non-metallic character, these are called as metalloids.
These include 8 elements namely ; B, Si, Ge, As, Sb, Te, Po and At. The oxides of metalloids are
generally amphoteric in nature.
Note :The elements in group 18 do not behave like metals, nor do they behave like non-metals. So they are classified
separately as Noble Gases. Also the element Hydrogen (H) is different from any other element and cannot be
easily classified into a particular group (however it is placed along with the Alkali Metals, though it does
not exhibit metallic character).

PERIODIC PROPERTIES Section - 3
Properties of Elements like valency, atomic and ionic radii, ionization enthalpy, electron gain enthalpy,
electronegativity etc. follow some regular trends as we move down a group or along a period. This is
because all these properties depends on the electronic configuration of the atoms.
Beside there some properties like melting point, boiling point, density, atomic volume etc. which are not
defined for individual atoms but for a bulk (collection) of atoms. These properties are also indirectly related
to electronic configuration of atoms and follow a regular trends along periods and groups.
 As we proceed down a column (group), outer-shell electronic configuration remains the same. The
only difference in the atoms as we go down the table is that the nuclear charge and the number of inner
shells increase. This thing happens in regular manner.
 As we proceed across the periods (from left to right), electronic configuration of each element differ
from that of one before in terms of an additional electron and some nuclear charge being added
successively. Note that the number of shells in a period remains constant.
Let us discuss some of the important periodic properties.

1. Valency
It is defined as combining capacity of an element. It can also be defined in terms of valence electrons (electrons
in the outer most shells). The valency is equal to number of valence electrons (or equal to 8 minus the
number of valence electrons).
For representative elements, in general, valency of elements belonging to a chemical family i.e., in a group is
constant. It is known from its general electronic configuration. To illustrate, for group 1 (Alkali metals), valency
is 1 (ns1), for group 2 (Alkaline earth metals), it is 2 (ns2) and for group 3, it is 3 (ns2 np1).
For transition elements, no general trend is observed in the valency of elements. The reason is that those
elements have variable valencies due to availability of vacant d-subshells in them.
Similar is the case with inner-transition elements ( f-block elements) i.e., no general trend is observed due
to variable valency.
2. Types of atomic radii :
It is impossible to define the size of atoms, as we know that atoms have no sharp boundaries due to delocalized
picture of electron cloud. This is necessary in order to explain a number of chemical properties of different
elements in terms of the size of their atoms of ions. There are four operational concepts which have been widely
used. These are :
(i) Covalent radii (ii) Ionic radii (iii) van der Waals’ radii (iv) Metallic radii
(i) Covalent Radii

One of techniques to define size is to study molecules that are made up of two atoms (for example. H2,
Cl2, O2 etc). These are held together by covalent bonds. In a molecule, two nuclei remain at a fixed
average distance (d) from each other.

Atomic Radius is now defined as the average distance between the centres of two nuclei forming the covalent
bond divided by 2. In this case atomic radius is called as covalent radius given by d/2.
1
Thus, for a homonuclear diatomic molecule, rcovalent  [Internuclear distance between two bonded atoms]
2
Since the internuclear distance between two bonded atoms is called the bond length. Therefore,
1
rcovalent  [bond length]
2
For atoms which do not form such molecules 3s, same technique can be applied to their molecules with other
atoms For example. C-Cl bond in CCl4 etc.
Down the group : The sizes of atoms increases as we go down a column (group) of a periodic table. Each
time we go down one step, the outer shell configuration is same, but there is an additional inner shell being
added continuously. Consequently, the atomic size increases.
Increasing order of sizes in some families is shown below.
Li (1.33) Be (0.90) …………… O (0.74) F (0.71)
Na (1.54) Mg (1.36) …………… S (1.02) Cl (0.99)
K (1.96) Ca (1.74) …………… Se (1.16) Br (1.14)
Rb (2.16) Sr (1.92) …………… Te (1.35) I (1.33)
(Sizes given in brackets are in Å)
Along the period : In general, the sizes of the atoms decrease as we go down from left to right along the
horizontal rows (periods) except group 18 (Noble Gases). All the electrons in an atom are under two influences.
One is attraction of the electrons for the positive nucleus and other is mutual repulsion of the electrons for each
other. It is important to note that both the forces are inversely proportional to the square of the distance
between the electrons and the protons. Now as we go across the period, number of shells remains the same
and electrons and protons are continuously added. This leads to considerable force of attraction between
electrons and protons and consequently atoms become smaller. You can observe in above illustration that
rLi > rBe > rO > rF ,where r denotes atomic radii. Some Exceptions occur in case of d-block elements i.e.
Ni < Cu < Zn, Pd < Ag < Cd.
(ii) Ionic Radii
It is defined as the distance between the nucleus and outermost shell of an ion. Losing an electron or two from
the neutral atom forms a cation.
A positive ion is formed when the electrons are lost from the outer most shell. This ion is always smaller than the
corresponding neutral atom. because it contains smaller number of electrons compared to neutral atom, while
both contain same number of protons. The electrons in positive ions therefore experience a stronger pull
towards nucleus as compared to neutral atoms and hence ion becomes smaller.
A negative ion is formed when an extra electron is added to a neutral atom.This ion is always larger than the
corresponding neutral atom. because it has more electrons than neutral atom. Additional electron in negative
ion creates more repulsion in the outer most shell and thus outer shell expands.

 The sizes of ions increase as we go down a group provided that we are comparing ions of same charge.
For example Li+ < Na+ < K+ < Rb+
Be2+ < Mg2+ < Ca2+ < Sr2+
F¯ < Cl¯ < Br¯ < I¯
 Atoms or ions with the same electronic configuration are called as isoelectronic. If we consider a series
of iso-electronic species (atoms or ions), the size decreases with the increasing atomic number. This is
beacuse the number of electrons and shell remain constant while positive charge of nucleus increase which
pull the electrons more strongly. To illustrate the concept, Consider the following iso-electronic species all
having 10 electrons.
Iso-electronic species O2– (1.401) F– (1.36) Ne (1.31) Na+ (0.95) Mg2+ (0.65)
Atomic number (Z) 8 9 10 11 12
(sizes given in the bracket are in Å)
 The size of cations of same element decreases with the increase in the magnitude of positive charge. For
example. Cu2+ is smaller than Cu+ , Fe3+ is smaller than Fe2+ , Sn4+ is smaller than Sn2+.
(iii) Van der Waals’ radius

It is defined as one-half the distance between the nuclei of two identical non-bonded isolated atoms or two
adjacent identical atoms belonging to two neighbouring molecules of an element in the solid state.
The magnitude of the van der Waals’ radii depends upon the packing of the atoms when the element is in the
solid state.
(iv) Metallic radius

It is defined as one-half the inter-nuclear distance between the two adjacent metal ions in the metallic lattice.
According to Electron-sea model, a metal lattice or crystal consists of positive kernels or metal ions (left after
the removal of valence electrons) arranged in a definite pattern in a sea of mobile valence electrons. Thus, each
kernel (i.e., metal ion) is simultaneously attracted by a number of mobile electrons and each mobile electron is
attracted by a number of metal ions. This simultaneous force of attraction between the mobile electrons and the
positive kernels is called the metallic bond.
The inter-nuclear distance is determined by X-ray studies and the metallic radius is usually expressed in angstrom
units or picometers.
Since in a metallic lattice, the valence electrons are mobile, therefore, they are only weakly attracted by the
metal ions or kernels. In contrast to covalent bond, a pair of electrons is strongly attracted by the nuclei of two
atoms. Thus, a metallic radius is always longer than its covalent radius.
Comparison of covalent radius and van der Waal’s radius

Van der Waal’s radius of an element is always larger than its covalent
radius because of the following two reasons :

(i) Since the van der Waal’s forces of attraction are weak, therefore the
inter-nuclear distances in case of atoms held by van der Waal’s forces
are much larger than those between covalently bonded atoms.
Therefore, van der Waal’s radii are always larger than covalent
radii.
(ii) Since a covalent bond is formed by overlap of two half-filled atomic orbitals, a part of the electron cloud
becomes common. Therefore, covalent radii are always smaller than the van der Waals’ radii.
A comparison of three types of atomic radii discussed above reveals that van der Waal’s radius is the longest
while covalent radius of an atom is the shortest, i.e., vander Waal’s radius > metallic radius > covalent
radius.
3. Ionisation energy
First ionization energy is defined as the energy required to remove a single electron from the outer shell of
a neutral gaseous atom. Consequently the atom changes to a mono-valent cation
M(g) + IE1 
 M+ (g) + e–
Down the Group: First ionization energy decreases as we go down a group in the table. It measures the ease
of removing an electron from the outer shell. As we go down a group, this shell is farther away from the nucleus.
It is true that the positive charge of nucleus increases, but its effect is weakened due to the shielding supplied by
the inner shells to the outer most shell. As a result nuclear attraction decreases. Some exception occurs in
group 13 where the ionisation energy of Ga is more than that of Al. It is due to the fact that Ga has electrons
filled in d-shell and shielding of d shell to nucleus is compratively small. So increased nuclear charge effect
dominates here.
Along the period: As we go from left to right across a period, the atomic size decreases. As the number of
shells in a particular period remains same and new electrons are being continuously introduced in the outer
shell, the outer electrons are greatly attracted to the nucleus. Hence it becomes difficult to remove them and
consequently first ionization energy increases.
In the following table, I ionization energies (in eV) of II period are shown :
Li Be B C N O F Ne
5.39 9.32 8.3 11.26 14.53 13.62 17.42 21.56
You should have clearly noted two irregularities as we move from left to right in the above table.

 I.E. of B < I.E. of Be. When Be loses an electron, it is removed from a fully filled 2s sub-shell, whereas
B gives its lone 2p electron. Hence extra-stability of fully filled sub-shell is the cause of this irregularity.
 I.E. of O < I.E. of N. Here half filled (2p3) outer most sub-shell of N is highly stable and hence it becomes
difficult to remove the electron. Thus extra-stability of half filled sub-shells is the cause of irregularity.
Second ionization energy is defined as the amount of energy required to remove the second electron from an
atom that has already lost an electron, i.e. to remove an electron from a mono-valent cation. Third and higher
I.E.(s) are analogously defined.
M+ + IE2 
 M+ + e–
M2+ + IE2 
 M3+ + e–
In general : IE1 < IE2 < IE3 < ………..
This happens because, as the number of electrons decreases regularly, the attraction of the nucleus for the
remaining electrons increases considerably (which are now less in number), and hence subsequent I.E.(s)
increase.
 Whenever all the outer-shell electrons are removed, the next I.E. is much greater than the previous value of
I.E. for the same element. Note that first I.E. of Li is 5.39 eV and the second I.E. for the same is 75.64 eV.
 If we compare first I.E.s of the elements in a period (e.g., Li……Ne), the noble gas (Ne in present case)
had the highest I.E. A noble gas configuration (ns2 np6) is completely filled and hence highly stable.
 The electrons in different orbitals (s, p, d or f) belonging to the same energy level (i.e., same value of n)
experience different pull of the nucleus. The I.E. for pulling out an s-electron is maximum and it decreases
in pulling out p-electron, a d-electron or a f-electron of the same principal energy shell in the order of their
mention. Hence we can say that I.E. for pulling out an electron from a given energy level decreases in the
order s > p > d > f orbitals. For example first I.E. of AI is lower than that of Mg. Here two factors govern
the first I.E. the extra stability of fully filled sub-shells apart from the above mentioned factor.
Factors affecting the ionisation energy

1. The charge on the nucleus 2. The size of the aotm
3. Presence of half filled or fully filled orbitals 4. Shielding of s, p, d or f orbitals.
4. Electron Affinity
It is defined as the energy given out when a neutral gaseous atom takes up an extra electron.
X(g) + e– 
 X– (g) where X represents a neutral gaseous atom.
Electron affinity of an atom measures the tightness with an atom bonds an extra electron to it. The value of
electron affinity shows the same trend as atomic size and ionization energy. It is also known as Electron Gain
Enthalpy.

 It decreases down a group, because as the atom gets larger (due to increasing atomic size), the attraction
of positive nucleus for an outside electron decreases. Exception: in halogens, Fluorine (F) has lower electron
affinity than Chlorine (Cl). It is mainly due to extremely small size of F atom as compared to that of Cl. The
addition of an extra electron creates a high electron density and hence strong electron-electron repulsion is
not highly favoured. Due to the same reason oxygen has smaller affinity than sulphur.
 It in general increases when one moves from left to right across a period. It is due to decreasing atomic size
(across a period) that the nuclear attraction for an additional electron increases. Hence the electron affinity
and I.E. of metals is low while that of non-metals is high.
 The electronic configuration of elements also affects their electron affinities. Electron affinities of Noble
gases are zero. It is attributed to their fully filled stable configuration (ns2 np6). Also the electron affinity of
N and Be atoms are quite low due to extra stability of half filled orbitals and fully-filled orbitals (p3 in N
and s2 in Be).
 The concept of higher electron affinities is rather interesting. After taking up an extra electron an atom
becomes negatively charged (anion) and now a second electron is to be added to it. The anion will repel
the incoming of an electron and an additional energy will be required to add it to the anion. This means first
E.A is the energy released while the second E.A. is the energy required. If one considers the energy
released as negative and that required as positive then first E.A of O is – 141 KJ/mol and second E.A.
is +770 KJ/mol.
Factors on which the Electron Gain Enthalpy depends

Some important factors on which electron affinity depend are discussed below:
(i) Atomic size : As the size of the atom increases, the distance between the nucleus and the last shell
which receives the incoming electron, increases. As a result, the force of attraction between the nucleus
and the incoming electron decreases and hence the electron gain enthalpy becomes less negative.
(ii) Nuclear charge : As the nuclear charge increases, the force of attraction between the nucleus and the
incoming electron increases and hence the electron gain enthalpy becomes more negative.
(iii) Electronic configuration : Elements having exactly half-filled or completely filled orbitals are very
stable. As a result, energy has to be supplied to add an electron. Hence their electron gain enthalpies
have large positive values the additional electron so easily and easily and hence their electron affinities
are either very low or are almost zero.
5. Electronegativity
It is the measure of the ability of an atom in a combined state (i.e. in a molecule) to attract to itself the electrons
within a chemical bond. In general in the covalent bond both the atoms don’t share the electron pair equally. It
depends upon the pulling power (electronegativity) of the atom for electrons that which atom will share the
electron pair dominetly. More the electronegativity of the atom, more dominently it will share the electron pair.
Electron pair will get slightly shifted towards the more electronegative atom and this atom will aquire a δ
charge resulting in δ charge on the other atom.

In general, non-metals have high value of electronegativity while the metals have a quite low value. For example
F, O, N and Cl (non-metals) are highly electronegative whereas K, Rb and Cs (metals) are non-electronegative,
in fact they are electropositive.
 It follows the same trends as shown by electron affinity or ionization energy. This means that higher I.E.
and greater E.A., both results in high electronegativity.
 Across a period from left to right the electronegativity increases due to increase in the nuclear charge and
decrease in atomic size. Down the group electronegativity decreases due to the increase in effective nuclear
attraction force. Fluorine has the highest electronegativity of any element.
 The difference in electronegative values of two atoms in a compound predicts the nature of chemical bond
formed between two atoms. More the difference between the electronegativity of two atoms involved in a
bond more will be the ionic character. There is no direct method to measure the value of electronegativity,
however there are some scales to measure its value.
Pauling scale
According to Pauling, electronegativity difference (XA – XB) in between two atoms A & B is given by :
XA – XB = 0.208  where  = EA-B – E A  A  E B B where EA-B, EA-A and EB-B are bond energy of
molecules AB, A2 and B2 respectively in kcal/mole. This scale is the most popular scale.
Mulliken scale
According to Mulliken, the electronegativity of an atom is the average of the two values i.e.. electron affinity
and ionization energy.
IE  EA
Electronegativity = where I.E. and E.A. are in kJ/mol. Note : X Mulliken  X Pauling  2.8
2
Allred - Rechow scale

According to this concept, electronegativity of an atom is simple electrostatic force of attraction between
atoms and an electron separated from the nucleus by the covalent radius. i.e. electronegativity
0.359 Zeff
= + 0.744, where Zeff is the effective nuclear charge and r is covalent radius of atom in Å.
r2
6. Atomic Volume
Atomic volume of an element is the ratio of its gram-atomic weight to its density. In a group, atomic volume
generally increases from top to the bottom. Actually it is not a very good periodic property as different elements
have different packing arrangements in solid states, so a general trend is not observed. This is particularly true
in right side of the periodic table where in halogens and Fe-Pt sub-groups it becomes nearly constant. Note
that atomic volume is a bulk property. It depends on the packing of atoms as well.

7. Metallic Character
Metallic character or the electropositive character of an element is defined as its tandency to loose electrons
and form positive ions. Metallic character increases down the group and decreases along the period (from left
to right). There is a series of metallic (electropositive) character that is good to remember.
K > Na > Ba > Ca > Mg > Al > Zn > Fe > Ni > Sn > Pb > H > Cu > Hg > Ag > Au > Pt
The trick to remeber this series is to remember the name PSBC MAZINTL CHAAP
In PSBC P = Potassium, S = Sodium, B = Barium, C = Calsssium. In MAZINTL, M = Mg, A = Al, Z = Zn,

I = Iron, N = Nickel, T = Tin, L = Lead. In chaap C = Cu, A = Ag, A = Au, P = Pt. Also note that Hydrogen
(not a metal) comes between Mazintl and Chaap.
Note that Electronegativity, Ionisation Enthalpy, electron gain Enthalpy follow the same trends because they
all represent the same character - attraction of nucleus for the outermost shell electron. While Atomic radius
follows trends opposite the three.
There are some effects which sometimes affect the periodic properties.
(i) Penetration effect of the electrons
Ionization enthalpy increases as the penetration effect of the electrons increases. It is a well known fact that in
case of multi-electron atoms, the electrons of the s-orbital has the maximum probability of being found near

the nucleus and this probability goes on decreasing in case of p, d and f-orbitals of the same shell. In other
words, s-electrons of any shell are more penetrating towards the nucleus than p-electrons of the same shell.
Thus, within the same shell, the penetration effect decreases in the order : s > p > d > f
Obviously, if the penetration effect of the electron is more, it will be closer to the nucleus and hence will be held
more firmly by the nucleus. Consequently, the ionization enthalpy will be high. In other words, ionization
enthalpy increases with the increase in the penetration effect of electrons. Thus, the ionization enthalpy will
be more to knock out a s-electron of the same shell, which in turn, will be more than that required to
remove a d-electron and so on.
(ii) Screening (shielding) Effect

The electrons in the valence shell experience an attractive force from the nucleus and a repulsive force from
the electrons in the inner shells. The overall effect of these two opposing forces is that the attractive force
exerted by the nucleus on the valence shell electrons is somewhat reduced by the repulsive force exerted by
the electrons present in the inner shells. This affects the nuclear attraction of the positive nucleus for the outer
electrons. In d-block elements (transition elements), while writing electronic configuration of elements, it is
seen that the new electrons are being added to the inner shell i.e., penultimate shell (3d after 4s, 4d after 5s
and so on). As the differentiating electron enters the inner shells, they tend to screen or shield the outer shell
electrons from the nucleus and hence offset the nuclear attractive force.
The actual charge felt by the valence shell electrons is called effective nuclear charge and the repulsive
force felt by the valence shell electrons from the electrons present in the inner shells is called the shielding effect
or screening effect. Shielding effect of shells closer to nucleus is higher and it follows the trends s > p > d >
f. Due to this effect, the atomic size of transition elements (which should have been decreasing across a
period) remains nearly same or constant. The same is the case with ionisation energy, electron affinity and
other periodic properties when one moves across a period.
(iii) Inert Pair Effect

Inert pair effect occurs when electrons are pulled closer to nucleus making them stabler and more difficult to
ionise. It is basically the tendency of outermost (or valence) ‘s’ electrons to remain non-ionised (and not
participate in bonding ). It occurs because of the poor shielding of the nucleus by the inner ‘d’ -electrons due
to which the outer ‘s’ electrons are more tightly bound to the nucleus and become less able to participate in
bond formation. This effect is espcially seen in group 13 and 14 of the periodic table, in which the heavier
elements in the group tend to form compounds with valency two lower than the expected group valency. For
e.g. the lighter elements in Group IV tend to have a valency of +4 whereas the heavier elements from 2+ ions
that are more stable than 4+ ions. For example, PbO is much more stable than PbO2 which decomposes
readily to PbO.
Magnetic Properties
Each element has some kind of magnetics properties associated with it. These magnetics properties are direct
consequence of the electronic configuration of the atom. An electron in an atom has two kind of motions. One
is its motion about the nucleus and the other is its spin about its own axis. A single electron spinning about its

own axis generates a magnetic field. For two electrons in an orbital the spins are opposite and hence the fields
cancel each other. Thus on the basis of magnetic properties substances can be classified broadly into three
categaries (i) Paramagnetic (ii) Diamagnetic (iii) Ferromagnetic.
(i) Paramagnetism: Some substances has one or more unpaired electrons in their atoms. These
substances are called as paramagnetic substances. There substance are weekly attracted by magnetics
field. Cu2+, Fe3+, Cr3+ and O2 are some examples of these kind of substances.
(ii) Diamagnetism: Some substances have all the electrons paired in their atoms. There substances are
called as diamagnetic substances. Thus substances are weekly repelled by magnetic field. NaCl and
H2O are some examples of diamagnetic substances.
(iii) Ferromagnetism: Beside paragnetic and diamagnetic substances there are some kind of substances
which are strongly attracted by magnetic field. These substances are called Ferromagnetic substances.
Ferromagnetism is much stronger than paramagnetism and diamagnetism. Ferromagnetic substances
keep their magnetism even after the field is removed while paramagnetic and diamagnetic substances
fail to do so. Iron, cabalt and Nickel are some examples of these kind of substances.
Some Additional Information

All the elements with Z = 101 – 112 and Z = 114 have recently been identified. Although names and symbols
to many of these elements have been assigned but these are still not universally accepted. Also some of these
elements have been assigned two names/symbols. For example, element with Z = 104 is called either
Kuruchatovium (Ku) or Rutherfordium (Rf) while element with Z = 107 is called Neilsbohrium (Ns) or simply
Bohrium (Bh). To overcome all these difficulties, IUPAC approved the official names for elements with
Z = 104 to Z = 109 and suggested a systematic nomenclature for naming other elements with Z > 100 (also
collectively called as super heavy elements) till their names are officially announced.
The main points of this nomenclature are :
(i) The names are derived directive from the atomic numbers using numerical roots for 0 and numbers from 1 – 9
and adding the suffix ium. A strange mixture of Latin Greek roots has been chosen to ensure that the symbols
are all different. The roots for the numbers 0 – 9 are :
Roots for IUPAC Nomenclature of Elements
Digit 0 1 2 3 4 5 6 7 8 9
Root nil un bi tri quad pent hex sept oct enn
Abbreviation n u b t q p h s o e
(ii) In certain cases, the names are shortened. For example, bi ium and tri ium are shortened to bium and trium
and enn nil is shortened to ennil.
(iii) The symbol of the element is then obtained from the first letters of the roots of numbers which make up the
atomic number of the element. The recommended and official names of some super heavy element are given in
Table.
IUPAC
Self Study Nomenclature
Course of elements
for IITJEE with Online Support with Atomic Number above Section
100 3 17

Illustration - 1 The formation of F - (g) from F(g) is exothermic whereas that of O2- (g) from O(g) is
endothermic. Explain.
SOLUTION :
The addition of an electron to a neutral atom is Thus, the addition of an electron to O- requires energy
an exothermic process. to overcome the force of repulsion.
F  e  F  energy O  e   energy  O 2 . . . . (ii)
O  e   O   energy . . . . (i)
The energy absorbed in (ii) step is more than the
The addition of second electron to a
energy in the step(i). Hence, the formation of O2- from
monovalent anion O-, as to make it O2- is
O is endothermic in nature.
difficult because both have the same charge
and experience a lot of repulsion.
Illustration - 2 (a) Why chlorine has higher negative electron gain enthalpy than F ?
(b) Why N has higher 1st ionization enthalpy than O-atom ?
(c) Why Mg has higher 1st ionization enthalpy than Al-atom ?
SOLUTION :
(a) The size of fluorine atom is small and thus (c) The electronic configurations of Mg and Al are
electron density is high. This resists the addition as follows:
of electron, hence electron gain enthalpy of
Mg : 1s 2 , 2s 2 2 p6 ,3s 2
fluorine is less.
Al : 1s 2 , 2s 2 2 p6 ,3s 2 3 p1
(b) The electronic configurations of nitrogen and
oxygen are follows: It is difficult to remove an electron from 3s in
comparison to 3p (3s paired and 3p singly
N : 1s 2 , 2s 2 2 p1x 2 p1y 2 p1z
occupied).
O : 1s 2 , 2s 2 2 px2 2 p1y 2 p1z Hence, IE of Mg is higher than Al.
In, N p-orbitals are half and hence, its structure
is stable. It requires more energy to remove an
electron. Hence, the IE of nitrogen is higher than
oxygen atom which has less stable structure.

Illustration - 3 Arrange the following in order of increasing radii :

(i) I, I+, I- (ii) C, N, Si, P (iii) O2-, F-, Ne, Mg2+ (iv) Fe, Fe2+, Fe3+
SOLUTION :
(i) I+ < I < I-
53 53 53
z/e values are , , respectively..
52 53 54
Since z/e decreases, hence size increases.
(ii) N<C<P<Si (a) Effective nuclear charge in nitrogen is higher than in carbon, hence N<C.
(b) Effective nuclear charge I phosphorus is higher than in silicon, hence P<Si.
(c) C and Si both belong to same group.
C 1s2, 2s2 2p2 (Two orbits)
Si 1s2, 2s2 2p6, 3s23p2 (Three orbits) C<Si
(iii) Mg2+<Ne<F-<O2- (iv) Fe3+<Fe2+<Fe

12 10 9 8 26 26 26
z/e values are , , , respectively.. z/e values are , , respectively..
10 10 10 10 23 24 26
Since z/e decreases, hence size increases. Since z/e decreases, hence size increases.
Illustration - 4 Give the formula of a species that will be isoelectronic with the following atoms or ions :
(i) Ar (ii) F- (iii) K+ (iv) Sr2+
SOLUTION :
(i) Ar has 18 electrons. Therefore, the species P3-, S2-, Cl-, K+, Ca2+, etc., are isoelectronic to Ar.
(ii) F- has 10 electrons. Therefore, the species N3-, O2-, Ne, Na+, Mg2+, etc., are isoelectronic to F-.
(iii) K+ has 18 electrons. Therefore, the species P3-, S2-, Cl-, Ar, Ca2+, etc., are isoelectronic to K+.
(iv) Sr2+ has 36 electrons. Therefore, the species Br-, Kr, Rb+, etc., are isoelectronic to Sr2+.
Illustration - 5 The ionization enthalpy of lithium is 520 kJ mol-1. Calculate the amount of energy
required to covert 140 mg of lithium atoms in gaseous state into Li+ ion.
SOLUTION :
Mass of lithium  140 mg  140  103 g  14  102 g
14  102
No. of moles of lithium   2  102 mole
7
Energy required to convert 2  102 mole atoms of lithium into Li+ ions = 520  2  102  10.4 kJ

Illustration - 6 The first and second ionization enthalpies (kJ mol- ) of three elements I, II and are given
below.
I II III
i H1 403 549 1142
i H 2 2640 1060 2080
Identify the element which is likely to be :

(a) non-metal (b) an alkali metal (c) an alkaline earth metal.
SOLUTIONS :
(a) Element (III) is a non-metal because its i H1 is highest among the three.
(b) Element (I) is an alkali metal as its first ionization enthalpy is lowest and second ionization enthalpy
is very high.
(c) Element (II) is an alkaline earth metal because its first ionisation enthalpy is near to enthalpy of
element (I) and second ionisation enthalpy is not very high.

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes The Chemical Bond - I
The Chemical Bond - I

INTRODUCTION Section - 1
We have come across the terms molecules and compounds. Molecule can be defined as an uncharged
entity in which atoms of same kind or of different kinds are held together by some forces. Compound is the
collective name of a set of molecules of same kind.
For example : Sulphur dioxide is a compound which contains the molecules of SO2, which is made up of
atoms of S and O. Cane sugar consists the molecules of C12H22O11, which is made up of atoms of C, H and
O.
The forces that hold together the atoms in a molecule are known as Chemical forces or Valence forces.
The association between atoms in a molecule by valence forces is called as Chemical Bond.
An atom possesses its greatest stability when its valence electron shell (outer shell) is complete. The K shell
(n = 1) is complete when it contains two electrons, while the remaining shells are complete when they
contain eight electrons. This is referred to as Lewis Octet Rule.
Note : The arrangement of electrons in Noble Gases is the criteria of stability, i.e., fully filled sub-shells (ns2np6).
The atoms of these elements are in a state of great stability and hence do not form compounds and in general
are chemically inert.
So it is the valence electrons that determine the chemical behavior of an atom. In a compound, a definite
number of valence electrons are involved in the bonding process. The chemical association among atoms can
be achieved by many ways depending upon number of valence electrons contained in the atoms. Three
major types of chemical bonding are as follows:
Ionic Bonding : Stability through transfer of electrons.

Covalent Bonding : Stability through mutual sharing of electrons.
Coordinate Bonding : Stability through partial transfer and partial
sharing of electrons.
1. Kossel – Lewis’s Electronic Theory of Chemical Bonding :

Lewis pictured the atom in terms of :
(a) A positively charged ‘Kernel’ (the nucleus plus the inner electrons) and
(b) The outer shell that could accommodate a maximum of eight electrons. He, further assumed that these
eight electrons occupy the corners of a cube which surround the ‘Kernel’.

The Chemical Bond - I Vidyamandir Classes
When all the eight corners of the cube are occupied then an atom is said to have stable electronic configuration.
Clearly noble gases which have 8 outer most electrons already have stable configuration while all other
atomic achieve stable octet of electrons (set of 8) when they are linked by chemical bonds.
Note :
 Valence electrons : It refers to the outer shell electrons (of an atom) that take part in chemical combination
in the formation of a molecule.
 The inner shell electrons are well protected and are generally not involved in the combination process.
 Common or group valence of an element : It generally refers to no of valence electrons or 8 minus the
number of valence electrons.
 Atoms can combine either by transfer of valence electrons from one atom to another (gaining or losing) or
by sharing of valence electrons in order to have an octet in their valence shells. This is known as octet rule.
IONIC OR ELECTROVALENT BONDING Section - 2
The chemical bond formed due to electrostatic attraction between cations and anions (which are formed by
the complete transfer of electron(s) from one atom to the other atom) is called as Electrovalent or Ionic
Bond. The Ionic valency or Electrovalence is referred to as the number of electrons that an atom can give up
or gain. In other words it is equal to the number of unit charge(s) on the ion, eg. In NaCl, sodium is assigned
a positive electrovalence of one, while chlorine a negative electrovalence of one.
The formation of a positive ion involves ionization, i.e., removal electron(s) from the neutral atomand that of
the negative ion involves the addition of electron(s) to the neutral atom.
 M (g)  e  ;
M(g)  Ionization enthalpy
X(g)  e 
 X  (g) ; Electron gain enthalpy
M  (g)  X  (g) 
 MX(s) ; Lattice energy
Formation of Lattice :
The compounds which are formed by ionic bonds are mostly solids. These compounds crystallize in different
crystal structures determined by factors such as size of the ions, their packing arrangements etc. In the
crystalline state, these compounds consist of orderly three-dimensional arrangements of cations and anions
(which is called lattice) held together by coulombic interaction energies. The energy released when such an
arrangement is formed (due to electrostatic attraction) is known as Lattice Energy.
The lattice is a highly stable arrangement and hence all ionic compounds have high melting and boiling points.
The higher is the lattice energy, the more stable is the ionic bond.

Factors affecting lattice energy :

Magnitude of charge : More is the magnitude of charge on cation or anion, the more is the lattice energy.
For example, the lattice energy of MgCl2 is higher than that of NaCl.
Size of ions : For higher lattice energy, the cations should be smaller and anion should be larger. The smaller
is the cation, the more effective is the nucleus in pulling the neighbouring anions towards it. As a result, the
lattice formed is highly stable or we can say that the lattice energy is high. Eg : Lattice energy of NaCl is
greater than that of CsCl, as Na+ cation is smaller than Cs+ cation though the ionisation energy of Cs is much
lower than that of Na.
Elaboration :
 There is a formation of negative ion from a halogen atom and and a positive ion from an alkali metal
atom due to gain and loss of an electron by the respcetive atoms.
 The negative and positive ions thus formed attain stable noble gas electronic configurations. The noble
gases (with the exception of helium which has a duplet of electrons) have a particularly stable outer
shell configuration of eight (octet), electrons, ns2np6.
 The negative and positive ions are stabilized by electrostatic attraction.
For example, the formation of NaCl from sodium and chlorine, according to the above scheme, can be
explained as :
Na   Na+ + e–
[Ne] 3s1 [Ne]
Cl + e– 
 Cl–
[Ne] 3s2 3p5 
 [Ne] 3s2 3p6 or [Ar]
Na+ + Cl– NaCl or Na+ Cl–
Similarly the formation of CaF2 may be shown as :
Ca   Ca2+ + 2e–
[Ar] 4s2 [Ar]
F + e– 
 F–
[He] 2s2 2p5 [He] 2s2 2p6 or [Ne]
Ca2+ + 2F– 
 CaF2 or Ca2+ (F–)2
Other examples of molecules involving ionic bonds are MgO, AlCl3, KI, CaS, MgBr2 , etc.
Ionic Bonding formation depends on the following :
1. Ionisation Enthalpy (i H) or ease of formation of positive ions.
2. Electron Gain Enthapy (eg H) / Eectron Affinity (Ae) or ease of formation of negative ions.
3. Lattice Enthalpy
Ionisation Enthalpy (i H) : It is the energy required to remove an electron from an isolated gaseous atom
in its ground state.

Electron Gain Enthalpy (eg H) : It is the energy required to add an electron to a gas phase atom in its
ground state to form a negative gaseous ion.
Note : The electron gain process may be exothermic or endothermic. The ionization, on the other hand, is always
endothermic.
Electron affinity (Ae) : It is the energy released when an electron is added to a neutral gaseous atom in its
ground state to form a negative ion. Electron Affinity of an atom is defined only at absolute zero
temperature.
Lattice Energy : Energy released when gaseous positive and negative ions come together to form 1 mol of
solid (crystalline) ionic compound.
Lattice Enthalpy : The Lattice Enthalpy of an ionic solid is defined as the energy required to completely
separate one mole of a solid ionic compound into gaseous constituent ions. For example, the lattice enthalpy
of NaCl is 788 kJ/mole (and Lattice energy = –788 kJ/mol). This means that 788 kJ of energy is required
to separate one mole of solid NaCl into one mole of Na+(g) and one mole of Cl– to an infinite distance.
Note : Condition for formation of a stable ionic compound is :

Total Ionisation enthalpy + Total Electron Gain Enthalpy – Total Lattice Enthalpy < 0
Simple Binary Ionic Compounds

Metal Nonmetal General Formula Ions Present Example
IA VIIA MX  M , X  LiBr
HA VIIA MX2  M2 , 2X   MgCl2
HIA VIIA MX3  M3 , 3X   GaF3
IA VIA M2X  2M  , X 2  Li2O
IIA VIA MX  M 2 , X   CaO
IIIA VIA M2X3  2M3 ,3X 2  Al2O3
IA VA M3X 3M2 , X3  Li3N
IIA VA M3X2 3M2 , 2X3  Ca3P2
IIIA VA MX  M 3 , X 3  AlP

Properties of Ionic Compounds :

(i) The ionic substances are good conductors of heat and electricity in molten state or aqueous medium.
In both these states, the lattice is broken and ions are free to conduct electricity and heat.
(ii) Due to stability of lattice, ionic compounds have high melting and boiling points.
(iii) The bond in ionic compounds is non-directional. In these compounds, each ion (cation or anion) has
a uniformly distributed electric field, so one can not predict whether a particular ion is bonded to this
or that ion.
(iv) These are soluble in polar solvents like water, which acts as a dielectric (dielectric is a material
which weakens the electric field). When the electric field is weakened, the ions are relatively free to
go in water.
COVALENT BONDING Section - 3
Certain elements which have high ionisation energies are incapable of transferring electrons and other having
low electron affinities, fail to take up electrons. The atoms of such elements share their electrons with the
atoms of other elements (and sometimes among themselves) in such a manner that both the atoms form
complete outer shell. In this manner they achieve stability. Such an association through sharing of electron
pairs among atoms of different or of same kinds is known as Covalent Bond. This was proposed by G.N.
Lewis.
The covalent bonding can be achieved in two ways :
(i) Sharing electrons between atoms of same kinds, formation of F2, O2, Cl2, etc.
(ii) Sharing of electrons between atoms of different kinds, formation of HCl, CO2, H2O, CH4, etc.
Lewis Symbols : To represent valence electrons in an atom, Lewis introduced simple notations called as
Lewis symbols. For example, the Lewis symbols for the elements of second period are as under
The number of dots around the symbol represents the number of valence electrons. This number of valence
electrons helps to calculate the common or group valence of an element.
Formation of F2 and other like molecules : A Fluorine atom has seven electrons in its outermost shell
and thus it needs one more electron to complete an octet of electrons and attain a noble gas configuration. A
F2 molecule is thus formed by combination of two F atoms by sharing one electron each. It is represented by
Lewis dot structure as follows:

Note that now both of F atoms now have eight (8) electrons each in their outer shell. In a more simple way,
electron (Lewis) dot formula can be expressed by using ‘’ (a dash) instead of • x.
Note :
 Pair of electrons depicted as • • or x x is called as Lone pair (p) and that by x • is called as shared pair or
Bond pair (bp). Lone pair is the pair of electrons belonging to one atom only. Thus F2 has one bp(s) and six
p(s).
 When two atoms share one/two/three electron pair(s) they are said to be joined by a single/double/triple
covalent bond respectively. Eg in the above example of F2 molecule there is a single bond between the two
fluorine atoms.
The Lewis Representation of some molecules is as follows :
H2 H–H
O2
O3
NF3
CO32 
HNO3
CO 2 O C O O C O
H H
H H
C2H4 C C C C
H H
H H

N2 N N N N
C2H2 H C C H H C C H
Explanation for O2 and N2 :

O2 : Oxygen (O) has six electrons in valence shell, hence requires 2 more to achieve stability. It can accept
two electrons to form ionic bond. It can also share two electrons with another atom of O to form covalent
bond as shown in the above table. Here, 2 pairs of electrons are shared, thus double covalent bond is formed
between the two oxygen atoms. In simpler way it can be represented by sign ‘=’. So O2 molecule can be
shown as O = O.
N2 : Nitrogen (N) has five electrons in valence shell and requires 3 electrons to achieve stability. It does so by
sharing 3 electrons with another N atom to form covalent bond as shown above. Here, 3 pairs of electrons
are shared, so there is a triple covalent bond between two nitrogen atoms. In simpler way it can be represented
by sign ‘’. So N2 molecule can be written as N  N.
Rules for writing Lewis dot structures :

(i) Add valence electrons of combining atoms of the molecules to get total no. of electrons (T) to be
represented in the Lewis structure.
(ii) In case of ions, number of electrons equal to charge on the ion must also be added (for anions) or
subtracted (for cations) from T.
(iii) Least electronegative atom occupies the central position in the molecule/ion.
(iv) Draw skeletal structure of the compound/ion using chemical symbols of the combining atom.
(v) Now use pairs of electrons to represent single bonds between bonding atoms of the molecules/ion
and represent the rest of the electrons to as lone pairs of atoms or to show multiple bonds between
them (in case each of the bonding atom does not have an octet of electrons).
Note : Lewis dot structure, in general, do not represent the actual shapes of the molecules.

Illustration - 1 Write a Lewis structure for CCl2F2, one of the compounds implicated in the depletion of
stratospheric ozone.
SOLUTION :
Step : 1 Place the atoms relative to each other. In Step : 3 Draw single bonds to the central atom and
CCl2F2 carbon has the lowest group number subtract 2e– for each bond : single bonds use
and EN, so it is the central atom. The other 8e–,so 32e– – 8e– leaves 24e– remaining.
atoms surround it but their specific positions Step : 4 Distribute the remaining electrons in pairs,
are not important. beginning with the surround-atoms, so that
each atom has an octet.
Step : 2 Determine the total number of valence

electrons :
      
1  C 4e     2  F 7e  

  2  Cl  7e    32 valence e
–
 
Illustration - 2 Writing Lewis Structures for Molecules with More than One central atom. Write the Lewis
structure for methanol (molecular formula CH4O), an important industrial alcohol that is being used as a
gasoline alternative in car engines.
SOLUTION :
Step : 1 Place the atoms relative to each other. The Five bonds use 10e–, so 14e– – 10e– leaves
H atoms can have only 1 bond, so C and H 4e– remaining.
must be adjacent to each other. In nearly all Step : 4 Add remaining electrons in pairs.
their compounds, C has four bonds and has
two, so we arrange the H atoms to shown
this.
Step : 2 Find sum of valence electrons
      
1  C 4e   1  O 6e  

Carbon already has an octet, so the four
remaining valence e– form two lone pairs on
  4  H 1e    14e O and give the Lewis structure for methanol.
 
Step : 3 Add single bonds and subtract 2e– for each
bond.

Illustration - 3 Write the Lewis dot structure of CO molecule.

SOLUTION :
Step : 1 The skeletal structure of CO is written as :
CO
This does not complete the octet on carbon
Step : 2 Count the total number of outer valence shell and hence we have to resort to multiple
electrons of carbon (2s2 2p2) and oxygen bonding (in this case a triple bond) between
(2s2 2p4) atoms. C and O atoms. This satisfies the octet rule
Thus the total number of valence electrons condition for both atoms.
available are 4 + 6 = 10.
Step : 3 & 4 .
Draw a single bond (one shared electron pair)
between C and O and complete the octet on
O, the remaining two electrons will constitute
a lone pair on C.
Writing Lewis Structures for Molecules with Multiple Bonds
Illustration - 4 Write the Lewis structure of the nitrite ion NO 

2
SOLUTION :
Step : 1 The skeletal structure of NO 2 is written This, however, does not complete the octet
as : on nitrogen if the remaining two electrons
O N O constitute lone pair on it.
Step : 2 Count the total number of valence electrons
of the nitrogen atom, the oxygen atoms and Hence we have to resort to multiple bonding
the additional one negative charge (equal to between nitrogen and one of the oxygen
one electron). N(2s 2 2p3 ), O (2s 2 2p 4 ) atoms (in this case a double bond). This leads
to the following Lewis dot structures.
 5  (2  6)  1  18 electrons
Step : 3 & 4
Draw a single bond (one shared electron pair)
between the nitrogen and each of the oxygen
atoms completing the octets on oxygen
atoms.

Writing Lewis Structures for Molecules with Multiple Bonds

Illustration - 5 Write Lewis structures for the following :
(a) Ethylene (C2H4), the most important reactant in polymer manufacture
(b) Nitrogen (N2), the most abundant atmospheric gas
Plan : We begin the solution after Steps 1 to 4 : placing the atoms, counting the total valence electrons, making single
bonds, and distributing the remaining valence electrons in pairs to attain octets. Then are continue with step 5, if
needed.
SOLUTION :
(a) For C2H4. After Steps 1 to 4, we have (b) For N2. After steps 1 to 4 : we have
Step : 6 Neither N has an octet, so we change a lone
pair to bonding pair :
In this case, moving one lone pair to make a
Step : 5 Change a lone pair to a bonding pair. The C double bond still does not give each N an
on the right has an octet, but the C on the left octet, so we move another lone pair to make
has only 6e–, so we convert the lone pair to a triple bond :
another bonding pair between the two C
atoms.
Formal Charge
Formal charge is an accounting procedure. If allows chemists to determine the location of charge in a molecule
as well as compare how good a Lewis structure might be. The formal charge of an atom in a polyatomic
molecule or ion may be defined as the difference between the number of valence electrons and the number of
electrons assigned to that atom in the Lewis structure. It is expressed as :
Formal charge = number of valence e– on neutral atom – (2  LP) – BP

The counting is based on the assumption that the atom in the molecule owns one electron of each shared pair
and both the electrons of a lone pair.

Let us consider the ozone molecule (O3). The Lewis structure of O3 may be drawn as :
The atoms have been numbered as 1, 2 and 3. The formal charge on :

1
 The centre O atom marked 1 62 (6)   1
2
1
 The end O atom marked 2  6  4  (4)  0
2
1
 The end O atom marked 3  6  6  (2)   1
2
Hence, we represent O3 along with the formal charges as follows :
If there are more than one possible Lewis structures for a molecule having same number of bonds, the better
structure is one which has the least formal charge on each individual atom. If takes energy to get a separation
of charge in the molecule (as indicated by the formal charge) so the structure with the least formal charge
should be lower in energy and thereby be the better Lewis structure. The non-zero formal charge on any
atoms in the molecule are written near the atom.
Formal charge and bond polarity

Formal charge calculations do not indicate how charge is actually distributed in molecules. Remember that
most bonds are polar, meaning that the electrons in an bond are skewed toward the more electronegative
atom. Formal charges, however, are found by assuming that all bonding electrons are shared equally. As a
result, formal charge calculations are extremely useful for assessing whether a valence electron distribution is
reasonable, but they do not reliably indicate actual bond polarity or the actual distribution of charge. Some of
the following examples illustrate this point.
In chlorine trifluoride, all formal charges are zero. Based on electronegativities, however, each F – Cl bond
is significantly polar. The electronegativity of F is 4.0. Indicating that a fluorine atom attracts electrons more
strongly than a chlorine atom. In a CIF3) molecule, each F atom has a small net negative charge (less than one
unit), and the Cl atom has a net positive charge of 3 times this amount (also less than one unit). These partial
charges are symbolized + or –.
The ammonium cation illustrates the difference between formal and actual charge even more dramatically.
The nitrogen atom of NH4+ has a formal charge of 5 – 4 = +1, but electronegativity values indicate that N
attracts electrons more strongly than H ( N = 3.0 = 2.1). Thus the actual electron distribution in an N – H
bond is skewed forward nitrogen, leaving each H atom with a partial positive charge and the N atom with a
partial negative charge.
The positively charged environment of the hydrogen atoms is reflected in its chemical behaviour. This ion
readily gives up a hydrogen cation to a hydroxide anion : NH 4   OH    NH3  H 2O

Remember that formal charge are not annual charges. Instead, formal charges are simply a device that helps
us determine the most stable distribution of a molecule’s valence electron.

CO-ORDINATE COVALENT BONDING Section - 4
The bonding in which one atom furnishes a pair of electrons to the other atom, in such a manner that both of
the atoms achieve stability (i.e. 8 electrons in outer shell), is called as Co-ordinate Covalent or Dative
Bonding.
Compounds such as NH3, having one lone pair readily forms coordinate bonds. It combines with H+ ion
(Hydrogen cation) to from Ammonium ion (NH4+) as follows :

 H 
 | 

H+ + NH3 
 NH4 + H  N  H 
 | 
 H 
Similarly, H2O forms Hydronium ion (H3O+ ion) by combining with H+.

 
   
H + + H 2O 
 H 3O +  H O  H 
 | 
 H 
Exception to Octet Rule

The octet rule, though useful, is not universal. It is quite useful for understanding the structures of most of the
organic compounds and it applies mainly to the second period elements of the periodic table. Up to now we
have studied the molecules which follow Lewis Octet Rule while forming bonds. It is observed that atoms in
some molecules could exist with some other number of electrons in their valence shells, rather than eight
electrons without affecting the stability.
There are three types of exceptions to the octet rule :

(i) The incomplete octet of the central atom
In some compounds, the number of electrons surrounding the central atom is less than eight. This is especially
the case with elements having less than four valence electrons. Examples are LiCl, BeH2, BCl3, AlCl3, BF3
etc. Li, Be and B have 1.2 and 3 valence electrons only.
F
BF3 : Boron atom has only six electrons in its outer-shell even after making three single FB
bonds with three F atoms (i.e., it completes only sixet). F
BeCl2 : Beryllium has only four electrons in its outershell even after making two single
bonds with two Cl atoms.
(ii) Odd-electron molecules
In molecules with an odd number of electrons like nitric oxide, NO and nitrogen dioxide, NO2, the octet rule
is not satisfied for all the atoms (as shown below)
N=O O N O

(iii) The expanded octet

Elements in and beyond the third period of the periodic table have, apart from 3s and 3p orbitals, 3d orbitals
also available for bonding. In a number of compounds of these elements there are more than eight valence
electrons around the central atom. This is termed as the expanded octet. Obviously the octet rule does not
apply in such cases. Eg : PF5, SF6, H2SO4 and a number of coordination compounds.
Cl F O
Cl F F
Cl P S H O S O H
Cl F F
Cl F O
PCl5 SF6 H 2 SO4
10 electrons around 12 electrons around 12 electrons around
the P atom the S atom the S atom
PCl5 : Phosphorus after making five single bonds with five Cl atoms has ten electrons in its outershell.
SF6 : Sulphur makes six single bonds with six F atoms and thus has 12 electrons in its outershell.
H2SO4 : Sulphur makes 2 single bonds and 2 double bonds with 4 oxygen atoms and thereby has 12
electrons in its outermost shell
Other drawbacks of the octet theory
 It is clear that octet rule is based upon the chemical inertness of noble gases. However, some noble
gases (for example xenon and krypton) also combine with oxygen and fluorine to form a number of
compounds like XeF2, KrF2, XeOF2 etc.,
 This theory does not account for the shape of molecules.
 It does not explain the relative stability and energy of the molecules.
Some Terminologies related to a Chemical Bond :

(i) Bond Energetics
The basic rule followed when a chemical bond is formed is that the total energy of the system must be lower
in the bonded state than in the non-bonded state (or free atomic state). For both Ionic and Covalent bonding,
association can take place only when the combined state achieves the stability, i.e., a state of minimum
energy.
When two atoms combine to form ionic covalent bond, the total energy of the system must be lowered.
Therefore energy must be given off when bonding occurs. This evolved energy is known as Bond Energy. It
means, whenever a bond is to be formed the energy will be released and to break it, energy must be
supplied. The covalent bonding is understood in terms of electrostatic interactions. The electrons in atoms
are negatively charged and protons are positively charged, so it is electrical columbic interactions between
these particles that give rise to covalent bonding.
We know that Ionic bonding is formed through electrostatic attractive force. So in both types of bonding the
formation of compounds is the result of electrical interactions by columbic forces in some sense or the other.
(You will study more about electrical forces in Physics).

(ii) Bond Length

rA rB
Bond length is defined as the equilibrium distance between the nuclei of
two bonded atoms in a molecule. In the case of a covalent bond, the
contribution from each atom is called the covalent radius of that atom.
R = rA + rB
(R is the bond length and rA and rB are the covalent radii of atoms A and
A B
B respectively The Bond length in a covalent molecule AB
(iii) Bond Angle

It is defined as the angle between the orbitals containing bonding electron pairs around the central atom in a
molecule/complex ion. Bond angle is expressed in degree which can be experimentally determined by
spectroscopic methods.
It gives some idea regarding the distribution of orbitals around the central atom in
a molecule/complex ion and hence it helps us in determining its shape. For example
H – O – H bond angle in water can be represented as under :
Ionic Character in covalent bonds (Polar Covalent Bond) :

Covalent bond when formed between two alike atoms, bonded pair of electrons is equally shared. However
when it is formed between two atoms of different kinds (unlike atoms), bonded pair is not equally shared. An
atom which has more tendency to attract the shared pair of electrons towards itself (high electronegativity)
will pull the bond pair towards itself.
For example: Let us consider a single covalent bond between A and B, i.e., A  B.
Let B be more electronegative than A, then the bond pair will be shifted towards B, i.e., the electron cloud of
bond will distort and moves slightly over to B. As a result B acquires a partial negative charge (denoted by 
). Since the molecule is neutral, A will acquire a partial positive charge (denoted by + ). Such a state where
+ve and ve charges are separated by a certain distance, is known as Polarised state and the process is
known as Polarisation, and the covalent bond is known as Polar Covalent Bond.
A molecule with positive and negative charge centres in equilibrium is called as dipole and is characterised
by possessing a quantity dipole moment (µ) defined as the product of the magnitude of charge (q) and the
distance (d) separating the centres of +ve and ve charges.  = q × d, Its unit in CGS system is debye (D).
1 D = 1 × 1018 esu.cm. The charge q is measured in esu. The distance d is measured in cm and is of order
of 1 Å, i.e., 108 cm. The direction of dipole moment is from +ve end to –ve end. Note : Charge on 1
electron = 1.6 × 1019 C = 4.8 × 1010 esu.
Here, A+  B- is characterised as dipole and is known as Bond Dipole. The overall dipole moment of a
molecule is the vector sum of the dipole moments of all bond dipoles in a molecule.
Now covalent molecules having bond dipoles are classified into two categories :
(a) Polar molecules (b) Non-polar molecules

A molecule is said to be polar if the net dipole moment of a molecule is not equal to zero. For example : HF,
H2O, NH3, CH3OH, etc, are polar as in all of these, the net dipole moment is not equal to zero (net  0).
For a molecule to be polar both of the following conditions must be satisfied :

(i) There must be at least one polar bond present.
(ii) The polar bonds, (if there are more than one), and lone pairs must not be so symmetrically arranged
that their bond polarities cancel each other.
This means if there are no polar bonds or lone pairs on the central atom, the molecule cannot be polar. And
even if these are present, they may be arranged in such a manner that their polarities cancel each other,
resulting in a non-polar molecule. So a molecule is nonpolar if its net dipole moment is equal to zero. For
example : H2, Cl2, BF3, CO2, BeCl2, etc, are non-polar as net = 0. In such molecules, in spite of bond
dipoles, the molecules are non-polar.
HH Cl  Cl
(no bond dipole, net = 0) (no bond dipole, net = 0)
δ
δ
Cl — Be— Clδ 
(2 bond dipoles but net = 0) (3 bond dipoles but net = 0)

The conclusion is that, the dipole moment of a molecule, (zero or nonzero), depends upon the structure or
shape (or on geometry) of the molecule. For example H2O is polar whereas HgCl2 is nonpolar. The
difference lies in the shapes of two molecules. H2O is angular (  0) and HgCl2 is linear ( = 0). Both have
polar bonds, OH bond in water while HgCl bond in mercuric chloride, but due to structure of HgCl2 being
linear, the dipole moments of two bond dipoles cancel each other whereas in water, due to angular shape the
dipole moments of two bond dipoles do not cancel and give rise to a net dipole moment.
Applications of Dipole Moment

(i) To decide polarity of the molecule : Molecules having zero dipole moment are said to be non-
polar molecules and those having R  0 (resultant dipole moment) are polar in nature.
(ii) To determine percentage of ionic charcter : The value of dipole moment can be used for
determining the amount of ionic character in a bond.
 =q×d
Consider a diatomic molecules say HCl. Suppose this molecule is completely ionic. Under this condition H
and Cl ions would bear a unit charge equal to 4.8 × 1010 esu and the bond distance between H and Cl
atoms = 1.27 Å.
Thus, theoretical value of = 4.8 × 1010 × 1.27 × 108 = 6.09 D
Dipole moment of HCl is also determined experimentally. Let the experimental value be 1.03 D.

Percentage of ionic character in H — Cl bond in HCl molecule

Experimental value of μ 1.03
 100  100  16.9%
Theoretical valueof μ 6.09
Experimental value of dipole moment

Thus, Percentage of ionic character   100
Theoretical value of dipole moment
(iii) To determine geometry of molecules : The values of dipole moments provide value information
about the structure of molecules.
(a) CO2, CS2 molecules are linear as value of their dipole moments are zero.
(b) H2O is not a linear molecule as it has dipole moment. Actually, it has V-shaped structure and
the bond angle is 105. Similarly, SO2 has a bent structure.
(c) In ammonia, three hydrogen atoms do not lie symmetrically with respect to nitrogen as it has
dipole moment. It has pyramidal structure.
Molecular Geometry and Dipole Moment

General Formula Molecular Geometry Dipole Moment Example
AX Linear May be non-zero HF, HCl
AX2 Linear Zero CO2, CS2

Bent or V-shape Non-zero H2O, NO2
AX3 Trigonal planar Zero BF3

Pyramidal Non-zero NH3, PCl3
T-shape Non-zero ClF3
AX4 Tetrahedral Zero CH4, CCl4

Square planar Zero XeF4
See saw Non-zero SF4, TeCl4
AX5 Trigonal bipyramidal Zero PCl5

Square pyramidal Non-zero BrCl5
AX6 Octahedral Zero SF6

Distorted octahedral Non-zero XeF6
AX7 Pentagonal bipyramidal zero IF7
(v) Bond moment : The contribution of individual bond in the dipole moment of a polyatomic molecule
is termed bond moment. The measured dipole moment of water molecule is 1.85 D. This dipole
moment is the vectorial sum of the individual bond moments of two OH bonds having bond angle
104.5.

Thus, μ obs  2μ O  H cos 52.25

1.85  2μ O H  0.6129
μ O  H  1.51 D
Illustration - 6 (a) A diatomic molecules has a diple moment of 1.2 D. If the bond distance is 1.0Å, what
fraction of an electron charge, e, exists on each atom ?
(b) The diple moment of LiH is 1.964 × 1029 Cm and the interatomic distance between Li and H in this
molecule is 1.596Å. What is the per cent ionic character in LiH ?
SOLUTION :
Dipole moment
(a) Partical charge  = (1 electronic charge) (interatomic distance)
Bond distance
= (1.602 × 1019 C) (1.596 × 1010 m)
1.2×1018esu cm = 2.577 × 1029 Cm

1.0×108 cm Fractional ionic character
= 1.2 × 1010 esu Exp. vlaue of dipole moment


The fractional of an electronic charge Theoretical value of dipole moment
1.2×1010 1.964×1029
  0.25  25% of e.   0.768
4.8  1010 2.557×1029
(b) The diple moment of 100% ionic molecule (LiH) The bond in LiH is 76.8% ionic.
Illustration - 7 Predict whether each of the following molecules has a dipole moment :
(a) IBr (b) BF3 (c) CH2Cl2
SOLUTION :
(a) Since IBr molecules is diatomic, it has a linear (c) CH2Cl2 is similar to CH4 (tetrahedral), but it has
geometry. Bromine is more electronegative than three different bond angles : HCH, HCCl, and
iodine, hence, IBr is polar with bromine at the ClCCl, which are close to but not equal to 109.5°.
negative end. Thus, the molecules does have a dipole Since Cl is more electronative than C and which is
moment. more electronagetive than H, the bond moments
do not cancel and the molecule possesses a dipole
(b) Since fluorine is more electronegative moment. CH2Cl is thus a polar molecule.
than boron, each B – F bond in BF3
is polar and three bond moments are
equal. However, the symmetry of a
trigonal planar shape means that the
three bond moments exactly cancel
one another.
Resultant diple moment is indicated by

Covalent Character in Ionic bonds :

When a cation is placed near an anion, it distorts the spherical shape of the anionic electron cloud due to
its attractive force. Such a distorted anion is said to be polarized.
Since the electrons now have a better tendency to stay between the two nuclei rather than entirely on the
anion, the ionic compound is said to have acquired a certain covalent character. The tendency of cation to
polarize the anion is called its polarizing power.
The tendency of the anion to undergo polarisation is called its polarisability.
Greater the polarizing power of cation or polarisability of anion, greater is the covalent character of the
molecule.
The covalent character of an ionic compound is favoured by :

(a) A small cation : In a small cation the positive charge is concentrated over a small surface area and as
a result its effect in polarizing the anion would be large. e.g, the covalent character of the chorides of
the Be group decreases in the order, Be > Mg > Ca > Sr > Ba.
(b) A large anion : Large anions have a high polarisability since their outermost orbitals are shielded from
the positive nuclear field by a number of completely occupied orbitals and are thus readily polarized by
a suitable cation. E.g, the halides of Ca; the covalent character increases in order
CaF2 < CaCl2 < CaBr2 < CaI2. ; polarisability is F < Cl < Br < I
(c) There should be a high charge on either the cation or the anion or both. It is obvious that the electrostatic
forces which cause polarization will be considerably enhanced, if the ions are highly charged. e.g.,
polarizing power of cations increases in the order Na+ < Mg2+ < Al3+ (all the three are isoelectronic).
(d) The cation should possess an electronic configuration which is not that of an “inert” gas. It follows that
the noble gas electronic configuration must be the most effective in shielding the nuclear charge of a
cation from its surface. Cations without this configuration will have high positive field at their surface
and consequently will have high polarizing powers.
The combined influence, of ionic size and charge on the polarizing power of a cation is sometimes
cationic charge
expressed in terms of ionic potential.  
cation radius

Vidyamandir Classes The Chemical bond - I
Fazan rule is used to decide relative ionic and covalent character in molecules. According to this rule a
molecule is predominant covalent if :
 smaller the size of cation
 larger the size of anion
 greater the charge on cation and anion.
 ion does not have inert gas configuration.
We can also say that these factors favour polarisation.
Note : Greater the covalent nature
 lower the mp/bp
 smaller conducting nature
 lower solubility in polar solvent
 higher solubility in non polar solvent.
(a) LiCl, NaCl, KCl, RbCl, CsCl
Size of cation is the deciding factor (charge of each ion and size of Cl is same)
  
Li  Na  K  Rb  Cs  
  size of cation

 polarisation
LiCl  NaCl  KCl  RbCl  CsCl
 covalent
 mp/bp

 conductivity

 solubility in H2O (polar solvents)



 solubility in non polar solvent
(b) NaF, NaCl, NaBr, NaI
Deciding factor is the size of the anion. Larger size of the anion, greater the polarization hence greater
the covalent nature.
 
F  Cl  Br  I  
 size of cation
F  Cl  Br   I
 polarisation
NaF  NaCl  NaBr  NaI
 covalent nature

(c) NaCl, MgCl2, AlCl3, SiCl4, PCl5
Na   Mg 2   Al3  Si4   P5
 size of cation
 charge on cation


Note : Greater the charge, smaller the size then greater the polarisation
Na   Mg 2  Al3  Si4   P5

 polarisation
2NaCl  MgCl  AlCl  SiCl  PCl
3 4 5  covalent nature

(d) NaF, Na2O, Na3N
F  O 2   N 3
  size of anion
F  O2   N3
 charge on anion

F  O2   N3
  polarisation
NaF  Na O  Na N
2 3 covalent nature

(e) CuCl and NaCl
[Cu+] [Ar] 3d10
[Na+] [Ne]
Cations with 18– electron shells have greater polarising power than the 8-electron shell ions with the same
charge and size. This is due to the increased electronegativity of the 18-electron shell ions as the inner
electrons have poor shielding effect on the nucleus. Thus CuCl is covalent and NaCl is ionic.
SHAPES OF MOLECULES (VSEPR THEORY) Section - 5
The shapes or geometry of a molecule is quite accurately predicted by VSEPR (Valence Shell Electron Pair
Repulsion) theory. According to this theory all valence shell electron pairs surrounding the central atom
arrange themselves in such a manner as to be as far away from each other as possible. By separating
the electrons from each other, the electrostatic repulsion, (that is the cause of higher energy), is minimised. As
a result each molecule tends to acquire a state of lowest energy.
The basic ideas can be summarized as follows :
Valence shell pairs of electrons are arranged about the central atoms so that repulsion among them is minimised,
or so that there is maximum separation among the regions of high electron density (bond pairs) about the
atom. For instance, two regions of high electron density would be most stable on opposite side of the central
atom (Linear arrangement), while three regions would be most stable when they are arranged at the
corners of an equilateral triangle Trigonal planar arrangement). The resulting arrangement of these regions
is referred to as the electronic geometry of the the central atom.

Number of Bond Pairs Electronic Geometry Bond Angles

2 Linear 180o
3 Trigonal planar 120o
4 Tetrahedral 109o 28
5 Trigonal Bi-pyramidal 90o, 120o , 180o
6 Octahedral 90o, 180o
As mentioned earlier, there are two distinct types of electron pairs around the central atom : Bonding electron
pairs (bp) and Nonbonding electron pairs or lone pairs (–lp). The strength of repulsion between the electron
pairs varies as :
–lp-–lp > –lp-bp > bp-bp
This is very significant while deciding the final geometry of a molecule. We will divide our study of shapes in
two categories :
 The molecules containing only bondpairs of electrons and
 The molecules containing both bondpairs and lone (non-bonding) pairs.
Note : Before we go into the details of shapes, first let us discuss the Theory of Covalent Bonding.
THEORIES OF COVALENT BONDING Section - 6
Orbital theory of Covalent Bonding :

As discussed earlier that covalent bonding is the result of sharing of electrons between atoms. The main
requirement for sharing of electrons is: only a single electron must be present in an orbital of the outer
shell. Such an orbital (i.e. containing an odd electron) will combine with another orbital (containing an odd
electron but of opposite spin) of same kind or of another kind of atom to form covalent bond. This combination
of orbitals is known as overlapping of orbitals. So according to atomic orbital theory, the covalent bond is
formed by the overlapping of atomic orbitals having electrons with opposite spins, belonging to the
external shells of two atoms of same or of different kinds. After overlapping the electronpair now belongs
to both the orbitals of two atoms.
Depending upon the types of orbitals which take part in overlapping, we can classify overlapping as follows:
(a) ss overlapping (b) sp overlapping (c) pp overlapping
From above, we observe that overlapping can further be analysed as lateral and end to end. ss, sp and one
of pp type overlapping is of end-to-end type and one of the pp overlapping is of lateral type.

Sigma () bond : The bond formed as a result of end to end type of overlapping is called as  bond. Here
overlapping of orbitals takes place along the same axis. The bond formed by this type of overlapping is very
strong as the extent of overlapping is sufficiently high. The extent of overlapping determines the strength
of covalent bond. In sigma bond, the electron density accumulates between the centres of the atoms being
bonded and lies on the imaginary line joining the nuclei of bonded atoms.
Pi () bond : The bond formed between two atoms by the sideways overlapping (also called lateral
overlapping) of the two halffilled orbitals is called a pi () bond. The extent of overlapping in case of a pi
bond is much less than in sigma bond, so strength of pi bond is low. In this bond, the electron density lies
above and below the imaginary line joining the centres of nuclei of bonded atoms. Whenever there is multiple
bonding, i.e., double and triple bonds, pi bond is formed.
Hybridisation and Hybrid Orbital :

The electronic configuration of carbon (C), 1s2 2s22p2, is rather misleading if we talk about the tetravalency
of carbon (which is its most common valency in its compounds). Its configuration predicts the carbon to
divalent due to two unpaired p electrons. This is actually not the case. In bond formation, the atomic orbitals
of carbon atom are mixed in such a manner as to produce four equivalent orbitals, which are confined to
the corners of a regular tetrahedron, in order to maximise the separation among them (VSEPR theory). The
mixing of atomic orbitals in order to produce new orbitals is called as Hybridisation. This concept was given
by Linus Pauling in 1937. This concept not only predicts the correct shapes but also explains the actual
microscopic observations of the geometry of molecules. The different cases of hybridisation arise by mixing
of s, p and d orbitals are discussed below.
sp3 Hybridisation :
This type of hybridisation results from mixing of one s, three p orbitals of outer (valence) shell of an atom. To
understand the concept clearly, let us consider the formation of CH4 molecule. The outer-shell configuration
of C atom in ground state is 2s22px12py1. Note that 2pz orbital is empty. One of the electrons in the 2s2
orbital is excited (or promoted) to this vacant 2pz orbital. This results in the following picture.

Ground state Excited state

2s2 2px1 2py1 
 one electron excited   2s1 2px1 2py1 2pz1
to a 2pz orbital
(This step requires energy)
After the electron is promoted, all the four orbitals are mixed to give four equivalent hybrid orbitals (in sense
that all of them are of equal energy) called as sp3 hybrid orbitals.
2s1 2px1 2py1 2pz1   mixed or hybridised   four sp3 hybrid orbitals
These four hybrid orbitals are of same energy and equivalent in every other way. They are directed at the
corners of a regular tetrahedron. This is best geometry for four bonded pairs to be at the maximum distance
apart and thus minimise the repulsion and hence the energy of the system is minimised. Each of four sp3
orbitals in carbon can now combine with a 1s orbital of a hydrogen atom, forming four equivalent CH bonds
involving sp3s overlapping and forming four sigma bonds. The extent of overlapping by hybrid orbitals is
very high due to their strong orientation in space or one can now imagine a bond formed by hybrid orbital to
be highly stable. This additional stability accounts for the energy required in the promotion step before
mixing.
sp2 hybridisation :
To account for the shapes of molecules like BF3, BCl3 etc., let us consider the valence-shell configuration of
Boron: 2s2 2px1. Note that py and pz orbitals are vacant, so promotion of one 2s electron takes place to 2py
orbital to account for three B-F bonds in BF3.
2s2 2px1   2s1 2px1 2py1
 one electron excited 
to a 2py1 orbital
from a 2s orbital
The three orbitals in excited state are mixed to give three sp2 hybrid orbitals of equivalent energy. These are
all in a same plane with central atom (Boron) at the centre of an equilateral triangle with three sp2 orbitals at
its corners. This is the best possible geometry for three bondpairs to be at maximum distance (VSEPR
theory). Each of these orbitals now form three sigma bonds with three 2p orbitals of F atoms to form BF
bonds and hence forms a BF3 molecule.

sp hybridization :
A sp hybrid orbital is formed when in an atom one s and one p orbital mix with each other to form two
equivalent orbitals. Two such orbitals, i.e., sp hybrid orbitals are most stable when they adopt an angle of
180 between them so that they are at the maximum distance apart. It means that the molecule involving sp
hybrid orbitals will be linear in shape. The geometry of BeF2 is linear and is explained by sp hybridisation of
Be atom. The valence shell configuration of Be is 2s2 which means one electron from 2s orbital can be
promoted to vacant 2p orbital and form the excited state.
2s2   2s1 2px1
 promotion of one s electron 
to a px orbital
The 2s1 and 2px1 electron can now mix or hybridised to give two sp hybrid orbitals, which form two sigma
bonds with F atoms (as in BF3) to form BeF2 molecule.
sp3d hybridisation (PF5 molecule) :

Since phosphorus is the central element in PF5 molecules, it must have five halffilled orbitals to form bonds
with five Fluorine atoms. Hybridisation is again the answer. This time using one d orbital from the vacant set
of 3d orbitals in addition ot the 3s and 3p orbitals of the phosphorus atom.
3s2 3p3 3d0   3s13px1 3py13pz1 3d1
 promotion of one s electron 
to a vacant d orbital

The five sp3d hybrid orbitals are directed toward the corners of a trigonal
bipyramid. Each is overlapped by the (only) 2p orbital of a Fluorine atom
that contains a single electron. The resulting pairing of P and F electrons
forms a total of five covalent bonds.
sp3d2 hybridisation (SF6) :

The sulphur atoms can form six hybrid orbitals to accommodate six electron pairs, and in Valence Bond
theory terminology, we have :
2 4 0  3s13px1 3py13pz1 3d13d1
3s 3p 3d   promotion of one s electron 
and p electron to a vacant d orbitals
The six sp3d2 hybrid orbitals are directed toward the corners of a regular
octahedron. Each sp3d2 hybrid orbital is overlapped by a halffilled 2p
orbital from Fluorine to form a total of six covalent bonds.
We should note the sp3d hybridisation involves utilisation of an available d
orbital in the outermost shell of the central atom, P. The heavier Group 15
elements P, As, and Sb, can form five co-ordinate compounds utilising this
hybridisation. But it is not possible for Nitrogen (also in Group 15) to form
such fivecoordinate compounds. Why ?
(i) Nitrogen is too small to accommodate five (even very small) substituents without excessive crowding
which causes instability.
(ii) It has no low-energy d orbitals.
In fact, we can generalise; no element of the second period can be central element in five–coordinate molecules
(or higher–coordinate ones) because they have no low energy d orbitals available for hybridisation and
because they are too small.
It is important to realise that the set of s and p orbitals in a given energy level, and therefore any set of hybrids
composed only of them, can accommodate a maximum of eight electrons and participate in a maximum of
four covalent bonds.
In the following section, we will discuss the hybridisation of molecules in which the central atom has
lone pair(s). The actual geometry of the molecule containing one or more lone pairs of electrons is
different from the geometry (distorted Geometry) which is expected from the type of hybridisation
involved in the molecule.

sp2 hybridisation in SnCl2:

The outer electronic configuration of Sn is 5s2 5px1 5py1. To explain the
shape of SnCl2, the concept of hybridisation is applied. Here one 5s, two
5p orbitals hybridise to give three sp2 hybridised orbitals of equivalent
energy.
In this case one of the hybrid orbitals contains a lone pair, whereas other two contain an electron each. These
two orbitals containing one electron overlap with two 3p orbitals of two chlorine atoms to form two SnCl
bonds. The geometry of SnCl2 molecule should have been Trigonal planer, but due to presence of lone pair
over the central atom (Sn), there is some distortion in the shape of the molecule. The bond angle is slightly
less than 120 and the molecule is bent or Vshaped. The reason is the greater repulsion between a bp
and a –!p than normal bpbp repulsion.
sp3 hybridisation in NH3 and H2O molecule :

In Ammonia, NH3 : N is the central atom and its outershell configuration is
2s2 2px1 2py1 2pz1. One s orbital (containing a lone pair) hybridises with
three p orbitals (containing one electron each) to give four sp3 hybrid orbitals.
Of these four hybrid orbitals, the three orbitals containing one electron each
overlap with three 1s orbitals of three Hatoms to form NH bonds.
Due to lone pair over N, the geometry of the molecule gets distorted from regular tetrahedron (which is the
exact geometry for sp3 hybrid orbitals) and the bond angle changes from 109.5 to 107 The final shape is
pyramidal where N is at the centre with three Hatoms forming the base and the lone pair forming the apex
of the pyramid.
In Water, H2O : O is the central atom with 2s2 2px2 2py1 2pz1 as its
outershell configuration. Here, one s orbital (containing a p), one p
orbital (containing a p) and two p orbitals (containing one electron
each) hybridises to give four sp3 hybrid orbitals of equivalent energy.
Of these two orbitals (containing one electron each) overlap with two
1s orbitals of H atoms to form two OH bonds.
Due to two ps over O atom, the actual geometry of molecule is distorted. Apart from pbp repulsion,
pp repulsion also exists in this molecule, so the distortion is much greater than the ammonia molecule. The
bond angle changes form 109.5 to 104.5 in water and the final is bent or Vshaped.
Note : The actual geometry of the molecule containing one or more p of electrons is different form the geometry
which is expected from the type of hybridisation involved in the molecule.

Hybridisation and Multiple Bonding : (Shapes of C2H4 and C2H2)

Geometry of C2H4 molecule :
In ethylene (C2H4), two carbon atoms in the excited state
undergo hybridisation in a different manner than the carbon
atom in C2H4 molecule. After the promotion of one 2s
electron to the vacant 2p orbital, one s orbital and two p
orbitals of two carbon atoms hybridises to form three sp2
hybrid orbitals (leaving one p orbital in unhybridised state).
Now one of the sp2 hybrid orbitals of each carbon atom overlaps with each other to form one CC bond
(sigma bond) and other two hybrid orbital of two carbons overlaps with 1s orbitals of H atoms to form four
CH bond (sigma bonds) in total. It is important to note that two unhybridised p orbitals are perpendicular
to the plane of three sp2 orbitals. These two p orbitals form a pi () bond with each other (Recall the
formation of pi bond).
We, now observe that two covalent bonds that make up the double bond between the carbon atoms are not
equivalent, they are different. One of them is a sigma () bond and other is the pi () bond.
Geometry of C2H2 molecule :

In acetylene (C2H2), after achieving the excited states, both
the carbon atoms undergo sp hybridisation. One s orbital
and one p orbital hybridise to form two sp hybrid orbitals
(leaving two p orbitals in unhybridised state perpendicular
to the plane of sp hybrid orbitals). Now one sp hybrid
orbital belonging to each carbon atom form a CH sigma
bond and other sp hybrid orbital form sigma bond with 1s
orbital of H atom (in all two CH bonds).
Two unhybridised p orbitals of each carbon atom form two pi bonds with each other. This means that a
carbon-carbon triple bond comprises of one sigma bond and two pi bonds.

TYPES OF BONDING IN A COMPOUND & INTERMOLECULAR FORCES Section - 7

From the difference in electronegativities of the atoms forming a bond, it can be predicted what type of
bond is formed by the atoms. When the difference is zero or very small, the bond is essentially covalent,
and the electron density is more or less equally share d by two atoms. When the difference is large, one atom
more-or-less completely withdraws the electron pair to it (one having higher electronegativity) and the bond
is ionic. A bond AB (between two atoms A and B) is Ionic if difference in electronegativities of A and B is
greater than 1.7 and it is Covalent, if it is less than 1.7.
 Metals form Ionic bonds by losing electrons. However some metals form covalent bonds also and some
don’t form covalent bonds at all. The tendency of normal metals increases to form covalent bond as we
proceed from left to right across a period in the Periodic Table, e.g., Ce and Ba form only Ionic bonds, Pb
and Bi form both Ionic as well as Covalent bonds. Also metals rarely form bonds with other metals.
 Non-metals form Ionic bonds by gaining electrons. All non-metals can also form Covalent bonds as well.
The tendency to form Ionic bond increases in going from left to right across a period and in going down the
group, e.g., C forms only Covalent bond, F forms both Covalent as well as Ionic bonds. O forms O2– in few
compounds whereas S forms S2– in many compounds.
Note : Most compounds of metals with non-metals are ionic and most compounds of non-metals with nonmetals
are covalent.
 Some non-metals such as C, Si, Ge, N, P, O are very reluctant to form negative ions. C, Si, Ge form only.
Covalent bonds whereas N, P, O can form both Ionic and Covalent bonds.
Note : If these atoms form Ionic bonds, they also form Covalent bond with some other atom in the same compound.
For example: In KOH, O forms Ionic bond with K but forms Covalent bond with H.
Metallic Bond :
Metals have low ionisation energies and hence valence electrons in them
are weakly bounded to the positive charged nucleus or kernel (kernel
means nucleus and the electrons other than the valence electrons). In
metals the number of valence electrons is less than the number of orbitals
to hold them. This makes possible for an electron to pass from one another
through overlapping orbitals. Consider the case of Li, which has one s
valence electron. In the solid crystal, each Li atom is close to eight other
atoms, so that its orbitals will overlap with all of them at the same time and
this picture is continued throughout the crystal. The electrons are shared
by all the atoms, i.e., they are delocalised throughout the crystal.
So metal is network of ions (kernels) in a sea of electrons, with the electron sea acting as the binding force
which holds the metal ions (kernels) together.

The valence electrons are not associated with any particular atom and can therefore move here and there. If
the two ends of piece of a metal are connected to the poles of a battery, electrons will move towards the
positive pole of the battery where they will flow out of the metal into the battery, being replaced by fresh
electrons from the negative pole of the battery. In this manner an electric current can be conducted by the
metals.
Intermolecular Forces
Intermolecular forces are the sum of the forces of attraction and repulsion between interacting particles
(atoms and molecules). Attractive intermolecular forces are known as van der Waals forces, in honour of
Dutch scientist Johannes van der Waals (1837-1923), who explained the deviation of real gases from the
ideal behaviour through these forces (You will study about this in ‘States of Matter’). These forces are other
than due to covalent bonds, the hydrogen bonds, or the electrostatic interaction of ions with one another or
with neutral molecules or charged molecules. The term includes:
 force between two instantaneously induced dipoles (London disperison force)
 force between two permanent dipoles
 force between a permanent dipole and a corresponding induced dipole
Note that attractive forces between an ion and a dipole are known as ion-dipole forces and these are
not van der Waals forces.
Dispersion Forces or London Forces

Atoms and nonpolar molecules are electrically symmetrical and have no dipole moment because their electronic
charge cloud is symmetrically distributed. But a dipole may develop momentarily even in such atoms and
molecules. This can be understood as follows. Suppose we have two atoms ‘A’ and ‘B’ in the close vicinity
of each other [Figure (a)]. It may so happen that momentarily electronic charge distribution in one of the
atoms, say ‘A’, becomes unsymmetrical i.e., the charge cloud is more on one side than the other [Figure (b
and c)]. This results in the development of instantaneous dipole on the atom ‘A’ for a very short time. This
instantaneous or transient dipole distorts the electron density of the other atom ‘B’, which is close to it and as
a consequence a dipole is induced in the atom ‘B’.
The temporary dipoles of atom ‘A’ and ‘B’ attract each other. Similarly temporary dipoles are induced in
molecules also. This force of attraction was first proposed by the German physicist Fritz London, and for this
reason force of attraction between two temporary dipoles is known as London forces. Another name for this
forces is dispersion force.

These forces are always attractive and interaction energy is inversely proportional to the sixth power of the
distance between two interacting particles (i.e., 1/r6 where r is the distance between two particles). These
forces are important only at short distances (~500 pm) and their magnitude depends on the polarisability of
the particle.
Dipole - Dipole Forces

Dipole-dipole forces act between the molecules possessing permanent dipole. Ends of the dipoles possess
“particle charges” and these charges are shown by Greek letter delta (). Partial charges are always less
than the unit electronic charge (1.6 × 10–19 C). The polar molecules interact with neighbouring molecules.
Figure (a) shows electron cloud distribution in the dipole of hydrogen chloride and Figure (b) shows dipole-
dipole interaction between two HCl molecules. This interaction is stronger than the London forces but is
weaker than ion-ion interaction because only partial charges are involved.
The attractive force decreases with the increase of distance between the dipoles. As in the above case here
also, the interaction energy is inversely proportional to distance between polar molecules.
(a) Distribution of electron cloud in HCl a polar molecule, (b) Dipole-dipole interaction between two molecules
Dipole-dipole interaction energy between stationary polar molecules (as in solids) is proportional to 1/r3
and that between rotating polar molecules is proportional to /r6, where r is the distance between polar
molecules. Besides dipoledipole interaction, polar molecules can interact by London forces also. This
cumulative effect is that the total of intermolecular forces in polar molecules increase.

Dipole-Induced Dipole Forces

This type of attractive forces operate between the polar molecules having permanent dipole and the molecules
lacking permanent dipole. Permanent dipole of the polar molecule induces dipole on the electrically neutral
molecule by deforming its electronic cloud. Thus an induced dipole is developed in the other molecule. In this
case also interaction energy is proportional to 1/r6 where r is the distance between two molecules. Induced
dipole moment depends upon the dipole moment present in the permanent dipole and the polarisabilityof the
electrically neutral molecule. We have already learnt in Unit 4 that molecules of large size can be easily
polarized. High polarisability increases the strength of attractive interactions.
In this case also cumulative effect of dispersion forces and dipole-induced dipole interactions exists.
Hydrogen Bonding :
Molecules that contain FH, OH, NH bonds (e.g., Water, Alcohols, Organic acids, Amines, Aromatic
alcohols, etc.) show a strong tendency to associate, i.e., to link up to form larger molecules. This feature
exists in solid form and as well as in solutions in certain solvents. In all of such compounds, OH, or NH or
FH, bond is highly polar due to large difference in electronegativity. The electrostatic attraction between
such molecules should be quite strong. The positive end of one molecule attracts and is strongly attracted by
the negative end of the neighbouring molecule. In this manner a large number of molecules are associated to
form a cluster of molecules. Since in each case the hydrogen atom is responsible for the formation of linkages,
this is known as Hydrogen bond or H-bond. It is impossible for hydrogen to form a second covalent bond
so the additional linkage is shown by a dotted line. Hydrogen bonds are always of type : AH....B,
where A and B may be atoms of O, F, N. Hydrogen bonds are comparatively weak, with bond energies of
10100 kJ/mol, but they are widespread and have important effect on many physical properties of many
Organic and Inorganic compounds.
δ δ δ δ δ δ
H  F ........... H  F R O ............ H  O
| |
H R

Hydrogen Bonding is of two types :

(i) Intermolecular H-bonding (ii) Intramolecular H-bonding
You will learn about Hydrogen Bonding in the Chapter Chemical Bonding-II
RESONANCE Section - 8
There are certain molecules whose properties can not be explained by a single structure.
For example : The molecules of CO32 ion, three Lewis dot structures are possible. Similarly Lewis structure
for ozone (O3) shows that one of O atom is bounded to a O atom by a double bond and by a coordinate
covalent bond to the other O atom and there are two possible structures for it.
2 2 2
 O   O   O 
 |   |   || 
 O  C  O    O  C  O 
  O  C  O 

The length of three bonds in CO32 ions and two bonds in O3 is expected to be different. However from
spectroscopic analysis, it is observed that the lengths of bonds are equal and lie somewhere between that of
a single and double bond. Hence a particular structure is not sufficient to account for the observed facts.
The actual structure of CO32 ion and O3 molecule has neither of these Lewis structures. The real structure is
an average (midway between) of these structures. This phenomenon of representing the actual structure in
such a manner is called as Resonance. The individual structures are known as Canonical forms or Resonance
structures. The actual structure is called as Resonance hybrid.
Thus resonance hybrid may be defined as the actual structure of all the canonical forms that are possible for
a given molecule without changing the relative positions of its atoms. The resonance hybrid is more stable
than any of the other canonical forms. The difference in the energy between the resonance hybrid and the
most stable canonical form is called as Resonance energy. The more the number of possible resonating
forms, the higher is the resonance energy and hence more is the stability of the compound.

The resonating structure of a few more molecules and ions are shown below :
Total number of bonds

Note : Bond order (B.O.) =
Number of resonating structure
Effects of Resonance :
 It imparts stability to the molecule and hence decreases its reactivity. The reactivity of the molecule is
decreased due to delocalisation of electrons over the entire surface of the molecule.
 Since the electrons are not localised between any particular atoms, and are uniformly distributed in the
resonance hybrid, all the bond are similar and are of equal bond lengths. The bond length of a single
covalent is decreased as a result of resonance.
Illustration - 8 The bond length of normal C = O double bond is 121 pm. However each carbon to
oxygen bond length in CO2 is found to be 115 pm. Explain the structure of CO2 molecule.
SOLUTION :
If we consider only structure I for CO2 molecules there should be two carbon to oxygen double bonds.
As per question the bond length of normal C = O double bond is 121 pm. However, each carbon to
oxygen bond length in CO2 is found to be 115 pm which is in between that of C = O DOUBLE BOND
(121 pm) and C = O triple bond (110 pm). Hence, CO2 is considered a resonance hybrid of the follow
ing three Lewis structures.
 
O = C = O  O  C  O   O  C  O
[I] [II] [III]

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Chemical Bonding - II
Chemical Bonding - II
Till now we have learnt about the various aspects of chemical bonding. In this part of the chapter we will try to
summarize the method to find shapes and hybridisation of molecules and will also learn about Molecular Orbital
Theory.
BACK BONDING Section - 1
Back () bond is a co-ordinate bond formed between electron rich atom (donor) and neighbouring electron
deficient atom or atom having vacant orbital (acceptor) of a molecular species. For example in BF3 back
bonding is due to by donation of an electron pair from filled orbital of fluorine atom to vacant p-orbital of
boron.
This back () bonding may results in change in hybridization state, molecular geometry, bond angle, bond
strength and Lewis basic strength. For example in N(SiH3)3 hybridization state of nitrogen atom is sp2 and it
is not a Lewis base.
Further this back () bonding can be PP and Pdtype depending upon type of filled orbital and
vacant orbital. For example:

Chemical Bonding - II Vidyamandir Classes
Illustration - 1 Account for the fact that Lewis acid character of BF , BCl and BBr increases as BF <
3 3 3 3
BCl3 < BBr3 .
SOLUTION:
The increasing order of Lewis acid strength (or Back bonding in BF3 molecule is supported
character) (BF3 < BCl3 < BBr3) can be by the fact that the observed BF bond length
explained on the basis of the concept of (p
in BF3 which is equal to 1.30 is significantly
p) back bonding that takes place in given
shorter than the sum of the covalent radii of B
halides.
and F atoms (B = 0.80 , F = 0.72 , Sum
We know that in each of the given trihalide
molecules B-atom is sp2 hybridised and has = 0.80 +0.72 = 1.52 ).
one unused vacant 2p orbital. Each of the three The formation of (pp) bond results in that
halogen atoms in each BX3 molecule (X : F, the electron pair is transfered from Fatom to
Cl, Br) has three pairs of electrons which are the electron deficient Batom and hence
present in s and p-orbitals respectively ( F = electron density on Batom in BF3 molecule is
2s2 2p2 2p2 2p1 ; Cl = 3s2 3p2 3p1 ; Br = 4s2 increased or the tendency of Batom to accept
4p2 4p2 4p1). porbital having unpaired the electron pair is decreased, i.e. the Lewis
electron is used up in forming BX bond in acid strength of BF3 molecule, according to
BX3 molecule by overlapping with singly-filled lewis concept, is also decreased.
sp2 hybrid orbital of Batom.
We have seen above that (pp) back
In BF3 molecule, vacant 2p orbital on Batom bonding in BF3 molecule result from [2p2(F)
an fully-filled 2p orbital of Fatom overlap 2p0(B)] sidewise overlap, but the same in BCl3
sidewise to form (FB) bond which is called and BBr3 molecules is obtained by [3p2(Cl)
dative or (pp) bonding It is due to (p 2p 0(B)] and [4p 2(Br)2p0 (B)] sidewise
p) back bonding that BF bond acquire overlaps respectively.
some double bond character.
Now since the energy and shape of two 2p
orbitals (one 2p orbital on Batom an one 2p
orbital on F-atom) involved in [2p2(F)2p0(B)]
overlap to from (pp) bonding in BF3
molecule is the same, this overlap is symmetrical
and hence is the most effective. Consequently
the transfer of electron pair from 2p orbital of
Fatom to the vacant 2p orbital of Batom
takes place to the maximum extent and hence
maximum electron density developed on B
Formation of pp back bonding in one of
atom in BF3 molecule. Due to maximum
the three BF bonds in BF3.

electron density developed on B-atom in BF3 developed on Batom in BBr3 molecule. Due
molecule, this molecule shows minimum to minimum electron density developed on B
tendency to accept electron pair donated by a atom, BBr3 molecule shows maximum tendency
Lewis base (electron pair donor species) and to accept electron pair donated by a Lewis base
hence is the weakest Lewis acid. On the other and hence is the strongest Lewis acid.
hand, since the energy and shape of 4p orbital
of Br atom and 2p orbital of B-atom involved Above discussion shows that the tendency to
in [4p2 (Br)2p0 (B)] overlap in BBr3 molecule form (pp) back bonding decreases rapidly
is largely different, this overlap is unsymmetrical as we move from BF3 to BBr3 and hence the
and hence is the least effective. tendency of BF3, BCl3 and BBr3 molecules to
accept electron pair from Lewis bases
Consequently the transfer of electron pair from increases in the same direction, i.e. Lewis acid
4p orbital of Bratom to the vacant 2p orbital strength (or character) increases as BF3 < BCl3
of B-atom takes place to the minimum extent < BBr3.
and hence minimum electron density is
Illustration - 2 (pp) back bonding occurs in the halides of boron but not in those of aluminium. Explain.
SOLUTION :
The tendency of the central atom (A) in AX3 molecules (A = B or Al, X = halogen) to from (pp) back
bonding depends on the size of the central atom (A). Smaller is the size of the central atom, greater is its
tendency to form (pp) back bonding. Since Batom is smaller in size than Alatom, BX3 molecules
have (pp) back bonding while AlX3 molecules do not have this type of back bonding.
Illustration - 3 Explain why AlCl exists as a dimer, (AlCl ) or Al Cl while BCl exits as a monomer.
3 3 2 2 6 3
OR Explain the formation of dimeric structure of AlCl3 in benzene (inert solvent) and in the vapour
state.
OR Explain why all Al-Cl bonds in Al2Cl6 are not equivalent.
SOLUTION :
In AlCl3 molecule, Al-atom is surrounded by six electrons which are less by two electrons from an octet. In
dimeric structure (Al2Cl6), Alatom of both AlCl3 molecules completes its octet by accepting an electron
pair from Cl-atom of the other AlCl3 molecule as shown. Thus we see that in Al2Cl6 dimer each Al-atom is
holding four large-sized Cl-atoms around it.
Since B-atom is very small in size, this atom is not capable of holding four large-sized Cl-atoms around it in
B2Cl6 molecule and hence BCl3 molecule cannot dimerise to form dimeric molecule, (BCl3)2 or B2Cl6.

The formation of dimeric molecule, Al2Cl6 can be explained on the basic of hybridisation concept as follows.
We know that in AlCl3 molecule Al-atom (Al = 3s1 3p1 3p1 3p0) is sp2 hybridised and one 3p orbital remains
vacant and unhybridised. In AlCl3 molecule Al has coordination number equal to 3. In the formation of
Al2Cl6, the vacant and unhybridised 3p orbital on Al-atom of one AlCl3 molecule receives a lone pair of
electrons from 3p orbital of Cl-atom (Cl = 3s2 3p2 3p2 3p1) of the other AlCl3 molecule and thus forms a
[3p2 (Cl) 3p0 (Al)] coordinate bond. In this way each Al-atom completes its octet and coordination
number of Al-atom is increased from 3 (in AlCl3) to 4 (Al2Cl6). Thus we see that two bridges are formed by
two Cl-atoms between two Al-atoms.
The structure of Al2Cl6 has six Al-Cl covalent bonds and two Cl Al coordinate bonds, these bonds
donot have equal length, i.e. all Al-Cl bonds in Al2Cl6 are not equivalent.
APPLICATION OF DIPOLE MOMENT Section - 2

(i) To decide polarity of the molecule : Molecules having zero dipole moment  are said to be non-polar
molecules and those having R 0 (resultant dipole moment) are polar in nature.
(ii) To determine percentage of ionic charcter : The value of dipole moment can be used for determining
the amount of ionic character in a bond.
 = q  d
Consier a diatomic molecules say HCl. Suppose this molecule is completely ionic. Under this condition H+
and Cl– ions would bear a unit charge equal to 4.8 × 10–10 esu and the bond distance between H and Cl
atoms = 1.27 Å.
Thus, theoretical value of  = 4.8 × 10–10 × 1.27 × 10–8 = 6.09 D
Dipole moment of HCl is also determined experimentally. Let the experimental value be 1.03 D. Percentage
Experimental value of  1.03
of ionic character in H — Cl bond in HCl molecule = 100  100  16.9%
Theoretical valueof  6.09
Experimental value of dipole moment

Thus, percentage of ionic character =  100
Theoretical value of dipole moment
(iii) To determine geometry of molecules : The values of dipole moments provide value information about
the structure of molecules.
(a) CO2, CS2 molecules are linear as value of their dipole moments are zero.
(b) H2O is not a linear molecule as it has dipole moment. Actually, it has V-shaped structure and the
bond angle is 105°. Similary, SO2 has a bent structure.
(c) In ammonia, three hydrogen atoms do not lie symmetrically with respect to nitrogen as it has dipole
moment. It has pyramidal structure.

(iv) To determine orientation in benzene ring : Dipole moment is useful to ascertain the orientation of
substituents. In general, dipole moment follows the order :
Ortho-isomer > meta-isomer > p-isomer
Observe that :
o  m  p
In ortho isomers, experimental value of dipole moment is found different from theoretical value of dipole
moment. This difference is due to dipole-dipole interaction of two groups.
(v) Bond moment : The contribution of individual bond in the dipole moment of a polyatomic molecule is
termed bond moment. The measured dipole moment of water molecule is 1.85 D. This dipole moment is
the vectorial sum of the individual bond moments of two O — H bond having bond angle 104.5°.
Thus, obs = 2O — H cos 52.25
1.85 = 2O — H × 0.6129
O — H = 1.51 D

PREDICTION OF GEOMETRY (SHAPE) OF COVALENT MOLECULES Section - 3
Geometry of a molecule can be predicted if the state of hybridization at central atom is known. State of
hybridization at central atom in a molecule can be known by counting the number of orbitals involved in co-
axial overlapping and the number of orbitals with lone pair of electons, i.e., by counting the number of -
bonds and the number of lone pair of electrons at central atom. Adding the two if total is 4, the hybridization
is sp3, if this total is 3, the hybridization is sp2 and if this total is 2, the hybridization is sp. A few examples are
being given below :
(a) Beryllium chloride (BeCl2)

Outer Electronic Configuration of Be = 2s2
Since there are two chlorine atoms, hence Beryllium must be forming a single bond with each of them (as
chlorine has a valency equal to 1).
 This implies that before bonding there should be two orbitals around Beryllium having exactly one
electron in each of them so that they are available for overlapping with the respective orbitals of the
chlorine atoms.
 Thus we excite one of the electrons present in 2s orbital to 2p orbital to generate two singly occupied
orbitals.
 Outer Electronic Configuration of Be (after excitation of electrons) = 2s1 2p1.
6 Section 3 Section
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 Now before bonding 2s and 2p orbital hybridize to produce two sp orbitals of same energy and
same shape which overlap with p orbital of incoming chlorine atom to form two sigma bonds.
 Number of -bonds (bond pairs) at Be atom = 2 and
Number of lone pair of electrons at Be atom = 0 , Total number of electron pairs = 2 + 0 = 2
Hybridization is sp, i.e., BeCl2 is linear and bond angle is 180
(b) Boron trichloride (BCl3)
Boron is forming three bonds with three chlorine atoms.

Outer Electronic Configuration of B = 2s2 2p1
 Outer Electronic Configuration of B (after excitation of electrons)
= 2s1 2px1 2py1
 Number of -bonds (bond pairs) at B atom = 3
Number of lone pair of electrons at B atom = 0, Total number of electron pairs = 3
Hybridization is sp2, i.e., BCl3 is trigonal planar and bond angles are 120 each.
(c) Carbon tetrachloride (CCl4)

Carbon is forming four bonds with four Chlorine atoms.
Outer Electronic Configuration of C = 2s2 2p2
 Outer Electronic Configuration of C (after excitation of electrons)
= 2s1 2px1 2py1 2pz1
 Number of -bonds (bond pairs) at C atom = 4
Number of lone pair of electrons at C atom = 0, Total number of electron pairs = 4
3
Hybridization is sp , i.e., CCl4 is tetrahedral and bond angles are 10928 each.
(d) Ammonia (NH3)

Nitrogen is forming three bonds with three hydrogen atoms.
Outer Electronic Configuration of N = 2s2 2p3
 Outer Electronic Configuration of N (before bonding)
= 2s2 2px1 2py1 2pz1
 Number -bonds (bond pairs) at N atom = 3
Number of lone pair of electrons at N atom = 1, Total number of electron pairs = 3 + 1 = 4

Hybridization is sp3 and geometry of NH3 molecule is tetrahedral, however the shape is trigonal pyramidal
and bond angles are not 10928 but 10645.
(e) Water (H2O)

Oxygen is forming two bonds with two hydrogen atoms.
Outer Electronic Configuration of O = 2s2 2p4
 Outer Electronic Configuration of C (before bonding)
= 2s2 2px2 2py1 2pz1
 Number of -bonds (bond pairs) at O atom = 2
Number of lone pair of electrons at O atom = 2 Total number of electron pairs = 2 + 2 = 4
Hybridization is sp3 and geometry of water molecule is tetrahedral, however the shape is bent and bond
angles are not 10928 but 104.5.
Molcecular Shapes
Note : (a) For Column 2 (Type) : Type AB3L2 means in this molecule central atom (denoted by A) has three
bond pairs (denoted by B3) and two lone pairs (denoted by L2) .
(b) For Column 3 : E = B + L
E : stands for total number of electron pairs present in the outer most shell of the central atom.
B : stands for the number of bond pairs present around the central atom.
L : stands for the number of lone pairs present around the central atom.
Hybridisation and Geometry Type E(B + L) Actual shape Bond Examples

of molecules of molecules Angle
CO2 , HgCl2 ,
AB2 2(2  0) o
180 BeF2 , ZnCl2 ,
MgCl2 , C2 H 2 ,
HCN, BeCl2
ABL 2(1  1) N 2 , CN 

BF3 , AlCl3 ,
AB3 3(3  0) o SO3 , C 2H 4 ,
120
NO3 , CO2  ,
HCHO, C6 H 6
NO 2 , SO 2 ,
AB2 L 3(2  1)  120o
SnCl2
CH 4 ,SiH 4 ,
AB4 4(4  0) 109o 28 ' SO 24  , SnCl4
ClO 4 , BF4 ,
NH 4
NH3 , PCl3 ,
AB3L 4(3  1)  109.5o
PH3 , AsH3 ,
ClO3 , NF3
 109.5o H 2 O, H 2S,
AB2 L2 4(2  2) ~ (90o PbCl2 , OF2 ,
104o ) NH 2 , ClO 2

120o
(equatorial)
AB5 5(5  0) PCl5 , SbCl5
and 90o
(Axial)
 120o
TeCl4 ,SF4 ,
AB4 L 5(4  1) and
XeO 2F2 , IF4
 90o
AB3L2 5(3  2)  90o CIF3 , IF3
AB2 L3 5(2  3) 180o I3 , XeF2
AB6 6(6  0) 90o SF6 , PF6 ,

SnCl6

90o
AB5L 6(5  1) (equatorial) ICl5 , BrF5
and  90o IF5 , XeOF4
(axial)
AB4 L2 6(4  2) 90o XeF4 , ICl4
72o
AB7 7(7  0) (equatorial) IF7
and 90o
(axial)
90o
AB6L 7(6  1) (equatorial) XeF6
o
and 90
(axial)
A summary of possible shapes is given on the next page.


VSEPR and More than six Electron Pairs
It is considerably less easy to draw a distinction between apparently reasonable seven coordinate
geometries.There are several possibilities, including the pentagonal bipyramid and the capped octahedron.
Iodine heptafluoride, I F7, is a good example of a pentagonal bipyramidal geometry. The molecule XeF6 is
an interesting case. As with IF7, application of VSEPR rules suggests seven electron pairs, XeF6 is made up
from six bonding pairs and one lone pair. In fact, the structure of XeF6 is based upon a distorted octahedron,
probably towards a monocapped octahedron.
Illustration - 4 Determine the hybridisation, geometry, number of lone pair, bond pairs in the following
compounds.
SO2, SO3, NH4+, IF4+, ClF3, I3-, PF -6, XeOF4
SOLUTION :
(a) Sulphur dioxide (SO2)  Each Oxygen will form another bond
with the Sulphur atom by sideways
In SO2 molecule sulphur forms bonds with (overlap or  bond).
two oxygen atoms
 Each Oxygen atom forms 1 sigma and
Outer Eletronic Configuration of O = 2s2 2p4 1 pie bond with Sulphur atom.
= 2s2 2px2 2py1 2pz1
 Sulphur atom will make 2 sigma and 2
Now between any two atoms there can only pie bonds with the oxygen atoms.
one sigma (diect) overlap. Outer Eletronic Configuration of S
 Each oxygen atom will form one sigma = 3s2 3p4 = 3s2 3px2 3py1 3pz1
bond with the sulphur atom.
 However, to complete its octet of

electrons each oxygen atom needs 2
more electrons and hence it needs to
form two bonds (or two overlaps).

Since Sulphur will form 2 pie bonds, hence Each Oxygen atom forms 1 sigma and 1 pie
remove two of its outer electrons as they will bond with Sulphur atom.
take part in sideways overlap (to form the pie  Sulphur atom will make 3 sigma and 3
bond). pie bonds with oxygen atoms.
 Outer Electronic Configuration of S Outer Electronic Configuration of S
(with electrons removed) = 3s2 3px2 = 3s2 3p4 = 3s2 3px2 3py1 3pz1
 Outer Electronic Configuration of S Since Sulphur will form 3 pie bonds, hence
(before bonding) = 3s2 3px1 3py1 remove three of its outer electrons as they will
 Now before bonding 3s, 3px and 3py take part in sideways overlap (to form the pie
orbitals hybridize to produce three sp2 bond).
orbitals of same energy and same shape,  Outer Electronic Configuration of S
out of which one orbitals has two (with electrons removed) = 3s2 3px1
electrons and two orbitals are singly
occupied (one electron each) which  Outer Electronic Configuration of S
overlap with p orbitals of incoming (before bonding) = 3s1 3px1 3py1
Oxygen atoms to form two sigma  Now before bonding 3s, 3px and 3py
bonds. orbitals hybridize to produce three sp2
 Number of -bonds (bond pairs) at S orbitals of same energy and same shape,
atom = 2 which are singly occupied (one electron
each) which overlap with p orbitals of
incoming Oxygen atoms to form three
Number of lone pair of electrons at S sigma bonds.
atom = 1
 Number of s-bonds (bond pairs) at S
atom = 3
Total number of electron pairs
=2+1=3 Number of lone pair of electrons at S
atom = 0
Hybridization of sulphur in SO2 is sp2 and
geometry of the molecule is trigonal planar, Total number of eletron pairs = 3+ 0 = 3
however since one of the electron pair, hence Hybridization of sulphur is sp2 and geometry
its actual shape is bent and the O-S-O bond as well as shape of SO3 is trigonal planar.
angle is less than 120o (as lp-bp) repulsion is
more than bp-bp repulsion). of incoming hydrogen atoms to form four sigma
bonds.
(b) Sulphur trioxide (SO3)
In SO3 molecule, sulphur is bonding with three
oxygen atoms.
Outer Electronic Configuration of O
= 2s2 2p4
= 2s2 2px2 2py1 2pz1

(c) Ammonium ion (NH4+) Outer Electronic Configuration of I = 5s2 5p5

In NH4+ ion, nitrogen forms four bonds with Since there is a positive charge on the ion,
four hydrogen atoms. hence remove one electron from I.
Outer Electronic Configuration of N  Outer Electronic Configuration of I (with
electron removed) = 5s2 5p4
= 2s2 2p3
 Electronic Configuration of I (after
Since there is a positive charge on the ion,
excitation of electrons)
hence remove one electron from N.
= 5s2 5px1 5py1 5pz1 5d1
 Outer Electronic Configuration of N
(with electron removed) = 2s2 2p2  Now before bonding 5s, 5px, 5py, 5pz
and 5d orbitals hybridize of produce five
 Outer Electronic Configuration of N
sp3d orbitals of same energy and same
(after excitation of electron)
shape, out of which one orbital has two
= 2s1 2px1 2py1 2pz1
electrons and the other four orbitals are
 Now before bonding 2s, 2px, 2py and singly occupied (one electron each)
2pz orbitals hybridize to produce four which overlap with the p orbitals of
sp3 orbitals of same energy and same incoming fluorine atoms to form four
shape, which are singly occupied (one sigma bonds.
electron each) which overlap with s
 Number of -bonds (bond pairs) at I
orbitals
atom = 4
 Number of -bonds (bond pairs) at N
Number of lone pair of electrons at I
atom = 4
atom = 1
Those number of electron pairs = 5
Number of lone pair of electrons at N
atom = 0. Thus hybridisation of iodine is sp3d and
geometry of IF4+ is trigonal bipyramidal,
Total number of electron pairs = 4
however since one of the electron pairs is a
Hybridization in nitrogen is sp3 and geometry lone pair, hence its actual shape is seesaw.
as well as shape of NH4+ is tetrahedral
(d) IF4+
In IF4+ ion, iodine forms four bonds with four
flourine atoms.

(e) ClF3 (f) I3-
In ClF3 molecule, chlorine forms three bonds In I3- ion, iodine forms two bonds with two
with three flourine atoms. other Iodine atoms.
Outer Electronic configuration of I = 5s2 5p5
Outer Electronic Configuration of Cl
= 3s2 3p5 Since there is a negative charge on the ion,
hence add one electron in I.
 Outer Electronic Configuration of Cl
(before bonding  Outer Electronic Configuration of I (with
= 3s2 3px2 3py1 3pz1 3d1 an electron added) = 5s2 5p6
 Electronic Configuration of I (after
 Now before bonding 5s, 5px, 5py, 5pz
excitation of electrons)
and 5d orbitals hybridize to produce five
sp3d orbitals of same energy and same = 5s2 5px2 5py2 5pz1 5d1
shape, out of which two orbitals has two
 Now before bonding 5s 5px 5py 5pz 5d
electrons and the other three orbitals are
orbitals hybridize to produce five sp3d
singly occupied (one electron each)
orbitals of same energy and same shape,
which oerlap with the p orbitals of
out of which three orbitals have two
incoming fluorine atoms to form three
electrons each and two orbitals are
sigma bonds.
singly occupied which overlap with p
 Number s-bonds (bond pairs) at Cl orbitals of incoming iodine atoms to form
atom = 3 two sigma bonds.
 Number of -bonds (bond pairs) at I
Number of lone pair of electrons at Cl
atom = 2
atom = 2
Number of lone pair of electrons at I
Total number of electron pairs atom = 3
=3+2=5
Total number of electron pairs = 5
Hybridization of chlorine is sp3d and geometry
Thus hybridization of iodine is sp3d and
of ClF3 molecule trigonal bipyramidal,
geometry of I3- ion is trigonal bipyramidal,
however it actually is a T-shaped molecule
however its actual shape is a linear because of
becuase of the presence of two lone pairs of
the presence of three lone pair of electrons.
electrons.

(g) PF6- The Oxygen atom forms 1 sigma and 1 pie

bond with Xenon atom and the four fluorine
In this ion phosphorous forms six bonds with
atoms form 1 sigma bond each with the xenon
six flourine atoms.
atom.
Outer Electronic Configuration of P = 3s2 3p3
 Xenon atom forms 5 sigma bonds and
Since there is a negative charge on the ion,
1 pie bond.
hence add one electron in P.
Since Xenon will form 1 pie bond, hence
 Outer Electronic Configuration of P
remove one of its outer electrons as they will
(with an electron added) = 3s2 3p4
take part in sideways overlap (to form the pie
 Outer Electronic Configuration of P bond).
(after excitation of electrons)
 Outer Electronic Configuration of Xe
= 3s1 3px1 3py1 3pz1 3dxy1 3dyz1 (with an electron removed)
 Now before bonding 3s, 3px, 3py, 3pz, = 5s2 5px2 5py2 5pz1
3dxy and 3dyz orbitals hybridize to
 Outer Electronic Configuration of Xe
produce six sp3d2 orbitals of same
(before bonding)
energy and same shape, having one
= 5s2 5px1 5py1 5pz1 5dxy1 5dyz1
 Number of -bonds (bond pairs) at P
atom = 6  Now before bonding 5s, 5px, 5py, 5pz,
5dxy and 5dyz orbitals hybridize to
Number of lone pair of electrons at P
produce six sp3d2 orbitals of same
atom = 0
energy and same shape, out of which
Total number of electron pairs = 6 one orbital has two electrons and 5
orbitals are singly occupied which
Thus hybridisation of PF6- is sp3d2 and
overlap with p orbitals of incoming
geometry as well as shape is a Octahedral.
oxygen and fluorine atoms to form five
sigma bonds.
 Number of -bonds (bond pairs) at Xe
atom = 5
Number of lone pair of electrons at Xe
atom = 1
Total number of electron pairs
(h) XeOF4 =5+1=6
In this molecule xenon forms bonds with one Thus hybridisation of Xenon in XeOF4 is sp3d2
oxygen and four fluorine atoms. and geometry is octaheral, however its actual
shape is square pyramidal as one of the
Outer Electronic Configuration of Xe electron pairs is a lone pair.
= 5s2 5p6
= 5s2 5px2 5py2 5pz2

Illustration - 5 Match the column.

Column 1 Column 2
(A) ClO2F3 (P) Central atom is sp3d hybridised.
(B) ClOF3 (Q) All fluorine atoms lie in the same plane
(C) XeO2F2 (R) All fluorine atoms does not lie in same plane
(D) XeO3F2 (S) All oxygen atoms lie in equatorial plane.
(T) All lone pair of central atom lie in equatorial plane.
SOLUTION:
(A) : PQS (B) : PRST (C) : PRST (D) : PQS
Structures of Mulitcentre Polyatomic Species :

Remember : For oxy-anions, negative charge is carried by ox ygen.
1. S2 O 32  ; 2. S2 O 52  ;
3. S2 O 62  ; 4. S2 O 72  ;

5. S4O62  ; 6. S2O82  ;
7. P2O5 ; 8. N 2O5 ;
9. N 2O3 ; 10. N 2O ;
11. P4 O6 ; 12. P4O10 ;
13. N 2O 4 ; 14. NO 2 ;
15. S2 O 42  ; 16. H 2O 2 ;
Sectionfor3 IITJEE with Online Support

Self Study Course Section 3 19
17. Berylium Chloride

(a) In vapour state (at very high temperature T > 1200 K) Cl-Be-Cl
(b) In vapour state (at lower temperature T < 1200 K)
(c) In solid state
18. Diborane
Note : Diborane is a dimer of borane BH3 and it shows 3c-2e bond (banana bond) a multicentre
bond.
19. Inorganic Benzene: = =
20. P4S3 : 21. Sulphur (S8) :

22. Carbon suboxide (C3O2) : O=C=C=C=O 23. Hydrazoic acid(HN3) : H  N  N  N
24. Phosphorus (P4) :

Illustration - 6 IF5 in liquid state can conduct electricity because it dissociate to form cation and anion
according to the following reaction, 2IF5  IF4  IF6 . Draw the structure and determine hybridisation of
all the species.
SOLUTION :
Species N/ 2 Value No. of l  p Shape Structure
12
IF5 6 1 Sq. pyramidal
2
10
IF4+ 5 1 See-saw shaped
2
14
IF6- 7 1 Capped octahedron
2
Illustration - 7
I2Cl6 is a yellow solid. In liquid state, it dissociated to form ions, the cation has sp3
hybridisation and anion has sp3d2 hybridization and anion has sp3d2 hybridization. Find the exact structure of
cation and anion, if 1 molecule of I2Cl6 dissociate to form 1 cation and 1 anion having unit charge each.
SOLUTION :
I 2 Cl6  ICln+ + ICl 6 n
N 7  n 1 6  n
ICl+n : 4 
2 2 2
8 = 6+ n, n = 2
 Cation is ICl2+ and anion is ICl4-.

Illustration - 8 PCl5 is covalent in gaseous state but ionic in liquid and solid state. Find the actual structure
of covalent PCl5, cationic form and anionic part in liquid or solid state.
SOLUTION :
PCl5  PCl 4  PCl6
Species N/2 Value No. of l  p Shape Structure
10
PCl5 5 0 Trigonal bipyramidal
2
8
PCl4+ 4 0 Tetrahedral
2
12
PCl6- 6 0 Octahedral
2
Illustration - 9
PBr5 exist in solid state as PBr4+ and Br . Find the hybridisation of PBr4+. PI5 exist in the
same manner as that of PBr5 as PI4+ and I. Draw the structure of PI4+.
SOLUTION :
N 5  4 1 8 N 5  4 1 8
PBr4+ :   4 PI +4 :   4
2 2 2 2 2 2
sp3 hybridization, tetrahedral shape. sp3 hybridisation, tetrahedral shape.

Illustration - 10 Discuss the hybridization of carbon atoms in allene (C3H4) and show the p-orbital overlaps.
SOLUTION :
I II III
Allene is CH 2  C  C H 2 carbon atoms I and III are in sp2 hybridized state while carbon II is in sp
hybridized state. Two unhybridized orbitals of carbon II overlap sidewise to form -bonds besides it also
forms a sigma bond with each of the carbon atoms using hybridized orbitals. Two hybridized orbitals of each
of carbon I and III form sigma bonds with hydrogen atoms.
Effect of Electronegativity
NF3 and NH3 both have structures based on tetrahedron with one corner occupied by a lone pair. The high
electronegativity of F pulls the bonding electronics further away from N than in NH3. Thus, repulsion
between bond pairs is less in NF3 than NH3. Hence, the lone pair in NF3 causes a greater distortion from
tetrahedral and gives F  N  F bond angles of 102 30 compared with 10748 in NH3. The same effect
is found in H2O (bond angle 104 27) and F2O (bond angle 102) and also in H2O (bond angle 104 27’)
and H2S (bond angle 90).
Isoelectronic Principle
Isoelectronic species usually have the same structure. This may be extended to species with the same
number of valence electrons (on the central atom).
Species Structures
CH 4 , NH 4 , BF4 Tetrahedral
CO 32  , NO3 , SO3 Planar Triangle
CO 2 , N 3 , NO 2 Linear

Illustration - 11 One member of each of the following sets of compounds is not iso-electronic with the
others. Which one in each set is the odd one out?
(a) NO 2 , CO 2 NO 2 and N 3 (b) CN - , N 2 , CO, NO + and O 22 
(c) SiF62  , PF6 , AlF63  and BrF6

SOLUTION :
(a) NO +2 , CO and N 3 are isoelectronic and have same structure that is linear while NO 2 is angular
(b) CN  , N 2 , CO and NO  are isoelectronic, all have 14 electrons.
(c) SiF62  , PF6 , AlF63 are iso-electronic and have octahedral geometry. BrF6 has pentagonal bipyramidal
geometry.
Illustration - 12
According to valence bond theory which one of the following isoelectronic species shows
resonance.
N 2 , CO, [CN] , [NO]
SOLUTION :
CO, [CN]- and [NO]+ shows resonance and N2 does not show resonance.
; ;
MOLECULAR ORBITAL THEORY Section - 4
Molecular Orbital Theory for the Formation of Covalent Bond

1. This theory suggest that when two atoms come close towards each other, then the atomic orbitals of
each atom overlaps with each other to form new bigger orbitals known as Molecular Orbitals (MO).
2. When atomic orbitals overlap then two MOs are produced.
(a) Bonding Molecular Orbital (BMO)
(b) Anti-bonding Molecular Orbital (ABMO)

3. Bonding molecular orbital has less energy than separate atomic orbital.
4. Anti-bonding molecular orbital has higher energy than separate atomic orbital.
5. These new MOs are spread over the atomic nuclei of both the atoms, consequently, the electrons
present in the MOs are attracted by both the nuclei.
Linear Combination of Atomic Orbitals (LCAO)

According to the principle of Linear Combination of Atomic Orbitals (LCAO), bonding MO is formed by
addition of wave functions (constructive interference) of the electron waves of atomic orbitals while anti-
bonding MO is formed by substraction of the wave functions of the atomic orbitals (destructive interference).
Illustration - 3
Note :  MO is an in-phase (bonding) interaction whereas *MO is an out of phase (anti-bonding) interaction.
Further out of phase interaction results in a nodal plane in the MOs.
1. Only AO’s of comparable energies and proper orientations combine to form MO’s. For example, 1s
can combine with 1s and not with 2s. Similarly, if z is the molecular axis pz can combine with pz but
not with px or py to form -molecular orbitals.
2. The bonding MO’s are represented as  and  while the corresponding anti-bonding MO’s are
represented as *, and *. Of the 2p orbitals, if z is the molecular axis, two pz orbitals form 
bond, i.e.  (2pz) while 2px and 2py orbitals form - bonds, i.e.,  (2px),  (2py), * (2px) and
* (2py).
3. The shapes of MO’s formed depend upon the type of the combining AO’s.

Atomic Orbital Interaction diagrams :
4. The filling of the MO’s occurs according to the same principle as applicable to filling of AO’s i.e.,
Aufbau principle (MO’s are filled in order of their increasing energies), Pauli’s exclusion principle (a
MO can have a maximum of two electrons and these must have opposite spins) and Hund’s rule of
maximum multiplicity (pairing of electrons in degenerate MO’s does not take place until each one of
the them has one electron with the same spin).

5. Molecular Orbital Diagram :
For atoms with atomic number greater than 7 e.g., For atoms with atomic number less than or equal to
O2 , F2 or For species with total number of 7 e.g., H2 , C2 , N2 or For species with total number
electrons greater than 14 e.g., NO of electrons less than 14 e.g., B 2 C 2 ,CN
Atomic Molecular Atomic Atomic Molecular Atomic

orbitals orbitals orbitals orbitals orbitals orbitals
Note : The ordering of the MOs in B2, C2 and N2 is different from that in F2 and O2 because of orbital mixing.
6. Magnetic Character :
If all the electrons in a molecule are paired, the compound is diamagnetic; while when the molecule
has one or more electrons unpaired, it will be paramagnetic.
7. The stability of the molecule formed or the strength of bonds between the bonding atoms is determined
by bond order.
N - Na
Bond order = b
2

Nb : Number of electrons in bonding molecular orbitals.

Na : Number of electrons in anti-bonding molecular orbitas.
 Greater the bond order, greater is the stability of the molecule.

 A bond order of +1 indicates that the specie is stable and that the two atoms in a molecule are held
together by a single bond. A bond order of +2 indicates that the specie is stable and that the two
atoms are united together with a double bond. A bond order of +3 indicates that the specie is stable
and that the two atoms are held together by a triple bond.
 Bond order may be fractional and even zero.
 A zero bond order indicates the equal number of bonding and anti-bonding electrons.
 When bond order is less than zero, the species does not exist.
 A bond order of + 1/2 indicates that the species exists but is unstable, e.g. H2+ and He2+.
 The bond order of a molecule is directly proportional to its bond dissociation energy and inversely
proportional to its bond length. For example,
Molecule Bond order Bond length Bond diss. Energy (kJ mol–1)
Li2 (Li  Li) 1 267 pm 110
B2 (B  B) 1 159 pm 297
F2 (F  F) 1 142 pm 158
C2 (C  C) 2 124 pm 607
O2 (O = O) 2 121 pm 498
N2 (N  N) 3 110 pm 945
 
CO ( C  O ) 3 113 pm 1076
Note : We cannot exactly correlate particular values of the bond dissociation enthalpy and distance with a given
bond order. Factors such as inter-nuclear and inter-electron repulsion play an important part in determining
the observed values of these parameters.

Structures of some Homonuclear Diatomic Molecules

(i) Hydrogen molecule (H2) :
Total number of electrons in 2H atoms = 1 + 1 = 2
Electronic configuration of H 2 molecule =  1s2
1 1
Bond order =  N b  Na    2  0   1
2 2
(ii) Hydrogen molecule ion, H2+ :
Number of electrons in H2   2  1  1
Electronic configuration =  1s1
1 1
 Bond order 1  0  
2 2
1
Since the bond order is , H 2 ion can exist but it is unstable. Further as it has 1 unpaired electron,it
2
is paramagnetic.
(iii) B2 : B2 is found only in the gas phase ; solid boron is found in several very hard forms with complex
bonding, primarily involving B12 icosahedra [Structure of B12 icosahedron is described in chapter p-
Block Elements - I.
B2 is paramagnetic. The Lewis dot model cannot account for the paramagnetic behaviour of this
molecule. The electronic configuration of boron atom shows that it has 5 electrons, hence the molecular
orbitals of B2 molecule have 10 electrons which are distributed in the following manner.
KK*, (2s)2 (*2s)2 (2px)1 (2py)1
Note : K indicates first bonding MO and K* antibonding MO, thus KK* is same as 1s2 *1s2 .
Thus molecular orbital of B2 has 6 electrons in bonding and 4 electrons in anti-bonding molecular
orbitals. Thus the bond order of B2 molecule is calculated as below:
1
Bond order  [Number of bonding electrons] - [ Number of anti-bonding electrons]
2
1 1
 [6  4]   2  1
2 2

The highest energy occupied molecular orbital (HOMOs) of B2 is 2 P x and 2 Py .
Note : B2 is a good example of the energy level shift cause by the mixing of s and p orbitals. In the absence of
mixing the 2 Pz orbital is expected to be lower in energy than the 2Px and 2Py orbitals and the resulting
molecule would be diamagnetic. However, mixing of orbitals lowers the energy of the 2s orbital and
increases the energy of the 2 Pz orbitals to a higher level than the 2 Px and 2 Py orbitals, giving the order
of energies shown in molecular orbital diagram. The lowest energy unoccupied molecular orbital (LUMOs)
of B2 molecule is 2 Pz .
(iv) C2 : C2 is found only in the gas phase. It is not a commonly encountered chemical species (carbon is
more stable as diamond, graphite and the fullerenes described in chapter p-block-I).
The electronic configuration of carbon atom shows that it has 6 electrons, hence the molecular orbitals,
hence the molecular orbitals of C2 molecule have 12 electrons which are distributed in the following
manner.
KK*, (2s)2, (*2s)2, (2Px)2 (2Py)2
Thus molecular orbitals of C2 has 8 electrons in bonding and 4 electrons in anti-bonding molecular
orbitals. The bond order of C2 molecule is calculated as below:
1
Bond order = [Number of bonding electrons]-[Number of anti-bonding electrons]
2
1 1
= [8 - 4] =  4  2
2 2
The simple MO picture of C2 predicts a double bonded molecule with all electrons paired, but with
both highest occupied molecular orbitals (HOMOs) having  symmetry. It is unusual because it has
two  bonds and no -bond.
Note : The acetylide ion, C 22  , is well known, particularly in compounds with alkali metals (Na2C2), alkaline earth
metal (CaC2), and lanthanides. According to the molecular orbitals model C 22  should have a bond order of
3. This is supported by the similar C-C distances in acetylene (C2H2) and calcium carbide (CaC2).
C-C bond distance (pm)
HC  CH 120.5
Ca 2  C  C 119.1

(v) Nitrogen (N2) :

The electronic configuration of nitrogen atom shows that it has 7 electrons, hence the molecular
orbitals of nitrogen molecule have 14 electrons which are distributed in the following manner :
K K * , ( 2s)2 (*2s)2 (2px)2 (2py)2 (2pz)2
Thus the molecular orbital of nitrogen has 10 bonding and 4 electrons in anti-bonding orbitals. Thus
the bond order or the number of bonds in nitrogen molecule may be calculated as below :
1
Bond order = [Number of bonding electron – Number of anti-bonding electrons]
2
1 1
 [10  4]   6  3
2 2
(vi) Oxygen (O2) :
Oxygen (Z = 8) has the electronic configuration 1s2 2s2 2p4, so 12 electrons are to be filled in the
molecular orbitals of oxygen (leaving aside the electrons of the K shell). These 12 electrons are filled
in the following manner :
KK*, (2s)2 (*2s)2 (2pz)2 (2px)2 (2py)2 (2px)1 (2py)1
Note that the 11th and 12th electrons in the molecular orbital of oxygen go to 2px and 2py
orbital (Hund’s rule) ; it is because of the fact that these two anti-bonding orbitals are of equal
energy. Since now there are two unpaired electrons, the oxygen molecule is paramagnetic.
1
Bond order = [Number of bonding electron – Number of anti-bonding electrons]
2
1
 [10  6 ]  2
2
Hence, the two oxygen atoms in oxygen molecule are linked by a double bond.
(v) Molecular orbital configuration of O2+ :

Number of electrons in O2+ = 16 – 1 = 15
MO configuration : KK*, (2s)2 (*2s)2 (2pz)2 (2px)2 (2py)2 (*2px)1 (*2py)0
1 1
Bond order = [10  5]  2
2 2
1
Bond order of 2 indicates that O 2 is more stable than O2. As O 2 has 1 unpaired electrons, it is
2
paramagnetic.

Note : The addition of one or more electrons corresponds to reduction and the removal of one or more electrons
is oxidation. The addition of electrons will follow the aufbau principle ; the removal of electrons follows the
same rules but in reverse.
MO Electronic Configuration of Diatomic Species having upto 14 electrons :
Paramagnetic(P)
Electronic Configuration
Diamagnetic (D)
Molecule Total No.
or ion of
Electron 1s *1s 2s *2s  2px  2py 2p z NB NA Bond
order
H2 2 2 2 0 1.0 D
H2+ 1 1 1 0 0.5 P
He2 4 2 2 2 2 0.0 D
He2+ 3 2 1 2 1 0.5 P
Li2 6 2 2 2 4 2 1.0 D
Be2 8 2 2 2 2 4 4 0.0 D
B2 10 2 2 2 2 1 1 6 4 1.0 P
C2 12 2 2 2 2 2 2 8 4 2.0 D
N2 14 2 2 2 2 2 2 2 10 4 3.0 D
O22+ 14 same as N2 10 4 3.0 D
N2+ 13 2 2 2 2 2 2 1 9 4 2.5 P
CN- 14 same as N2 10 4 3.0 D
32 Section 4 Self Study Course for IITJEESection 4

with Online Support
MO Electrionic Configuration of Diatomic Species having more than 14 electrons :
Paramagnetic(P)
Electronic Configuration
Diamagnetic (D)
Molecule of ion
Total No. of
Electrons
 1s *1s  2s *2s  2pz 2px 2py  2px 2py 2pz NB NA Bond
order
O2 16 2 2 2 2 2 2 2 1 1 10 6 2.0 P
O2+ 15 2 2 2 2 2 2 2 1 10 5 2.5 P
NO 15 2 2 2 2 2 2 2 1 10 5 2.5 P
O2- 17 2 2 2 2 2 2 2 2 1 10 7 1.5 P
O22- 18 2 2 2 2 2 2 2 2 2 10 8 1.0 D
F2 18 2 2 2 2 2 2 2 2 2 10 8 1.0 D
Ne2 20 2 2 2 2 2 2 2 2 2 2 10 10 0.0 D
Note : O2 superoxide ion , O22  : peroxide ion [Rmember as a fact : Bond order of CO+ is 3.5]
Illustration - 13 Which of the two peroxide ion or superoxide ion has larger bond length ?
SOLUTION :
The bond length in a molecule is dependent on Superoxide ion, O 2
bond order. The higher is the bond order,
smaller will be the bond length.
O 2 : KK*( 2s)2 ( 2s)2 ( 2pz)2 ( 2px)2
Peroxide ion, O 22  (2py)2 (2px)2 ( 2py)1
10  7
O 22  : KK*(2s)2 ( 2s)2 ( 2pz)2 Bond order = 1.5
2
(2px)2 (2py)2 ( 2px)2 ( 2py)2
Bond order of superoxide ion is higher than
10  8 peroxide ion, hence bond length of peroxide
Bond order = 1
2 ion is larger.

Illustration - 14 (a) How bond energy varies form N 2 to N 2 and why ?

(b) On the basis of molecular orbital theory what is similarity between
(i) F2 and O22– (ii) CO, N2, NO+ ?
SOLUTION :
(a) Bond energy of N2+ = Bond energy of N2– (b) (i) Both F2 and O 22  have same bond order same
because bond order is same in both the species.
bond length and are diamagnetic.
[However, N2+ is slightly more stable than N2–
as antibonding electrons number is higher in (ii) These are isoelectronic species, possess same
N2– than in N2+.] bond order and same bond length.
Illustration - 15 Arrange the following compounds in the increasing order of bond length of O – O bond O ,
2
O2 [AsF6], KO2 and peroxide ion. Explain on the basis of ground state electronic configuration of dioxygen in
these molecules.
SOLUTION :
O2[AsF6] has O 2 ion while KO2 has O 2 ion (superoxide ion) and peroxide is O2–.
E.C. of O2 = KK * (2s)2  *(2s)2 (2p z )2 (2p x )2 (2p y )2  *(2p x )1  *(2p y )1
E.C. of O 2 = KK * (2s)2  *(2s)2 (2p z ) 2 (2p x )2 (2p y )2  *(2p x )1
E.C. of O2  KK * (2s)2  *(2s)2 (2pz )2 (2p x )2 (2p y )2  *(2p x )2  *(2p y )1
E.C. of O22   KK * (2s)2  *(2s) 2 (2p z )2 (2p x )2 (2p y )2  *(2p x )2  *(2p y )2

B.O. of O2 = 1/2 (10 – 6) = 2
B.O. of O 2 = 1/2 (10 – 5) = 2.5
B.O. of O 2 = 1/2 (10 – 7) = 1.5
B.O. of O 22  = 1/2 (10 – 8) = 1

Higher is the B.O., smaller is the bond length. Hence, order of O – O bond length is
O 2 > O2 > O 2 > O 22  i.e.,
1
O2[AsF6] > O2 > KO2 > O 22  Note : bond strength 
bond length

CONCEPT OF HYDROGEN BONDING Section - 5
Molecules that contain FH, OH, NH bonds (e.g., Water, Alcohols, Organic acids, Amines, Aromatic
alcohols, etc.) show a strong tendency to associate, i.e., to link up to form larger molecules. This feature
exists in solid form and as well as in solutions in certain solvents. In all of such compounds, OH, or NH
or FH, bond is highly polar due to large difference in electronegativity. The electrostatic attraction be-
tween such molecules should be quite strong. The positive end of one molecule attracts and is strongly
attracted by the negative end of the neighbouring molecule. In this manner a large number of molecules are
associated to form a cluster of molecules. Since in each case the hydrogen atom is responsible for the
formation of linkages, this is known as Hydrogen bond or Hbond. It is impossible for hydrogen to form a
second covalent bond so the additional linkage is shown by a dotted line. Hydrogen bonds are always of
type : AH....B, where A and B may be atoms of O, F, N. Hydrogen bonds are comparatively weak,
with bond energies of 1030 KJ/mol, but they are widespread and have important effect on many physical
properties of many Organic and Inorganic compounds.
     
H  F .......... H  F R O .......... H  O
| |
H R
Types of H-Bonding :
Intermolecular H-Bonding :
This type of H-bonding takes place between H and electronegative element present in the different mol-
ecules of the same substance (as in between H2O and H2O) or different substances (as in between H2O and
NH3).
       
(a) In water molecules : H  O --- -H
|
 O --- -H
|
|
O --- - H  O
|
Due to polar nature of H2O, there is association of
H  H  H  H 
water molecules giving a liquid state of abnormally
high b.p.
If we actually observe, one water molecule is joined
to four water molecules, two with H-atoms and
other twowith O-atom. Thus coordination number
of water molecules in water is four as shown in
figure :

Note : Although many compounds can form intermolecular hydrogen bonds, the difference between H2O and
other polar molecules, such as NH3 and HF, is that each oxygen atom can form two hydrogen bonds, the
same as the number of lone electron pairs on the oxygen atom. Thus, water molecules are joined together
in an extensive three-dimensional network in which each oxygen atom is approximately tetrahedrally
boded to four hydrogen atoms, two by covalent bonds and two by hydrogen bonds. This equality in the
number of hydrogen atoms and lone pairs is not characteristic of NH3 or HF or, for that matter, of any
other molecule capable of forming hydrogen bonds. Consequently, these other molecules can form rings
or chains, but not three-dimensional structure.
When ice is formed from liquid water, some air gap is formed (in tetrahedral packing of water molecules).
Due to this volume of ice is greater than liquid water and thus ice is lighter than water. We can say that
density decreases when ice is formed. Reversely when ice melts, density increases but only upto 4C,
after this intermolecular H-bonding between water molecules breaks hence volume increases and hence
density increases. Thus water has maximum density at 4C.
(b) In hydrofluoric acid (HF), there is again association by H-bonding.
However in the gaseous state, several polymeric forms of the HF molecules exist in which the monomers are
held together through H-bonding to form a pentagonal arrangement.
(c) There is also similar H-bonding in alcohol (R  OH) ammonia (NH3) and phenol (C6H5OH) molecules.
(d) Carboxylic acid dimerizes is gaseous state due to H-bonding.
(e) Alcohol is said to be highly soluble in water due to crossed intermolecular H-bonding (between H2O
and R – OH molecules).

However isomeric ether is less soluble in water due to ether’s non-polar (or weakly polar) nature.
(f) Though the hydrogen atoms in a methyl groups are not polarized, if an electronegative group like
chloro, carbonyl, nitro or cyano is attached to it, the C  H bond gets polarised due to the inductive
effect and the hydrogen atom becomes slightly acidic resulting in the formation of weak hydrogen
bonds.
Consequences of the Intermolecular Hydrogen bonding :
(a) Due to H-bonding boiling points of water, ammonia, hydrofluoric acid are abnormally high shown in figure.
(b) Solubility of the organic compounds in water is due to H-bond formation.
(c) Due to hydrogen-bonding, viscosity () of the liquid increases as given below in centipoises (CP).

Intramolecular H-bonding :
This type of H-bonding occurs when polar H and electronegative atom are present in the same molecule.
The necessary conditions for the formation of intramolecular hydrogen bonding are :
(a) The ring formed as a result of hydrogen bonding should be planar.
(b) A five or six membered ring should be formed.
(c) Interacting atoms should be placed in such a way that there is minimum strain during the ring closure.
In case of anti-form of pyridine-2-carboxaldoxime there is intramolecular hydrogen bonding but it is not shown in
syn-form.
In this type of Hbonding, the bonding occurs within two atoms of same molecule. Such type of bonding generally
occurs in aromatic organic compounds. It is also known as Chelation.
Consequences of the Intramolecular Hydrogen bonding :

Presence of Intramolecular H-bonding decreases the boiling points as well as there solubility in water.
(a) Hydrogen bonding between two atoms of the same molecule (intramolecular H-bonding) leads to unavailability
of these atoms to bond with atoms of other molecule. In other words intra-molecular H-bonding between
atoms of same molecule, makes them unavailable for inter-molecular H-bonding and hence compounds
showing such type of bonding tends to show lower boiling points. For example, o-chlorophenol, o-nitrophenol
and other o-derivatives (isomers) of hydroxy, carbonyl and acids show low boiling as well as melting points
as compared to their m-or p- derivatives (which exhibit intermolecular H-bonding).
(b) The solubility of all such compounds also decreases for the same reason i.e., bonding between atoms of
same molecules or chelation, does not allow these molecules to form inter-molecular bonds. For example in

o-Nitrophenol, O-H group is busy making intramolecular H-bond with O atom of the NO2- group and
becomes unavailable for intermolecular H-bonding and hence it is very less soluble in water.
Illustration - 16 Why H2O is liquid while H2S is a gas at ordinary temperature ?

SOLUTION :
Oxygen has high electronegativity than sulphur. As a result, H2O forms hydrogen bonding. Consequently,
molecules of water come nearer to each other through hydrogen bonding. This result is higher boiling point
of water and hence it is a liquid.
Illustration - 17 The density of ice is less than that of water or ice floats over water. Explain.
SOLUTION :
In ice, water molecule is associated with four other molecules through hydrogen bonding in a tetrahedral
manner, i.e., it has open-cage like structure in which lesser molecules are paked per unit volume. When ice
melts, the molecules come closer to one another. Consequently the density of water in liquid state is more
than solid state. Thus, ice floats over water.
Illustration - 18 The boiling point of H2O is more than the boiling point of HF although fluorine is more
electronegative than oxygen and form stronger H-bond.
SOLUTION :
The strength of a hydrogen bond is determined by the coulombic interaction between the lone-pair
electrons of the electronegative atom and the hydrogen nucleus. Fluorine is more electronegative
than oxygen, and so we would expect a stronger hydrogen bond to exist in liquid HF than in H2O. But
boiling point of HF is lower than that of water because each H2O takes part in four intermolecular
hydrogen bonds. Therefore, the forces holding the molecules together are stronger in H2O than in HF.

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes States of Matter
States of Matter
Gases, Liquids and Solids
ANALYSIS OF IDEAL GASES Section - 1

In this section, we are going to study laws governing the behavior of gases. Gases don’t have definite shape
and volume. They tend to fill all the space available to them and take on the shape and volume of the
container. In gases, the molecules are relatively far apart and thus influence each other to a lesser extent
(than they do so in solids and liquids).
Three fundamental measurements that we can perform on any sample of a gas are :
Volume, Pressure and Temperature
Volume :
The volume of any sample of a gas is considered to be the space of the container that it occupies (the space
occupied by the molecules of gas is negligible as compared to the volume of container). The volume is
expressed in liters (or ml) or m3 (or cm3).
1 L  103 ml  103 m3  1 dm3  103 cc
Pressure :
The molecules of gases are in continuous random motion. They frequently collide with each other and with
the walls of the container. The collisions of the molecules with the walls of the container give rise to what is
called as the Pressure. It is measured as force per unit area and is uniform in all the directions. It is measured
by instruments: Manometer and Barometer (for atmospheric pressure). It is expressed in N/m2 or mm of
Hg or atmospheres (atm) or torr.
1 atm  1.013  105 N / m 2  1.013  105 Pa 1Pa  1N / m2 

1 bar = 105 N/m2
1 atm = 760 mm of Hg column = 76 cm of Hg column = 760 torr = 1.013 bar
Temperature :
The temperature can be discussed in terms of hotness or coldness. The measurement is based on the
expansion of certain material (most often it is mercury) with increasing temperature.
One of the scale to measure the temperature is taken as Celsius (C) scale. The freezing point of water is
taken as 0 C and its boiling point as 100 C.
It was observed by Gay Lussac that the rise in volume of a given mass of gas for each degree rise in
temperature is nearly equal to 1/273 time of the volume of gas at 0 C. If Vo is the volume of gas at 0 C and
VT is the volume of gas at T C, then :
 T 
VT  V  1  
 273 

States of Matter Vidyamandir Classes
Thus, VT = 0 if T =  273 C i.e., the volume of a given mass of a gas is zero at constant pressure or we can
say that the gas would completely disappear if T =  273 C.
So T = 273 C (or more precisely 273.15 C) is the lowest possible temperature that can be achieved
(since below  273 C, the volume will be negative, which is impossible). This temperature  273.15 C
is called as absolute zero. Now a new scale called as absolute scale or Kelvin scale is defined where
273 C = 0 K (Kelvin).
Note : 0 K = 273 C or 273 K = 0 C or 373 K = 100 C
 9 
Also, T ( F)  32   T ( C) [F Fahrenheit]
5
Standard Temperature and Pressure conditions (S.T.P.) :
For gases, the S.T.P. conditions are 273 K (0 C) and 1 atm pressure. A gas at this temperature is said
to be at S.T.P. (or N.T.P.  Normal Temperature and Pressure) conditions.
Definition of Ideal Gas :

A gas is said to be an ideal gas if it has the following properties :
(a) There is no intermolecular forces between the gas molecules, i.e., gas molecules don’t exert any kind
of force on each other.
(b) Size of the gas molecules is negligible as compared to the volume occupied by the gas (i.e., container
volume).
Note : The concept of Ideal gas is theoretical and no gas exists which satisfy the above requirements at all the
conditions. Thus, all the gases are Real gases but they may behave as ideal under certain conditions of
Pressure, Volume and Temperature.
Gas Laws (For Ideal gases only) :

Boyle’s Law :
At a constant temperature (T), the pressure (P) of a given mass
(or moles (n)) of any gas varies inversely with the volume (V).
1
Mathematically : P  (for given n and T)
V
 PV = constant
If P1 is the pressure when volume is V1 and P2 is the pressure when volume is V2 (T is same), then :
P1 V1 = P2 V2
Graphically, it can be represented as shown in the figure. Each line is called as Isotherm.
Note : In the P-V curve, as we move away from origin, each isotherm represents a higher temperature.

Boyle’s law can also be represented using following graphs :
Charles Law :
At a constant pressure, the volume of a given mass of any gas varies
directly with the absolute temperature.
Mathematically : V  T (for a given n and P)
V
 = constant
T
If V1 and V2 are volumes of a gas at temperature T1 and T2 respectively and the pressure is kept constant,
then :
V1 V2
 
T1 T2
Graphically it is expressed as shown in the figure.

Each line is called as Isobar.
Note : In the V-T curve, an isobar with lesser slope will have a higher pressure.
The Combined Gas Law :

For any sample of an ideal gas, the pressure times the volume divided by the absolute temperature is a
constant.
PV
Mathematically : = constant
T
If at one condition, for a given mass of a gas P1, V1 and T1 are pressure, volume and temperature
respectively and at some other condition P2, V2 and T2 are new pressure, volume and temperature
respectively then :
P1V1 P2V2

T1 T2

Gay Lussac’s Law :

The pressure of a given mass of any gas is directly proportional to
the absolute temperature at constant volume.
Mathematically : P  T (for constant n and V)
P
 = constant
T
If P1 and P2 are volumes of a gas at temperature T1 and T2 respectively
and the volume is kept constant, then :
P1 P2
 
T1 T2
Graphically it is expressed as follows. Each line is called as Isochor.
Note that slope is greater for lower volume.
Note : In the P-T curve, an isochor with lesser slope will have a higher volume.
Gay Lussac’s Law of Combining Volumes :

When measured at same temperature and pressure, the ratios of volumes of the gases that were reactants
and of gases that were products (in a chemical reaction), were always small whole numbers.
Illustration :
(a) 2 H2 (g) + O2 (g)  2 H2O (g)
2 volumes 1 volume 2 volumes (ratio = 2 : 1 : 2)
(b) N2 (g) + O2 (g)  2 NO (g)
1 volume 1 volume 2 volumes (ratio = 1 : 1 : 2)
(c) CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O (g)
1 volume 2 volume 1 volume 2 volume (ratio = 1 : 2 : 1 : 2)
Avogadro’s Law :
It states that equal volume of all gases at same pressure and temperature contain equal number of molecules.
We know that 1 mole contains 6.023 × 1023 molecules (a number called as Avogadro Number). It is
obvious that if two gases contain equal number of molecules, they must also contain the same number of
moles. So, at given temperature and pressure, the volume of any gas is also proportional to the number of
moles.
 V  n (at given T and P) This is also a form of Avogadro’s Law.

At any given temperature and pressure, there must be some volume that will contain 6.023 × 1023 molecules
or 1 mole of a gas. At S.T.P. (0C and 1 atm), this volume is 22.4 L or 22400 mL. This is known as Molar
volume.
Avogadro’s Law can be used in determination of molecular masses of gases. As 1 mole of any gas at S.T.P.
occupies 22.4 L, we can calculate the molecular weight of a gas as follows :
If Mo be the molecular weight of a gas A weighing gA grams and occupying V L of volume at S.T.P., then :
g A  22.4
M 
VL  at S.T.P.
Also, Mo = (density in g/L)  22.4
The Ideal Gas Equation :

PV
We know that = constant = K
T
The constant K depends upon the amount of gas. Now at constant P and T, V depends upon number of
moles of gas (Avogadro Law). This implies that K is directly proportional to the number of moles (n).
 K n  K = nR R : a constant independent of amount of gas.
PV
  K  nR  PV = nRT
T
This is called as ideal gas equation. R is same for all gases and is known as universal gas constant.
Values of R :
PV
Note : R 
nT
L atm
(i) R = 0.0821 mol.K (use this value when P is in atm. and V is in L)
J
(ii) R = 8.31 (use this value when P is in N/m2 and V is in m3) [This is the S.I. unit of R]
mol.K
cal
(iii) R = 2 (4.184 J = 1 cal)
mol.K
Different forms of Ideal Gas Equation :

(i) PV=nRT
g
(ii) PV  RT
M
(iii) PM0 = d R T (density d = g/V)


When 3.2 gm of sulphur is vapourised at 450 C and 723 mm pressure, the vapour occupies a volume
of 780 cm3, what is the formula for the sulphur under these conditions ?
The molecular weight of a poly-atomic element = number of atoms × atomic mass
So let us find the molecular weight of S from the data given.
gRT 3.2  0.0821 723
M  
PV  723 / 760    780 /1000 = 256
256
 Number of atoms = =8
32
Hence, molecular formula of sulphur = S8
Vapour Density :
It is defined as the ratio of the mass of the gas (X) occupying a certain volume at a certain temperature and
pressure to the mass of hydrogen occupying the same volume at the same temperature and pressure.
g PVM 
Now, PV = nRT =  RT  g X 
M RT
PV  2
and g H 2 
RT
  M   2 for H 2 gas 
gX M
  X  vapour density
gH2 2
Thus, it can be seen that vapour density of a gas does not depend on pressure or temperature or volume.
Dalton’s Law of Partial Pressures :

Total pressure of a mixture of number of non-reacting gases is equal to the sum of pressures exerted by
individual gases.
PTotal = p1 + p2 + p3 + p4 +..............
where PTotal : Total pressure of the mixture and p1, p2, p3, p4,... are the partial pressures exerted by individual
gases in the mixture.
Assumption : All the gases spread uniformly to occupy the volume of the vessel.
The partial pressure is defined as the pressure a gas would exert if it were alone in the container at the same
temperature of the mixture.
Let p1, p2 be the partial pressures of gases 1 and 2 present in the mixture and n1 and n2 be their respective
moles. Let V be the volume of the container and T be the temperature at which the gases are mixed.

RT RT
Then, using Gas Equation, we have : P1  n1 . . . (i) and P2  n 2 . . . (ii)
V V
Using Dalton’s Law :
PTotal = P1 + P2
RT RT
 PTotal  n1  n2
V V
RT
or PTotal   n1  n 2  . . . (iii)
V
From (i), (ii) and (iii), it can be seen that :
n1 n2
P1  PTotal and P2  PTotal
n1  n 2 n1  n 2
or P1  1 PTotal and P2   2 PTotal
where 1 and  2 are the mole fractions of gases 1 and 2 respectively..

So in general, Partial pressure of a gas = Its mole fraction ×Total pressure exerted by the mixture
in a mixture in the mixture
Its partial pressure

Also, % of a gas in the mixture (by moles) =  100  (mole fraction of that gas)100
Total pressure
A 2.5L flask contains 0.25 mol each of SO2 and CO2 gas at 27C. Calculate the partial pressure
exerted by each gas and total pressure .
RT
Now, Partial pressure of SO2 = nSO 2 V
vessel
RT 0.25  0.0821  300
= 0.25 V   2.46 atm
vessel 2.5
RT
and Partial pressure of CO2 = n CO2 V
vessel
RT 0.25  0.0821  300

= 0.25 V   2.46 atm
vessel 2.5
 PTotal = 2.46 + 2.46 = 4.92 atm

Application of Dalton’s Law of Partial Pressure

Many gases in the laboratory are collected by the downward displacement of water. The gas collected in this
way also contains molecules of water that have been evaporated into the gas. The pressure exerted by these
molecules depends on the temperature of water. The partial pressure of water in the gas mixture collected is
called the aqueous tension and is equal to the vapour pressure of water at that temperature.
 Pressure of the dry gas obtained  Pdry gas = Pobserved  Aqueous tension
Note : Pressure of air decreases with the increase in altitude (height from the sea level).

6.52 gm of a sample of oxygen is collected over water at a total pressure of 735.5 torr measured
5.45L at a temperature of 27 C. Find the vapour pressure of water vapours.
Using gas equation, calculate the pressure of the gas and then subtract it from the pressure of the gas
measured (observed).
gRT 6.52  0.0821 300
P  = 0.92 atm. = 699.8 mm of Hg [ 1atm. 760 mm of Hg]
M0V 32  5.45
Now this is pressure of dry gas, hence
Vapour pressure of water = 735.5  699.8 = 35.7 mm of Hg

Assume that the air is essentially a mixture of nitrogen and oxygen in mole ratio of 4 : 1 by volume.
Calculate the partial pressures of N2 and O2 on a day when the atmospheric pressure is 750 mm of Hg.
Neglect the pressure of other gases.
From Dalton’s Law of partial pressure, we have :
Partial pressure of nitrogen = p N 2   N 2  P and Partial pressure of oxygen = pO2  O2  P
Now,  N 2  4 / 5 , and O 2  1/ 5 ; P = 750 mm of Hg

4
 p N2   750  600 mm of Hg
5
1
and pO2   750  150 mm of Hg
5


One of the best rocket fuels is dimethyl hydrazine (an organic compound with molecular formula :
(CH3)2N2H2 ). When mixed with dinitrogen tetroxide, N2O4, it reacts according to the equation :
 CH 3 2 N 2 H 2 (l ) + 2N 2O 4 (l ) 
 3N 2 (g) + 4H 2O (l ) + 2CO 2 (g)
If 2.5 mol of dimethyl hydrazine reacts completely with N2O4 and if the product gases are collected at
20C in a 250 L vessel, what is the pressure in the vessel?
From stiochiometry of above reaction : 1 mol (CH3)2N2H2 3 mol N2  4 mol H2O  2 mol CO2
Moles of N2 formed = 3  2.5 = 7.5
Moles H2O formed = 4  2.5 = 10 [H2O will not exert any pressure at 20C as it will become a liquid]
Moles CO2 formed = 2  2.5 = 5
n TotalRT  7.5  5.0   0.0821  293
 PTotal =   1.20 atm
V 250
When 2 gm of a gaseous substance A is introduced into an initially evacuated flask at 25C, the
pressure is found to be 1 atm. 3 gm of another gaseous substance B is then added to it at the same
temperature and pressure. The final pressure is found to be 1.5 atm. Assuming ideal gas behaviour,
calculate the ratio of the molecular weights of A and B.
Let MA and MB be the molecular weights of A and B.
Using PV = nRT for A, we get :
2
RT
MA . . . . . . (i)
1
V
 2 3 
 +  RT
 n A + n B  RT  MA MB 
and using Dalton’s Law : PTotal =  1.5 = . . . . . . (ii)
V V
MA 1
Solving (i) and (ii), we get : M  3
B
Graham’s Law of Diffusion :

A gas expands to fill the entire container even if other gas(es) is (are) already present in the container.
This process of spreading of gas is called as diffusion. A gas confined to a container at high pressure
than the surrounding atmosphere will escape from a small hole which is opened in the container until the
pressure outside and inside have been equalized. This process is called as effusion.
Example of effusion: Escaping of air through a punctured tyre.
Note : The process of effusion is always followed by the process of diffusion.

According to Graham’s Law :

When compared at the same temperature and pressure, the rates of diffusion (or effusion) of any two gases
are inversely proportional to the square roots of their densities.
1
rate 
density
Note : This is why lighter gases diffuse faster than the denser gases.
It t1, t2 are the time required for the passage of the same volume, Vm , of two gases with densities d1 and d2
respectively at the same temperature and pressure, through the same orifice, then:
Volume effused Vm
Rate of effusion (r) = 
Time taken t
Vm Vm
 r1  t and r2  t
1 2
r1 Vm / t1 d2 M2 t2 d2 M2
By Graham’s Law : r  V / t  d  M   
2 m 2 1 1 t1 d1 M1
(Densities of gases at given temperature and pressure are proportional to molecular weights)
It has been found that the rate of diffusion (r) is also proportional to the pressure of a gas (or number of
molecules) at a given temperature. In that case, the rate of diffusion is given as :
P
r
d
If two gases 1 and 2 at different pressures P1 and P2 respectively are allowed to effuse through a small hole
in a container, then the ratio of rates of diffusion of two gases is given by:
r1 P1 d 2 P1 M2
 
r2 P2 d1 P2 M1
Note : Rate of effusion (r) can be defined in the following ways (depending on the analysis of a problem):
Volume effused distance travelled in a tube

(i) r=  (if the cross sectional area is uniform).
time taken time taken
moles effused  n
(ii) r=
time taken =  t
Drop in Pressure due to effusion  P
(iii) r= = t
time taken


As shown in the figure, NH3(g) and HCl (g) are
introduced in a cylindrical container of uniform
crossection. At what distance from NH3 inlet,will
NH4Cl form ?
Using Graham’s law :
rNH3 x/t M HCl 36.5
    1.46
rHCl    x  / t M NH3 17
 M HCl M NH3 
 x   0.59 
1  M HCl M NH 
 3 
Ammonia will diffuse faster than hydrogen chloride gas.
Application of Graham’s Law of diffusion :

 Separation of isotopes and other gaseous mixture is based on this law.
 It provides a method for the determination of molar mass.
Effective molecular weight of the mixture effusing out through a hole:

Let a container A contains 3 moles of He and 2 moles of N2 at some temperature and pressure. Suppose the
container has a hole through which this gaseous mixture is effusing out.
Let us first calculate the effective molecular mass of the mixture present initially in the container.
From the very definition of molecular mass, we have :
Molecular mass is the mass of an element or compound contained in 1 mole of that element or compound.
Now, total mass of 3 moles He and 2 moles N2 (i.e., mass of the gas mixture)
 3  4 + 2  28 = 68 gm.
And the total moles of gas mixture = 3 + 2 = 5
68
Thus, molecular mass of the mixture  M mix   13.6 gm/mole
5
We can generalize the above result as :
n
 M mix   i M i
i  1
where i is the mole fraction of the ith gas in the mixture and Mi is the molar mass of the ith gas in that mixture.

Now, to find the Mmix of the gas mixture effusing out, we have to determine the relative rates of effusion of the
mixture components.
rHe P M N2 n He M N2
  He 
rN 2 PN 2 M He n N2 M He
rHe 3 28
   3.97
rN 2 2 4
 moles He 
   3.97
 In the mixture effusing out :
 moles N 2 at t  0
moles N 2
 Mole fraction of N2 effusing out at t = 0 = moles N  moles He
2
1 1
   0.2
1  3.97 4.97
  N2  0.2 and He  1   N 2  0.8
 M mix  He M He   N 2 M N 2 = 0.8  4  0.2  28  8.8 gm / mole
Illustration - 1 At 30°C and 720 mm of Hg, the density of a gas is 1.5 g/L.Calculate molecular mass of the
gas. Also find the number of molecules in 1 cc of the gas at the same temperature.
SOLUTION :
Assuming ideal behavior and applying ideal gas Now number of molecules = n  NA
equation :
PV 720 / 760  1  103
PV = nRT =  N A   6.023  1023
RT 0.0821  303
Another form of gas equation is PMo = dRT
= 2.29  1019
dRT 1.5  0.0821  303
 M  
P 720 / 760
(T = 30 + 273 K)
 Mo = 39.38 gm/mol
Illustration - 2 The pressure exerted by 12 gm of an ideal gas at temperature T in Kelvin in a vessel of

volume V litre is one atm. When the temperature is increased by 10 K at the same volume, the pressure rises
by 10%. Calculate the temperature T and volume V. (Molecular mass of the gas = 120 gm/mole)

SOLUTION :
Using Gas equation : PV = nRT Putting the value of T in (i), we get :
We have,  1  V = 0.1  0.0821  100
1  V  0.1  R  T . . . . . . . (i) V = 0.821 L
and 1.1  V  0.1  R  (T  10) . . . . . . . (ii)

T 1
Using (i) and (ii), we have : 
T  10 1.1
 T = 100 K
Illustration - 3 An open vessel at 27C is heated until three fifth of the air has been expelled. Assuming
that the volume of the vessel remains constant, find the temperature to which the vessel has been heated.
SOLUTION :
In the given question, volume is constant. Also, as the Now let n1 = initial moles and n2 = final moles
vessel is open to atmosphere, the pressure is constant.  n2 = 2/5 × n1
This means that the gas equation is simply reduced to the
(as 3/5 th of the air has been expelled)
following form:
n1T1 nT 5
 T2   1 1  T1
nT = constant (Use PV = nRT) n2 2 / 5n1 2
or n1 T1 = n2 T2 5
 T2   300  = 750 K = 477 C
2
Illustration - 4 A spherical balloon of 21 cm diameter is to be filled with H2 at NTP from a cylinder con-
taining the gas at 20 atm at 27C. If the cylinder can hold 2.80L of water, calculate the number of balloons
that can be filled up using pumping.
SOLUTION :
(Note: the balloons are being filled at NTP)
The capacity of cylinder = 2.80 L
3
Let n = moles of hydrogen contained in cylinder and no = 4 / 3πr3 4 / 3× 3.14× 10.5 
no = = = 0.216
moles of hydrogen required to fill one balloon. 22400 22400
PV 20  2.80  Number of balloons that can be filled
n  = 2.273
RT 0.0821 300
n
volume of balloon =  10.50  10
n  n
22400

Illustration - 5 A 672 mL of a mixture of oxygen-ozone at N.T.P. were found to be weigh 1 gm. Calculate
the volume of ozone in the mixture.
SOLUTION :
672  V
Let V mL of ozone are there in the mixture Mass of oxygen at N.T.P. =  32
22400
 volume of oxygen = (672  V) mL
V 672  V
V   48   32  1
Mass of ozone at N.T.P. =  48 22400 22400
22400
 On solving we get : V = 56 ml
Illustration - 6 Two flasks of equal volume connected by a narrow tube (of negligible volume) are at 27C
and contain 0.70 mole of H2 at 0.5 atm pressure. One of the flask is then immersed into a bath kept at 127C,
while the other remains at 27C. Calculate the final pressure and the number of moles of H2 in each flask.
SOLUTION :
Moles of H2 initially = 0.7 = 2no . . . . . (i) and P1Vo = n2RTo (Finally)
 n1 + n2 = 2no . . . . . (ii)
Flask A : PoVo = no RTo (Initially)
P1Vo = n1RT1 (Finally) P n 
  . . . . .(iv)
P1 n2
Solve to get :
P n  T n1 = 0.3 ; n2 = 0.4
   . . . . (iii) Using (iv),
P1 n1 T1
P n 0.4
Flask B : PoVo = noRTo (Initially) P1   2  0.5  atm  0.56 atm
n 0.35
Illustration - 7 1 gm of an alloy of Al and Mg reacts with excess HCl to form AlCl3, MgCl2 and H2. The
evolved H2 collected over mercury at 27C occupied 1200 mL at 684 mm Hg. What is the composition of
alloy?
SOLUTION :
 Mass of Mg will be (1  x) gm
3
Al  3HCl   AlCl3  H 2 . . . . . (i) From stoichiometry of reactions (i) & (ii) ;
2
684
 1.2 Moles H 2 
3

x

1  x   1  0.044
PV 
Also, Moles of H 2   760  0.044 2 27 24
RT 0.0821  300  0.0555 x + 0.0416 + (1  x) = 0.044
 MgCl2  H2 . . . . . (ii)
Mg  2HCl   0.0139x = 2.4  10–3  x = 0.172 gm
Let mass of Al be x gm Thus, % Al = 17.2 % and % Mg = 82.8 %

EUDIOMETRY Section - 2
Application of Gay Lussac’s Law of combining Volumes

It is a method used to analyze the gaseous mixtures of hydrocarbons and to determine their molecular
formulae.
Here, the combustible gases (i.e., hydrocarbons) are exploded in a tube with the excess of O2 so that C and
H in the gas are converted to CO2(g) and H2O(g) respectively. After cooling and contraction, the volume of
contents of the tube are measured (this does not include H2O as it condenses). At this stage, the contents
include CO2 (g), unused O2 (if any left) and N2 (if any in the air).
Now NaOH is used to separate out CO2 (2 NaOH + CO2   Na2CO3 + H2O). As a result a further
contraction in volume takes place. After this, the unused O2 is left which is generally absorbed by the pyro-
gallol solution. In general after cooling, the contraction in volume is given as :
V = VR  VP (VR: volume of reactants, VP: volume of products after cooling)
Note : NaOH also absorbs Cl2, apart from CO2
From the measurements made, and applying Gay Lussac’s Law of combining volumes, we can calculate molecular
formulae and compositions of gaseous mixtures. Please read the given Illustrations on the next page carefully to
understand the application of law.
Illustration - 8 8.4 mL of a gaseous hydrocarbon (A) was burnt with 50 ml of O2 in an eudiometer tube.
The volume of the products after cooling to room temperature was 37.4 mL, when reacted with NaOH, the
volume contracted to 3.8 ml. What is the molecular formula of A?
SOLUTION :
Let CxHy (g) be the hydrocarbon. Contraction in volume
= VR  VP = (8.4 + 50)  (37.4) = 21 ml
 y y
Cx H y(g)   x   O 2(g) 
 x CO2(g)  H 2O(g) From equation, we have, the contraction
 4 2
= 1 + (x + y/4)  (x + 0)
[Remember this balanced combustion equation
for CxHy] (Note: Vol. of water is not taken as it has condensed)
From Gay Lussac’s Law of combining volume, we get :  Contraction = 1 + y/4
 y  For 8.4 mL of CxHy, the contraction
1 vol. of CxHy =  x   vol. of O 2
 4 = 8.4 (1 + y/4)
 x vol. of CO 2  y / 2 vol. of H 2O  8.4 (1 + y/4) = 21  y=6

After treating with NaOH, there is a contraction of Another method to calculate y:

(37.4  3.8) = 33.6 mL, which is equal to the volume After NaOH treatment, the volume is reduced to 3.8 ml,
of CO2 produced. this corresponds to the volume of O2 unused.
Volume of CO2 produced by 8.4 ml of hydrocarbon Volume of O2 unused = 50  8.4 (x + y/4) = 3.8
= 8.4 x Solve to get : y=6
 8.4 x = 33.6  x=4 Hence hydrocarbon is C4H6.
Illustration - 9 15 ml of gaseous hydrocarbon required for complete combustion 357 ml of air (21 % of O
2
by volume) and the gaseous products occupied 327 ml (all volumes being measured at S.T.P.). What is the
formula of hydrocarbon ?
SOLUTION :
Let CxHy (g) be the hydrocarbon. The gaseous products after contraction = 327 ml
This includes volume of CO2 plus volume of N2 in the
 y y
C x H y(g)   x   O 2(g) 
 x CO2(g)  H 2O (g) air (O2 is completely used up). So let us calculate the
 4 2 volume of N2 in the air.
From Gay Lussac’s Law of combining volume, we get :
Vol. of O2 = 0.21 × 357 = 75 ml
1 vol. of Cx Hy
 Vol. of N2 = 357  75 = 282 ml
 y
  x   vol. of O2  x vol. of CO2 Now, Vol. of N2 + Vol. of CO2 = 327 ml
 4
 Vol. of CO2 = 327  282 = 45ml
y
 vol. of H2O The volume of CO2 produced = 15 x
2
From equation, we have, the contraction  15x = 45  x=3
= 1 + (x + y/4)  (x + 0) = 1 + y/4 Hence the hydrocarbon is C3H8
 For 15 mL gas, contraction = 15(1 + y/4)
Also contraction = VR  VP= (15 + 357)  (327) = 45
 y=8
Illustration - 10 60 ml of a mixture of equal volumes of Cl and an oxide of chlorine were heated and then
2
cooled back to the original temperature. The resulting gas mixture was found to have a volume of 75 ml. On
treatment with caustic soda, the volume was contracted to 15 ml. Assuming that all measurements were
made at the same temperature and pressure, deduce the simplest formula of the oxide of Cl2. (The oxide of
chlorine on heating decomposes quantitative to O2 and Cl2).

SOLUTION :
Let ClxOy be the oxide. NaOH apart from CO2 also absorbs Cl2. So after NaOH
ClxOy 
 x/2 Cl2 + y/2 O2 treatment, the residual volume corresponds to the volume
of O2 = 15 ml
1 vol. x/2 vol. y/2 vol.
 Vol. of Cl2 = 45  15 = 30 ml
 Volume of ClxOy = volume of Cl2 = 30 ml
Now from equation :
After cooling volume = 75 ml
Vol. of Cl2 = 30 (x/2) = 30  x=2
This corresponds to vol. of Cl2 initially plus vol. of Cl2
produced and O2 produced. Vol. of O2 = 30 (y/2) = 15  y=1
 V(Cl2) + V(Cl2 produced) + V(O2) = 75 Hence formula of chloride is Cl2O
 V(Cl2 produced) + V(O2) = 75  30 = 45 ml
(vol. of Cl2 initially = 30 ml)
Illustration - 11 20 ml of a mixture of ethane (C H ), ethylene (C H ) and CO are heated with O . After the
2 6 2 4 2 2
explosion there was a contraction of 28 ml and after treatment with KOH there was a further contraction of
32 ml. What is the composition of the mixture ?
SOLUTION :
Let volume of ethane = a ml  VR = (a + 7/2 a) + (b + 3b) + (20  a  b)
and volume of ethylene = b ml and VP = (2a + 2b) + (20  a  b)
 Volume of CO2 = (20  a  b) mL
 VR  VP = 5/2 a + 2b = 28
Now contraction after cooling = 28
 VR  VP = 28 5a
 + 2b = 28 or 5a + 4b = 56 . . . . . . (i)
2
VR = volume of ethane + volume of ethylene + volume of
Also there is a further contraction of 32 mL on treatment
CO2 + volume of O2 used for combustion
with KOH.
VP = volume of CO2 produced (volume of H2O is not
 Volume of CO2 produced + Vol. of CO2 origi-
taken as it condenses)
Considering combustion of gases : nal = 32
 (2a + 2b) + (20  a  b) = 32
1. C2H6 + 7/2 O2   2 CO2 + 3 H2O
a vol. (7/2)a vol. 2a vol.  a + b = 12 . . . . . . (ii)
On solving (i) and (ii), we get :
2. C2H4 + 3 O2   2 CO2 + 2 H2O
a=8  Vol. of ethane = 8 ml
b vol. 3b vol. 2b vol.
b=4  Vol. of ethylene = 4 ml
3. CO2   CO2 (no reaction)
 Volume of CO2 = 8 ml
(20  a  b) volume

Illustration - 12 9 volumes of gaseous mixture consisting of gaseous organic compound A and just
sufficient amount of O2 required for complete combustion yielded on burning 4 volumes of CO2, 6 volumes of
water vapour and 2 volumes of N2 all volumes measured at the same temperature and pressure. If the
compound A contained only C, H and N,
(a) How many volumes of O2 required for complete combustion ?
(b) What is the molecular formula of the compound A ?
SOLUTION :
Let the molecular formula of A be C x H y Nz y
Volume of H2O = a  6
 y y z 2
C x H y N z   x   O2   xCO 2  H 2O  N 2
 4 2 2 1
y So, 4  12  9a
 4
1vol C x H y N z   x   vol of O 2  x vol CO 2
 4  7=9–a  a=2
y z z
 vol of H 2O  vol N 2
2 3 Volume of N2 = a   2
2
Let a volumes of Cx Hy Nz were taken.
Thus, x = 2, y = 6, z = 2
 y
Volume of O2 = a  x    9  a  Molecular formula of A  C2H6N2
 4
and O2 used = 9  a = 7 volumes.
 Volume of CO2 = ax = 4
KINETIC MOLECULAR MODEL OF A GAS Section - 3
In the previous sections, we have studied the macroscopic properties of gases and their relationships in the
form of gas laws. Now, we know that for a given amount of gas, volume is directly proportional to the
absolute temperature but gas laws do not provide any reason for this.
To understand the underlying principles, a theory based on a model is proposed. If the theoretical results on
the basis of this particular model agree with the experimental observations, it indicates that the model is
realistic. The theory that provides an explanation for the various experimental observations about a gas is
based on the Kinetic Molecular Model.
Maxwell proposed the postulates for the behavior of gas molecules known as Kinetic Theory of gases.
The postulates of this model are :
 Each gas is made up of a large number of identical and small (tiny) particles known as molecules (i.e.,
the dimensions of these molecules are very-very small as compared to the space between them).
 The volume of a molecule is so small that it may be neglected in comparison to the total volume
occupied by the gas.

 There are practically no attractive forces between the molecules. Thus, the molecules move indepen
dently.
 The molecules are never in stationary state but are believed to be in random motion in a straight line
motion in all possible directions with altogether different but constant velocities. The direction of motion
is changed only when it collides with the walls of container or with other molecules.
 The molecules are perfectly elastic and bear no change in energy during collisions.
 The effect of gravity on molecular motion is negligible.
 The temperature of gas is the measure of its kinetic energy. K.E. of molecules is proportional to
absolute temperature of the gas.
 The pressure of the gas is due to the continuous collision of molecules on the walls of container.
Consider a container of volume V occupied by a gas.
Let m = mass of the gas in the container and N = number of molecules in the container
If mo is the mass of one molecule  m = moN
If No is the Avogadro number and M is the molecular weight of the gas,
 M = moNo
Root mean Square (Crms) speed :
2 c12  c22  c32  ..........  c 2N

It is defined as : crms  c 
N
[where bar   represents average  c2 = Average of c2 values]
2
c dN c
 
3k BT 3RT
Since the distribution is continuous, we can write : c2rms  c2  
N m M
Where Mo = Mol. mass of the gas (in Kg)
3RT
 crms 
M
Note : Derivation of the above integrals is not required.

Illustrating the concept:

The escape velocity, the velocity required by an object to escape from the gravitational field of earth,
is given by ce  2gr where r = 6400 km for earth. At what temperature will the crms of an H2
molecule attain escape velocity ? (g = 10 ms2)
ce  2  10  6400  103  11313.7 ms 1
3RT 3  8.314  T
crms   [Note : M H 2  2  103 kg ]
M 2  103
As crms = ce  T = 10263.8 K
Average speed (cavg) :
c  c  c  .....  c N
This is defined as : cavg  c  1 2 3
N
For a continuous distribution, it can be written as : cavg 

 c dNc 
8RT
N M
Note : This is actually “average speed”. Since, the molecule move randomly, average velocity of the gas is
zero.

The average speed of a gas molecule is 400 m/s. Calculate its rms velocity at the same temperature.
3RT 8RT 3
crms  and cavg   crms   400 ms 1  434.24 ms1
M M 8
Most Probable speed (CMP) :
A very small fraction of molecules occupy either very small or very high speeds. The speed occupied by
majority of molecules is known as most probable speed.
2RT
It is given by : c MP 
M


For a gas consisting of only six molecular having speeds as 2 ms 1 , 3ms 1 , 3ms 1, 3ms 1, 4 ms 1, 5ms 1,
find crms, cavg and cMP.
N
 ci
i 1 c  c2  . . .  c N 2  3  3  3  4  5
cavg.  c   1   3.33ms 1
N N 6
N
 ci 2
i 1 c12  c 22  . . .  c N 2 22  32  32  32  42  52
crms  c2     3.46 ms 1
N N 6
c MP  3ms1 (Since maximum numbers of molecules are having a speed of 3 ms–1)
Note :
(i) cMP < cavg. < crms
8
cMP : cavg : c rms : : 2 : : 3

1 : 1.128 : 1.224
Also, cavg = crms  0.9215
(ii) cavg and crms values lie in the vicinities of cMP values.
(iii) The numerical values of cMP , cavg , crms increases with increase in temperature.
(iv) Also, it is important to note that the average translational kinetic energy of a gas molecule is given by :
1 2 1 2
K.E avg  m crms  m  cavg
2 2
If in a gas, there are N molecules, their total K.E. is :
1 1 1
K.E Total  K.E1  K.E 2  . . .  K.E N  m c12  m c 22  . . .  m c2N
2 2 2
1 1 1
mc12  mc 22  . . . .  mc 2N
Thus, average kinetic energy of each molecule  2 2 2
N
1  c2  c2  . . . .  c2 
 m  1 2 N
2  N 
 
1
m c2rms

2
(v) The sharpness of maximum in curves decreases with increase in temperature which reveals that number of
molecules having speeds in the vicinities of cMP increase.

Kinetic Energy of Gas

The pressure exerted by the gas is :
1 m N 2 1 2 m N
P c rms or P crms where  = density of gas = 
3 V 3 V
Using the above relation and gas laws, a relation between the average translational kinetic energy  1 mc 2rms 
2 
of a molecule at the temperature, T of the gas can be derived.
Using PV = nRT
1 m N 2 N  1 m0 N 2 
 crms V  RT  Using P  3 V Crms 
3 V N  
Note :
 c2  c2  . . .  c2 2
K.E avg. 
1 2
m crms
1 2
 m cavg  1 2 N   c1  c2  . . .  c N  
2 2 N  N 
   
1 1
or m c2rms  RT
3 N
1 3 RT 3
 mc 2rms   k BT
2 2 N 2
 Average Translational K.E. of a molecule is directly proportional to the temperature of the gas.
3 R
K.Eavg = k BT [where k B  is known as Boltzmann constant]
2 N
3 3
PV  RT
Also, K.E./mole =
2 2
Illustration - 13 Find the temperature at which methane and ethane will have the same rms speed as car-
bon dioxide at 400C. Also calculate the mean velocity and most probable velocity of methane molecules at
400C.
SOLUTION :
3RT 673
crms  (b) TC2 H6   30  458.86K
M 44
Let 1: CO2 and 2: Methane 8RT 8  8.31 673

Mean speed  
 CH4  M 3.14  16  103
For crms to be same for 1 and 2
T1 T = 943.68 m/s
  2
M1 M 2 2RT 2  8.31 673
Most probable speed  
673  CH4  M 16 103
(a) TCH 4   16  244.73K
44 = 836.11 m/s

Illustration - 14 A gas bulb of 1 L capacity contains 2.0  1021 molecules of nitrogen exerting a pressure of
7.57  103 Nm2. Calculate the root mean square (rms) speed and the temperature of the gas molecules. The
ratio of the most probable speed to the root mean square speed is 0.82, calculate the most probable speed for
these molecules at this temperature.
SOLUTION :
3RT 3  8.314  274.2
crms  T=? crms   494.22 m / s
M 28  103
Using, PV = nRT 1
Most probable speed (cMP) =  494.22
1.224
PV 7.57 103 1103
 T= = = 274.2 K = 403.77 m/s
nR 2.0 1021
 8.314
6.023  1023
Illustration - 15 Two gases A and B have the same magnitude of most probable speed at 298 K for A and
 MA 
150 K for B. Calculate the ratio of their molor masses  M  .
 B
(A) 2 : 1 (B) 1 : 0.75 (C) 1:2 (D) 3:1
SOLUTION : (A)
1/ 2 M A TA 298
 2RT     2
Most Probable    M B TB 150
 M 
 M A : M B  2 :1
T T
According to the problem A  B
MA M B
Illustration - 16 What is the ratio of kinetic energy per mole of Argon at 27°C and Helium at 127°C ?
(A) 0.75 : 1 (B) 1:1 (C) 1 : 0.67 (D) 1 : 1.25
SOLUTION : (A)
3
Kinetic energy (K.E)  RT KE Ar TAr 300 3
2   
KEHe THe 400 4
3
KE Ar = RTAr KE Ar : KE He is 0.75 : 1
2
3
KE He = RTHe
2

REAL GAS ANALYSIS Section - 4
Equation of state describes the variables of a gas (P, V, T) in a single equation completely. The gas equation
PV = nRT is an equation of state which is followed only by ideal gases. This equation is not always applicable
for a real gas (especially at high pressure and low temperature). There are many equation of states which can
be used to represent a real gas but the most commonly used equation is van der Waal’s Equation and is given
by :
 an 2 
 P  2   V  nb   nRT . . . . . . (i)
 V 

where P = Real Gas Pressure ; V = Volume occupied by the Gas ( Container Volume)
T = Gas temperature ; R = Universal Gas Constant ; n = Moles of Gas
a, b = Characteristic constants for a gas independent of the temperature but depends on the nature of the
gas.
L2 atm L
Note : (i) Units of a  ;b
mol2 mol
(ii) a  Relates to the forces interacting between the gas molecules and modifies the pressure term.
(‘a’ is high if the gas molecules have more attractive forces)
(iii) b  Relates to the volume occupied by the gas molecules and takes into account the fact that the space
actually occupied by the molecules themselves is unavailable for the molecules to move in and is given
by :
b = 4  volume of 1 mol of gas molecules.
(iv) For a given gas Van der Waal’s constant ‘a’ is always greater than ‘b’.
(v) The gas having higher values of ‘a’ can be liquefied easily. (to be discussed later)
Equation (i) is similar to the ideal gas equation with some correction factors taking into account the factors
responsible for a gas to deviate from the ideal gas behaviour.
Equation (i) is written in a more familiar form by dividing it by “n” :
 a 
 P  2   Vm  b   RT . . . . . .(ii)
 Vm 
 
V
where Vm  = Molar volume (volume occupied by 1 mole gas)
n

Pressure correction :
a
The term 2
is known as Pressure correction. The pressure exerted by a real gas is always less than
Vm
that by an ideal gas. So, this has to be added to the real gas pressure such that : Pideal  Preal  a
2
Vm
Note : Preal is the pressure exerted by the real gas and has been denoted by ‘P’ in the van der Waal’s equation.
Volume correction :
The term ‘nb’ is known as volume correction (also known as co-volume or excluded volume). The volume
of the gas molecules is not zero and hence the actual compressible volume is less thanV m and thus has to be
subtracted from Vm
We can also write a Universal Equation of state for any gas as :
PV = Z (nRT) . . . . . .(iii)
where Z = compressibility factor
Note : (i) For ideal gas, PV = nRT  Z = 1 at all conditions of P, V, T.

(ii) For real gas, PV = ZnRT
It should be clear that “Z” represents a quantitative deviation of real gas from ideal gas behaviour.
Explanation for deviation from Ideal Gas Behavior :

The deviation from ideal gas behavior is mainly due to two assumptions made while formulating the kinetic
molecular theory :
(i) Molecules were considered as point masses. However all real molecules have definite volume which
cannot be neglected when the volume occupied by the gas is small.
(ii) It was assumed that there are no intermolecular forces and molecules move independently. This cannot
be true as otherwise gases could not condense into liquid.
If we assume that gas molecules are hard spheres of radius say, 2  10–10 m, the volume of one mole of gas
molecules = (volume of each molecule)  No
4 3
=
3
 
 2  108  6  1023 cm3 = 2.01  10–2 L
and volume of the gas at P = 1atm and T = 0C is nearly 22.4 L

 % volume occupied by gas molecules  0.09%
It can be shown that at P = 10 atm and T = 0C, volume of the gas is nearly 2.24 L
% volume occupied by gas molecules  0.9%
Thus, as pressure increases, space available for gas molecules for free movement decreases.

With an increase in pressure, the average distance between the gas molecules decreases, then the molecular
interactions start operating. Thus, the number of molecular collisions with the walls of the container gets
affected resulting in smaller values of pressure than what actually would have been in the absence of intermo-
lecular interaction.
Let us plot the variation of Z as a function of P.

We can, theoretically, describe the above behaviour
by using van der Waal’s equation :
This equation is a cubic in Vm. Thus, verification for
the variation of Z versus P from this equation, directly,
is difficult. Instead, the whole variation can be divided
into three regions.
Region : I Low Pressure : This region is represented by that portion of the graph where Vm  b  Vm ,
i.e., Vm >> b or when the gas has a large molar volume or very small pressure.
 a 
Thus, we have :  P    Vm   RT
 Vm 2 
 
RT a a a
 P  [Here, both P and 2 are small numbers. So, P   P]
Vm Vm 2 Vm 2
Vm
PVm a
 Z 1 . . . . . . (iv)
RT RTVm
 In the region I, Vm is large  Z < 1 but Z  1
Thus, as P increases (Vm decreases), Z decreases [see equation (iv)]
Region : III High Pressure : This region is represented by that portion of the graph where
a
P
2
P  Vm  b  Vm 
Vm
 Van der Waal’s equation reduces to : P  Vm  b   RT

PVm Pb
 PVm = Pb + RT  Z 1 [Note : Z vs P is linear here]
RT RT
Thus, as P increases, Z increases and Z > 1.
Region : III Intermediate Pressure :

In this region, neither of the two approximations are valid, i.e.,
a
Vm  b  Vm and P  2
P
Vm
So, the direct analysis is difficult.

Observations from the graph :

(i) In the low pressure Region-I and in most of the Intermediate Pressure Region-II : Z < 1
 Gas is more compressible. Thus, attractive forces dominate between the gas molecules
(ii) In the high Pressure Region-III, Z > 1
 Gas is less compressible. Thus, repulsive forces dominate between the gas molecules.
The graph () shows the variation of Z vs P for different gases

and following can be observed :
(i) H2 and He gases have very low attractive forces between

the gas molecules and we can assume their van der waal’s
gas constant ‘a’  0.
 P  Vm  b   RT
[For H2 and He even at low Pressures we can assume
a
[P   P]
2
Vm
(ii) Z < 1 (as for CH4, CO2) can be attributed to the predominance of attractive forces among the mol-
ecules of these gases at the temperature of experimentation whereas Z > 1 can be attributed to the
dominance of strong repulsive forces among the molecules.
(iii) All gases at sufficiently high pressure (i.e., when sizes of the molecules are comparable to the volume
of the gas) will have Z > 1.
Variation of Z vs Temperature (T) :
In the low pressure region : a (Z < 1)
Z 1
RTVm
 As T increases  Z increases and reaches close to 1.
In the high pressure region : Pb (Z > 1)

Z 1
RT
 As T increases  Z decreases and reaches close to 1.
It can be seen that Z approaches 1 as T increases and Z approaches 1 as P approaches 0.
Thus, a real gas behaves more closely to ideal gas at low pressure and high temperature.
Note : Large value of “a” denotes a larger dip in Z in the intermediate pressure region.
a NH3  a N2 as NH3 molecules exerts attractive forces due to Hydrogen Bonding but in N2 there are only
Van der Waal’s forces of attraction between the molecules which is actually small.
b NH3  b N 2 as N2 molecule is larger as compared to NH3 molecule.
All isotherms in the above graph will have a common point of intersection ‘A’.


 Find the temperature at which 3 mole of SO2 obeying van der Waal’s equation occupies a

volumes of 10 L at a pressure of 15 atm. a  6.71 L2atm / mol2 , b  0.0564 L / mol 
 n 2a 
Using van der Waal’s equation of state :  P  2   V  nb   nRT
 V 

 32  6.71 
we get,  15   (10 – 3  0.0564) = 3  0.0821  T  T = 349.8C
 102 
 The compressibility factor for 1 mole of a van der Waal’s gas at 0C and 100 atm pressure is
found to be 0.5. Assuming that the volume of gas molecular is negligible, calculate the van der
Waal’s constant ‘a’.
 a 
Using van der Waal’s equation of state :  P  2   Vm  b   RT
 Vm 
Now : Vm – b  Vm (given)
 a  PVm a
 The equation is reduced to :  P   V  RT or Z   1
 2  m RT RTVm
 Vm
100  Vm
Also, 0.5   Vm  0.112 L
0.0821  273
Substitute the values of Vm and T :  a = 1.25 L2 atm mol2

 Calculate the pressure exerted by 5 mole of CO2 in 1 L vessel at 47C using van der waal’s
equation. Also report the pressure of gas if it behaves ideally in nature.
(a = 3.592 atm L2/ mol2, b = 0.0427 L/mol)
Using van der Waal’s equation of state :
 n2 a 
 P  2   V  nb   nRT
 V 

Substituting the given values, we get :
 52  3.592 
P   (1 – 5  0.0427) = 5  0.0821  320
 1 2 
 
 P = 77.218 atm
If the gas behaves ideally, then using : PV = nRT
5  0.0821  320
 P atm = 131.36 atm.
1

 Van der Waal’s constant b of Ar is 3.22  10–5 m3 mol1. Calculate molecular diameter of Ar.
Use, b = 4  volume occupied by the molecules in 1 mol of a gas
4 
 b  4  N    r 3 
3 
4 22
3.22  105  4  6.023  10 23    r3
3 7
1/3
 3.22  105  3  7 
r   0.1472  109 m  0.1472 nm
23
 4  6.023  10  4  22 
d = 2r = 0.2944 nm.
Critical phenomenon and Liquefaction of gases :

The phenomenon of converting a gas into liquid is known as liquefaction. The liquefaction of gas is achieved
by controlling P and T as follows :
 Increasing pressure : An increase in pressure results in increase in attraction among molecules.
 Decreasing temperature : A decrease in temperature results in decrease in kinetic energy of molecules.
 The temperature of gas must be lower than its critical temperature TC.
Note :
(i) Condition for a real gas to get liquefied is :
Low Temperature : Molecules don’t have sufficient energy to overcome the attractive forces between the
gas molecules.
High Pressure : Molecules are close to each other so that they can exert sufficient attraction on each
other required for the liquefication of the gas.
(ii) An ideal gas can never be liquefied whatever be the temperature and pressure conditions due to the absence
of the attractive forces between its gas molecules.
Critical temperature (TC ) :

It is defined as the characteristic temperature for a given gas below which a continuous increase in pressure
will bring liquefaction of gas and above which no liquefaction is noticed although pressure may be increased
For example : TC for CO2 is 31.2C.
Critical pressure (PC ) :

It is defined as the minimum pressure applied on 1 mol of gas placed at critical temperature, to just liquefy the
gas.

Critical Volume (Vm,C) :

The volume occupied by 1 mol of gas placed at critical conditions.
(i.e. P = PC and T = TC ).
Note : (i) PC, Vm,C ,TC are characteristic values for each gas.
(ii) The numerical values of critical constants derived from Van der Waal’s equation are:
8a a
TC  ; PC  ; Vm, C  3b [a, b are the van der Waal’s gas constants]
27 Rb 27 b 2
(iii) The gas having its temperature much lower than its critical temperature, less pressure is sufficient to
liquefy it.
RTC 8
(iv) The numerical value of  (on substituting TC, PC, Vm, C ). Thus one can write that the
PC Vm, C 3
value of RT/PV at critical conditions is 8/3 of normal conditions.
RTC 8 8 RT  RT 
i.e.,     1
PC Vm, C 3 3 PV  PV 
PC Vm, C 3
 At critical conditions, Z  
RTC 8
Boyle’s Temperature (TB)

It is that temperature at which a real gas behaves ideally over a large pressure range as shown :
a
TB is given by : where a, b are van der Waals gas constant
Rb
Note : Boyle’s temperature of a gas is always higher than its critical temperature (TC ).

Collision Frequency and Mean Free Path

The collision rate (i.e., the number of collisions taking place in unit time per unit volume) is called collision
frequency (z) and is given by
n 2 2cavg
z
2
The average of distances traveled by a molecule between successive collisions is called mean free path
().
1

2n2
where n is the number of molecules per unit molar volume.
6.02  1023 3
n m
0.0224
cavg , average velocity, the collision diameter i.e., the minimum distance between the centres of two
molecules when at the point of collision.
T
Also based on kinetic theory of gases, mean free path   . Thus,
P
 Larger the size of the molecules, smaller the mean free path.
 Greater the number of molecules per unit volume, smaller the mean free path.
 Larger the temperature, larger the mean free path.
 Larger the pressure, smaller the mean free path.

MORE ILLUSTRATIONS
Illustration - 17 A mixture containing 1.12L of H and 1.12L of D (deuterium) at S.T.P., is taken inside a
2 2
bulb connected to another bulb by a stop-cock with a small opening. The second bulb is fully evacuated. The
stop-cock is opened for a certain time and then closed. The first bulb is found to contain 0.05 gm of H2.
Determine the percentage composition by weight of the gases in the second bulb.
SOLUTION :
In the first bulb : From Graham’s Law :
1.12 1 n 2
Initial moles of H2 =  
22.4 20 1/ 40 4
1.12 1 2
Initial moles of D2 =   n = moles of D2 in second bulb.
22.4 20 80
Now after opening of stop-cock, mass of H2 left in the In the second bulb:
first bulb = 0.05 1
The mass of H2 gas =  2  0.05 gm
40
0.05 1
 Moles of H2 =  2
2 40 The mass of D2 gas =  4  0.07 gm
80
 Moles of H2 effused into second bulb  Total mass = 0.05 + 0.07 = 0.12 gm.
1 1 1 0.05
=    100  41.67 %
20 40 40  % of H2 =
0.12
Let n be number of moles of D2 effused. 0.07
and % of D2 =  100  58.33%
0.12
Illustration - 18 A mixture of ethane and ethene occupies 40 L at 1.0 atm and 400K. The mixture reacts
completely with 130 gm of O2 to produce CO2 and H2O, Assuming ideal gas behaviour, calculate the mole
fractions of C2H4 and C2H6 in the mixture.
SOLUTION :
Let x = moles of C2H6 and y = moles of C2H4 7x 130

  3y   3.5x + 3y = 4.06
C2H6 + 7/2 O2  2CO2 + 3H2O 2 32
PV 1  40
C2H4 + 3O2  2CO2 + 2H2O Also, x + y =  = 1.218
RT 0.0821  400
 7x 
 moles of O2 used =   3 y  Solving for x and y, we get :
 2 
130  x = 0.812 and y = 0.406
and moles of O2 available =
32 0.812
 C 2 H 6   0.67 and C2H 4  0.33
1.218

Illustration - 19 1 mole of CCl vapours at 77C occupies a volume of 35.0 L. If van der Waal’s constants
4
are a = 20.39 L2 atm mol–2 and b = 0.1383 L mol–1, calculate compressibility factor Z under,
(a) low pressure region (b) high pressure region.
SOLUTION :
(a) Under low pressure region, Vm is high (b) Under high pressure region P is high,
(Vm – b)  Vm  a 
P  2   P
  Vm 
a  
  P  2  Vm  RT
 Vm   P(Vm – b) = RT or PVm – Pb = RT

a RT
PVm   RT  P
 Vm Vm  b
20.39 PVm Vm 1
Z 1  0.98 Z  
0.0821  350  35  RT Vm  b 1  b
 a  Vm
 Z  1  
 RTVm  1
 Z  1.004
0.138
1
35
Illustration - 20 At 20C, two balloons of equal volume and porosity are filled to a pressure of 2 atm, one
with 14 kg N2 and other with 1 kg of H2. The N2 balloon leaks to a pressure of 1/2 atm in 1 hr. How long will
it take for H2 balloon to reach a pressure of 1/2 atm ?
SOLUTION : 1
Thus, for N2 : P1 = 2 atm. P2  atm. at t = 1 hr
r1 M2 2
Note : r  w1 = 14 kg w2 = ?
2 M1
P1 w
n1 / t1 M2   1
 P2 w 2
 n2 / t 2 M1
2 14 14
 w1 M1  t1 M2    w2  kg N 2
 1 2 w2 4

 w 2 M2  t2 M1 14 42 21
Wt. of N2 diffused = 14    kg
w1 t1 M1 4 4 2
 
w2 t2 M2 1
Similarly, for H2 : P1 = 2 atm, P2  atm, at t = t hr
2
where w1, w2 are the weights of gas 1 and 2 effused in w1 = 1 kg w2 = ?
time t1 and t2 respectively.
P1 w1 2 1 1
At constant V and T for a gas P  w  P  w  
1 2 w2  w 2  kg
2 2 4

1 3 Alternative approach :
Wt. of H2 diffused  1   kg
4 4 r1 P M2
 1
rN 2  MH  r2 P2 M1
2
Now    for diffusion of N2 and H2
rH2   P1 / t1 P M2
 M N2   1
P2 / t 2 P2 M1
w N2 t H2 M N2
  1
or w H2 t N2 M H2 Here : P1  P2  2  atm and
2
P1 = P2 = 2 atm
21 2 t H 2 28
   t2 M2
34 60 2 

60 t1 M1
 t H2  min
14 M H2 60
 t H2  t N2  min
M N2 14
Illustration - 21 A gaseous mixture of helium and oxygen is found to have a density of 0.518 g dm–3 at 25C
and 720 torr. What is the per cent by mass of helium in this mixture ?
SOLUTION :
We know, PMo = dRT Average molecular mass =   MHe + (1 – ) M O2
720  13.37 =   4 + (1 – ) 32
  M   0.518  0.0821  298
760   = 0.666
 Mo = 13.37 g/mol
0.666  4
Let mole fraction of He in mixture be . % by mass of He = 0.666  4  0.334  32  100
 χ He  , O 2  1    = 19.95%

THE LIQUID STATE Section - 5

The liquid state is intermediate between gaseous and solid states. In the gaseous state the molecular
interactions are very weak practically negligible and molecules are in random motion. Molecules continue to
move unless they are reflected back by the walls of the vessel. Otherwise molecules would continue to move
and the gas would expand to any volume. This is why gases do not have a definite volume.
In case of liquid, the molecular interactions are quite strong and a given quantity of liquid occupies a definite
volume. Molecules of the liquid have so much freedom that they can flow readily and take up the shape of the
container due to continuous breaking and making of weak van der Waal’s bonds between the neighbouring
molecules.
Molecules in solids completely lack in translation motion. The thermal motion of the molecules is so greatly
reduced that they can only oscillate with respect to their fixed positions in the crystals. Each molecule in a
solid has generally 6 to 12 nearest neighbours called coordination number. In the liquid state the coordination
number of a molecule is not fixed but is only slightly less than in solid. The distance between the nearest
neighbours in liquid is only slightly higher than that in solids. This is why there is very little expansion of solids
on melting.
Vapour Pressure
The kinetic theory is the idea that there is distribution
of kinetic energies and hence the molecular speeds,
depending on the absolute temperature. Therefore,
in any gas, liquid or solid at room temperature, a
small fraction of molecules have relatively high
kinetic energy. Some of these high energy molecules
at the liquid surface become free resulting into its
evaporation. With the departure of high energy
molecules the average kinetic energy decreases
leading to a fall in temperature of the liquid. This
explains why evaporation causes cooling.
In a closed vessel, some free space above the liquid, the evaporated molecules cannot escape to the
atmosphere. Initially the vapour pressure increases and then comes to a constant value. The volume of the
liquid decreases initially and then becomes constant over a period of time. Increase in pressure means more
number of collisions with the walls of the container.
I nside a closed vessel, the liquid and its vapours are in dynamic equilibrium. The pressure exerted by the
vapours is then known as equilibrium vapour pressure. Since the vapour pressure is a kinetic phenomena,
it is independent of the amount of a liquid .It only depends on the temperature. The temperature must,
therefore, be specified with the vapour pressure of a liquid.
A liquid is said to be at its boiling temperature if its vapour pressure is equal to external pressure. Therefore,
the boiling point of water in particular and of liquids in general decreases as altitude of a place increases
where the external pressure is less than one atmospheric pressure

Vapour pressure of solids

When a solid is directly converted to its vapour state, then the process is called sublimation. Substances like
ammonium chloride, iodine, camphor, solid carbon dioxide sublime at ordinary temperature and pressure.
The white cloud like trail that we see coming out of the high flying jet is water vapours issuing from the
exhausts of high flying jets, getting converted directly into microcrystalline ice which is slowly reconverted
into water vapour without passing through the liquid state. This property of sublimation is used in the process
called freeze drying.
Surface Tension
Surface tension is one of the characteristic properties of liquids. Each molecule in the liquid state is influenced
by the nearest neighbour molecules. A molecule in the bulk of liquid experiences equal attractive forces from
all sides. There is no resultant force on the molecule which tries to move it
in any direction, whereas for a molecule at the surface of the liquid, the net
attraction towards the liquid is greater than that towards the vapour state.
The energy required to increase the surface area of the liquid by one unit, is
defined as its surface tension. It is represented by the Greek letter 
(gamma). The liquid surface, in the absence of any other force tends to
attain a minimum area. Mathematically it can be shown that for a given
volume, the sphere has a minimum area. Hence the water drop acquires a
spherical shape. Liquid in a capillary tube rises due to its surface tension.
Surface tension is also defined as the force acting per unit length perpendicular
to the line drawn on the surface. The units of surface tension is Nm–1 .
Viscosity of liquids
The ease with which a fluid can flow is determined by its property called viscosity. Viscosity arises due to the
internal friction between layers of fluids as they pass over each other. When a liquid is steadily flowing over
a fixed horizontal surface the layer immediately in contact with the surface is stationary. The velocity of the
layers increases with the distance from the fixed surface. if we select a layer, the layer immediately below tries
to retard its flow(velocity),while the one above tries to accelerate the flow. Force required to maintain the
flow in the three layers described above is directly proportional to the area of contact and velocity gradient.
Example - 7

Force is proportional to area in contact and velocity gradient, i.e.,

FA (Area) . . . . . .(i)
dv
and F  (velocity gradient) . . . . . .(ii)
dx
dv
On combining (i) & (ii) , we get : F 
dx
dv
 F= A
dx
where  is a constant, called as the coefficient of viscosity and it has the unit of poise, g cm–1s–1.
THE SOLID STATE Section - 6
The substance is said to be in solid state if the molecular interaction energy predominates over the disruptive
thermal energy.
Covalent Solids
A covalent solid is a giant molecule having a three dimensional network of covalent bonds. Examples are
diamond, silicon carbide, silica. These are generally very hard.
Ionic Solids
Ionic solids are three dimensional arrangements of cations and anions bound by coulombic forces .The
crystal on the whole are electrically neutral. Such solids are characterized by high melting and boiling points.
The ionic solids do not conduct electricity as ions present therein are not free to move. Examples are sodium
chloride, barium oxide and calcium fluoride.
Metallic Solids
Metals are orderly collection of positive ions surrounded by and held together by free electrons, each metal
atom donating one or more electrons. The bonding is not directional. The metals are good conductors of heat
and electricity. They are highly malleable and ductile. These sets of properties can be attributed to this
structure of metals. Metals like sodium crystallize- in simple cubic lattice. The presence of a sea of mobile
electrons in a metal accounts for its high electrical and thermal conductivity.
Molecular Solids
Many combinations of elements result into covalent molecules. These are discrete units capable of independent
existence. Thus we have molecules like di-hydrogen, di-nitrogen, methane etc. which are called covalent
compounds. They have weak molecular interaction. Even mono-atomic molecules like the noble gases, form
molecular solids. These solids are characterized by low melting points.

Recapitulating and Summarizing THINGS TO REMEMBER

2. Boyle’s Law : PV = constant (Keeping T and n constant)
V
3. Charle’s Law : = constant (Keeping P and n constant)
T
PV
4. Combined Gas Law : = constant(Keeping n constant)
T
P
5. Gay Lussac’s Law : = constant (Keeping V and n constant)
T
6. 1 mol Ideal Gas = 22.4 L at STP.
7. Ideal gas Equation : PV = nRT or PVm = RT (Vm = V/n)
8. Dalton’s law of Partial Pressure :

 n  n 2  . . .  RT
PTotal  1 Partial pressure of a gas = Gas  PTotal
V
n P V
9. Graham’s Law of Diffusion : Rate of diffusion/effusion = or or
t t t
P

M
3RT 8RT 2 RT
10. Maxwell’s speed distribution : Crms  ; Cavg  ; CMP 
M M M
[ T is in Kelvin : M is in kg/mol : R = 8.314 kJ/mol ]
3
11. Kinetic Energy of Gas : KE avg  k BT
2
 an 2 
12. Real Gas Equation :  P    V  nb   nRT and Z  PVm
 2 
V  RT

b = 4  volume of 1 mol of gas molecules.
13. Critical constants for a real gas TC  8a ; PC  a , Vm, C  3b

27Rb 27 b2
14.
 a  a
In low Pressure Region : P  2  Vm  R T & Z  1 
 Vm  R T Vm
 
Pb
In High Pressure Region : P  Vm  b   RT & Z  1 
RT
38 Things to Remember Self Study Course for IITJEE with Online Support
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Stoichiometry - 1
Stoichiometry - 1
BASIC IDEAS Section - 1
In this chapter, we are going to build the basics of solving the numerical problems in chemistry. The concepts
here involve, understanding of mole concept, gram equivalents and their applications in various chemical
processes.
Concept of Gram Atom :

One gram-atom of an element means collection of 6.023 × 1023 atoms. This concept applies only to the
elements, which exist in poly-atomic states (e.g. O as O2, Cl as Cl2, S as S8, P as P4 etc.).
Mass of 1 atom of an element

Atomic mass 
1 / 12 th the weight of C12
(in a.m.u. where 1 a.m.u. = Atomic Mass Unit = 1.66 × 1027 kg)
(a) The number of gmatoms in ‘g’ gm of an element whose atomic mass is A is :
g
gm - atoms 
A
Illustrating the Concept :

g 142
 
gm-atoms in 142 grams of chlorine = 4
A 35.5
g 16
 gm-atoms in 16 grams of Oxygen =   1
A 16
(b) The number of atoms in ‘g’ gms of an element is given by :
g
No. of atoms =  N0 (N0 = Avogadro number = 6.023 × 1023)
A
Note : The concept of gm-atom is useful in Radioactivity as it gives us number of nuclei i.e.
g
No. of nuclei = Number of atoms = gm-atoms  N0 =  N0
A
56
Number of atoms in 56 grams of Nitrogen =  6.023 1023  2.4092  1024
14
Note : Atomic masses of some common elements are given at the end of this chapter.

Stoichiometry - 1 Vidyamandir Classes
Concept of Gram Mole :

The collection of 6.023  1023 molecules of an element or ions or a compound constitute 1 mole of that
element or of ions or of compound. This magical number 6.023  1023 is known as Avogadro Number (N0).
 The number of moles (n) in ‘g’ grams of a substance, whose molecular weight is M0 is given by :
g
Number of moles = n 
M0
 The number of molecules in n moles :
g
Number of molecules = nN0   N0
M0
 The number of millimoles :
g
Millimoles (m.moles) =  1000
M0
 Number of moles in 46 grams of sodium (Na)
g 46
moles   2 (Atomic Mass of Na = 23 = molecular mass as Na is monoatomic)
M 0 23
 Number of moles in 100 gm of Chlorine (Cl2)
g 100
moles    1.4 (Mol. Mass Cl2 = 2  35.5 = 71)
M 0 71
 Number of moles in 54 grams of phosphorus (P4)
g 54
moles    0.4355 (Mol. Mass of P4 = 4  Atomic weight = 4  31 = 124)
M 0 124
 Number of moles in 49 grams of sulphuric acid (H2SO4)
49 1
moles    0.5 (Mol. Mass = 2  1 + 32 + 16  4 = 98)
98 2
 Number of moles in 25 gm of CaCO3 (calcium carbonate)
25
moles   0.25 (Mol. Mass = 40 + 12 + 16 × 3 = 100)
100

Concept of Gram Equivalents :

We can define gram-equivalent (gm eq) in ‘g’ gms of a substance whose equivalent weight is E as follows :
grams g
gram equivalents (gm.eq)  
Equivalent weight E
To understand the concept of gram equivalent, one must know the meaning of equivalent weight (E) of an
element or a compound.
Theoretically, Equivalent weight (E) of an element or a compound is defined as the weight of an element
or a compound which would combine with or displace (by weight) 1 part of hydrogen or 8 parts of
oxygen or 35.5 parts of chlorine.
Analytically, Equivalent weight (E) is defined for elements/ions/compounds as :
Molecular Weight
E 
x
where x is known as Valence factor or ‘n’factor and its value varies depending upon the compound being
considered.
(i) Equivalent Weight (E) of an Element :
Atomic weight of an element

E
Valency of element
27 24
E(Aluminium) = 9 E(magnesium) =  12
3 2
16 35.5
E(oxygen) = 8 E(chlorine) =  35.5
2 1
(ii) Equivalent Weight (E) of an Acid :

Molecular weight of acid
E=
Basicity
Acid : A species capable of giving H+ ions (protons) in its aqueous solution is an acid. It is generally represented
as HA. The number of H+ ions furnished by an acid determines the basicity of acid.
 Basicity of HCl (Hydrochloric acid) = 1 (As it furnishes only 1 H+ ion)
 Basicity of H2SO4 (Sulphuric acid) = 2
 Basicity of H3PO4 (Phosphoric acid) = 3  Basicity of H2C2O4 (Oxalic acid) = 2
Note : It is not necessary that basicity of an acid is equal to the number of H+ ions contained in its formula.
It is the number of furnishable H+ ions which determines the basicity of an acid.

Basicity of CH3COOH (Acetic acid) = 1

Basicity of H3PO3 (Phosphorus acid) = 2
This can be deduced from its structure shown ( 

):
As it can be seen that number of –OH groups are 2, the number of

furnishable H+ ions will also be 2.
Note that bond between P and –OH will not break as it is a stronger bond compared to the bond strength
between H and O in –OH group. So, H3PO3 is not a base although it contains 2 –OH groups. The H
attached directly to P atom will not be able to furnish in the solution as this bond is quite strong.
On the similar grounds, try to calculate the basicity of H3PO2 (Hypophosphorus acid).
Its structure is shown on right..
(Ans: Basicity of H3PO2 = 1)
Also, note the structure of H3PO4 (Phosphoric acid) and its basicity (= 3).
36.5 98 90
E HCl   36.5 E H 2SO4   49.0 E H 2C2O 4   45.0
1 2 2
(oxalic acid)
98 82 60
E H3PO4   32.6 E H3PO3   41.0 E CH3COOH   60
3 2 1
(iii) Equivalent Weight (E) of a Base:
Molecular weight of base

E=
Acidity
Base:A species capable of giving OH ions (hydroxyl) in its aqueous solution. It is generally represented as
BOH. The number of OH ions furnished by a base determines the acidity of base.
 Acidity of NaOH (Sodium hydroxide) = 1
 Acidity of Mg(OH)2 (Magnesium hydroxide) = 2
 Acidity of Al(OH)3 (Aluminium hydroxide) = 3
40 58 74
E NaOH   40.0 E Mg(OH)2   29 E Ca(OH)   37.0
1 2 2 2
(iv) Equivalent Weight (E) of an Ion :

E of an ion is determined by the charge on an ion irrespective of anion and cation.
Molecular weight of ion
E of an ion =
Magnitude of charge on ion

35.5 16 27
E    35.5 E 2  8 E 3   9.0
Cl 1 O 2 Al 3
60 95 88
E   30.0 E   31.66 E 2   44.0
CO32 2 PO34 3 C2O 4 2
(oxalate)
(v) Equivalent Weight (E) of a Compound :

Equivalent of a compound (E) depends upon how a given compound reacts in a particular reaction.
It means that equivalent weight can be variable. However, there are certain compounds for which
equivalent weight remains constant. The equivalent weight of alkali metal salts (Na, K etc) and alkaline-
earth metals salts (Mg, Ca etc) is constant. It depends upon the magnitude of total charge on cation or
anion.
Molecular weight
E=
Magnitude of total charge on cation or anion
106
E Na 2 CO3   53 (Magnitude of total charge on cation or anion = 2)
2
234
E Al  CO    39 (Magnitude of total charge on cation or anion = 6)
2 3 3 6
(vi) Equivalent weight (E) of an Oxidising and Reducing Agent :
For the compounds taking part in redox reactions, the calculation of E becomes rather complex and
one has to be very cautious. First, one should make sure which compound is acting as oxidising agent
(O.A) and which is acting as reducing agent (R.A). Then find the number of electrons transferred by
one mole of O. A or R.A in the reaction.
Molecular weight
E of compound =
Electron transfer per mole of O.A or R.A
Note : We will discuss this concept in the study of Redox Reactions in more detail in upcoming modules.

71
 gm. eq. in 71 gms of Chlorine atoms : gmeq.  2 (E Cl  35.5)
35.5
g 16
 gm. eq in 16 gms. of Oxygen atoms : gm.eq   2 (EO = 8)
E 8
g 500 M0
 gm. eq in 500 gms of H3PO4 : gm.eq    15.3 (Ea  )
E 32.67 basicity

g 150 M0
 gm. eq in 150 gms of Mg(OH)2 : gm.eq    5.17 (Eb  )
E 29 acidity
Note : In practical cases, a smaller unit of moles and gram equivalent is used and is given by :
g
 The number of milli moles (m.moles) in g grams =  1000
M0
g
 The number of milli equivalents (meq) in g grams =  1000
E
Relationship between Moles and Gram Equivalents :

g g g
Gram equivalents =  x  = x × moles
E M0 / x M0
Expressing Concentration of Solutions :
Solution is a homogenous mixture of two or more components in which intermingling particles are of atomic
or molecular dimensions. A solution consists of a dissolved substance known as solute and the substance in
which the solute is dissolved is known as solvent. The concentration of a solution means the quantity of
solute dissolved per unit volume of solution, or per unit quantity of solvent.
Concentration of solute  Amount of solute

Amount of solution (or solvent)
Note : While discussing various methods for expressing concentration, we have taken solute as B dissolved in
solvent as A and gB as grams of solute and gA as grams of solvent.
1. Mass fraction is the fractional part of a component that is contributed by it to the total mass of solution.
gB gA
mass fraction of (WB ) B = mass fraction (WA ) A =
gA  gB gA  gB
Note : WB  WB  1
2. Mole fraction is the fractional part of the moles that is contributed by each component to the total number
of moles that comprises the solution. In a solution containing nA moles of solvent and nB moles of solute ;
nB nA
mole fraction of B B = mole fraction of A A =
n A  nB n A  nB
Note :  A   B  1.


A given solution consists of 230 gm of C2H5OH (ethyl alcohol) and 720 gm of H2O (water). How to
determine the mole fraction of each component.
First, calculate moles of ethyl alcohol and water.
230 720
moles of C2H5OH =  5.0 and moles of H2O =  40.0
46 18
Now let A = mole fraction of H2O and B = mole fraction of C2H5OH
40
A   0.88 and  B  1   A  0.12
40  5
3. Molality (m) is expressed as number of moles of solute dissolved in 1000 gms (1.0 Kg) of solvent. It is
denoted by m. The unit is mol/kg. It can also be denoted by m.
moles of solute
i.e. m 
kg of solvent
nB
If nB represent moles of solute and gA represent gms of solvent, then, m =  1000
gA

How to determine the molality of solution containing 87.7 gm of NaCl (sodium chloride) dissolved
in 1500 gm of water ?
g 87.7
First, calculate moles of NaCl : moles 
  1.5
M 58.5
n B  1000 1.5  1000
Now, molality (m) =   1.0 m
gA 1500
4. Molarity (M) is expressed as moles of solute contained in one litre of solution or it is also taken as millimoles
of solute in 1 cc (ml) of solution. Its unit is mol/t. It is also denoted by M.
moles of solute millimoles of solute
Molarity (M) = =
litres of solution millilitres of solution
If nB represents number of moles of solute and VL be volume of solution in litres.

nB g MB
M=  B
VL VL
Note : moles of solute = Molarity  Volume in litres  nB = MVL (M : molarity).
or m.moles of solute = Molarity  Volume in cm3 (ml) = MVcc

1 mL = 1 millilitre, 1 cc = 1 ml = 1 cubic centimetres


How to determine the molarity of a solution containing 149 gram of KCl (potassium chloride)
dissolved in sufficient water to make 1500mL of a solution.
moles of KCl  g 
Molarity   where moles  
litres of solution  M0 
149 2.0
moles of KCl   2.0  Molarity   1.33 molar or written as 1.33 M
74.5 1500 /1000
How to calculate grams of solute (solid NaOH) in a 500 cc of 0.25M solution of NaOH ?
Moles = MVL M : molarity of solution;VL : volume of solution in litres.
500
Moles  0.25   0.125  gram of NaOH = 0.125  40 = 5 gm (mass = nM0).
1000
5. Normality (N) is expressed as the number of gram equivalents (gmeq) of solute contained in one litre of
solution or it can also be taken as number of mill equivalents (meq) in 1cc (mL) of solution. It is denoted by N.
gmeq of solute meq of solute
Normality of solution (N) = 
litres of solution millilitres of solution
If gB represents grams of solute, E represents Equivalent weight of solute and VL be volume of solution in
litres,
gmeq g B / E
Normality  
VL VL
Important Concepts in Stoichiometric Calculations :

[A] (a) gm.eq. of solute = normality  volume in litres = NVL
or meq of solute = normality  volume in cm3 (mL) = NVcc
(b) moles of solute = Molarity VL = MVL
or m.mol of solute = Molarity  VmL = MVmL
gm.eq x  moles
[B] Normality    x  Molarity
VL VL
For acidic solutions : N = x M [x : basicity of acid ; M : molarity of acid]
For basic solutions : N = x M [x : acidity of base ; M : molarity of base]
For a mono acidic base (acidity =1) and mono basic acid (Basicity = 1) Normality = Molarity
[C] Relation between molality(m), molarity (M), density(d) of solution and molar mass of solute (M0) :
Molarity (M) means M moles of the solute in 1 L of the solution. If density is in g/mL and M0 is molar
mass in g mol1 , then

mass of solute = MM0 grams ; mass of solution = 1000 × d grams

 mass of solvent = 1000d  MM 0
M
 Molality (m) =  1000
1000d  MM 0
[D] Relationship between molality (m) and mole fraction (B) of the solute :
nB n nB
B  ; m  B  1000   1000
nA  nB g n M
A A A
m nA MA m n A M A / 1000
 nB  or B 
1000 n A  m n A M A / 1000
m MA B 1000 1   A 1000
 B   m   
1000  m M A 1  B M A A MA

A solution was prepared by adding sufficient water to 100g of NaOH to make 0.50 L of solution.
Calculate molarity and normality of solution.
gmeq 100 / 40  g M0 
Normality    5N  gmeq  , E  
VL 0.5  E acidity 
Now using N = x M ;
5
 M  5 M solution [x = 1 for NaOH (Mono-acidic base)]
1
A solution was prepared containing 14.80 gm of Ca(OH)2 in 3000 ml of solution. Calculate:

(a) molarity of solution (b) normality of solution
(c) moles in a 2.5 L of same solution (d) gmeq contained in 1.5L of solution.
moles of Ca(OH) 2 14.8 / 74
(a) Molarity    0.067M
VL 3000 / 1000
gm eq of Ca(OH) 2 14.8 / E 14.8 / 37  M0 74 

(b) Normality     0.133N  E  acidity  2 
VL 3 3  
(c) moles in 2.5 L of sample = MVL = 0.067  2.5= 0.167 moles (in 2.5 L sample).
(d) gmeq in 1.5 L of sample = NVL = 0.133  1.5 = 0.2 gmeq (in 1.5 L).
6. Strength of a solution : It is expressed as grams of solute in 1 L of a solution.

grams of solute
Strength 
VL
g
We know, NVL   gmeq
E

g
Strength   NE
VL
g
Similarly, Strength   MM 0
VL

How to calculate normality when Strength is given ?
(i) HNO3 containing 6.3 g/L of acid
(ii) KOH solution containing 11.2 g/L of base
63 6.3  strength 
(i) EHNO3   63  N  0.1N  N  
1 63  E 
56 11.2
(ii) E KOH   56  N  0.2N
1 56
How to calculate E when Strength is given ?

(i) 10N HCl acid solution containing 3.65 g/10 ml
(ii) N/3.5 H2SO4 acid solution containing 14 g/L.
Strength
Eq. wt 
Normality
(i) E HCl  ? Strength = 3.65 g /10 ml = 365 g /L
365
E HCl   36.5
10
14
(ii) Similarly, E H 2SO4   49
1 / 3.5

1. If molarity of a solute Ax By in a solution is ‘M’, assuming the solute to have complete dissociation (100%)
 x Ay+ + y Bx–
Ax By   1mole A x B y gives 
 
Then, molarity of Ay+ ions = x  M ; molarity of Bx– ions = y  M  x moles of A y  and 
 x

 y moles of B 
But, same is not applicable to normality.
If normality of solute Ax By is ‘N’, assuming the solute to have complete dissociation (100%) :
 x Ay+ + y Bx–
Ax By 
gmeq.of A x B y  gmeq.of A y  
Then, normality of A ions = N ; normality of B ions = N 
y+ x– 
  gmeq.of Bx  
(Correlate the above results, with the definitions of molarity and normality respectively).


0.1 M H2SO4  0.2 M H+  0.1 M SO 24  0.1 N H2SO4  0.1 N H+  0.1 N SO 24 
2. When Solute is Solid :

(a) x% by mass of solute (B) in the solution (A): It means x gm of solute (B) are present in 100 gm
of solution (A)
(b) x% by volume of solute (B) in the solution (A): It means x gm of solute (B) are present in
100 cm3 of solution (A).
3. When Solute is also a Liquid :
(a) x% by mass of solute (B) in the solution (A): It means x gm of solute (B) are present in 100 gm
of solution (A)
(b) x% by volume of solute (B) in the solution (A): It means x cm3 of solute are present in 100 cm3
of solution (A).

The molarity and normality of solution of H 2SO 4 containing x% H 2 SO 4 by weight.
(dsolution = d gm/cc.)
First, you must understand meaning of x% H2SO4 by weight.
This means x gms of actual amount of H2SO4 in 100 gms of solution or if W (in gms) be the total
x
mass of solution, then the mass of solute (H2SO4) contained =  W gms .
100
Now coming back to original problem ;
Let us consider 1 L or 1000 cc of solution
 mass 
Mass of solution in 1 L = 1000 d d  
 volume 
x
Mass of actual H2SO4 in 1 L   1000 d   10 xd
100
10 xd  g 
moles of H2SO4 in 1 L =  moles  
M0  M0 
10 x d
 Molarity   M   M
0
For normality, M0 is replaced by E
10 xd
 normality   N  
E

Illustration -1 (a) Concentrated acid H2SO4 has a density of 1.8 g/ml and contains 49% acid by weight.
Compute molarity of the solution. Also calculate the number of gmeq of H2SO4 contained in 1 L solution.
(b) What is the normality of a solution which is prepared by dissolving 100 ml of conc. H 2SO4 in
part (a) in sufficient water to make 500 ml of solution?
(c) If we take 50 ml sample of above solution [in part (b)], find number of milli moles and milli
equivalents in the sample.
10 xd
Solution : (a) We have : Molarity 
M0
10  49  1.8
molarity(M)   9.0M (x = 49, d = 1.8 g/mL = 1.8 g/cc, M0 = 98)
98
To calculate gmeq, it is better to calculate normality first.
N = x M = 2  9 = 18 N x : Basicity of H2SO4 = 2
gm.eq. = NVcc = 1 × 18 = 18 gmeq are contained in 1 L of given solution.
(b) N of H2SO4 = 18 [calculated above in part (a)]

18.0  100
gmeq in 100 cc of conc. H2SO4   1.8
1000
So, 1.8 gmeq of concentrated acid are to be added in water to make 500mL solution.
gmeq 1.8
Normality of required solution = N    3.6
VL 500 / 1000
(c) Milli equivalents = Normality x Volume (in ml) = NVCC
= 3.6 × 50 = 180 meq.
Millimoles = Molarity × Volume (in ml) = MVCC
3.6
=  50  90 m.moles [N = x M and x = 2 for H2SO4, a dibasic acid]
2
Note : If a naturally occurring atom exists in the form of isotopes (say of molecular masses A1, A2, . . . . . etc) with
their percentages as (x1 %, x2 % . . . . . . . etc), then average atomic mass, Aavg of the atom is given as :
x1 x
Aavg   A1  2  A 2  ............
100 100

The mass spectrum of carbon shows that 98.892% of carbon atom are C-12 with a mass of 12.000
amu and 1.108% are C-13 with a mass of 13.000335 amu. Calculate the atomic weight of naturally
occurring carbon.
98.892 1.108
Atomic weight of carbon =  12.000   13.00335 = 12.011 amu
100 100

If isotopic distribution of isotopes (relative abundance) C-12 and C-14 is 98% and 2% respec
tively then the number of C-14 atoms in 12g of carbon is :
(A) 1.20 × 1022 (B) 3.01 × 1022 (C) 5.55 × 1023 (D) 6.023 × 1023
 98   2 
Average atomic mass =   12     14   12
 100   100 
12
 Total No. of C atoms in 12g of C   6.023  1023  6.023  1023
12
2
And Total No. of C-14 atoms in 12g of C =  6.023  1023 = 12.046  1021  1.20  10 22 (A)
100
There are two isotopes of an element with atomic mass z. Heavier one has atomic mass z + 2 and
lighter one has z – 1, then abundance of lighter one is :
(A) 66.6% (B) 96.7% (C) 6.67% (D) 33.3%
(100  x) x
Let x% be abundance of lighter one. Then  (z  2)   (z  1)  z So, x=66.6
100 100

1. Dilution : Whenever a given solution of known concentration i.e. normality and molarity (known as standard
solution) is diluted (adding solvent), the number of millimoles (or milli equivalents) of solute remain unchanged.
The concentration of solution however changes.
In such a case if :
N1 = normality of original solution ; V1 = volume of original solution
and N2 = normality of diluted solution ; V2 = total volume of diluted solution
Since the number of milli equivalents remains same,
 N1V1 = N2V2 (This also called equation of normality)
Also, M1V1 = M2V2 (This also called equation of molarity)
2. Whenever a small sample (volume) is taken from a standard solution, the concentration of sample is same as
that of standard solution. However number of millimoles (or milli equivalents) in sample differs from that of
standard solution.
From a 3.5 L of 0.5 N H2SO4 solution, a sample of 500mL is taken, then normality of a 500 mL solution is
also 0.5N.
But meq in standard solution = 0.5  3500 = 1750 meq
and meq in small sample = 0.5  500 = 250 meq

Illustration - 2 What volume of water must be added to a 0.5 litre of 10 N acid solution to make it
exactly 0.5 N solution?
Solution : Let Vcc of water is added to given solution of acid.
Apply equation of normality (for dilution) i.e. N1V1 = N2V2
V1  vol.of original solution  0.5L  500 cc ; N1  normality of solution

V2  final volume of solution ; N 2  normality of finalsolution
 10  500 = 0.5  (500 + Vcc)  Vcc = 9500 cc = 9.5 L.

 9.5 L of H2O will have to be added.
Illustration - 3 A commercial sample of oxalic acid is labelled as 22.5% H2C2O4 by weight (density =
1.5 g/cc). Calculate (a) molarity (b) volume of acid having same amount of solute as in 1 L of
0.2 M H2C2O4.
Solution :
10 xd
(a) Using standard formula : molarity =
M0
10  22.5  1.5
M  3.75 M
90
(b) Let Vcc of acid is required.
m.moles of concentrated sample = m.moles of desired sample
Using M1V1 = M2V2 ; 3.75 × Vcc = 0.2 × 1000  Vcc = 53.34 cc
Illustration - 4 A 0.25 molar aqueous solution of NaOH is found to have a density of 1.26 g/cc.
Determine its molality with respect to NaOH. Also determine its mole fraction.
Solution : = 1000  1.26 = 1260 gm
0.25 M NaOH  0.25 moles/litre of NaOH Now mass of NaOH = (moles  M0)
 0.25 moles of NaOH in 1 L of solution = 0.25  40 = 10 gm
 moles of solute   Mass of H2O = 1260  10 = 1250 gms

Use : m   1000 
 gms of solvent  0.25
Hence molality (m) =  1000 = 0.2 m
1250
First find the mass of water.
For conversion of molality into mole fraction, use the
Mass of solution = Volume  density following relation.
Mass of solution in 1.0 litre solution

B 1000 In given case : m = 0.202, MA = M H 2O  18

m 
1  B MA
 NaOH 1000
 0.2  
B = mole fraction of solute 1   NaOH 18
MA = molecular mass of solvent.
Solve to get: NaOH = 0.00358
Note : TRY to derive the above relation yourself.
Illustration - 5 An aqueous solution of ethyl alcohol (C2H5OH) is found to be 10/9 molal. If the density
of the alcohol solution is 0.8 g/cc, find mole fraction and molarity of solution with respect to ethyl alcohol.
Solution : Mass of solution

= mass of solute (C2H5OH) + mass of water.
   1000
Use m =  B  = (10/9  46) + 1000
 1  B  M A
( = mole fraction of alcohol) = 51.1 + 1000 = 1051.1
10  B  1000 Volume (in cc)

     = 0.0196
9  1  B  18 mass 1051.1
   1313.89cc  1.314 L
density 0.8
10 10
molal solution  mol of C2H5OH in = 1.314 L
9 9
1000 gms of H2O. moles 1019 10
 Molarity     0.845 M
For molarity, find volume of solution and for VL 1.382 11.825
volume of solution, first calculate mass of
solution.
Illustration - 6 One litre solution of 0.5N is heated. The volume of the solution is reduced to 750cc
and 2.675 gm of HCl is lost. Calculate :
(i) normality of the resultant solution.
(ii) number of meq of HCl in 100 cc of the original solution.
Solution :
(i) First calculate grams of HCl in original solution  wt. of HCl in resultant solution
g = 18.25  2.675 = 15.575 gm
Use: NVL 
E Now normality of new solution, N :
g
 0.5  1  g / E 15.575 / 36.5
 36.5 /1 N   0.57N
VL 750 / 1000
 g = 18.25 gm
(ii) meq in 100 cc of original sample
Now wt. of HCl lost due to heating = 2.675 gm meq = NVcc = 0.5  100  50 meq

STOICHIOMETRIC CALCULATIONS Section - 2

In this section, we will discuss the problems based on balanced chemical equations and application of mole
concept.
The analysis of a chemical reaction is generally carried out in the form of mass of reacting species taking part
in a given reaction (gravimetric analysis) or in terms of concentrations of reacting species taking part in a
given reaction (volumetric analysis).
In Gravimetric Analysis, we generally analyse reactions such as : decomposition of compounds under heat to
produce a residue and a gas, or displacement reactions, action of acids on metals, or simple balanced
chemical equations involving Weight (solid)  Volume (gas) relationships.
In Volumetric Analysis, we generally analyse Neutralisation and Redox Titrations involving aqueous solutions
in general.
Neutralisation :
A reaction in which an acid (or a base) completely reacts with a base (or an acid) to form salt and water is
called as Neutralisation. If HA be the acid, BOH be the base and BA be the salt, then neutralisation
reaction can be represented as follows :
HA + BOH  BA + H2O
Redox Reactions :
A reaction in which both oxidation and reduction takes place simultaneously is called as Redox reaction. A
redox reaction always involves a pair of oxidising agent and a reducing agent.
Note : We will deal with Redox Reactions in the next chapter.
Before we move on to study the balanced chemical equations, let us first analyse meaning of some terms.
Moles of NaCl : NaCl  Na+ + Cl

1 mole 1 mole 1 mole
 1 mole of NaCl contains 1 mole of Na+ (ion) & 1 mole of Cl ion
 2 moles of NaCl contains 2 moles of Na+ ion & 2 moles of Cl ion
Moles of CaCl2 : CaCl2  Ca2+ + 2Cl

1 mole 1 mole 2 mole
 4 moles 4 moles 8 moles
x-moles of H2SO4 : H2SO4  2H+ + SO42

1 mole 2 moles 1 mole
x moles 2x moles x moles

Application of Mole Concept on Balanced Chemical Equations :

Consider a general balanced chemical reaction or equation :
mA + nB  pC + qD
where A and B are reactants; C and D are products; m, n, p, q are the stoichiometric coefficients.
The above balanced reaction is analysed as :
m moles of A react with n moles of B to produce p moles of C plus q moles of D.

This can be represented (written) as :
m moles of A  n moles of B  p moles of C  q moles of D
Illustrating the mole concept :

What weight of KCl (Potassium Chloride) will be formed on heating 12.25 gm of KClO3 ?
Also calculate weight of O2 will be liberated.
First write a balanced chemical equation for decomposition of KClO3.

2KClO3 
 2KCl  3O2
(2 moles) (2moles) (3 moles)
From Stoichiometry, we have :

2 moles of KClO3  2 moles of KCl  3 moles of O2
 M (KClO )  122.5
 0 3

12.25  g 
moles of KClO3 =  0.1
122.5  moles  M 
 0 
 M 0(KCl)  74.5 
Now, 2 moles of KClO3  2 moles of KCl

 0.1 moles of KClO3 0.1 moles of KCl
 0.1  74.5 gm of KCl [ g  moles  M 0 ]
 7.45 gms of KCl are formed.
Similarly, 2 moles of KClO3  3 moles of O2

3 3
 0.1 moles of KClO 3   0.1moles of O 2   0.1  32 gms of O 2
2 2
= 4.8 gm of O2.

1. Some Important Anions used in Stoichiometry

X   halides  Cl :Chloride, Br  : Bromide I : Iodide
O2  Oxide S2  Sulphide
N3 Nitride P3  Phosphide
CO32  Carbonate HCO3 Bicarbonate
NO3 Nitrate NO 2 Nitrite
SO 24  Sulphate HSO 4 Bisulphate
SO 32  Sulphite PO34 Phosphate
C2 O 42  Oxalate HC 2 O 4 Bioxalate
S2 O 32  Thiosulphate S4 O 62  Tetrathionate
ClO3 : Chlorate ; BrO3 : Bromate ; IO3 : Iodate
MnO 4 Permanganate Cr2 O72  Dichromate
2. Action of Heat on Some Important Compounds :

Alkali Metals Alkaline Earth Metals
Carbonate Stable Unstable
 
Na 2CO3 
 No Re action CaCO3 
 CaO  CO2
Bicarbonates Unstable Unstable
 
2NaHCO3 
 Na 2CO3  CO2  H2O Ca  HCO 3 2 
 CaO  H 2O  2CO 2
Sulphates Stable Stable


Na 2SO4 
 No Re action
3. Some Basic Chemical Equations :
(i) 2 KClO3   
(ii) 2 NaHCO3 
 2 KCl  3 O 2  Na 2CO3  CO2  H 2O
 1 
(iii) NaNO3   NaNO 2  O 2 (iv) 2 Pb  NO3 2 
 2 PbO  4 NO 2  O 2
2

(v) 2 Na 2S2O3  I2  
(vi) Na 2C2O 4 
 Na 2S4O6  2 NaI  Na 2CO3  CO

(vii) 2 FeSO4  
(viii) 2 AgNO3 
 Fe2O3  SO2  SO3  2 Ag  2 NO 2  O 2
 2 Mg  O 
 2 MgO 
 NH NO   N 2O  2H 2O
2 4 3
(ix)  (x) 
3 Mg  N  Mg3 N 2 
 NH NO   N 2  2H 2O
 2  4 2
 Calcium behaves similarly 
Vidyamandir Classes Vidyamandir
Stoichiometry
Classes
-1
PROBLEM SOLVING TECHNIQUE (Using Mole Concept)

Follow the given sequence :
1. First write a balanced chemical equation.
2. Analyse the reactants and products according to their respective stoichiometric coefficients i.e.
i.e. m mole of A  n moles of B  p moles of C  q moles of D
3. According to data given, proceed as explained in the above illustration
4. In stoichiometric problems involving gases, we will assume all the gases to be ideal and apply
Gas Equation : PV = nRT.
(P : Pressure of gas in atm units, V : Volume of gas in L and T : Temperature in Kelvin and R : Universal gas
constants = 0.0821 atm L mol1 K1)
(a) At S.T.P., the volume occupied by 1 mole of a gaseous compound is equal to 22.4 L (or 22400 mL). This
is also called as Molar volume.
(b) At room temperature, T = 298 K, P = 1.0 atm., volume of 1 mole of gas is 24.48 L.
(c) N.T.P. (Normal temperature and pressure) condition is same as S.T.P. condition.
Illustration - 7 A flash bulb used for taking photograph in poor light contains 30 mL of O 2 at 780 mm
pressure at 27C. Suppose that metal wire flashed in the bulb is pure Aluminium (Al) and it is oxidised to
Al2O3 in the process of flashing, calculate the minimum weight of Al-wire that is to be used for maximum
efficiency.
Solution : From stoichiometry of the reaction :
Al is oxidised to Al2O3 as follows. 3 mole of O2  4 mole of Al
4 Al + 3 O2  2 Al2O3 4
1.25 × 103 mole of O2  (1.25 × 103) mole of Al
First, calculate the moles (n) of O2. 3
Use PV = nRT 4
gram of Al = (1.25 × 103)  27 = 0.045 gm
PV (780 / 760) (30 /1000) 3
 n   = 1.25  103
RT 0.082  300
Illustration - 8 A mixture of NaCl and Na2CO3 is given. On heating 12 gm of the mixture with dilute
HCl, 2.24 gm of CO2 is evolved at normal temperature. Calculate the amounts of two components in the
mixture.
Solution : From stoichiometry, we have :
Consider the effect of heat on the mixture. 1 mole of Na2CO3  1 mole of CO2
NaCl + HCl  nothing happens x x
moles of Na2CO3 = mol of CO2
106 106
Na2CO3 + 2 HCl  2 NaCl + CO2 + H2O x 2.24
  or x = 5.4 gm.
Let x grams of Na2CO3 are there in the mixture. 106 44
g x Hence grams of NaCl in the mixture
 moles of Na2CO3 = M  106 = 12  x = 6.60 gm
0
Section
Self Study Course for2IITJEE with Online Support Section 2 19
Section 2
Stoichiometry -1
Vidyamandir Classes Vidyamandir Classes
Illustration - 9 A mixture of FeO and Fe3O4 when heated in air to a constant weight, gains 5% of its
weight. Find the composition of the initial mixture.
Solution : 4 moles of Fe3O4  6 moles of Fe2O3

In such type of problems, in order to simplify the 100 – x 6  100 – x 
calculations, let us assume that the initial weight of the  232 moles  4  232  moles of Fe2O3
mixture is 100 gm.
x 6  100 – x 
Then the final weight of the mixture after heating in air will Total moles of Fe O =   
2 3 144 4  232 
be 105 gm.
Let x be the weight of FeO in the initial mixture, then the  x 6  100 – x  
Weight of Fe2O3 =      160 = 105
weight of Fe3O4 = 100  x 144 4  232  
When the mixture is heated in air (O2): Solving for x, we get ;
4 FeO + O2  2 Fe2O3
x = 20.25 gm = weight of FeO
4 Fe3O4 + O2  6 Fe2O3
 weight of Fe3O4 = 100 – x = 79.75 gm.
 4 moles FeO  2 moles of Fe2O3
x x % FeO = 20.25 and % Fe3O4 = 79.75
 moles  moles of Fe2O3
72 144
Illustration -10 Brass is an alloy of Cu-Zn. A sample of brass weighing 6.0 g, when treated with excess
of dil. H2SO4 gives 328 mL of dry H2 at 27oC and 760 mm pressure. What is the percentage of Cu by weight
in the alloy? (Atomic mass of Zn = 65.4 gm)
Solution : 760 / 760  0.328
n  = 0.0133
Only Zn reacts with dil. H2SO4 and produces H2, 0.082  300
whereas Cu does not.
Zn(s) + H2SO4  ZnSO4 + H2 (g) The amount of Zn in the alloy
1 mol of Zn  1 mol of H2
= 0.0133  65.4 = 0.87 g
PV 5.13
 moles of H2 evolved = n  or % Cu =  100  85.5%
RT 6.0
Illustration -11 Calculate the weight of iron which will be converted into its oxide by the action of 18g
of steam.
Solution :
18
Remember that iron reacts with steam, it Moles H 2 O  1
18
forms Fe3O4
3 3
Moles Fe  1 
3Fe  4H2O 
 Fe3O4  4H 2 4 4
From stoichiometry of the reaction : 3
Weight of Fe   56  42g
3 moles of Fe  4 moles H 2 O 4
20 Section 2 Section
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Vidyamandir Classes Stoichiometry
Vidyamandir -1
Classes

1. (a) Finding the Equivalent Weight of Basic Compounds :
Oxides, Carbonates and Bicarbonates of alkali metals and alkaline earth metal are basic in nature e.g.
MgO, Na2CO3 and NaHCO3 are basic.
The n-factor (acidity of carbonates, bicarbonates & oxides) is equal to the magnitude of total charge on
cations or anions. It can also be confirmed by visualizing the neutralisation reaction as follows:
Na2CO3 + 2 HCl 
 2 NaCl + H2O + CO2
The above reaction shows that 1 mole of Na2CO3 requires two moles of H+ ions. Thus, its equivalent weight
106
is i.e. 53 gm/mol. [Note: Acidity also refers to the number of H+ ions required to react with the base.]
2
(b) Finding the Equivalent Weight of Acidic Compounds :
The oxides of non-metals are acidic in nature, such as SO2 & SO3 are popular acidic oxides used in
neutralisation. The n-factor (basicity) can be determined as follows:
SO3 + 2 NaOH 
 Na2SO4 + H2O
The above reaction shows that 1 mole of SO3 requires two moles of ions. Thus, its equivalent weight is
80/2 = 40 gm/mol. Note : Basicity also refers to the number of OH- ions required to react with the acid.
2. Concept of Limiting Reagent :
Whenever, the amount of two reacting species (reagents) is given, very rarely they react completely (unless
calculated beforehand). In such cases, one of reagent reacts completely (as per Stoichiometry of the reaction)
leaving behind the other in excess. The reagent which reacts completely is known as Limiting Reagent.
Read the following example carefully to understand the concept.
Illustrating the Concept:
A closed vessel is found to certain 192 gm of Mg and 96 gm of O2 . This mixture is burnt.
(a) Which is the limiting reagent ?
(b) Find the weight of reagent in excess (the other one) ?
2 Mg  O 2  2 MgO 2
 3moles of O 2   3  6 moles of Mg
1
2 moles of Mg  1 mole of O 2
 2 moles of MgO  Mg is in excess.
192 Hence O2 is the limiting reagent as it is consumed fully.
Initial moles of Mg  8 Excess of Mg = 8 – 6 = 2 moles
24
96  Grams of excess Mg = 2  24 = 48 gm
Initial moles of O 2  3 moles of MgO formed
32
= moles of Mg consumed = 6
1 mole of O 2  2 moles of Mg
 Grams of MgO formed = 6  40 =240 gm
Read the following Illustrations carefully to understand the concept of limiting reagent.

Stoichiometry -1
Illustration -12 Consider the reaction : 2A + 3B   4C + 5D

In the above reaction A and B are reactants and C and D are products. If one mole of each of A and B
are reacted. Then:
I. 2.25 mole of of D is formed II. 1.6 mole of D is formed
III. 0.33 mole of A are left after complete reaction IV. 1.33 mole of C is formed
The correct choice is :
(A) I, II (B) II, III, IV (C) I, III, IV (D) I, II, IV
Solution : (B)
2A  3B   4C  5D
2 moles of A  3 moles of B  4 moles of C  5 moles of D [From Stoichiometry]
Initial n A  n B  1.
[For 1 mole of A,1.5 moles of B are needed. But only 1 mole of B is given. Hence, B is the limiting reagent]
2 1 4 5
n A  1    0.33 ; n B  1  1  0 ; n C   1.33 ; n D   1.66
3 3 3 3
Illustration -13 In the following reaction : MnO2 + 4HCl 
 MnCl 2 + 2H 2O + Cl 2 .When 2 moles
of MnO2 reacted with 4 moles of HCl, 11.2 L Cl 2 was collected at STP. Find the percent yield of Cl 2 .
(A) 25% (B) 50% (C) 100% (D) 75%
Solution : (B)
MnO2 + 4HCl   MnCl2 + 2H 2 O + Cl2
From Stoichiometry 1 mole 4 moles 1 mole 2 moles 1 mole
Initial (Given) 2 moles 4 moles [For 2 moles of MnO 2 , 8 moles of HCl are needed,
but only 4 moles of HCl are given. Hence, HCl is the limiting reagent]
Finally 1 mole 0 mole 1 mole 2 moles 1 mole = 22.4 L at STP (Theoretical yield)
11.2
% yield of Cl2   100 %  50%
22.4
Illustration -14 What is the number of moles of Fe  OH  3  s  that can be produced by allowing 1 mole
of Fe2 S 3 , 2 moles of H 2 O and 3 moles of O2 to react as : 2Fe2 S 3 + 6H 2O + 3O2   4Fe  OH  3 + 6S ?

(A) 1 mol (B) 1.84 mol (C) 1.34 mol (D) 1.29 mol
Solution : (C)
 4Fe  OH 3  6S
2Fe2S3  6H 2 O  3O 2 
From Stoichiometry 2 moles 6 moles 3 moles 4 moles 6 moles
Initial 1 moles 2 moles 3 moles
[For 1 mole of Fe 2S3 , 3 moles of H 2O are needed & 1.5 mole of O 2 . But only 2 moles of H 2O are
given and 3 moles of O 2 are given. Hence, H 2 O is the limiting reagent.]
Finally 1/3 mole 0 moles 2 moles 4/3 moles 2 moles
22 Section 2 Section
with Online Support
NEUTRALISATION Section - 3
As we know that an acid may be monobasic (HCl, HNO3 etc.), dibasic (H2SO4, H2C2O4 etc.) or tribasic
(H3PO4 etc.) and similarly a base may be monoacidic (NaOH, NaHCO3 etc.), diacidic [Ca(OH)2, Na2CO3
etc.] or triacidic [Al(OH)3 etc.], so it is better to define the neutralisation reaction in the following manner:
A reaction in which 1 gram equivalent (or 1 meq) of an acid (or a base) completely reacts with 1 gram
equivalent (or 1 meq) of a base (or an acid) to form 1 gram equivalent (or 1 meq) of corresponding salt.
A stage at which the process of neutralisation is complete is known as end point or neutral point and the
process carried out to study neutralisation of acids and base is called as Titration.
At equivalence point :
gm eq. (or meq) of acid = gm eq. (or meq) of base
Na Va = Nb Vb (N : normality, V : volume in mL or L, a: acid, b : base)

This relation can be used in two ways (modified form) :
1. If ga grams of acid are neutralised by a base whose normality is Nb and volume required for neutralisation of
given acid is Vb (in cc), then
ga M0
 1000  N b Vb Ea 
Ea basicity
2. If gb grams of a base are neutralised by an acid of normality Na and volume Va (in cc), then
gb M0
 1000  N a Va Eb 
Eb acidity
 How many grams of borax (Na2B4O7.10H2O) are required to neutralize 25 ml of 0.2 M of HCl and
H2SO4 separately.
Borax in water gives : B4 O72  7H 2O 

 4H3BO3  2OH  (Remember it as fact)
 1 mol of borax  2 mol OH  acidity = 2
(i) meq of borax = meq of HCl

g
 1000   0.2  1  25 [ HCl is monobasic acid]
382 / 2
 g = 0.955 gm = mass of Borax
(ii) meq of borax = meq of H2SO4
g
 1000   0.2  2   25 [ H2SO4 is diabasic acid] g = 1.91 gm = mass of Borax
382 / 2

 How many mL of 0.5 N HCl acid will be required to completely neutralise 500 ml of a 0.1 N NaOH
solution?
Let VmL of acid is required for neutralisation. Using equation of neutralisation we have : NaVa = NbVb
 0.5  Vcc = 0.1  500  Vcc = 100 cc = 100 mL
 0.5 gm of fuming H2SO4 (oleum) is dilute with water. This solution is completely neutralised by
30.0 mL of 0.4 N NaOH. Find the % age of free SO3 in the sample.
Oleum is (H2SO4 + SO3 = H2S2O7)
Note that SO3 is acidic oxide and hence reacts  x 0.5  x 
     1000 = 0.4  30
with NaOH.
 ESO3 E H 2SO 4 
2 NaOH + SO3  Na2SO4 + H2O ;
 x 0.5  x 
i.e., it acts as a dibasic acid.   80 / 2  98 / 2   1000 = 0.4  30
 
Let gms. of SO3 in 0.5 gm = x ;  x  0.4 gm = mass of SO3
Then, gms of H2SO4 = 0.5  x 0.4
 % age of SO3 =  100  80%
At neutralisation stage : meq of sample 0.5
= meq of NaOH

1. Salts formed by the reactions between a strong acid (like HCl, H2SO4, HNO3, H3PO4 etc. . . ) and a
strong base like NaOH, KOH, Mg(OH)2, Ca(OH)2) when dissolved in water does not effect the acidity
or basicity of the solution. For example : A solution having Na2SO4 (formed by the reaction between
NaOH and H2SO4) as its solute is neutral as Na2SO4 is a salt of strong acid and strong base.
2. Back Titration : This concept comes into picture while analyzing the Neutralization in case any of the acid
or base is found to be in excess (Over stepping of the end point).
Both of the above concepts can be clearly understood on careful examination of the following
illustrations :
Illustration -15 M
What volume of H3 PO4 solution will completely react with 200 ml of a solution of
6
M
aluminium carbonate ?
2
(A) 600 mL (B) 900 mL (C) 1200 mL (D) 1800 mL
Solution : (C) [Total charge on all cations or on all anions]

Applying equation of neutralisation : 1  1 
 3    VmL   6    200 
meq.of H3PO4 (acid) = meq of Al2(CO3)3 (base) 6  2 
[Meq. = n-factor  mmoles]
n-factor of Al2 (CO3)3 as base = 6
VmL = 1200 mL

Illustration -16 100 mL of mixture of NaOH and Na2SO4 is neutralised by 10 mL of 0.5 M H2SO4.
Hence, and mass of NaOH in 100 mL solution is :
(A) 0.2 g (B) 0.4 g (C) 0.6 g (D) None of these
Solution : (B)
As Na2SO4 , neutral being a salt of strong acid and strong base, only NaOH will be neutralised by H2SO4.
Applying equation of neutralisation : meq. of H2SO4 (acid) = meq of NaOH (base)
 
2  0.5  10  103  1  n NaOH   n(moles)  0.01
 Mass of NaOH = 0.01  40 = 0.4 g
Illustration -17 1.0 g of the carbonate of a metal was dissolved in 25 mL of 1.0 N HCl. The resulting
liquid required 5 mL of 1.0N NaOH for neutralization. The equivalent weight of the metal carbonate is :
(A) 50 (B) 30 (C) 20 (D) None of these
Solution : (A)
Meq. of acid (HCl) used = 25  1  25 [Meq = n-factor  mmoles]
Excess of meq. of acid (HCl) = Meq. of NaOH = 5  1  5 [Back titration]
Meq. of acid used for metal carbonate = 25 – 5 = 20 = Meq. of carbonate
1  g 
 Meq of carbonate = 20   1000  E  50  Meq.   1000 
E  E 
Illustration -18 5.3g of M2CO3 is dissolved in 150 ml of 1 N HCl. Unused acid required 100 ml of 0.5 N
NaOH. Hence equivalent weight of M is :
(A) 53 (B) 46 (C) 2 (D) 23
SOLUTION : (D)
gmeq of Acid (HCl) = gmeq of M2CO3 + gmeq of NaOH
 gmeq of M2CO3 = gmeq of Acid  gmeq of NaOH = (150  1  10–3) – (100  0.5  10–3)
 n M 2CO3  2  0.1 ;  n M 2CO3  0.05
g M 2CO3
 0.05 5.3
 M M 2CO3  M M 2CO3  2M  60   2M + 60 = 106 M = 23
0.05
Illustration -19 100 ml solution of 0.1N HCl was titrated with 0.2 M NaOH solution. The titration was
discontinued after adding 30 ml of NaOH solution. The remaining titration was completed by adding 0.5
M KOH solution. The volume of KOH required for completing the titration is:
(A) 8ml (B) 16ml (C) 32ml (D) 64ml
SOLUTION : (A) For excess of HCl, now KOH is used.
meq of HCl  0.1100  10  meq of KOH=meq of HCl remaining
meq of NaOH soln  30  0.2  6
0.5  VmL  4  VmL ( KOH )  8mL
meq of HCl remaining  10  6  4
Section
Stoichiometry -1
Illustration -20 5 mL of 8 N HNO3 , 4.8 mL of 5 N HCl and a certain volume of 17 M H2 SO4 are mixed
together and made upto 2 L. 30 mL of the acid mixture exactly neutralises 42.9 mL of Na2CO3 solution
containing 0.1 gm of Na2CO3 .10H 2O in 10 mL of water. Calculate : (a) the volume of H2 SO4 added to
the mixture (b) the amount (in gm) of the sulphate ions in the solution.
Solution :
meq. of acid mixture = meq of HNO3 + meq of HCl + meq of H 2SO 4
Let N be the normality of the acid mixture and VCC be the volume of H 2SO 4 added.
N  2000  8  5  5  4.8  2 17   VCC ......(I)
strength
Now find N of carbonate as follows : N 
E
Strength = 0.1 g/10 ml  10 g/L ; E= M 0 /2 = 286/2 = 143 ;( M 0  106  180 ; adding the mass of 10 H 2 O )
10
N
143
Now meq of acid mixture = meq of Na 2 CO3 solution
10
N  30  42.9   N  0.1  normality of acid mixture
143
Substituting in equation (I), we get : 0.1 2000  40  24  34  VCC   VCC  4 cc
For gms of sulphate ions :
meq of H 2SO4  2 17  VCC  136  VCC  4 
Now, meq of SO 24   meq of H 2SO 4

g g
  1000  136  1000  136  g  grams of SO 24 ions  6.53gm
E 96 / 2
So24
Illustration -21 A sample of chalk  CaCO3  is contaminated with calcium sulphate  CaSO4  ; 1 gm of
the solid mixture is dissolved in 230 mL of N/10 HCl ; 40 mL of N/10 NaOH is required to neutralise the
excess of acid. Find the percentage of chalk in the mixture.
Solution :
Here, note that CaSO 4 does not react with HCl as it gives a netural solution in aqueous medium (a salt of strong
acid and strong base) whereas, CaCO3 being basic reacts with HCl.
So now it is a simple problem of neutralisation, First find the meq of NaOH used for excess
Note that volume of HCl used against CaCO3 is not of HCl.
given. To calculate the volume of HCl for CaCO3 , meq of NaOH  1/10   40  4
proceed as follows : meq of excess of HCl =
Excess of HCl is neutralised by NaOH 4 (def. of neutralisation)
meq of excess of HCl = meq. of NaOH Now Find the initial meq of HCl taken.

Vidyamandir -1
Classes
Initial meq of HCl = (1/10)  230 = 23 meq of g

HCl used for neutralisation of carbonate   1000  19
E
= 23 – 4 = 19
 g  0.95 gm  95%
 meq of CaCO3  19
Illustration -22 1 gm of impure Na 2CO3 is dissolved in water and the solution is made upto 250 mL. Too
50 mL of this solution, 50 mL of 0.1N HCl is added and the mixture after shaking well, required 10 mL of
0.16 N NaOH solution for complete neutralization. Calculate % purity of the sample of Na 2CO3.
Solution :
1.0 gm of (impure)
So meq of Na 2CO3 (pure) in 50 mL = 3.4
Na 2CO3  H 2O  250 mL
 meq of pure Na 2CO3 is 250 mL
 50 mL Na 2CO3  50mL of 0.1N HCl 
250 g
 10mL of 0.16 N NaOH  3.4   17 or  1000  17
50 E
In this question, HCl is in excess.
 excess meq of HCl = meq of NaOH 17  106 / 2 
 g  0.901gm
 0.16 10  1.6 1000
meq of HCl added to Na 2CO3  0.1 50  5 Na 2CO3 is a diacidic base  E = 106/2

So mass of pure
 meq of HCl used to neutralised Na 2CO3
0.901
 5  1.6  3.4 Na 2CO3  100  90.1%
1
 Yield of a Chemical Reaction:

In general, in any chemical reaction, the amount of product formed is always less than the calculated
amount due to reversibilities in the chemical reaction. Therefore, yield of a chemical reaction (Y) comes
into picture and is given by :
Actual yield of the product

Y  100  Actual yield  % yield   Theoretical value 
Theoretical yield of the product

Stoichiometry -1
Illustration -23 NH 3 is formed in the following steps :
I. Ca  2C 
 CaC2 50 % yield
II. CaC2  N 2 
 CaCN2  C 100% yield
III. CaCN2  3H2O 

 2NH3  CaCO3 50% yield
Find the moles of calcium needed to produce 2 moles of ammonia
Solution :
Actual yield = % yield  (Theoretical value) ; Let x mole of Ca are needed.
From I : Yield of CaC 2  50%  x  x / 2
From II : Yield of CaCN 2  100%   x / 2   x / 2
From III : Yield of NH3  50%  2   x / 2   x / 2
Given : Moles of ammonia  2  x / 2  x  4 moles
USE OF DOUBLE INDICATORS IN NEUTRALISATION Section - 4
For studying the titrations of alkali mixtures such as NaOH and Na2 CO3 ; NaOH and NaHCO3 ;
Na2CO3 and NaHCO3, two indicators phenolphthalein and methyl orange are used.
 Phenolphthalein is a weak orange acid and gives end point between pH range of 8-10, while methyl
orange, a weak base gives end point between pH range of 3-4.4.
 When methyl orange is used as an indicator for studying the neutralisation titrations for above
mixtures, it indicates complete neutralisation for these, i.e. at the end point (colour change for
indicator) the above mixtures are fully neutralised.
 When phenolphthalein is used as an indicator for the above mixtures:
(a) it indicates complete neutralisation of NaOH (or KOH, i.e. strong alkali).
(b) it indicates half neutralisation of Na2CO3 (at the end point NaHCO3 is formed).
Note: It fails to indicate the neutralisation of NaHCO3 at all. Why? Because CO2 is the product of final
neutralisation of NaHCO3.CO2 is acidic oxide and in acidic medium phenolphthalein fails.
So, in an analysis of such alkali mixtures, both the indicators are used:
 one after the other in the same volumetric mixture
or
 two indicators are used seperately in two different titrations.
28 Section 4 Self Study Course for IITJEE with Online

Section 3 Support
Vidyamandir -1
Classes
FOR EXAMPLE :
1. In the Neutralisation mixture of NaOH and Na2CO3 :
(a) Use of methyl orange:
NaOH and Na2CO3, both are fully neutralised. i.e.
milliequivalent (meq or gmeq) of acid used = meq of NaOH + meq of Na2CO3
(b) Use of Phenolphthalein :
NaOH is fully neutralised and Na2CO3 is half neutralised
l
milliequivalent (meq. or gm.eq) of acid used = meq of NaOH + meq of Na2CO3
2
2. In the Neutralisation mixture of NaHCO3 and Na2CO3 :
(a) Use of Methyl Orange :
NaHCO3 and Na2CO3, both are fully neutralised, i.e.
milliequivalent (meq or gmeq) of acid used = meq of NaHCO3 + meq of Na2CO3
(b) Use of Phenolphthalein :
Na2CO3 is half neutralised and NaHCO3 is not neutralised at all.
1
milliequivalent (meq or gmeq) of acid used = meq of Na2CO3
2
Illustration -24 A solution of NaOH and Na2CO3 is prepared. 25 ml of this solution required for
neutralisation:
(a) 25.0 mL of 0.10 N HCl when phenolphthalein is used as indicator.
(b) 35.0 mL of 0.10 N HCl when methyl orange is used as indicator.
Find the strength of NaOH and Na2CO3.
Solution :
NaOH 25mL, 0.1 N HCl

 Experiment - I
 (Phenolphthalein)
Na 2CO3 
35 mL, 0.1 N HCl
 Experiment - II
(Methyl Orange)
(25 mL)
Let m moles of NaOH be x and that of Na2CO3 be [Note: Na2CO3 is half neutralised with phenolphtha-
y in 25 ml  3.5 = x + 2y ...(ii) lein as indicator]
Experiment - I :  25  x  y .....(i)
Meq. of Acid = Meq. of Base (For complete Experiment - II:
neutralisation)
Meq of Acids = Meq. of Base (For complete
1 neutralisation)
25  0.1  1 x  2  y 
2 35  0.1  1 x  2  y
[ meq = n-factor  m moles]
Section
Solving.....(i) and ....(ii), we get: y = 1 and x = 1.5 1 106

 g Na 2CO3   0.106 gm
g NaOH 1000
x  1000 (in 25 ml )
M NaOH
1000
1.5  40 Thus, strength of NaOH  0.06   2.4 g / L
 g NaOH   0.06 gm 25
( in 25 ml ) 1000
1000
and strength of Na2CO3  0.106   4.24 g / L
g Na 2CO3 25
y  1000
M Na 2CO3
Illustration -25 8 gm of a mixture of anhydrous Na CO and NaHCO was dissolved in water and
2 3 3
made upto 1000 mL, 25 mL of this solution required for neutralisation:
(a) 32.0 mL of N/10 HCl using methyl orange and
(b) 12.0 mL of N/10 HCl using phenolphthalein.
Find the strength of NaHCO3 and Na2CO3.
Solution :
Na 2CO3
 25 mL 12 mL, N/ 10 HCl
Experiment  I
NaHCO3 sample phenolphthalein
8gm
32 mL, N / 10 HCl
Experiment  II
Methyl Orange
Let m moles of Na2CO3 be x and that of NaHCO3 be y in 25 ml sample.
Experiment - I : Meq. of Acid = Meq. of Base (For complete Neutralisation)
1 1
12   2  x   1 y  0  1.2 = x + 0  x = 1.2 ....(i)
10 2
Experiment - II : Meq. of Acids = Meq of Base (For complete neutralization)
1
32   2  x  1  1 y  1  3.2 = 2x + y
10
Solving (i) and (ii), we get : x = 1.2 and y = 0.8
g Na 2 CO3 1.2  106
x 1000  g Na 2 CO3   0.127 gm
Thus, M Na 2CO3 1000
(in 25 ml)
g NaHCO3 0.8  84
y  1000  g NaHCO3   0.0672 gm
and M NaHCO3 1000
(in 25 ml)

1000
Thus, strength of Na2CO3 in the sample  0.127   5.28gm / L
25
1000
and strength of NaHCO3 in the sample  0.0672   2.69 gm / L
25
THINGS TO REMEMBER
1. Atomic Weights of Most Commonly used Elements :

ELEMENT SYMBOL ATOMIC WEIGHT ELEMENT SYMBOL ATOMIC WEIGHT
Hydrogen H 1.0 Helium He 4.0

Carbon C 12.0 Nitrogen N 14.0
Oxygen O 16.0 Fluorine F 19.0
Sodium Na 23.0 Magnesium Mg 24.0
Aluminium Al 27.0 Phosphorus P 31.0
Sulphur S 32.0 Chlorine Cl 35.5
Potassium K 39.0 Calcium Ca 40.0
Chromium Cr 52.0 Manganese Mn 55.0
Iron Fe 56.0 Copper Cu 63.5
Zinc Zn 65.4 Arsenic As 75.0
Bromine Br 80.0 Silver Ag 108.0
Tin Sn 119.7 Iodine I 127.0
Barium Ba 137.4 Gold Au 197.0
Mercury Hg 200.0 Lead Pb 207.0
2. Recapitulating and Summarizing:

 g
 gmeq   NVL
 g E

 moles  M  MVL  meq  g  1000  NV
 0 mL
 E
 g
 mmoles  M  1000  MVmL
 0
Self Study Course for IITJEE with Online Support Thing to Remmeber 29
 gmeq  x  moles
 meq  x  m.moles x = n - factor

 N  x  M
 n B  1000 1000 B
 molality(m)  gA

MA A

 m
B  1000
 m
 MA
 10 xd
M  M gB
 0 Strength = = N E = M M0
 10 xd litres of solution
 N  E
Note : (i) In experiments involving neutralisation, we should use concept of gmeq (or meq) i.e.,
gmeq of acid = gmeq of base
(ii) In experiments (usually gravimetric analysis) we should use mole concept i.e. first balance the chemical
equation and then correlate the reactants and products as per their stoichiometric coefficient.
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Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Chemical Thermodynamics
Chemical Thermodynamics - I
BASICS Section - 1
Internal Energy :
When we talk about our chemical system losing or gaining energy, we need to introduce a quantity
which represents the total energy of the system. It may be chemical, electrical, mechanical or any other
type of energy you may think of, the sum of all these is the energy of the system. In thermodynamics,
we call it the internal energy, U of the system, which may change, when
heat passes into or out of the system,
work is done on or by the system,
matter enters or leaves the system.
Let us consider the general case in which a change of state is brought about both by doing work and by
transfer of heat. We write change in internal energy for this case as : U = q + w . . . .(i)
For a given change in state, q and w can vary depending on how the change is carried out. However,
q + w = U will depend only on initial and final state. It will be independent of the way the change is
carried out. If there is no transfer of energy as heat or as work (isolated system) i.e., if w = 0 and
q = 0 , then U = 0.
The equation, U = q + w is mathematical statement of the first law of thermodynamics, which states
that the energy of an isolated system is constant.
Many chemical reactions involve the generation of gases capable of doing mechanical work or the
generation of heat. It is important for us to quantify these changes and relate them to the changes in the
internal energy. Let us see how!
Pressure-Volume work :
For understanding pressure-volume work, let
us consider a cylinder which contains one
mole of an ideal gas fitted with a frictionless
piston. Total volume of the gas is Vi and
pressure of the gas inside is p. If external
pressure is pex which is greater than p, piston
is moved inward till the pressure inside
becomes equal to pex. Let this change be
achieved in a single step and the final volume
be Vf.
During this compression, suppose piston
moves a distance, and is cross-sectional area
of the piston is A (figure shown).

Chemical Thermodynamics Vidyamandir Classes
force
We also know, pressure = Therefore, force on the piston = p ex . A
area
If w is the work done on the system by movement of the piston then
w = force  distance = pex . A . l = pex . (–V) = –pex V = –pex (Vf – Vi) . . . .(ii)
The negative sign of this expression is required to obtain conventional sign for w, which will be positive.
It indicates that in case of compression work is done on the system. Here (V f – Vi) will be negative
and negative multiplied by negative will be positive.
If the pressure is not constant at every stage of compression, but changes in number of finite steps,
work done on the gas will be summed over all the steps and will be equal to – pV.
If the pressure is not constant but changes during the process such that it is always infinitesimally
greater than the pressure of the gas, then, at each stage of compression, the volume decreases by an
infinitesimal amount, dV. In such a case we can calculate the work done on the gas by the relation
Vf
w  pex dV . . . .(iii)
Vi
Here, pex at each stage is equal to (pin + dp) in case of compression. In an expansion process under
similar conditions, the external pressure is always less than the pressure of the system i.e., pex = (pin –
dp). In general case we can write, p ex = (pin  dp). Such processes are called reversible processes.
A process or change is said to be reversible, if a change is brought out in such a way that the process
could, at any moment, be reversed by an infinitesimal change. A reversible process proceeds infinitely
slowly by a series of equilibrium state such that system and the surroundings are always in near equilibrium
with each other. Processes other than reversible are known as irreversible processes.

In chemistry, we face problems that can be solved if we relate the work term to the internal pressure of
the system. We can relate work to internal pressure of the system under reversible conditions by
writing equation (iii) as follows:
Vf
w rev    pex dV
Vi
Since dpxdV is very small we can write
Vf
w rev    pin dV
Vi
Now, the pressure of the gas (p in which we can write as p now) can be expressed in terms of its
volume through ideal gas equation. For n mol of an ideal gas i.e., pV = nRT
nRT
 p
V
Therefore, at constant temperature (isothermal process),
Vf
dV Vf
w rev    nRT  2.303nRT log
Vi
V Vi
Free Expansion: Expansion of a gas in vacuum (pex = 0) is called free expansion. No work is done
during free expansion of an ideal gas whether the process is reversible or irreversible (equation (ii) and
(iii)).
Now, we can write equation (i) in number of ways depending on the type of processes.
Let us substitute w = – pex V from equation (ii) in equation (i), and we get :
U = q – pex V
If a process is carried out at constant volume (V = 0), then
U = qv
the subscript v in qv denotes that heat is supplied at constant volume.

Isothermal and free expansion of an ideal gas :

For isothermal (T = constant) expansion of an ideal gas into vacuum : w = 0 since pex = 0. Also, Joule
determined experimentally that q = 0 ; therefore, U = 0.
Equation U = q + w can be expressed for isothermal irreversible and reversible changes as follows:
1. For isothermal irreversible change q = – w = pex (Vf – Vi)
V V
2. For isothermal reversible change q   w  nRT ln f  2.303 nRT log f
Vi Vi
3. For adiabatic change, q  0, U  w ad

4. For isochoric process : –w = 0
5. For isobaric process : –w = P gas V
Note :  In many cases, an irreversible process can be easily recognized by using the fact that the process
involving constant external pressure is an irreversible process.
 In a reversible process, an equilibrium exists (known as quasi-equilibrium) at every stage of the

process.
 Work done by system in a reversible expansion process will always be greater than that in irreversible
expansion process.
Heat Capacity :
Heat Capacity (C) : Heat required to raise the temperature of a system by 1°C or 1 K.
Units : J/K; kJ/K
Specific Heat Capacity (c) : Heat required to raise the temperature of a 1gm of a system by 1°C
or 1 K.
Units : J/g/K; kJ/Kg/K
Molar Heat Capacity (Cm) : Heat required to raise the temperature of a 1 mole of a system by 1°C
or 1 K.
Units : J/mole/K; kJ/mole/K
Mathematically, the above quantities are defined as :
q  C  T; q  n  C m  T; q  m  c  T
where q = amount of heat absorbed by the system; T = Rise in the temperature;
m = mass of the system;
n = moles of the system

Note : Molar heat capacity has 2 forms : CP (at constant pressure) and Cv (at constant volume) defined as :
 q   H   q   U 
CP      ; CV      [H  q P ; U  q V ]
 T  P  T  P  T  V  T  V
The subscript after the brackets in the above equation denotes the parameter kept constant during the
process.
 H 
i.e.  T  denotes change in Enthalpy per unit change in Temperature keeping Pressure constant.
 P
In terms of differentials :
 dq   dH   dq   dU 
CP      ; CV      [dH  dq P ; dU  dq V ]
 dT  P  dT  P  dT V  dT  V
C
Also, C P  C V  R ; P  
Cv
Determination of w, q, H and U for a process and a reaction :

Clearly, we need to create 4 equations to solve 4 variables (w, q, H and U) as follows :
Whether it is a process or a reaction, the first equation will always be applicable :
q  U  (  w) . . . . (i) [From First law of Thermodynamics]
Calculating H and U will be different in case of a process and a reaction and explained as follows :
(i) For a process :
H  nC P T . . . . (ii) [From definition of CP]
T2
or H   nCP dT [When CP is also a function of Temperature]
T1
U  nC V T . . . . (iii) [From definition of CV]
T2
or U   nC VdT [When CV is also a function of Temperature]
T1
Also, H  U   (PV) or dH  dU  dPV  VdP [ H  U  PV]
Many a times, we also write : (PV)  P2 V2  P1V1   ( nRT  nRT )
(ii) For a reaction :

For a reaction, H is the most important parameter and can be calculated as :
H   H Pr oducts  H Re ac tan ts . . . . (ii)
Also,  r H   r U  P V [As Chemical reactions occur at constant pressure and constant tem
-perature]

or  r H   r U   n g RT . . . . (iii)
Thus, to get the interconversion between  r H and r U , we must need to write down the balanced
chemical reaction with states of all the reactants and products and then calculate the change in the
number of gaseous moles.
The fourth variable can be calculated based on the process / situation as explained in the illustrations
below :
Illustration - 1 Calculate w, q, H and U for an ideal gas expanding in vaccum (i) isothermally (ii)
adiabatically
SOLUTION :
(i) w=0 [As PExt. = 0]
H = U = 0 [As T = constant for isothermal process]
q=0 [Using First law of Thermodynamics]
(ii) q=0 [Adiabatic Process]
w=0 [As PExt. = 0]
U = 0 [Using First law of Thermodynamics]  T is constant
H = 0 [As T = constant]
Note : For an ideal gas, U = U(T) and H = H (T) but for real gas, U = U(T,V) and H = H (T,P)
Illustration - 2 Five mole of an ideal gas at 293 K are expanded isothermally from an initial pressure 0.4
kPa to a final pressure of 0.1 kPa against a constant external pressure of 0.1 kPa.
(a) Calculate q, w, U and H.
(b) Calculate the corresponding value of q, w, U and H if the above process is carried out reversibly.
SOLUTION :
(a) For an isothermal expansion against a constant pressure, we have:
 w = PExt (V2 – V1)
 nRT nRT  1 1 
= PExt  P  P   PExt nRT  P  P   w = 9135 J
 2 1   1 2
Since temperature is constant: U = 0, H = 0
q = w = 9135 J [Using First law of Thermodynamics ]
(b) For isothermal reversible expansion :
P 0.4
  w  2.303nRT log10 1  2.303  5  8.314  293log10  w = 16888 J
P2 0.1

Since temperature is constant : U = 0H = 0,

q = w = 16888 J [Using First Law of Thermodynamics]
Illustration - 3 The magnitude of enthalpy changes for reversible adiabatic expansion of a gas from vol-
ume V1 to V2 (in L) is H1 and for reversible adiabatic expansion for the same expansion is H2. Then :
(A) H1 > H2 (B) H1 < H2 (C) H1 = H2 (D) H1 = U1 and H2 = U2
where U1 and U2 are the changes in magnitudes for internal energy of gas in the two expansions.
SOLUTION : (A)
We know that work done in a reversible expansion process is always greater than in an irreversible expan-
sion process.
Using First Law of Therodynamics : q = 0 = U + (–w)
Thus, decrease in U will be larger in reversible adiabatic than irreversible adiabatic expansion and since
U = nCvT, we can conclude that T in reversible adiabatic expansion will be greater than in irreversible
adiabatic expansion.
Now, H1 = nCpT1 , and H2 = nCPT2  H1 > H2
SPONTANEITY Section - 2
The first law of thermodynamics tells us about the relationship between the heat absorbed and the work
performed on or by a system. It puts no restrictions on the direction of heat flow. However, the flow of heat is
unidirectional from higher temperature to lower temperature. In fact, all naturally occurring processes whether
chemical or physical will tend to proceed spontaneously in one direction only. For example, a gas expanding
to fill the available volume, burning carbon in dioxygen giving carbon dioxide.
Second Law of Themodynamics :
It is impossible to construct a machine that is able to convey heat by a process from a colder to a hotter
body unless work is done on the machine by some outside agency.
Second law of Thermodynamics also helps in predicting the spontaneity of a reaction/process.
A process which proceeds of its own accord without any outside help is termed as a spontaneous process. To
understand the concept of spontaneity, we first need to understand the most important factor involved which
is Entropy (S) and is explained below :
1. Entropy (S) :
Entropy is a thermodynamic state quantity which is a measure of randomness or disorder of the system. More
is the randomness in the system, more is the entropy of the system.
(i) Entropy is a state function and depends only on initial and final states of the system.

(ii) Whenever heat is added to the system, it increases molecular motions causing increased randomness
in the system. The distribution of heat also depends on the temperature at which heat is added to the
system.
Entropy change of the system for a reversible process is mathematically defined as :
dq Rev dq Rev  q Rev 

dS = or ΔS =  =  [when the heat is absorbed reversibly at constant T]
T T  T 
If heat is absorbed, then S is positive (increase in entropy). If heat is released, then S is negative
(decrease in entropy). Also, for the same amount of heat absorbed, increase in entropy will be more
at lower temperature than at higher temperature.
(iii) If the temperature of a system increases, entropy increases. If the temperature of a system decreases,
entropy decreases.
(iv) For a fixed volume system, entropy increases if the number of molecules is increased in the system
and vice – versa.
(v) For a system with fixed number of molecules, entropy increases as volume increases and vice – versa.
(vi) Entropy of a system increases with change in the state of a system as : S(s) 
 S( ) 
 S(g)
(vii) Entropy of more complex molecules is larger than those of simpler molecules as in more complex
molecules there are more ways of arranging atoms in 3D (i.e. more ramdomness).
e.g. S propane > Sethane.
(viii) Entropy of compounds with similar molecular masses increases (with increase) in their sizes.
e.g. SAr  SCO2  SC3H8
(ix) Entropies of ionic solids becomes larger as the attraction amongst the ions become weaker.
e.g. SNaF > SMgO as in MgO, +2 and –2 charges result in greater attraction.
(x) Harder substances have smaller entropies than softer substances.
e.g. SC(diamond) < SC(graphite) < SFe < SAl < SNa
(xi) All spontaneous processes are irreversible processes or vice - versa.
(xii) When a system is in equilibrium, the entropy is maximum, and the change to entropy, S  0.
For both reversible and irreversible expansion for an ideal gas, under isothermal conditions, U  0,
but  STotal is not zero for irreversible process. Thus,  U does not discriminate between reversible
and irreversible process, whereas  S does.

2. Criteria for Spontaneity :

First law of thermodynamics is basically the law of conservation of energy. It has no restriction on the way
energy can flow. Thus, energy can flow from higher to lower temperature or lower to higher temperature, as
per first law of thermodynamics. But, natural processes tend to flow only in one direction (known as direction
of spontaneity).
It has been observed that in most of the spontaneous processes/reactions, there is a decrease in energy which
seems to be the crieria for spontaneity but it is not the only criteria, Evaporation of water is an endothermic
reaction yet it spontaneous.
There are two criterias which decide the direction of spontaneity :
(a) Decrease in energy (b) Increase in entropy
In other words, a chemical reaction or process tends to follow the direction of minimum energy and maximum
randomness, i.e. reaction will be more probable to occur if it is exothermic or there is an increase in entropy.
A reaction will occur if the value of H is negative and the value of S is positive. But the endothermic
reactions in which H is positive, also take place. There are also reactions in which there is decrease in
entropy, i.e., S is negative but still they occur. It is, thus, clear that for the spontaneity of a reaction both H
and S should be considered simultaneously.
Thus, for processes which do not involve a heat change, increase in entropy is the only criteria. It should be
noted that the criterias for the prediction of direction of spontaneity have been derived through mere observations.
No process/reaction has been found to violate these.
Consider the adiabatic expansion of an ideal gas in vaccum. This system is an isolated system (as no exchange
of energy and mass between system and surroundings). So, direction of spontaneity is expansion process
because expansion will cause an increase in the entropy of the system.
3. Finding the direction of spontaneity :
For spontaneity, Second Law of Thermodyamics defines the following statements:
(i) In an isolated system, direction of increase in entropy of the system is the direction of spontaneity.
(ii) In a non-isolated system, direction of increase in total entropy i.e. STotal = SSystem + SSurroundings, is
the direction of spontaneity.
 For a reaction/process to be spontaneous: STotal = SSystem + SSurroundings > 0
To focus on the system for thermodynamic analysis, SSurroundings is defined and eliminated as :
(a) For a reaction :
q Surroundings q System
SSurroundings  
T T
HSystem
SSurroundings  [Chemical reactions occur at constant T and P]
T
H System
 STotal  SSystem   – TSTotal = HSystem – TSSystem
T

(b) For a process:

T T
STotal  SSystem  SSurroundings [In a short while, we will learn to calculate SSystem ]
Also, a new thermodynamic function, Gibbs energy ‘G’ is introduced to check the spontaneity of the reaction
directly and is defined as :
G = H – TS
 G = H – (TS) or dG = dH – TdS – SdT
Thus, for a reaction taking place at a certain temperature, we can also define spontaineity of a reaction in
terms of change in Gibbs energy as : G System   T STotal =HSystem – TSSystem
(i) If STotal  0  G System  0 [Spontaneous]
(ii) If STotal  0  G System  0 [Non- spontaneous]
(iii) If STotal  0  G System  0 [At Equilibrium]
The free energy of a reaction is the chemical analogue of ‘potential energy’ of mechanical systems. A body
moves in the direction in which there is decrease in potential energy. Similarly, in chemical system, the substance
moves in a direction in which there is decrease in free enrgy, i.e., G is negative.
For any system in which a reaction/process taking place, G = 0 denotes the attainment of equilibrium. In
other words, a reaction/process proceeds till its entropy has become maximum i.e. no furthur change in
entropy is possible. A very famous example is the mixing of two ideal gases which happens till the new system
has become homogenous (because in that state only it will have maximum entropy).
Calculation of Gibbs energy is very important in finding out the direction of spontaineity and is widely, mostly
and mainly used in chemical reactions. We will discuss more on this in the upcoming portions of this chapter.
SSystem  0 
Case (i) :   STotal > 0
SSurroundings  0 
SSystem  0 
Case (ii) :   STotal > 0 or < 0
SSurroundigs  0 
SSystem  0 
Case (iii) :   STotal > 0 or < 0
SSurroundigs  0 
SSystem  0 
Case (iv) :   STotal < 0
SSurroundigs  0 

Clearly, Case (i) is always spontaneous since change in total entopy is always positive i.e. total entropy is
increasing. Case (ii) and (iii) may or may not be spontaneous. Case (iv) is always non-spontaneous since
change in total entopy is always negative i.e. total entropy is decreasing.
4. Calculating entropy change in phase change :

When a substance changes phase (e.g., solid to liquid), there is a change in entropy associated with it (even
though temperature is constant at phase change).
H melting
(a) Melting : Smelting  = Entropy change due to melting (takes place at constant
Tmelting
temperature)
e.g. Entropy change for 1 kg ice at its melting point :
 1000 
 18   6  1000
 Smelting     1220.8 J / K
273
[ Enthalpy of fusion of water = 6 kJ/mole ]
H vaporisation
(b) Vaporisation : Svaporisation 
Tboiling
e.g. Entropy change for 1 kg water at its boiling point :
 1000 
 18   44  1000
Svaporisation     6552.8 J / K
373
[ Enthalpy of vaporisation of water = 44 kJ/mole ]
H Transition
(c) Allotropic Transition : STransition  T
Transition
e.g. Transition of 1 mole of Sulphur from Rhombic to Monoclinic :
402
Stransition   1.09 JK 1 mol1
368.5
[ Enthalpy of transition from rhombic to monoclinic Sulphur = 402 J mole–1 and Ttransition = 368.5 K ]

Entropy of a substance :
First of all, we need to know an important law helpful the entropy of a substance i.e. Third Law of
Thermodynamics. As per Third Law of Thermodynamic (also knows as Nernst heat theorem) :
(a) All substance have same heat capacities at 0 K.
(b) Heat capacity of every substance is zero at 0 K.
(c) Entropy of a perfectly crystalline substance is zero at 0 K.
This law provides an absolute reference point for the determination of entropy. The entropy determined
relative to this point is the absolute entropy.
Entropy change of a reaction :

To calculate Ssystem for a reaction at say T (K), simply balance the reaction and use the following formula:
q  qSys. HSys.
ΔSSystem =  rS   S Products  SReactants and ΔSSurroundings  Surr.  
TSurr. TSurr. TSurr.
as chemical reactions occur at constant T and P.
At standard conditions :  rSΘ   SΘ Θ

P   SR
Note : Every reactant/product will have a non-zero Entropy for T above 0 K.
Variation of Spontaneity of a reaction with temperature :

We can have an idea of the spontaneity of reaction with temperature using :
In general, |H| >> |TS|. Clearly, Entropy factor increases as T increase and decreases as T decreases.
For an exothermic reaction proceeding with a decrease in entropy, G is in general, negative i.e. spontaneous
reaction.
For an endothermic reaction proceeding with an increases in entropy, G is in general, positive i.e. non-
spontaneous reaction.
Thus, in general, exothermic reaction are spontaneous at room temperature and may tend to become non-
spontanceous (if Ssystem < 0) at higher temperatures. In general, endothermic reactions are non-spontaneous
at room temperature and may tend to become spontaneous (if S > 0) at higher temperatures.
Thus, we need to calculate :STotal = SSystem + SSurroundings for the reaction/process and if it comes out
to be > 0 then that direction will be spontaneous.

Note :  The decrease in Gibbs energy is a measure of the maximum useful work that can be obtained from
a system. The Gibbs energy is the maximum amount of non-expansion work that can be extracted
from a system and this maximum can be attained only in a completely reversible process.
 We can have a rough idea of temperature about which there is a spontaneity change for a reaction and
is given by :
Θ
HSystem
TSwitch  Here, we have assumed that H ΘSystem and SSystem
Θ
doesn’t vary with
Θ
SSystem
temperature just to get an idea of TSwitch
Illustration - 4 Assuming  r H Θ and  r S Θ to be independent of temperaturee, at what temperature will the

reaction given below becomes spontaneous?
N2(g) + O2(g) 
 2NO(g) ;  r H Θ = 180.8 kJ mol1.
S Θ / JK 1mol 1 191.4 204.9 210.5

SOLUTION :
First calculate  rSΘ for the given reaction as follows :
 rSΘ   SΘ Θ Θ Θ Θ –1
P   SR  2S NO  S N 2  S O 2 = 2  210.5 – 191.4 – 204.9 = 24.7 J K mol
–1
Using:  r G Θ   r H Θ  T  rSΘ = 180.8 – 298  24.7  10–3 = 173.4 kJ mol–1

Clearly, the given endothermic reaction is non–spontaneous at room temperature. So, we need to increase the
temperature to make the reaction spontaneous.
 r G Θ = 180.8 – (T  24.7  10 ) kJ mol
–3 –1

For spontaneity, put  r G Θ = 0 to get :

Θ
 r HSysstem 180.8  103
TSwitch   Tswitch   7320 K
Θ 24.7
 r SSystem
The reaction becomes spontaneous above a temperature of 7320K.
Illustration - 5 Sulphur exists in more than one solid form. The stable form at room temperature is rhombic
sulphur. But above room temperature the following reaction occurs :
S (rhombic)   S (monoclinic)
If  r H = 276.144 J at 298 K and 1 atm and  r G = 75.312 J
(a) Calculate  r S at 298 K
(b) Assume that r H and  r S do not vary significantly with temperature, calculate Teq, the temperaturee
at which rhombic and monoclinic sulphur exist in equilibrium with each other.
SOLUTION :
(a) Since  r G =  r H  T rS
 H   r G 276.144  75.312
 rS  r  = 0.674 J K– 1
T 298
(b) Under equilibrium condition  r G = 0
 r H 276.144
  r H  Teq  r S = 0  Teq  
 rS 0.674 = 409.7 K
Free energy change of a reaction :

rG for a reaction can be calculated using following two methods :
(i) Using : rG = rH – TrS
(ii) Using : rG =  G Poducts   G Reactants
Take note of the followings while calculating Gibbs energy change for a reaction :
(a) Chemical reaction in which a compound in its standard state is formed from its elements in their
standard states, the Gibbs energy change is the Standard Gibbs energy of formation,  f G Θ .
(b)  f G Θ = 0 for an element in its standard state.
(c) f GΘ =  G Θproducts   G Θreactants =  r H Θ  T rSΘ

(d) rG is an extensive property.
(e) rG changes sign when a process is reversed. [ It can be treated in a similar manner as with rH]

Illustration - 6 Compute the Gibbs energy change of the reaction at 27C for the combustion of methane.
CH4(g) + 2O2(g) 
 CO (g) + 2H O()
2 2
 f H Θ (in kJ mol–1) –74.8  –393.5 –285.8

Θ (in J K–1 mol–1) 186 205 214 70
Sm
SOLUTION :
Θ Θ Θ
 r H Θ =  f H (CO 2 )  2 f H (H 2O)   f H (CH 4 ) = –393.5 + 2  (–285.8) – (–74.8) = –890 kJ mol
–1
Θ Θ Θ Θ
 rSΘ = S(CO )  2S(H O)  S(CH )  2S(O )  214  2  70  186  2  205  242 J/ K/ mol
2 2 4 2
  r G =  r H Θ  T  rSΘ = –890 – 300  (–242  10–3) = –890 + 72.6 = –817.4 kJ mol–1
Illustration - 7 Show that the reaction CO(g) + (1/2)O2(g)   CO2(g) at 300 K, is spontaneous and
1 1
exothermic, when the standard entropy change is 0.094 kJ mol K . The standard Gibbs free energies of
formation for CO2 and CO are 394.4 and 137.2 kJ mol1, respectively.
SOLUTION :
1
For the given reaction, we have : CO(g) + O (g) 
 CO2(g)  r SΘ  0.094 kJ K 1 mol 1
2 2
The free-energy change of the reaction is :
1
 rG Θ  f G Θ
CO 2
 f GΘ Θ
CO   f G O 2
2
Θ
= (–394.4 + 137.2) kJ mol1 = – 257.2 kJ mol–1 [  f G O  0 ]
2
Since  r G Θ is negative, the reaction is spontaneous. The enthalpy change of the reaction is:
 8.314 J mol1 K 1 = [– 257.2 + (300) (– 0.094)] kJ mol = –285.4 kJ mol

–1 –1
Since  r H Θ is negative, the reaction is exothermic.
Gibbs energy and Equilibrium Constant:

We can relate rG for a reaction under any set of conditions to its value for standard conditions, that is, to
 r G Θ by:
rG =  r G Θ + 2.303 RT log10 Q where Q is reaction quotient.
If a system is at equilibrium,  r G Θ = 0. Thus from the above equation :

 r G Θ = 2.303 RT log10 Keq where Keq is thermodynamic equilibrium constant.

Magnitude of  r G Θ determines the value of Keq. Consider three cases:
(i) Keq >> 1 : Reaction proceeds mainly in forward direction and is almost complete
(XProducts  1; XReactants  0)
(ii) Keq << 1 : Reaction does not “wish” to proceed in forward direction (XProduts  0; XReactants  1)
(iii) Keq  1 : Both products and reactants exists in appreciable amounts, at equilibrium.
We have seen how a knowledge of the sign and magnitude of the free energy change of a chemical reaction
allows :
1. Prediction of the spontaneity of the chemical reaction.
2. Prediction of the useful work that could be extracted from it.
So far we have considered free energy changes in irreversible reactions. Let us now examine the free energy
changes in reversible reactions.
‘Reversible’ under strict thermodynamic sense is a special way of carrying out a process such that system is all
times in perfect equilibrium with its surroundings. When applied to a chemical reaction the term ‘reversible’
indicates that a given reaction can proceed in either direction simultaneously, so that a synamic equilibrium is
set up. This means that the reactions in both the directions should proceed with a decrease in free energy,
which seems impossible. It is possible only if at equilibrium the free energy of the system is minimum. If it is
not, the system would spontaneously change to configuration of lower free energy.
So, the criterion for equilibrium
A  B  C D is
r G  0
Variation of Gibbs Energy and Equilibrium Constant :
Note :  Equilibrium is the point of minimum in the above diagrams.

 If we move away from the point of minimum, there will be an increase in Gibbs energy which is non-
spontaneous.

Equilibrium constant vs. Temperature :

For a reaction : r G  r H T r S
At standard conditions :  r G Θ   r H Θ  T  rSΘ
When the reaction reaches equilibrium at temperature T, we have :  r G Θ   RT ln K eq
Thus, we have at temperature T1 :  RT1 ln (K eq )1   r H Θ  T1  rSΘ
and at temperature T2 :  RT2 ln (K eq ) 2   r H Θ  T2  rSΘ
(K eq .) 2  r HΘ 1 1 
Solve to get : ln    
(K eq .)1 R  T1 T2 
Illustration - 8 A certain gas in expanded from (1L, 10 atm) to ( 4 L, 5 atm) against a constant external
pressure of 1 atm. If the initial temperature of gas is 300 K and heat capacity for the process is 50J / C, the
enthalpy change during the process : ( Use : 1 L atm  100 J )
(A) 15 kJ (B) 15.7 kJ (C) 14.3 kJ (D) 14.7 kJ
SOLUTION : (B)
Use : H  U   (PV)  U  (P2 V2  P1V1 )
Calculate U as follows :
P1V1 P2V2 10  1 5  4
(i) Use :     T2  600 K
T1 T2 300 T2
(ii) q  CT  50  (600  300)  15 kJ
(iii)  w  PExt V  (4  1)  3 L atm  0.3 kJ

(iv) q  U  (  w)  15  U  0.3  U  14.7kJ
 H  14.7  (5  4  10 1)  100  103  15.7 kJ

Illustration - 9 For the reaction : N2O4(g)   2NO (g)

2
Calculate rG of the system in a mixture of 5 mol of N2O4 (g) and 5 mol of NO2(g) at 298 K at a total pressure
of 20 atm. Use the following data in kJ mol :  f G Θ (NO2,g) = 50 ;  f G Θ (N2O4,g) = 100
–1
SOLUTION :
We need to calculate rG.. Use : rG =   r G Θ + RT n Q
So, first calculate rG° using :  r G Θ =  G ΘPoducts   GΘReactants

=    f G Θ Pr oducts    f GΘ Reactants
[ At standard conditions : G Θ Θ
compound   f G compound ]
= 2 ×  f G Θ (NO2, g) –  f G Θ (N2O4, g) = 2 × 50 – 100 = 0
 102  –1
and  r G   r G Θ + RT nQ= 0 + 8.314 × 298 n   = 5.70 kJ mol
 10 
 
 2
 5 
 p 2NO   20  
10
 Q  2
  
 p N 2O 4  5  
   20  
  10  
Note :  f G Θ of an element in its standard state is zero.
Illustration - 10 Calculate  G at 298 K for the following reaction if the reaction mixture consists of 1 atm
r
of N2, 3 atm of H2 and 1 atm of NH3.  2 NH 3 ( g );  r G Θ   33.32 kJ

N 2 ( g )  3H 2 ( g ) 
SOLUTION :
–1
 2NH 3 ( g )  r G Θ = – 33.2 kJ mol
N 2 ( g )  3H 2 ( g ) 
Using : rG =  r G Θ + RT nQ
p2
NH 3 l2 l
 
where Q p p3 1  33 27 ; T = 298 K ; R = 8.314 J mol 1 K 1
N2 H2
–3 l –1
 rG = – 33.2 + (8.314 × 10 ) × 298 × 2.303 log10 = – 33.2 – 8.16 = – 41.36 kJmol
27

Illustration - 11 The temperature dependence of equilibrium constant of a reaction is given by :

2059
ln K eq  4.8  Find  r G Θ ,  r H Θ ,  r S Θ .
T
SOLUTION :
2059  rSΘ  r H Θ
Compare ln K eq  4.8  with ln K eq  
T R RT
 rSΘ
We have :  4.8   rSΘ = 4.8 × 8.314 J/K = 39.9 J/K
R
 r HΘ
 2059   r H Θ = 2059 × 8.314 J/K = 17.12 kJ /K
R
 r G Θ   r H Θ  T  rSΘ = 17.12 – 298 × 39.9 × 10 = 5.31 kJ/K
–3
and
Illustration - 12 –5 –5
Ka for acetic acid at 27°C is 2.0 × 10 and at 77° C, Ka is 2.5 × 10 . What are
H Θ and S Θ for the ionization of acetic acid ?
SOLUTION :
 K eq 2  r HΘ  1 1 
Using : n    
 K eq 1 R  T1 T2 
 2.5  10 5   r H Θ  1 1 
n   
  2.0 10  8.314  300 350 
 5
 
–1
  r H Θ = 3.89 kJ mol
Also,  r G Θ = – RT n Keq
–5 –1
   r G Θ = – 8.314 × 298 ×n (2.0 × 10 ) = 26.81 kJ mole
 Taking (K eq ) 25C  (K eq ) 27C 
 
Using :   r G Θ   r H Θ  T  rSΘ
–3 –1 –1
 26.81 = 3.89 – (298 × 10 ) ×  rSΘ    rSΘ = 76.9 J mole K

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Chemical Thermodynamics - II
BASICS Section - 1
1. Heat Capacity :
Heat Capacity (C) : Heat required to raise the temperature of a system by 1°C or 1 K.
Units : J/K; kJ/K
Specific Heat Capacity (c) : Heat required to raise the temperature of a 1gm of a system by 1°C
or 1 K.
Units : J/g/K; kJ/Kg/K
Molar Heat Capacity (Cm) : Heat required to raise the temperature of a 1 mole of a system by 1°C
or 1 K.
Units : J/mole/K; kJ/mole/K
Mathematically, the above quantities are defined as :
q  C  T; q  n  C m  T; q  m  c  T
where q = amount of heat absorbed by the system; T = Rise in the temperature; m = mass of
the system;
n = moles of the system
Note : Molar heat capacity has 2 forms : CP (at constant pressure) and Cv (at constant volume) defined as :
 q   H   q   U 
CP      ; CV      [H  q P ; U  q V ]
 T  P  T  P  T  V  T  V
The subscript after the brackets in the above equation denotes the parameter kept constant during the
process.
 H 
i.e.  T  denotes change in Enthalpy per unit change in Temperature keeping Pressure constant.
 P
In terms of differentials :
 dq   dH   dq   dU 
CP      ; CV      [dH  dq P ; dU  dq V ]
 dT  P  dT  P  dT V  dT  V
C
Also, C P  C V  R ; P  
Cv

Illustration - 1 The molar heat capacity of water in equilibrium with ice at constant pressure is :
(A) zero (B) infinity () (C) 40.45 kJ K 1mol 1 (D) 75.48 kJ K 1mol 1
SOLUTION :
We know that heat capacity at pressure is given by Since the phase transformation i.e., ice  water,,
 H  taken plane at a fixed temperature so T  0.
Cp   
 T P H
 Cp    (B)
0
2. Reversible and Irreversible process :

Reversible process : Process which is carried out in such a manner that it could be reversed by an infinitesimal
change. A reversible process takes infinitesimally small, infinite steps to complete and
time taken to complete the process is infinite. So, it is a theoretical process and it sets
a ceiling on the processes carried out practically.
Irreversible process : Process which doesn’t satisfy the reversible criteria.
Examples of irreversible process :
1. Fee expansion of gas
2. Melting of ice in warmer liquid
3. Anything that is real.
We can also define the reversible and irreversible process in a more of mathematical sense as follows :
Reversible process : Process in which there is an infinitesimally small difference between the driving
force and opposing force.
Irreversible process : Process in which there is a finite difference between the driving force and opposing
force.
For example :
(i) Consider the following two diagrams showing reversible and irreversible expansions :
Here, Opposing force is PExt. and Driving force is PGas .

(ii) Consider the following two diagrams showing reversible and irreversible compressions :
Here, Driving force is PExt. and Opposing force is PGas.

Note :  In many cases, an irreversible process can be easily recognized by using the fact that the process
involving constant external pressure is an irreversible process.
 In a reversible process, an equilibrium exists (known as quasi-equilibrium) at every stage of the
process.
3. Calculating Work (w) for Reversible and Irreversible process :

To calculate work, use the formula :  w   PExt.dV
(i) For an irreversible process, PExt. is constant, thus  w  PExt.V . . . . (iv)
(ii) For a reversible process, PExt.  PGas  dP   w   PGas dV   dPdV   PGas dV
Thus, work (w) depends on the process equation i.e. how PGas and V varies in the process :
I. For Isothermal process :
V  P 
w  2.303nRT log10  2   2.303nRT log10  1  [ P1V1  P2 V2 ]
 V1   P2 
(P V  P2 V2 )
II. For Adiabatic process  w  1 1   U  nC v (T2  T1)
(  1)
Cp
where   (ratio of molar heat capacities at constant P and constant V)
Cv
5 3
(a) Monoatomic gas: C p  R, C v  R,   1.66
2 2
7 5
(b) Diatomic gas : C p  R, C v  R,   1.40
2 2
(c) Polyatomic gas : Cp = 4R, CV = 3R,  = 1.33
III. For Isochoric process : –w = 0
IV. For Isobaric process :  w  PGas V
Note : Work done by system in a reversible expansion process will always be greater than that in irreversible
expansion process.

4. Graphical interpretation of Work :

(i) For a reversible process :
Work can also be graphically calculated for a reversible
process.
It is the area under Pressure vs. Volume diagram as shown :
(ii) For an irreversible process :

For an irreversible process, Pressure vs. Volume graph cannot
be plotted.However, we can represent the irreversible work
(PExt. V) on a Pressure vs. Volume diagram as shown :
5. Types of Irreversible expansion :

(i) Free expansion : Expansion of a gas against vaccum (i.e. PExt. = 0)
(ii) Intermediate expansion : Expansion of a gas when PExt.  0
6. Calculate w, q, H and U for a process and a reaction :

Clearly, we need to create 4 equations to solve 4 variables (w, q, H and U) as follows :
Whether it is a process or a reaction, the first equation will always be applicable :
q  U  (  w) . . . . (i) [From First law of Thermodynamics]
Calculating H and U will be different in case of a process and a reaction and explained as follows :
(i) For a process :
H  nC P T . . . . (ii) [From definition of CP]
T2
or H   nCP dT [When CP is also a function of Temperature]
T1
U  nC V T . . . . (iii) [From definition of CV]
T2
or U   nC VdT [When CV is also a function of Temperature]
T1

Also, H  U   (PV) or dH  dU  dPV  VdP [ H  U  PV]

Many a times, we also write : (PV)  P2 V2  P1V1   ( nRT )  nRT
(ii) For a reaction :

For a reaction, H is the most important parameter and can be calculated as :
rH   HPr oducts  H Re ac tan ts . . . . (ii)
Also,  r H   U  P  V [As Chemical reactions occur at constant pressure and constant tem-
perature]
or r H  U  n g RT . . . . (iii)
Thus, to get the interconversion between  r H and  r U, we must need to write down the balanced
chemical reaction with states of all the reactants and products and then calculate the change in the
number of gaseous moles.
The fourth variable can be calculated based on the process / situation as explained in the illustrations
below :
7. Calculating final temperature T2 in a reversible and irreversible adiabatic expansion pro-
cess :
(i) For a reversible adiabatic expansion process, use :
T1V1 1  T2V2 1 or P11 T1  P21 T2

(ii) For an irreversible adiabatic expansion process, we cannot use the equation :
TV r 1  const . or P1 T   const .
We have to find another way out (use first law of thermodynamics).
Proceed as follows : q  0  U  ( w)
[  Adiabatic process and using First Law of Thermodynamics]
 0 = nC v (T2 - T1 ) + PExt .  V [  w = PExt .  V]
 0  nC v (T2  T1) + PExt . (V2  V1 )
  PExt  
 Cv    R
 nRT2 nRT1   T2    P1  T
 0  nCv (T2  T1 )  PExt.    1
 P  
 P2 P1   Cv   Ext  R
  P2  
Where PExt . is the constant pressure against which system is doing work.
 C   PExt .   R 
If P2 = PExt . (i.e. system expands to external pressure)  T2   v  T1
 Cv  R 

Illustration - 2 1 mole of an ideal gas at 400 K and 10 atm is allowed to expand, adiabatically, against 2.0
 5 
atm external pressure. Find the final temperature of the gas. Use : CV  R 
 2 
SOLUTION :
Finally P2  PExt. and  U  Pext V (as q  0)
 nRT2 nRT1 
n C v (T2  T1)  2   
 2 10 
5 2 
 2 R  10 R   2.7 R 
 T2     400 K     400 K = 308.6 K
5  3.5 R 
 RR 
 2 
8. Comparison between reversible isothermal and reversible adiabatic process :

We can compare reversible isothermal (I) and reversible adiabatic (II) process for two cases through P–V
diagram as follows :
Clearly, work done in reversible isothermal process is greater than in reversible adiabatic process.
Also, we can see that in case (i), final volume is greater in reversible isothermal process and in case (ii) final
pressure is greater in reversible isothermal process.
Note : Sometimes P–V diagrams come as a handy tool to calculate the final conditions rather than doing
rigorous calculations.
 Adiabatic curves are steeper than isothermal curves [madiabatic =  misothermal where ‘m’ denotes slope].

Illustration - 3  3 
1m3 of neon gas  Cv  2 R  at 273.2 K and 10 atm undergoes three different expansions
 
to a final pressure of 1 atm. Calculated the final volume and the work done in three different expansions.
(i) Isothermal reversible expansion (ii) Adiabatic reversible expansion
(iii) Irreversible adiabatic expansion
SOLUTION :
PV (1) (10) The final temperature is obtained from
(i) Final volume, v2  1 1   10 m3
P2 (1) P2V2  nRT2
The work done by the gas in expanding equals
the heat absorbed by the gas from its surrounding.
T2  

P2V2 (1) 3.981  10
3

 108.8 K
V nR (446.1) 0.0821
  w  q  nRT ln 2
V1 For an adiabatic process, q = 0 &  E = w
10  103  3 
w  nCv (T2  T1 )   n R  T2  T1 
n  446.1mol
0.0821  273.2  2 
 w  (446.1) (8.314) (273.2) (2.303) log10 10 3 

 (446.1)  R  (108.8  273.2)  914.1 kJ
 232.85 kJ 2 
(ii) For adiabatic reversible expansion, (iii) For irreversible adiabatic expansion,
1 T T 
Cv (T2  T1)  nRP2  2  1 
 P1  
V2     V1  P2 P1 
 P2 
3 T 273.2 
 T2  273.2   nR(1)  2  
3 2  1 10 
Cp RR 5
  2   T2  174.8 K
Cv 3 3
R
2 3
 E  w  nR(174.8  273.2)  547.4 kJ
2
 V2  (10)3/5 (1)  3.981 m3 Note that there is considerable less cooling
of the gas and less work is done by the gas
in the irreversible adiabatic expansion than
in the reversible adiabatic expansion.

Illustration - 4 A sample of argon gas at 1 atm pressure and 27C expands reversibly and adiabatically
from 1.25 dm3 to 2.50 dm 3 . Calculate the enthalpy change in process ?
SOLUTION :
PV 1.25  1 On solving, T2 = 188.55 K

n=   0.05
RT 0.0821  300  H  nCp  T  0.05  20.794  111.45
TV 1 = constant for adiabatic process  115.87 J
 T1V1 -1 = T2 V2 -1
Illustration - 5 An ideal gas having initial pressure P, volume V and temperature T is allowed to expand
adiabatically until volume becomes 5.66 V while its temperature falls to T/2.
(i) What is the atomicity of gas molecules.
(ii) Obtain an expression for the work done by the gas during the expansion as a function of the initial
pressure P and volume V.
SOLUTION :
For a adiabatic process,
TV 1  constant
T
 T1V1 1  T2V2 1  1 (5.66 V1 ) 1
2
Hence, 2  (5.66) 1 or log 2  (  1) log 5.66    1.4
The gas is, therefore a diatomic gas.
P V P V
The work done by a gas during an adiabatic process is W  2 2 1 1
 -1
Since P1V1 = P2 V2 = P2 (5.66 V1 )
P1  P1(5.66 V1 )  1
P2 =  W  P1V1   1.25 P1V1 or W  1.25 PV

(5.66)  (5.66)  0.4

9. Second Law of Thermodynamics :

It is impossible to consstruct a machine that is able to convey heat by a cyclic process from a colder to
a hotter body unless work is done the machine by some outside agency.
Second law of Thermodynamics also helps in predicting the spontancity of a reaction/process.
A process which proceeds of its own accord without any outside help is termed as a spontaneous process. To
understand the concept of spontaneity, we first need to understand the most important factor involved which
is Entropy (S) and is explained below :
1. Entropy (S) :
Entropy is a thermodynamic state quantity which is a measure of randomness or disorder of the system. More
is the randomness in the system, more is the entropy of the system.
(i) Entropy is a state function and depends only on initial and final states of the system.
(ii) Entropy change of the system for a reversible process is mathematically defined as :
dq Rev dq Rev  q Rev 
dS = or ΔS =  =  [when the heat is absorbed reversibly at constant T]
T T  T 
If heat is absorbed, then S is positive (increase in entropy). If heat is released, then S is negative
(decrease in entropy). Also, for the same amount of heat absorbed, increase in entropy will be more
at lower temperature than at higher temperature.
(iii) If the temperature of a system increases, entropy increases. If the temperature of a system decreases,
entropy decreases.
2. Criteria for Spontaneity :
First law of thermodynamics is basically the law of conservation of energy. It has no restriction on the way
energy can flow. Thus, energy can flow from higher to lower temperature or lower to higher temperature, as
per first law of thermodynamics. But, natural processes tend to flow only in one direction (known as direction
of spontaneity).
A chemical reaction or process tends to follow the direction of minimum energy and maximum randomness,
i.e. reaction will be more probable to occur if it is exothermic or there is an increase in entropy. A reaction
will occur if the value of  H is negative and the value of S is positive. But the endothermic reactions in
which  H is positive, also take place. There are also reactions in which there is decrease in entropy, i.e.,
S is negative but still they occur. It is, thus, clear that for the spontaneity of a reaction both H and S
should be considered simultaneously.
Thus, for processes which do not involve a heat change, increase in entropy is the only criteria. It should be
noted that the criterias for the prediction of direction of spontaneity have been derived through mere observations.
No process/reaction has been found to violate these.
Consider the adiabatic expansion of an ideal gas in vaccum. This system is an isolated system (as no exchange
of energy and mass between system and surroundings). So, direction of spontaneity is expansion process
because expansion will cause an increase in the entropy of the system.

3. Finding the direction of spontaneity :

For spontaneity, Second Law of Thermodyamics defines the following statements:
(i) In an isolated system, direction of increase in entropy of the system is the direction of spontaneity.
(ii) In a non-isolated system, direction of increase in total entropy i.e. STotal = SSystem + SSurroundings, is
the direction of spontaneity.
 For a reaction/process to be spontaneous: STotal = SSystem + SSurroundings > 0
To focus on the system for thermodynamic analysis, SSurroundings is defined and eliminated as :
(a) For a reaction :
T T
HSystem
SSurroundings  [Chemical reactions occur at constant T and P]
T
H System
 STotal  SSystem   – TSTotal = HSystem – TSSystem
T
(b) For a process:
T T
STotal  SSystem  SSurroundings
[In a short while, we will learn to calculate SSystem ]
Also, a new thermodynamic function, Gibbs energy ‘G’ is introduced to check the spontaneity of the reaction
directly and is defined as :
G = H – TS
 G = H – (TS) or dG = dH – TdS – SdT
Thus, for a reaction taking place at a certain temperature, we can also define spontaineity of a reaction in
terms of change in Gibbs energy as : G System   T STotal =HSystem – TSSystem
(i) If STotal  0  G System  0 [Spontaneous]
(ii) If STotal  0  G System  0 [Non- spontaneous]

(iii) If STotal  0  G System  0 [At Equilibrium]
The free energy of a reaction is the chemical analogue of ‘potential energy’ of mechanical systems. A body
moves in the direction in which there is decrease in potential energy. Similarly, in chemical system, the substance
moves in a direction in which there is decrease in free enrgy, i.e., G is negative.
For any system in which a reaction/process taking place, G = 0 denotes the attainment of equilibrium. In
other words, a reaction/process proceeds till its entropy has become maximum i.e. no furthur change in
entropy is possible. A very famous example is the mixing of two ideal gases which happens till the new system
has become homogenous (because in that state only it will have maximum entropy).

4. Calculating entropy change in phase change :

When a substance changes phase (e.g., solid to liquid), there is a change in entropy associated with it
(even though temperature is constant at phase change).
H melting
(a) Melting : Smelting  = Entropy change due to melting (takes place at constant
Tmelting
temperature)
e.g. Entropy change for 1 kg ice at its melting point :
 1000 
 18   6  1000
 Smelting     1220.8 J / K [ Enthalpy of fusion of water = 6 kJ/mole ]
273
H vaporisation
(b) Vaporisation : Svaporisation 
Tboiling
e.g. Entropy change for 1 kg water at its boiling point :
 1000 
 18   44  1000
Svaporisation     6552.8 J / K
373
[ Enthalpy of vaporisation of water = 44 kJ/mole ]
H Transition
(c) Allotropic Transition : STransition  T
Transition
e.g. Transition of 1 mole of Sulphur from Rhombic to Monoclinic :
402
Stransition   1.09 JK 1 mol1
368.5
[ Enthalpy of transition from rhombic to monoclinic Sulphur = 402 J mole–1 and Ttransition = 368.5 K ]

Illustration - 6 A mole of steam is condensed at 100C , the water is cooled to 0C and frozen to ice.
What is the difference in entropies of the steam and ice? The heats of vaporization and fusion are 540 cal gm1
and 80 cal gm1 respectively. Use the average heat capacity of liquid water as
SOLUTION :
Entropy change during condensation of steam
18  540
S1  cal /   26.06 cal / 
373
Entropy change during cooling of water from 100C to 0C
273
S2  18  1ln cal /   5.62 cal / 
373
Entropy change during freezing of water at 0C
18  80
S3   cal /   5.27 cal / 
273
So total entropy change  26.06  5.62  5.27  36.95 cal / 
Hence difference in entropy between steam and ice  36.95 cal / 
5. Calculating S for a process :

To calculate Ssystem for a reversible process, proceed as follows :
dq rev
As per the definition : dS =
T
 TdS = q rev = dU + ( dw) [From First Law of Thermodynamics]
or TdS = n C v dT + P dV [dU = nC v dT and dw = PdV]
nRT nC vdT nR
or TdS = n C v dT + dV  dS = + dV
V T V
Integrating the above equation with appropriate limits, we get :
T  V  q qSys.
Ssystem  nC v In  2   n R In  2  and SSurroundings  Surr. 
 T1   V1  TSurr. TSurr.
Note: Although the above relation has been derived asuming the process to be reversible but this relation can also be
used for an irreversible process as well since Entropy change is a state function.

Illustration - 7 Calculate the total entropy change for the following reversible processes :
(a) Isothermal (b) Adiabatic.
SOLUTION :
T V qsystem
Entropy change for a process is given by : Ssystem  n C V n 2  nR n 2 ; Ssurrounding =
T1 V1 Tsurr.
(a) For isothermal process : T2 = T1
V2
V2 qsystem  n R T  n
 Ssystem  n R n Ssurroundings  V1
  n R n 2
V
V1 and Tsurr  T V1
V2
[ qsystem = nRTn V for isothermal process]
1
 S Total  S system  Ssurroundings  0

T2 V2
(b) For adiabatic process : Ssystem  n CV n T  n R n V
1 1
nR T V
  n 2  n R n 2
   1 T1 V1
 1
T V 
Also, TV –1
= const.  T1V1 1  T2 V2  1  2  1
T1  V2 
nR  V    1  V
 Ssystem  n   1    n R n 2  0
   1  V2   V1
qsystem
and Ssurroundings  0 [ q = 0 in adiabatic process]
Tsurr.
 STotal  Ssystem  Ssurroundings  0
T2 V2
Note : Ssystem  n C V n T  n R n V for both reversible and irreversible process since S is a state
1 1
function.
 Ssystem for irreversible adiabatic process is > 0. This is because (T2)Reversible adiabatic (T2)Irreversible adiabatic
 STotal = 0 for any reversible process and STotal > 0 for any irreversible (i.e. spontaneous) process.

The table below shows the Ssystem and Ssurroundings for some of the famous type of processes in
thermodynamics :
6. Entropy change due to isothermal mixing of two gases (at constant P):
Consider the following diagram which shows two gases before and after mixing :
To find the change in entropy of the system due to mixing, proceed as follows :
V 1  V2  1 
SGas1 due to mixing = n1R  n  n1R  ln   [For ideal gases : n  V at const T and P]
V1  1 
V 1  V2  1 
SGas2 due to mixing = n1R  n  n1R  ln   [For ideal gases : n  V at const T and P]
V2  2 
Total change in entropy of the system : Ssystem (mixing) = S Gas1due to mixing + S Gas2 due to mixing
= –n1R n 1 – n2R n2= –R [n1 n 1 + n2 n 2]
Thus, in general, Ssystem (mixing) = R  n i n i
The above expression can also be expressed as :
 n1 n2 
Ssystem (mixing) 
= –R (n1 + n2) (n  n  n 1   n  2
 1 2) (n1  n 2 ) 

=  R   n i   1  n 1   2  n  2 
Ssystem (mixing) = –R   n i     i n  i 
Illustration - 8 Two vessels divided by a partition contain one mole of N2 and two moles of O2 gas. If
partition is removed and gases mixed isothermally, find the change in entropy due to mixing assuming initial
and final pressure are same.
SOLUTION :
Using Ssystem (mixing) = R  n i n i
 1 2 
= R 1   n    2   n   
 3 3 
  3 
= R   n 3  2  n    = 8.314(1.0 + 2 × 0.4) = 15.9 JK–1
  2 
6. Calculating entropy for a substance :

First of all, we need to know an important law helpful in finding the entropy of a substance i.e. Third Law of
Thermodynamics.
As per Third Law of Thermodynamics (also knows as Nernst heat theorem) :
(a) All substance have same heat capacities at 0 K.
(b) Heat capacity of every substance is zero at 0 K.
(c) Entropy of a perfectly crystalline substance is zero at 0 K.
This law provides an absolute reference point for the determination of entropy. The entropy determined
relative to this point is the absolute entropy.
dq dU + (  w) dU + PdV dU
(d) dS = = = =
T T T T
nC v dT dT
= = n(b + 2 cT) 
T T
T2 T2
nbdT T
 S   T
  2ncdT  nbn T12  2nc(T2  T1)
T1 T1
600
 S  1  16  n  2  1  6  103  (600  300)  14.8 J mol 1K 1
300
T2 V2
Note : Here, we can apply S system  nCv n T  nRn V as Cv  Cv (T )
1 1

Illustration - 9 A sample of an ideal gas is expanded to twice its original volume of 1m3 in a reversible
process for which P  V 2 where   5atm / m 6 . If CV,m = 20 J mol–1 k–1, determine molar change in entropy
(Sm ) for the process.
SOLUTION :
T V
S  nC V  n 2  nR  n 2 (n  1)
Using : T1 V1
P1V1 P2 V2 T2 P2 V2 V23
and     
3 (P =  V2) = 8 ( V2 = 2V1)
T1 T2 T1 P1 V1 V1
–1 –1
 S = 1 × 20 × n 8 + 8.134n 2 = 45.8 J mol K
10. Calculating rG for a process :
By definition : G = H – TS  dG  dH  TdS  SdT . . . .(i)

Also, H  U  PV  dH  dU  PdV  VdP . . . . (ii)
and dq  dU  ( dw) . . . . (iii)
and TdS  dq . . . . (iv)
Using (i), (ii) (iii) and (iv), we have : dG = VdP – SdT
(a) For a process at constant pressure : dP = 0  dG 

 dG   SdT     S
 dT  P
Since ‘S’ is always positive, above equation tells us that as temperature increase keeping pressure
constant, Gibbs energy decrease with rise in temperature.
 dG 
(b) For a process at constant temperature : dT = 0  dG = VdP    V
 dP T
Thus, at constant temperature, Gibbs energy increases with a rise in pressure since ‘V’ is always
positive.
Illustration - 10 1.0 mol of an ideal gas, initially present in a 2.0 L insulated cylinder at 300 K is allowed to
expand against vacuum to 8.0 L, Determine, w, U , H , STotal and G.
SOLUTION :
w   Pext V  0; q = 0 (Insulated Cylinder)  U  0  H
 T f  300 K

V
S sys  nR ln 2  2 R ln 2  11.52 JK 1
V1
and S surr  0  qsys  qsurr  0
 STotal  11.52 JK 1  G  T STotal  300  11.52  3456 J .
Illustration - 11 Which of the following processes thermodynamic relation(s) is (are) correct ?

(A) In a cyclic process,  dS  0 (B) G  H  T S
 G 
(C)    S (D)  r G   r G   RT ln Q, Q = Reaction quotient
 T  P
SOLUTION :
As we know for a cyclic process For constant pressure
 dS  0  G 
 T    S
Also dG = Vdp – SdT  T
dG VdP G  H  T S true for a reaction only..
  S
dT dT G  G  RT n Q true for a reaction only..
Illustration - 12 Calculate the entropy change per mole of substance in each of the following cases.
(i)  Liquid )  4540 J mol 1.

The freezing of isobutene at 160C. H ( Solid 
(ii) Vapour )  407 mod 1 .

The vaporization of water at its boiling point, 100C. H ( Liquid 
(iii) Expansion reversible and isothermally of an ideal gas from a volume of 2 dm3 to 10 dm3 at 27C .
Also calculate entropy change of surroundings due to the process.
(iv) Expansion irreversibly and isothermally of an ideal gas from dm3 to 10 dm3 against a constant pressuree
of 1 atm, at 27C . Also calculate entropy change of surrounding due to the process.
SOLUTION :
(i) Freezing temperature of isobutene  160C  (160  273) K  113K
q
S  rev
T
4540
Here qrev  4540 J mol 1  S   40.2 JK 1mol 1
113

Note that is freezing, the substance becomes more ordered. Hence, entropy is lost by the substance
(S is  ve).
(ii) For the reversible vaporization of water at 100C ,
q L H vap 407000
S  rev     1091.2 JK 1mol 1
T T T 373
P
(iii) For an isothermal process, S  R ln 1
P2
1 1  P2V2
At constant temperature, PV
P1 V2 V 10
   S  R ln 2  8.314  2.303 log  13.4 JK 1 mol
P2 V1 V1 2
If we treat system and surroundings as an isolated system, entropy change of surrounding
 S  13.4 JK 1mol 1.
 For a reversible process entropy of universe remains constant. Total entropy change for isolated
system = 0
(iv) Total entropy change of the system, has to be calculated assuming a reversible path,
dqrev V
S system    R ln 2  13.4 JK 1mol 1 [Same as in (iii)]
T V1
If we consider system and surrounding as an isolated system, entropy change of surrounding,
Heat exchanged by surrounding q
S surrounding  
T T
For the system,
E '  0  q  w   w  P (V2  V1 ). For surrounding, q   P(V2  V1 ).
1(10  2) L atm 8 8.314
 S surrounding     2.7 J / mol 1K .
300 K 300 0.0821
Entropy change of isolated system S system  S surrounding  13.4  2.7  10.7 J / mol 1K . For an
irreversible process, entropy of universe increase.

IN - CHAPTER EXERCISE
1. One mole of an ideal gas is put through a series of reversible changes

as shown in the graph A, B, C. At each stage the variables are shown
in the graph. Calculate the pressure at three stages of the system and
net work done in the cylic process.
2. A gas contained in a cylinder fitted with a frictionless piston expands against a constant pressure 1
atmosphere from a volume of 4 litre to a volume of 14 litre. In doing so, it absorbs 800 J thermal energy
from surroundings. Determine U for the process.
SOLUTIONS TO IN-CHAPTER EXERCISE
n RT 1  0.08 2  300
1. Using PV = nRT  PA  A A   1.02 atm
VA 24
1  0.082  600 1  0.082  300
and PB   2.04 atm ; PC   2.04 atm
24 12
 w A  B  0 ;  w B  C  PBV  2.04(12  24) Latm  w B  C  24.48 Latm  2.48 kJ
(Isochoric) (Isobaric)
V 24
 w C  A  nRT n 2  1  8.314  300 n  w C  A   1.73 kJ
V1 12
(Isothermal)
 wnet = 0 + 2.45 – 1.73 = 0.72 KJ
2. 800  U  1  (14  4)  101.3  U  800  1013  213 J
ANSWERS TO IN - CHAPTER EXERCISE
1. PA  1.02 atm ; PB  2.04 atm ; PC  2.04 ; 0.72 kJ 2. 213 J
Self Study Course for IITJEE with Online Support Solutions & Answers 19
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Thermochemistry
Thermochemistry
BASICS Section - 1
In this chapter, we will study the heat changes that take place when a chemical process occurs. Heat
(a form of energy) is either evolved or absorbed in the course of chemical reaction. The study of energetics
considers the relationship between thermodynamical functions : heat (q), work (W) and internal energy
(U or E).
1. Definitions :
System :
A small portion of the universe with-in which we confine our study of energy changes is called as a system.
Surroundings :
The remainder of the universe (i.e., apart from the system), which can interact with the system is called as
surroundings.
Open System :
This type of system can exchange matter as well as energy
with surroundings. The boundary is not sealed and not
insulated. Sodium reacting with water in an open bea-
ker is an example of open system.
Closed System :
This type of system can exchange energy in the form of
heat, work or radiations but not matter with its sur-
roundings. The boundary between system and surround-
ings is sealed but not insulated. For example, liquid in con-
tact with vapour in a sealed forms a closed system. Heat
can be transferred through the walls of the tube to the sur-
roundings but total amount of matter remains the same as
vapours cannot escape.

Thermochemistry Vidyamandir Classes
Isolated System :
This type of system has no interaction with its sur-

roundings. Neither matter nor energy can be exchanged
with surroundings. A substance contained in an ideal ther-
mos-flask is an example of an isolated system.
2. Thermodynamics Properties :
(i) Intensive Properties :
The properties which do not depend upon the quantity of matter present in the system are called
Intensive properties. Pressure, temperature, specific heat, surface tension, refractive index, viscos-
ity, melting point, boiling point, volume per mole (molar volume), concentration, colour potential
electrical field electrical resistivity, specific energy, etc. are examples of intensive properties of the
system.
(ii) Extensive Properties :
The properties whose magnitude depends upon the quantity of matter present in the system are
called Extensive Properties. Internal energy, total moles, volume, enthalpy, entropy, Gibbs en-
ergy, length, mass, electrical resistance etc. are examples of extensive properties.
3. Internal Energy (U) :
All the possible forms of energy that are associated with a system are referred to as Internal Energy. It
includes kinetic energy due to all kind of motion of the particles of the system, and their potential energy due
to intermolecular forces (interaction). It is impossible to measure the exact value of the internal energy of a
system. It can be measured when the system changes its state i.e. as change in internal energy (U).
The internal energy change of a system depends upon the state of the system and not on how the system
achieved the particular state. Such a thermodynamic function is called as state function. Other examples
are: temperature, pressure volume, enthalpy, entropy, Gibbs energy etc.
If U1 is the internal energy of a system in state 1, and U2 in the state 2, then the change in the internal energy
of the system (U) is given by : U = U2 – U1
As stated above, U is independent of the process which takes the system from state 1 to state 2.

4. First law of Thermodynamics :

Energy can neither be created nor destroyed, although it can be transformed from one form
to another.
If we supply an amount of heat (= q) to the system in state 1, the system does a work w and goes to achieve
the state 2. The heat supplied to the system gets converted into two parts :
(a) Work done by the system
(b) Change in internal energy of the system.
From law of conservation of Energy, we have :
q = U + (– w) . . . . (i)
This equation is known as First Law of Thermodynamics.
5. Sign Convention :
 w is positive, when the work is done on the system.
 w is negative, when the work is done by the system.
 q is positive, when the heat is supplied to the system.
 q is negative, when the heat is lost by the system.
6. Enthalpy :
It is a thermodynamic function (H) defined to study heat changes in chemical reactions. It is also known as
heat content of the stem defined as :
H = U + PV where P : Pressure V : Volume
If the change of state takes place at constant pressure, q is denoted as qp (heat transfer at constant pres-
sure). It is also known as change in enthalpy of the system, represented as
H = qp (H : Enthalpy of the system).
In such a process, volume of the system will change and work done is given as :
w = – P V V : change in volume
 qp = U + P V [Using first law of thermodynamics]
or qp = U2 – U1 + P (V2 – V1)
or qp = (U2 + PV2) – (U1 + PV1)
or qp = H2 – H1 = H where H1 = U1 + PV1 = enthalpy of the system in state 1
and H2 = U2 + PV2 = enthalpy of the system in state 2
Enthalpy change like internal energy change in a state function.

Heat change in all chemical reactions is studied as enthalpy change of the reaction (rH). System in state 1
is taken as system of reactants and in state 2 taken as system of products. Enthalpy change (Heat change)
accompanying the reaction is given as :
rH = Enthalpy of products – Enthalpy of reactants =  (Hproduct) –  (Hreactants)
If the change of state takes place at constant volume, q is denoted as qv (heat transfer at constant volume).
U = qv
7. Exothermic and Endothermic reactions :

(a) Exothermic reactions :
Chemical reactions in which heat is evolved are known as exothermic reactions.
For example : 2Mg(s) + O2(g) 
 2MgO(g)
N2(g) + 3H2(g) 
 2NH3(g)
Both of the above reactions are exothermic reactions because heat is evolved in them.
In general, an exothermic reaction is represented as : Reactants 
 Products + heat
Here enthalpy (or heat content) of reactions is partially transferred to the enthalpy of the products
and partially evolved as heat.
If HR : enthalpy of reactants and HP : enthalpy of products
Clearly, HP < HR  rH < 0 [rH = HP – HR]
i.e. for exothermic reaction, rH (reaction enthalpy) will bear a – ve sign (evolution of heat)
Note : In exothermic reaction, for some time (i.e. during the change) temperature of the products will rise above
room temperature. But, very soon the heat is lost to surroundings and the same temperature is maintained.
(b) Endothermic Reactions :

Chemical reactions in which the heat is absorbed from the surroundings are known as
endothermic reactions.
For example : N2 (g) + O2 (g) 
 2 NO (g)
H2 (g) + I2 (g) 
 2 HI (g)
Both of the above reactions are endothermic reactions because in them heat is absorbed from the
surroundings.
In general, an endothermic reaction can be expressed as :
Reactants + heat 
 Products

Here, enthalpy of products is derived from enthalpy of reactants plus the absorbed heat.
Clearly HP > HR
 rH > 0 [rH = HP – HR]
i.e. for endothermic reactions, rH (reaction enthalpy) will bear a +ve sign (absorption of heat)
Note : In endothermic reactions, (unlike exothermic reactions), temperature of the reacting mixture falls during the
change. But very soon, heat is absorbed from the surrounding and same temperature is restored.
8. Enthalpy Change at Standard Conditions :

rH depends upon the conditions under which a reaction is performed. So to compare enthalpy changes of
various reactions, they are performed at standard conditions.
Standard conditions for temperature and pressure are 298 K (or 25°C) and 1.0 atm pressure. Any enthalpy
change measured under these conditions is known as Standard Enthalpy change or Standard Heat of
reaction and it is denoted as  r H  .
It is also important to specify the states of all reactants and products in a reaction. [‘s’ for solids, ‘l’ for
liquids, ‘g’ for gases (or free atoms), ‘aq’ for solution in water].
A chemical reaction which clearly informs about the heat change accompanying it (i.e. exothermic or endot-
hermic) and the physical state of all reactants and products is known as Thermochemical Equation.
1
For example :  CO( g ) ;
C(s)  O2 ( g )  rH1 = – 385.2 kJ (Exothermic)
2
1 1
N2 ( g )  O2 ( g ) 
 NO( g ) ; rH = + 90.25 kJ (Endothermic)
2 2
Note : rH is the reaction enthalpy for a reaction in any form (i.e. stoichiometric coefficients) e.g. refer to the
reaction below :
2C(s) + O2 (g) 
 2 CO(g) ; rH2 = – 770.4 kJ (Exothermic)
Here, rH2 =2 rH1
9. Enthalpy of a Compound :
To define the enthalpy of a compound, it is taken that the enthalpy of an element in its most stable state at
standard conditions is zero.

Standard states of some elements :

C : Graphite ; S : Rhombic ; Br as Br2 () ; I as I2 (s); H as H2 (g) ;
Cl as Cl2 (g); N as N2 (g) ; O as O2 (g);
P : White (Exception : Red Phosphorus is more stable than White Phosphorus)
e.g. H
Cl 2 (g)
 0 ; H
H 2 (g)
0; H
O 2 (g)
 0; H
Br2 ( )
 0 ; H
I2 (s)
0;
Consider the following thermochemical equations at 25°C and 1 atm.
1 1
H2 (g) + Cl2 (g) 
 HCl (g)
2 2
It represents formation of HCl at standard conditions i.e.  f H   H of given reaction
From definition : rH =  (Hproducts) –  (Hreactants) =  ai (H)m, products –  bi (H)m, reactants
[Hm is the molar enthalpy of the compound and ai & bi the stoichiometric coefficients of products and
reactants respectively]
1  1  
  r H   f H   H 
HCl   H H 2  H Cl2  [see definition of  f H  in Section – 2]
2 2 
  f H   H HCl  0 [Enthalpy of elements in standard state = 0]
 H 
(HCl)   f H(HCl)
Hence the enthalpy of a compound is the standard heat of formation of the compound OR enthalpy
of a compound is often taken as standard enthalpy of formation of that compound.
Enthalpy of a compound A at standard conditions =  f H  of A
 
Note : By convention,  f H  H   aq   0
Illustration - 1 How much heat is evolved by the preparation of 100 gm of iron by the following
reaction ?
 2 Fe(s) + Al2O3 (s) ; rH = – 202.6 kcal/mol
2 Al (s) + Fe2O3 (s) 
SOLUTION :
From thermochemical reaction, it is clear that 202.6 kcal of heat is involved when two moles of Fe (iron) is
formed.
 2 moles of Fe  202.6 kcal
 1 mole of Fe  101.3 kcal
 100/56 mole of Fe  101.3 × 100/56 = 180.9 kcal

Heat of Reaction Section - 2
The heat of a reaction can be assigned special names in the following manner :
(a) Standard Heat of Formation (  f H  ) :

The heat evolved or absorbed when one mol of any compound is formed from its elements in their
standard states. It is usually denoted by  f H    f H  can be given –ve or +ve sign, depending
upon whether formation is exothermic or endothermic.
C(s, graphite) + 2 H2 (g) 

 CH4 (g) ;  f H  = – 74.3 kJ/mol
1 1
H2 (g) + I2 (s) 
 HI (g) ;  f H  = 25.92 kJ/mol
2 2
Note : To write chemical equations for formation, balance the reaction for one mole of compound whose formation
is to be studied.
(b) Standard Heat of Combustion (  c H  ) :

The heat evolved (or enthalpy change) when one mole of any substance is completely burnt in excess
of oxygen.
 c H  will always bear –ve sign for it being enthalpy change of an exothermic reaction.
CH4(g) + 2 O2(g) 
 CO2(g) + 2 H2O() ;  c H  = –212 kcal/mol
C(s, graphite) + O2(g) 

 CO2 (g) ;  c H  = –94 kcal/mol
Note : To write chemical equations for combustion, balance the reaction for one mole of compound whose com
bustion is to be studied.
Illustration - 2 15
Calculate  r H  for the reaction : C6H6 () + O (g) 
 6 CO2 (g) + 3 H2O ()
2 2
Given the standard heat of formations (  f H  ) of H2O (), CO2 (g) and C6H6 () are – 57.80 kcal/mol,
– 94.05 kcal/mol and 19.8 kcal/mol respectively.
SOLUTION :
Whenever, standard heat of formation (  f H  ) of a compound is given it means that enthalpy of
that particular compound at standard state is given. Also, note that in the question, molar enthalpy
changes are given.

Using the definition of enthalpy change as : rH = H(products) – H (reactants)
For the given reaction :  r H   (H  

products )   (H reactants )
or  r H   (f H  
products )  (  f H reactants )
15
C6H6 () + O (g) 
 6 CO2 (g) + 3 H2O ()
2 2
f H 19.8 0 (–94.05) (–57.8)
  r H  = [6 × (–94.05) + 3 × (–57.8)] – [19.8] = – 757.50 kcal/mol.
(c) Heat of Dissociation (  bond H  ) :

It is the amount of energy required to break one mole of bonds in a molecule (in gas phase) into
gaseous atoms.
 2H (g) ;  bond H  = 103 kcal/mol

H – H (g) 
 2C (g) ;  bond H  = 80 kcal/mol

C – C (g) 
Note : (i)  bond H  is always positive i.e. energy is always required to break the bond between two atoms.
(ii) Whenever a bond is formed between two atoms in gaseous state, energy is always released.
(d) Heat of Phase change :

It is the amount of energy required to change the phase of a substance under the particular conditions
for the phase change.
H2O (s) 
 H2O () ;  fus H  = 6 kJ/mol at 273 K and 1 atm
H2O () 
 H2O (g) ;  vap H  = 40.8 kJ/mol at 373 K and 1 atm
CO2 (s) 
 CO2 (g) ; sub H = 108 kcal/mol at 195 K and 1 atm
Note : (i)  fus H  : Amount of heat required to melt one mole of a substance at a constant temperature
and 1atm pressure.
(ii)  vap H  : Amount of heat required to vaporize one mole of a substance at a constant
temperature and 1 atm pressure.
(iii) sub H : Amount of heat required to sublime one mole of a substance at a constant
temperature and 1 atm pressure.

(e) Heat of Atomization (  a H  ) :

It is the amount of energy required to break the bonds in a molecule (in gas phase) into gaseous
atoms.
Na (s) 
 Na (g) ;  a H  = 108 kJ/mol
H – H (g) 
 2H (g) ;  a H  = 435 kJ/mol
CH4 (g) 
 C (g) + 4 H (g) ;  a H  = 1665 kJ/mol
Note : (i) For a monoatomic molecule (i.e. atom) in solid phase,  a H  is also called as sub H  .
(ii) For a diatomic molecule,  a H  is also called as  bond H  .
(iii) For a polyatomic molecule, it is the enery required to break all the bonds to form gaseous atoms.
(f) Average Heat of Dissociation ( mean, bond H  ) :
It is the average amount of energy required to break one mole of bonds in a polyatomic
molecule (in gas phase) into gaseous atoms.
CH4 (g) 
 C (g) + 4 H (g) ;  a H  = 1665 kJ/mol
Note : In general, in a polyatomic molecule, the energy required to break a bond changes in the successive bond
dissociations. For example :
CH4 (g) 
 CH3 (g) + H (g) ;  bond H1
CH3 (g) 
 CH2 (g) + H (g) ;  bond H 
2
CH2 (g) 
 CH (g) + H (g) ;  bond H 3
CH (g) 
 C (g) + H (g) ;  bond H 
4
 1 
Here :  bond H1   bond H 2   bond H3   bond H 4 and  mean, bond H   a H
4

(g) Heat of Lattice(  lattice H  ) and Heat of Hydration(  hyd H  ) :
 lattice H  : It is the energy required to break one mole of an ionic compound into ions in their
gaseous atoms.
 Na+ (g) + Cl– (g)

NaCl (s)  ;  lattice H  = 787 kJ/mol
 hyd H  : It is the energy released when atoms (gaseous) in one mole of an ionic compound gets
hydated.
Na+ (g) + Cl– (g) (  NaCl ) 

 Na+ (aq.) + Cl– (aq.) ;
 hyd H  = –783 kJ/mol

Note :  lattice H  is always positive and  hyd H is always negative.
(h) Heat of Solution ( sol H  ) :
It is the change in enthalpy when one mole of a substance (solute) is completely dissolved in excess of
water.
 Na+(aq) + Cl–(aq)
NaCl(s) + aq  ; sol H  = 5 kJ
HCl(g) + aq 
 HCl(aq) ; sol H  = –x kJ

Note : (i) sol H  =  lattice H  +  hyd H (can be positive or negative)
(ii) Generally, when gases are dissolved, heat is evolved. In case of salts (solids), heat is absorbed
except when anhydrous salts are dissolved.
(i) Heat of Ionisation ( ionisation H  ) :
It is the amount of heat absorbed when one mole of a compound completely dissociates into ions in a
solution.
 H+(aq) + CN–(aq)
HCN(aq)  ; ionisation H  = + p
 NH4+(aq) + OH–(aq)
NH4OH(aq)  ; ionisation H  = + q

(j) Heat of Neutralisation (  neutralisation H  ) :
It is the amount of heat liberated when one gm-equivalent of acid completely neutralises by one gm-
equivalent of base. In water, all strong acids (HCl, H2SO4, HNO3) and strong bases [NaOH, Ca(OH)2,
etc] ionise completely.  neutralisation H  is constant for strong acid and base neutralization and is
equal to –13.7 kcal/mol = –57.27 kJ/mol.
Neutralisation can be treated as :
H +(aq) + OH–(aq)  H2O ()

 ;  neutralisation H  = –13.7 kcal/mol
Note : (i)  neutralisation H  for weak acids (HCN, CH3COOH, benzoic acid) and weak bases (NH4OH,
amines) is lower than that for strong acids and bases. The reason is that heat is absorbed in complete
ionisation of weak acids and bases (unlike in case of strong acids and bases where no heat is required
for ionisation).
(ii)  neutralisation H  for the reaction between HCl and NaOH in aprotic solvents (solvents which doesn’t
ionizes) e.g. benzene etc. is less than –13.7 kcal/mol because HCl is a polar covalent substance and
doesnt get ionizes in aprotic solvent so requires non-zero ionisation H  for neutralization.
(iii)  neutralisation H  for the reaction between HF and NaOH is –16.27 kcal/mol which is greater than
the expected value of –13.7 kcal/mol (obviously to be compared in terms of magnitude). The differ-
ence is due to a very high heat of hydration of flouride ion due to its small size.

Hess’s Law of Constant Heat Summation Section - 3
It states that change in enthalpy for any chemical reaction is constant, whether the reaction occurs
in one step (directly) or in several steps (indirectly).
OR
The enthalpy change in a reaction depends upon initial and final states and is independent of the
route followed to complete the reaction.
It is the direct consequence of law of conservation of energy. rH of overall reaction will be obtained by
“appropriate summation” of the changes in enthalpies of various intermediate steps.
Find the enthalpy change for formation of NO2(g).
1
N (g) + O2 (g) 
 NO2(g) ; f H = ?
2 2
Using given thermochemical equations, and applying Hess’s Law :
1 1
(i) N2 (g) + O2 (g) 
 NO (g) ; rH1  (f H) NO
2 2
1
(ii) NO (g) + O (g) 
 NO2 (g) ; rH2  (c H) NO  ( f H) NO2
2 2
Adding two equations, we get :
1
N (g) + O2 (g) 
 NO2 (g)  rH = rH1 + rH2
2 2
1
Find rH of reaction : H2 (g) + O (g) 
 H2O (g)
2 2
1
(i) H2(g) + O (g) 
 H2O () ; rH1= –68.3 kcal/mol  (f H)H 2O  (c H)H 2
2 2
(ii) H2O () 

 H2O (g) ; rH2 = 10.52 kcal/mol  ( vap H)H 2 O
From Hess’s Law : rH = rH1 + rH2 = (–68.3) + (10.52) = –57.78 kcal/mol

Illustration - 3Enthalpy of neutralisation of acetic acid by NaOH is 50.6 kJ/mol. Calculate H for ionisation
of CH3COOH. Given, the heat of neutralisation of a strong acid with a strong base is –57.3 kJ/mol.
SOLUTION :
The neutralisation of a strong acid by a strong base is represented as :
H+ (aq) + OH– (aq) 

 H2O () ;  Neutralisation H   57.3 kJ / mol
Now acetic acid is a weak acid, so its neutralisation is represented in two stages: First complete ionisation
of weak acid and then complete neutralisation of the fully ionised acid by the base.
1.  CH3COO– (aq) + H+ (aq) ;  Io n isatio n H   ?

CH3COOH (aq) 
2. H+ (aq) + OH– (aq) 

 H2O () ;  Neutralisation H   57.3 kJ / mol
Now adding the two equations to get the equation of neutralisation ;
 CH3COO– (aq) + H2O () ;  Neutralisation H   50.6 kJ / mol

CH3COOH (aq) + OH– (aq) 
From Hess’s Law :  Ionisation H   ( 57.3)  50.6   Ionisation H   6.7 kJ / mol
Illustration - 4 Find the heat of formation of ethyl alcohol from following data :
C (s) + O2 (g) 
 CO2 (g) ; rH = –94 kcal/mol
1
H2 (g) + O (g) 
 H2O () ; rH = –68 kcal/mol
2 2
C2H5OH () + 3O2 (g) 
 2 CO2 (g) + 3 H2O () ; rH = –327 kcal/mol
SOLUTION :
Always write the balanced thermodynamic equation for which rH is to be calculated.
1
2 C (s) + 3 H2 (g) +  C2H5OH () ; fH = ?
O (g) 
2 2
Given :
I. C (s) + O2 (g) 
 CO2 (g) ; rH1 = –94 kcal/mol  (f H)CO 2  (c H)C
1
II. H2 (g) + O (g) 
 H2O () ; rH2 = –68 kcal/mol  (f H)H 2O  (c H)H 2
2 2
 2 CO2 (g) + 3 H2O () ; rH3 = –327 kcal  (c H)C2 H5OH
III. C2H5OH () + 3O2 (g) 

Now adding appropriately to get the required equation (Using Hess’s Law) :
Operate : 2 (I) + 3(II) – (III) to get :
1
2 C (s) + 3 H2 (g) + O (g) 
 C2H5OH ()
2 2
From Hess’s Law : fH = 2(rH1) + 3(rH2) - rH3 = 2 (–94) + 3(–68) – (–327) = –65 kcal/mol
Illustration - 5 From the following data, calculate the standard enthalpy change for the combustion of
cyclopropane at 298 K :
The enthalpy of formation of CO 2 (g), H 2 O() and propene(g) are –393.5, –285.8 and 20.42 kJ mol–1
respectively.
The enthalpy of isomerisation of cyclopropane to propene is –33.0 kJ mol–1.
SOLUTION :
9
CH3CH = CH2(g) + O (g) 
 3CO2(g) + 3H2O() . . . . (i)
2 2
       9  
c H (Propene) = 3 f H(CO2 )  3 f H (H 2O)     f H(Propene)   f H O2 
 2 
= 3 (– 393.5) + 3 (– 285.8) – (20.42) = – 2058.32 kJ mol–1
To the above reaction, if we add the reaction :
isomerization H   33.0 kJ mol1
we get :

Hence, c H(cyclopropane)  (2058.32  33.0) kJ mol 1  2091.32 kJ mol 1

Heat of Reaction and Bond Energy Section - 4
Let us consider that the bond energy of AB molecule is x kcal/mol.

Bond Formation :  A – B ; rH = – x
A + B  (Bond formation is exothermic)
Bond Dissociation :  A + B ; rH = + x
A – B  (Bond dissociation is endothermic)
During a chemical reaction, atoms and molecules are rearranged to form new molecules. During
the course of chemical reaction, old bonds are broken (of reactants) and new ones are formed (of
products).
A given chemical reaction can be analysed energetically into two parts :
(i) Bond Breaking (endothermic, rH > 0)
(ii) Bond Formation (exothermic, rH < 0)
If rH1 is the enthalpy change during bond breaking (i) and rH2 is the enthalpy change during bond
formation (ii), then overall enthalpy change of the reaction (rH) is given by Hess’s Law:
rH = rH1 + rH2
As discussed, rH can be calculated using Hess’s law of constant heat summation or using :
rH = H Product  H Reactants .
rH can also be theoretically calculated using bond energies in the following manner :
(i) On the reactants side, calculate the energy required to break all the bonds. If there is an element in
Solid / Liquid state, also consider the energy required to convert it into gaseous state.
(ii) On the products side, calculate the energy released when products are formed. If there is an ele-
ments/compound in Solid/Liquid state, also consider the energy released when it is converted from
gaseous state to the required state.
(iii) Add total energy released and absorbed to get rH.
Illustration - 6 Find rH of the reaction : OF2 (g) + H2O (g) 

 O2 (g) + 2 HF (g) ;
Average bond energies of O–F, O–H, O = O, H–F are 44, 111, 118 and 135 kcal/mol respectively.
SOLUTION :
OF2 (g) + H2O (g) 
 O2 (g) + 2 HF (g) ; rH = ?
(i) Bond Breaking: (endothermic) : rH1
 O (g) + 2 F (g) ; rH = + 2 × 44
F – O – F (g)  [bond energy of O – F = 44]
 O (g) + 2 H (g) ; rH = + 2 × 111
H – O – H(g)  1 [bond energy of O – H = 111]
 rH1 = 2 × 44 + 2 × 111 = + 310 kcal.

(ii) Bond Formation: (exothermic) : rH2

O (g) + O (g) 
 O = O(g) ; rH = –118 [bond energy of O = O = 118]
2[H (g) + F (g) 
 H – F (g)] ; rH = – 2 × 135 [bond energy of H – F = 135]
 rH2 = –118 + (–2 × 135) = –388 kcal
Now using Hess’s Law ; rH = rH 1 + rH2 = 310 + (–388) = –78 kcal
Illustration - 7 Find f H of HCl (g) if bond energies of H2, Cl2 and HCl are 104, 58, 103 kcal/mol respec-
tively.
SOLUTION :
1 1
H2 (g) + Cl2(g) 
 HCl (g) ; f H = ?
2 2
Now analyse the given thermochemical equation in two parts :
(i) Bond Breaking [rH1] : Endothermic Reaction
H2(g) 
 2 H(g) ; rH = 104 kcal/mol
Cl2(g) 
 2 Cl(g) ; rH = 58 kcal/mol
1
[H (g) 
 2 H(g) ; 104] [as we need mole of each reactant]
2 2
1
[ Cl2(g) 
 2 Cl(g) ; 58]
2
1 1
 rH1 = × 104 + × 58 = 81 kcal
2 2
(ii) Bond Formation : (rH2) : Exothermic reaction
 HCl (g) ; r H = –103 kcal

H(g)+ Cl (g)  (Bond energy of HCl = 103 kJ/mol)
r H2 = –103 kcal
Now r H = f H = r H1 + r H2 (using Hess’s Law)
 f H = 81 + (–103) = –22 kcal/mol

Illustration - 8 Calculate rH for the following homogeous gaseous reaction :

CH3COCH3(g) + 2O2(g) 
 CH3COOH(g) + CO2(g) + H2O(g)
Use the data in kcal mol–1. bond C – H = 99 ; bond C – C = 83 ; bond C = O = 173 ;
bond O = O = 118 ; bond C – O = 84 ; bond O – H = 110
SOLUTION :
First calculate the energy required to break all the bonds in reactants side and to convert them into gaseous
atoms.
H O
| ||
(i) 4H(g) + 2C(g) + 2O(g) 
 H  C  C  O – H (g)
|
H
Energy released = 3Bond C – H + Bond C – C + Bond C = O + Bond C–O + Bond O–H
= 3 × 99 + 83 + 173 + 84 + 110 = 747 kcal

(ii) C (g) + 2O (g) 
 O = C = O (g)
Energy released = 2Bond C = O = 2 × 173 = 346 kcal
 Total energy released = 1313 kcal
 rH = 1169 + (–1313) = –144 kcal mol–1
(iii) 2H(g) + O(g) 
 H – O – H(g)
Energy released = 2Bond O – H = 2 × 110 = 220 kcal
Note : (i) While calculating rH using the bond energy concept, it is important to know the structure of the
molecules/compounds taking part in the reaction.
(ii) If the reaction would have been :
CH3COCH3(g) + 2O2(g) 
 CH3COOH(g) + CO2(g) + H2O()
then we also need to consider the energy released for the conversion of H2O(g) 
 H2O()
rH = –144 – 9.72 = – 153.72 kcal

Illustration - 9 Compute the heat of formation of liquid methyl alcohol, using the following data (in
kJ/mol) : Heat of vaporization of liquid methyl alcohol = 38.
Heat of formation of gaseous atoms from the elements in their standard states: H = 218; C = 715; O = 249.
Average bond energies : C – H = 415; C – O = 356; O – H = 463.
SOLUTION :
The given data is as follows :
(i) CH3OH() 
 CH3OH(g)  r H1Θ  38 kJ mol1
1
(ii) H 2 ( g ) 
 H( g )  r HΘ
2  218 kJ mol
1
2
(iii) C(graphite) 
 C(g)  r H3Θ  715 kJ mol1
1
(iv) O 2 ( g ) 
 O( g ) r HΘ
4  249 kJ mol
1
2
(v) CH(g) 
 C(g) + H(g)  r H5Θ  415 kJ mol1
(vi) CO(g) 
 C(g) + O(g) r HΘ
6  356 kJ mol
1
(vii) OH(g) 
 O(g) + H(g) r HΘ
7  463kJ mol
1
We have to calculate the enthalpy of formation of liquid methyl alcohol, i.e.,
1
(viii) C(graphite) + 2H2(g) + O (g) 
 CH3OH()  r H 8Θ  ?
2 2
First of all, we calculate the enthalpy of reaction :
(ix) CH3OH(g) 
 C(g) + 4H(g) + O(g) ;  r H 9Θ  ?
 H 
 | 
 CH3OH  H  C  O  H 
 | 
 r H 9Θ  3  r H 5Θ   r H Θ Θ
6  r H7  
H
 contains one C  O, one O  H 
 
 and three C  H bonds 
 r H 9Θ = (3415 + 356 + 463) kJ mol = 2064 kJ mol

–1 –1

The equation (viii) can be generated as follows :

Eq. (iii) + 4  Eq. (ii) + Eq. (iv) – Eq. (ix) – Eq. (i)
Hence, the enthalpy of reaction of equation (viii) is given as :
 r H8Θ   r H3Θ  4  r HΘ Θ Θ Θ
2   r H 4   r H9   r H1
= (715 + 4 218 + 249 – 2064 – 38) kJ mol–1 = – 266 kJ mol–1
Illustration - 10 The heat of formation of ethane is –19.5 kcal. Bond energies of H – H, C – H and C – C
bonds are 104.2, 99.0 and 80.0 kcal/mol respectively. Calculate the heat of atomisation of graphite.
SOLUTION :
f H of ethane (C2H6) = –19.5 kcal/mol
2 C (s) + 3 H2 (g) 
 C2H6 (g) ; f H = –19.5 kcal/mol
Let the heat of atomisation is x kcal/mol
Bond Breaking : (rH1) Bond Formation : (rH2)
2[C (s) 
 C(g); +x] 1[C (g) + C (g) 
 C – C (g) ; – 80]
3[H2 (g) 
 2 H (g) ; +104.2] 6[C (g) + H (g) 
 C – H (g) ; – 99]
rH1 = 2x + 312.6 rH2 = (80) + (6 × 99) = 674
From Hess’s Law : f H = r H1 + r H2
–19.5 = (2x + 312.6) – 674  x = 171 kcal.
Illustration - 11 Using the data given below (all values are in kcal/mol at 25°C), calculate the bond ener-
gies of C–C and C–H bonds.
c H Θ ethane   372.0 ; c H Θ propane   530.0 ; a H Θ  172.0 ;

C  Graphite 
 bond H Θ H  H  104.0 ;  f H Θ H O   68.0 ;  f H Θ CO   94.0

2 2
SOLUTION :
From the data given for heats of combustion for ethane and propane, we can calculate the heats of formation
of two compounds (C2H6 and C3H8) as follows :
(a) Writing the equation for combustion of ethane:
7
C2H6 (g) + O (g) 
 2 CO2 (g) + 3 H2O () ;  c H Θ   372.0
2 2

From definition of rH of a reaction : rH = HProducts – HReactants
The enthalpy of a compound is the enthalpy of formation of that compound at standard conditions (i.e.  f H Θ ).
 7 
Δ c H Θ =  2 Δ f HΘ CO  + 3 Δ f HΘ  H O    Δ f HΘ  C H   Δ f HΘ  O  
 2 2   2 6 2 2 
Note that f HΘ(O 2 ) = 0 (as enthalpy of formation of an element in standard state is taken as zero).
 –372 = 2 × (–94) + 3 × (–68) – f HΘ(C2 H6 )
 f HΘ(C2 H6 ) = –20 kcal/mol
(b) Writing the equation for combustion of propane :
C3H8 (g) + 5 O2 (g) 

 3 CO2 (g) + 4 H2O () ;  c H Θ   530.0
From definition of rH of a reaction : rH = HProducts – HReactants
 c HΘ  3 Δ f HΘ CO  + 4 Δ f HΘ H O    Δ f HΘ C H  + 5Δ f H Θ O  

 2 2   3 8 2 
  530  3    94   4  (68)  Δ f HΘ C H 

3 8
 Δf HΘ C H    24 kcal / mol

3 8
Calculations of bond energies :

Let the bond energy of C – C bond = x kcal mol–1 and the bond energy of C – H bond = y kcal mol–1
(a) For ethane, heat of formation is given as :
 f H Θ = – 20 kcal mol
–1
2 C(s) + 3 H2 (g) 
 C2H6(g) ;
Bond breaking (rH1) : Bond formation (rH2) :

2[ C(s)  C(g) ; + 172 ]
 1[ C (g) + C (g) 
 C – C (g) ; –x ]
3[ H2(g) 
 2H(g) ; + 104 ] 6[ C (g) + H (g) 
 C – H (g) ; –y ]
 rH1 = 2 × 172 + 3 × 104 = 656  rH2 = – (x + 6y)
  f H Θ = heat absorbed + heat released = rH1 + rH2

 – 20 = 656 – (x + 6y)  x + 6y = 676 . . . . (i)

(b) For propane, heat of formation is given as :
 r H Θ = –24 kcal mol

–1
3 C(s) + 4 H2 (g) 
 C3H8 (g) ;
Bond breaking (rH1) : Bond formation (rH2) :

3[ C(s) 
 C(g) ; +172 ] 2[ C(g) + C(g) 
 C – C(g) ; –x ]
4[ H2(g) 
 2H(g) ; +104 ] 8[ C(g) + H(g) 
 C – H(g) ; –y ]
rH1 = 3 × 172 + 4 × 104 = 932  rH2 = – (2x + 8y)
  f H Θ = rH1 + rH2
 – 24 = 932 – (2x + 8y)  x + 4y = 478 . . . . (ii)

Solving (i) and (ii), we get x = 82 and y = 99.
 Bond energy of C – C bond = 82 kcal mol–1 and C – H bond = 99 kcal mol–1
Born Haber’s Cycle Section - 5
The energy binding ions together in a crystal is called as lattice energy (  Lattice H Θ ). Lattice energy is
defined as the enthalpy change which occurs when one mole of an ionic compound dissociates into its ions
in gaseous state which means  Lattice H Θ is +ve i.e.,
 Na  ( g )  Cl ( g )
NaCl( s)   LatticeHΘ   790 kJ mol1
These crystal lattice energies cannot be measured directly. By applying Hess’s Law to a series of elemen-
tary processes starting with Na (s) and Cl2 (g) and ending with formation of NaCl(s),  Lattice H Θ can be
calculated. Such a sequence of reactions for ionic compounds is called as Born-Haber Cycle. The
concept is illustrated below by taking the formation of NaCl(s).
The heat of formation of sodium chloride can be calculated from bond energies very easily.
1
 f H Θ = – 411 kJ mol
–1
Na(s) + Cl (g) 
 NaCl(s)
2 2
The following sequences can give the above equation :
1. Sublimation of one mole of Na(s) :
Na (s) 
 Na (g) sub HΘ   109 kJ mol1

2. Dissociation of half mole of Cl2 :
1
Cl (g) 
 Cl (g)
2 2
1
 Bond H Θ  122 kJ mol1
2
(Bond energy of Cl2 is Bond HΘ
= 244 kJ/mole)
3. Ionisation of one mole of Na atoms :
 Na+ (g) + 1e–
Na (g) 
IE HΘ   496 kJ mol1

(First ionisation energy of Na atoms is 496 kJ/mole)
4. Addition of one mole of electrons to one mole of chlo
rine atoms:
Cl (g) + 1e– 
 Cl– (g)
 EA HΘ   348 kJ mol1
(Electron affinity of chlorine is 348 kJ/mole)

(Electron affinity is the energy released, so H is negative).
5. Condensation of gaseous ions to form one mole of solid NaCl :
This can not be calculated directly.
Na+ (g) + Cl– (g) 
 NaCl (s) r HΘ    Lattice HΘ
The summation of the above five reactions and their H values allows us to calculate the value of  Lattice H Θ .
1
f H Θ (–411) = sub HΘ (+109kJ) +  Bond HΘ (+122kJ) +  IE HΘ (+496kJ) + EA HΘ
2
(–348kJ) –  Lattice H Θ
  Lattice H Θ = +790 kJ/mol of solid NaCl.

Note : The crystal lattice is a measure of the stability of an ionic solid. The more negative its value, the more energy
is released in the hypothetical reaction in which a mole of ionic solid is formed from its constituent ions in the
gaseous state.

Illustration - 12 Find the electron affinity of chlorine from the following data (in kcal/mol).
Enthalpy of formation of LiCl is –97.5 ; Lattice energy of LiCl = 197.7 ; Dissociation energy of chlorine
= 57.6 ; Sublimation enthalpy of Lithium = 38.3 ; Ionisation energy of Lithium = 123.8
SOLUTION :
For a ionic compound of type LiCl :
1
 Lattice HΘ Θ Θ
LiCl   EA H Cl   f H LiCl   bond HΘ Θ Θ
Cl2   sub H Li   IE H Li
2
Θ 1
197.7   EA HCl  ( 97.5)   57.6  38.3  123.8
2
  EA H Θ
Cl   90.7 kcal / mol
Relation between rH and rU Section - 6
Enthalpy (H) and Internal Energy (U) are related as :

H = U + PV
 H = U + (PV)
or d H = d U + d (PV)
Now, for a reaction, we can write : rH = rU + PV
[Chemical reactions occur at constant T and P]
or rH = rU + ngRT
where n g   (n g ) products –  (n g ) reactants = Change in the number of gaseous moles
Illustration - 13 Find the sign of rH – rU for the following reactions :
(i) H2(g) + Cl2(g) 
 HCl(g) (ii) N2(g) + O2(g) 
 NO2(g)
7
(iii) PH3(g) 
 P4(s) + H2(g) (iv) C2 H 6 ( g )   CO2 ( g )  H 2O()
O2 ( g ) 
2

SOLUTION :
First, balance each reaction :
(i) H2(g) + Cl2(g) 
 2HCl(g)
(ii) N2(g) + 2O2(g) 
 2NO2(g)
(iii) 4PH3(g) 
 P4(s) + 6H2(g)
7
(iv) C2H 6 ( g )   2CO 2 ( g )  3H 2O()
O 2 ( g ) 
2
Now, Use : rH – rU = ngRT and n g   (n g ) products –  (n g ) reactants
 If ng > 0, rH – rU > 0 ;
If ng < 0, rH – rU < 0 ;
If ng = 0, rH – rU = 0
(i) ng = 2 – (1 + 1) = 0 (ii) ng = 2 – (1 + 2) = – 1
(iii) ng = (6 + 0) – 4 = 2
 7 5
(iv) ng = (2 + 0) –  1     [Note : For H2O(), ng = 0]
 2 2
Illustration - 14 The enthalpies of combustion of carbon and carbon monoxide in excess of oxygen at
298 K and constant pressure are –393.5 kJ/mol and –283.0 kJ/mol respectively. Calculate the heat of
formation of carbon monoxide at constant volume.
SOLUTION :
Heat change at constant pressure means enthalpy change (rH = qp)
1
Heat of formation of CO is written as : C (s) +  CO (g) ;  f H Θ  ?
O (g) 
2 2
Now we have :
I. C (g) + O2 (g) 
 CO2 (g) ;  c H1Θ  393.5 kJ / mol
1
II. CO (g) + O (g) 
 CO2 (g) ; c HΘ
2  283 kJ / mol
2 2

1
Adding appropriately (i.e., I – II), we get ; C (s) +  CO(g) ;  f H Θ
O (g) 
2 2
From Hess’s Law :  f H Θ   c H1Θ   c H Θ

2
 f HΘ = – 393.5 – (– 283) = – 110.5 kJ/mol
Now, calculation of the heat of formation at constant volume means that we have to calculate change in
internal energy (i.e. rU).
Using : rH = rU + PV [For a chemical reaction]
= rU + ngRT [ng = gaseous moles of products – gaseous moles of reactant]
 rU = rH – ngRT
Now putting the values :
1 1
n g  1   T = 298 K R = 8.314 J/K/mol.  f H Θ = –110.5 kJ/mol
2 2
1
  f U Θ = –110.5 – × 8.314 × 298 × 10–3 = –111.7 kJ/mol
2
Illustration - 15 Standard enthalpy of formation of C3H7NO2(s), CO2(g) and H2O() are –133.6, – 94.0
and – 68.3 kcal/mol respectively. Standard enthalpy of combustion of CH4(g) at 25°C is – 212.8 kcal/mol.
1 1
Calculate r H Θ for the reaction: 2CH4(g) + CO2(g) + N2(g)   C3H7NO2(s) + H2(g)
2 2
Also calculate heat of reaction at constant volume for combustion of C3H7NO2(s).
SOLUTION :
1 1
2CH4(g) + CO2(g) + N2(g) 
 C3H7NO2(s) + H (g) :  r H Θ  ?
2 2 2
To calculate  r H Θ of the above reaction, we need to find out the  f H Θ for CH4 as :
Given : CH4(g) + 2O2(g) 

 CO2(g) + 2H2O() :  c H Θ = – 212.8 kcal/mol
Using the definition of rH, we have :

 r HΘ  [f H Θ(CO2 )  2  f HΘ(H 2O) ]  [f H Θ(CH 4 )  2  f HΘO2 ] [Note : f H Θ(O2 )  0 ]
 – 212.8 = [– 94.0 + 2(– 68.3)] – f HΘ (CH 4 )
 f HΘ(CH ) = –17.8 kcal/mol

4
Θ
Now find the  f HΘ of the required equation using f H (CH ) .
4
 r HΘ  [f HΘ (C3H7 NO2 )  0]  [2  f HΘ(CH 4 )  f HΘ(CO2 ) ]
  r H Θ  ( 133.6)  2( 17.8)  ( 94.0)  4.0 kcal / mol

Now calculate
15 1 7
c HΘ (C3H7 NO2 ) : C3H 7 NO 2 ( s )   3CO 2 ( g )  N 2 ( g )  H 2O()
O2 ( g ) 
4 2 2
7
c HΘ (C3H7 NO2 ) = 3( 94.0)  ( 68.3)  ( 133.6)  387.45 kcal / mol
2
 1
Find  r UΘ   r HΘ  n g RT  387.45      2  10 3 (298)
 4
  1  5 
 387.6 kcal / mol  n g   3  2   4 
   
Illustration - 16 From Navogardo atoms of an element A, when half the atoms transfer one electron to
another atom, 405 kJ/mol of energy was found to be consumed. An additional energy of 745 kJ was further
required to convert all the A– ions to A+. Calculate the ionisation energy and the electron affinity of atom A
in eV.
SOLUTION :
Let I.E. be x eV/atom and E.A. be y eV/atom (magnitudes)
 A+ + e–
A  ; rH = I.E. = x A + e– 
 A– ; rH = E.A. = – y
405  103
I: Energy absorbed in eV =
1.6  1019
405  103 6.02  1023 6.02  1023

  x y . . . . (i)
1.6  1019 2 2

A–   A+
 A 
745  103
II : Energy absorbed in eV =
1.6  10 19
745  103 6.02  1023 6.02  1023

  x  y . . . . (ii)
1.6  1019 2 2
Solve for IE and EA using (i) and (ii), IE = 11.93 eV/atom and EA = 3.52 eV/atom (Magnitudes)
Illustration - 17 In order to get maximum calorific output, a burner should have an optimum fuel to
oxygen ratio which corresponds to 3 times as much oxygen as is required theoretically for complete
combustion of the fuel. A burner which has been adjusted for methane as fuel (with x litre/hour of CH4 and
6x litre/hour of O2) is to be readjusted for butane, C4H10. In order to get the same calorific output, what
should be the rate of supply of butane and oxygen ? Assume that losses due to incomplete combustion etc. are
the same for both fuels and that the gases behave ideally. Heats of combustion : CH4 = 809 kJ/mol;
C4H10 = 2878 kJ /mol.
SOLUTION :
First calculate the amount of energy required in the burner per hour using methane as follows :
809
 c HΘCH  809 kJ mol1  kJ / L (at 25C)
4 24.48
 1 mol CH4 ( 24.48 L at 25°C) on combustion produces 809 kJ
x
 x L/hr CH4 on combustion produces energy =  809 kJ / hr
24.48
Now, this much energy will be required by burning of butane and we can find its rate of consumptiom as :
2878
 c HΘ C H  2878 kJ mol1  kJ / L (at 25C)
4 10 24.48
x
 809
L
 Required Rate of combustion of propane  24.48  0.28 x L / hr
2878 hr
24.48
13
C4H10(g) + O (g)  4CO2(g) + 5H2O()
2 2
13
 1 mol CH4  mol O2 (theoretically)
2

 13 
  3   mol of O2 is required/mol of CH4 (practically) [Given]
 2
 39 
 rate of O2 per hour = (0.28x)     (5.48 x ) L O 2
 2 
Bomb Calorimeter
Calorimetry is study of heat transfer during physical and chemical processes. A calorimeter is device for
measuring energy transferred as heat. The most common device for measuring U is the adiabatic bomb
calorimeter, shown in figure (figure 1 & 2). The inner vesel or the ‘bomb’ (figure 2) and its cover are made
of strong steel coated inside with gold or platinum or some other non-oxidisable material. The cover can be
fitted tightly to the vessel by means of a metallid screwed down on a lead washer. A weighed amount of the
substance is taken in a platinum cup C which is supported on a rod R.
Stirrer
T
O2
Water
Bomb G
R Platinum cup
W
Figure 1 : The Bomb Calorimeter Figure 2 : The Bomb
A thin platinum wire W is connected between the rods R and G as shown. This serves to initiate the
combustion when heated electrically. The bomb is tightly closed and oxygen introduced through the inlet
tube T unit a pressure of about 20 – 25 atmospheres is attained. The bomb is then lowered in water placed
in a double jacketed and polished metallic calorimeter so as to minimise error due to radiation. The
arrangement ensures that there is no net loss of heat from the calorimeter to the surroundings (the bath) and
hence that the process is adiabatic. A mechanical stirrer is provided as shown. When the temperature of the
water become steady, the substance of inginited by calorimeter is noted after every minute by means of a
Beckmann thermometer graduate to read up to hundredth of a degree. The final temperature when cor-
rected for the radiation error in the usual way, minus the initial temperature, gives the rise of temperature.
The heat capacity of the calorimeter system, called the calorimeter constant, C, is obtained by burning a
known mass of a substance of known enthalpy of combustion. For this purpose, usually benzoic acid of high
grade purity is taken. Its qv which has been very carefully measured in taken as – 3226.7 kJ mol–1. Suppose

the thermal capacity of the calorimeter system including water is C and  is the change in temperature
produced by burning a quantity m of the given substance of molar mass M. Then, the constant volume heat
of combustion, qv of the substance is given by C  q  M/m. The enthalpy of combustion qp is then
obtianed with the help of the equation qp = qv + ngRT.
Illustrating the concepts :

(i) 0.50 of benzoic acid was subjected to combustion in a bomb calorimeter when the temperature of the
calorimeter system (including water) was found to rise by 0.55oC. Calculate the enthalpy of combus-
tion of benzoic acid. The T calorimeter constant was found to be 23.85 kJ K–1.
qv = C  q  M/m
= 23.85 kJ K–1  0.55 K  122 g mol–1 / 0.50 g
= 3200.7 mol–1
= – 3200.7 kJ mol–1 (Heat of combustion has alwas a negative sign)
15
C 6 H 5COOH(s)   7CO 2 (g)  3H 2O()
O 2 (g) 
2
We know that q p  q v  n g RT ; n  7  7.5  0.5
q p  3200.7 kJ mol 1  ( 0.5)(8.314 10 3 kJ K 1mol 1)(298K)
 3201.9 kJ mol 1
(ii) Explain why the following statement, made by a student doing an experiment on bomb calorim-
eter, is wrong : “H = U + PV. Since in the experiment, V = 0, hence, H = U.”
The error is due to the fact that the student has applied the equation H = U + PV, which holds at
constant pressure, to a process which occurs at constant volume.
We know that H = U + PV
 H = U + (PV) = U + PV + VP
For a constant pressure process, P = 0 so that H = U + PV
However, for a constant volume process, V = 0 so that H = U + VP
We many meantion here that a calorimeter for studying processes at constant pressure, called an
isobaric calorimeter is also available commercially. A simple example is thermally insulated vessel open
to the atmosphere ; the heat released in the reaction monitored by measuring the change in tempera-
ture of the contents. For a combustion reaction, an adiabatic flame calorimeter can be used
to measure T when a given amount of substance burns in oxygen.

Enthalpy of Polymerization :
The difference between the enthalpy of one mole of monomer and the enthalpy of the products of the
polymerization reaction. Addition polymerizations are exothermic, values ranging from about 35 to 100 kJ/
mol
Let us consider an example of polythene.
n  H 2 C  CH 2  
 ...........  CH 2  CH 2  CH 2  CH 2  .............
H (Per mole) = B.E. of Reactants – B.E. of Products
(B.E. of C = C + 4  B.E. of C – H) – ( 2  B.E. of C – C + 4  B.E. of C – H)

Same logic can also be used in following reactions as well
nN 2(g)  nH 2(g) 
 ( NH  NH 
) n (g)
n(H 3C  C  C  CH 3 ) (g) 
 ( CH 2  CH  CH  CH 2 
) n(g)
CALCULATING RESONANCE ENERGY Section - 7
Resonance energy, as we know, is the difference in energy between resonance hybrid and the canonical
form of the compound. It can be easily calculated using the following key points :
(i) If the resonance hybrid is more stable than the canonical forms, resonance energy is negative otherwise
positive.
(ii) Simply figure out, which of the resonance hybrid and the canonical form is more stable based on the
rH values as explained :
(a)  f H Θ : More negative is  f H Θ , more is the stability as this means when compound is formed,
energy is getting lost to attain lower energy than the reactants.
(b)  c H Θ or  Hydrogenation H Θ : More negative value in this case means less stability as more heat
released means this compound is more reactive.
Note : In (a), the compound under analysis is the product whereas in (b), that compound is the reactant.
(iii) Now, calculate H for the theoretical (canomical) and actual (resonance hybrid) compound and
calculate the difference between the two to get resonance energy.

Illustration - 18 The standard molar enthalpies of formation of cyclohexane() and benzene() at 25C are
156 and +49 kJ/mole respectively. The standard enthalpy of hydrogenation of cyclohexene() at 25C is
–119 kJ/mole. Use this data to estimate the magnitude of the resonance energy of benzene.
SOLUTION :
Given : C6H10 () + H2(g) 
 C6H12() ;  Hydrogenation H Θ = 119 kJ/mole
Find the actual heat of hydrogenation of benzene from Hess’s law as follows :
1. 6C(s) + 6H2(g) 
 C6H12() ;  f H Θ = 156 kJ/mole
2. 6C (s) + 3H2(g) 
 C6H6() ;  f H Θ = +49 kJ/mole
C6H6 () + 3H2(g) 

 C6H12() ;  Hydrogenation H Θ
 ( Hydrogenation H Θ ) = 156  49 = 205 kJ/mole

Actual
[Note :  Hydrogenation H  is always negative ]
 hypothetical heat of   heat of hydrogenation of 

Now,     cyclo hexatriene

 hydrogenation of benzene   
 heat of hydrogenation 
3   
 of cyclohexane 
= 3  (119) = 357 kJ/mole
Here, we have assumed that there are only 3 double bonds in benzene (kekule’s structure) and in
hydrogenating it, the energy obtained will be roughly 3 times of hydrogenating cyclohexene.
and
Clearly, heat of hydrogenation for theoretical benzene is more negative and thus, it is less stable. So,
Resonance energy should be negative (since actual benzene is more stable).
 Resonance energy = 357  (205) = 152 kJ/mole of benzene

Illustration - 19 Calculate the resonance energy of isoprene (C H ) from the data given.
5 8
Standard Heats of combustion of isoprene, carbon and water are 3186, 393.5 and 285.83 kJ/mole respec-
tively. Bond energies of C = C, C  C, C  H and H  H bonds are 615, 348, 413, 435.8 kJ/mole respectively.
Standard Heat of sublimation of graphite is 718.3 kJ/mole.
SOLUTION :
Calculate  f H Θ of isoprene from its heat of combustion (This will give the value for the actual isoprene
existing in nature).
5C (s) + 4H2 (g) 
 C5H8 (g) ; f HΘ = ?
1. C5H8 (g) + 7 O2 (g) 

 5 CO2 (g) + 4 H2O () ;  r H1Θ = 3186 kJ/mole
2. C(s) + O2 (g) 
 CO2 (g) ; rHΘ
2 = 393.5 kJ/mole
3. H2 (g) + 1/2 O2 (g)  H2O ()

 ;  r H 3Θ = 285.83 kJ/mole
Now operating 5(2) + 4(3)  1 to get the equation of heat of formation.
From Hess’s Law we have :
 f H Θ = 5 r H Θ Θ Θ
2  4  r H 3   r H1
  f H Θ = 5(393.5) + 4(285.83)  (3186)  (  f H Θ ) actual = 75.18 kJ / mole
 H 2C  C  HC  CH 2 
Now calculate heat of formation using the bond energies and structure of isoprene.  | 
 CH 3 
Note : Data calculations from the bond energy concept is always theoretical.
1. Bond Breaking : (H1)

5 [ C(s) 
 C(g) ; +718.3 ]
4 [ H2 (g)  2H ; +435.8 ]

 H1 = 5 × 718.3 + 4 × 435.8
= + 5334.7 kJ
2. Bond Formation : (H2)
8[ C + H 
 C  H ; 413 ]
2[ C + C 
 C  C ; 348 ]
2[ C + C   C = C ; 615 ]
 H2 = (8 × 413 + 2 × 348 + 2 × 615)
= 5230 kJ

From Hess’s Law : (  f H Θ )Theoretical = H1 + H2
(  f H Θ )Theoretical = 5334.7 + (5230) = 104.7 kJ
 Resonance Energy = 75.18  104.7 = 29.52 kJ

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Chemical Equilibrium
Chemical Equilibrium
ANALYSIS OF REVERSIBLE CHEMICAL REACTION Section - 1
Chemical reactions in one sense can be divided into two categories : molecular chemical reactions
(involving molecules as reactants and products) and ionic reactions (involving ions along with
molecules as reactants and products).
In another sense, reactions can also be divided into two categories : Irreversible chemical reactions
(the reactions which proceed to completion and the products fail to recombine to give back reactants)
and reversible reactions (the reactions which never go to completion and that can occur in either
direction, i.e., the products recombine to give back reactants).
Analysis of reversible chemical processes is of great importance and interest. We divide their study in two
parts :
(i) molecular (reversible) reactions and (ii) ionic (reversible) reactions.
In chemical equilibrium, we will consider molecular reversible reactions, such as :
3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2 (g)
N2(g) + 3H2 (g) 2NH3(g)
N2(g) + O2 (g) 2 NO (g)
2SO3(g) 2 SO2 (g) + O2 (g)
Each reversible reaction consists of one pair of reaction : One is forward reaction and other is backward or
reverse reaction and these two are referred to as two opposing chemical changes.
At one stage during reversible reactions, two reactions, i.e., forward and backward reactions proceed at
the same time with the same speed, the reaction is then said to be in equilibrium. A chemical equilibrium
is the state that exists when two opposing reactions, i.e., forward and backward reactions are proceeding at
the same rate in a reversible reaction.
For a simple case : A+ B C+D
Initially, when A and B are mixed, they react. When they react, the rate of forward reaction decreases since
the concentration of A and B decreases with time. As C and D are formed, they react to give back A and B.
The rate of reaction between C and D increases with time as more C and D molecules are formed, more they
collide and react. Eventually, the two reactions occur at the same rate and the system is at equilibrium.
To understand the concept more clearly, let us consider the manufacturing of NH3 (ammonia) from N2 and
H2. The reaction between N2 (g) and H2 (g) to form NH3 (g) is a reversible reaction. Instead of “  ”,
we use double arrow for a reversible reaction “ ” i.e. N2 (g) + 3H2 (g) 2NH3 (g)
Forward Reaction : N2 (g) + 3H2 (g)  
  2NH3 (g) . . . . (i)
Backward Reaction :2NH3 (g)  
  N2 (g) + 3H2 (g) . . . . (ii)

Chemical Equilibrium Vidyamandir Classes
Note :
 Regardless of whether we start with NH3 or with pure hydrogen and nitrogen, the reaction does not go to
completion.
 If we start with only H2 and N2, the reaction (ii) cannot at first occur because there is no NH3. As the
forward reaction proceeds, NH3 forms and reaction (ii) starts.
 Initially, the rate of forward reaction is fast. But as the time goes on, rate of forward reaction decreases and
the rate of reaction (ii) i.e., reverse reaction increases.
 Eventually, the rate at which NH3 is being formed (Forward Reaction) becomes equal to the rate at which
NH3 is being decomposed (Reverse Reaction). This state is called as Chemical equilibrium.
 Once the equilibrium is reached, relative concentrations of H2, N2 and NH3 do not change as long as
temperature remains constant.
 At equilibrium, both reactions, i.e., forward and backward continue to perform (but their rate is same) and
such a state of equilibrium where both opposing forces balance each other and molecular activity still continues,
is known as dynamic equilibrium.
 In dynamic chemical equilibrium, molecular activity never ceases, at each instant some molecules are
being formed and some are being broken ; only the rate of two forces is same.
At Equilibrium Stage (at a given temperature) :

(i) Rate of forward reaction = Rate of backward reaction
(ii) At no instant, any reaction (forward or backward) stops.
(iii) Relative concentrations of reactants and products do not change.
(iv) Any change i.e., external stress (pressure, temperature or concentration) causes disturbance in
equilibrium state. The state of equilibrium being stable, is again reached by some adjustment.
Reaction Coefficients and Equilibrium Constant (Q and K)

In 1863, Guldberg and Waage (two Norwegian chemists) stated that, at constant temperature, the rate of
chemical reaction is directly proportional to the product of active masses (raised to power their stoichiomet-
ric coefficients) of reactants present at any given time.
For a reversible reaction : mA + nB pC + qD
Forward reaction. : kf
mA + nB    pC + qD
Rate of forward reaction (rf )  aAm aBn a : denotes activity (active masses)
 m n
rf = kf aA kf = rate constant for forward reaction
aB
kb
Backward reaction : pC + qD  mA + nB
Rate of backward reaction (rb )  aCP aDq

 rb = kb aCP aDq kb = rate constant for backward reaction

a p aq
For a reversible reaction, reaction coefficient (Q) is defined as Q  C D
m n
aA aB
At equilibrium :
p q
k f  aC aD 
rf = rb and Q is called equilibrium constant (Keq ) at this stage K eq   
m n 
k b  aA
 aB  at equilibrium
Note :(i) Activity is denoted by a.

Activity of aqueous solution is expressed in concentration (Mol/L)
Activity of gases is expressed in partial pressure (atm).
Activity of pure solids and liquids is unity i.e. asolid = 1 [for example aFe = 1, awater = 1]
(ii) When activities are expressed in concentration (Mol/L), then equilibrium constant Keq is denoted as KC .
p q
KC 
 C D 
where [ ] denotes concentration.
 A m  B n
When activities are expressed in terms of partial pressure, then equilibrium constant Keq is denoted as KP .
p q
KP 
 PC   PD 
P : partial pressure (= mole fraction  total pressure)
 PA m  PB n
When activities are expressed in terms of mole fraction, then equilibrium constant Keq is denoted as K .
K 
 C p  D q
where  denotes mol fraction.
  A m   B n
(iii) Keq changes only when the temperature changes. There is no effect of change in pressure or concentrations
on the value of Keq.
(iv) Analysis of a reversible system on the basis of activities of reacting species is done in terms of reaction
coefficient (Q). First an expression for Q (or Keq at equilibrium) is written properly and activity values are
then substituted.
Comparing the value of Q with the standard value of Keq (at a given T), one can comment on the status of
reversible system by following the table given below.
Q < Keq it means equilibrium has not yet reached. The system is essentially moving to right (forward
direction) increasing product concentration and simultaneously decreasing reactant concen-
trations. One can say that forward reaction is dominant at this instant over backward
reaction.
Q = Keq it means equilibrium has been established and concentrations of reactants and products will
remain constant.
Q > Keq it means equilibrium has not yet established. The reaction must proceed to left (Reverse or
backward direction), increasing reactant concentrations and simultaneously decreasing product
concentrations.


Consider the reaction SO2Cl2 (g) SO2(g) + Cl2(g) ; at 375C, the value of equilibrium
constant for the reaction is 0.0032. It was observed that concentration of the three species is 0.050
mol/L each at a certain instant. Discuss what will happen in the reaction vessel ?
SOLUTION :
In this question, concentration of three species, i.e., SO2Cl2(g), SO2(g) and Cl2(g) each is given, but it is not
mentioned that whether the system is at equilibrium or not. So first check it.
Find reaction coefficient for given equation.
Q
SO2  Cl2    0.05  0.05  0.05
SO2Cl2   0.05
 Q  Keq , so system is not at equilibrium state.
As Q > Keq, the concentrations must adjust till Q = Keq for equilibrium. This can happen only if reaction shifts
backwards, and products recombine to give back reactants. Hence in the reaction vessel, the system will
move backward so that it can achieve equilibrium state.
Writing Keq for reversible reactions :

Homogenous Reactions : (Reactions in which all the reactants and products are in the same phase)
Here, we will discuss some important reversible reactions and explain how to approach while analysing the
equilibrium state for those reactions.

H2 (g) + I2 (g) 2 HI(g)
Let ‘a’ moles of H2 and ‘b’ moles of I2 are taken initially and let at equilibrium ‘x’ moles each of H2 and I2
are reacted at a total pressure of P atm.
We will write the expression for Kp for this reaction.
KP 
 pHI 2
pi = Partial pressure
 p H 2   pI 2 
[for each mole of H2 and I2 ,2 moles of HI are

produced]
Total moles at equilibrium = (a  x) + (b  x) + 2x = (a + b) [Note : Consider only the gaseous moles]
pHI 
2x
P ; pH2 
a  x  P ; p   b  x P
 pHI = mole fraction  P  I2
ab a b a b

2
 2x 
P
Kp 
 pHI 2 

 ab 

4x2

 pH 2   pI2   a  x   b  x  a  x b  x
 P  P
ab  ab 
Note : Try to write expression for KC and observe.

2NH3 (g) N2 (g) + 3H2 (g)
Let ‘a’ moles of NH3 are given initially and let x moles of NH3 are decomposed at equilibrium and V Lt be
the capacity of vessel in which reaction is being studied. We will write an expression for Kc for this reaction.
3
Kc 
 N2   H 2 
 NH3 2
Concentrations (mol/L) at equilibrium
3
 x   3x 
 a  x , 3   
x 3x
 K c   2   2 
N H 2V   2V  27 x 4
 NH3    N2   , H2    
V 2V 2V 2 2
16V 2  a  x 
2
NH 3  ax
 
Note : Try to write expression for KP .  V 

PCl5 (g) PCl3 (g) + Cl2 (g)
If a moles of PCl5 be put in a container of volume V Lt and at equilibrium ‘x’ moles of it were decomposed,
find its Kp and Kc at equilibrium pressure of Patm.
pPCl3  pCl2
Kp  Find partial pressures of each component at equilibrium
pPCl5
Total moles (nT )  (a  x)  x  x  a  x
pPCl 5 
 a  x  P, pPCl3  pCl2 
x
P

 a  x ax

 x  x 
 P  P
pPCl3  pCl2 ax  ax  x2 P
 Kp   Kp    Kp 
pPCl5 ax 

ax 
P  a 2  x2 
Kc 
PCl3  Cl2 
For
PCl5  , find molar concentrations of each component
2
at equilibrium.
x
ax x V x2
 PCl5   ;  PCl3    Cl2    KC    
V V  a  x  a  x V
 
 V 
CH3COOC2H5 (aq) + H2O () CH3COOH(aq) + C2H5OH(aq)
Kc 
CH3COOHC2H5OH
CH3COOC2H5 
Note : [H2O] = 1, as it is pure solvent. For reactions in aqueous medium, KP has no meaning.
Heterogeneous Reactions : (Reactions involving reactants and products in more than one phase)

 3Fe(s) + 4H2O (g) Fe3O4(s) + 4H2 (g)
4
Kp 
 pH2 
4
 pH2 O 
Note : Activities of Fe(s) and Fe3O4(s) are equal to unity as both are pure solids.
 CaCO3 (s) CaO(s) + CO2(g)
Kp  pCO2
Note : Activities of CaCO3 (s) and CaO(s) are equal to unity as both are pure solids.
 NH4HS (s) NH3 (g) + H2S (g)
Kp  pNH3 .pH2S
Note : For heterogeneous reactions, genrally Kp is written and the anaysis is done in terms of partial ressure of
components.
 If K1 be the equilibrium constant for A + B C + D, then
Equilibrium constant for reverse reaction C + D A + B is 1/K1
Equilibrium constant for nA + nB nC + nD is (K1)n , n can be fraction also (+ve only)

 If K1 be equilibrium constant for P Q and K2 be equilibrium constant for R

S
then equilibrium constant for P + R Q + S is K1. K2
 If K1 be the equilibrium constant for A B and K2 be the equilibrium constant for
C D
then equilibrium constant for the reaction : A  C B  D i.e. A + D B + C is

K1
K2
Relation between Kp , Kc and K

For the equilibrium mA + nB pC + qD
p p pq
KP  C D and KC 
C p  Dq and K 
  C p   D  q
pm
A pB
n
 A m  Bn   A m   B n
n
Use ideal gas equation : pV = nRT  p RT  CRT (where C [ ] is the concentration)
V
Thus, pA = [A] RT ; pB = [B] RT ; pC = [C] RT ; pD = [D] RT
Substituting the values of partial pressure in terms of concentration to get : KP  KC  RT ng
ng = number of moles of gaseous products  number of moles of gaseous reactants = (p + q)  (m + n)

[Note : Only gaseous moles have been considered since PV = nRT is applicable only for ideal gas]
p q
ppC pqD  C PT   D PT  n g
Also, K P   KP    PT  K  (where PT = Total Pressure)
pm n
A pB  A PT m  B PT n
Note : For ng = 0, KP = KC  K
For example ;
(i) H2(g) + I2(g) 2HI(g) (ii) CO2(g) + H2(g) CO(g) + H2O(g)
Illustration - 1 For a homogenous gaseous reaction X (g) + 2Y (g) Z (g), at 473 K, the value of
Kc = 0.35 concentration units. When 2 moles of Y are mixed with 1 mole of X, at what pressure 60% of X is
converted to Z ?

SOLUTION :
Since pressure is to be calculated, so first find Kp Let P = equilibrium pressure
using the relation between Kc and Kp. 1 x
Kc = 0.35, R = 0.0821, T = 473, ng  PX  P,
3  2x
= 1  3 = 2
2  2x x
ng 2 pY  P, p Z  P
K p  K c  RT   0.35   0.0821  473  3  2x 3  2x
 2.32  10  4 x
P 2
3  2x x  3  2x 
Kp  
[Note : V of flask is also not given. So, convert  1  x  2  2x 
2
P2 1  x  2  2 x 
2
Kc to Kp]  3  2 x P  3  2 x P 
  
PZ  x = 0.6 (given)
Kp 
The expression for Kp is : 2 2
pX  pY  0.6  3  1.2 
Kp   2.32  104
2 2
P 1  0.6   2  1.2 
 P2 = (1.8  102)2  P = 180 atm
 Total moles (nT) = 3  2x

[Z]
Alternative approach : Solve for volume of flask using KC  and use PV = nRT to solve for P]
[X][Y]2
Illustration - 2 Solid NH4HS (s) (Ammonium hydrogen sulphate) dissociates to give NH3(g) and H2S (g)
and is allowed to attain equilibrium at 100C. If the value of KP for its dissociation is found to be 0.34, find
the total pressure at equilibrium and partial pressure of each component.
SOLUTION : Total moles at equilibrium = moles of NH3 +

NH4HS(s) NH3(g) + H2S(g) ; since H2S = 2x (Only gaseous moles)
P = ? Kp = 0.34
NH4HS is a solid, hence a NH4HS = 1 and its un-
x P x P
dissociated amount will not effect the total pres- pH2S  P  and pNH3  P 
2x 2 2x 2
sure (due to gaseous NH3 and H2S only). Let
(for equimolar proportions, partial pressures
‘x’ be its moles decomposed at equilibrium and are equal)
P be the equilibrium pressure. KP  pH2S .pNH3 ( a NH4HS = 1)
P P
 0.34  
2 2
P2
  0.34  P  4  0.34  1.17 atm
4

P 1.17 P 1.17
 p NH3    0.585 atm and pH2S    0.585 atm
2 2 2 2
Note :In heterogeneous reactions, or even in homogenous gaseous reactions, sometimes it is better to analyse the
species directly in terms of partial pressures, rather first taking moles and then calculating their partial pressures.
Illustration - 3
The value of Kc . for the reaction : A2(g) + B2(g) 2AB(g) at 100C is 49. If 1.0
L flask containing one mole of A2 is connected with a 2.0 L flask containing two moles of B2 , how many moles
of AB will be formed at 100C ?
SOLUTION :
A2(g) + B2(g) 2AB(g) Concentration of species at equilibrium are :
As the two vessels are connected, the final vol- [A2] = (1  x)/3, [B2] = (1  x)/3, [AB]
ume is now 3.0 L. Let x mole each of A2 and = 2x/3
B2 react to form 2x moles of AB2 (from sto- 2
ichiometry of reaction)  2x 
  4 x2
KC   3    49
 1  x   1  x  (1  x)2
  
 3  3 
Taking square root on both sides :
2x
2   7  x  0.78
KC 
 AB  49 1 x
 A 2   B2   Moles of AB(g) formed at equilibrium
= 2x = 1.56
Illustration - 4 The value of Kc for the reaction : H2 (g) + I2 (g) 2HI (g) is 64 at 773 K. If one
mole of H2 , one mole of I2 and three moles of HI are taken in a 1L flask, find the concentrations of I2 and HI
at equilibrium at 773 K.
SOLUTION : For the reaction Let x mole of H2 and I2 combine to produce 2x

mole of HI.
2
 HI  32
Q   9[V  1L]
 H 2 I2  1  2
Note : When ng = 0, not only KP = KC , but
volume terms always cancels in the expression
of K.
 Q < Keq (= 64). Hence the reaction pro- [HI]2 = 64

KC 
ceeds to forward direction to achieve equilib- [H 2 ][I2 ]
rium.

Concentration of species at equilibrium are :  x = 0.05

H2] = (1  x)/1, [I2] = (1  x)/1, [AB] = (3 +
2x)/1 1 x
[I 2 ]   1  0.5  0.5 M
1
2
 3  2x 
  2 3  2x
KC   1 

 3  2x
 64 [HI]   3  1.0  4.0 M
1 x 1 x  2 1
   1 x
 1  1 
Illustration - 5 At 1000 K, the pressure of iodine gas is found to be 0.1 atm due to partial dissociation of
I2(g) into I(g). Had there been no dissociation, the pressure would have been 0.07 atm. Calculate the value of
KP for the reaction : I2 (g) 2I (g).
SOLUTION : Analysing in terms of pressure directly :  p = 0.03 atm.
(p I ) 2 (2p) 2 (2  0.03) 2
KP   
pI2 (0.07  p) 0.07  0.03
Substituting value of p
 Total pressure at equilibrium  KP = 0.09 atm units.
= (0.07  p) + 2p = 0.1 (given)
Illustration - 6 Calculate the % age dissociation of H2 S(g) if 0.1 mole of H2S is kept in a 0.5 L vessel at
1000 K. The value of KC for the reaction 2H2S(g) 2H2(g) + S2(g) is 1.0  107.
SOLUTION :
2H2S (g) 2H2 (g) + S2 (g) ;
Assuming 0.1 – 0.1x  0.1, we get :
Volume of vessel = V = 0.5 L
Let x be the degree of dissociation x3
  106  x  0.01
2V
Check : 0.1–0.1x  0.1
Degree of dissociation
Amount dissociated 0.1x

2   x
 0.1 x   0.1 x  Initial amount 0.1
2
 H  S2    V   2V   107
KC  2  1 % dissociation of H2S.
 H2S2  0.1  0.1 x 
2
 
 V 

LE-CHAPTELIER’S PRINCIPLE Section - 2
How an equilibrium state relieves the external stress ?

How a state in equilibrium (a stable state) adjusts to the external stress (change in Temperature, pres-
sure or concentration of reactants/products) is generalised in Le Chatelier’s principle.
Le Chatelier’s Principal states that :

If a stress is applied to a system in equilibrium, the equilibrium condition is upset; A net reaction
occurs in that direction which tends to relieve the external stress and finally a new equilibrium is
attained.
To understand its application to a system, let us consider following example :

N2(g) + 3H2(g) 2NH3(g)
H =  92 kJ for Forward Reaction
H = + 92 kJ for Backward Reaction
Note : H : Enthalpy Change is a measure of heat evolved or heat absorbed in a chemical reaction. It is negative
when heat is evolved and positive when heat is absorbed during a chemical change. You will learn details of
it later in the Chapter on Chemical Energetics.
Note that in the above reaction :

(a) Forward reaction is exothermic (favours formation of NH3) and backward reaction is endothermic
(favours decomposition of NH3)
(b) Formation of NH3 results in decrease in number of moles (from 4 total moles of N2 and H2 to 2 total
moles of NH3) is a decrease in volume to right (in forward reaction)
(c) Both reactants and products are gases and they will be influenced by changes in P, T and changing
concentrations.
Effect of Temperature
Temperature can be increased by adding heat and can be decreased by taking out heat from the system.
 Increase the temperature by supplying heat: According to Le Chatelier’s principle the disturbed equi-
librium state will move in that direction where heat is being absorbed (where stress is relieved) i.e. in
endothermic direction. In case of given situation, reverse direction will be favoured (that being endot
hermic) till whole of extra heat in consumed.So NH3 will decompose on increasing temperature.
 Decrease the temperature by extracting heat: According to Le Chatelier’s principle, the system will go
in the direction where heat is evolved i.e. in exothermic direction. In given situation, forward reaction
will be favoured (i.e. formation of NH3) till the new equilibrium is again established.
Note : The new equilibrium state has a new value of equilibrium constant K on changing the temperature.

Effect of Pressure
 Increase in pressure would result in decrease in volume thereby increasing the concentration (mol/L).
The system will shift in a direction where number of moles decreases (decreasing concentration). In
given situation, there is decrease in number of moles in forward direction, so increasing pressure
favours forward reaction (i.e, formation of NH3).
 Decreasing the pressure would mean lower number of moles/L. The system will shift in a direction
which will produce more moles. In given situation, there is increase is number of moles in reverse
direction, so decreasing pressure favours backward reaction (i.e., decomposition of NH3)
Effect of Concentration :
The Concentration can be changed in two ways :
(a) By removing some of a component or (b) By adding some more of a component.
According to Le Chatelier’s principle :
 The addition of any component to a side (reactants and products) of a reaction in equilibrium shifts the
equilibrium in the direction away from that side or one can say that equilibrium shifts in that direction
which consumes the increased concentration.
 In given situation ;
increasing amount of pure N2 and H2 would favour formation of NH3.
increasing amount of NH3 would favour decomposition of NH3
 The removal of any component from a side (reactants and products) of a reaction in equilibrium shifts
the equilibrium in the direction towards that side, or one can say the equilibrium shifts in that direction
which produces the decreased concentration.
 In given situation :
Decreasing the amount of NH3 from right side drives the equilibrium to forward direction i.e. favours
formation of NH3. Decreasing amount of N2 or H2 from left drives the equilibrium to reverse direction
i.e. favours decomposition of NH3
Effect of Catalyst :
 Catalyst increases the rate of both forward and backward reactions simultaneously and to the same
extent in a reversible reaction. By increasing both rates, catalyst reduces the time to reach
equilibrium state.
 Catalyst does not change the relative amounts of either reactants or products, hence it has no effect on
equilibrium constant
Evaluation of Keq at different temperatures :
If K1 be the equilibrium constant at T1 (in Kelwin) and K2 be the equilibrium constant at T2 (in Kelwin)
(T2 > T1), the two constants are related by Van’t Hoff equation as follows :
K2 H  T2  T1 
log10    Where R is gas constant and H is the standard heat of reaction.
K1 2.303R  T1T2 
Note : The value of H is negative for exothermic reaction and is positive for endothermic reaction.

Le Chatelier’s principle and Physical equilibrium :

Consider the physical equilibrium of change of state :
solid liquid
Effect of pressure on melting :

When a solid melts, there is a decrease in volume for some solids (ice, diamond, carborundum, magnesium
nitride, quartz etc.) and there is an increase in volume for some solids (sulphur, iron, copper, silver, gold
etc.).
When ice melts, there is a decrease in volume. On this kind of system where there is a decrease in volume
due to melting, increasing pressure will reduce the melting point of the system. Thus, increasing the pressure
will favor the melting of ice.
Similarly, when sulphur melts, there is an increase in volume. On this kind of system where there is an
increase in volume due to melting, decreasing pressure will reduce the melting point of the system. Thus,
decreasing the pressure will favor the melting of sulphur.
Vapour pressure of liquids :

Consider liquid vapour equilibrium :
This is an endothermic reaction in forward direction. Hence rise in temperature will favour evaporation. This
means, increase in temperature results in increase in vapour pressure of the system.
Effect of pressure on boiling point :

As we increase pressure on the system : Liquid vapour ; vapours condense lowering the vapour
pressure of system. This means boiling point rises on increasing pressure as to reach the pressure required
for the liquid to start boiling, needs to be increased.
Effect of temperature on solubility :

In most cases, formation of solution (solute in solvent) is an endothermic process. In such cases, increasing
temperature, increases the solubility of solutes. In cases, where dissolution of solute is followed by evolution
of heat ; increasing temperature lowers the solubility of solutes.
Solubility of gases in liquid : As the temperature increases, the solubility of a gas decreases. This means that
more gas is present in a solution with a lower temperature as compared to a solution with higher tempera-
ture.
Effect of pressure on solubility :

When a gas dissolves in liquid, there is a decrease in volume of the gas . Thus,
increase of pressure will favour the dissolution of gas in liquid.

Illustration - 7 For the reaction : CO2 (g) + H2 (g) CO(g) + H2O (g), K is 0.63 at 727C and
1.26 at 927C.
(a) What is the average H for the temperature range considered ? [Use log10 2 = 0.3]
(b) What is the value of K at 1227C ?
SOLUTION :
(a) T1 = 1000 K, T2 =1200 K, (b) Let K2 be the equilibrium constant at T2 = 1500K
K1 = 0.63, K2 = 1.26 T1 = 1000 K and then K1 = 0.63

Using the Vant’ Hoff equation :  K  8.32  103  1500  1000 
 log10  2    
K2 H  T2  T1   0.63  2.303  2   1500 1000 
log10   
K1 2.303R  T1T2 
K2
 1.26  H  1200 1000   log10  0.6  log10 4
 log10     0.63
 0.63  2.303  2  1200  1000 
 K2 = 0.63 4 = 2.52
 H = 8.32 kcal/mol
Note : The units of R and H must be same.
Illustration- 8 What would be the effect of increasing the volume of each of the following systems at
equilibrium ?
(i) 2CO (g) + O2(g) 2CO2 (g) (ii) Ni(s) + 4CO(g) Ni(CO)4(g)
(iii) N2O4 (g) 2NO2(g)
SOLUTION :
Increasing volume (at constant temperature) will result in a decrease in the concentration of all the gases. As
per Le-Chatelier’s Principle, the reaction should move in a direction of increase in total number of gaseous
moles (thereby increasing concentration). Thus, shift is in a direction of n g  0
(i)  Backward direction  0]

[Backward direction  ng
(ii) [Backward direction   ng Backward direction  0]

(iii) [Forward direction  (ng )forwarddirection  0]
Illustration- 9 What happens when an inert gas is added to

(i) PCl5 (g) PCl3 (g) + Cl2(g) (ii) 2SO2 (g) + O2 (g) 2SO3 (g) at equilib-
rium at : (a) constant volume and temperature, (b) constant pressure and temperature.
SOLUTION :
Lets discuss what happens when an inert gas is
added to the following reaction at equilibrium stage

Illust
If the reaction is at equilibrium, we have :

Similarly,
K eq  Q . . . .(i)
 n g  1  0  Q  K eq
Any factor (e.g. change in conc. of Reactants/Prod-
ucts or both) can have impact (in terms of change in (Reaction will move in the backward direction)
the conc. of reactants/products) On that reaction at
equilibrium only if that factor changes the equations (b) Inert gas addition at constant volume :
(i) so that K eq  Q p q
pC p D
K eq  Q  (at equilibrium)
pm n
A pB
Two cases occur :
(a) Inert gas addition at constant pressure : and partial pressure (p)  PTotal
p C p qD
p
K eq  Q  (at equilibrium)  n 
pm n
A pB  where   n  Mole fraction 
and partial pressure (p)  PTotal  Total 
 n  Now, when inert gas is added at constant volume,

 where   n  Mole fraction 
PTotal  and   but partial pressure of each gas
 Total 
remains same, since :
Thus, when an inert gas is added, of each of the
gas decreases and since PTotal is constant, partial n
pressure decreases leading to a new equation : Partial pressure (p)  . PTotal and using
nTotal
Q > Keq or Q < Keq Dalton’s Law and ideal gas equation :
which will depend on whether PTotal . V  n Total RT
n g   (n g ) R   (n g ) R  0 or  0  PTotal RT 
 Check : n   const.
respectively  Total V 
 Thus, Keq = Q even on adding inert gas at constant
n g  1  0  Q  K eq volume Thus, adding inert gas at constant volume
(Reaction will move in forward direction) has no effect on a reaction at equilibrium.
Degree of Dissociation and Density :

When a gas decomposes (dissociates), its volume increase in accordance with increase in the total number
of moles (at constant pressure). As the total mass remains same, its density decreases in the same proportion.
 Initial mass of gas mixture = mass of gas mixture at any time  i Vi  f Vf [mass = density 
volume]
= niMmix,i = nfMmix, f [mass = moles  Mole. mass]
where i  Initial density of the mixture ; f  Final density of the mixture ; Vi and Vf = Initial and final
volume of the system
Mmix,i  Initial molecular weight of the mixture and Mmix, f  Final molecular weight of the mixture.

nf M mix,i d
 =  i
ni M mix, f df
where di  Initial vapour density of the mixture and df  Final vapour density of the mixture.
Consider the dissociation of PCl5 to clearly understand the concept.
where   degree of dissciation of  x / a
Total moles = a  a
a d d
 = mix  mix d mix = density of mixture PCl5, PCl3, Cl2
a + a d0 d PCl5
M mix, i M PCl5 1

Using the correlation for vapour density and moles, we have :  
M mix, f M mix, f 1
Mmix, f can be found out by experiments. Thus,  can be calculated.
Illustration - 10 When PCl5 is heated, it dissociates inot PCl3 and Cl2. The vapor density of the gas mixture
at 200oC and at 250oC is 70 and 58 respectively. Find the degree of dissociation at two temperatures.
SOLUTION :
d0 v.d.PCl5 M /2 a a
   0 
d mix v.d.mix 70 a
208.5 / 2
 1     0.49
70
Total moles  a  a  Using the result At T = 250 C

d0 v.d.PCl5 M0 / 2 a  a 
 d a + a = = 
 0 =  d mix v.d.mix 58 a
 d mix a 
d 0 = density of PCl5 208.5 / 2

  1     0.80
At T = 200 C (v.d.  vapour density) 58

Illustration - 11 KP for the reaction PCl5 (g) PCl3(g) + Cl2(g) at 250C is 0.82. Calculate the
degree of dissociation at given temperature under a total pressure of 5 atm. What will be the degree of
dissociation if the equilibrium pressure is 10 atm. at same temperature.
SOLUTION :
Let 1 mole of PCl5 be taken initially. If ‘x‘ moles x2
 Kp  P = 0.82
of PCl5 dissociate at equilibrium, its degree of 1  x2
dissociation = x
x 2 (5) 0.82
or  0.82  x 2 
2 5.82
1 x
x = 0.375 (or 37.5%)
Now the new pressure P = 10 atm.
Let y be the new degree of dissociation. As the
temperature is same (250 C), the value of KP
Total moles  1  x  x  x  1  x will remain same.
P = 5 atm and Kp = 0.82 Proceeding in the same manner,
1 x  x
y2P y2
pPCl 5    P ; pPCl 3  P
 1 x  1 x Kp   0.82   10
1  y2 1  y2
x
and pCl 2  P
1 x 0.82
 y or y = 0.275 (or 27.5%)
(PPCl5 )(pCl2 ) 10.82
Now, Kp 
(pPCl5 )
Note :
 By increasing pressure, degree of dissociation has decreased, i.e., the system shifts to reverse direction.
Compare the result by applying Le Chatelier’s principle.
 Read the following example very carefully, In the following example, the volume is suddenly doubled, so first
the initial concentration of all species at equilibrium will be halved and a new equilibrium will be re-established.
Illustration - 12 At a given temperature and a total pressure of 1.0 atm for the homogenous gaseous
reaction N2O4 (g) 2NO2 (g), the partial pressure of NO2 is 0.5 atm.
(a) Find the value of KP .

(b) If the volume of the vessel is decreased to half of its original volume, at constant temperature, what
are the partial pressures of the components of the equilibrium mixture ?

SOLUTION :
For equilibrium system, N2O4 (g) direction, as there is a decrease in mole (ng = 2
2NO2 (g), the total pressure is 1.0 atm.  1 = 1) i.e, the NO2 will be converted to N2O4.
 The total pressure = PN2O4  PNO2  1.0 Let the decrease in pressure of NO2 be x atm.
 PN2O4 = 0.5atm and PNO2 = 0.5 atm
(PNO 2 ) 2 0.52
(i) KP    0.5 atm
PN 2 O 4 0.5
(ii) As volume is decreased to half its original (1  x)2

volume, equilibrium is disturbed and the new  KP   0.5
(1  x / 2)
initial conditions for the re-establishment of
new equilibrium are :  4x2  9x + 2 = 0
PN2O4 = 1.0 atm and PNO2 = 1.0 atm  x=2 or 0.25
[ P is doubled as V is halved at cons tan t T] (x  2, as initial pressure = 1.0)

 x = 0.25
According to Le Chatelier principle, when volume
is decreased, the system moves in that direction x
PN2O4  1   1.125 atm
where there is decrease in number of moles. 2
Hence, the system (here) will move in reverse
and PNO2  1  x  0.75 atm
Illustration - 13 1 mole of N2 and 3 moles of PCl5 are placed in a 82.1L container heated to 127 C. The
equilibrium pressure is 2.0 atm. Assuming ideal behaviour, Calculate the degree of dissociation of PCl5 and
value of Kp for its dissociation.
SOLUTION :
Dissociation of PCl5 is written as :  nT = moles of (PCl5 + PCl3 + Cl2 ) +
PCl5 (g) PCl3 + Cl2(g) moles of N2
 nT = 3  x + x + x + 1 = 4 + x
Let x be the no. of moles of PCl5 decomposed
at equilibrium. The mixture behaves ideally, hence PV = nT
RT
Let us calculate no. of moles by using gas
equation
PV 2  82.1
 nT    nT = 5
RT 0.082  400
Now total gaseous moles in the container = nT Now, equating the two values of nT, we have :
4+x=5  x = 1.

 Degree of dissociation = 1/3 = 0.333 2

  2.0  0.8 atm
PPCl3  PCl2 5
KP  x 1
PPCl5 PCl2  PPCl3  P   2.0  0.4 atm
3 x
4 x 5
Now PPCl5  P P = equilibrium pressure
4 x 0.4  0.4
 Kp   0.20 atm
0.8
Note :
 The inert gases like N2 or noble gases (He, Ne etc) though do not take part in the reaction, but still they affect
the degree of dissociation and equilibrium concentrations for the reactions in which ng  0. They add to the
total pressure of the equilibrium mixture (p  n)..
Illustration - 14 At temperature T, a compound AB2(g) dissociates according to the reaction :

2AB2(g) 2AB(g) + B2(g)
with a degree of dissociation which is small compared to the unity. Deduce the expression for in terms of
the equilibrium constant Kp and the total pressure P.
SOLUTION :
a / 2
2AB2(g) 2AB(g) + B2(g) ; p B2  .P
a  a / 2
a
As a << 1 a a
2
a  a  a

a  pAB  P;pAB2  P ; pB2  P
 Total moles = nT = a  2
2
 
 P 2 . P
3
2
(pAB ) (pB2 )  Kp  2   P
Kp  2
2
(pAB2 ) 2 P
a a  a 2K p
pAB  .P ; pB2  P;
a  a / 2 a  a / 2  3
P
Illustration - 15
The equilibrium constant Kp of the reaction: is 900 at
800 K. A mixture containing SO3 and O2 having initial partial pressures of 1 and 2 atm. respectively heated
at constant volume is allowed to equilibrate. Calculate the pratial pressures of each gas at 800 K.

SOLUTION :
Now : x2  4  x  1
 
2 900
2 1  x 

Assume that x is very small (as Kp <<1and O2
 O2  g  K p  1 / 900 is already present at the time of dissociation).
and initial pressure of SO3 = 1 and O2 = 2 atm.

Let x be the decrease in pratial pressure of
SO3 at equilibrium. x2  4  1 1
   x  0.023
2 900 30 2
2 1
 PSO2  x  0.023 atm
and PSO3  1  x  0.977 atm
2 x
 Kp 
 PSO2   PO2 and PO 2  2   2.0115 atm
2
 PSO3 
Note: Check the correctness of your approximaion.
 x
x2   2  
 2 1
 KP  
2 900
1  x 

Example - 1 H2 and I2 are mixed at 400C in a 1.0 L container and when equilibrium is established, the
following concentrations are present : [HI] = 0.8 M, [H2] = 0.08 M and [I2] = 0.08 M. If now an additional 0.4
mol of HI are added, what are the new equilibrium concentrations, when the new equilibrium
H2 (g) + I2 (g) 2HI (g) is reeestablished ?
SOLUTION :
First determine the equilibrium constant Let 2x = concentration of HI consumed (while

going left) then concentration of each of H2 and
Kc for H2 (g) + I2 (g) 2HI (g) I2 formed = x
 [HI] = 1.2  2x, [H2] = 0.08 + x,
[HI]2 (0.8)2
Kc    100 [I2] = 0.08 + x and Kc = 100
[H 2 ][I2 ] 0.08  0.08
When 0.4 mol of HI are added, equilibrium is

Kc 
1.2  2 x 2  100
disturbed. 
 0.08  x   0.08  x 
At that instant, [HI] = 0.8 + 0.4 = 1.2 M
 Take square root on both side to get :
2
(1.2) x = 0.033
 Q > Kc since Q   225
0.08  0.08
Finally, the equilibrium concentrations are :
 Backward reaction dominates and the [HI] = 1.2  2x = 1.2  0.033  2 = 1.13 M
equilibrium shifts to the left. [H2] = 0.08 + x = 0.08 + 0.033 = 0.11 M
[I2] = 0.08 + x = 0.08 + 0.033 = 0.11 M
Example - 2 0.25 mol of CO taken in a 1.5 L flask is maintained at 500 K along with a catalyst so that the
following reaction can take place ; CO(g) + H2g CH3OH(g). Hydrogen is introduced until the total
pressure of the system is 8.2 atm. at equilibrium and 0.1 mol of methanol is formed. Calculate :
(i) Kp and Kc
(ii) The final pressure if the amount of CO and H2 as before are used but no catalyst so that the
reaction does not take place.
SOLUTION :
First balance the equation as : Let y moles of H2 were present initially
CO(g) + 2H2(g) CH3OH(g)
KC 
CH 3OH 
CO  H 2 2
Self Study Course for IITJEE with Online Support Solved Examples 21
x  0.10 (given) 0.10

 moles of CO = 0.25 – 0.10 = 0.15, Kc 
CH3OH   1.5  600
moles of H2 = y – 0.2 and CO  H 2  0.15  0.05 2
2
 
1.5  1.5 
moles of CH3OH = 0.10
Now find Kp using the relation :
 Total moles = nT = 0.15 + (y – 0.2) +
0.10 = 0.05 + y n g
K p  K c  RT 
Equilibrium pressure (P) = 8.2 atm
Volume of vessel (V) = 1.5 L, T = 500 K ng 1  3   2
Using the Gas equation, PV = nRT, we have : 2

 K p  600  0.0821  500   0.356
PV 8.2 1.5
nT    0.3 (ii) When no reaction takes place, then the total
RT 0.0821  500
pressure is simply due to H2 and CO
 0.30 = 0.05 + y y = 0.25 moles present initially.
 moles of H2 at equilibrium = y – 0.2 nT  nCO   nH 2  0.25  0.25  0.5

= 0.25 – 0.2 = 0.05
nRT 0.5  0.0821 500
Now find Kc as follows :  P   13.68 atm
V 1.5
Example - 3 Ammonia under a pressure of 15 atm. at 27oC is heated to 327oC is a closed vessel in the
presence of catalyst. Under these conditions, NH3 partially decomposes to H2 and N2. The vessel is such that
the volume remains effectively constant, whereas the pressure increases to 50 atm. Calculate the % age of
NH3 actually decomposed.
SOLUTION :
P1 P2
Ammonia decomposes to N2 and H2 as follows :  
T1 T2
PT 15  600
 P2  1 1   30 atm
T1 300
at 27oC at 327oC
(15 atm.) (P = ?) V remains constant
First, let us find initial pressure of NH3 at 327oC.
 P  T (V is constant)
Now final equilibrium pressure = 50 atm
22 Solved Examples Self Study Course for IITJEE with Online Support
3 x
 50  30  x  x   x  20 atm initial moles initial presseur
2 2 
final moles final pressure
20
% NH3 decomposed = 100  66.7 %
30 a 30 20
  
Alternative method : a  a 50 30
20
 % dissociation   100  66.7%
30
Let  be the degree of dissociation

 Total mole  a  a 
 Total mole  a  a 
Example - 4 Solid Ammonium carbamate dissociates as : NH2COONH4(s) 2NH3(g) + CO2(g). In
a closed vessel solid ammonium carbamate is in equilibrium with its dissociation products. At equilibrium
ammonia is added such that the partial pressure of NH3 at new equilibrium now equals the original total
pressure. Calculate the ratio of total pressure at new equilibrium to that of original total pressure. Also find
the partial pressure of ammonia gas added.
SOLUTION : 31
P
NH 2 COONH 4 (s) 2NH 3(g) + PNew 31
 Ratio =  27 
CO2(g) Poriginal P 27
Let P = original equilibrium pressure, Let x be the partial pressure of NH3 added at
From the mole ratio of NH3 and CO2 at original equilibrium.
equilibrium, we have ;
NH2COOHNH4(s) NH3(g) + CO2(g)
2 P
PNH 3  P and PCO2  2 1
3 3 At eq : P P
3 3
2
 
K P  PNH 3  . PCO2 2
P x
1
P
When NH3 is added :
2
3 3
2  P 4
  P     P3
 3   3  27 2 1
At new eq : P  x  2y P y
Now NH3 is added such that , PNH 3  P 3 3
Find the pressure of CO2. 2
 p  x  2 y  PNH 3
4 3 4 3
 P  P 2 PCO  PCO2  P
27 2 27 1 4
 P and P  y  PCO2  P
Total new pressure = Pnew  PNH 3  PCO2 3 27
4 31 19
 PNew  P  P P  Solve to get : x  P
27 27 27
Example - 5 Two solids X and Y dissociates into gaseous products at a certain temperature as follows :
X(s) A(g) + C(g), and Y(s) B(g) + C(g). At a given temperature, pressure over excess solid
X is 40 mm and total pressure over solid Y is 80 mm. Calculate.
(a) the value of KP for two reactions.
(b) the ratio of moles of A and B in the vapour state over a mixture of X and Y.
(c) the total pressure of gases over a mixture of X and Y.
SOLUTION :
(a) X(s) A(g) + C(g)
 pB   a  b  mm
At equilibrium, A and C are in equal proportions,
so their pressures will be same. K p  for X   p A .pC  a  a  b   400 …(i)
pA = pC
K p  for Y   p B .pC  b  a  b  1600 …(ii)
Also pA  pC  40  pA = pC  20 mm
Form (i) and (ii), we get :
 K P = p A .pC  202  400 mm 2 a 1

b 4
Similarly for Y(s) B(g) + C(g),
as volume and temperature are constant, the mole
PB = PC = 40 mm  PB + PB = 80  ratio will be same as the pressure ratio.
(c) The total pressure = PT = p A + p B + pC

 K P = PB .PC = 402 =1600 mm 2
(b) Now for a mixture of X and Y, we will have  a  b   a  b  2  a  b 
consider both t he equilibrium
Adding (i) and (ii),
simultaneously.
a + b = K PX + K PY = 2000 = 20 5 mm
 Total pressure = 2 (a + b) = 89.44 mm

and
Let p A  a mm, pB  b mm
Not that the pressure of C due to dissociation
of X will also be a mm and similarly the ressure
of C due to dissociation of Y will also be b mm.
Example - 6 Consider the equilibrium : When the reaction between P and Q

is carried out at a certain temperature, the equilibrium concentrations of P and Q are 3 M and 4 M
respectively. When the volume of the vessel is doubled and equilibrium is allowed to re-established, the
concentration of Q is found to be 3 M. Find the :
(a) Value of KC
(b) Concentration of R at two equilibrium stages.
SOLUTION :
Given : [Q] = 3 M at new equilibrium

at equilibrium, [P] = 3 M, [Q] = 4 M and let  2 + 2y = 3  y = 0.5 M
[R] = x M,
 At new equilibrium, [P] = 1.5 + 0.5 = 2 M;
KC =
R  = x  x [Q] = 3 M (given) ; [R] = x/2 – 0.5 M
…(i)
 P  Q2 3 × 42 48
Now the volume is doubled, hence the  Q=
 R  =  x / 2 -0.5
concentrations are halved and a new equilibrium  P Q2  2 32
will re-established with same value of KC.
Calculate Q and determine the direction of Equating this value of KC with (i)
equilibrium.
 x / 2  0.5   x  x4M
[ R] x/2 x 
Q 2
 
2 12  2  32 48
[ P][Q]  3 / 2  4 / 2 
Hence [R] = 4 M and
 Q > K C Hence the system will
predominately move in backward direction at new equilibrium [R] = x/2 – 0.5 = 1.5 M
so as to achieve new equilibrium state. Let x 1
y M be the decrease in concentration of R. and K C = =
48 12
Example - 7 The degree of dissociation of HI at a particular temperature is 0.8. Find the volume of 1.6 M
sodium thiosulphate solution required to react completely with the iodine present at equilibrium in acidic
condition, when 0.1 mol each of H2 and I2 are heated at 440 K in a closed vessel of capacity 2.0 L.
SOLUTION :
2 2
First find the value of KC for dissociation of HI  HI  2x / V  1
 KC = = =
from its degree of dissociation.  H 2  I2   0.1 x    0.1 x  4
V V
 x  0.02
(degree of dissociation is 0.8)
Now find the moles of I2 left un-reacted at
equilibrium.
n  I2   0.1  0.02  0.08
I2 reacts with sodium thiosulphate (Na2S2O3)

as follows :
KC 
 H 2  I2    a / 2 a / 2    2
 HI2  a  a  2 4 1   
2
Applying the mole concept, we have,
0.82 2 moles of Na 2S2O3  1 mole of I2

Here   0.8  K C  4
2
4 1  0.8 
 0.08 mole of I2  2  0.08
Now we have to start with 0.1 mol each of H2
and I2 and the following equilibrium will be = 0.16 moles of Na 2S2O3
established.  Moles = MVL
(M = molarity, VL = volume in litres)
 0.16 = 1.6 VL
 2 HI with K C  1/ 4
H 2  I2   VL = 0.1 L = 100 mL
Example - 8 At 25oC and 1 atm, N 2O4 dissociates by the reactio n If it is 35%

dissociated at given condition, find the volume of above mixture will diffuse if 20 ml of pure O2 diffuses in 10
minutes at same temperature and pressure.
SOLUTION :
a + a  M mix,i M N 2 O4
For equilibrium system, Using = 
a M mix, f M mix, f
92
 1  0.35 
M mix, f
92
 M mix, f = = 68.15
 Total moles at equilibrium = a + a  1.35
a a 2a  Let V(ml) volume of mixture diffused in.

p N 2 O4  P and p NO2  P
a a  a a  From Graham’s law of diffusion.
Here P = 1.0 atm and rO2 M mix, f

=
p2NO 4a 2 p
rmix, f MO2
2
Kp = =   0.35
p N 2 O4 1 2
20 / 10 68.15
  V 13.70 ml
2 V/10 32
4×  0.35 
 Kp = 2
×1= 0.56 atm
1-  0.35 
Example - 9
For the reaction
1/ 2
 3 3 P 
Show that the degree of dissociation of NH3 is given as   1   where P is the equilibrium
 4 K p 
pressure and  is the degree of dissociation. If Kp of the above reaction is 82.1 atm at 727oC, determine the
value of Kc.
SOLUTION :  3 3 P   2 
Let  be the degree of dissociation of   
2
NH3(g).  4  1   
1 2 3 3 P
 
2 4 Kp
Initial moles 1 0 0
At equilibrium 1  /2 3 / 2
1  3 3 P 
Total number of moles at equilibrium 1     1  
2 4 KP 
 
Now,
1  /2 1/ 2
p NH3  P, p N 2   3 3 P 
1  1  or   1  
 4 Kp 
3 / 2
and pH 2  P
1 
 n g , change in number of the moles of the
1/2 3/2 given reaction = +1
Kp =
 p N2   pH2 
p NH3 ng ng
K P = K C  RT   K C = K P  RT 
1/2 1
    3   K C = 82.1×  0.0821×1000 =1.0 mol/ L
 P  P
  2 1      2 1    
1 
P
1 
THINGS TO REMEMBER
1. To predict the net direction of a system, calculate Q and compare it with its Keq.
Use : Q < Keq (Forward reaction) ; Q > Keq (Backward reaction)
Q = Keq (No net reaction i.e. system is at equilibrium)
2. 2. Le Chatelier’s Principle : ( : increases ;  decreases)
(i) TReaction is shifted in a direction where energy is getting absorbed
T  Reaction is shifted in a direction where energy is getting absorbed
(ii) P: Reaction is shifted in a direction where ng < 0

P: Reaction is shifted in a direction where ng > 0
(iii) Inert gas addition :
Constant V : No effect
Constant P : Reaction is shifted in a direction where ng > 0
(iv) V: Reaction is shifted in a direction where ng > 0
V: Reaction is shifted in a direction where ng < 0
(v) Melting (with increase in volume e.g. S (s) S (l)
P  More melting ; T  More melting

P  Less melting ; T  Less melting
Melting (with decrease in volume) e.g. Ice water
P  Less melting ; T  More melting
P  More melting ; T  Less melting
(Note that Melting is endothermic process)
3. Degree of dissociation and Density :

n i M mix, f d
= = f
n f M mix,i di
4. Whenever an approximation is applied, always check for approximations assumed before finalizing
the answer.
Self Study Course for IITJEE with Online Support Things to Remember 29
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Ionic Equilibrium
Ionic Equilibrium
CONCEPT OF ACIDS AND BASES Section - 1
Concept of Acids and Bases

Three main concepts in defining the acids and bases are :
1. The Arrhenius concept
2. Bronsted-Lowry concept
3. Lewis concept
1. The Arrhenius concept :
According to this concept, an acid and a base can defined as follows :
Acid : It is a substance that produces hydrogen ions (H  ) in water..
Base : It is a substance that produces hydroxyl ions (OH  ) in water..

HCl, H 2SO4 , HNO3 etc. are the examples ofArrhenius acids while NaOH, KOH, Mg(OH)2 etc.
are the examples Arrhenius bases.
Let us represent an acid as HX and a base as BOH.
The ionization of acid as (HX) can be represented by the following equation :
HX(aq)  H 2O()  H3O (aq)  X  (aq)

(hydronium ion)
or simply, HX(aq)  H  (aq)  X  (aq)
Hydronium ion (H3O  ) is used to represent a hydrated H  ion i.e., H  , ion surrounded by
water molecules.
Note : The Arrhenius concept of acids and bases is only limited to aqueous solutions.
Limitations of Arrhenius Concept

(i) It is applicable only to aqueous solutions. For the acidic or basic properties, the presence of water is
absolutely necessary. Dry HCl shall not act as an acid.
(ii) The concept does not explain acidic or basic properties of acids and bases in non-aqueous solvents
respectively.
(iii) It fails to explain the acidic nature of the non-protic compounds such as SO 2 , NO2 , CO 2 , P2O5
etc. which do not have OH in the molecules to furnishing H  ions.

Ionic Equilibrium Vidyamandir Classes
(iv) It fails to explain the basic nature of compounds like NH3 , Na 2CO3 etc. which do not have OH
in the molecules to furnish OH  ions.
(v) It fails to explain the acidic nature of certain salts such as AlCl3 in aqueous solution.
2. Bronsted-Lowry Acids and Bases

According to this concept, an acid and a base can defined as follows :
Acid : It is a substance that can donate a proton.
Base : It is a substance that can accept a proton.
Example :
When HCl is dissolved in water, it donates a proton to H 2O which behaves as a base.
HCl(aq)  H 2 O( )  Cl  (aq)  H 3O  (aq)
Other examples of Bronsted Lowry acids (underlined) are :
(a) NH 4 (aq)  H 2O()  NH3 (aq)  H3O (aq)
(b) HSO4 (aq)  H 2O()  SO 42  (aq)  H3O (aq)
(c) HCl(aq)  NH3 (aq)  Cl (aq)  NH 4 (aq)
(d) HCO3 (aq)  NH3 (aq)  CO32 (aq)  NH 4 (aq)

Some examples of Bronsted Lowry bases (underlined) are :
(a) O 2  (aq)  H 2 O( )  OH  (aq)  OH  (aq)
(b) NH 3 (aq )  H 2O()  NH 4 (aq )  OH  (aq)
(c) CO32  (aq)  H 2O()  HCO3 (aq)  OH  (aq)
Note :  This theory requires that an acid must contain transferable hydrogen and it offers great freedom in
defining what constitutes base.
 When an acid has donated its proton, the remaining portion of the molecule or ion is a base.
 When a base accepts a proton, it forms an acid.
 The base must have an unshared pair of electrons so as to accept a proton.
The base formed from an acid is known as the conjugate base of the acid. Correspondingly, the acid
formed from a base is called the conjugate acid of the base.
HCl  NH 3  Cl   NH 4
Acid1 Base Base1 Acid
2 2

In the above reaction, Cl is the conjugate base of HCl and NH 4 is the conjugate acid NH3 .

Note : (i) The conjugate acid always has one more proton than its conjugate base.
(ii) To obtain a conjugate acid of a compound, add a proton (H  ) from it and to obtain the conjugate
base of the same, remove a proton to the compound, e.g., Conjugate acid of NH3 is NH 4 while
the conjugate base of NH3 is NH 2 .

(iii) This concept has the advantage that it can be applied to a solvent other than water, having the tendency
to accept or lose a proton.
(iv) The terms acid and base are comparative. A substance can behave as an aid in one solvent and as a
base in another.
For example : Acetic acid (CH3COOH) behaves as an acid in water but as a base in HF..
CH 3COOH(aq)  H 2O(aq)  CH3COO  (aq)  H 3O + (aq)

Acid Base
CH3COOH(aq) HF(aq)  CH3COOH 2+  F (aq)

Base Acid
Strength of Bronsted-Lowry Acid and Bases :

The strength of an acid or base is measured by its tendency to lose or gain proton. A strong acid is a
substance which loses a proton easily to a base. Consequently, the conjugate base of a strong is a weak
base.
The ability of an acid to lose a proton is experimentally measured by its equilibrium constant know as Ka.
The larger the value of K a , the more complete reaction or higher the concentration of H3O+ and the
stronger is the acid Similarly: For bases, we have the equilibrium constant, K b which determines the extent
of the completion of the reaction.

Acid-Base Chart Containing Some Common Conjugate Acid-Base Pairs
Note : In general, solvents can be of four types :

(a) Protophillic : Solvents having a tendency to accept protons. For example water, alcohol, liq. Ammonia
etc.
(b) Protogenic : Solvents having a tendency to donate protons. For example water, liq. HF, liq. HCl
etc.
(c) Amphiprotic : Solvents having a tendency to accept or donate. For example water, liq. ammonia
etc.
(d) Aprotic : Solvents which neither accept nor donate protons. For example benzene, carbon tetrachloride
etc.
Amphoteric Compounds :
The compounds which can act either as acids or as bases, H 2O, NH3 and CH3COOH are some of the
examples.
(a) Water : H 2O  NH3  OH   NH 4 H 2O  H 2O  H3O+  OH 

Acid Base Acid Base

(b) Blcarbonate : HCO3  NH3  CO32   NH 4 HCl HCO3  Cl  H 2CO3

Acid Base Acid Base
Note : The reaction H 2O  H 2O  H3O+  OH  is known as auto-ionization of water..
Limitations of Bronsted Concept :

(i) A substance is termed as an acid or base if it reacts with some other substance, i.e., if it donates
proton to other substance, it is an acid and if it accepts proton from substance, it is a base.
(ii) There are number of acid-base reaction in which no proton transfer takes place, e.g.,
SO 2  SO 2  SO 2+  SO32 
Acid1 Base 2 Acid 2 Base1
Thus, the protonic definition cannot be used to explain the reaction occurring in nonprotonic solvents
such as COCl2 ,SO 2 , N 2O4 etc.
3. Lewis Acid and BasesAcid :
Acid : It is a substance that can form a covalent bond by accepting a shared pair of electrons.
Base : It is a substance that possess at least one unshared pair of electrons.
Monoprotic Acids : Acids that give up one proton per molecule.

Polyprotic Acids : Acids that can give up more than one proton per molecule.
Substance that are bases in the Bronsted sysem are also bases according to the Lewis concept. However
the Lewis definition of an acid considerably expands that number of substances that are classified as acid.
A Lewis acid must have an empty orbital capable of receiving the electron pair of the base.
Lewis acids include molecules or atoms that have incomplete octets. For example molecules like
BF3 , AlCl3 etc., act as Lewis Acid.
Many simple cations can act as Lewis acids :

Cu 2+  4 NH3  Cu(NH3 )2+
4 Fe3+  6 : C  N : Fe(C  N)36
Some metal atoms can function as acids in the formation of compounds such as:
Ni  4 C    Ni(CO)4
Compounds that have central atoms capable of expanding their valence shells are Lewis acids in reactions
in which this expansion occurs.

SnCl4  2 Cl  SnCl62  SiF4  2 F  SiF62  PF5  F  PF6

Some compounds have an acidic site because of one or more multiple bonds in the molecule.
BASICS OF IONIC EQULIBRIUM Section - 2
The type of equilibrium studied in Chemical Equilibrium is known as molecular equilibrium (the
involvement of molecules only). Now, we will study reversible reactions involving formation of ions in water
under Ionic Equilibrium.
Ionic Equilibrium is the study of equilibrium in the reactions where formation of ions takes place in aqueous
solution.
Ions in solution arises mainly from two ways :
 When solute is ionic compound i.e., strong electrolyte (a compound whose aqueous solution conducts
electricity) e.g. NaCl, MgCl2, KBr, NaNO3, NaOH etc. In such compounds, ions maintain their
identity even in solid state. As such solutes are dissolved in water, ions get separated. In solution,
whole of electrolyte is ionised i.e., ionisation is almost 100% complete.
 When solute is polar covalent compound and reacts with water to form ions. These may be strong or
weak electrolytes depending upon their respective degree of ionizations () e.g., HCl, NH3, H2SO4,
HNO3, CH3COOH, HCN, NH4OH etc.
Dissociation (or ionisation) of strong electrolytes and some weak electrolytes such as HNO3, HCl, H2SO4
etc. is nearly complete in dilute solution i.e. almost 100% of electrolyte is converted to ions or one can say
that degree of ionisation () is nearly 1.
Let BA be an electrolyte and dissolved in water. It ionises as follows : BA + aq.  B  aq. + A  aq.
Case - I : (  1)
The extent of forward reaction is very high (i.e. such reactions are nearly complete). So, it is of no use to
study equilibrium in such reactions.
Case - II : (  1)
In aqueous solution of these compounds, only slight amount of reactant (i.e. electrolyte) undergoes dissociation
and there exists an equilibrium between ionised molecules and unionized molecules (ions). Such electrolytes
are weak electrolytes.
BA  aq.  B+ (aq .)  A  (aq .)
 ionised molecules (ions)
unionised molecules 

Weak Electrolytes are categorized into three types for easy understanding :
1. Weak Acids : CH3COOH , HCN (and all organic acids)
2. Weak Bases : NH4OH and all organic bases
3. Sparingly soluble salts : AgCl, PbCl2, Ag2C2O4, MnS, H2S, PbS etc.
Weak Acids (HA) and Weak Bases (BOH)

Weak Acids :
Let HA be a monoprotic (monobasic) acid whose equilibrium is to be studied. The aqueous solution of HA
can be studied in either of two ways :
HA + H2O  H O+ (aq) + A(aq)

 (H3O+ = hydronium ion)
3
or simply as : HA(aq)  H+(aq) + A(aq)


The equilibrium constant for the above reaction is known as ionisation constant for an acid (Ka).
[ ] = concentration in mol/L
[CH 3COO  ][H  ]

e.g., CH 3COOH(aq)  CH 3COO  (aq)  H + (aq) Ka 
CH3COOH 
Note : The ion A– formed due to the ionization of HA is known as its Conjugate base. Thus, to find a conjugate
base of any acid, simply remove a Proton (H+) ion from that acid.
 Conjugate base of CH3COOH is CH3COO ; of H 2PO 4 is and so on.

Lets study the equilibrium of a weak acid HA in an aqueous solution as follows :
If ‘c’ be the molar concentration of weak acid HA and ‘’ be its degree of dissociation (i.e. the fraction of
total concentration which exist in ionic state), then : HA  aq   H   aq   A   aq 
[H  ][A  ] (cα ) (cα ) cα 2

 Ka   
 HA  (c - cα ) 1- α
[H ][A ] [H ] 2

Also, Ka   ( [H ]  [A ]  c )
 HA c  H 
 
For weak acids having  << 1, we can take 1   1

Ka
 Ka = c 2  α=
c
Note : (i) In general, if Ka < 105 and ‘c’ is fairly high (generally 0.1 M or 0.01 M) then 1   can be taken as
unity.
If c is very low (i.e. for very dilute solutions),  is higher. In that case, we can’t take 1   as 1. In
such cases we have to solve a quadratic equation in . i.e. (1  ) Ka = c 2.
(ii) Basically, if decision on whether to go for approximation or not, is not easy, then just use approximation
and solve but remember that you should always validate your approximation before reaching to a final
answer. We will see more on this in illustrations and examples.
Weak Bases :
Let BOH be the weak base, its aqueous solution is represented as follows :
 B+(aq) + OH(aq)

BOH(aq) 
The equilibrium constant for the above equilibrium is known as ionisation constant of a base (Kb).
[B ][OH  ]
Kb  [ ] = concentration in mol/L
 BOH 
[NH 4 ] [OH  ]
 NH4
For : NH4OH(aq)  +(aq) + OH(aq) Kb 
 BOH 
Note : Similar to the concept of Conjugate base, there is a concept of Conjugate acid. e.g. NH 4 is a conjugate acid
of base NH3. Thus, to find a conjugate acid of any base, simply add a Proton (H+) ion to that.
 H2PO4– : Its conjugate base is H2PO42– and its conjugate acid H3PO4
 H2O : Its Conjugate base is OH– and its conjugate acid is H3O+
A substance is known as amphiprotic if it can both donate or accept a proton e.g. , H2O
Now, if ‘c’ be the molar concentration of BOH and ‘’ be its degree of dissociation, then :
 B+(aq) + OH(aq)
BOH(aq) 
[B ][OH  ] (cα) (cα) cα 2

 Kb   
 BOH  (c - cα) 1- α

[B ][OH  ] [OH  ] 2

Also, K b   ( [B ]  [OH  ]  c)
 BOH  c  OH  
 
For weak bases having  << 1, 1   1
Kb
 Kb = c 2 or α=
c
Note : At a given temperature, Ka and Kb are directly proportional to  i.e. comparing Ka of different acids
(Kb for bases), one can compare their strengths or comparing ‘’ of different acids (or bases) at a given
temperature and given concentrations, acids strengths (base strengths) can be compared.
For example in case of bases :
α1 K b1
= (two bases having same concentrations)
α2 K b2
or Kb = c112= c222 (two samples of same base have same value of Kb)
α1 c
 = 2
α2 c1
In the above relations, it has been assumed that the degree of dissociation is small as compared to unity.
Self Ionisation of Water
Water ionises as follows : H2O ( ) 
 H+ (aq) + OH(aq)
The equilibrium constant here is denfined in a different way, and is called as ionic product (Kw) of water
and is given by :
 Kw0 = [H+] [OH] where K w = K a [H 2O]

K a : ionisation constant of H O and[H O]is
2 2
constant at a given temperature
At 25C (298 K) ; Kw = 1.0  1014
Since pure water is neutral, [H+] = [OH] = K w = 107 M at 25C.
 If a strong acid is added to it, [H+] increases and hence [OH] < 107 M (at 25C) and solution is said
to be acidic.
 If a strong base is added to it, [OH] increases and hence [H+] must decrease in order to keep Kw
constant. Now [OH] > 107 M and solution is basic (or alkaline)
Note : The dissociation of water is an endothermic reaction. Thus, increasing the temperature will increase Kw of
water and thereby increasing the [OH] and [H+].

pH Scale :
Sorensen, a French chemist developed a scale to measure the acidity in terms of concentrations of H+ in a
solution. As defined by him :
pH of a solution is the negative logarithm to the base 10 of the concentration of H+ ions which it contains.
(Basically “p” acts as a mathematical operator : p(A) = log10 [A])
 pH =  log10 [H+] and pOH = log10 [OH–]
At 25C, using this definition, a scale called pH Scale is developed as follows:

For pure H2O ; [H+] = [OH] = 107 M
pH =  log10 (107) = 7 = pOH  For pure water at 25C ; pH = pOH = 7
(i) If [H+] > 107 M in a solution i.e., solution is acidic then pH < 7
(ii) If [H+] < 107 M (or [OH] > 107 M) i.e. solution is basic then pH > 7
In general, we talk about pH of a solution, whether it is basic or acidic.

For an aqueous solution : pH + pOH = pKW [Use Kw = [H+] [OH] and take “log10 on both sides]
At 25C, pH + pOH = pKw = 14 [Kw = 1  1014 at 25C]
Now one can very easily re-define pH of a basic solution as : pH = 14 + log10 [OH]
Note : “p” operator is generally applied on any variable whose value is < 1. In most of the cases, we will use pKw,
pKa, pKb etc.
Also, we can see that as temperature increases, both pH and pOH of pure water will decrease since there
will be an increase in [H+] and [OH–] due to increased dissociation.
Dissociation constant (K a and K b ) of conjugate ion of weak acid and weak base :

HA is a weak acid and A is its conjugate base.
Dissociation equilibrium of HA :
+  [H + ][A  ]
HA(aq)  H (aq) + A (aq) : K a = …(i)
[HA]

Dissociation equilibrium of conjugate base A  :
[HA][OH  ]
A  (aq) + H 2O()  HA(aq) + OH  (aq): K b = ...(ii)
[A  ]
H 2O()  H  (aq)  OH  (aq) : K W
1
H  (aq)  A  (aq)  HA(aq) :
Ka
A  (aq)  H 2O()  HA(aq)  OH  (aq): K b
K a acid  K bconjugatebase  K W  pK a(HA)  pK  pK w

b(A  )
Similarly for dissociation constant of weak base (K b ) and dissociation constant of conjugate acid (K a ) we
can write
Kbweak base  Kaconjugatebase  KW  pKb(BOH)  pK  pKw
a(B+ )
pH of a Weak Acid and Weak Base :

Weak acid (HA)
 H+(aq) + A(aq)
HA(aq) 
For c molar HA, we have : [H+] = c  pH = log10 c
Ka
Also : α = [If the approximation 1 –   1 is valid]
c
1
 pH =  log10 K a c  (pK a  log10 c)
2
Weak base (BOH) :

 B+(aq) + OH(aq)
BOH(aq) 
For c molar BOH, we have : [OH] = c  pH = 14 + log10 [OH] = 14 + log10 c
Kb
Also : α = [If the approximation 1 –   1 is valid]
c
1
 pH  14  log10 K bc  14  (pK b  log10 c)
2

Illustration - 1 Determine the hydrogen ion concentration in 1.0 M solution of HCN, if its dissociation
constant is 4.0  1010
SOLUTION :
HCN (aq)  H+ (aq) + CN (aq) i.e. c  [H+]  c = 1.0 M (given)
C 0 0
C – C C C  [H  ]  K a c  2 105 M
[H+] = c and [H+] = [CN] Now, check the approximation : c  [H+]  c
[H  ]2  c  [H+] = 1" 2  105  1.0 M = c

Use Ka  ; c = 1.0 M
c  [H  ]
Thus, the answer obtained as above is correct.
Neglecting [H+] against c, as the given acid is
very weak (Ka = 4.0  1010) and c is quite
high .
Illustration - 2 What is the pH of a 0.2 M solution of acetic acid ? To what volume must one litre of this
solution be diluted so that the pH of the resulting solution will be twice the original value ?
Given : Ka = 2.0  105
SOLUTION :
(Doubling the pH value is simply equivalent to
CH 3COOH(aq)  CH 3COO  (aq)  H  (aq)
squaring the [H+])
C 0 0
C – C C C [H  ]2
Using : Ka =
c  [H  ]
[H  ]2 [H  ]2
 Ka  
c  [H  ] c
 [H  ]2
 c  [H ]  4.8  106 M
(as Ka is too Low) Ka
Thus, [H+] = K a c = 2  103 M ; Check yourself that new degree of dissociation
[H  ] [H  ]new
Also,   0.01  c  [ H  ]  c of acetic acid = new   0.83
c cnew
 pH = 2.7 (pH = log10[H+]) which clearly suggests that using approximations
would have generated poor/wrong results.
Now solution is diluted to make pH = 5.4 (twice
the original) Originally the solution was 0.2 M and 1 L, using
molarity equation we have :
Note :On dilution,  increases, so 1  can’t be
taken as unity. So solve the quadratic in . 4.8  106  V = 0.2  1
For pH = 5.4, [H+] = 4  106 M (C1V1 = C2V2)

 V = 4.17  10 4 L3

Illustration - 3 Calculate [H+] and % dissociation of 0.1 M solution of ammonium hydroxide solution. The
ionisation constant for NH4OH is Kb = 2.0  105.
SOLUTION :
 NH +
NH4OH  + OH Kb
4
 α  2 104
C 0 0 c
2
C  C C C = 1.41  10 =1.41 %
[Check that 1   1 holds]
[NH 4 ][OH  ] cα 2 [OH] = C = 0.1  1.41  102
Kb    cα 2 and
[NH 4OH] 1 α
= 1.41  103 M
(Neglecting , in denominator i.e. 1    1)
Kw
 [H + ]   7.09 1012 M

[OH ]
Illustration - 4 Calculate the pH of 108 M HCl solution.

SOLUTION :
 H+ + OH
H2O 
[HCl] = 108 M
x x
 [H+] = 108 M
 K w = [H + ][OH  ] = 10 14
 pH = 8 which is absolutely wrong since the
solution must be acidic as it is an acidic solution [H+]total = [H+]acid + [H+]water = 108 + x
i.e., pH < 7  Kw = (x + 108) x = 1014
The catch here is that since HCl has been added in  x2 + 108 x  1014 = 0
water (which also dissociates) so we need to Solve the above quadratic equation to get :
consider [H+] from dissociation of H2O as well. In x = 9.52  108 M
the earlier illustrations, we didn’t consider this
because [H+] from acid comes out to be much higher Now, [H+]total = 108 + 9.52  108
than that furnished by water but in this case we can = 1.05  107 M
not neglect the water contribution.
 pH =  log10 [1.05  107] = 6.978

COMMON ION EFFECT Section - 3
The addition of an ionic salt having a common ion (anion or cation) to weak acids or weak bases, suppresses
their degree of dissociation (following LeChatelier’s principle).
Weak Acids :
Let HA be a weak acid (like CH3COOH, HCN etc) and B+ A be the ionic salt (100% dissociation in
solution) containing common anion (A) that is added to the acid.
 H+ (aq) + A (aq)
HA (aq) 
BA (aq)  B+ (aq) + A (aq)

Now, the solution has excess of A ions. This means increasing concentration of products, in an equilibrium
 H+ + A ) must go in backward direction,
state, (following LeChatelier’s principle) the reaction (HA 
in order to nullify the effect of added A ions. As a consequence, amount of H+ in new equilibrium state will
be less than before, or one can see that the degree of dissociation of acid (HA) is decreased.
Quantitative Aspect :
Consider a weak acid HA which dissociates as :  H+ (aq) + A (aq)
HA(aq) 
Ka
Its degree of dissociation =  = [Assuming Ka to be small]
c
Let M molar BA be added to it and  be its new degree of dissociation
BA 
 B+ (aq) + A (aq) (Assuming BA to be 100% ionised)
M M
HA 
 H+ (aq) + A (aq)
c  c c c
Now in solution : [HA] = c  c ; [H+] = c

[A]total = [A]From HA + [A]From BA = c + M
[H  ][A  ]  cα  cα  M  α  cα  M 

Ka   
 HA   c  cα 1  α
 Ka = c α2  Mα (Assuming 1    1)
 K a = Mα (Neglecting c '2 in comparison to M as  << 1  α2  1 ]

Ka
 α =
M
By looking at the expressions of  and , we can clearly figure out that ’ >> 
Note : On similar lines, you can find  for a weak base, BOH and adding B+ ions to it.

[H  ][A  ]ext.
Also, expression for Ka becomes : K a  where [A  ]ext . is the externally added salt
 
HA
Buffer Solutions
A solution whose pH does not change very much when H+ (H3O+) or OH are added to it is referred to as
a buffer solution.
A buffer solution is prepared by mixing a weak acid and its salt having common anion (i.e. HA + BA forms
an acidic Buffer) or a weak base and its salt having common cation (i.e. BOH + BA forms a Basic Buffer).
It can be prepared to have a desired value of pH by controlling the amounts of acids and their salts in case
of acidic buffer and of bases and their salts in basic buffer.
Acidic buffer : CH3COOH + CH3COONa, HCN + NaCN
Basic buffer : NH4OH + NH4Cl
Note : See yourself that buffer solutions are actually conjugate acid-base pairs.
Consider an acidic buffer containing an acid HA and say common ions A. Now, any H+ (or H3O+) added
externally to this solution with in certain limits are neutralized by A ions as :
H  A 
 HA
external from salt undissociated acid
While, addition of OH ions externally (with in certain limits) are neutralised by acid HA as :
 H O + A
HA + OH  2
Hence in both the cases, effect of addition of H+ or OH is almost compensated for (i.e. pH almost remains
constant).
Such a system (may be acidic or basic) finds enormous use not only in industrial processes but also (most
importantly) in biological reactions. Like the pH of normal blood is 7.4 and for good health and even for the
survival, it should not change below 7.1 or greater than 7.7, the body maintains it through a buffer system
made of carbonate and bicarbonate ions and H2PO4 and HPO42 . Similarly, the pH of gastric juice is
kept constant in order to operate good digestive functions.
pH of an Acidic Buffer
If [acid] = concentration of a weak acid and [salt] = concentration of the salt that is mixed with acid to make
the buffer
K a  HA  K a  acid 
We have : [H+] =  [See the derivation in the Common Ion effect section]
 A  salt 
  ext.
 pH = pKa + log10
salt  (pKa =  log10 Ka)
acid 
pH of a Basic Buffer
We have : pH = 14  pOH
If [base] = concentration of weak base and [salt] = concentration of salt that is mixed to make the buffer
K b  BOH  K b  base 
 [OH ] = 
 B  salt 
  ext.
salt 
 pOH = pKb + log10 base (pKb = log10 Kb)
 
salt 
 pH = 14  pKb  log10 base
 
Note : The above equations representing the pH of a buffer are known as Henderson’s Equations.
pH of a Buffer (When an acid or a base is added)

We have just discussed that addition of H+ ions or OH ions to an acidic buffer (HA/A) does not appreciably
changes the pH of buffer. Similarly, we can analyse the same for a basic buffer (BOH/B+).
In actual, pH of a buffer solution changes by a small quantity. Let us calculate this change in pH quantitatively.
Consider an acidic buffer HA/A where [salt] = [A] and [acid] = [HA]
An acidic buffer is rich in A ions. Let us add x mole per litre of HCl to it. This added HCl (H+) reacts with
A (salt) to give undissociated acid as : H   A    HA

 salt   acid 
After adding x M H+ ions : [salt  x] [acid + x]
salt 
Now using Henderson’s Equation : pH ( original buffer) = pKa + log10 and pH (new)
 acid 
= pKa + log10
salt  x 
 acid  x 
 pH of buffer decreases.
Change or difference in pH = pH (new)  pH (original)

Let us add x M NaOH to the buffer. This added NaOH (OH ions) react with acid (HA) to produce salt
and H2O.
OH   HA 
 A   H 2O
 acid   salt 
After adding x M OH ions : [acid  x] [salt + x]
salt  x 
 pH (new) = pKa + log10 acid  x  pH of buffer increases.
 
Change in pH = pH (new)  pH (original)
Note : (i) In exactly similar manner, we can calculate the change in pH of a basic buffer (BOH/B+). Try to get a
relation like this for basic buffer. Remember, it is not to be used as standard result.
(ii) A buffer solution is assumed to be destroyed if on addition of strong acid or base, its pH changes
by  1 unit i.e.,
pH (new) = pKa  1 [if the initial pH of the buffer solution was pKa].
salt  salt 
This means the ratio acid OR base = 10 or 1/10.
   
Illustration - 5
To 1.0 L of a decimolar solution of acetic acid, how much dry sodium acetate be added
(in moles) so as to decrease the concentration of H+ ion to 1/10th of its previous value ? Ka = 2.0  105.
SOLUTION :
 CH COO (aq)+ H+ (aq)
CH3COOH (aq)  3
 [H+] = c  = K a c  2.0  10 5  0.1  1.41  103 M [Ceck yourself that approximations are valid]
Note that when salt, CH3COONa is added, the solution will behave just like an acidic Buffer solution.
[salt] [acid] [acid]

Using, Henderson equation : pH = pK a + log10  [H + ] = K a or [salt] = K a
[acid] [salt] [H + ]
1
Now, [H + ]new =  1.41 103 M = 1.41  10–4 M
10
(2.0 × 105 )(0.1)

 [salt] = = 0.0142 M
1.41  104
 moles of salt, sodium acetate = 0.0142 ( 14.2 mmoles) per 1.0 L is required. (V = 1.0 L)

Illustration - 6 (a) A buffer solution of pH value = 4 is to be prepared, using CH3COOH and

H3COONa. How much amount of sodium acetate is to be added to 1.0 L of M/10 acetic acid ?
Ka = 2.0  105.
(b) What will be the pH if 0.01 mol of HCl is dissolved in the above Buffer solution ? Find the change in pH
value.
(c) How will the pH be affected if 1.5 L of H2O is added to above buffer ?
SOLUTION :
(a) For an acidic buffer containing acetic acid, CH3COO + H+   CH3COOH
CH3COOH and sodium acetate, CH3COONa, 0.02 0.005 0.1
we have : 0.015 0.105
K a  acid  [acid] = 0.11 M and [salt] = 0.01 M [V
+
[H ] =
salt  = 1.0 L]
[salt] 0.015
Use this rather than : pH = pK a + log10  pHnew = pKa + log10
[acid] 0.105
[CH3COOH] = 0.1 M ; = 4.7 + (  0.84) = 3.86 [Use log107 = 1.0.84]

 Change in pH = 3.86  4.0 = -0.14
[H+] = 10–4 M and let [CH3COONa] = x M
(c) Now, if 1.5 L of H2O is added, it just increases the
5 volume, thereby decreasing concentrations of both
2 10  0.1
 [H+] = 104 
x [salt]
 x = 0.02 moles i.e. 0.02 moles of acid and salt. The ratio log10 remains constant.
[acid]
CH3COONa is required. Hence pH remains same.
(b) Now 0.01 mol of HCl ([H+] = 0.01 M) is added
to 1 L of buffer, this will react with acetate ion
(CH3COO ) as :
Illustration - 7 How many of the following combination can act as buffer.

(i) HCl + NaOH (ii) HCl  CH 3COO  Na  (iii) H 2 SO4  NaHSO4
(iv) H 2CO3  NaOH (v) NaOH  PhCOOH (vi) HBr  NH 4OH
(vii) CH 3COOH  NH 4OH (viii) NaOH  NH 4OH (ix) HCl  CH 3COOH
(x) Borax ( Na2 B4O7 )  Boric acid ( H 3 BO3 ) (xi) NaH 2 PO4  Na2 HPO4
(xii) Na2CO3  NaHCO3
SOLUTION :
As we know that buffer is a mixture having weak acid and its salt with strong base or weak base and its salt
with strong acid. Further a mixture of acid and base may also acid and base may also acts as buffer depend
-ing on the nature of acid and base (strong or weak) and their moles taken for preparation of mixture,

because acid and base reacts to form salt. The combination (i) and (iii) can’t acts as buffer because it does
not contain weak electrolyte (weak acid or base) but combination (ii) can act as buffer if axcess of
CH 3COONa is mixed with limited amount of HCl.
Resulting mixture contains weak acid (CH3COOH) and its salt with strong base (CH3COONa). Similarly
combinations (H2CO3 + NaOH),(PhCOOH + NaOH),(NH4OH + HBr)can also act as buffer..
The combinations(viii) and (ix) can’t acts as buffer because salt component is missing.
Mixture of two salts of weak polyprotic acid can also acts as buffer because because in such cases we will
visualize a mixture of acid and its conjugate base as salt.
NaHCO3 [having weak acid HCO3 ] and Na 2CO3 [having conjugate base CO32  ] acts as buffer.fer.
Hence the combination (ii), (iv), (v), (vi), (vii), (x), (xi) and (xii) can acts as buffer.

Illustration - 8 The pH of blood stream is maintained by a proper balance of H 2CO3 and NaHCO3 con-
centrations. What volume of 5M NaHCO3 solution, should be mixed with 10 mL sample of blood which is
2M in H 2CO3 in order to maintain a pH of 7.4 Ka for H 2CO3 in blood is 4.0  10–7 ?
SOLUTION :
(5  V)
[H2CO3] in blood = 2M [NaHCO3] in mixture = (V  10)
Volume of blood = 10 mL
[salt]
[NaHCO3] = 5M pH = pKa + log
[acid]
Let volume of NaHCO3 used = V mL
2  10 (5  V) / (V  10)
[H2CO3] in mixture = 7.4 = log 7.8  107 + log (2  10) / (V  10)
(V  10)
V = 40 mL
Illustration - 9 Consider a buffer solution containing 0.1 mole each of acetic acid and sodium acetate in
1.0 L of solution. 0.01 mole of NaOH is gradually added to this buffer solution. Calculate the new [H+] is the
resulting solution. [Ka = 2  10–5]
SOLUTION :
pH of the solution is given by : [salt] = 0.11 M and [acid] = 0.09 M
[salt]  Final pH of solution :

pH = pK a + log10
[acid] 0.11
pH = pK a + log10  4.787
Initial pH of solution : 0.09
[acid]
0.1  [H + ] = K a
pH = pK a + log10  4.7 [salt]
0.1
5 0.09
When 0.01 M NaOH is added,   2  10   1.64 10 5 M
0.11
Illustration - 10 500 ml of 0.2 m aqueous solution of acetic acid is mixed with 500 ml of 0.2 M HCl at
25C .
(i) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution.
(ii) If 6g of NaOH is added to the above solution, determine the final pH. [ K a acetic acid  2 105 ]
SOLUTION :
0.2
(i) [CH 3COOH ]Just after mising   0.1 M
2
0.2
[ HCl ] just after mising   0.1M  [ H  ]From HCl
2

Note : Equal volumes added.
CH 3COOH  CH 3COO   H 
i0 c 0 0
(conc.)
t  ieq c  c c c
[CH 3COO  ][ H  ] c .(c  0.1)

Ka  
[CH 3COOH ] c  c
 [ H  ]   
 Total  [ H ]From CH 3COOH  [ H ]From HCl 
 c  0.1  0.1 ; c  c  c
[   will be small due to common ion effect]
 K a    0.1
Ka
   2  104 [Check : 1    1  2  104  1] and
0.1
[H ]Total  c  0.1  0.1 2104  0.1 0.1M
 pH  1
6
(ii) 6gm NaOH   0.15 gmeq  150 mmoles NaOH
40 / 1
Mmoles HCl = 500  0.2  100 mmoles.
NaOH will first react with HCl and if there is a leftover then it will react with CH 3COOH
 Mmoles NaOH left  150  100  50
These will react with CH 3COOH as :
NaOH + CH3COOH  CH3COONa + H 2O

50 100 
 50 50
 Formation of an acidic buffer
[Salt]
 pH = pK a  log10
[Acid]
50 / VTotal
= 4.7 + log10 = 4.7
50 / VTotal

HYDROLYSIS OF SALTS Section - 4
It involves the study of the reactions between a salt and water to yield an acid and a base. The salts are
generally ionised in water. Here we will deal with salts which are almost fully soluble (not sparingly soluble
salts).
Water in the presence of ionic impurites is visualized as follows :
 H+ (aq) + OH (aq) with [H+] = [OH] (i.e neutral)
H 2O (aq) 
Now, when a salt is put in the water, there is an interaction between ions of salt and ions of water. The
phenomenon of interaction of cations and anions of the salts with H+ and OH ions furnished by water so
that there is some net change in the pH of the resulting solution is known as Hydrolysis of a salt.
Four cases have been discussed here to understand the behavior of various type of salts.
1. Salts of strong acids and strong bases [SA-SB]

When such salts are dissolved in water, they do not undergo hydrolysis. They simply ionises and fail to
change the H+ ion concentration of solution and hence the pH of the solution remains same. e.g. NaCl,
CaCl2, BaCl2, KCl, NaNO3, Na2SO4, Ca(NO3)2
 Na+ (aq) + Cl(aq)
NaCl (aq) 
 H+ (aq) + OH (aq)
H2O (aq) 
The final pH of the solution remains 7 at 25C.
(If NaOH and HCl are formed, they neutralises each other to keep the pH same)
2. Salts of weak acids and strong bases [WA-SB]

Such salts give alkaline solutions in water. Some of such salts are : CH3COONa, Na2CO3, K2CO3, KCN
etc . For our discussion, we consider CH3COONa (sodium acetate) in water. When CH3COONa is put in
water, it completely ionises to give CH3COO (acetate) ions and Na+ ions.
Now acetate ions (CH3COO) absorb some H+ ions from weakly dissociated H2O molecules to form
undissociated CH3COOH. Na+ remains in ionic state in water.
Now for Kw (ionic product) of water to remain constant, H2O further ionises to produce more H+ and OH
ions. H+ ions are taken up by CH3COO ions leaving OH ions in excess and hence an alkaline solution.
Let BA represents such a salt. As it is put in water ;
 BOH (aq) + HA (aq)
BA (aq) + H2O (aq) 
BA dissociates into ions and BOH being strong base also ionises.
 B+ (aq) + OH (aq) + HA (aq)
B+ + A + H2O 
So, the net reaction is :  OH (aq) + HA (aq)

A (aq) + H2O  [Anionic Hydrolysis]

The above equation is known as equation of hydrolysis and equilibrium constant for such reactions is
called as Hydrolysis Constant (Kh).
[OH  ][HA]
Kh 
[A  ]
Degree of Hydrolysis :
It is defined as the fraction of total salt that has undergone hydrolysis on attainment of equilibrium. It is
denoted by h.
Let c be the concentration of salt and h be its degree of hydrolysis.
A + H2O 
 OH + HA (Equation of hydrolysis)
c
c  ch ch ch
[OH  ][HA]  ch  ch  ch 2
Kh   
[A  ] c - ch 1- h
Kh
 Kh = ch2 [assuming h <<1]  h=
c
Now considering, dissociations of weak acid HA and H2O
[H  ][A  ]
 H+ + A
HA  ; Ka = . . . . (i)
[HA]
 H+ + OH
H2O  ; Kw = [ H+] [OH] . . . . (ii)
Kw
 Kh = (Subtracting (i) from (ii), we get equation of hydrolysis)
Ka
Note :  Weaker is the acid, greater is the hydrolysis constant.

 Degree of hydrolysis increases when ‘c’ decreases i.e. with dilution.
Now substituting the value of Kh in expression of h,

Kw
 h
Ka c
pH of solution :
pH of a basic solution is given as :
pH = 14 + log [OH] and [OH] = ch = K h c

Substituting for Kh , we get :
Kwc Kwc
[OH] = Ka  pH = 14 + log10
Ka
1 1
 pH = (pKw + pKa + log10 c) or pH (at 25 C ) = 7 + (pKa + log10 c)
2 2
3. Salts of strong acids and weak bases [SA-SB]

Such salts give acidic solutions in water. Some of such salts are : NH4Cl, ZnCl2, FeCl3 etc. For the purpose
of discussion, we will consider hydrolysis of NH4Cl.
When NH4Cl is put in water, it completely ionises in water to give NH4+ and Cl ions. NH4+ ions combine
with OH ions furnished by weakly dissociated water to form NH4OH (weak base). Now for keeping Kw
constant, water further ionises to give H+ and OH ions, where OH ions are consumed by NH4+ ions
leaving behind H+ ions in solution to give an acidic solution.
Let BA be one of such salts. When it is put into water, the reaction is as follows.
B+ + A + H2O   BOH + H+ (aq) + A (aq) [HA is strong acid]
The net reaction of hydrolysis is :
 BOH (aq) + H+(aq)
B+ + H2O  [Cationic Hydrolysis]
c  ch ch ch
[BOH][H ] (ch)(ch) ch2 Kh

 Kh =   ch2 (h << 1)  h =
 c  ch 1 h 2
[B ] c
Considering ionisation of weak base BOH and H2O.
[B ][[OH  ]
 B+ + OH
BOH  ; Kb 
[BOH]
 H+ + OH
H2O  ; Kw = [H+] [OH–]
From expressions for Kh, Kb and Kw , we have : (As done in previous case)
Kw Kw
Kh   h
Kb K bc
pH of solution :
Now, pH = log [ H+]
Kh Kw c
and [H+] = ch = c = K h c  [H+] =
c Kb

Kwc
 pH =  log10 Kb
1 1
 pH   pK w  pK b  log10 c  or pH (at 25C) = 7   pK b + log10 c 
2 2
Try Your Self :

1. Calculate pH of M/100 solution of CH3COONa at 25C where Ka of CH3COOH is 2.0  105.
[Ans : 8.37]
2. Calculate pH of M/100 solution of NH4Cl at 25C where Kb for NH4Cl is 2.0  105.
[Ans : 5.63]
3. In above two cases, find the degree of hydrolysis taking Kw = 1014.
Note : The results of above two cases of hydrolysis of salts can be used directly.
4. Salts of weak acids and weak bases [WA-WB]

Let us consider ammonium acetate (CH3COONH4) for our discussion. Both NH4+ ions and CH3COO
ions react respectively with OH and H+ ions furnished by water to form NH4OH (weak base) and
CH3COOH (acetic acid).
Let BA represents such a salt.
B  A   H 2O 
 BOH  HA
 weak base   weak acid 
Initially c c 0
At equilibrium c  ch c  ch ch ch
[BOH] [HA] c h  c h 
 Kh = =
[B ][A  ]  c  ch 2
h2
 Kh  ; Taking square root on both sides to get :
1  h 2
Kh
h (Here, 1  h  ; Think why ?)
1 Kh
Hence the degree of hydrolysis of such salts is independent of concentration of salt solution.
Now considering the dissociation of both weak base and acid.
[H  ][A  ]
HA 
 H+ + A ; Ka =
[HA]
[ B  ][OH  ]
BOH 
 B+ + OH ; Kb 
[ BOH ]

 H+ + OH
H2O  ; Kw = [H+] [OH–]
Combining Kh , Kb , Ka and Kw , we have

Kw Kh
Kh = and h= [Cation - Anionic Hydrolysis]
Ka K b 1  Kh
(Observe that 1  h  1 )
pH of Solution :
[H  ][A  ] [HA]
Consider, Ka =  [H+] = K a
[HA] [A  ]
Since, base and acids are weaker, hence,
[BOH ] = [HA]  [B+] = [A]
[BOH][HA] [HA]2 K w Ka
 Kh    [H+] = K a K h =
   2 Kb
[B ][A ] [A ]
K w Ka
pH =  log [H+] =  log Kb
1 1
 pH   pK w  pK a  pK b  or at 25C, pH = 7 +  pK a  pK b 
2 2
Illutrating the concept :
What is the pH of a 0.50 M aqueous NaCN solution ? pKb of CN– is 4.70.
SOLUTION :
NaCN is a salt of weak acid and strong base. The pH of its aqueous solution is given by :
1
pH (at 25C) = 7 + (pKa + log10 c)
2
Remember that for any acid and its conjugate base or vice-versa : pKa + pKb = pKw
e.g. For acid (say HA), pKa corresponds to HA and pKb corresponds to its conjugate base : A
Thus, pKa of HCN = 14  4.7 = 9.3
1 1
So, pH (at 25C) = 7 + (pKa + log10 c) = 7 + (9.3 + log10 0.5) = 11.5
2 2

Illustration - 11 Calculate the degree of hydrolysis of a mixture of aniline and acetic acid each of them
being 0.01 M. Ka of acetic acid = 1.8  105 and Kb (aniline) = 4.5  1010. Also calculate pH of the mixture.
SOLUTION :
C6 H 5 NH 2 + CH 3COOH  C6 H 5 NHCOCH3 + H 2O
(Acetanilide)
Now when we mix equal concentrations of aniline and acetic acid, they will neutralise each other to form
acetanilide (salt). The salt is of weak base and weak acid, so hydrolysis takes place. The degree of hydrolysis
of the salt of weak acid and weak base is given by :
Kh
h
1 Kh
Kw 1014
Here, K h  
K a .K b 1.8  105  4.5  1010
= 1.23
 h = 0.52
However the pH of solution can be calculated by using the standard result :

1
pH  7   pK a  pK b 
2
1
 pH= 7 
2

 log 101.8  105   log10 4.5  1010 

1 4.5  1010
 pH  7  log10  4.7
2 1.8  105
Note :  Solution in this case is acidic. In such salts, pH depends upon which of two i.e. weak acid or weak
base is stronger than the other, i.e. by comparing Ka and Kb; one can theoretically get an idea about
the pH of solution.
1
 The formula pH  7   pK a  pK b  is applicable even when ‘h’ is large as no approximation of
2
‘h’ comparison with unity, has been taken in the derivation (see derivation yourself).

Illustration - 12

2.5 mL of 0.4 M weak mono-acidic base K b  1 10
12
at 25 C is titrated with 2/15 M


HCl in water at 25C. Find the concentration of H+ ions at equivalence point. K w  1 10
14
at 25 C 
SOLUTION :
First find the volume of HCl required to reach the equivalence point.
meq. of Base = meq of HCl
 2 
 2.5  (0.4  1)   1 VHCl
 15 
 VHCl  7.5 mL
The net volume of the solution at the equivalent point = Vbase + VHCl = 2.5 + 7.5 = 10 mL
0.4  2.5
 salt   c  10
 0.1M
pH of an aqueous solution of such a salt is given by :

1 1
pH  7   pK b  log10 c   7  12  log10 0.1  1.5
2 2
  H    101.5  1  3.2  102 M

  10 10
Please note that the above solution is Incorrect. (Why?)
1
Actually, pH  7   pK b  log10 c  is valid only when 1  h  1
2
To check, calculate h using :
Kh Kw 1014
h    0.1  1  0.1  1
c Kb c 1012  0.1
So we have solve from basics as follows :
 BOH  H 
B  H 2O 
c – ch ch ch
[BOH][H  ] (ch) (ch) Kw [H  ]2
 Kh 

[B ]

c  ch
 Kh 
Kb
 102 
c  [H  ]
 ch  [H ]
 102  104  4 103
 [H ]    2.7  102 M
2

SOLUBILITY PRODUCT (Ksp) AND PRECIPITATION OF SALTS Section - 5
Here, we will study those salts which are generally considered as insoluble in water. (e.g. AgCl, BaSO4,
Ag2S, PbS etc) Actually no insoluble salt is actually completely insoluble, they have a very small solubility.
Consider a vessel containing water with a sufficient amount of AgCl being put into it. A very small amount of
it dissolves in water (because generally salts are composed of ions or contain polarised atoms). The
small amount which is soluble is almost 100% ionised.
The situation achieved at this stage is Dynamic in nature; with same of ions (soluble) being solidifying and
some solid always dissolving. Thus a state of equilibrium exists (like in earlier cases). This means at a given
temperature, the concentration of Ag+ ions and Cl ions in aqueous solution remains constant. The following
equilibrium exists. In this equilibrium, the equilibrium state is known as Saturated state.
 Ag+ + Cl

AgCl (s)  [insoluble  soluble (ions)]
The equilibrium constant for this reaction is known as solubility product (Ksp) and is written as :
Ksp = [Ag+] [ Cl]
Ksp is expressed in concentration units. The reaction coefficient, Q in such system is known as ionic product
(I.P)
Note :  The solubility of a salt in water depends upon other substances (ions) present is water (at that time)
and the solubility product is a constant value (at a given temperature) and is independent of presence
of any other ion present. Like other equilibrium constants such as : Kp, Kc, Ka and Kb , it is also
constant at a certain temperature and can change only when temperature changes.
 The salts like AgCl are regarded as sparingly soluble salts. Some of them are : Ag2SO4, Ag2CO3,
PbCl2, PbCrO4, PbS, ZnS, Al(OH)3, Ca3(PO4)2, BaSO4, CaSO4, MnS etc.
Ksp for Ag2SO4 :  2Ag+ + SO 2(aq)

Ag2SO4 (s) + aq.  4
Ksp = [Ag+]2 [SO42]
Ksp for Ca3(PO4)2 :  3Ca2+ + 2PO 3(aq)

Ca3(PO4)2(s) + aq.  4
Ksp = [Ca2+]3 [PO43]2
Note : In the solubilities of sparingly soluble salts, we will deal with mainly two types of problems : one to find out
the solubility in water if Ksp of a salt is given and vice-versa. Second, to find out solubility of a salt in
presence of other (common) ions in water.

Illustration - 13 If K of calcium iodate Ca(IO ) = 6.3  107 at 18C, find the solubility of salt in (i) gm/
sp 3 3
L (ii) mol/L in water at 18C.
SOLUTION :
In questions, solubility is sometime asked Now, Ksp = [Ca2+] [IO3]2
(or given) to be expressed in gm/L.  6.3  107 = (x) (2x)2
Now the following equilibrium is established :  4x3 = 6.3  107
 Ca2+ (aq) + 2IO3(aq)

Ca(IO3)2   x = 5.4  103 M.
Now answer is to expressed in gm/L
Let x mole/L be solubility of Ca(IO3)2 in water
 solubility = x  M0
 [Ca2+] = x M and [IO3]= 2x M = (5.4  103)  390 = 2.106 g/L
Illustration - 14 The K of AgCl at 25°C is 1.5  1010. Find the solubility of AgCl (in gm/L) in an aqueous
sp
solution containing 0.01 M AgNO3.
SOLUTION :
Now this is quite similar to finding the degree of dissociation of a weak acid or weak base in presence of its
common ion (Le Chatelier’s principle).
Here 0.01 M AgNO3 will give 0.01 M Ag+ ions in solution before the addition of AgCl.
(AgNO3 is 100% soluble in water).
Let the solubility be c mol/L in AgNO3.
 Ag+ + Cl
AgCl 
c c
 Ag+ + NO3
AgNO3 
0.01M
In solution :
[Ag+] = c + 0.01 and [Cl] = c
Now Ksp is a constant and is independent of presence of any ion in water.
 Ksp = [Ag+][Cl] = (0.01 + c) (c) = 1.50  1010
(Now assuming 0.01 + c  0.01 as c << 1 for sparingly soluble salt)
K sp
 c  1.5  108 M
0.01
[Check that c + 0.01  0.01 M]
or solubility = (1.5  108)  143.5 = 2.15  106g/L
Note : The solubility of AgCl in water containing Ag+ (a common ion) is much less than in pure water.

Illustration - 15 The solubility of BaSO4 in water is 2.33  104 gm/100 mL. Calculate the % age loss in
weight when 0.2 gm of BaSO4 is washed with
(a) 1 L of water (b) 1 L of 0.01 N H2SO4.  M 0 BaSO4  233 gm / mol 
SOLUTION :
(a) Solubility is in general expressed in gm/L, Now let x be solubility in mol/L in H 2SO 4
so solubility of BaSO4 = 2.33  10 3
g/L  [Ba2+ ] in solution = x mol/L
Loss in weight of BaSO4 = amount of BaSO4 and [ SO42] in solution = (x + 0.005) mol/L
soluble. Ionic product = [ Ba2+ ] [SO42]
2.33 103 = (x) (x + 0.005)
 % loss =  100 = 1.16 %
0.2
Ksp = Ionic Product at equilibrium (saturation)
(b) 0.01 N H2SO4  0.01 N SO42 ions  1.0  1010 = (x) (x + 0.005)
 0.005 M SO42 ions Assuming x to be a small number
x + 0.005 ~ 0.005
Now presence of SO42 prior to washing
BaSO4 will suppress the solubility of BaSO4 1010
 x= = 2  108 mol /L
(due to common ion effect). The suppression 0.005
will be governed by Ksp value of BaSO4. So
= 2  108  233 g/L
first calculate Ksp of BaSO4.
= 4.66  106 g /L
Solubility of BaSO4 in fresh water
 4.66  106 gm of BaSO4 are washed
= 2.33  103 g/L
away.
2.33 103
 mol/L =105 M 4.66 106 100
233  % loss =
0.2
Ksp = [ Ba2+] [ SO42] = (105)2 = 1010
= 2.33  103 %
Note : Third type of problem are related to the precipitation of salts (sparingly soluble). To understand and
solve such problems, let us read following article carefully.
Precipitation of salts
Now we will study (application of Ksp) how to determine whether or not a precipitate will form when we
mix known concentrations of ions which combine to give a sparingly soluble salt. To understand and solve
such problems let us analyse the expression of solubility product.
For a salt (sparingly soluble) when dissolved in water :  B+ (aq) + A (aq)
BA 
At equilibrium (saturation) : Ksp = [B+] [A]

When we mix ions or if there be two or more ions in water, we define reaction coefficient (Q) called as
ionic-product (I.P.), giving the products of ions in water (ions of soluble salts and other common ions).
I.P. is product of ionic concentration due to ions already present in water or from a salt. It may be and
may not be equal to Ksp. To illustrate it more clearly, consider a case when 500 ml of 0.005 M solution
of AgNO3 is added to 500 ml of 0.001 M solution of KCl. Now in solution (mixture), there are Ag+,
NO3, K+ and Cl ions. The concentration of [Ag+] = [NO3] = 0.005/2 = 0.0025 M (equal volumes
0.001
are mixed) and [K+] = [Cl]   0.0005 M as equal volumes of two solutions are mixed.
2
Now, we know that Ag+ will react with Cl ions to form AgCl since :
 Ag+ + Cl is a reversible reaction with a high tendency towards left (solidifying or precipitating).
AgCl 
Now, question is, whether AgCl will be formed or not (precipitation of Ag+ and Cl as AgCl) and if it
formed, how much of it will be formed ? For this we define some rules.
1. If Ionic Product (IP) > Ksp ; precipitation takes place till I.P. equals Ksp.
2. If Ionic Product < Ksp ; a precipitate will not be formed and the solution will be unsaturated.
3. If Ionic Product = Ksp ; a precipitate will not be formed and the solution is saturated in that salt.
(or we can say that solution is at a critical stage, when precipitation just begins, but actually
has not occurred)
In present case, I.P. = [Ag+] [Cl] = (0.0025) (0.0005) = 1.25  107

(Only for the salt which is sparingly soluble not for KNO3)
Ionic product > Ksp in this case (Ksp AgCl = 1.56  1010) which mean precipitation takes place.
Illustration - 16 When 15mL of 0.05 M AgNO is mixed with 45.0 mL of 0.03 M K CrO , predict whether
3 2 4
precipitation of Ag2CrO4 occurs or not ? Ksp of Ag2CrO4 = 1.9  1012.
SOLUTION :
First find the concentrations of Ag+ and CrO42 The ionic product for Ag2CrO4 is given as
ions in the resulting mixture. follows.
 2Ag+ + CrO 2
Ag2CrO4  4
15× 0.05
[Ag + ] = = 1.25×102 M Ionic product (I.P.) = [Ag+]2[CrO42]
15 + 45
= (1.25 102)2 (2.25  102)
45  0.03 = 3.51  106 > Ksp
[CrO 24  ]   2.25  10 2 M
15  45 Hence precipitation occurs.

Illustration - 17 The concentration of Ni2+ ions in a given NiS solution is 2.0  106 moles/L. Find the
minimum S2 ions necessary to cause precipitation of NiS. The solubility product, Ksp of NiS = 1.4  1014.
SOLUTION :
Note :Solubility product, Ksp gives an idea of maximum K sp

 For [S2] = , NiS will just start to
possible concentration of an ion which can be [Ni2  ]
retained in solution.
precipitate and
Ksp = ionic product (I.P.) for saturated solution
K sp
 If [S2] > , NiS will precipitate.
For  Ni2+ + S2
NiS  [Ni2  ]
Now, Ksp = [Ni2+][S2] K sp
This means is minimum concentration
K sp [Ni2  ]
 [S2] =
[Ni2  ] of S2 ion above which precipitation occurs.
It is the maximum permissible concentration 1.4  1014
 [S2]min=  7  109 M
of S2 ion in solution. 2  10 6
Illustration - 18 A solution contains 0.01 M each of CaCl and SrCl . A 0.005 M solution of SO 2 is slowly
2 2 4
added to the given solution.
(a) Which substance begins to precipitate first ?
(b) If H2SO4 is continuously added, determine when will other salt be precipitated ?
(c) When second salt starts to precipitate, find the concentration of cation of first salt.
Assume that CaCl2 and SrCl2 are 100% ionised and volume of the solution remains constant.
Ksp of CaSO4 = 1.3 × 104 and Ksp of SrSO4 = 3.2 × 107.
SOLUTION :
K sp [SrSO4 ]
The solution contains 0.01 M Ca2+ ion and 0.01 SO 24   
  Min. for SrSO4 [Sr
2
]
M Sr2+ ions (100% ionization). Now SO42 ions
are added gradually and slowly……………..
(a) First calculate the minimum [SO 42 ions 3.2 107
  3.2 105 M
required to start precipitation of CaSO4 and 0.01
SrSO4 Since [SO42] for SrSO4 is much lower that
K sp [CaSO4 ] required for CaSO4, so SrSO4 will precipitate
SO 24    FIRST.
  Min. for CaSO4 [Ca
2
]
(b) Now, if i.e., SO42 ions are continuously added,
at some instant, its concentration will become
1.3 104
  1.3 102 M equal to that minimum required for precipitating
0.01 out Ca2+ ions.

Hence CaSO4 will start precipitating if [SO42]

2
 2.46  105 M
= 1.3 × 10 M.
(c) Now, find the concentration of Sr 2+ ions  2.46 105 M  0.01M 
 
when[SO42] = 1.3 × 102 M in the solution.
Can you observe that when CaSO4 starts to
K 7 precipitate, SrSO4 is almost precipitated out as
Sr 2    sp SrSO 4  3.2  10 the value of Sr2+ is very very low ?
  [SO 2  ]
4 1.3  102
Note : The above illustration represents a case of selective precipitation (or separation of metals cations) by adding
a common anion. Observe that there is a vast difference in the Ksp values of two sulphates, and hence in the
minimum values of sulphate ion for precipitating out the two metals ions.
Illustration - 19 How much the concentration of Ag+ ions in a saturated solution of AgCl diminish if such
an amount of HCl is added to it that the concentration of Cl ions in the solution becomes equal to 0.03 M ?
Also fine the amount of AgCl precipitated at the given concentration. Ksp of AgCl = 1.8 × 1010.
SOLUTION :
HCl is added to a solution containing Ag+ ions in
I.P.  [Ag+ ] [Cl ]  Ksp
saturated solution. First find the concentration of
Ag+ ion in this solution. K sp 1.8  1010
 [Ag + ]    6.0  109 M


AgCl (s)  +
 Ag + Cl
 [Cl ] (0.03)
Now this is the amount of Ag+ ions left un-precipitated.
 Ksp = [Ag+][Cl] = x2 where x is solubility
of AgCl in mol/L  [Ag+] diminishes in the solution by
6.0  109  1 
 +
[Ag ]  Ksp  1.8  10 10   times
5  2233 
1.34  10
= 1.34  10–5 M The concentration ofAgCl precipitated out of the solution
When HCl is added, the ionic product of AgCl = [Ag+]initial – [Ag+]left
approaches the Ksp value of AgCl, the precipitation = 1.34  10–5 – 6.0  10–8 M
of Ag+ ions will occur. As ionic product increases
It means almost whole of AgCl is precipitated out of the
(i.e. becomes greater than Ksp value), an appreciable
solution at [Cl] = 0.03 M.
amount of AgCl precipitates out, and precipitation
continues till ionic product (I.P.) equals solubility
product (Ksp).

Precipitation through H2S

The most typical technique used in precipitating the metals ions or selectively precipitating (separation) the
two metal ions, is passing H2S gas in a solution of metal ion (s) whose acidity is externally controlled (or
preset by adding HCl). First consider the ionisation (equilibrium) of H2S gas in an aqueous solution and then
in an acidic solution.
 Passing H2S(g) in an aqueous solution :

H2S is a dibasic acid. We have to visualize two stage ionisation for it as follows:
H 2S(aq) 
 H  (aq)  HS (aq) ; K1 . . . (i)
HS (aq) 

 H  (aq)  S2  (aq) ; K2 . . . (ii)
K1 and K2 are Ist and IInd ionisation constants respectively for H2S (aq). Since K2 << K1 (due to common
ion effect), we usually neglect the concentration of H+ ions from second equilibrium.
 [H  ]in Solution  [H  ]from H 2S  [H  ]  [H  ]from H 2S
from HS
   2
[H ][HS ] [H ][S ]
Now, K1  and K2 
[H 2S] [HS ]
From (i), [H + ] = [HS ] and neglecting [H+] from (ii), we have from second ionisation constant :
[H  ][S2  ]
K2   [S2  ] or [S2  ]  K 2

[HS ]
So if we pass H2S in an aqueous solution, sulphide ion concentration is simply equal to the value of second
ionisation constant. We can determine whether precipitation of metal sulphide will occur or not by comparing
ionic product (I.P.) with solubility constant (Ksp).
 Passing H2S(g) in an acidic solution :

Now if we pass H2S in an acidic solution of a metal ion till saturation, we simply neglect the concentration of
H+ ion from H2S (both from first and second ionisations) totally as the concentration of H+ from acid (strong
acid added externally) is very high. In that case we can simply add two equilibriums (i) and (ii) to get :
 2H  (aq)  S2  (aq) ; K a (H 2S)

H 2S(aq) 
[H  ]2 [S2  ]
K a  K1  K 2 
[H 2S]
Note that in a saturated solution of H2S at 25C, [H 2 S] is constant at 0.1 M.
 Ka  (0.1 M) = [H+]2 [S2–]

([H+] [S2–] = Ksp of H2S)

K a  (0.1 M) K  K 2  (0.1 M)
 [S2 ]   1
[H  ]2 [H  ]2
In this way, we now know the concentration of sulphide ion in an acidic solution, so accordingly we can plan
precipitation of metal ions. The important aspect of this method is that we can always increase or decrease
the concentration of sulphide ion by controlling the amount of acid.
Illustration - 20 Calculate the maximum possible concentration of Mn2+ in water that is saturated with
H2S (which is 0.1 M at 300K) and maintained at pH = 3 with HCl. The equilibrium constant(s) for dissociation
of H2S are :
 H+ + HS ;
H2S  K1 = 9  108
 H+ + S2- ;
HS  K2 = 1  1012 and Ksp of MnS = 3  10–22.
SOLUTION :
Note that solution contains S2 ions (from H2S).
So Mn2+ will react with S2 ions to give a precipitate of MnS (being sparingly soluble salt). Hence the
concentration of S2– at saturation will determine the maximum possible concentration of Mn2+ ions in solution
that will not be precipitating. So first calculate [S2] at saturation.
Calculate Ka for dissociation of H2S.
Ka of H2S = K1  K2 = 9  1020
 2H+ + S2
H2S 
[H  ]2 [S2  ] K a  H 2S
 Ka =  [S2] =
[H 2S] [H  ]2
Note that pH of solution is maintained at 3 (externally).

 [H+] = 103 M
9 1020  0.1
 [S2] = 2
= 9  1015
10 
3
In a saturated solution, ionic product = Ksp

Now ionic product = [Mn2+] [S2] = [Mn2+] (9  1015)
 [Mn2+] (9  1015) = 3  1022
 [Mn2+] = 3.33  108 M

ACID BASE TITRATIONS Section - 6

pH of Mixtures of Acids and Bases
Let us take x millimoles of acid (HA) and y millimoles of base (BOH). Note that acid is monobasic and base
is monoacidic.
(a) Strong acid and strong base
 If x = y, then complete neutralization takes place and we get x (= y). Millimoles of salt (BA) of strong
acid and strong base which means no hydrolysis takes place and pH of solution = 7.
 If x > y, then there is an excess of strong acid and resulting solution is acidic with millimoles of acid
left in excess = x  y. Now if V (in cc) be the volume of mixture, then :
x y
 M= . Now calculate pH using the equation pH = log10 [H+]
V
 If x < y, then there is an excess of strong base and resulting solution is basic with millimoles of base left
in excess = y  x. Now if V (in cc) be the volume of mixture, then :
yx
 M . Now calculate pH using the equation pH = 14 log10 [OH  ]
V
(b) Strong base and weak acid
 If x = y, first of all neutralization takes place to give x (= y) millimoles of salt (BA). The salt will now
undergo hydrolysis to give an alkaline solution. Calculate pH by using the standard result :
1
pH  7   pK a  log10 c  ; c is concentration expressed in M (mol/L)
2
 If x > y, there is excess of weak acid whose millimoles = x  y and y millimoles of salt is formed. This
will give an acidic buffer solution. Calculate pH of buffer solution using Henderson’s Equation.
salt  y
pH = pKa + log10 acid = pKa + log10
  x-y
 If x < y, the solution in this case contains excess of strong base whose millimoles are y  x.
y -x
M= Calculate pH using the equation pH = 14 log10 [OH–]
V
(c) Strong acid and weak base

 If x = y, first of all complete neutralisation takes place to produce x (= y) millimoles of salt (BA). The
salt (BA) is of strong acid and weak base, hence hydrolysis takes place to give an acidic solution.
Calculate its pH by using standard result.
1
pH  7   pK b  log10 c  ; c : mol/L
2
 If x > y, then solution contain excess of strong acid whose millimoles = x  y.

x y
M Now calculate pH using the equation pH = log10 [H+]
V
 If x < y, then there is an excess of weak base whose millimoles are y  x and millimoles of salt (BA)
are x. This will give a basic buffer solution. Calculate the pH by using Henderson’s Equation.
pH  14  pK b  log10
salt  x
= 14  pKb  log10
 base  yx
(d) Weak acid and weak base
 If x = y, neutralisation takes place completely with the formation of x (= y) millimoles of salt (BA) of
weak acid and weak base. So hydrolysis takes place. Calculate the pH by using :
1
pH  7   pK a  pK b 
2
Indicators
Definition : An “indicator” is a dye (or substance) which change color over a short pH range.
Example: Methyl orange changes color in the pH range of 3.1 to 4.5
pH Range and color change of some common Acid-base indicators

End Point : It is the point at which the reaction between an acid and a base is “observed” to be
complete i.e. the pH at which an indicator changes it color.
Equivalence Point: It is the point at which the reaction between an acid and a base is “theoretically”
complete (as per the balanced equation for the reaction).
Note :  At “equivalence point”, meq. of acid = meq. of base but the “end point” can only be detected by
measuring the pH at different points of time during the titration. It is usually more convenient to add an
indicator to the solution and detect the “observed end” of the reaction through a color change in the
solution.
 An indicator is usually a weak acid or a weak base for acid-base titration. The color change occurs
when protons are transferred to form a conjugate base or a conjugate acid of a different color.

Let us represent an indicator as HIn (Weak Acid)


HIn  H 2O  H3O  In 
Acid Conjugate Base
(color 1) (color 2)
or simply, HIn  H+ + In
(color 1) (color 2)
Necessary property of Indicator : Color of ionised form must be remarkably different from that of
unionized form.
[H  ][In  ]
Now, KIn = Equilibrium Constant for the dissociation of the indicator =
[HIn]
[In  ]
 pH = pKIn + log10
[HIn]
Note :  An indicator changes color over a pH range (the so called “transition range”). It is the range over
which color change in the solution is detectable by the “observer”.
 The smaller the transition range, the better the indicator in detecting “equivalence point”. (Equivalence
Point  End Point)
With indicator in which both the forms, ionized and unionized form are colored, generally one colored is
visible if the ratio of the concentration of the two forms is 10 : 1.
 HIn   10
Thus, when only the color of un-ionized (HIn) form is seen :
[In  ] 1
 pH1 = pKa + log10 1 = pKa  1

10
[In  ] 10

and when only the color of ionized (In ) form is seen: 
 HIn  1
10
 pH2 = pKa + log10 = pKa + 1
1
Thus, pH change required in going from one color to other is pH = pH2  pH1 = 2
In the midway between the two colors (i.e. in the transition range), one can assume that [HIn] = [In]
 pH = pKa + log10 1 = pKa  pH = pKa
 The pKa of the indicator should be close to the pH of the equivalence point
For weak-base indicators, same transition range is observed and pOH = pKb at the midway.

(i) Phenophthalein : It is a weak acid represented by PhH.

PhH  Ph + H+
 . . . . (i)
Colorless Pink in base
 Phenolphthalein is colorless in acid solution and pink in basic solution.
 When a strong base like NaOH is added, it displaces the equilibrium (I) towards left direction and
there is a color change.
(ii) Methyl Orange : It is a weak base represented as MeOH.

MeOH   Me+ + OH . . . . (ii)
Yellow in base Red in acid
 When a strong acid is added, equilibrium (II) is shifted towards right and color change to red is
detected..
(a) What is the equivalence point of 0.1 M NH4Br solution ?
[ (pK b ) NH 4OH = 4.74]
When a strong acid reacts with a strong base, equivalence point is the neutralisation point (i.e pH of
the solution = 7 if both of acid and base have same meq.) but when a strong acid reacts with a weak
base or vice-versa, pH at the equivalence point  7 as the salt formed will get hydrolysed and pH
of the solution > 7 or < 7 at the equivalence point. NH4Br is a salt of Strong acid and Weak base.
1 1
 pH = 7   pK b + log10 c  = 7   4.74 + log10 0.1  5.13
2 2
(b) What will be the color of the mehtyl red indicator in the solution of NH4Br in part (a) ? At pH <
3.1, the indicator methyl red is colored pink, at pH > 6.3, it is yellow and at the intermediate
values of the pH it is orange.
Since the pH of NH4Br solution is 5.13 and it lies in the intermediate range of methyl orange, its color
will be orange. (3.1 < pH < 6.3)
(c) An acid indicator has pKIn = 5.3. In a certain solution, this indicator is found to be 80% ionised.
What is the pH of the solution ?
 H+ + In
HIn 
1 0 0
1x x x
Indicator is 80% ionized in acid form :  x = 0.8
[In 1 ] 0.8
 pH = pK a + log10  pH = 5.3  log10  5.9
[HIn] 0.2

Acid Base titration curves :

Titration Curve : It is a curve in which pH of the solution is titrated against volume of the titrate
added.
(i) Strong Acid and Strong Base :
(HCl) (NaOH)
In this case, both the titrants are completely ionized.
 NaCl + H O
HCl + NaOH  2
As OH is added to an acid solution, [H+] decreases and [OH] increases  pH goes on increasing.
As the equivalence point is reached, [H+] is rapidly reduced. Above this point, [OH] increases
rapidly from 107 M and after that pH of the solution remains fairly constant. Thus, there is an inflexion
point at the equivalence point.
The difference in the volume of NaOH solution between the end point and the equivalence point is
not significant for most of the commonly used indicators as there is a large change in the pH value
around the equivalence point and most of them change their color across this pH change.
(ii) Weak Acid and Strong Base :

(CH3COOH) (NaOH)
Initially, when a few drops of OH are added to the weak acid, it forms an acidic buffer CH3COOH/
CH3COONa and thus, pH of the solution changes slowly. At the equivalence point, solution will be
alkaline. If OH addition is continued after the equivalence point, [OH] will increase rapidly.

1 1
(pH) at equivalence point = 7 +  4.76 + log10 c   7 +  4.76 + log10 0.05   8.72
2 2
[Here c = concentration of the salt formed at equivalence point]
Thus, methyl red, methyl orange are inappropriate for use in the detection of the end point between a
weak acid and a strong base.
Also note that the buffer capacity of the buffer solution will be maximum at 50% equivalence point i.e.
when the volume of NaOH is 10 ml.
(iii) Strong Acid and Weak Base :

(HCl) (NH4OH)
Initially, when a few drops of H+ are added to the weak acid, it forms a basic buffer NH4OH/
NH4Cl and thus, pH of the solution changes slowly. At the equivalence point, solution will be
alkaline. If H+ addition is continued after the
equivalence point, [H+] will increase rapidly.

Thus, phenolphthalein, thymolphthalein are quite inappropriate to be used as an indicator to detect the end
point between a strong acid and weak base neutralization.
Also note that the buffer capacity of the buffer solution will be maximum at 50% equivalence point i.e. when
the volume of HCl is 10 ml.
Note : The selection of an indicator therefore is determined by the pH of the solution at the equivalence point.
Illustration - 21 0.1 M NaOH is titrated with 0.1 M, 20 ml HA till the end point. K ( HA) = 6 × 10-6 and
a
degree of dissociation of HA is negligible (small) as compared to unity. Calculate the pH of the resulting
solution at the end point [Use log10 6  0.8]
SOLUTION :
2
NaOH + HA   NaA + H2O Here c = [NaA] =  0.05 M
20  20
At end point 2 2 -
(mmoles) ( 0.1  20) and pKa = –log10 (6  10–6) = 5.2
- - 2 - 1
Note : 20ml of NaOH is required for the complete
pHat end point  7   pK a  log10 c 
2
neutralisation of HA.
1
NaA is a salt of strong base and weak acid. 7  5.2  log10 0.05   8.95
2
Thus, will undergo hydrolysis and solution will
become basic.

Illustration - 22 The equivalence point in a titration of 40.0 mL of a solution of a weak monoprotic acid
occurs when 35.0 mL of a 0.10 M NaOH solution has been added. The pH of the solution is 5.5 after the
addition of 2.0 mL of NaOH solution. What is the dissociation constant of the acid ?
SOLUTION :
Let x milimoles of HA are taken initially. Find x :
 millimoles of HA left x  y  1.5
Consider the equation of neutralization : and millimoles of NaA formed = 2
Now such a solution will behave as an acidic buffer,
HA  NaOH 
 NaA  H 2O
whose pH is given as :
x y 
K a [acid] 1.5
x y  y [H + ] =  1055 = K a =
[salt] 2
At equivalent point, millimoles of acid = milimoles of
aicd = NaOH [i.e. x = y]  K a  4.22  106 [105.5  10  106 ]
 millimoles HA = x = 3.5 [35 ml of 0.1 M NaOH]
At pH = 5.5, millimoles of NaOH added = 2 = y
[20 ml of 0.1 M NaOH]
SIMULTANEOUS EQUILIBRIUM Section - 7
When two slats having a common ion (either cation or anion) are together in water, then their respective
solubilities are not independent of each other.
Consider a solution containing two salt : CaF2 (K sp = 3.4 × 1011 ) and SrF2 (K sp = 2.9 × 109 ). Compare
their Ksp values. Let us assume that most of F ion concentration in the saturated solution is from SrF2 ,
as its Ksp is much higher than that of CaF2 . It means that first SrF2 will establish its equilibrium (as if there
is no CaF2 ), then CaF2 will dissolve in presence of ions furnished only by SrF2 .
Let the solubility of SrF2 bw x mol/L.
SrF2 ( s )  Sr 2  (aq)  2 F  (aq )

 [Sr 2  ]  x and [ F  ]  2 x
K sp  [ Sr 2  ][ F  ]2  ( x) (2 x) 2  4 x3
1/3
 K sp 
 x   9 104
 4 

Now the solubility of CaF2 is determined in presence of 9  104 M F ions. It means neglect the
contribution of F  ions from CaF2 .

K sp 3.4  1011
K sp  [Ca 2  ][ F  ]2  [Ca 2  ]    1.0  105 M
 2 4 2
[F ] (2  9  10 )
Hence the solubility of CaF2 is 1.0  10 5 mol/ L.
Note : Let us check our assumption. F  ions from CaF2 is twice the amount of Ca 2  ions i.e., 2.0  105 M ,
whereas, F  ions from SrF2 is 2  9.0  104 i.e. 1.8  103 M, which is much higher than 2.0  105 M.
Illustration - 23 Calculate the simultaneous solubilities of AgSCN and AgBr.
K sp ( AgSCN )  1.0  1012 ; K sp ( AgBr )  5.0  1013

SOLUTION :
In this case, please note that the Ksp values of two
and [ Ag  ][ SCN  ]  K sp AgSCN
salts are very similar. So the concentration of Ag +
Note that : [ Ag  ]  [ Br  ]  [ SCN  ]
ions (the common ion) can not be calculated from a
[This is an Electrical charge neutrality equation]
single salt alone and we have to consider the
equilibrium of the two salts simultaneously. K sp AgBr K sp AgSCN
[ Ag  ]  
Let the simultaneous solubilities ofAgSCN and AgBr [ Ag  ] [ Ag  ]
be x and y respectively in mol/L.
 [ Ag  ]  K sp AgBr  K sp AgSCN
 
AgSCN (s )  Ag (aq )  SCN (aq )
x x  x  y  1.22  106 . . . (i)
AgBr ( s)  Ag  (aq )  Br  (aq ) [ Br  ] y K sp AgBr

Also,    0.5 . . . (ii)
y y [SCN  ] x K sp AgSCN
At equilibrium : Using (i) and (ii), we get :
[ Ag  ]  x  y ; [ SCN  ]  x ; [ Br  ]  y x  8.0  107 ; y  4.0  10 7
[ Ag  ][ Br  ]  K sp AgBr

Illustration - 24 Two weak monobasic organic acids HA and HB have dissociation constants as 3.0  105
and 1.5 105 respectively at 25C . If 500 ml of 1 M solutions of each of these two acids are mixed to
produce 1 litre of mixed acid solution, what is the pH of the resulting solution ?
SOLUTION :
Note that K a of two acids is nearly same. In such ( x  y) x
cases, we have to consider H  from both HA and  K a( HA)  and
c
HB simultaneously. The concentration of HA and
( x  y) y
HB in the mixture = 5.0 M K a ( HB ) 
c
[equal volume are mixed] = cM Divide the two expressions to get :
HA  H   A 1 x
  x  2y
c x x 2 y
HB  H   B 
1 x 2  xy
Substitute for y  x in K a ( HA) 
2 c
c
c y y y x 2  0.5 x 2
 3.0  105 
0.5
Now, [ H  ]final  [ H  ] from HA  [ H  ] from HB
 x  10  103 M
( x  y) x ( x  y) y
 K aHA  and K aHB  10
cx cy and y   103 M
2
As K a of both acid  105 and H  from one acid
3 10
acts as common ion for other’s dissociation, x and y [H  ]  x  y   103 M
are very less as compared to c.
2
 c  x  c and c  y  c  3 10 
pH   log10   103   pH  2.32
 2 
 
Illustration - 25 Determine the solubility of AgCN in a buffer solution maintained at pH = 3.

K sp ( AgCN )  2.0 1016 ; K a ( HCN )  6.0  1010
SOLUTION :
AgCN is a sparingly soluble salt in aqueous The CN  ions will react with H  in the solution to
medium. form HCN. (a weakly dissociated acid) and we have
AgCN (s )  Ag  (aq )  CN  (aq) to assume that in solution [CN  ]  y M finally which
Let the solubility of AgCN be x M. Thus, will be decided by the dissociation of HCN as
[ Ag ]  xM and [CN  ]  x M from salt but it

explained below : AgCN (s )  Ag  (aq )  CN  (aq)
will not be equal to x finally.

K sp ( AgCN )  [ Ag  ][CN  ]  xy  2  1016

H  CN  
 HCN
and
103 x
103  x [ H  ][CN  ] 103 y
x K a ( HCN )    6  1010
HCN x y
Solve the equation to get :

HCN  H  CN
K sp
x 103 x  [ Ag  ] 
Ka
[ H  ]  K a   1.82  105 M
x y 103  y y
Note that in the solution :
 103
[ Ag  ]  [CN  ]  [ HCN ]
We have two equations now : (Electrical charge neutrality equation)
Note : In this example, since the dissociation constant
of acid is very low and pH of the solution is
fairly high, we could have assumed that [ H  ]
and K a in the expression for x.
Illustration - 26 How much AgBr could dissolver in 1.0 L of 0.4 M NH ? Assume that Ag ( NH ) is the
3 3 2
 
only complex formed Given: The dissociation constant for Ag ( NH 3 )2  Ag  2 NH 3 ; K d  6.0  108
and K sp ( AgBr )  5.0 1013.

SOLUTION :

Let solubility of AgBr be xM. Thus, [ Br ]  x M Ag    Ag ( NH 3 )2
2 NH 3 
 x 0.4
but [ Ag ]  x M since it will react with NH 3 to
form a complex and thus, its concentration will be 0.4  2 x x
decided by the dissociation of the complex. So, let
[ Ag  ]  y M.
Ag ( NH 3 )2  Ag   2 NH 3 ; K d  5.0  1013
AgBr ( s )  Ag  (aq )  Br  (aq ) x 0.4  2 x
 K sp  [ Ag  ][ Br  ]  y x  5.0  1013 x y y 0.4  2 x  2 y ( 0.4)
Since the formation constant ( K f ) of the complex [ Ag  ][ NH 3 ]2y (0.4  2 x  2 y ) 2

Kd    6  108
is very high, assume that whole of Ag  formed is 
[ Ag ( NH 3 ) 2 ] x y
consumed.

Assuming x  y  x since K d is low and << 0.4, Solving for x : x  1.15  103 M
we get : (Verify the approximation yourself)
y (0.4)2
Kd 
x
Illustration - 27 HN (hydroazoic acid) is a weak acid dissociating as : NH  H   N  . Find the con-

3 3 3
centration of Ag  ions, if excess of solid AgN3 is added to a solution maintained at pH = 4. The ionization
constant K a of NH 3 is 2.0 105. The solubility of AgN3 in pure water is found to be 5.4 103 M at
25C.
SOLUTION :
AgN3 is a sparingly soluble salt, dissociating in Now HN3 dissociates as follows :
water as : AgN3  Ag   N 3 HN3  H  N3
K sp  [ Ag  ][ N3 ] x 104 
Since solubility of AgN3 in water is 5.4  103 , x y 104  y  104 y
K sp  (5.4  103 )2  2.92 105 [As pH is maintained at 4 hence [ H  ]  104 M ]

Now we have a simultaneous equilibrium in aqueous
Now we have to find the solubility of AgN3 in
solution involving dissociation of AgN3 and HN 3.
solution having pH = 4.
Let solubility of AgN3 be x M at pH = 4. K sp of AgN3  [ Ag  ][ N3 ]  xy … (i)

 [ Ag  ]  xM , but [ N3 ]  x M [ H  ][ N3 ] [ H  ] y
K a of HN3   … (ii)
( [ N 3 ] will be decided by dissociation of HN3 ). [ HN 3 ] ( x  y)
Solving (i) and (ii) simultaneously, we have :
Let [ N3 ]  yM
K sp
First, assume that whole of N3 (xM) formed from x  [ Ag  ] 
Ka
[ H  ]  K a 
AgN3 reacts with H  ions to form HN 3.
Substitute the values of K sp , K a and [ H  ] to
 [ HN 3 ]  xM
get x = 0.0132 mol/L
Note : In this example, since the dissociation constant of acid is quite high and pH of the solution is quite low, we
can not assumed that x  y  x. You can check the same by comparing [ H  ] and K a in the expression
for x.

Example - 1 A solution contains a mixture of Ag+(0.1M) and Hg22+ (0.10 M) which are separated by
selective precipitation. Calculate maximum concentration of Iodide ion at which one of them gets precipitated
almost completely. What % age of that metal ion is precipitated ?
 Ksp AgI  8.51017 M; Ksp HgI 2

 2.51026 
SOLUTION :
First determine, which ion starts precipitating. first But when [I] reaches 5  1013 M then precipitation
of Hg2I2 also starts.
Ksp of AgI So [Ag+] left at that stage is given as :
[I ]Min.for AgI 

[Ag ] K sp of AgI
[Ag+] =
8.5 1017 [I ]Hg 2 I 2
=  8.5 1016 M
0.1
8.5  1017
K sp of Hg 2 I 2 =  1.7  104 M
 13
[I ]Min.for Hg 2 I2  5.0  10
2 +
[Hg 2 ] % of Ag left un-precipitated
1.7 104
2.5 1026 =  100 = 0.17%
= = 5  1013 M 0.1
0.1
 % age of Ag+ = 99.83 %
This means that AgI will be precipitated first as [I ] This means when Hg2I2 starts precipitating, Ag+ is
required for AgI is less. almost precipitated.
Example - 2 Carbonic acid, H CO , is a diprotic acid for which K  107 and K  1011. Which solution
2 3 1 2
will produce a pH closest to 9 ?
(A) 0.1M H 2CO3 (B) 0.1M Na2CO3
(C) 0.1 M NaHCO3 (D) 0.1 M NaHCO3 and 0.1 M Na2CO3
SOLUTION :
Amphiprotic salt is a salt that can donate proton well as can accept a proton. For example : NaHS, NaHCO3
etc.
 Na   HS 
NaHS 
HS   H   H 2 S
HS   S 2   H 
pH of amphiprotic salt of weak acid is calculated by using following expression.

1
pH   pK a  pK a 
2 1 2
1 1
pH   pK a1  pK a2   [7  11]  9
2 2
Example - 3 For the reaction Ag(CN)     Ag+ + 2CN, in an aqueous medium, the equilibrium
2
constant KC at 25°C is 4  1019. Calculate the Ag+ ion concentration in the solution which was originally 0.1
M in KCN and 0.03 M AgNO3.
SOLUTION :
[Ag  ][CN  ]2
0.1 M KCN and 0.03 M AgNO3 are mixed.  4 1019
KC = 
 Ag(CN)  is very-
Since Keq for Ag+ + 2CN  [Ag  CN 2 ]
2

 1 19  KC [Ag  CN2 ]
very high  K   10  , first assume that whole +
 [Ag ] =
 4  [CN ]2
of Ag is converted to Ag(CN)2.
+
4  1019  0.03  x 
=
Ag   2CN  
 Ag(CN)2  0.04  2 x 2
0.03 M 0.1 M 0
Solve the above equation by assuming ‘x’ to be very
0 0.1  2  0.03 M 0.03 M
small.
Now, Let 0.03 M Ag(CN)2 (Keq = 4  1019) to
dissociate as follows : 4  1019  0.03
 Ag+ + 2 CN
+
 [Ag ] = 2 = 7.51018 M
Ag (CN)2   0.04 
0.03 M - 0.04 M [Verify the approximation yourself]
0.03  x x (0.04 + 2x)
Example - 4 Calculate [NH4+] (derived from NH4Cl) needed to prevent Mg(OH)2 from precipitating in a
litre of solution which contains 0.2 mole of ammonia and 0.001 mole of Mg2+ ions. The ionisation constant of
ammonia is 2.0  105 and Ksp of Mg(OH)2 is 1.0  1011.
SOLUTION :
 Kb 
Note that aq. ammonia is NH4OH.     102  1   ~ 1
 c 
First check whether we need to add NH4Cl.
 I.PMg(OH)2  103  (2  103 ) 2
 3
[OH ]From NH3  K b c  2  10 M
 4  109  K sp
Thus, precipitation will take place if NH4Cl is not added If [OH]  1.0  104M, Mg2+ ions will not be
and hence, NH4Cl is required to be added so as to precipitated. So, maximum concentration of OH in
suppress the dissociation of NH4OH. As a result, the solution should be 1.0  104 M. As [OH] is
[OH–] will decreases. derived from dissociation of ammonia.
Now, calculate the concentration of OH ions in  NH + + OH
NH4OH  4
equilibrium with Mg2+ ions from Ksp of Mg(OH)2.
K b [NH 4OH]
Ksp of Mg(OH)2 = [Mg2+] [OH]2  [NH 4 ] 
[OH  ]
 K sp 1.0  10 11 (2.0  105 ) (0.2)

 [OH ]    1.0  104  [NH 4 ]min 
[Mg 2  ] 0.001 [1.0  104 ]
 4.0  10 2 M
For this much concentration of NH4+ ions, Mg2+ will
not be precipitated.
Example - 5 When a 40 mL of a 0.1 M weak base, BOH is titrated with 0.10 M HCl, the pH of the solution
at the end point is 5.5. What will be the pH if 10 mL of 0.10 M NaOH is added to the resulting solution ?
SOLUTION :
At the end point, pH = 5.5 (i.e. an acidic solution). K wc (10 14 )  (0.05)
 Kb    5.0  10 5
It means salt formed at the end of neutralisation  2  5.5 2
[H ] (10 )
undergoes hydrolysis.
When 10 mL of 0.12 M NaOH is added :
For 4 millimoles (40  0.1) of weak base, 4 millimoles
BCl + NaOH   BOH + NaCl
of acid is required at the end point.
Initially 4 m.moles 10  0.10
 BCl + H O
BOH + HCl  Finally 4  10  0.10
2
4 4 4  1 = 3.0 – 1.0
– – 4
It means a basic buffer containing 3.0 m.moles of BCl
 millimoles of salt (BCl) formed = 4 and 1.0 m.moles of BOH is fomed. Find the pH by using
 [BCl] = 4/V where V = VHCl + Vbase Henderson’s equation for basic buffer.
At the end point : 4 = 0.10  VHCl [BCI]
 VHCl = 40 mL pOH  pK b  log
[BOH]
 V = 40 + 40 = 80 mL
[3.0 / V ]
 [BCl] = 4 / 80 = 0.05 M  pOH   log(5  105 )  log
[1.0 / V ]
Note that BCl is a salt of strong acid and weak base.
 pOH = 4.77 (pKb = 4.3)
 K wc
 [H ]   pH = 14  pOH = 9.22
Kb
Example - 6
It is given that 0.001 mol each of Cd2+ and Fe2+ ions are contained in 1.0 L of 0.02M HCl
solution. This solution is now saturated with H2S gas at 25°C.
(a) Determine whether or not each of these ions will be precipitated as sulphide ?
(b) How much Cd2+ ions remain in the solution at equilibrium ?
K1 ( H 2 S ) = 1.0 × 107 ; K 2 ( H 2 S ) = 1.0 × 1014 ; K sp (CdS ) = 8 × 1027 ; K sp ( FeS ) = 3.7 × 1019
SOLUTION :
Note that two salts are of same type (i.e., AB type) 1021  0.1
 [S2  ]   2.5  1019 M
and Ksp of CdS is lower than that of FeS. This means 0.02 2
CdS will precipitate first if at all any precipitation takes
place. 8 1027
 [Cd 2  ]Left   3.2 108 M
Calculate the minimum concentration of Sulphide ion 2.5 10 19
required to initiate the precipitation of each of the metal
Thus, only CdS will get precipitated.
sulphide.
[S2–]Min for CdS To calculate the remaining concentration of Cd2+ ion
(more accurately) ion in the solution, first assume that
K sp CdS 8  1027 whole of the Cd2+ has been precipitated as :
=   8 1024 M
[Cd 2  ] 0.001
Cd2+ + H2S 
 CdS + 2 H+
[S2–]Min for FeS Thus, [ H +]new = 0.02 + 0.001  2 = 0.022 M
K sp FeS 3.7  1019 1021  0.1
=   3.7  1016 M 2–
[Fe 2
] 0.001  [S ]At new equilibrium =
0.0222
Now calculate the sulphide ion concentration in the = 2.07  10–19 M
saturated solution, using :
8 1027
[H ] [S ]  2 2  [Cd2 ]Left   3.86 108 M
19
K a  K1  K 2   1021 2.07 10
[H 2S]
Note : FeS will not be precipitated at all.
Example - 7
The solubility product, K sp of Ca(OH )2 at 25C is 4.0  106. A 500 mL of saturated of
Ca(OH )2 is mixed with equal volume of 0.4 M NaOH solution. How much Ca(OH )2 in milligrams is
precipitated ?
SOLUTION :
First find the concentration of Ca 2  ions at saturation using K sp of Ca(OH )2 .
Ca(OH ) 2  Ca 2   2OH 
 K sp  [Ca 2  ][OH  ]2
Let [Ca 2  ]  x mol / L  [OH  ]  2 x
K sp
 K sp  4 x3 or x  3  0.01 M
4
 [Ca 2  ]  0.01 M and [OH  ]  0.02 M

As equal volumes of saturated solution and 0.4 M NaOH are mixed :
0.01
[Ca 2  ]   5  103 M
2
 0.02 0.4
and [OH ]Total    0.21 M
2 2
[ [OH  ]Total  [OH  ]NaOH  [OH  ]From Ca (OH )2 ]
Now, calculate I. PCa (OH )2  [Ca 2  ][OH  ]2  (5  103 ) (0.21) 2  2.2 104  K sp
Since concentration of OH  is quite high, Ca 2  will be precipitated till a new saturation state is reached.
Let at new saturated state. [OH  ]  0.21 M (Assuming no change in [OH  ] )
2 K sp (4  106 )
[Ca ]left    9.07  105 M
 2 2
[OH ] (0.21)
 [Ca 2  ]precipitated  5  103  9.07  10 5 M  4.91 103 M
 amount of Ca 2   4.91 103  74  103 mg / L  363.3 mg / L
Check the approximation : [OH  ]left  0.21 M . How ??
Find out the [OH  ]used  2[Ca 2  ]used (see Reation’s Stoichichiometry)
 2  4.91 103 M  9.8  103 M

 [OH  ]left  0.21  9.8 103 M  0.2M  0.21M
Alternate Approach :
Ca (OH )2  Ca 2 (aq)  2OH  (aq )

t  teq : concentration : 0.01 0.02 I .P.  K sp
t  0(new) concentration : 5 103 0.21 I .P.  K sp

( After mixing equal volumes with NaOH )
t  teq (new) 5  103  x 0.21  2 x I .P.  K sp
Now, I.P. = K sp at equilibrium
(5  103  x ) (0.21  2 x ) 2  4  10 6  This equation in ‘x’ is clearly a cubic.

To solve the above equation approximately, assume 0.21  2 x  0.21 which is what has been done in the
previous approach.
Example - 8 The solubility product of Ag C O at 25C is

2 2 4 1.20  1011. A solution of K 2C2O4 containing
0.15 moles in 500 ml water is mixed with excess of Ag 2CO3 till the following equilibrium established :
Ag 2CO3  K 2C2O4  Ag 2C2O4  K 2CO3.
At equilibrium, the solution contains 0.03 mole of K 2CO3. Assuming that the degree of dissociation of
K 2C2O4 and K 2CO3 to be equal, calculate the solubility product of Ag 2CO3. [Take 100% ionisation of
K 2C2O4 and K 2CO3 ]
SOLUTION :
0.15 Now find [ Ag  ] at equilibrium as :
[ K 2C2O4 ]   0.30 M  P
initial 0.5
K sp of Ag 2C2O4
0.03 [ Ag  ] 
and [ K 2CO3 ]  0.5  0.06 M  x [C2O42  ]
final
Ag 2CO3  K 2C2O4  K 2CO3  Ag 2C2O4 1.20  1011 1.20  1011

 
P  Px 0.3  0.06
Px x  7.07  10 6 M
1 mol K 2CO3  1 mole K 2C2O 4 and since both [CO32  ] final  x  0.06 M
are completely ionized :
Now, K sp of Ag 2CO3  [ Ag  ]2 [CO32 ]
 K sp of Ag 2CO3  (7.07 106 ) 2  0.06
 3  1012
Example - 9 Malonic acid is an organic dibasic acid like H 2 S having first ionization constant,
K1  1.42 103 and second ionization constant, K 2  2.0  106. Compute the divalent malonate ion
concentration in :
(a) 0.001 M Malonic acid (b) in a solution that is 0.0001 M in malonic acid and 0.0004 M HCl.
(c) in a solution that is 0.0001 M in malonic acid and 0.1 M HCl.
SOLUTION :
(a) Consider malonic acid to be H 2 A, where malonate ion is A2  . For dibasis acids, we consider ionization
in two stages as follows :
[ H  ][ HA ] x2
 K1    1.42  103
[ H 2 A] cx
Solving the quadratic, x 2  1.42  103 x  1.42  106  0  x  6.75  104 M

Note that K1  K 2 . so concentration of H  in solution is considered only from dissociation i.e.,
[ H  ]  x M (neglect H  concentration from second ionization).

Consider second ionisation :
[ H  ][ A2 ] ( x  y) y
 K2  
 x y
[ HA ]
Note : [ H  ] [ H  ]  x  y  x [ HA ]  x  y  x ( y  x )
 K 2  y  [ A2  ]  2.0 106 M
Note : Usually, [ A2  ] for H 2 A (dibasic acid) can be approximately taken to be K 2 .
(b) Here  104 M , [ H  ]  4  104 M (From HCl)
[ H  ][ HA] (4 104  x ) ( x)
 K1    1.42  103
[ H 2 A]  4
10  x
Important : Note that, we can not go for approximation in this case, since the concentration of HCl
is so low that H  is considered both from HCl and molonic acid.
Solving the quadratic, x 2  1.82  103 x  1.42  107  0  x  7.5  105 M
Now consider, second ionisation and substitute for value of x.
[ H  ][ A2  ] (4  104  x )
K2    2.0  106
[ HA] x
(4  104  7.5  105 ) y

  2.0  106
5
7.5  10
 y  [ A2  ]  3.2 107 M
(c) Here c  104 M , [ H  ]  0.1M
[ H  ]2 [ A2  ] (0.1)2 [ A2  ]
 K a  K1K 2    2.84  109
[ H 2 A]  4
10
 [ A2  ]  2.84 1011 M
Important : Note that, we will do the approximation in this case, since the concentration of HCl is so high
that H  is considered from malonic acid is negligible. Recall the ionization of H 2 S (g) in an
acidic solution.
Example - 10
Calculate the [ F  ] in a solution saturated with respect to MgF2 and SrF2 .
K sp ( MgF2 )  6.0  109 ; K sp ( SrF2 )  3.0 109

SOLUTION :
In this case, please note that the K sp values of two salts are very similar. So the concentration of F  ions
(the common ion) can not be calculated from a single salt alone.
Let the simultaneous solubilities of MgF2 and SrF2 be x and y respectively in mol/L.
MgF2 ( s )  Mg 2   2F 
x 2x
SrF2 ( s )  Sr 2 2 F 
y 2y
At eq : [ F  ]  2 x  2 y ; [ Mg 2  ]  x ; [ Sr 2  ]  y
 [Mg 2  ][ F  ]2  K sp MgF2
and [Sr 2  ][ F  ]2  K sp Sr F2
Note that : 
[ F  ]  2 [Mg 2 ]  [ Sr 2  ]  [This is an Electrical charge neutrality equation]
 K sp MgF2 K sp SrF2 
[F  ]  2   
 [ F  ]2 [ F  ]2
 
 
[ F  ]  3 2 K sp MgF2  K sp SrF2   2.62  10 3 M
THINGS TO REMEMBER
1. Weak Electrolyte
[H  ]2 c 2 [H  ]2
(a) Weak Acid : K a   ; c  [H  ] 
c  [H  ] 1  Ka
If 1 –  ~ 1, then Ka = c2 and [H  ]  K a c
[OH  ]2 c 2 [OH  ]2
(b) Weak Base : Kb   ; c  [OH  ] 
c  [OH  ] 1  Kb
If 1 –  ~ 1, then Kb = c2 and [OH  ]  K b c
 For any acid – conjugate base pair, Ka.Kb = Kw

 “” of weak electrolytes increase on dilution.
 
H 2O  
 H  OH

Kw = [H+] [OH–] or pH + pOH = pKw

Kw increases as T increases and decreases as T decreases.
2. Buffer solution :
salt 
(a) Acidic : HA + A–  pH = pKa + log10
 acid 
salt 
(b) Basic : BOH + B+  pOH = pKb + log10 base
 
 Buffer capacity of the buffer solution is maximum at pH = pKa or pOH = pKb.
 pH of a buffer solution does not change on dilution.
3. Hydrolysis :
 Salts of SA – SB do not get hydrolysed.
 Salts of SA – WB on hydrolysis give acidic solution.
ch 2 K 1
Kh   w ; pH   pK w   pK b  log10 c 
1 h Kb 2
 Salts of WA – SB on hydrolysis give basic solution.
ch 2 K 1
Kh   w ; pH   pK w   pK a  log10 c 
1 h Ka 2 
58 Things to Remember Self Study Course for IITJEE with Online Support
 Salts of WA – SB on hydrolysis may give acidic, basic or neutral solution.
h2 Kw 1
Kh   ; pH   pK w   pK a  pK b  
1  h 2 Ka . Kb 2
Kh : hydrolysis constant ; h : degree of hydrolysis
4. Sparingly soluble salts and Precipitation :

 Solubility of a sparingly soluble salt is expressed in mol / L or gm/L
1/  x  y 
 (Ksp ) 
 Solubility (in Mol/L) of any salt AxBy in pure water is given by : So lub ility  
x y
 x  y 
 Solubility of a salt decreases in the presence of a common ion.
In general, we can neglect the contribution of common ion from the sparingly soluble salt.
Ksp AgCl K sp AgCl
e.g. solubility of AgCl in pM NaCl = 
[Cl ] p
 Selective precipitation : When difference in the minimum concentrations of common cation/anion
required to start the precipitation is very high.
To check, always calculate the conc. of the cation/anion left in the solution when the second cation/
anion starts to precipitate, and so on……….
 Simultaneous Solubility : Solubility of two or more salts having a common cation / anion when
their Ksp values are comparable. Solve the governing equations simultaneously.
5. Use of Indicators :
 Transition range of an indicator : pKIn– 1 to pKIn + 1
 For SA - SB titration, almost every indicator is effective.
 For SA - WB and WA - SB, indicator selection is important and depends on the pH at equivalence
point.
6. Miscellaneous :
 For dissociation of H2A, [A2–]  K2 ; For H3A, [A3– ]  K3 and so on.
 For any polyprotic acid, K a1 >> K a 2 >> K a 3 and so on.
 Solubility of a salt can be increased by adding a substance that makes a stable complex / compound
with any of the cation / anion in the salt.
e.g. AgCl dissolves more in aq. NH3 solution due to the formation of Ag(NH3)2+ and AgCN dissolves
more in an acidic solution due to the formation of HCN (weak electrolyte)
Self Study Course for IITJEE with Online Support Things to Remember 59
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes s-Block
s-BlockElements
Elements&&Compounds
Compounds
s-Block Elements & Compounds

PROPERTIES OF s-BLOCK ELEMENTS Section - 1
Group - I
Introduction :
All the alkali metals have loosely held one s-electron in the outermost shell which they can readily lose to
give monovalent (M+) cation having stable noble gas configuration. Due to their tendency of loosing s-
electron easily, they have low ionization energy and high metallic character. The size of atoms and ions of
alkali metals increases down the group.
Physical Properties :
(i) Electropositive character
Alakali metals are highly electropositive in nature and electropositive character increases down the
group.
(ii) Ionization Energy
Alkali metals have low ionisation energy and it decreases down the group. In fact K and Cs are used
as cathodes in photoelectric cells.
(iii) Density
The density of alkali metals is quite low as compared to other metals. Li, Na and K are even lighter
than water. As we go down the group, the mass and volume of alkali metals increases but mass
increases by larger factor than the volume and the resulatant effect is that the density increases down
the group with an exeption that potassium beigh lighter than Sodium. So, the trend is :
Li  K  Na  Rb  Cs
(iv) Melting Point and Boiling Point :

Melthing point and boiling point of alkali metals decreases down the group. The melting points range
from lithium 181C to caesium 28.5C. These are extremely low values for metals, and contrast with
the melting point of the transition metals, most of which are above 1000C.
(v) Flame Test :
Group I elements give a varied range of colours in their flame test. Li emits crimson light, Na emits
yellow, K emits lilac and Rb and Cs emit violer light.

s-Block Elements & Compounds Vidyamandir Classes
Chemical Properties :
The alkali metals are highly reactive due to low ionization enthalpy and therfore they never occur in free
state. The reactivity of these metals increases down the group.
(i) Reactivity towards air
Li react with air forming oxide Li2O (and some Li2O2) and nitride Li3N. Na react with air forming
oxide (Na2O) and peroxide (Na2O2). Peroxide is formed in large amount. K, Cs and Rb forms oxide
(M2O), peroxide (M2O2) and superoxide (MO2). Superoxide is fromed in large amount. (Where M
is K, Cs, Rb).
You can note here except Li all other alkali metals are forming oxide only, whereas Li form nitride also
on buring in air. Li3N is a ruby red salt which gives LiOH and NH 3  on dissolving in water while Li
and nitrogen on simply heating. The increasing stability of peroxide or super-oxide, as size of the metal
ion increases, is due to the stabilization of large anions by larger cation through higher lattice energies.
(ii) Reactivity towards water
Group 1 metals all react vigorously with water liberating hydrogen. The reaction becomes increasingly
violent on descending the group.
1
M s   M sq  le ; H 2O  le  OH   H2
  2
1
 M   OH  
M  H 2O  H2 (M  Li, Na, K, Rb, Cs)
2
Reaction of sodium is os violent that it catches fire and is thus kept in kerosene in the laboratory.
Standard Reduction Potential

Standard Reduction potential of akali metals M is a value that represents the tendency to gain an electron
M aq  le  M s 

 
If standard Reduction potential is positive it means element desires to gain electrons and if it is negative
it means element desires to loose electron.
Further, lower the standard reduction potential, higher will be the tendency to loose electron.
Standard reduction potential (Eo) for an alkali metal represents the overall change :
M  s   M  g  Sub lim ation enthalpy
M  g   M   le  Ionization enthalpy

g 
M  M
 H 2O  hydration enthalpy
g   aq 

Vidyamandir Classes s-Block Elements & Compounds
Lithium has the most negative standard reduction potential than any other element in the periodic table.
Why ?
a Li  H  159 KJ /mol
ion Li  H  520.2 KJ/ mol
Lis   Li g  
 hydr H Li   520
Li   le  Li   le 
g   aq 
Total energy aborbed  aH Li  ion H Li   hydn H Li  159  520.2  520  159.2 KJ / mol.
a Na  H  107 KJ/ mol

ion Na  H  495.8 KJ/ mol
Na  s  
 Na  g  

 hydr H Na   406 K / mol

Na   le 
 Na   le
g   aq 
Total energy absorbed
 a H Na  ion H Na   hydr HNa   107  495.8  406  196.8 KJ ? mol
Hnece total energy absored in Lis   Li  aq   le  is less and also least as compared to any
other element. Therefore it has most negative standard reduction potential.
Li has most negative standard reduction ptoential (or highest tendency for Li  s   Li   aq   le  ).
It seems that reaction of Li with water should be most vigourous. But it is surprising that Li reacts less
vigorously with water than other alkali metals. The explanation lies in the kinetics (that is the rate at which
the reaction proceeds) rather than in the thermodynamics (that is total amount of energy absorbed). You
will study more about kinetics in upcoming modules.
(iii) Reducing Character
Among alkali metals, Lithium has strongest reducing character and sodium has least reducing
character and rest are almost the same.
[Lower the standard reduction potential (considering the sign also) higher is the reducing character]
(iv) Solution in liquid Ammonia
Liquid Ammonia is also a good polar solvent next the water. Ammonia gas (b.p. = - 33oC) is
condensed to give liquid ammonia. Both water and ammonia undergo self - ionization :


2H 2O  
 H3O  OH

; 

2NH3   
 NH 4  NH 2

When small amount of sodium is added in liquid ammonia (i.e. : Dilute Solutions of Na in liquid
Ammonia), sodium metal looses an electron to give sodium cation, both of these ions are solvated by
liquid ammonia to give a blue coloured solution which is highly conducting.
 
M   x  y  NH3   M  NH3  x   e  NH3  y 
 
The blue colour of the solution is due to the ‘ammoniated electron’ which absorbs energy in the visible
region of light and thus imparts blue colour to the solution. The conducting nature is also mainly due to
solvated electron.
The solution is paramagnetic in nature and on standing slowly liberates hydrogen resulting in the
formation of amide.
1
e  NH3    NH 2 ammoniated   H 2 g 
2
Concentrated solution of Na in liquid ammonia is metallic bronze in colour and diamagnetic in nature
due to formation of metal ion clusters.
Group - II
Introduction :
All the alkaline earth metals have two s-electron in the outermost shell which if they lose, they will give
divalent (M2+) cation having stable noble gas configuration. The size of atoms and ions of alkaline earth
metals increases down the group.
(i) Electropositive character
Alkaline earth metals are highly electropositive in nature and Electropositive character increase down
the group.
(ii) Ionization Enthalpy
Second ionization enthalpy is very high than first ionization enthalpy. It is due to the fact that extracting
an electron from a positive ion bcomes difficult. Both first and second ionization energy decreases
down the group.
(iii) Density
The density of alkaline earth metals is high as compared to alkali metals. And as we go down the
group both the mass and volume of alkali metals increases but the resultant effect that is the density do
not show a regular change. As we move down the group, it first decrease (upto Ca) and then increases.
So, the trend is : Ba > Sr > Be > Mg > Ca

(iv) Melting point and Boiling Point

Melthing point and boiling point of alkaline earth metals is higher than the alkali metals. As we move
down the group,
Melthing point and Boiling point don’t show a regular change.
Chemical propeties :
(i) Reactivity towards air
Alakaline earth metals react with air forming an oxide and a nitride.
air
M s   MO  M 3 N 2  where M  Be, Mg, Ca, Sr, Ba 
The case of above reaction depends on electropositive character and hence increases down the
group. In the case of Mg, it burns with a dazzling white light which is used to provide light in flash
photography using light bulks.
(ii) Reactivity towards water

 M 2aq
OHC : Ms    2e  RHC : 2H 2O    2e 
 H 2  2OH 
 
Now, to check the case of reaction for different metals, we have to check the Oxidation Half Cell
reaction and this reaction refers to the reducing ability (Standard Reduction Potential) of the metal.
And, Since for alkaline earth metals reducing character increases down the group, the case of reaction
of alkaline earth metals with water increases down the group.
Experimentally, it is see that Be reacts only with steam and Magnesium can react with both hot water
and steam and Ca. Sr, Ba ract even with cold water rapidly.
(iii) Solution in liquid ammonia

In liquid ammonia, group II metals form bright blue dilute solutions containing solvated electrons and
metal hexaammoniates. The metal hexammoniates form ammides on heating which further form nitrides
and NH3 concentrated solution are bronze coloured.
(iv) Reducing character

Less is the standard reduction potential more will be reducing character and since the standard reduction
potential decreases down the group, the reducing character of alkaline earth metals increases down
the group.

IMPORTANT CONCEPTS Section - 2
In this section we will discuss some important concepts related to s-block elemets.
Lattice enthalpy
It is the energy required to separate one mole of a solid ionic compound completely in gaseous ions.
Lattice Enthalpy of breaking solid NaCl in gaseous Na+ and Cl– is + 788 KJ/mol.
In a system of + ve and -ve ion the energy required to separate the two ions is inversely proportion to the
distance between the centres of the two ions.
1
 LE 
r  r 
(r+ is the radius of +ve ion and r– is the radius of -ve ion.)
For a given anion and different cations as we move down the group the size of cation increase and conse-
quently the interionic distance between cation and anion increases. Hence, the lattice enthalpy would de-
crease dwon the group.
Also you may not that as the charge of ion increases the Lattice Enthalpy increases. Therefore, Lattice
Enthalpy of group II metal salt is more as compared to corresponding group I metal salts.
Hydration Enthalpy
Hydration Enthalpy refets to the energy released when one mole of gaseous ion is dissolved (or hydrated) in
water. Strictly speacking, value of Hydration Enthalpy is equal to the energy absorbed when one mole of
gaseous ion is dissolved in water. For example, if energy is released on dissolving some ion in water, its
hydration enthalpy will be negative quantity and its magnitude will be equal to the magnitude of energy
released.
When an ion is dissolved in water it attracts water molecules. Thus, a number of water molecules surround
it and a cluster is formed. The number of water molecules surrounded by a cation depend on the ability of
the cation to polarise the water molecule. More the polarizing power of cation, the large the number of
water molecules will surround it. Among alkalie metals cations, Li+ has highest polarising power, hence, a
large number of water molecules will surround it. The numbere is so large that the hydrated Li+ becomes
heavier than hydrated Na+. The hydrated Na+ being lighter moves easily in water as compared to hydrated
Li+, hence Na+ is more conduction than the solution of Li+.
Also, note that more that polarising power of cation, more it will be hydrated and more energy will be
released. And therefore, hydration enthalpy will be more negative. Thus down the group magnitude of
hydration enthalpies of metal ions decreases.

Thermal Stability
Hereby we will discuss the thermal stability of group I and group II metal oxosalts. i.e. carbonates, nitrates,
sulphates etc. For simplicity let us consider metal carbonates and discuss their thermal stability.
Example :
The effect of Heat on the metal carbonates :
All the carbonates undergo thermal decomposition to give the metal oxide and carbon dioxide gas. Thermal
decompostion is the term given to splitting up a compound by heating it.
XCO3  s   XO  s   CO 2  g 
As you go down the group, the carbonates have to be heated more strongly before they will decompose.
i.e. Thermal stability of metal carbonates increase down the group. Let us try to understand the explanation
of this fact.
Explanining the trend the terms of the polarising ability of the positive ion :
A small cation has a lot of charge packed into a small volume of space. It has a high charge density and will
have a marked distorting effect on any negative ions which happen to be near it.
A bigger cation has the same charge spread over a larger volume of space. Its charge denisty will be lower,
and it will cause less distortion to nearby negative ions.
The structure of the carbonate ion :

If you worked out the structure of a carbonate ion, you would probably come up with :
This show two single carbon-oxygen bonds and one double one, with two of the oxygens each carrying a
negative charge. Unfortunately, in real carbonate ions all the bonds are identical, and the charges are spread
out over the whole ion - although concentrated on the oxygen atoms. We say that the charges are delocalised.
The next diagram shows the delocalised electrons. The shading is intended to show that there is a greater
chance of finding them around the oxygen atoms than near the carbon.

Polarisin the carbonate ion :

Now imagine what happens when this ion is placed next to a positive ion. The positive ion attracts the
delocalised electrons in the carbonate ion towards itself. The carbonate ion becomes polarised.
If this is heated, the carbond dioxide breaks free to leave the metal oxide.
How much you need to heat the carbonate before that happens depends on how polarised the ion was. If it
is highly polarised, you need less heat than if it is only slightly polarised.
The smaller the positive ion is, the higher the charge density, and the greater effect it will have on the
carbonate ion. As the positive ions get bigger as you go down the Group, they have less effect on the
carbonate ions near them. To compenstate for that, you have to heat the compound more in order to
persuade the carbond dioxide to break free and leave the metal oxide. In other words, as you go down the
Group, the carbonates become more themally stable.
In case of Nitrates, Group II metal nitrates decompose to give metal oxide, nitrogen dioxide and oxygen gas
while Group I metal nitrates except lithium) decompose to give metal nitrite and oxygen gas. Lithium nitrate
behaves in a way similer to group II metals giving. LiO, NO2 and O2 on decopostion.

Ca  NO3 2  CaO  NO 2  O 2

Li(NO3 ) 2  Li 2O  NO 2  O 2
500C
NaNO3 
 NaNO 2  O 2
800C
NaNO3 
 Na 2O  N 2  O 2
NaNO3 on very strong heating gives Na2O, N2 and O2. Metals sulphates decompose to give metal oxide,
SO2 and O2. Thermal stability of all these oxosalts increases down the group and the explanation lies in a
way similar to as given for metal carbonates.

IMPORTANT COMPOUNDS OF s-BLOCK Section - 3
1. Oxides, Peroxide, Superoxides
Gruop - I
Alkali metals generally burn in air to form oxides, peroxides and superoxides (Lithium forms some nitride
also). Lithium forms Li2O (and some Li2O2 ) and Li3N. Sodium form Na2O2 (and some Na2O), and rest of
the alkali metals form superoxides (major). The increasing stability of oxides, peroxides and superoxides, as
the size of the metal ion increases, is due to the stabilisation of large anions by larger cations through lattice
energy effects. The oxides and peroxides are colourless but the superoxides are orange or yellow. Oxides
and peroxides ae diamagnetic while superoxides are paramagnetic. Alkali metal oxides, peroxides and
superoxides dissove readily in water to give hydroxides along with a lot of heat. Peroxides and superoxides
are good oxidants and generally used in bleaching.
1. Sodium Oxide [Na2O]

Preparation :
(i) Controlled oxidation of sodium in air gives Na2O
(ii) Industrially, Na2O is prepared by heating sodium nitrate of nitrite with sodium.
NaNO3  Na 
 Na 2O  N2 ; 2NaNO2  6Na 
 4Na 2O  N2
(iii) In laboratory pure Na2O is formed by heating mixture of sodium azide and sodium Nitrite.

3NaN3  NaNO2  2Na 2O  5N 2
(pure)
Porperties :
Na2O is a white ionic solid and its aqueous solution is a strong base.
Na 2O  H 2O 
 2NaOH
2. Sodium Peroxide [Na2O2]

The trade name of sodium peroxide is oxone.
Preparation :
Burning Sodium in air mainly forms sodium peroxide.

Properties :
(i) Na2O2 is colourless in pure form and stable at room temperature.
(ii) Na2O2 is diamagnetic. All peroxides are regarded as salts of dibasic acid H2O2.
Na 2O2  2H2O 
 2NaOH  H2O 2
(iii) Cold dilute acids always produce H2O2.
Cold
Na 2 O2  HCl  NaCl  H 2O2
The reaction with CO2 is used to purify air in submarinas but KO2 is even better for this purpose.
(iv) It is strong oxidising agent. It oxidises Al to Al2O3 , Cr 3 to CrO42  and SO 2 to SO 42  .
Na 2O2  Al 
 Al2O3  Na 2O
Na 2O 2  CO 2 
 Na 2SO4
The reaction with CO2 is used to purify air in submarines but KO2 is even better for this purpose.
Uses :
It is a powerful oxidant and used for bleaching wood pulp, paper and fabrics.
3. Potassium Superoxide [KO2]

Preparation :
It is prepared by burning potassium in excess of oxygen.
K  O 2  excess   KO 2
Porperties :
(i) It is paramagnetic and orange coloured solid.
(ii) Potassium superoxide is stronger oxidizing agent and gives both H2O2 and O2 with either water
or acids.
2KO2  2H 2O 
 2KOH  H 2O2  O 2 ; 2KO 2  2HCl 
 2KCl  H 2O 2  O 2
(iii) It readily reacts with CO and CO2 producing Oxygen.
2KO 2  CO 
 K 2CO3  O 2 ; 2KO 2  CO 2  K 2CO3  3 / 2O2

User :
Being oxidant, KO2 produces oxygen and simulataneoulsy it absorbs CO2 and becuase of its above
life supporting properties it is used in space capsules, submarines and breathing masks.
Gruop - II
Alkaline earth metals burn in air to give normal metal nitrides. Generally, there are two methods of forming
oxides, one is buring in air and other decomposing their oxosalts.
Metal oxides and hydroxides of group II are more stable than of group I, that is why oxosalts (carbonates,
sulphates, nitrates,....) of group II are less stable to heat and decompose to give corresponding oxides.
Note : The stability of metal oxides decreases down the group. That is why, down the group metal oxides become
more reactive. Down the group, alkaline earth metal oxide’s basic character increases. BeO is amphoteric
in nature.
1. Magnesium Oxide
Preparation
(i) Magnesium burns in air with a dazzaling flame and forms magnesium oxide.
2Mg  O 2 
 2MgO
(ii) Decomposing the oxosalt MgCO3 also gives magnesium oxide.


MgCO3 
 MgO  CO2
Properties :
(i) It is light infusible (fusibility refers to conversion in liquid form) white powder. It fuses at 2800oC.
(ii) It is reduced by carbon at very high temperature.
2000C
MgO  C 
 Mg  CO
Uses :
(i) Buring of magnesium ribbon is used to initiate the thermite reaction.The thermite reaction goes
as :
Fe 2O3  2Al   2Fe  Al2O3

(ii) MgO being very less reactive and having high m.p., is used as a refractory material. Good
conductivity of MgO towards heat and bad conductivtiy towards electricity also adds to its
usefulness as refractory material.

2. Calcium Oxide [CaO] (Quick lime)

Prepartion :
It is prepared by decompostion of CaCO3 in lime kilns (900oC).

CaCO3  CaO  CO2
Properties
(i) Calcium oxide is a white amorphous solid, having high melting point of about 2870K.
(ii) Being a basic oxide, it combines with acidic oxides at high temperaure.
CaO  SiO 2  CaSiO3 ;  2Ca 3  PO 4 2

6CaO  P4O10 
300C
(iii) CaO  3C 
 CaC2  CO 
Uses :
(i) It is used in metallurgy to remove phosphates and silicates as slag.
(ii) By mixing with SiO2 and alumina or clay it is used to make cement.
(iii) It is used for softening of water.
2. Hydroxides
Gruop - I
Hydroxides of alkali metals are strong base. Their basic character increases down the group. They
dissolve readily in water giving much heat due to intense hydration. If we go down the group solubility
of alkali metal hydroxides increases.
1. Sodium hydroxide [NaOH] (Caustic Soda)

Preparation :
(i) Heating 10%Na2CO3 Sol. with mild of lime (Lime - Caustic Soda process) :


Na 2CO3  Ca(OH)2 
 2NaOH  CaCO3

(ii) Electrolysis of brine :

Commercially, NaOH and Cl2 are manufactured simultaneously by the electrolysis of brine (NaCl
solution).
Reactions occuring at anode and cathode are :


NaCl  
 Na  Cl

At Anode : 2Cl 
 Cl2  2e
At Cathode : Na  le   Na
2Na  2H2O  2NaOH  H2
Another reaction may occur at the anode to a small extent.
4OH  
 O 2  2H 2O  4e 
Electrolysis is carried in either of two types of cell today, diaphragm and mercury cathode cells.
NaOH made in this way always contanins some amount of NaCl.
(a) Diaphragm cell / Nelson : A porous diaphragm of asbestos is used to keep the H 2 and Cl2
gases separated otherwise they react in an explosive chain reaction in dylight. Diaphragm also
seperates the carbon anod and cathod.
(b) Mercury Cathod Cell / Castner - Kellner Cell : The anode is made up of carbon and the
cathode of mercury. The reaction occuring at Hg cathode are thus :
Cathod : Na   e  
 Na
Na  Hg  Na  Hg amalg am 

The amalgam is pumped in a different comartment called denuder where water trickles over.
1
Na  Hg  H 2O 
 NaOH  H 2  Hg  recycled back to electrolysis tan k 
2
Properties :
(i) It is a white crystalline solid, deliquiscent (absorbs moisture from air), soluble in water, good conductor
and gives silky touch like soap.
(ii) It reacts with acid and acidic oxides to form salts
NaOH  HCl 
 NaCl  H 2O
2NaOH  SiO 2 
 Na 2SiO3  H 2O
2NaOH  CO 2 
 Na 2CO3  H 2O
(iii) It reacts with amphoteric metals such as Sn, Al, Zn and amphoteric metal oxides.
Zn  2NaOH   Na 2 ZnO 2  H 2 Sodium Zincate 

3
Al  NaOH  H 2O 
 NaAlO 2  H 2  Sodium Aluminate 
2
Sn  2NaOH 
 Na 2SnO 2  H 2  Sodium Stannate 
SnO  2NaOH 
 Na 2SnO2  H 2O
SnO2  2NaOH 
Al2O3  2NaOH 
 2NaAlO2  H 2O
(iv) It reacts with ammonium salts to give ammonia, whcih serves as a test for ammonia.
NH 4Cl  NaOH 
 NaCl  NH3   H 2 O
The above reaction is double displacement reaction only. NH4OH must be formed as second product.
But NH4OH is never formed as a product. It decomposes to give NH3 + H2O.
(v) Disproportion of some non-metals in NaOH : (Learn these reactions)
X2  NaOH 
 NaX  NaOX  H 2O  X  Cl, Br, I
 Cold & Conc.

X2  NaOH 
 NaX  NaOX3  H 2O
 hot and Conc.
P4  NaOH  
 NaH 2 PO 2  PH 3
 phosphine 
[This reaction is used in the preparation of phosphine gas.]
S  NaOH 
 Na 2S  Na 2S2O3  H2O
(All above reactions can be balanced as Redox Reactions)

(vi) Reactio with salts of transition metals :
 Fe  OH 3  3NaCl
FeCl3  3NaOH 
When hydroxides are unstable, the oxides are precipitated.
 HgO     H 2O  2NaCl
HgCl2  2NaOH 

Hg  OH  2
 Ag 2O     H 2O  2NaNO3
2AgNO3  2NaOH 
  
AgOH
2. Potassium Hydroxide [KOH] (Caustic Potash)

Preparation :
It can be prepared by electrolysis of KCl solution similar to electrolysis NaCl solution (brine)
At Cathode : 2K   2H 2O  2e  
 2KOH  H 2 
At anode : 2Cl  2e 

 Cl2 
Properties :
(i) The properties are similar to those of NaOH but being expensive is less used.
(ii) KOH is more soluble in alcohol than NaOH and produces OC2H5 ions.

 


C2 H5OH  O H 
 OC2 H5  H 2O
This accounts for use of elcoholic KOH in OrganicChemistry which you will study in modules of organic.
Uses :
(i) It is used in organic chemistry
(ii) KOH is used as an absorbent for CO2, for which is perferred over NaOH, since after absorption
of CO2, the KHCO3 formed is solube whereas NaHCO3 being sparingly soluble separates out,
and chokes the absorption bulbs.
Gruop - 2
Alkaline earth metal oxides react with water to form sparingly soluble metal hydroxides.
Alkaline earth metal hydrooxides are less basic and more stable than alkali metal hydroxides. The solubility,
thermal stability and basic character of the hydroxides increases down the group. Beryllium hydroxide is
amphoteric in nature as it reacts with both acids and bases.
Be  OH 2  2NaOH 
 Na 2  Be  OH 4 
Sodium beryllate
Be  OH 2  2HCl  2H 2O 
  Be  OH 4  Cl2
Rest of the alkaline earth metal hydroxide are basic in nature.
1. M agn esi u m H y d r o x id e [ M g(OH ) 2]

Preparation :
Mg(OH)2 is pepared by dissolving magnesium oxide in water.
 Mg  OH 2
MgO  H 2O 
Properties :
(i) It is a white powder extermely insoluble in water.
(ii) It is weakly basic and suspension Mg(OH)2 in water [milk of Magnesia] is used as an antacid.
2. Calcium Hydroxide [CaOH)2]

Preparation :
Calcium hydroxide is prepared by adding water to quick lime (CaO).
 Ca  OH  2
CaO  H 2O 

Properties
(i) It is white powder, sparingly soluble in water.
(ii) The aqueous sturated solution of Ca(OH)2. is known as lime water and the suspension of slaked
lime (solid Ca(OH)2) in water is known as milk of lime.
(iii) Bleaching powder is formed when chloring gas is passed through lime water.
3Ca(OH)2  2Cl2 
 Ca(OCl)2 . Ca(OH)2 . CaCl2 . 2H2O
Uses :
(i) It is used in white wash.
(ii) It is used in the solvay’s process.
(iii) It is used to remove temperaray hardness of water :
Ca(HCO3 ) 2  Ca  OH 2 
 2CaCO 3   2H 2O
Mg(HCO3 )2  Ca(OH)2 
 2CaCO3   Mg(OH)2   2H2O
(iv) When carbon dioxide is bubbled through lime water it turns milky and when excess carbon dioxide is
passed, the precipitate (CaCO3) dissolves forming Ca(HCO3)2.
CO
2  CaCO () 
2  Ca(HCO ) CO
Ca(OH)2(aq)  3 3 2(aq)
white precipitate Excess
soluble
Similaraly, Ba(OH)2 (Baryta water) responds, when CO2 is bubbled through it.
CO
2  BaCO () 
2  Ba(HCO ) CO
Ba(OH)2  3 3 2(aq)
milky so ln. Excess
milkiness disappears
In this reaction Ba(OH)2 is even more sensitive ot CO2 but Ba(OH)2 being more expensive,
Ca(OH)2, is preffered to detect CO2 in laboratory.
Note : The caustic alkalis (NaOH and KOH) are the strongest bases known in aqueous solution. Soda lime is a
mixture of NaOH and Ca(OH)2 and is made from quick lime (CaO) and aqueous NaOH. Soda lime is
much easier to handle than NaOH.

3. Halides
Gruop - I
Alakali metal halides like NaCl and KCl are generally found in sea water. Among Sodium halides,
stability, melthing point and boiling point decreases down the group. Solubility for alkali metal halides
doesnot show a regular trend.
1. NaCl
Preparation :
It occurs in sea water as deposits in mines as rock salt. It is extracted from sea water simply by
solar evaporation. The crystals of NaCl are washed to remove more soluble MgCl2.
Properties :
(i) It is colourless crystalline (in pure form). it is NOT hydroscopic but pressence of MgCl2
makes it deliquescent due to the high polarizing power of MgCl2 (that attracts H2O molecules)
(ii) It is used to produce industrially important compounds like Na2CO3 and Cl2.
(a) Na2CO3 is produced by Solvay’s Process. (discussed later)
(b) Cl2 is produced by :
(i) Electrolysis (NaOH is also a product) of brine.
(ii) Leblanc Process : NaCl  conc. H 2SO4 
 NaHSO4  HCl
heat
NaHSO4  NaCl 
 Na 2SO4  HCl
 Cl2  Mn 2 
HCl  MnO2 
Uses :
(i) Eating salt in food.
(ii) It is used to lower the melting point of ice. Kulfi seller uses NaCl to sustain Kulfi for long time
in summer.
KCl is also extracted from sea water. Its properties are almost similar to NaCl. It has an important
use in producing fertilizers.
Gruop - II
Alkaline earth metal halides are generally made by heating matals with halogen or by action of halogen
acid on metal or metal or metal carbonates. Beryllium halides are covalent while rest of the alkaline
earth metals form ionic halides.
BeCl2 has a chain structure as shown in the figure.

Here Cl bonded to one Be uses a lone pair of e–s to form a coordinate bond to another Be atom.
Dehydration of hydrated chlorides, bromides and iodies of Ca, Sr, Ba can be achieved on heating but the
hydrated halides of Be and Mg suffer hydrolysis on heating. In aqueous solution BeCl2 , Be exists as
2
 Be  H 2O   or  Be  H 2O 4  Cl2 .
 4
heat
 Be  H 2O   Cl2   Be  OH  2  2HCl
 4
1. Magnesium Chloride [MgCl2 . 6H2O]

Preparation
(i) It is prepared by passing dry HCl over Magnesium.
Mg  2HCl 
 MgCl2  H 2 
(ii) Dow’s process :

The extraction of Magnesium from sea water depends on the fact that Mg(OH)2 is very much less
soluble than Ca(OH)2.
Ca(OH)2  MgCl2 
 Mg (OH)2   CaCl2
(in sea water )
acidified
Mg(OH)3  MgCl2(aq) ( MgCl2 . 6H 2O)
with HCl
dry HCl
MgCl 2 . 6H 2 O  MgCl2  6H 2 O
Cl 2 /SOCl 2
Note : If MgCl2 . 6H2O is heated, then the products are MgO and HCl. So water of crystallisation are removed
by passing dry HCl/Cl2 or SOCl2.
Properties
(i) It is colourless solid, highly soluble in water.
(i) When heated, it decomposes


MgCl2 . 6H2O 
 Mg(OH) Cl  HCl  5H2O

Mg(OH) Cl 
 MgO  HCl
Uses :
It is used in electrolytic method for extracting Magnesium.
2. Calcium Chlorid [CaCl2 . 6H2O]
Preparation
It is formed as Solvay’s Process’ by-product.
Properties
(i) It reduces the freezing pt. of water.
(ii) Anhydrous salt is an excellent drying agent. It forms addition compounds with NH3 and CH3OH
(CaCl2 . 8NH2 and CaCl2 . 4CH2OH) and hence cannot be used to dry them.
Uses :
It is sprinkled on roads in hilly areas to remove snow.
4. Carbonates :
Gruop - I
Alakli metal carbonates are basic salts. The stability of alkali metal carbonates towards heat increases
down the gourp. Thye quite stable and melt before they eventually decompose into oxides (at above
1000oC).
1. Sodium Carbonate (Na2CO3) :
Washing soda is Na2CO3 . 10H2O
Soda ash in Na2CO3
Preparation :
Solvays’s Process (Ammonia-Soda Process)
The process is much more complicated than the overall equation and since the reactions involved
are reversible only 75% of the NaCl is converted.
The purified brine (NaCl) solution is first saturated with ammonia and then carbonated with CO2
forming NaHCO3
 HCO3  H 
CO2  H2O  ; NH3  H 
 NH 4
NH 4  HCO3  NaCl 
 NaHCO3  NH 4Cl

The NaHCO3 formed is insoluble in the brine solution becasue of the common ion effect and so can
be filtered off. This is then heated to form anhydrous Na 2CO3 .
150C
2NaHCO3  Na 2CO3  H2O  CO 2
NH4Cl produced above reacts with lime water forming a very good dehydrating agent (CaCl2) and
evolving NH3 gas.
2NH 4Cl  Ca  OH 2 
 CaCl 2  2NH 3  2H 2O
Lime water used above was prepared instantaneously by heating CaCO3 and passing water through
quick lime.

CaCO3  CaO  CO 2 ;  Ca  OH  2
CaO  H 2O 
The materials consumed are NaCl and CaCO3 and the useful product is Na2CO3. CaCl2 which is a
by prodcut is little used and the rest is wasted. CO2 and NH3 formed are used again to continue the
process.
The whole process can be diagrammatically shown as :
Properties :
(i) On passing CO2 through aqueons solution of Na2CO3, NaHCO3 is formed.
Na 2CO3  CO2  H2O 

 2NaHCO3 
(ii) When aqueous solution of sodium carbonate containing sulphur is treated with sulphur dioxide,
sodium thiosulphate is formed.
Na 2CO3  SO2  H2O 

 Na 2SO3  CO2 
Na 2SO3 + S 
 Na 2S2O3

(iii) On heating washing soda (Na 2CO3 10 H 2O) it forms monohydrate called heavy ash or crystal
carbonate.

Na 2CO3 . 10H 2O 
 Na 2CO3 . H 2O  9H 2O
Uses :
(i) Used in water softening and cleaning.
(ii) Used in paper, paint and textile industries
Potassium carbonate (Pearl Ash) is not much important. Its properties resemble closely with
Na2CO3. It is prepared by carbonation of caustic potash.
KOH  CO2 
 K 2CO3  H2O
Note : K2CO3 cannot be prepared by Solvay’s Process because KHCO3 formed in the reaction is highly soluble
and hence cannot be separated form (NH4Cl + KHCO3) mixture easily.
Gruop - II
Carbonates are basic salts. BeCO3 is covalent while other carbonates are ionic. On heating, alkaline earth
metal carbonates forms an oxide and carbon dioxide is evolved.
1. Calcium Carbonate [CaCO3] :
Preparation :
It is mainly extracted from its ores. It can be prepared by these methods also :
(i) It can be prepared by passing limited CO2 through lime water.
Ca(OH)2  CO 2 
 CaCO3  H 2O
(ii) It can be obtained by adding sodium carbonate solution to CaCl2.
CaCl2  Na 2CO3 
 CaCO3  2NaCl
Properties :
(i) It is white powder, almost insoluble in water.
1200 K
(ii) On heating at 1200 K, CO2 is evolved CaCO3   CaO  CO2 (  )
(iii) CaCO3  HCl 

 CaCl2  H2O  CO2 (  )



H2CO3

Uses :
(i) It used in manufacture of cement and quick lime.
(ii) Used in Solvay’s process in the manufacture of Ca(OH)2.
(iii) It is used in toothpaste.
5. Bicarbonates
Gruop - I
Alkali metal are strongly basic and form solid bicarbonates (execpt lithium) while no other melal forms
solid bicarbonates LiHCO3 can exist only in solution. Alkali metal hydrogen carbonates are soulble in
water. On heating, they decompose to give carbonates.
The hydrongen bonding in bicarbonates enhances the stability. In NaHCO3, the HCO3 ions are
linked to form infinite chain while in KHCO3, a dimeric anion is formed.
As the electropositive character increase down the group, the stability of hydrogen carbonates also
increases down the group.
1. Sodium Bicarbonate [NaHCO3] (Baking Soda)
Preparation :
It is an intermediate product of Solvay’s process.
NaCl  NH 4  HCO3 
 NaHCO3  NH 4Cl
Properties :
On heating, it decomposes to give Na2CO3, evolving CO2 which is used to detect bicarbonates.

NaHCO3 
 Na2CO3  H2O(  )  CO2 (  )
Uses :
(i) It used in fire extinguisher.
(ii) It is used as baking powder in manufacturing of cake making it fluffy. Backing powder contains
NaHCO3 and Ca(H2PO4)2

50  100C
2NaHCO3  Na 2CO3  H 2O  CO 2 
Ca  H 2 PO 4  2  NaHCO3 
 CO 2 
The CO2 produced makes cake or bread rise.
6. Sulphates
Gruop - I
Sodium sulphate (Na2SO4 . 10H2O) is named as Glauber’s salt. It is produced as a by-product while
manufacturing HCl.

NaCl  H 2SO 4 
 NaHSO4  HCl  ; NaHSO 4  NaCl 
 Na 2SO 4  HCl 
 conc. salt cake 
Fomation of hydrated salts of Na2SO4 :
T  32C T  12C
Na 2SO4 
 Na 2SO 4 .10H 2O ; Na 2SO 4 
 Na 2SO4 . 7H 2O
It is used in paper industry.
Gruop - II
Sulphates of the alkaline earth metals are all white solids & stable to heat. Be and Mg sulphate are
highly soluble while other alkaline earth metal sulphates are very less soluble. This is due to very high
hydration enthalpy of Be2+ and Mg2+. Thermal stability of alkaline earth metal sulphates increases
down the group while solubility decreases.
1. Magnesium Sulhate [MgSO4]
It is a colourless soluble salt whcih decomposes to MgO, SO2 and O2 on heating.
MgSO4 . 7H2O is called Epsom salt while MgSO4.H2O is called Kieserite.
2. Calcium Sulphate [CaSO4]

Preparation :
It is prepared in lab by adding dil. H2SO4 to the solution of calcium salt.
CaCl2  H 2SO 4  dil  

 CaSO 4  2HCl

Properties :
In nature it occurs as Gypsum CaSO 4 . 2H 2O.
150C 1 200C 1100C 1

CaSO 4 .2H 2O  CaSO4 . .H 2O   CaSO 4   CaO  SO 2  O 2
2 2
gypsum Plaster of paris anhydrite
When powdered plaster of paris CaSO4 . 1/2 H2O is mixed with the correct amout of water it sets
into a solid mass of CaSO4 . 2H2O (gysum). The process is used in plastering walls and plasters for
fractures.
ALUMS
The general representation of alums is [(M1 ) 2 SO 4 ] [(M III ) 2 (SO 4 )3 ]. 24 H 2O where M I represents the
metal with +1 Oxidation state and MIII represents the metal with +3 oxidation state. These alums are double
salts, which dissolve in water to give [M I  H 2O 6 ] , [M III  H 2O 6 ]3 and SO 42 ions and there-
fore., the alums are also represented as [M I  H 2O 6 ], [M III  H 2O 6 ] (SO 4 ) 2 . They form octahedral
crystals.
If MI is K  and M III is Al3 , Then the alum is potash alum  K2SO4 , Al2 (SO4 3 . 24H2O
     III
or [K(H 2O)6 ] [Al(H 2O)6 ] (SO 4 ) 2 M1 can be K , NH 4 , Rb , Cs , TL and M can be
Fe3 , Al3 , CO3 , Ga 3 , Mn 3 .  NH 4  2 SO 4 .Fe2 SO 4 3 .24H 2O is called ferric ammonium alum
while K 2SO4 .Cr2  SO 4 3 .24H 2O is chrome alum. Potash alum on heating dissolves in its own water of
crystallisation and on further heating forms K 2SO 4 .Al2  SO4 3 called burnt alum.
Micro Cosmic Salt [Na(NH4)HPO4]

Microcosmic salt is a white crystallion solid and is prepared NH4Cl and Na2HPO4 as follows :
 Na  NH 4  HPO4   NaCl
NH 4Cl  Na 2HPO 4 
On decomposition the following is obtained :


Na  NH 4  HPO 4 
 NH 4   NaH 2 PO 4

 NaPO3  Calgon   H 2O
NaH 2 PO 4 
Microcosmic salt can be used as a substitue for borax in the Bead Test

Similar salt are also formed by Magnesium :
 Mg  NH 4  PO 4
MgSO 4  NH 4 OH  Na 2HPO4 
 
Mg  NH 4  PO 4 
 NH3  MgHPO 4  Mg 2P2O7  H 2O
IMPORTANT THINGS TO REMEMBER Section - 4
Anomalous properties of Lithium :

The anomalour behaviour of lithium is due to the : (i) exceptionally small size of its atoms and ion, and (ii)
high polarizing power (i.e., charge/radius ratio). As a result, there is increased covalent character of lithium
compounds which is resposible for their solubility in organic solvents. Further, lithium showns diagonal
relationship to magnesium which has been discussed subsequently.
Points of Difference between Lithium and other Alkali Metals :
(i) Lithium is much harder. Its M.P. and B.P. are higher than the other alkali metals.
(ii) Lithium is least reactive but the strongest reducing agent among all the alkali metals. On combustion in
air it forms mainly monoxide, Li2O and the nitride, Li3N while other metals form only oxide.
(iii) LiCl is deliquescent and crystallizes as a hydrate, LiCl.2H2O whereas other alkali metal chlorides do
not form hydrates.
(iv) Lithium hydrogencarbonates being unstable is not obtained in the solid form while all other elements
form solid hydrogencarbonates.
(v) Li2CO3, LiNO3,LiOH all form oxide on gentle heating, throgh the analogus compounds of the rest of
the group are stable.
4LiNO3 
 2Li2O  4NO 2  O 2
2NaNO3 
 2NaNO2  O2
(vi) Li2CO3, LiF and Li2O are comparatively much less soluble in water than the corresponding com-
pounds of other alkali metals.
(vii) Lithium is much heavily hydrated than those of the rest of the group.
Points of Similarities between Lithium and Magnesium :

The similarity between lithium and magnesium is particularly striking and arises because of their similar sizes
: atomic radii, Li = 152 pm, Mg = 160 pm; ionic radii : Li+ = 76 pm, Mg2+ = 72 pm. The main points of
similarity are:

(i) Both lithium and magnesium are harder and lighter than other element in the respective group.
(ii) Lithium and magnesium react slowly with water. Their oxides and hydroxides are much less soluble
and their hydroxides decompose on heating. Both form a nitride, Li3N and Mg3N2, by direct combi-
nation with nitrogen.
(iii) The oxides Li2O and MgO do not combine with excess oxygen to give any superoxide.
(vi) The crbonates of lithium and magnesium decompose easily on heating to form the oxides and CO2.
Solid hydrogencarbonates are not formed by lithium and magnesium.
(v) Both LiCl and MgCl2 are soluble in ethanol.
(vi) Both LiCl and MgCl2 are deliquescent and crystallize from aqueous solution as hydrates. LiCl.2H2O
and MgCl2.8H2O
Anomalour Behaviour of Beryll ium :

Beryllium, the first member of the Group 2 metals, shows anomalous behaviour as compared to magnesium
and rest of the members. Further, it shows diagonal relationship to aluminium which is discussed subse-
quently.
(i) Beryllium has exceptionally small atomic and ionic sizes and thus does not compare well with other
members of the group. Because of high ionization enthalpy and small size it forms compounds which
are largely covalent and get easily hydrolysed.
(ii) The oxide and hydroxide of beryllium, unlike the hydroxides of other elements in the group, are
amphoteric in nature.
Diagonal Relationship between Beryllium and Aluminum :

The ionic radius of Be2+ is estimated to be 31 pm; the charge / radius ration is nearly the same as that of the
Al3+ ion. Hence beryllium resmebles aluminium in some ways. Some of the similarities are :
(i) Like aluminium, beryllium is not readily attacked by acids beacuse of the presence of an oxide film on
the surface of the metal.
(ii) Beryllium hydroxide dissolves in excess of alkali to give a beryllate ion, [Be(OH)4 ]2  just as alu-
minium hydroxide give aluminate ion, [Al(OH) 4 ] .
(iii) BeCl2 and AlCl3 exist in form to chain. BeCl2 form polymeric chain (chain with a large no. of BeCl2
molecules) and AlCl3 forms dimeric chain (chain with two AlCl3 molecules).
(iv) Beryllium and aluminium ions have strong tendency to form complexes, BeF42  , AlF63 .

IN-CHAPTER EXERCISE - D
1. NaHCO3 and NaOH can not exist together in solution. Why ?

2. The hydroxide and carbonates of Na and K are easily soluble in water while the corresponding salts
of Mg and Ca are sparingly soluble in water. Explain.
3. Solvay Process is used to manufacture sodium carbonate but it is not extended to the manufacture of
potassium carbonate. Why ?
4. Why are MgO and BeO used for the lining of steel making furnance.
5. On the treatment with cold water, an element (A) reacted quietly, liberating a colourless, odourless
gas (B) and a compound (C). Gas (B) further reacts with element (A) to yield a solid product (D)
which reacted with water to give a basic solution (E). (E) is found to be same as (C). When carbon
dioxide was bubbled through solution (C) initially a white precipitate (F) is formed, but this redissolved
forming solution (G) when more CO2 was added. Precipitate (F) was heated at 1000C , a white
compound (H) was formed which when heated with carbon at 1000C , gave a solid (I) of some
commercial importance. Name the substances (A) to (I).

HYDROGEN Section - 5
Postion of Hydrogen in the Periodic Table

Hydrogen has electronic configuration 1s1. On one hand, its electronic configuration is similar to the outer
electronic configuration (ns1) of alkali metals, which belong to the first group of the periodic table. On the
other hand, like halogens (with ns2 np5 configuration belonging to the seventeenth group of the periodic
table). it is short by one election to the corresponding noble gas configuration, Helium (1s2). Hydrogen,
therefore, has resemblance to alkali metals, which lose one electron to form uni-positive ions, as well as with
halogens, whcih gain one electron to form uni-negative ion. Like alkali metals, hydrogen forms oxides,
healides and sulphides. However, unlike alkali metals, it has a very high ionization enthalpy and does not
possess metallic characteistics under normal conditions. In fact, in terms of ionization enthalpy hydrogen
resembles more with halogens, i H of Li is 520 kJ mol 1, H of F is 1680 kJ mol1 and i H of H
is 1312 kJ mol 1. Like halogens, if forms a diatomic molecule, combines with elements to form hydrides
and a large number of covalent compounds. However, in terms of reactivity, it is very low as compared to
halogens. It is always a matter of debate in which group hydrogen should be placed. It is best placed
separtely in the periodic table.
Isotpes of Hydrogen
Hydrogen has three isotopes : Protium (11 H), Deuterium (12 H) or D and Tritium (13 H) or T. These isotopes
differ from one another in respect of the presence of neutrons. Ordinary hydrogen, Protium, has no neu-
trons. Deuterium (also know as Heavy Hydrogen) has one and Tritium has two neutrons in the nucleus.
The predominant form is Protium. Terrestrial hydrogen contains 0.156% of Deuterium mostly in the form of
HD. The Tritium concentration is about one atom per 1018 atoms of Protium. Of these isotopes, only Tritium
is radioactiver and emits low energy Particles (t1/2 = 12.33 years).
Since the isotopes have the same electronic configuration, they have almost the same chemical properties.
The only difference is in their rates of reactions, mainly due to their different enthyalpy of bond dissociation.
Property Hydrogen Deuterium Tritium

Relative abundance (%) 99.985 0.0156 10-15
Relative atomic mass (g mol) 1.008 2.014 3.016
Melting point (K) 13.96 18.73 20.62
Boiling point (K) 20.39 23.67 25.0
Density (g L-1) 0.09 0.18 0.27

Prepartion of Dihydrogen, H2
There are a number of methods for preparing dihydrogen from metals and metals and hydrides.
Laboratory Preparation of Dihydrogen
1. It is usually prepared by the reaction granulated zinc with dilute hydrochloric acid.
Zn  2H  
 Zn 2   H 2
2. It can also be prepared by the reaction of zinc with aqueous alkali.
Zn  2NaOH 
 Na 2 ZnO 2  H2
Sodium Zincate
Commercial Production of Dihydrogen :

1. Electroysis of acidified water using platinum electrodes gives hydrogen. This method gives very pure
H2 but it is very expensive
Electrolysis
2H2O 1 
 2H2  g   O2  g 
Traces of acid /base
2. It is obtained as a by product in the manufacture of sodium hydroxide and chlorine by the electrolysis
of brine solutionn. During electrolysis, the reactions that take place are :
At anode : 2Cl  aq  
 Cl2  g   2e
At cathode : 2H 2O  l   2e  
 H 2  g   2OH   aq 
The overall reaction is
2Na   aq   2Cl  aq   2H 2O  l  
 Cl2  g   H 2  g   2Na   aq   2OH   aq 
3. Reaction of steam on hydrocarbons or coke at high temperatures in the presence of catalyst yields
hydrogen.
1270K
 nCO   2n  1 H 2
Cn H 2n  2  nH 2O 
Ni
1270K
CH 4  g   H 2O  g  
 CO  g   3H 2  g 
Ni
The mixture of CO and H2 is called Water gas. As this mixture of CO and H2 is used for the synthesis
of methanol and a number of hydrocarbons, it is also called sythesis gas or ‘Syngas’.Nowadys‘syngas’
is produced from sewage, saw-dust, scrap wood, newspapers etc. The process of producing ‘synags’
from coal is called ‘Coal gasification’.
1270K
C  s   H 2O  g  
 CO  g   H 2  g 

It is difficult to obtain pure H 2 from water gas, since CO is difficult to remove. Still CO may be liquified at
a low temperature under pressure. Thus seperating it from H 2 . One more thing that can be done is the gas
mixture can be mixed with steam, cooled to 400°C and passed over iron oxide to give H 2 and CO2 .
Fe
CO + H 2O  CO2 + H 2
This is called Water - gas shift reacrion. This reaction increases the amount of H2 and gives a method to
extract H2 easily. CO2 in mixture of CO2 and H2 can be removed by dissolving mixture in water under
pressure, or reacting mixture K2CO3 solution giving KHCO3, or by scrubbing mixture with sodium arsenite
solution.
 Dihydrogen is a colouless, odourless, tasteless, combustible gas. It is lighter than air and insoluble in
water.
The chemical behaviour of dihydrogen (and for that mattter any molecule) is determined, to a large extent,
by bond issociation enthyalpy. The H-H bond dissociations enthalpy is the highest for a single bond between
two atoms any element. It is because of this factor that the dissociation of dihydrogen into its atoms is only
 0.081% around 2000K which increases to 95.5% at 5000K. Also, it is relatively inert at room tempera-
ture due to the high H-H bond enthalpy.
1. Reaction with halogens : It reacts with halogens, X2 to give hydrogen haliides, HX.
H 2  g   X 2  g  
 2HX  g   X  F, Cl, Br, I 
While the reaction with fluorine occurs even in the dark, with iodine it requires a catalyst.
2. Reaction with Dioxygen : It reacts with dioxygen to form water. The reaction is highly exothermic.
catalyst of heating
2H 2  g   O 2  g  
 2H 2O  l  ; H   285.9 kJ mol 1
3. Reaction with dinitrogen : It reacts with dinitrogen to form ammonia.
673K, 200atm
3H 2  g   N 2  g   2NH3  g  ; H   92.6 kJ mol1
Fe
This is the method for the manufacture of ammonia by the Haber’s process.
4. Reactions with metals : With many metals it combines at a high temperature to yield the corre-
sponding hydrides.
H 2  g   2M  g  
 2MH  s  ; where M is an alkali metal

5. Reaction with metal ions and metal oxides : It reduces some metal ions in aqueous solution
and oxides of metals (less active than iron) into corresponding metals.
H 2  g   Pd 2   aq  
 Pd  s   2H  (aq)
yH 2  g   M x O y  s  
 xM  s   yH 2O 1
6. React ion w it h organic com pounds : It reacts with many organic compounds in the presence of
catalysts to give useful hydrogenated products of commercial importance. For example :
Hydrogenation of vegetable oils using nickel as catalyst give edible fats (margarine and vanaspathi
ghee).
Uses of Dihydrogen
 The largest single use of dihydrogen is in the synthesis of ammonia which is used in the manufacture of
nitric acid and nitrogenous fertilizers.
 Dihydrogen is used in the manufacture of vanaspati fat by the hydrogenation of polyunsaturated veg-
etable oils like soyabean, cotton seeds etc.
 It is used in the manufacture of bulk organic chemicals, particularly methanol.
cobalt
CO  g   2H 2  g   CH3OH  l 
catalyst
 It is widely used for the manufacture of metal hydrides.
 It is used a rocket fuel in space research.
 Dihydrgoen is used in fuel cells for generating electrical energy. If has many advantages over the
conventional fossil fuels and electric power. It does not produce any pollutions and releases greater
energy per unit mass of fuel in comparison to gasoline and other fuels.
Hydrides
Binary compounds of the elements with hydrogen are called hydrides. The type of hydride which an element
forms depends upon its electronegativity and hence on the type of bond formed. Hydrides are conveniently
studied under three classes.
(i) Ionic or salt like hydrides
(ii) Covalent or molecular hydrides
(iii) Metallic or interstitial hydrides
 Ionic or salt like hydrides : These are formed by metals of low electronegativity, i.e. alkali and
alkaline earth metals by direct reaction with H2 and some highly positive members of lanthanide series
with the exception of Be and Mg whose hydrides show significiant covalent character.

Te stability of the hydrides decreases as the size of the cation increases.
LiH  NaH  KH  RbH  CsH

CaH 2  SrH 2  BaH 2
CaH2 is called Hydrolith.

 Covalent or Molecular hydrides : These hydrides are formed by all the true non-metals (except
zero group elements) and the elements like Al, Ga, Sn, Pb, Sb, Bi. Po, etc., which are normally
metallic in nature. The simple hydride of B and Ga are dimeric materials B2H6 (diborane) and Ga2H6
respectively and the hydride of aluminium is polymeric in nature, (AlH3)n.
 Metallic or interstitial hydrides : Many transition and inner-transition elements at elevated tem-
peratures absorb hydrogen into the interstices of their lattices to yield metal-like hydrides, often called
the interstitial hydrides. These hydrides are often non-stoichiometric and their composition vary with
temperature and pressure. Formulae of some of the hydrides of this class are :
TiH1.73 , CeH 2.7 , LaH 2.8 , PdH 0.60 , ZrH1.92
The interstitial hydrides have metallic appearance and their properties are closely related to those of
the parent metal. They posses reducing properties probably due to the presence of free hydrogen
atoms in the metal lattice.
Water
In the gas phase water is a bent molecule with a bond angle of 104.5o, and O-H bond length of 95.7 pm. It
is a highly polar molecule. Its orbital overlap is shown in figure below. In liquid phase, water molecules are
associated together by hydrogen bonds. In ice each oxygen atom is surrounded tetrahedrally by four other
oxygen atoms at a distance of 276 pm.
Chemical Properties of Water :

Water reacts with a large number of substances. Some of the important reactions are given below.
1. Amphoteric Nature : It has the ability to act as an acid as well as a base i.e., it behaves as an
amphoteric substance. In the Bronsted sense it acts as an acid with NH3 and a base with H2S.


H 2O  l   NH3  aq    
 OH  aq   NH 4  aq 


H 2O  l   H 2S  aq    
 H3O  aq   HS  aq 

The auto-protolysis (self-ionization) of water takes places as follows :


H 2O  l   H 2O  l   
 H3O  aq   OH   aq 
acid 1 base  2 acid  2 base  1
 acid   base   conjugate acid   conjugate base
2. Redox Reactions Involving Water : Water can be easily reduced to dihydrogen by highly electroposi-
tive metals.
2H 2O  l   2Na  s  
 2NaOH  aq   H 2  g 
Water is oxidised to O2 during photosynthesis.
6CO 2  g   12H 2O  l  
 C6 H12O6  aq   6H 2O  l   6O 2  g 
With fluorine also it is oxidized to O2.
 4H   aq   4F  aq   O 2  g 
2F2  g   2H 2O  l  
3. Hydrolysis Reaction : Due to high dielctric constant, it has a very strong hydrating tendency. It dissolves
many ionic compounds. However, certain covalent and some ionic compound are hydrolysed in water.
P4O10  s   6H 2O  l  
 4H3PO 4  aq 
SiCl4  l   2H 2O  l  
 SiO2  s   4HCl  aq 
N3  s   3H 2O  l  
 NH 3  g   3OH   aq 
4. Hydrates Formation : From aqueous solutions many salts can be crystallised as hydrated salts. Water of
hydration are water molecules atttached to a compound that can be removed on heating. Such an associa-
tion of water is of different types viz.,
3
(i) Coordinated water e.g.,  Cr  H 2O   3Cl
(ii) Interstitial water e.g., BaCl2 . 2H 2O
2
(iii) Hydrogen-bonded wate e.e.,  Cu  H 2O 4  SO42  . H 2O in CuSO4 . 5 H 2O
Here in CuSO 4 . 5H 2O, four water molecules of hydration are coordinate bonded and one is hydro-
gen bonded.
Note : You will learn about hyrates later in Coordination Compounds.

*Hard and Soft Water :

Rain water is almost pure (may contain some dissolved gases from the atmosphere). Being a good solvent,
when it flows on the surface of the earth, it dissolves many salts. Presence of calcium and magnesium salts
in the form of hydrogencarbonate, chloride and sulphate in water makes water ‘hard’. Hard water does not
give lather with soap. Water free from soluble salts of calcium and magnesium is called Soft water. It gives
lather with soap easily.
Hard water forms scum/precipitate with soap.Soap containg sodium strearate (C17H35COONa) reacts
with hard water precipitate out Ca/Mg strearate.
2 RCOONa(aq) + M 2+ (aq) 
 (RCOO)2 M  +2 Na + (aq) ; M is Ca/ Mg
Scum
e.g., 2C17 H35COONa  aq   Ca 2   aq  

  C17 H35COO 2 Ca   2Na   aq 
Scum
It is, therefore, unsuitable for laundry.
The hardness of water is of two types :
(i) Temporary hardness, and (ii) Permanent hardness.
Temporary Hardness :
Temporary hardness is due to the presence of magnesium and calcium hydrogen-carbonates. It can be
easily removed by :
1. Boiling : During boiling, the soluble Mg(HCO3)2 is converted into insoluble Mg(OH)2 and Ca(HCO3)2
changed to insoluble CaCO3. These precipitates can be removed by filteration.
Heating
Mg  HCO3 2 
 Mg  OH 2   2CO 2 
Heating
Ca  HCO3 2 
 CaCO3   H 2O  CO 2 
2. Clark’s method : In this method calculated amount of lime is added to hard water. It precipitates out
calcium carbonate and magnesium hydroxide which can be filtered off.
Ca  HCO3 2  Ca  OH  2 
 2CaCO3   2H 2O
Mg  HCO3 2  2Ca  OH 2 
 2CaCO3   Mg(OH)2   2H 2O
Note : Temporary hardness such as Ca(HCO3 )2 can also be removed by adding Na 2CO3 .
Ca(HCO3 )2 + Na 2CO3 
 CaCO3  +2 NaHCO3
Permanent Hardness :
It is due to the presence of soluble salts of magnesium and calcium in the form of chlorides and sulphates in
water. Permanent hardness is not removed by boiling. It can be removed by the following methods:

1. Treatment with washing soda (Sodium carbonate) :
MCl2  Na 2CO3 
 MCO3   2NaCl (M  Mg, Ca)
MSO4  Na 2CO3 
 MCO3   Na 2SO4
(Washing soda)
2. Calogen’s method : Sodium hexametaphosphate (Na6P6O18), commercially called ‘Calgon’ or Graham’

salt’, when added to hard water, the following reactions take place :
 2Na   Na 4 P6O182 
Na 6 P6O18  M  Mg, Ca 
2
M 2   Na 4 P6O182  
  Na 2 MP6O18   2Na 
The complex anion keeps the Mg 2  and Ca 2  ions in solution.

3. Ion-exchange method : This method is also called zeolite/permutit process. Hydrated sodium aluminium
silicate is zeolite/permult prcess. For the sake of simplicity, sodium aluminum silicate (NaAlSiO4) can be
written as NaZ. When this is added in hard water, exchange reactins take place.
2NaZ(s)  M 2  (aq) 
 MZ2 (s)  2Na  (aq) (M  Mg, Ca)
Permutit/zeolite is said to be exhausted when all the sodium in it is used up. It is regenerated for further use
by treating with an aqueous chloride solution.
MZ2 (s)  2NaCl (aq) 

 2NaZ (s)  MCl2 (aq)
4. Synthetic Resins Methods : It is used in the prodcution of deionised water and more efficient than the
Zeolite process.
Water is passed through two differnt ion-exchange columns :
1st Column (Cation Exchange Coloumn) :
The resin exchange H  with Na  , Ca 2  and Mg 2 
resin  SO3H  M  
 resin  SO3M  H 
 
sulphonic acid
resin
2nd Coloumn (Anion Exchange Column) :
The resin exchanges OH  with Cl  , HCO3 , SO 42 
resin  NR 4 OH   X  
 resin NR 4 X   OH 
 
re sin with basic
group

When all reactive sites on resins have been used they can be regenerated by treating first one with dil.
H 2SO 4 and second one with Na 2CO3 solution.
Heavy water, D2O

It is extensively used as a moderator in nuclear reactors and in exchange reactions for the study of reaction
mechanisms. It can be prepared by exhaustive electrolysis of water or as a by-product in some fertilizer
industries. It is used for the preparation of other deuterium compounds, for example :
 C2 D 2  Ca  OD 2
CaC2  2D 2O 
SO3  D2O 
 D 2SO 4
 3CD4  4Al  OD 3
Al4C3  12D 2O 
DEGREE OF HARDNESS Section - 6
Concentration of Solute in Terms of Parts per Million (or ppm) :

Concentration of solute ( in ppm) = mass of solute ( in gms) in 106 ml solution
It is used in determining the hardness of water which is due to the presence of bicarbonates (temporary
hardness), chlorides and sulphates (permanent hardness) of Calcium and Magnesium. Degree of Hardness
is defined as the number of parts of CaCO3 or equivalent to other calcium and magnesium salts present in
a million (106 ) parts of water..

Mass of CaCO3
Degree of Hardness   106 ppm
Mass of water

How to calculate degree of hardness in a water sample containing 111 ppm of CaCl2 ?
100 111
E CaCO3 = = 50 ; E CaCl 2 = = 55.5
2 2
which means 50 gm of CaCO3  55.5 gm CaCl2
or 55.5 gm CaCl2  50 gm of CaCO3
 111.0 gm CaCl2  100 gm of CaCO3  100 ppm

Illustration - 1Calculate the weight of CaO required to remove hardness of 106 L of water contain-
ing 1.62 gm of Ca(HCO3 )2 in 1.0 litre .
Solution :
Consider the reaction between CaO and Ca(HCO3 )2 .  moles of CaO required for 1.0 L of sample
= 0.01 (from stoichiometry)
CaO+ Ca(HCO3 )2 
 2 CaCO3 + H 2O
 moles of CaO required for 106 L of water
From stoichiometry, we have :
1 mole of Ca(HCO3 )2  1mole of CaO  0.01  106  104 moles.
 2 moles of CaCO3  grams of CaO  104  56  5.6  105 gm.
Now moles of bicarbonate in 1.0 L of sample
1.62
  0.01 [ M 0 of Ca(HCO 3 ) 2 = 162]
162
Illustration - 2 A particular water sample is found to contain 96.0 ppm of SO42  and 122.0 ppm of
HCO3 , with Ca 2  as the only cation. How many ppm of Ca 2  does this water contain ?
Solution :
CaSO 4  Ca 2+ + SO 42  96 ppm  96 g SO 24  in 106 mL H 2O
Ca(HCO3 ) 2  Ca 2+ + 2 HCO3  1.0 mol of SO 24   1.0 mol of Ca 2+

Every mol of CaSO 4 has equal mol of 122 ppm = 122 g HCO 3 in 10 6 mL H 2 O
Ca 2+ and SO 24  but every mole of
 2.0 mol of HCO3  1.0 mol of Ca 2+
Ca(HCO3 )2 has Ca 2+ half the mol of HCO3 .
Total Ca 2+ = 1+1 = 2.0 mol of Ca 2+
 80 g in10 6 mL H 2O
 Ca 2+  80 ppm

Illustration - 3 A sample of hard water contains 1 mg CaCl3 and 1 mg MgCl3 per litre. Calculate the
hardness of water in terms of CaCO3 present in per 106 parts of water..
Solution :
50
55.5 gm CaCl2  50 gm CaCO3  1 mg CaCl2  mg CaCO3  0.9 mg CaCO3
55.5
47.5 gm MgCl2  50 gm CaCO3 50

 1mg MgCl2  mg CaCO3  1.05 mg CaCO 3
47.5
(0.9 +1.05)×103 gm
 Hardness in CaCO3 ppm   1.95ppm
1/1000
Illustration - 4 A sample of hard water contains 244 ppm of HCO3 ions. What is the minimum mass of
CaO required to remove ions completely from 1 kg of such water sample ?
Solution :
244 ppm HCO3  244 gm HCO3 in 1000 L  244 mg HCO3 in 1.0 L  4 mmoles HCO3 in 1.0 L
 2 mmoles Ca(HCO3 )2 in 1.0 L
 2CaCO3 + H 2O 
CaO + Ca(HCO3 )2   2 mmoles CaO in 1.0 L  2  56  112 mg CaO
Illustration - 5 250 ml of hard water is treated with 100 ml of 0.1 N Na2 CO3 to remove temporary
hardness. Excess of Na2 CO3 required 40 ml, 0.1 N HCl for complete neutralization. Calculate degree of
hardness of water.
Solution :
Meq of Na 2CO3 = meq of Ca(HCO3 )2 + meq of HCl
in hard water
Meq of CaCO3 formed = meq of Ca(HCO3 )2 = meq of Na 2CO3 + meq of HCl

in hard water
 100  0.1  40  0.1  6

6
mmoles of CaCO3 formed  3 (in factor of CaCO3 = 2 )
2

Mass of CaCO3 formed  3  103  100  0.3 gm

Mass of hard water sample = 250 gm (Assuming density of water = 1 gm/ml)
Mass of CaCO3
Degree of Hardness  106 ppm
Mass of water
0.3
  106 ppm  1.2  103 ppm
250
IN-CHAPTER EXERCISE - E
1. How can the dihydrogen be obtained from coal gasification method ? How is its production enhanced ?
2. Arrange the following :
(i) CaH 2 , BeH 2 and TiH 2 in order of increasing electrical conductance.
(ii) LiH , NaH and CsH in order of increasing ionic character..
(iii) H - H, D - D and F – F in order of increasing bond dissolciation enthalpy.
(iv) NaH, MgH 2 and H 2O in order of increasing reducing property .

SOLUTION TO IN-CHAPTER EXERCISE - D
1. NaHCO3  NaOH   Na 2CO3  H 2O

2. It is because hydration energy of group 1 hydroxides and carbonates is higher than lattice energy where as
in group 2 hydroxides and carbonates lattice energy dominates hydration energy.
3. K2CO3 can’t be prepared from soluay’s process because KHCO3 formed in the reaction is highly soluble
and hence can’t be separated from NH4Cl + KHCO3 mixture easily.
4. MgO and BeO are used for lining of steel making furnance because they are less reactive, have high melting
point, good conductivity towards heat and bad conductivity towards electricity.
5. Note : Read the question as this :
On the treatment with cold water, an element (A) reacted quietly, liberating a colourless, odourless gas (B)
and a compound (C). Gas (B) further reacts with element (A) to yield a solid product (D) which reacted
with water to give a basic solution (E). (E) is found to be same as (C). When carbon dioxide was bubbled
through solution (C) initially a white precipitate (F) is formed, but this redissolved forming solution (G) when
more CO2 was added. Precipitate (F) effervesced when moistened with conc. HCl acid and gave deep red
colouration to the burner flame. When (F) was heated at 1000°C, a white compound (H) was formed
which when heated with carbon at 1000°C gave a solid (I) of some commercial importance. Name the
substances (A) to (I).
SOLUTION :
(A) is calcium metal which reacts with water and evolves hydrogen (B) and Ca(OH)2 solution (C).
Ca  2H 2O 
 Ca(OH)2  H 2
“Colourless and Odourless gas”
(A) (C) (B)
Ca  H 2 
 CaH 2
Solid product
(B) (D)
CaH 2  2H 2O 
 Ca(OH) 2  2H 2
(E)
2  Ca(HCO ) CO
Ca(OH)2  CO2 
 CaCO3  3 2
(F) (G)
CaCO3  2HCl 
 CaCl2  H 2O  CO 2 “Gives deep red colouration to flame”
 C
CaCO3 
 CaO 
 CaC2
(F) (H) (I)
Self Study Course for IITJEE with Online Support Solutions- INE 41
SOLUTION TO IN-CHAPTER EXERCISE - E

1. Reaction of steam on coal at high temperatures in presence of catalyst yields hydrogen. This process is called
as coal gasification.
1270K
C(s)  H 2O(g)   CO(g)  H 2 (g)
Mixing this CO and H2 gas mixture with steam, cooling to 400°C and passing over iron oxide gives CO2 + H2
which finally increases the amount of H2.
Fe
CO  H2  CO2  H2
The above reaction is also called as water gas shift reaction.
2. (i) BeH2(covelent) < TiH2 < CaH2

(ii) LiH < NaH < CsH
(iii) F–F<H–H<D–D
(iv) H2O < MgH2 < NaH
42 Solutions - INE Self Study Course for IITJEE with Online Support
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes p-Block Elements - I
p-Block Elements - I
SOLUBILITY OF SALTS Section - 1
[A] In Aqueous Solvent :

A solvent may be polar (having high dielectric constant such as water or mineral acids) or non-polar (having
low dielectric constant such as benzene and tetrachloromethane). Ionic compounds are usually soluble in
polar solvents while covalent compounds usually dissolve in covalent solvents. This rule may be stated as
‘like dissolves like’.
For a substance to dissolve in an aqueous solvent (water) the energy evolved when the ions are hydrated
(hydration energy) must be larger than the energy required to break the crystal lattice (lattice enthalpy). Thus
solubility in principle depends upon two major factors.
(i) Lattice Enthalpy : The lattice enthalpy is inversely proportional to the distance between the cation
and the anion (i.e. r++r-). Thus the lattice enthalpy decreases as we go down the group due to the
increase in size of cation if the anion being considered is came.
(ii) Hydration Enthalpy : Hydration enthalpy usually varies as the inverse of radius of cation (r+). This
is because as the size of cation increases, the polarizing power of cation decreases and thus the
tendency to attract water molecules decreases. (also known as Dehydration Capacity). This decrease
in dehydrating capacity decreases the hydration energy that is releases when a molecule is hydrated.
The General Solubility Rules in Water are as follows :

1. All nitrates (NO3 ) , chlorates (ClO3 ) are soluble. All sulphates (SO 24  ) are soluble except those
of [Sr 2  , Ba 2  and Pb2  ] which are sparingly soluble and hence are used in qualitative analysis.
2. All the carbonates (CO32  ), suphites (SO32  ) , phosphates (PO34 ) and dichromates (Cr2 O 72  )
are insoluble except of Group I, Na  ,   and NH 4 . Practically almost all salts of Group I,
Na  ,   and NH3 are soluble in water..

3. All simple salts of Group I metals dissolve in water producing ions. The solubility of most salts
(NO3 , CO32  , HCO3 ) decreases down the group. This is because the decrease in hydration energy
of metal ions is much more than the decrease in the lattice energy given.

p-Block Elements
p-Block -I -I
Elements Vidyamandir Classes
Exception : The solubility of alkali metal fluorides, hydroxides and carbonates increases rapidly down the
group. The reason is L. E. is proportional to 1/ (r   r  ) and thus the lattice energy will vary most when

r  is small (as in fluorides) and least when r is longer (with I ). Thus the change in lattice enthalpy
exceeds the change in hydration enthalpy in this case.
4. The solubility of most salts of Group II also decreases down the group. For
example, BeSO4 > MgSO4 >> CaSO4 > SrSO 4 > BaSO4 .(As has been stated, all sulphates
except these of Ca, Sr, Ba, Pb, Ag are very soluble).
Exception : The fluorides and hydroxide of Group II metals show an increase in solubility down
the group. The reason in same as that for Group I salts.
5. All hydroxides are insoluble except those of alkali metals (Group I) leaving LiOH. Those of
Ca 2  ,Sr 2  and Ba 2 are moderately soluble.
6. All sulphides (S2  ) are insoluble except those of alkali metals, alkali earth metals and the ammonium
(NH +4 ) ion.
7. All chlorides, bromides and iodides are soluble except those of Ag  , Hg 22  and Pb 2  which are
used in qualitative analysis.
8. It has been noticed that compounds with large difference in radii of ions are generally soluble while
the least soluble salts are those of ions with similar radii. Thus:
LiOH < NaOH < KOH < RbOH < CsOH
LiF < NaF < KF < RbF < CsF
[Here the difference in size between the cation and anion increases down the group].
while, LiBr > NaBr > KBr > RbBr > CsBr.
BeSO 4  MgSO4  CaSO 4  SrSO 4  BaSO 4
[Here the difference in size between the cation and anion decreases down the group].
[B] In Non-aqueous Solvents :

Important non-aqueous solvents include liquid hydrofluoric acid (HF), liquid NO2 and liquid ammonia
(NH3 ). Liquid ammonia is the most studied non aqueous solvent and it resembles the aqueous system quite
closely.
Thus substances producing NH 4 are acids (like NH 4 Cl) in liquid ammonia and those producing NH 2
are bases (like NaNH 2 )

Vidyamandir Classes p-Block
p-BlockElements
Elements- I- I
Similarly,
Thus in N 2O 4 substances containing NO+ are acid (like NOCl) and those containing NO3 are bases (like
NH 4 NO3 ).
Like in water, acid-base neutralization and precipitation reactions also occur in liquid ammonia. Liquid
ammonia is an extremely good solvent for the alkali metals and the heavier Group II metals Ca, Sr and Ba.
The metals are very soluble and solutions in liquid ammonia have a conductivity comparable to that of pure
metals. Thus solutions are very good reducing agents because of the presence of free electrons.
Liquid ammonia
[Na(NH3 )n ]  e 
Na 
GROUP 13 ELEMENTS Section - 2
Ionisation Energy
The first ionisation energies (IE1 ) of group 13 elements are lower than the corresponding elements of group
2 1
2 (alkaline earth metals). This is due to the fact that group 13 elements have ns , np configuration in their
valence shell and the electron thus has to be removed from the p  orbital. This is much easier than
removing an s  electron of group 2 elements which being nearer the nucleus is more strongly attracted.
Boron is considerable smaller than other elements of the group and thus has a higher ionization energy than
others. The ionization energy is so high that B is always covalent.
Oxidation States
Due to ns2 , np1 configuration of the valence shell, group 13 elements are expected to be trivalent but there
is increasing tendency to form univalent compounds on descending the group. B and Al show an O. S. of +3
while Ga, In, T1 show O. S. of both +1 and +3. This is due to the Inert Pair Effect.
Metallic Character/Reducing Power

The order is : B < Al > Ga > ln > Tl

p-Block Elements - I Vidyamandir Classes
The increase in metallic character from B to Al is the usual trend on descending a group associated with
increasing size. However Ga, In, Tl do not continue the trend. Ga, In and Tl follow immediately after a row
of ten transition elements and thus have ten d electrons which are less efficient at shielding the nuclear charge
than s,p electrons. Thus outer electrons being more firmly held by the nucleus are more difficult to remove
than would be expected. This leads to contraction in size as well as decreases in metallic character than
would be expected. The phenonmenon is know as d-block Contraction. Similarly Tl follows immediately
after 14-f-block elements and the size and metallic character are affected even more. This contraction due
to the f-block elements is called Lanthanide Contraction. Note that the size increases down the group as
usual but is less than that expected.
Acidic Character
On moving down the group acidic character decreases and basic character increases because ionization
energy increases. Thus we find that B(OH)3 , and B2O3 are acidic ; Al(OH)3 and Al2O3 are amphoteric
; Ga(OH)3 and Ga 2O3 are amphoteric ; and In (OH)3 , TIOH are basic.
Boron & its compound :

Physical Properties and Occurrence :
Boron occurs in two allotropic form :
(a) Crystalline – It is black, chemically inert and very hard
(b) Amorphous – It is brown, chemically active, a non – conductor and difficiult to fuse.
All allotropic form contain icosahedral unit with atoms at all 12 corners. The important minerals of boron
are :
Borax (Tincal) Na 2 B4 O2 . 10H 2O Boric aicd H3BO3
Kernite (Resorite) Na 2 B4O7 . 4H 2O Boronatro calcite CaB4O7 . NaBO 2 . 8H 2O
Colemanite Ca 2 B6O11 . 5H 2O Boracite 2Mg3B8O15 . MgCl2
Pandertie Ca 2 B6O11.3H 2O
Extraction of Boron : It includes 2 steps :

1. Preparation of Boric anhydride (B2O3) :
[Method l]
Na 2B4O7  2HCl 
 2NaCl  H 2 B4O7
 powdered Borax   conc.

H 2 B4 O7  5H 2O 
 4H3BO3
(sparingly soluble orthoboric acid)

2 H3BO3 
 B2O3 + H 2O
[Method ll]
Ca 2 B6O11  2Na 2CO3 

 2CaCO3  Na 2 B4O7  2NaBO2
 powdered
colemanite 
fuses
The fused mass is extracted with hot water. CaCO3 remains insoluble and filtrate containing borax and
sodium metaborate is put to crystallisation when borax crystals are obtained. The remaining solution is
treated with carbon dioxide.
4NaBO2  CO 2 
 Na 2 B4O7  Na 2CO3
borax
Then Method I is followed.

[Method lll]
Suspension of colemanite mineral in water is formed and SO 2 gas is passed to obtain crystal of boric acid
on cooling.
Ca 2 B6O11 + 4SO2 + 4 H 2O 
 2Ca(HSO3 ) 2 + H 4 B6O11
H 4B6O11 + 7 H 2O 
 6 H3BO3
Ca 2 B6O11 +11H2O+ 4SO2 

 2Ca(HSO3 ) 2 + 6 H3BO3

Then, 2 H3BO3   B2O3 + 3H 2O
crystals
2. Reduction B2O3 :
[Method 1]
heated in
B2O3  3M  2B  3MO  M  Na, K or Mg 
 crucible
fused
The fused mass is stirred with iron rod so as to oxidise unreacted metal M. The mass is then boiled with
dil. HCl to obtain insolube amorphous boron powder with is 95% pure.

[Method ll] : Modern Mehtod

A fused mixture containing boric anhydride, magnesium oxide and magnesium fluroide at 1100oC is electrolysed
in a carbon crucible (anode). Iron rod is used as cathod.
Cathode : Mg 2  2e  
 Mg
Mg  B2O3 
 B  MgO
amorphous
Anode : 2O2  
 O 2  4e
[Method lll]
To obtain crystalline boron in small amounts, B2O3 is redused with aluminium powder..
B2O3  2Al 
 2B  Al2O3
Aluminium is removed by heating the fused mass with NaOH solution.
Chemical Properties of Boron :

1. Boron is unaffected by water under ordinary conditions but :
2B  3H 2O 
 B2O3  3H 2 
 red hot  Steam 
2. Amorphous boron burns in air at 700oC with a reddish flame forming oxide and nitride.
4B  3O2 
 2B2O3 ; 2B  N 2 
 2BN
3. Boron is unaffected by reducing acids. With oxidising acids it gives boric acid.
B  3HNO3 
 H3BO3  3NO 2 
O.A.
4. Boron dissolves is fused alkalies liberating hydrogen.
2B  6NaOH 
 2Na 3BO3  H 2 
fused
5. Boron often forms non-stoichiometric compounds with metals (not of Group 1)
2B  3Mg 
 Mg3B2

6. Action of non-metals :
 
4B  C   B4C ; 2B  3Cl2 
 2BCl3
electric furnance
Uses : Boron caribide rods are used to control nuclear reactions. Boron has a very high cross-section
to capture the neutorns. Also B absorbs neutrons to make boron having an even number of neutrons.
10 1
 5 B11
5 B  0 n 
[a] Diborance B2H6 :

Sturcutre and Physical Porperties :
The bridge hydrogens form abnormal 3 centre 2 electron ‘banana-shaped’ bonds with two B atoms.
An sp3 hybrid orbital from each boron atom overlaps with the 1s orbital of the hydrogen to give a
delocalized molecular orbital covering all three nuclei.
Diborane is a colorless and highly reactive gas with a disagreeable odour. It is used as a reducing
agent in organic reactions and as a catalyst in polymerization reactions.
Preparation :
(i)
(ii) 8BF3  6LiH 

 B2 H 6  6LiBF4
1. It is instantly hydrolysed by water or aqueour alkali.

B2 H6  6H 2O 
 2H3BO3  3H 2
B2 H 6  2KOH  2H 2O 
 2KBO 2  6H 2
2. It catches fire spontaneously in air and explodes with dioxygen.
B2 H 6  3O2 
 B2O3  3H2O
Thus in the laboratory, it is handled in a vacuum frame.
red heat
3. B2 H 6   2B  3H 2
4. Other reactions :
ether
B2 H 6  2LiH  2LiB4 ; B2 H 6  3Cl2 
 2BCl3  6HCl
anhyd
B2 H 6  HCl  B2 H5Cl  H 2
dry AlCl3 Chlorodiborane
5. Reaction with ammonia and amines :
Borazole is called ‘ inorganic benzene’ due to its similar structure and aromatic character.

Boron nitride (BN) is a white slippery solid called ‘inorganic graphite’ which has a layer structure
similar to graphite.
[b] Orthoboric Acid H3BO3 :

Sturcture and Physical Properties :
Orthoboric acid is a weak monobasic acid, sparigly soluble in water. It is a Lewis acid and better
written as B(OH) .
3
Thus B  OH  alone is not titrated with NaOH as a sharp end point is not obtained. However if a cis-
3
diol is added then B  OH  behaves as a strong monobasic acid and can now be titrated with NaOH
3

using phenolphthalein as indicator Cis-diols form stable complexes with  B  OH  4  thus effectively
removing them and carrying the reaction forward.

1. Effect of heat :
100C 160C red heat

H3BO3  HBO 2  H 2 B4O7  B2O3
orthoboric Metaboric boron
acid acid sesquioxide
Thus, B2O3 is also called boric anhydride as it is the anhydride of boric acid.

 B  OCH3 3  3H 2O
2. H3BO3  3CH3OH 
methyl
borate
H 2O is removed by conc. H 2SO 4 and the mixture boruns with green flame. This is used as a
test for boron compounds.
3. Boric acid dissolves in HF(aq) to give fluorobroic acid HBF4 which is a strong acid. In dry
HF borates give BF3 which burns with a gree colour..
Uses :
Boric acid is used in glass industry and as an antisptic and eyewash under the name ‘Boric Lotion’.
[c] Borax :
Stucture
Borax  Na 2 B4O7 . 10H 2O  is better

written as Na2[B4O5(OH)4] . 8H2O
having 8 water molecules and the ion
2
 B4O5  OH   associated with
 4
Na  .
1. When borax dissolves in water equal amounts of weak acid and its salt are formed. Thus it is used
as a buffer.


2. Borax reacts with 2 moles of acid because only  B  OH  4  formed will react with H  .

2  B  OH 4   2H 3O  
 2B  OH 3  4H 2O
or Na 2 B4O7  2HCl  5H 2O 
 4H3BO3  2NaCl
The indicator used is methyl oranges as it is unffected by the boric acid formed.
3. Borax Bead Test :
Metaborates  M  BO 2   of many
transition elements have characteristic
colours and this provides a means of
identifying the metal through this test.
 
Na 2 B4O7 . 10H 2O 
 Na 2 B4O7 
 NaBO2  B2O3
 glassy bead 
Uses :
(i) It is used a flame retardant for wood and fabric.
(ii) It is used as a flux in brazing and silver soldering.
(iii) Used in glass industry.
(iv) Used in Borax Bead Test in analytical chemistry.
Aluminium :
1. Aluminium metal is moderately soft but much stronger and lighter when alloyed with metals.Some
alloys of Aluminium are :
Alloys Composition Uses
Magnalium Al – 95%, Mg – 5% In construction of airships,
balances.
Duralumin Al – 95%, Cu – 4%, Mg – 0.5%, Mn – 0.5% In areoplanes and
automobile parts
Aluminium bronze Cu – 90%, Al – 9.5%, Sn – 0.5% For making utensils, cheap
artificial jewellery.
Alnico Steel – 77%, Al – 20%, Ni – 2%, Co – 1% For making permanent
magnet.

2. Thermodynamically Al should react with water and air but in fact it is stable in both. The reason is that
a very this oxide film of Al2O3 forms on the surface and protects it. Due to this resistance to corrosion
and high thermal conductivity it is used in making domestic utensils .
3. Reduction of some metal oxides like Mn 3O 4 and Cr2 O3 require temperature high enough for carbon
to be used as a reducing agent. Thus Al, a highly electropositive metal which liberates a large amount
of energy on oxidation to Al2O3 is used as the reducing agent. This is know as thermite process. The
thermite reaction is :
3
2Al  s   O 2  g  
 Al2O3  s   energy H    1670 kJ
2
4. Al is amphoteric and dissolves in both acid and bases.
 2Al3  6Cl  3H 2
2Al  6HCl 
 2Na  Al  OH 4  or 2NaAlO 2 . 2H 2O  3H 2
2Al  2NaOH  6H 2O 
Sodium aluminat
However, con. HNO3 renders it passive due to the formation of a protective oxide layer..
[A] Aluminium Oxide Al2O3 (Alumina)
Aumina is a white crystalline powder, insoluble in water. It is stable, quite unreactive and amphoteric
in nature. The   from of Al2O3 called corundum and found as a mineral in nature.
[B] Aluminium Oxide AlCl3 :
AlCl3 exists as a dimer, thus attaining an octer of electrons. It is largely

covalent when anhydrous or in a non-polar solvent such as benzene.
However, when dissolved in water, the high enthalpy of hydration is suf-
3
ficient to break the covalent dimer into  Al.  H 2O  
 6
and 3Cl ions.
At low temperature, AlCl3 exists as a close packed lattice of
Cl with Al3 occupying octahedral holes.
Crystalline AlCl3 exist as AlCl3 .6 H 2O. This on heating cannot give anhydrous salt just like
MgCl2 .6 H 2O (diagnol relationship). Instead it undergoes hydrolysis on heating :


2AlCl3 . 6H 2O  2Al  OH 3  6HCl  6H 2O

2Al  OH 3 
 Al2O3  3H 2O
The anhydrous compoun is prepared by action of dry chlorine gas on aluminium or alumina :
Al  Cl2 
 AlCl3
Al2O3  C  Cl2 
 AlCl3  CO
IN-CHAPTER EXERCISE-A
1. Give reasons for the following :

(a) Phosphoric acid is preferred to sulphuric acid in the preparation of H 2O2 from barium perox-
ide.
(b) Red phosphorus is less volatile than white form.
(c) Diborane is called an electron-definient compound.
(d) Anhydrous AlCl3 fumes in moisture.
(e) A mixture of NaOH and Al pieces is used to open the drain.
2. Identify the unknown compounds in the following reactions :

2 5 1. C H OH
(a) Na2 B4O7  conc. H 2 SO4 
 A  B
2. Ignite
B is identified by the characteristic colour of the flame. Identify A and B.
(b)
140C Na [ BH ]
4  B  3 HCl
(c) BCl3  NH 4Cl 
 A  C
(d) LiH excess LiH

H 3 BO3  HF (non aqueous ) 
 A 
 B 
C
3. AlF3 is insoluble in anhydrous HF but when little KF is added to the compound it becomes stable.
On addition of BF3 ; AlF3 is precipitated. Write the balanced chemical equations.
4. RCN , RNO2 and RCHO can be reduced by B2 H 6 . What are the products due to reduction ?

GROUP 14 ELEMENTS Section - 3
Oxidation States :
C and Si show oxidation state of +4 while Ge, Sn, Pb show oxidation states of both +2 and +4 due to the
Inert Pair Effect.
Metallic Character :
It decreases down the group. Thus, C and Si are non – metals, Ge is a metalloid and Sn and Pb are metals.
Catenation :
Due to smaller size and higher electron negativity of carbon atom it has the property of linking to other
carbon atoms forming long chains. However as we move down, the tendency for catenation decreases in
the order :
C >> Si > Ge  Sn >> Pb.
Carbon and its compounds
Allotropy : carbon exists in a large number of allotropic forms. Two main form are diamond and graphite
Diamond Graphite
Extremely unreactive, colourless, non conductor Quite reactive and soft.

and shows brilliance due to total internal reflection.
It has a layer structure with layers held together
3 by weak van der wall’s forces. Each sheet
The structure comprises of sp hybrid C atoms
forming   bonds and aranged tetrahedrally.. consists of hybridised carbon atoms which are
covalently bonded to three carbon atoms by

  bonds. The fourth e is in unhybridised ‘p’
orbital and forms a partial '  ' bond
The crystal structure of diamomd.
(a) The structure of a graphite sheet.

(b) Structure of a-graphite
It is used as a lubricant due to slippery layers
and electricity is conducted only alog sheets.

1. Water gas is made by blowing air through red or white hot coke :
red heat
C  H 2O  H 2  CO
 
water gas
2. All allotropes burn in oxygen to form CO 2 .
C  O2   CO 2
Producer gas is made by blowing air through red hot coke.
C
C  O2  4N 2 
 CO2  4N 2 
 CO  N 2
  
red hot
air producer gas
3. Carbon as reducing agent :

C  2 H 2SO4  CO 2  SO 2  H 2O
 R.A  conc.
C  4 HNO3 
 CO 2  4NO 2  2H 2O
conc.
 Artificial Tannin  brown 

C  HNO3 
dil., hot
4. Carbon as Oxygen acceptor :
3C  Fe 2O3 
 2Fe  3CO
2C  SiO 2 
 SiC  2CO
Carborundum
2000C
6C  2Al2O3   Al4C3  6CO

Preparation of CO :
(i) In laboratory it is prepared by dehydrating formic acid with concentrated H 2SO 4
H SO
2 4  CO  H O
HCOOH  2
Conc.
Also,
conc. H SO
2 4  CO  CO  H O
 COOH 2  2 2
CO 2 is removed by passing through soda :
2KOH  CO2 
 K 2CO3  H 2O
(ii) C + oxides of heavy metal 

 CO   metal
(ZnO, Fe 2O3 ,..........)


(iii) K 4  Fe  CN 6   6H 2SO 4  6H 2O  2K 2SO4  2FSO 4  3  NH 4 2 SO 4  6CO 
Potassium conc.
Ferrocyanide
Note : Dil H 2SO 4 is not used, as it gives extremely poisonous HCN.
Prepation of CO2 :
(i) The main industrial source is as a by product from the manufacture of hydrogen for making ammonia :
(ii) It is recovered from alcoholic fermatation :
yeast under
C6H12O6   2C2 H5OH  2CO2
anacrobic condition
(iii) It is obtained by heating crabonates :

CaCO3 
 CaO  CO 2 

2NaHCO3  Na 2CO3  H 2O  CO3
(iv) In laboratory it is prepared by the action of dilute acids on carbonates :
CaCO3  2HCl 
 CaCl2  CO 2  H 2O

[a] Silicones
Silicones are a group of organo - silicon polymers containing Si - O - Si linkages.
Prepartaion :
Silicones are formed by the hydrolysis of alkyl or aryl substituted chlorosilanes (formed by reaction
Grignand regents and silicon tetrachloride) and their subsequent polymerization.

SiCl4  RMgCl 
 RSiCl3  MgCl2
 2RMgCl 
 R 2SiCl2  2MgCl2
 3RMgCl 
 R 3SiCl  3MgCl2
Grignard chlorosilanes
Re agent
(i) Formation of cross - linked silicones :
OH O R R
| | | |
3 3H O H O
2   O  Si  O  Si  O  Si 
R  SiC3  R  Si  OH 
| | | |
OH O O O
O O O
| | |
 O  Si  O  Si  O  Si 
| | |
R R R
(ii) Formation of linear polymers :
(iii) Formation of dimers :

Properties :
1. R 3SiCl is a chin stopping unit and reduces polymer size as it blocks the end of chain. While R SiCl3
is used to produce new cross – links and increase polymerization.
2. Silicones are electrical insulators, water-repellent, strong and inert. Their b.p. and viscosity increase
with increase in chain length.
3. Silicones are stable towards heat (hence used as electrical insulators). The order of stability varies
with R attached in the orders: ph  CH3  Et  Pr .
4. Being water – repellent they are used for treating glass ware and fabrics.
5. They are also used as hydraulic fluids and silicone rubbers.
[b] Silicates
Silicates are derivaties of silicic and Si  OH 4  or H 2SiO4 . They have basic tetrahedral units SiO 44
and Si – O bond may be considered 50% covalent and 50% ionic (suggested by a difference of 1.7
in electronegativities).
Preparation :
Silicates can be prepared by fusing an alkali metal carbonate with sand in an electric furnance at about
1400C.
1400C SiO
2 3  n , ......
Na 2CO3 
 CO 2  Na 2O  2  Na SiO , Na SiO
4 4
 sand   
soluble glass
Classification of Silicate Minerals :

(i) Orthosilicates : These silicates contain single discrete unit of SiO 44 tetrahedral.
For example : Zircon (gemstone) ZrSiO 4

Forestrite or Olivine Mg 2SiO 4
Phenacite Be 2SiO 4
Willemite Zn 2SiO 4

Number of shared oxygen atom = 0
(ii) Pyrosilicates : These silicates contain two units of SiO 44 joined along a corner containing oxygen
atom. These are also called as island silicate.
Pyrosilicate ion Si 2O76  .
For example : Thorteveititie Sc 2Si 2O7
Hemimorphite Zn 3  Si2O7  .Zn  OH 2 .H 2O

2 n
(iii) Cyclic Structure : Cyclic or ring silicates have general formula (SiO3 ) n .
Structure and example of cyclic silicates containing Si3O96  and Si6 O18
12 
ions are given below :

For example : Beryl Be3Al2Si6O18
Wollastonite Ca 3Si3O9
Number of shared oxygen atoms = 2
(iv) Chain silicates : Chain silicates are formed by sharing two oxygen atoms by each tetrahedral.
Anions of chain silicates have two general formula.

(a) SiO3 2n
n

(b) Si4O11 6n
n
Number of shared oxygen atom = 2.5
For example : Spodumene LiAl  SiO3  2
Diposide CaMg  SiO3 2
Tremolite Ca 2 Mg5  Si 4O11 2  OH  2

(v) Two Dimensional Sheet Silicates : In such silicates, three oxygen atoms of each tetrahedral are
shared with adjacent SiO 44 tetrahedral, such sharing forms two dimensional sheet structure with
2n 
general  Si 2O5 n .
For example : Tale Mg  Si2O5 2 Mg  OH 2
Kaolin Al2  OH  4 Si2O5 
(vi) Three Dimensional Sheet Silicates : These silicates involve all four oxygen atoms in sharing with
adjacent SiO 44 tetrahedral. For example, Quartz, Feldspars, Zeolites and Ultramarines. Here all 4
oxygen atoms are shared.
Tin and its compounds :

Tin is a white lustrous, soft, malleable metal. It produces a cracking sound called tinery whenever it is
bent.

Properties :
1. Tin reacts with steam to give SnO 2 and H 2 .
2. It dissolves in dilute HNO3 forming Sn  NO3 

2
 4Sn  NO3 2  NH 4 NO3  3H 2O

4Sn  10HNO3 
(cold dil.)
3. It is slowly attacked by cold alkalies and rapidly by hot alkalies. Thus it is amphoteric.
2
Sn  2OH   4H 2O 
 Sn  OH 6   2H 2  g 
4. Sn is used in tin plating (coting iron or steel sheets with tin) and making alloys like bronze
(75% Cu + 25% Sn) and solder (67% + 33% Pb).
Sn2+ and Sn4+

Tin ion exists in two states +II and +IV with the +IV state being more stable. SnO 2 is known as
cassiterite and found as a mineral in nature. The other oxide SnO is less stable and is obtained by
heating stannous oxalate.

Sn  C 2O 4  
 SnO  CO  CO2
Both SnO and SnO 2 are amphoteric but SnO is slightly more basic than SnO 2 and a good reducing
agent too.
SnO  2HCl 
 SnCl2  H 2O ; SnO 2  4HCl 
 SnCl 4  2H 2O
SnO  2NaOH 
 Na 2SnO 2  H 2O ; SnO 2  NaOH 
Sodium stannite sodium Stannate
Among halides, stannous chloride  SnCl2  and stannic chloride  SnCl4  are the most important.
SnCl2 exists as a di-hydrate which undergoes hydrolysis on heating
 Sn  OH  Cl  HCl  H 2O
SnCl2 .2H 2O 
The anhydrous salt SnCl2 is obtained by reaction of Sn with a calculated quantity of HgCl2 . Excess
of HgCl2 result in the formation of stannic chloride.


Sn  HgCl2  SnCl2  Hg

Sn  2HgCl2  excess  
 SnCl 4  2Hg
Most of the reactions of SnCl2 are due to its reducing character. It reduces
MnO 4 to Mn 2  , Cr2O72  to Cr 3 and itself get oxidized to Sn 4 .
Lead and its Compounds

(i) Lead is a bluish grey soft metal which can be cut with a knife and extremely poisonous.
(ii) Pb often appears more unreactive than expected from its standard electrode potential. The
unreactiveness is due to the surface coating of basic carbonate 2PbCO3.Pb  OH  2 which forms
over lead when exposed to air and moisture. Thus lead is unaffected by water.
(iii) Pb is amphoteric and dissolves in both acids and hot alkalies similar to Sn. In alkali it forms plumbates
like Na 2  Pb  OH 6  or Na 2 PbO3 . However, lead does not dissolve in concentrated HCl because
a surface coating of PbCl2 is formed.
(iv) Lead is used in making lead chamber for H 2SO 4 plant and certain alloys like solider (Sn  Pb)
[a] Oxides
Pb exists as Pb2 and Pb 4 with Pb 2 being more stable. This is due to the inert pair effect which
increases the stability of +II state while going down the group. Oxide formation is shown as :
 380  420C 
PB  O2 
 PbO  yellow    Pb3O4  red   PbO2  brown 
Litharge Re d lead O2
(i) PbO and PbO2 are both amphoteric and dissolve in both acids and bases.
PbO  2HCl 
 PbCl2  H2O ; PbO2  2HCl 
 PbCl2  H2O2
PbO  2NaOH 
 Na 2PbO2  H2 O ; PbO2  2NaOH 
 Na 2PbO3  H2O
(ii) Pb3O4 or Red Lead may be represented as 2PbO . PbO 2 and is used in paint to prevent the
rusting of iron and steel.
(iii) PbO (Litharge) is commercially important and is used in large amounts to make lead glass.
PbO2 is used as a strong oxidising agent and produced in lead storage batteries.

[b] Chlorides
Chlorides are prepared by passing lead through a current of chlorine gas.
2 Cl  excess 
Pb  Cl2 
 PbCl2  PbCl4
 
Dissolving Pb2  salt PbO, PbCO3 , Pb  NO3 2 in HCl produces PbCl2 .
PbCl4 is less stable and decomposes on heating at room temperature and liberates Cl2 .
25C
PbCl4  PbCl2  Cl2
[c] Tetraethyl Lead (CH2CH2)4Pb :

It is produced in large amount and used as an ‘anti-knock’ additive to increase the octane number of
petrol. The commercial preparation uses a sodium/lead alloy.
Na | Pb  4EtCl 
 PbEt 4  4NaCl
Once it was produced in larger tonnages than any other organometallic compound but the production
is declining rapidly as a result of legislation requiring that new cars must run on lead-free petrol.
IN-CHAPTER EXERCISE-B
1. Identify the group 14 element that best fits each of the following description :
(i) Prefers the +2 oxidation state
(ii) Forms the strongest  bonds.
(iii) Is the second most abundant element in the earth’s crust.
(iv) Forms the most acidic oxide.
2. Give reasons for the following observervations/applications :
(i) Solid CO2 is known as dry ice.
(ii) Carbon acts as an abrasive and also as a lubricant.
(iii) Glass toppers stick in NaOH bottles.
(iv) Thermodynamically, graphite is more stable than diamond but still diamond ( the less stable
forms) exists.
(v) CCl4 is unaffected by water whilst SiCl4 is rapidly hydrolysed.
(vi) SnCl4 fumes in moist air..

3. Identify A, B, C,. . . . .
(a)
HNO / HF
3 HF
2 BC H O
(b) Si  A 
 B ; A 
(conc.)
(c) Na2CO3  Si ( fused ) 

A
(d)  dil HCl

Sn(C2O4 ) 
 A  B( g )  C ( g ) ; A 
D
B is measured quantitatively using I 2O5 solution.
4. CO2 goes to the atmosphere (greenhouse effect) and thus gets dissolved in H 2O. pH of the water
increases or decreases and what is the effect on the fertility of the soil ?
5. Starting from SiCl4 prepare the following in steps not exceeding the number given in parenthesis :
(i) Silicon (1)
(ii) linear silicon containing methyl group only (4)
(iii) Na2 SiO3 (3)
6. How are the following compounds detected qualitatively ?
(i) CO (ii) CO2 (iii) silicates (iv) PbCl2

SOLUTION TO IN-CHAPTER EXERCISE - A
1. (a) In B2H6 (diborane), B doesnot have enough valency electrons to form conventional two - electron
bonds between all of the adjacent pairs of atoms and so it is termed as electron - deficient.
(b) AlCl3 hydrolyses in moist air to give fumes of HCl.
AlCl3  3H 2O 
 Al(OH)3  3HCl (white fames)
(c) NaOH reacts with Al and evolves hydrogen. The pressure of the evolved hydrogen opens up the
clogged drain.
2 2 1. C H OH
2. (a) Na 2 B4O7  conc. H 2SO4 
 H3BO3   B(OC2 H 2 )2 .
2. Ignite
(A) (B)
The colour of flam produced is green.
(b)
(c) 140C
BCl3  NH 4Cl  B3 N3H3Cl3
(d) LiH excess LiH

H3BO3  HF 
 HBF4 
 B2 H6  Li[BH4 ]
4. RCN 
 RCH 2 NH 2
RNO2 
 RNH 2
RCHO 
 RCH 2OH
SOLUTION TO IN-CHAPTER EXERCISE - B
1. (i) Pb (ii) C (iii) Si (iv) Sn

2. (i) Solid CO2 is used as dry ice to maintain low temperatures
(ii) Carbon in the form of diamond is used as abrasive and in the form of graphite as a lubricant. This is
due to the hardness of diamond and slipperiness of graphite.
(iii) NaOH reacts with glass (SiO2) forming silicates which block the stopper of the bottle.
(iv) Although thermodynamically it is favourable for diamonds to turn into graphite but this doesnot hap
pen because there is a high energy of activation required for the process. If this energy is available, the
change occurs.
(v) Carbon halides cannot hydrolyse because they donot have d orbitals and cannot form a hydrolysis
intermediate while silicon halides readily hydrolyse.
(vi) SnCl4 forms hydrates in moisture : -
2 H O
SnCl4  SnCl4 .3H2O (fumes)
(lim ite)
3. (a)
HNO |HF HF H O
(b) 3
Si   [SiF6 ]2 
 SiF4  ; 2  Si(OH)  HF
SiF4  4
(c) Na 2CO3  Si(fased) 

 Na 2SiO3  CO2
(d) 
Sn (C2O 4 ) 
 SnO  CO   CO 2 
dil. HCl
SnO  SnCl2
(A)
Among CO and CO2 ; CO is measured quantitatively by I2O5 solution. Thus (B) is CO and (C) is
CO2 .
4. CO2 being an acidic axide decreases the pH of water and thus makes the soil acidic.
5. (i) 2SiCl4  4Al 
 4AlCl3  3Si ; SiCl4  3Mg 
 Si  2MgCl2
(ii) SiCl4  CH3MgCl 
 CH3SiCl3  MgCl2 ;
CH3SiCl3  CH3MgCl 
 (CH3 ) 2 SiCl2  MgCl2
Self Study Course for IITJEE with Online Support Solutions - INE 29
2  2H O
(CH3 )SiCl2    CH3 2 Si(OH) 2
(iii) 3SiCl 4  4Al 

 3Si  4AlCl3
Si  O 2 
 SiO2
SiO2  2NaOH 
 Na 2SiO3  H 2 O
6. (i) CO is detected by flame test. It burns with a blue flame.
(ii) CO2 is detected by lime water test. It tarns lime water milky.
(iii) Silicates are detected by first dissolving them in HF to form SiF4 which when comes in contact with a
water droplet forms silicic acid (seen as floating white solid)
(iv) PbCl2 forms a yellow precipitate of PbCrO4 in presence of K2CrO4 which dissolves in NaOH
forming a yellow solution.
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Organic Concepts
Organic Concepts
BASIC OF REACTION MECHANISM OF ORGANIC COMPOUNDS Section - 1
Reaction of organic compounds can takes place in one step or in many step depending upon nature of
reactants and reaction conditions and also on nature of reactants and their functional group. These chemical
reactions involve breaking and making of the bonds that hold together the atoms of reactant and product
molecules.
In one step reactions, breaking and making of the bonds takes place simultaneous at the same instant. A one
step reaction is represented as : Reactant(s)   Transition State   Product(s)
A many steps reaction involve a time gap between bond breaking and bond making and it results in forma-
tion of an additional species called as reactive intermediate :
Reactant(s)   Transition State   Reactive intermediate [Step 1]
State 1
Reactive intermediate   Transition State   Product(s) [Step 2]
State 2
In two steps reaction one of the step is slow step and other one is fast step. The slowest step of many step
reaction is called as rate determining step (RDS).
Nature of reaction intermediate formed depends upon type of bond breaking. Bond breaking can be
homolytically or heterolytically as illustrated below.
The chemical reactions that involve only homolytic bond cleavage are called as free radical reactions and
those reactions that involve heterolytic bond cleavage are termed as ionic reactions.
The products of bond breaking, shown above are not stable in the usual sense and cannot be isolated for
prolonged study. Such species are reffered to as reactive intermediates, and are believed to be transient
intermediates in many reactions. The general structures and names of four such intermediates are given
below.

Organic Concepts Vidyamandir Classes
The shapes ideally assumed by these intermediates becomes important when considering the stereochem-
istry of reactions in which they play a role. A simple tetravalent compounds like methane, CH4 has a
tetrahedral configuration.
Carbocations have only three bonds to the charge bearing carbon, so it adopts a planar trigonal configura-
tion.
Carbanions are pyramidal in shape but these species invert rapidly at room temperature, passing through
a higher energy planar form in which the electron pair occupies a p-orbital. Radicals are intermediate in
configuration, the energy difference between pyramidal and planar forms being very small. Generally most
of the free radicals adopts a planar trigonal configuration. The shape of carbenes is planar, however, the
valance electron distribution varies.
You have already studied detailed aspect of these intermediates in ‘IOC’ chapter.
Note : CF3 radical is essentially pryamidal in shape. Less % of s-character of orbital help in stabilization
of free radical.
Note : Types of particular intermediate depends upon the type of carbon atom bearing charge. The stability
of charged intermediate is inversely releated to its charge density. The delocalisation of charge decreases
charge density hence increases stability. The presence of electron releasing group increases stability of both
free radical and carbocations. While presence of electron withdrawing group increases stability of carban-
ion.
Alkyl carbocations are stabilized by hyper conjugation.
Note : Hyperconjugation involve formation of 3C-2e bond.
Allylic and benzylic free radical, carbocation and carbanion are stabilized by resonance due to presence of
conjugation.
Note : A carbocation of lower stability can rearrange to a carbocation of higher stability by 1,2-hybride, methide or
phenide shift, if possible.
CH3 CH 3
|  |
1,2-Hydride
CH 3  C  C H 2  CH3  C  CH3
shift 
|
H

CH3 CH3
|  |
1,2-Methide
Ph  C  C H 2  Ph  C  CH 2  CH3
shift 
|
CH3
Alkyl carbocation having cyclo alkyl group (with number of carbon atoms less than six) may undergo ring
expansion because organic compound having five or six membered ring are more stable.
Such type of rearrangement is generally not observed in carbanion and free radicals.
The ionic organic reactions involve the bonding of a nucleophile (electron rich) to an electrophile (electron
deficient). While free radical reactions involve the bonding of a free radical to a radical or neutral molecule.
Electrophile : An electron deficient atom, ion or molecule that has an affinity for an electron pair, and will
bond to a Lewis base or nucleophile.
Nucleophile : An atom, ion or molecule that has an electron pair that may be donated in bonding to an
electrophile (or Lewis acid)

REVIEW EXERCISE
In the Chapter, “Introduction to Organic Chemistry”, you have already learned about details of above basic concepts
(Electrical effects, intermediates formed while visualising reaction mechanisms) and their simple uses in Section – 5 &
6. Before moving forward, please solve the following ‘Review Exercise’ so that you are not only able to review basic
fundamental but also consolidate your understanding.
1. What is the formal charge of oxygen in each of the following Lewis structures?
(A) (B) (C)
2. Consider structural formulas I, II, and III :
(A) Are I, II and III constitutional isomers, or are they resonance forms ?
(B) Which structure have a negatively charged carbon?
(C) Which structure have a positively charged carbon ?
(D) Which structure have a positively charged nitrogen?
(E) Which structures have a negatively charged nitrogen ?
(F) Which is a more stable structure?
(G) Which structure have nucleophilic carbon?
(H) Which structures have electrophilic carbon?
(I) What is the CNN geometry in each structure according to VSEPR?
Species [I], [II] and [III] have same molecular formula, the same atomic positions, and the same number of
electrons. They differ only in the arrangement of their electrons.
Classification of Organic Chemical Reactions :

1. Classification by Structural Change : On the basis of structural changes reactions of organic com-
pounds are of following types.

2. Classification by Functional Group : Functional groups are atoms or small groups of atoms (usually two
to four) that exhibit a characteristic reactivity when treated with certain reagents.
A particular functional group will almost always display its characteristic chemical behaviour when it is
present in a compound. The following table summarizes the general chemical behaviour of the common
functional groups.
For reference, the alkanes provide a background of behaviour in the absence of more localized functional
groups.

Illustration - 1 Some chemical reactions are shown below classify each as Addition, Elimination, Substi-
tution.
SOLUTION :
Addition : 1, 8, 9, 12 Reaction in which one of the atom or group (H,
Elimination : 2, 5, 11 halogen, OH etc.) is replaced by other substitu-
Substitution : 3, 4, 6, 7, 10 ent is called as substitution reaction.
Organic Compounds having multiple bonds Thus reaction
(C = C, C  C, C = O, C  N) undergoes 3 [Cl is replaced by OH]
addition reactions. Thus reaction 1, 8, 9 and 12 4 [CH3NH is replaced by OH]
are addition reactions.
6 [H is replaced by Br]
Reactions of organic compound that results in
formation of multiple bonds (C = C, C  C) 7 [Li is replaced by H]
are elimination reactions. 10 [Cl is replaced by acyl group] are substitu-
Thus reaction 2, 5 and 11 are elimination tion reactions.
reactions. Reaction 10 : Ring closure
Reaction 11 : Ring expansion
Reaction 12 : Rearrangement

3. Oxidation and Reduction Reactions :

Organic reactions can also be classified by oxidation-reduction terminology.
Carbon atoms may have any oxidation state from – 4(e.g. CH4) to + 4 (e.g. CO2), depending upon their
substituents. Fortunately, we need not determine the absolute oxidation state of each carbon atom in a
molecule, but only the change in oxidation state of those carbons involved in a chemical transformation. To
determine whether a carbon atom has undergone a redox change during a reaction, we simply note any
changes in the number of H bonded to carbon and the number of bonds to more electronegative atoms such
as O, N, F, Cl, Br, I, and S that has occurred. Bonds to other carbon atoms are ignored.
This count should be conducted for each carbon atom undergoing any change during a reaction.
(i) If the number of hydrogen atoms bonded to a carbon increases, and/or if the number of bonds to
more electronegative atoms decreases, the carbon in question has been reduced (i.e. it is in a lower
oxidation state).
NaBH
4  CH  CH  OH
CH3  CH = O  3 2
(ii) If the number of hydrogen atoms bonded to a carbon decreases, and/or of the number of bonds to
more electronegative atoms increases, the carbon in question has been oxidized (i.e. it is in a higher
oxidation state).
K Cr O
2 2 7 CH  COOH
CH3  CH2  OH  3
H+
(iii) If there has been no change in the number of such bond, then the carbon in question has not changed
its oxidation state. In the hydrolysis reaction of a nitrile shown below, the carbon atom of –CN group
has not changed its oxidation state.
O
+ ||
H
 C6 H5  C  OH + NH 4+
C6H 5  C  N + 2 H 2O 


Illustration - 2 Consider the following four addition re-

actions involving the same starting material, cyclohexene.
Identify in which reaction carbon in question has been re-
duced or oxidized or has not changed its oxidation state.
SOLUTION :
In the addition of hydrogen both carbon atoms are reduced, and the overall reaction is termed a reduction
(I). Peracid does epoxidation (III) and addition of Br2 (IV) oxidize both carbon atoms, so this will be
oxidation (IV). The addition of HBr in (II) reduces one of the double bond carbon atoms and oxidizes the
other ; consequently, there is no overall redox change in the substrate molecule (II).
The Variables of Organic Reactions :
The various important properties and characteristics of a reaction that may be observed and/or measured as
the reaction proceeds are listed below.
1. Reactant Structure : Variation in the structure of the reactant may have a marked influence on the
course of a reaction, even though the functional group is unchanged. Thus, reaction of 1-bromopropane
with sodium cyanide proceeds smoothly to yield butanenitrile, whereas 1-bromo-2, 2-dimethylpropane
fails to give any product and is recovered unchanged. In contrast, both alkylbromides form Grignard
reagents (RMgBr) on reaction with magnesium.
alcohol
CH 3CH 2CH 2 Br  CN  
 CH3CH 2CH 2CN  Br 
(fast)
alcohol
 CH 3 3 C CH 2 Br  CN    No Reaction
2. Reagent Characteristics : The minor changes in a reagent may lead to a significant change in the
course of a reaction. For example, 2-bromopropane gives a substitution reaction with sodium
methylthiolate (CH3SNa) but undergoes elimination on treatment with sodium methoxide (CH3ONa).
3. Product Selectivity :
(A) Regioselectivity : It is often the case that addition and elimination reactions may, in prin-
ciple, proceed to more than one product. Thus 1-butene might add HBr to give either 1-
bromobutane or 2-bromobutane, depending on which carbon of the double bond receives
the hydrogen and which the bromine. If one possible product out of two or more is formed
preferentially, the reaction is said to be regioselective.

CH 3CH 2CH  CH 2  HBr  CH3CH 2CHBr CH3 not CH 3CH 2CH 2 CH 2 Br
Regioselective
addition Major
Simple substitution reactions are not normally considered regioselective, since by definition only one consti
-tutional product is possible. However, rearrangements are known to occur during some reactions.
(B) Stereoselectivity : If the reaction’s products are such that stereoisomer may be formed ; a reaction that
yield one stereoisomer preferentially is said to be stereoselective. In the addition of bromine to cyclohexene,
for example, cis and trans-1, 2-dibromocyclohexane are both possible products of the addition. Since the
trans-isomer is the only isolated product, due to anti-addition, this reaction is stereoselective.
In the partial hydrogenation of 2-butyne using Lindlar’s catalyst, cis and trans-2-butene are both possible
products of the addition. Since the cis-isomer is the only product obtained, due to syn-addition, this reac-
tion is also sterco-selective.
(C) Stereospecifically : This term is applied to cases in which stereoisomeric reactants behave differently in a
given reaction. Examples
(i) Formation of different stereoisomeric products, as in the reaction of stereoisomeric 2-butene isomer
with Br2 / CCl4 , shown in the following diagram.

Here, the cis-isomer gives the racemic mixture and trans-isomer produces meso-isomers of 2, 3-dibromo
butane.
(ii) Different rates of reaction, as in the base-induced elimination of cis & trans-4-tert-butylcyclohexylbromide.
(iii) Different reaction paths leading to different products, as in the base-induced elimination of cis &
trans-2-methylcyclohexyl bromide.
Note : A reaction in which a reagent selectively reacts with one of the functional group of a poly functional group
compound is called as Chemoselective reaction.
Illustration - 3 Consider the following reactions and identify their correct classification.

SOLUTION : (B)
I and II are regioselective reaction.
In I and II two structural isomers of the product can be formed but only one isomer is formed as an exclusive
product or in major amount hence these two reactions are regioselective reaction.
III and V are chemoselective. In III MnO2 acts as an oxidising agent and it selectively oxidise only allylic or
benzylic C – OH bond to C = O bond. So this reaction is chemoselective. Similarly NaBH4 is selectively
reduces aldehyde to alcohols not carboxylic acid.
IV is stereoselective because only one stereoisomer of the product is formed.
VI and VII are stereoselective as well as stereospecific because a particular stereoisomeric reactant reacts
to give a particular stereoisomers of the product.
4. Factors that Influence Reactions : Some of the most important factors that influence reactions are
as follows.
(A) Energetics : The potential energy of a reacting system changes as the reaction progresses. The
overall change may be exothermic (energy is released) or endothermic (energy must be added)
and there is usually an activation energy requirement as well. As a rule, compounds constructed of
strong covalent bonds are more stable than compounds incorporating one or more relatively
weak bonds.
 CH3 — CH3 ; H  0 [Addition reaction]

CH 2  CH 2  H 2 
alc.KOH
CH 3 — CH 2 — Cl  CH 2  CH 2 ; H  0 [Elimination reaction]

(B) Electronic Effect : The distribution of electrons at sites of reaction (functional groups) is a par-
ticularly important factor. The charge distribution in a molecule is usually discussed with respect to
two interacting effects such as inductive effect and resonance effect. [As discussed in chapter
IOC]
  addition reaction
CH3  C H  C H 2  HCl   CH 3  CH(Cl)  CH3 [+I effect of CH3 group]

  addition reaction
 Cl3C  CH 2  CH 2  Cl [–I effect of CC3 group]
Cl3C  C H  C H 2  HCl 
(C) Steric Effect : Atoms occupy space, when they are crowded together, vander Waals repulsions
produce an unfavourable steric hinderance. Steric hinderance may influence conformational
equilibria, as well as destabilizing transition states of reactions.
CH 2  CH 2  Cl2  Cl  CH 2  CH 2  Cl
CCl4
CH 2  CH 2  I2  No reaction [Because of large size of I atoms]

CCl 4
H
|
CH3O 
CH 3  CH  CH  CH3   CH 3  CH  CH  CH3  CH3OH  Br 

(Smallsize base) (major)
|
Br
H  Sterically unhindered H atom

|
(CH3 )3 C  O
CH 2  CH  CH 2  CH3   CH 2  CH  CH 2  CH 3  Br   (CH3 )3 COH

(Largesize base) (major)
|
Br
(D) Solvent Effect : Most reactions are conducted in solution, not in a gaseous state. The sol-
vent selected for a given reactions may exert a strong influence on its course. Remember,
solvents are chemicals and most undergo chemical reaction under the right conditions.
For example nitrobenzene can be used as solvent for F.C. acylation reaction of aromatic
compounds although it is also an aromatic compound because -NO2 group deactivates ben-
zene ring for electrophilic substitution reaction. You will study role of solvent in later reac
-tions.
Stability :
Common use of the term stability implies an object, system or situation that is likely to remain unchanged for
a significant period of time. In chemistry, however, we often refer to two kinds of stability.
Thermodynamic Stability : Thermodynamic stability refers to the potential energy of a compound rela-
tive to a reference state. It is related to the bond energies of its constituent atoms. For exothermic reactions
we may say that the products are thermodynamically more stable than the reactants. The opposite would
be true for endothermic reactions.

Chemical Stability : The chemical stability refers to resistance of a compound or mixture of compounds
to chemical change (reaction) with a variety of reagents. It is related to the activation energy barrier it
presents to possible chemical change.
For example, benzene is thermodynamically unstable compared with elemental carbon and hydrogen, but
it is chemically stable under normal laboratory conditions, even when mixed with some reactive compounds
such as bromine.
Note : Compounds or mixtures that are chemically unstable are often called labile.
Kinetic Vs Thermodynamic Control :

In some reactions different products are formed at different temperature depending upon kinetics and
thermodynamics of the reaction. At low temperature, the products are formed irreversibly and reflect rates
of the two competing reaction. This is termed as kinetic control and product formed is called as kinetically
controlled product i.e. product that has higher rate of formation. At higher temperatures, equilibrium is
established between the products, and the thermodynamically favoured product dominates (product stable
at higher temperature). In the case it is called as thermodynamic control and product is called as thermody-
namically controlled product. For illustration refer Chapter hydrocarbon, reactions of conjugated dienes
Illustration - 4 Consider the following reactions of benzene and cyclohexene as given below.
Identify thermodynamically stable and chemically stable reactant.
(A) (B)
SOLUTION :
From heats of hydrogenation we find that cyclohexene has a potential
energy roughly 28.6 kcal/mol higher than cyclohexane, whereas benzene
is 48.9 kcal/mol above cyclohexane. We conclude from these
measurments that both cyclohexene and benzene are thermodynamically
less stable than cyclohexane, and that benzene is thermodynamically less
stable than cyclohexene. We know, however, that the chemical reactivity
of these unsaturated compounds does not reflect this stability order.
cyclohexene reacts rapidly with bromine, whereas benzene is relatively
inert to bromine (in the absence of catalyst and/or heat).The chemical
reactivity of benzene is therefore less than the reactivity of cyclohexene,
and we may say that benzene is chemically more stable than cyclohexene
-at least toward the reagent noted here.

Just as a chain is no stronger than its weakest link, a molecule may be rendered chemically unstable by one
weak bond. We see this in the chemical behaviour of peroxides (R–O–O–R). The O–O bond is less than
half as strong as a C–C bond, and peroxides are notoriously unstable, decomposing via alkoxy radicals
(R–O) on mild heating.
Illustration - 5 Different possible thermal decomposition pathways for peroxyesters are shown below.
Match each pathway from List I with an appropriate structure from List II and select the correct answer using
the code given below the lists.
List - I List - II
(P) Pathway P 1.
(Q) Pathway Q 2.
(R) Pathway R 3.
(S) Pathway S 4.
Codes :
P Q R S P Q R S
(A) 1 3 4 2 (B) 2 4 3 1
(C) 4 1 2 3 (D) 3 2 1 4
SOLUTION : (A)
(P)

(Q)
(R)
(S)
Note : Other radical initiators are given below.

REACTION MECHANISM (A Detailed view) Section - 2
Let us now discuss the mechanisms of Substitution, Addition and Elimination Reactions in detail.
2.A Substitution (Displacement) Reaction :
The replacement of an atom or group from a molecule by a different atom or group is called as substitution
reaction.
RH  X2   RX  HX
RX  NaOH(aq) 
 ROH  NaX
3 AlCl
C6H6  RCl  C6 H5R  HCl
These reactions are further divided into three types depending upon the type of attacking reagent.
(a) Free - radical (b) Nucleophilic (c) Electrophilic
Mechanism of Substitution Reactions :

(a) Free Radical Substitution : It is free radical reaction and involve homolytic cleavage of bonds.
Consider halogenation in alkanes :
It is supposed to proceed via the Free Radical Chain Mechanism involving the following three
steps.
h
(i) Initiation : Cl  Cl  Cl  Cl
hom olysis
Chlorine free radicals
(ii) Propagation : CH 4  Cl 

 CH3   H  Cl
Methyl free radicals
h
CH 3  Cl  Cl  CH3  Cl  Cl
Chlorine free radicals
The chlorine and methyl free radicals generated above, repeat these steps and thereby set up
a chain of reactions. Other propagation steps are also possible and may occur.
 ClCH 2  HCl
CH 3Cl  Cl 
ClCH2  Cl  Cl 
 CH 2Cl2  Cl
(iii) Termination :
The reaction stops after some time due to consumption of reactants and (or) due to the
following side reactions.

The possible chain terminating steps are :

Cl  Cl 
 Cl  Cl ; CH3  CH3 
 CH3  CH3
CH3  Cl 
 CH3  Cl
Halogenated alkane
The above mechanism justifies the formation of ethane, which is actually isolated as a by product
during chlorination of methane.
Note : (i) Rate of reaction of Halogens with alkanes, follows the order : F2 > Cl2 > Br2 > I2
Fluorination is too violent to be controlled, while Iodination is very slow and a reversible reaction.
Iodination can be carried out in the pressure of oxidizing agents such as HIO3 or HNO3.
CH 4  I4 
 CH3I  HI ; HIO3  5HI 
 3I2  3H 2O
(ii) Chlorination of most alkanes whose molecules contain more than two carbon atoms gives a mixture of
isomeric monochloro products (as well as more highly chlorinated compounds). Some examples are
given below. The percentages given are based on the total amount of monochloro products formed in
each reaction. The number of mono-halogenated products formed are equal to the number of different
type of H-atoms.
2 Cl
CH 3CH 2CH 3 
 CH 3CH 2CH 2Cl  CH 3 C HCH 3
light, 25 C |
Cl
Propane n - Propyl chloride Isopropyl chloride
(45%) (55%)
2 Cl
CH3CH 2CH 2CH3   CH3CH 2CH 2CH 2Cl  CH3  C H  CH 2  CH3
light, 25C
|
Cl
n-Butane n - Butyl chloride (28%) sec - Butyl chloride (72%)
CH 3 CH 3 CH 3
| Cl 2
| |
CH 3 C H 2CH 3  
 CH 3 HCH 2 Cl
C  CH 3 C CH 3
light, 25 C |
Cl
Isobutane Isobutyl chloride tert - Butyl chloride
(63%) (37%)
CH 3 CH 3 CH 3
| Cl 2
| |
CH 3 C CH 2CH 3   ClCH 2 C HCH 2CH 3  CH 3 C CH 2CH 3
| 300 C |
H Cl
2 - Methylbutane 1 - Chloro - 2 - methylbutane 2 - Chloro - 2 - methylbutane
(28%) (23%)

CH 3 CH 3
| |
 CH 3 C H C HCH 3  CH 3 C HCH 2CH 2 Cl
|
Cl
2 - Chloro - 3 - methylbutane 1 - Chloro - 3 - methylbutane
(35%) (14%)
 The ratios of products that we obtain in chlorination reactions of higher alkanes are not identical with what
we would except if all the hydrogen atoms of the alkane were equally reactive. We find that there is a
correlation between reactivity of different hydrogen atoms and the type of hydrogen atom (12or 3)
being replaced. The tertiary hydrogen atoms of an alkane are most reactive, secondary hydrogen atoms are
next most reactive, and primary hydrogen atoms are the least reactive.
(iii) Bromine is less reactive toward alkanes in general than chlorine, but bromine is more selective in the site
of attack when it does react. Bromine shows a much greater ability to discriminate among the different
types of hydrogenatoms.
The reaction of isobutane and bromine, for example, gives almost exclusive replacement of the tertiary
hydrogen atom.
CH 3 CH 3 CH 3
| Br2
| |
CH 3  C  CH 3   CH 3  C  CH 3  CH 3 C H 2Br
| light, 25 C | |
H Br H
(~ 99%) (Trace)
Thus bromination is highly selective reaction.

(iv) Relative rate of substitution of H-atoms of alkane in free radical halogenation is :
F2  3° H : 2° H : 1°H ; 1.4 :1.2 :1
Cl2  3° H : 2° H : 1°H ; 5 : 3.8 :1
Br2  3° H : 2° H : 1° H ; 1600 : 82 :1
(v) Fluorine, being much more reactive than chlorine, is even less selective than chlorine. Because the energy
of activation for the abstraction of any type of hydrogen by a fluorine atom is low, there is very little
difference in the rate at which a 1°, 2° or 3° hydrogen reacts with fluorine. Reactions of alkanes with fluorine
give (almost) the distribution of products that we would expect if all of the hydrogens of the alkane were
equally reactive.

Illustration - 6 The relative reactivity of 1 : 2 : 3 hydrogen to chlorination is 1 : 3.8 : 5. Calculate the

percentage of all the monochlorinated products obtained from 2-methylbutane.
SOLUTION :
Relative Amounts
Cl
|
IV. CH 3  C  CH 2CH 3 1  5  5
|
Observe that 2-Methyl butane has 9  1 H- CH3
atoms (6-H atoms are of one type and 3-H
atoms are of other type). Hence percentages of products are :
Hence products are : Relative Amounts 3
(i) 100  13.89
21.6
I. CH 3  CH  CH 2CH 2Cl  3  1 3
| 6
CH3 (ii)  100  27.78
21.6
II. CH 3  CH  CH 2CH3  6  1 6 7.6
| (iii)  100  35.18
21.6
CH 2Cl
5
(iv)  100  23.15
(Reactivity order of 1 : 2 : 3  1: 3.8 : 5 ) 21.6
Observe that there are 2  2 H-atoms ; accor- Note : This is true only for chlorination. Bromination
dingly the product is : is highly selective i.e. 3 bromides are the ab-
solute major product.
Cl
|
III. CH 3  CH  CH  CH3  2  3.8  7.6
|
CH3
Finally there is only 1  3 H-atom.
Allylic substitution :
Alkenes show substitution at allylic position when they react with low concentration of Cl2 at 500°C –
600°C along with addition product.
500C  600C
CH 3CH  CH 2  Cl2   C H 2  CH  CH 2
(gas phase) |
Cl
Allyl chloride

Note that at low temperature and absence of light in liquid phase alkenes show addition reaction. Alkenes
show allylic substitution is presence of NBS in CCl4 (N-bromosuccinimide). NBS is highly selective bromi-
nating reagent at allylic position in alkenes, -carbon to benzene ring (benzylic position) and -carbon to
–C  C and carbonyl group.
Note : (Markovnikov and Anti addition)
Mechanism
NBS reacts usually in presence of non-polar solvent, CCl4. NBS is very slightly soluble in CCl4, which
ensure that low concentration of bromine needed to avoid addition reaction is maintained. The reaction is
catalysed by sunlight or heat.

Br  CH3CH  CH 2 
 C H 2  CH  CH 2  HBr
H–Br is taken up by NBS to avoid addition across double bond.
Note : NBS provides a low concentration of bromide and use up the HBr formed (avoiding addition reaction)
 In case of unsymmetric allylic intermediates, allylic rearrangement takes place to give mixture of two
products.

(b) Nucleophillic Substitution Reactions :

1. Aliphatic Nucleophilic Substitution Reactions :
It proceeds by ionic mechanism. On the basis of time of bond cleavage and bond formation, a
nucleophilic substitution reaction can takes place by two different mechanisms.
They are divided into two categories :
(i) SN2 mechanism :
These are Bimolecular reactions. When rate of reaction depends upon concentration of both
substrate (organic compound) and the nucleophile, the reaction is said to follow bimolecular
mechanism (path) and is represented as SN2.
Consider the alkaline hydrolysis of CH3Cl 
H3C+  Cl + OH 
 H3C  OH + Cl
The nucleophile OH  attacks from the opposite side of Cl atom, and a transition state results
where both OH  and Cl- are partially bonded to carbon atom, to form a pentavalent activa-
ted complex known as transition state (T.S) in the slow step.The transition state then gives
the product and the halide ion. SN2 reaction mechanism is one step reaction mechanim.
(ii) SN1 mechanism :

These are Unimolecular reactions. When the rate of nucleophillic substitution depends only
on the concentration of the substrate, the reaction is said to follow unimolecular path and is
represented by SN1.
Consider hydrolysis of tertiary butyl bromide :
It follows two steps process :
 Heterolytic fission forming carbonium ion.
slow step
 CH3 3  C  X   CH3 3  C  X 
 Attack of nucleophilic on planar carbonium ion.
fast step
 CH 3 3  C   OH    CH3 3  C  OH

(Nu )

Note 1 :  Stronger is the nucleophile, more is the chance of SN2 mechanism.

(large and easily polarised groups are stronger nucleophiles : HS, I, CH3COO–)
 Higher is the concentration of nucleophile, higher is the rate of SN2 mechanism.
 1Alkyl Halides (RX) will always follow SN2 path (absence of steric hindrance).
 2Alkyl Halides will follow SN2 in presence of stronger nucleophile and non-ionising aprotic polar
solvents (such as acetone, DMSO).
Note 2 :  3Alkyl Halides (RX) will always follow SN1 path (greater stability of 3Alkyl carbocations).
 2Alkyl Halides will follow SN1 path when ionising solvents such as H2O or EtOH are used.
If H 2O acts as reagent :
fast step H
(CH3 )3  C+ + HOH  (CH3 )3  C OH 2 
(CH3 )3  C OH

(Nu ) Protonated alcohol
 Polarising medium such as water, alcohols favour heterolytic fission and hence favour SN1. These
solvents after ionising the substrate act as nucleophiles in fast step. This is referred to as solvolysis
(SN1). In solvolysis, we have to visualise rearrangement to get the most stable carbocations (Also
refer to addition & elimination reactions involving carbocations).
 Adjacent C = C or C = 0  system increase the rate of SN 2 reaction by stabilizing the transition
state.
 Adjacent C = C  system increase the rate SN 1 reactions by stabilizing the carbocation.
 Among the fastest of all SN 2 reactions are those where the leaving group is adjacent to a carbonyl
group.
i.e.
 Bicyclo bridge head 3 alkyl halide does not react with nucleophiles either by
SN 1 or by SN 2.
It does not react by SN 1 because the carbocation cannot become planar, nor
by SN 2 because the nucleophile cannot approach the carbon atom from the
opposite side.
Note 3 :  Ease of SN1 mechanism : benzyl > allyl > 3° > 2° > 1° > methyl
(It depends upon stability of carbonium ion).
 Ease of SN2 mechanism :   halocarbonyl > benzyl  methyl > allyl > 1 > 2 > 3
(It depends upon ease of attack of nucleophile ; steric factors).

 There are three outcomes for a reaction at an asymmetric carbon atom and these are inversion, retention
and racemisation. Consider the replacement of a group X by Y in the following reaction :
If (A) is the only compound obtained, the process is called retention of configuration.
If (B) is the only compound obtained, the process is called inversion of configuration.
If a 50 : 50 mixture of the above two is obtained then the process is called racemisation and the product is
optically inactive, as one isomer will rotate light in the direction opposite to another.
 Retention : Retention of configuration is the preservation of integrity of
the spatial arrangement of bonds to an asymmetric centre during a chemi-
cal reaction or transformation. It is also the configurational correlation
when a chemical species X Cabc is converted into the chemical species
Y Cabc having the same relative configuration.
In general, if during a reaction, no bond to the stereocentre is broken, the product will have the same general
configuration of groups around the stereocentre as that of reactant. Such a reaction is said to proceed with
retention of the configuration.
Note 4 : In SN2 mechanism, Nu attacks from back side i.e., side opposite to halide atom.
This means in SN 2 mechanism, the inversion of configuration takes place i.e., spatial arrangements of four
different substituents around chiral carbon atom get changed. In SN 2 path, the nucleophile attacks the
substrate from back side and forms an intermediary transition state giving a molecule with opposite configu-
ration. This means that there is complete inversion which is also referred to as Walden Inversion. Since

Nu  attacks   carbon from back, the steric hindrance around   carbon is the key to an effective SN2
attack. Note that hindrance is almost negligible around 1  C  atom. Therefore SN2 reaction is
stereoselective as well as stereospecific. Note that only one stereoisomer is formed.
Note 5 : In SN1 mechanism, first carbonium ion is formed which is sp2 hybridised and planar.
Hence in SN1 path, a racemic mixture (product) is expected. However on analysing the products, one
observes that only 90 – 95% racemization occurs. The above discussion (Note 4 & 5) provides a strong
evidence for SN1 and SN2 mechanisms.
Note 6 : The nature of solvent also affects the mechanism of the reaction.
 A polarising (ionising) solvent (water, alcohols, acids) favours SN1 path because of :
(i) the formation of carbonium ions is easy as the ions formed are easily solvated.
(ii) Nu– are also solvated (stabilised) in polaring solvents.
The ionising power of solvent depends upon its dielectric constant. e.g., the order of ionising
power of some solvents is : H2O > HCOOH > CH3OH > C2H5OH > CH3COOH (Such
solvents are also called as Protic Solvents).
 A Non-ionising solvent such as DMSO (Dimethyl Sulphoxide) : (CH3 )2 SO
or DMF : Dimethyl Formamide : H – CON(CH3)2 or Acetone favour SN2 path because :
(i) the formation of carbonium ions is not possible as such solvents does not stabilise anions
effectively.
(ii) the strength of nucleophile is increased as it being an anion is not solvated.
(Such solvents are also called as Aprotic Solvents)
Note 7 :Nature of leaving group (i.e. halide ion) :
A good leaving group is one, which is able to stabilise itself. It is observed that a weak base is a good
leaving group. Among halide ions, I  weakest base and hence a good leaving group. A good leaving group,
however cannot decide whether a given reaction will be SN 1 or SN 2. A good leaving group will enhance
the rate of both SN 1 or SN 2 reactions. Among halide ions, I  (weak base : conjugated base of strong
acid, HI) is best leaving group. [Nature of living group : I  > Br  > Cl >> F ] Other good leaving group
are : sulphonates such as tosylates or mesylates.

Note 8 :For a given alkyl group, the reactivity of the halide, R  X, follow the same order in both SN1 and SN2
mechanism.
R  I > R  Br > R  Cl >> R  F
Ambident Nucleophiles
A nucleophile which can attack a substrate through two possible sites.
e.g. Cyanide ion (CN  ) : can attack through ‘C’ or ‘N’ atom
Nitrite (NO 2 ) : can attrack through ‘N’ or ‘O’ atom
It is important to note that the atom of the ambident nucleophile, which attacks the electrophilec site
depends upon the nature of the attacking reagent.
 It KCN (Ionic) is there, then the attack takes place from the carbon side. This can be understood by
observing the structure of  CN which suggests the greater electron density over carbon making
it better nucleophilic site.
 It AgCN (covalent) is there then the attack takes place from nitrogen side (having lone pair). Since
AgCN is covalent therefore we do not expect free  CN ion, so the attack takes place from the lone
pair of nitrogen only.

 If KNO2 (Ionic) is there, then the attack takes place from oxygen side. In NO2 ion, negative charge
of oxygen makes it a better donor as compared with the lone pair of nitrogen.
 If AgNO2 (Covalent) is there, then the attack takes place from nitrogen side. This time there is a
competition between the lone pair of nitrogen and oxygen. Nitrogen being less electronegative comes
out as a better nucleophilic site.
RX + CN  
 RCN + RNC
Haloalkane Nitrile Isonitrile
RX + NO 2 
 RNO2 + R  ONO
Haloalkane Nitro Nitrite
Consider the following reactions :
CH 3 CH3
| |
3 CH OH
(i) CH 3  C  Br + AgCN  CH 3 C NC (Major)
| |
CH3 CH3

3 CH OH
(ii) CH3CH2 Br + KCN  CH3CH 2CN (Major)
CH3 CH3
| |
3 CH OH
(iii) CH3  C Br + AgNO2  CH3  C NO2 (Major)
| |
CH3 CH3
3 CH OH
(iv) CH3  CH2 Br + KNO2  CH3CH 2  ONO (Major)
Summary of structural variations and nucleophilic substitution.
Neighbouring group participation Reaction Mechanism :

Some compounds having a substituent with lone pair or   electron at the carbon next to the reaction
centre [at  carbon atom of leaving group] undergoes nucleophilic substitution reaction by a mechanism
known as neighbouring group participation (NGP). These substituents are called as neighbouring groups.

First Step : It is intramolecular nucleophilic attrack of neighbouring group through its lone pair electron or
  bond electron.
Second Step : It is intermolecular nucleophilic attack of attacking nucleophile on three membered ring inter-
mediate.
It is understood from reaction mechanism that NGP is two successive SN 2 reactions on reaction centre. The
involvement of neighbouring group increase the rate of the substitution reaction.
As you know, SN 2 reactions go with inversion but nucleophilic substitution by NGP on stereogenic centre
proceed with retention of configuration of stereogenic centre [Because of two successive SN 2 reactions on
same chiral carbon atom]
Note :  Retention of configuration in nucleophilic substitution reaction, is an indication of neighbouring group

participation.
 Sulphides, esters, carboxylate, ethers and amines, phenyl groups can assist substitution reactions
through NGP
 Intramolecular reactions (including participation of a neighbouring group) that give three, five, or six
membered rings are usually faster than intermolecular reactions.
 In some cases there may be rearrangement during nucleophilic substitution reaction by NGP mecha-
nism.

Illustration - 7 Find the major product of the reaction given :
SOLUTION :
It is neighbouring group participation (NGP) reaction in which a three membered cyclic intermediate is
formed in first step of reaction (intramolecular SN 2 attack).
In second step there is further SN 2 attack on least hindered carbon atom of three membered cyclic
intermediate.
Illustration - 8 Identify the product(s) formed in each of the following reactions, Identify the paths as
SN 1 or SN 2?
SOLUTION :
(a) OH  (aq) is a strong Nu  , will initiate an SN 2 attack in cyclo alkyl bromide (in 2 cycloalkyl halides,
the steric hindrance is not very high unlike in 2 alkyl halides). OH  will attack   carbon from
the side opposite to Br -atom resulting in the formation of trans product (equivalent to Walden inver--
sion in optically active compounds). This illustrates stereo-selective and stereo – specific aspect.
(b) H 2O (a weak Nu  ) being highly polarising will favour SN 1path (solvolysis).
Note that the Carbocation is planar, hence Nu  an attack it from two sides giving a mixture of two products.

Illustration - 9 Answer the following questions with proper explanation :

(i) KI in acetone, undergoes S N 2 reaction with each of P, Q, R and S. Compare their relative rates.
(ii)
SOLUTION :
(i) In SN 2 reactions, apart from strength of Nucleophile the steric factors are very important for the rate of
reaction.
But in special cases, where   carbon having a strongly electron withdrawing group (EWG), rate of
SN 2 is very fast as in option [S]. The relative rates of SN 2 are as follows :
(ii) It is NGP reaction so there is retention in configuration of chiral carbon atom.

In this reaction I can attack as nucleophile on benzylic C atom having
Br atom. But lone pair electron of oxygen of methoxy group will attack
intramolecularly so reaction proceed by NGP reaction mechanism.The
configuration of chiral carbon atom remain unchanged
Illustration - 10 What are the minor and major products, when the following compound undergoes hy-
drolysis in aqueous acetone?

SOLUTION :
Hydrolysis in aqueous acetone will involve solvolysis (SN 1).
II. Aromatic Nucleophilic Substitution Reaction : Activated SN 2

In general, nucleophilic substitution is not possible on unsaturated carbon
atom under normal reaction conditions. This is because of an increase in
bond dissociation energy of C – X bond due to resonance. Visualise the
case of Aromatic Halides and Vinyl Halides.
However, if a deactivating group (EWG) is present in the ring, it can

“activate” the ring for nucleophilic substitution reaction by the withdrawal
of benzene ring  e  s towards itself.
Aryl halide also undergoes nucleophilic substitution reaction under vigorous reaction conditions i.e. at high
  
temperature and high pressure by using stronger nucleophiles such as RO , NH 2 , R etc., or in presence
of KNH 2 .
On the basis of relative reactivity towards nucleophile, aryl halides are classified as follows.

Activated aryl halide :

Aryl halide having EWG on ortho and/or para positions.
Deactivated aryl halide:

Aryl halide having ERG on any positions.
Unactivated aryl halide :

Unsubstituted aryl halide or aryl halide having EWG on meta position.
Note :  Activated aryl halides means aryl halides activated for nucleophilic substitution reactions and
de-activated aryl halides means less reactive (de-activated) for nucleophilic substitution reaction.
 EWG-Electron withdrawing group ; ERG – Electron releasing group.
 The EWG must be present at ‘o’ or ‘p’ position w.r.t. the substituent (to be undergone nucleophilic
substitution).
 Any substituent that deactivates the benzene ring towards electrophilic substitution, activates the
same ring towards nucleophilic substitution.
 “To be replaced” substituent must be a weaker base as compared to the attacking nucleophile.
Activated aryl halide undergoes nucleophilic substitution reaction by two step reaction mechanism called as
addition-elimination reaction mechanism under proper reaction condition.
Consider the following reaction :

The generally accepted mechanism for the reaction is as shown below :

 Attack of the strong nucleophile on the halogen substituted aromatic carbon forming an anionic
intermediate (Cyclohexadienyl anion).
 Loss of the leaving group, the halide ion restores the aromaticity.
 Kinetics of the reaction are observed to be second order.

 The addition step (step – 1) is the rate determining step (Loss of aromaticity).
 Nucleophilic substitution, and therefore reaction rate, is facilitated by the presence of a strong elec-
tron withdrawing group ortho or para to the site of substitution, which stabilize the cyclohexadienyl
anion through resonance.
 Aryl halide reactivity order : Ar – F > Ar – Cl > Ar – Br > Ar – I (Note the contrast to simple
nucleophilic substitution).
 The more electronegative the group the greater the ability to attract electrons which increase the rate
of formation of cyclohexadienyl anion.
This addition-elimination reaction mechanism is a bimolecular nucleophilic substitution reaction mechanism
represented as SN 2 Ar. [Aromatic bimolecular nucleophilic substitution]
Note : Presence of EWG on ortho and/or para position increase rate of reaction because intermediate car-
banion is stabilized by EWGs
Order of reactivity :
Note : Deactivated and unactivated aryl halides undergoes nucleophilic substitution under proper reaction condi-
tions by elimination-addition reaction mechanism [Benzyne reaction mechanisms].

Illustration - 11 Explain the formation of products in the reaction given below.
SOLUTION :
Under normal reaction conditions chlorobenzene is inert towards nuleophilic substitution reaction. But in
presence of drastic reaction conditions (high temperature and high pressure) it under goes nucleophilic
substitution reaction by elimination-addition reaction mechanism or benzyne reaction mechanism. Benzyne
reaction mechanism is two steps reaction mechanism.
First step : Elimination of HCl (1, 2-elimination)
Second step : Addition of OH 
For the reaction given in question
Note : Benzyne is symmetrical intermediate hence nucleophile can attack on any carbon atom of C  C of benzyne
(c) Electrophillic Substitution (SE)

Substitution in benzene and its derivatives follows electrophillic substitution mechanism. Important SE reactions
include halogenation, nitration, sulphonation, Friedal Craft alkylation and acylation. The mechanisms proceeds
via the following three steps :

1. Formation of Electrophile (E+)

(a) Chlorination (Bromination), Alkylation and Acylation of benzene
In each of these reactions, in anhydrous AlCl3, being a Lewis acid, helps in the generation of the
electrophile.
 Cl  AlCl4
Cl  Cl  AlCl3 
Chlorinium ion
 CH3  AlCl4
CH3  Cl  AlCl3 
Alkyl carbocation

 CH 3 C O  AlCl 4
CH 3COCl  AlCl3 
Acyl carbocation

(b) In the case of Nitration, NO2 (Nitronium ion) is produced by the acid-base reaction of H2SO4
and HNO3, as shown below. H2SO4 acts as Bronsted acid (Proton donor) and HNO3 acts as
Bronsted base (Proton acceptor).
Step - 1
Step - 2
Note : In sulphonation SO3 acts as an electrophile.
2. Formation of Intermediate (Arenium ion) :

E+ attacks benzene due to nucleophillic character of ring and via Electromeric effect. This results in the
formation of a complex (an intermediate) known as arenium ion, in which one of the carbons is sp3 hybridised.
The arenium ion is resonance stabilized.

The complex does not have an Aromatic character because delocalisation of electrons stops at sp3
hybridised carbon.
3. Elimination of proton
In order to restore the Aromatic character, the complex release a proton.
AlCl4 (in case of halogenation, alkylation, and acylation) and HSO 4 (in case of nitration) abstracts a
proton from the sp3 hybridised carbon atom to give monosubstituted benzene derivative.
Note 1 :The number of products formed on monosubstitution is equal to the number of different types of H atoms in
the substrate.
Note 2 :In benzene derivatives (C6 H5  G), the functional group G can also be classified on basis of their polar
nature as : Activating or Deactivating.
The various groups are classified as electron donating and electron withdrawing. Those that withdraw
electrons inductively (polar effect) are said to exert a I effect and those that withdraw electron conjugatively
are said to exert a M effect. Similarly +I and +M effect terms are used for electron donating.
 An activating group (an electron donating group via mesomeric effect) is one which makes benzene
more reactive (nucleophillic) than benzene itself. Such groups are : NH2, OH, OR etc. Note
that these group exert –I effect over the ring, but in these cases +M effect > –I effect.
 A de-activating group (an electron withdrawing group via mesomeric effect) is one which makes
benzene less reactive (nucleophillic) than benzene itself. Such groups are COOH, C = O,CHO,
NO2, CN etc. Note that these group exert –I effect over the ring, which makes these even
more strongly deactivating.

 The halogens exert a very strong –I effect over the ring which outweighs their +M effect, hence these are
weakly deactivating groups. Note that these are weakly ortho & para directing due to +M effect.
 The alkyl group are weakly activating due to only +I effect. They are ortho & para directing because of
hyperconjugation effect (explained below).
In toluene,  CH3 has weak + I effect and considered to be a weaker activating group ; still it is an o/p
directing group for incoming electrophiles. It is due to hyperconjugation. Let us visualize hyperconjugation in
toluene.
More is the number of H – C bonds (  H ) attached to the unsaturated system, more is the probability of
electron release by this effect.
In the given reaction, which is the major product (A) or (B)?
Answer is obviously (A) since  CH3 is more activating than  CH(CH3 )2 as the former has ‘3’   H
whereas latter has only ‘1’   H .
Orientation of Electrophilic Substitution in Benzene :

A typical electrophilic substitution reaction in benzene can be represented as :
If there is already a substituent attached to the benzene ring (as a substrate), the incoming electrophile may
be directed to ‘o’, ‘m’ or ‘p’ positions (w.r.t. the substituent) based on the stability of   complex (arenium
ion) formed as an intermediate.

Consider the following reaction :
Out of the above shown products, which will form to what extent depends on the “behavior” of the substitu-
ent already attached to benzene ring. We can draw the intermediate arenium ion formed during the above
electrophilic substitution reaction based on the position of the electrophilic attack and then look at the
stability of the intermediate formed.
The product formed will depend on the stability of the resonance hybrid as per the “behavior” of substituent
‘X’.
(i) If ‘X’ has +I effect or electron donating effect (+R) e.g.  CH3 group, it will stabilize the carbocation
 CH3 can also stabilise the carbocation through hyperconjugation).
Thus, (1) and (5) will be the most stable resonating structures.
 ‘o’/ ‘p’ isomer will be formed in greater amount.


(ii) If ‘X’ has a –I effect (e.g.  NR 3 ) or electron withdrawing effect (e.g.  NO2 ), it will destabilise the
carbocation. Clearly, the destabilizing effect will be much lesser in case of (7), (8) and (9) as compared to
the ‘o’ and ‘p’ resonating structures.
 ‘m’ isomer will be formed
Note : Electrophilic substitution is quite interesting in case of halo benzenes. ( I) effect of halogens exceed their
(+M) effect, the overall effect of the substituent is deactivating but still it is o, p-directing.
[Remember : All groups that donate electrons by resonance are otho-para director]
As a special case consider hyperconjugation in benzotrichloride.
It means,  CCl3 is a strong m-directing group. Such type of hyperconjugation is known as Reverse
Hyperconjugation.
Note 1 : The presence of activating groups in benzene ring increases the ease of electrophillic substitution, whereas
the deactivating groups do just the opposite. Observe the ease of SE reaction in various substituted benzenes.
C6H 5 NO 2  C6 H5CN  C6 H5CCl3  C6 H5CHO  C6 H5COOH  C6 H5Cl
 C6 H 6  C6 H 5 CH 3  C6 H 5 OCH 3 ~ C 6 H 5 NHCOCH 3  C 6 H 5OH  C 6 H 5 NH 2
Note 2 : (i) In Friedal Craft (F.C.)alkylation, rearrangement in carbocation takes place to give most stable
carbocation via hydride (H–) or methide (CH3–) shift.
(ii) In F.C. alkylation, poly alkylation may occur as alkyl groups are ‘o’ & ‘p’ directing.

(iii) Mono substituted benzene having strongly deactivating groups such as –NO2,– SO3H and –CN do not
give F.C. alkylation.
(iv) There is no rearrangement in acyl carbocation (RCO) as it is resonance stabilised due to oxygen atom.
(v) In F.C. acylation, there is no change of poly acylated product formation as  COR group deativates the
ring.

(vi) In F.C. acylation, if alkyl group (R) in R C O is 3°, alkylation occurs as follows :
[3° Carbocation is highly stable]
(vi) Mono substituted benzene having strongly activating groups such as  NH 2 and  OH do not prefer F.C.
alkylation as AlCl3 being acidic coordinate with these groups.
Now this +ve charge over nitrogen atom deactivates the benzene ring.
In Friedel-Craft acylation reaction, phenolic ether reacts rapidly with the AlX3 catalyst to form complex.
Ph  OCH3 + AlX3 
 Ph(CH3 ) O  AlX3 
 Ph(CH3 ) O AlX3
Illustration - 12 For the reaction given in below, explain why different products are obtained when
different amounts of AlBr3 catalyst are used.
SOLUTION :
In Friedal-Craft acylation reaction, phenolic ether reacts rapidly with the AlX3 catalyst to form complex.
Ph  OCH3 + AlX3 
 Ph(CH3 ) O  AlX3 
 Ph(CH3 ) O AlX3

The adduct of phenolic ether and AlX3 is much less reactive than benzene or phenolic ether in electro-
philic aromatic substitution reactions because, as show in above equation, the oxygen electrons are delo-
calized onto the electron-deficient aluminium. Because of their delocalization away from the benzene ring,
these electrons are less available for resonance stabilization of the carbocation. Intermediate formed within
the ring during Friedal-Crafts acylation.
Note 3 : Orientation in Disubstituted Benzene :

1. When the two substituents are so situated that their influence reinforces at a point, further substitution
can be predicted without any difficulty.
2. When both groups are activating, further substitution is controlled by the stronger activating group.
3. When one substituent is meta-directing and the other is o, p-directing, but they are situated meta to
each other the third substituent goes otho to the meta directing group. This is known as ortho effect.

Note 4 : During intramolecular SE reaction electrophile attack on ortho-position of existing substituents. It is a

cyclization reaction. Five membered or six membered cyclic product is formed. Observe the following in
tramolecular F.C. alkylation.
Directive influence of substituents on Benzene

The following table illustrates the directive influence of various functional groups over benzene for second
substitution.

Note :  NH3 is strongly deactivating and both ‘p’ and ‘m’ directing. Think it in terms of –I effort NOT –M .
Remember it as a fact.
  NO group shows both  M as well as  M effect and it is weakly deactivating but o, p-directing.

Illustration - 13 Give the products in each of the following reactions.

3 AlCl
(a) C6 H 6  (CH 3 )3  C  CH 2Cl 
3 AlCl
3 1. BH /THF HF
(b) C6 H 6  CH 2  CHCH 2Cl  A 
 B 
C
 0C
2. H 2O2 / OH
SOLUTION :
(a) This reaction is an illustration of Friedel – Craft alkylation ( SE reaction).
Now it is simply F.C. alkylation. Here we have visualized the formation of 1C  as there is no
other pathway.
Note : In SE reaction involving carbocation (Friedal Craft alkylation), a stable carbocation is to be

taken as an attacking Electrophile (i.e. visualise rearrangement).
(b)
Note : Observe that Friedel –Craft Alkylation can also be achieved with ROH/HF or RCH = CH 2 / HF at
very low temperature.

Illustration - 14 Identify the product and propose the mechanism :
SOLUTION :
Try yourself : Propose the mechanism for the following reaction :
2.B Addition Reactions

Reactions in which atoms or groups of atoms are added to a molecule are called addition reactions. Usually
such reactions take place in unsaturated compounds containing double and triple covalent bonds.
These are also classified into three types depending upon type of attacking reagent.
(a) Electrophillic
(b) Free radical
(c) Nucleophillic

Mechanism of Addition Reactions :

(a) Electrophillic Addition Reactions :
Alkenes are  e  rich so are prone to be attacked by an electrophile, so predominantly undergo

electrophile addition reaction i.e. it gets converted to a saturated compound by undergoing addition
reaction, initiated by attack of electrophile. Electrophilic addition on alkenes proceed through follow
ing mechanisms :
Mechanism I :
Specific Features :
Electrophile causes shifting of   bond (i.e. electromeric effect) in a manner so as to form a stable
carbocation.
Carbocation intermediate may rearrange if possible. Racemisation is possible as carbocation is in-
volved and it is planar intermediate.
It’s a Markovnikov’s addition i.e. nucleophile gets attached to the carbon, where most stable carbocation is
favoured, after rearrangement (if possible). Addition of HX, H + / H 2O follows above mechanism.
Mechanism II :
Specific features :
(i) Electrophile causes polarization of  and e  density to form a cyclic ion.
(ii) No rearrangement, as carbocation is not involved.
(iii) Nucleophile attacks cyclic ion in an anti manner i.e. it attacks cyclic ion from theopposite side of at-
tached E in order to avoid steric and electrostatic repulsion.
(iv) It’s a Markovnikov’s addition i.e. the nucleophile attacks cyclic ion on the carbon where a stable
carbocation is possible, i.e. a carbon attached to stabilising alkyl groups (+I, +H)

Following reactions proceeds through above mechanism :
Oxymercuration-demercuration  Hg(CH3COO)2 / THF H2O, NaBH 4 / HO 

Addition of Halogen [X 2 / CCl4 , X 2 / H 2O]
Addition of HA :
Consider addition of HBr to ethylene :
Step 1 : Electrophile (H+) attacks the C = C bond via electromeric effect, (+E effect). Seeing the
incoming electrophile (H+), electromeric shift (effect) occurs, and  electron cloud is dis-
placed towards one of the carbon atoms.
Step 2 : Nucleophile (Br) adds to the carbonium ion :


CH3  CH 2  Br    CH3CH 2 Br
Fast
In case of CH3CH = CH2 (i.e., unsymmetrical alkenes), electromeric shift can occur in either direction to
give two carbocations.
+ +
H+ H+
CH3CH 2  CH 2 
 CH3CH = CH 2 
 CH3  H C CH 3
1° carbocation ; lessstable 2°carbocation ; more stable
Hence the major product formed is CH3  HC(Br)  CH3. This is in accordance with Markonikov’s
addition. In addition reactions of alkenes with HX and H 2 O/ H + , the same mechanism is followed.
 Reactivity of Halogen acids for addition reaction : HI > HBr > HCl
Such addition reactions are referred to as regioselective reactions.
Note : If an electron withdrawing group is present at one end of the alkene, then the addition is reversed. For
example consider addition of HCl to 3, 3-Dichloro propene.
 Cl 2CHCH 2CH 2Cl  Cl 2  CHCH  Cl  CH 3

Cl 2  CHCH  CH 2  HCl 
(m a jo r ) (mi n o r)
The reason for this is the stability of intermediate carbonium ion. I effect of the Cl atoms decreases stability
of carbonium. Try to compare the two possible carbonium ions formed.
 
Cl 2CHCH 2  C H 2 Cl 2CH C H 2  CH 3
(i) (ii)
(More stable) (Less stable)
In (i), two Cl atoms are at a greater distance from C+ site, whereas in (ii), two Cl atoms are nearer to C+
site. Hence I effect de-stabilises the carboction. (ii) to a much greater extent than it does in (i), and hence
the major product is with respect to intermediate (carbocation) (i).

Observe the following addition of HBr in 2-Methyl-2-butene.
CH3
|
Now the major product eventually will be : CH 3  C  C H  CH3
| |
Br H (tert. pentyl chloride)
So let us red line Markonikov’s rule as : “Electrophillic addition to a carbon - carbon double bond involves the
intermediate formation of the most stable carbocation”.
Rearrangement in addition reaction
Observe the following example of hydration of alkene in acidic medium carefully.
H
CH 3  C H  CH  CH 2  ?
| H2O
CH3
First visualise formation of initial carbocation via electromeric effect.
Now H– (hydride) from the adjacent 3° carbon occurs to give more stable 3° carbocation.
So, you have observed a rearrangement in addition reaction to give the most stable carbocation.

Illustration - 15 Predict the major products in the following reactions :
(i) HBr (ii)

CH3  CH  CH  CH 2  CH 3 

SOLUTION :
In all the given reactions, visualise the addition across the  bond (starting with addition of an electrophile)
through more stable carbocation.
(i)
or
Note : (II) is more stable than (I) due to more number of   H available for hyperconjugation.
 For major product :
(ii)

 Addition of X2 in CCl4 :
Addition of Halogens (X2) in CCl4 follows the mechanism involving cyclic intermedimate.
(i)
The bromine molecule is polarised when it approaches alkene. It then transfers a +ve Br atom (an
electrophile) to form a cyclic bromonium ion.
(ii)
The bromide ion (Br) attacks one of the carbon like an attack in SN2 reaction, which results in
opening of ring to give viccinal dibromide.
 Addition of X2 in H2O : ( HO  X  )
The first step is same as for halogens (Br2) shown above.
In next step, instead of bromide ion, H2O acts as a nucleophile and attacks a carbon of the ring
forming protonated halohydrin.

In the given example, the structure of the product tells us that what attacks the more highly substituted
carbon.
Br
2 (CH ) C  CH Br
(CH 3 ) 2 C = CH 2  3 2 2
H2O |
OH
2 - Methylpropene 1- Bromo- 2 - methyl- 2 - propanol (Major)
This suggests that, as water attacks the bromonium ion, positive charge develops on the carbon from which
the bromine departs. The transition state has some of the character of a carbocation. We know that more
substituted carbocation are more stable than less substituted ones ; therefore, when the bromonium ion ring
opens, it does so by breaking the bond between bromine and the more substituted carbon.
 The above additions are region-selective as one of the product dominates over the other.
 Whereas, the addition of Br2 in CCl4 and hydroxylation are sterco-specific and sterco-selective reac-
tions as illustrated by following examples.

Note : Both-cis-2-pentene and trans-2-pentene on reaction will Br2 form racemic mixture, as there will not be any
plane of symmetry in both cases.
Illustration - 16 When 3-Buten-2-ol reacts with HBr, two isomeric products are obtained. Explain with
proper mechanism.
SOLUTION :
Usually alcohols do not give nucleophilic substitution, as OH  , the leaving group is poor being strong base.
However, in presence of H + ions, 2 and 3 alcohols give SN 1 type of nucleophilic substitution as H 2O
(weak base) is now the good leaving group.
Allylic carbocations are resonance stabilised.

 Note that in the above question H  attacks on the lone pair in preference to   bond. If H + attacks

  bond, the intermediate formed is : CH 3CH (OH )  C HCH 3 , which is less stable as compared to
+
CH3  CH  CH = CH3
Carbocation (allylic)
 If both lone pair and   bond are in conjugation with each other, then H + attacks on   bond to give a
stable carbocation.
(b) Free radical addition

In the presence of peroxide, addition of HBr follows Anti-Markonikov’s addition (Peroxide or Kharash
effect).
Consider addition of HBr in propene in presence of Benzoyl peroxide. The following free radical chain
mechanism has been proposed :
Chain initiation :
O O O
|| || ||
Homolysis
(i) C6H 5  C  O  O  C  C6 H5    
 2C6 H5  C  O  2 C6 H5   2 CO 2
Benzoyl peroxide

Homolysis
(ii) C6H5   H  Br   C6 H6  Br
Chain Propagation Step :
(i)
Recall stability of free radicals via Hyperconjugation effect.

Homolysis
(ii) CH 3  CH  CH 2  Br  H  Br 
 CH 3  CH 2  CH 2  Br  Br
(Major product)
and CH3  C H 2  CH 2  H  Br 
 CH3  C H  CH3  Br
| |
Br Br
(Minor product)

Note : HCl and HI do not add similarly in the presence of peroxides because one of the step of chain propagation
steps becomes endothermic. The reaction with H  Cl fails because of higher H  Cl bond energy, which
prevents its cleavage by the free radical [step (ii)]. The H  I bond is weaker, but iodine free radicals com
-bine to form iodine molecules instead of adding to the double bond.
(c) Nucleophilic Addition Reaction

Consider the addition of CNtoaldehydes and ketones.
 In presence of CN (nucleophile),  e’s of bond are shifted towards more electrone-
gative oxygen atom via –E effect).
Presence of EWG increase reactivity while presence of ERG decrease reactivity towards nucleo-
philic addition reactions.
Reactivity Order in Carbonyl Compounds : H  C H > R  C H > R  C R
|| || ||
O O O
Addition of Grignard Reagent with carbonyl compounds follows the above mechanism. The conden-
sation reactions (to be studied later) usually follow nucleophilic addition reaction pathway.
2.C Elimination Reactions :
These reactions involve loss of atoms or group of atom from a molecule to form multiple bonds.
Mechanism of elimination reactions :

(a) Dehydrohalogenation of alkyl halides : It can be achieved by E1 (unimolecular)
or E2 (bimolecular) path.

E2 Elimination : It is one step reaction mechanism.

Consider elimination in tertiary butyl bromide by ethoxide ion.
 Base (B)is this case is ethoxide, C2H5O or (ethanolic KOH : OH– as base or NH2–) which forms a
transition state with alkyl halides as shown below (just like an SN2 path). Ethoxide EtO  attacks -
proton (H), and abstracts it.
Observe that the reaction is bimolecular i.e., it follows E2 path, just like SN2 path.
Note 1 :  Since all nucleophiles are good bases, SN2 products also follow along with E2 products.
 3 and 2 alkyl halides give alkene (E2) as major product.
 1 alkyl halides give SN2 as major product. (Williamson’s synthesis of ethers)
 1 alkyl halides, however give alkenes with strong and sterically (bulky) hindered bases such as tert.
butoxide.
Note 2 :  The reaction rate of elimination increases with increasing strength of the base :
CH3COO < HO < C2H5O < (CH3)3CO < NH2
 The ease of elimination follows : 3 > 2 > 1 (alkyl halides)
 The elimination occurs more easily when the halides are already unsaturated. e.g., elimination occurs
readily in
CH2 = CH  CH2CH2Br than in CH3CH2CH2CH2Br.
Visualise the product on elimination. (a conjugated diene is formed)
Note 3 : (Orientation of products)
 Two different alkenes may be formed when there are two -hydrogen atoms. The major is one having
more alkylation about the double bond (in accordance with Zaitsev Rule or Saytzeff Rule). It is also a
regio-selective reaction.

This is referred to as Saytzeff Rule. The exception to Saytzeff rule comes when a large (bulky) and strong
bases such as teritary butoxide are used, then due to steric hindrance (in base) less substituted alkene (Anti-
saytzeff product) is formed. It is also known as Hoffmann’s product.
 Note that Saytzeff’s (Zaitsev) rule is not used in cases, where alkyl halide has double bond or benzene ring.
In such cases, conjugated double bonds have a greater stability (including conjugation with benzene ring).
 In case of alkyl fluorides, the product of E2 reaction is also Anti-Zaitsev. F is a poor leaving group, so
remember it as a fact that Zaitsev product is minor.
3 CH O
CH 3  CH  CH 2CH3 H 2C = CH CH 2  CH3 + CH3  CH = CH  CH3
| CH3OH Major Minor
F
E2 An anti Elimination :
2
In the following substrate, observe that there are two  H -atoms. H1 atom is anti to Br atom and H atom
is in the same plane as that of Br atom. Note that E2 is an anti-elimination, which means  hydrogen and
the leaving halogen atom (Br) must leave from opposite planes. In the following Illustration, observed that
product formed is not a Saytzeff product. Which justifies the concept of anti-elimination.

E1 Elimination : Its is a two steps reaction mechanism.

Elimination may take a different path (E1 path is just like SN1 path). Consider the elimination of
(CH3 )3  C  Br via E1 as :
(i)  CH 3 3  C  Br   CH 3  3  C   Br 

(ii)  CH3 3  C  OEt 

  CH3  3  C  OEt

as Nu SN 1 product
(iii)  CH3 3  C  OEt 

 CH 3  C  CH 2
as Base |
CH 3
E1 product
 This means E1 path will always accompany SN1 and usually SN1 product dominate over E1 product. Note
that usually a good base is always a good Nucleophile and vice-versa except among halide ions. (I is a
good nucleophile, but weaker base and F is a poor nucleophile, but stronger base). Hence we should
visualize above elimination via E2 path, using strong bases and slightly polarised (weak) nucleophiles.
(RO  , OH abc , NH 2 )
 In such unimolecular reactions (i.e., in E1 and SN1), wherever structure permits, rearrangement occurs,
since reactivity depends upon stability of carbocations.
E1 is observed when using weak bases which are usually polarizing. (H 2O, EtOH)
CH3 CH3
| EtOH |
CH3  C H  C H  CH3   CH3  C H  C H  CH3 
| or H 2 O 
Br
The product I, II and III are formed. Product (II) is most stable and major product. In the above path,
we also expect SN1 product, as H 2O and EtOH are also weak nucleophiles. At low temperature, SN1
product usually dominate and at high temperature, E1 product dominate.

Note : E1 elimination also occurs in cases where there is no -hydrogen. Visualise rearrangement via CH3– (methide)
shift.
CH3 CH3 CH3

| alcoholic
| |
CH3  C CH 2 Br  CH3  C  CHCH3  CH 2  C CH 2CH3
| KOH
(Major) (Minor)
CH3
Neopentyl bromide
(E2 is not possible & SN2 is also not possible)
A double bond in a six-membered ring is usually more stable in an endocylic position than in an exocyclic
position.
Illustration - 17 Visualise both E1 and E 2 paths for dehydrohalogenation

of 1-Bromo-1-methyl cyclohexane.
SOLUTION : E1 path : First step is similar to that of SN 1 path.
It can give two E1 products losing a proton to base being used for dehydrobromination.
E2 path :
Base (such as RO or alcoholic KOH  OH  as base) abstracts a   H atom which simultaneously results
in loss of Br  ion in a bimolecular (E2) path. Note that in given case orientation of product is important as
there are two   H atoms.
If we take (CH3 )3 CO  as a base, the products ratio will get reversed.

Note : Just by change E1 and E2 both give same products. It is not necessary that two paths give the same
products. Usually dehydrohalogenation occurs via E2 pathways as SN 1 always competes with E1
at normal temperature.

Illustration - 18 Predict the product (X) of the following reaction :
SOLUTION :
Clearly the given reaction involves dehydrohalogenation of alkyl halides and under the given condition,
3 cycloalkyl halide will follow E2 path. Now E2 mechanism involves   elimination of hydrogen, so we
need to keep one thing in mind that the   H to be removed should be present in an anti-position (or
exactly opposite position) w.r.t the bromine atom. In other words, E2 mechanism involves “anti-elimina-
tion”.
Hence in this question, product (X) will be the less stable

anti-Saytzeff (Hoffmann’s product). The more stable
Saytzeff’s product (Y) would have formed if the substrate
was as shown in reaction :
E1 versus E2
 With respect to the substrate, the reacitivity of both E1 ad E2 increases from 1°, 2° and to 3° alkyl
halides. Note that reactivity of E2 increases due to greater stability of more highly branched alkenes
formation (Saytzeff Rule) ; whereas the reactivity of E1 increases because of the greater stability of
carbocations in rate determing step.
 The rate of E2 is proportional to concentration and strength of the base, whereas rate of E1 is inde-
pendent of nature of base.
 For a given substrate, E2 is the path for dehydrohalogenation in presence of more concentrated base
or a strong and slightly polarised base (RO–, NH2–, OH– ions).
 E1 path is followed by 2° and 3° alkyl halides in presence of weak bases such as alcohols i.e.
basically when base is the solvent.

ElcB is a rare mechanism of   elimination reaction of organic compound having poor leaving group and
more acidic   Hydrogen atom.
OH 
CH3  CH(OH)  CH2  CH = O  CH3  CH = CH CH = O ;

alc. KOH
Ph 2CH  CF3 
Ph 2C = CF2


Conditions for SN 2 reaction :

Steric hinderance should be minimum, so usually 1 and 2 substrate show SN 2 reactions. Hence it is not
possible for 3 substrate to show SN 2 reactions.
Nucleophilic should act as a pure nucleophile i.e. the basic nature of nucleophile should not dominate over
its nucleophilic character.
If any (or both) of the above two conditions are violated, it results in E2 reaction.
CH3
|
alc. KCN
CH3  CH 2  C CH3 
 E 2 (3°substrate)
|
Br
3 alkyl halide
alc.
CH3  CH 2  CH 2  Br 
SN 2 (Both conditions satisfied)
KCN
1 alkyl halide
NaNH
2  E 2 (strong base)
CH3  CH 2  CH 2  Br 
or
alcoholic KOH
1 alkyl halide
alc. KCN
CH 3  CH 2 CH 2  CH3 
 SN 2 (strong nucleophile)
|
Br
2 alkyl halide
Illustration - 19 Give major and minor products when each of the given compounds (bromides) reacts with
aqueous KOH. Also identify the path (SN1 or SN2).
CH 3 Br
| |
(A) CH 3  C H  CH 2 Br (B) CH 3  C  C H  CH 3
| |
CH 3 CH 3
(C) (D)

SOLUTION :
(A) Note that aq. KOH OH– as Nu– and alc. KOH OH– as base.
aq.
CH3 C H  CH 2 Br 
| KOH
CH 3
Observe that substrate is 1° halide and OH– is a strong Nu–. Hence product will be via SN2 path (1° halides
have no hindrance to Nucleophilic attack).

OH
CH 3 C HCH 2 Br  CH3 C HCH 2  OH  CH3  C  CH 2
SN 2 |
| |
(Minor)
CH3 CH3 CH3
(E2)
Note : SN1 path is not favoured as 1° carbocation is weakly stable.

(B) Observe that substrate is 2° halide, and reagent is aq. KOH. Aqueous solution i.e. H2O is a strong polarising
solvents, hence SN1 path will be followed.
Note that due to strong hindrance, SN 2 will not be possible.
(C)
Observe that substrate is 1° [as in (A)], so SN2 path is followed.
Note that SN1 Path will not occur as 1° carbocation is weakly stable.

(D)
Observe that substrate is 3°, so SN1 path will be favoured as intermediate will be highly stable 3° carbocation.
Note that in 3° halides, SN2 is not possible due to steric hindrance.
Illustration - 20 Give the major and minor products in the following reaction.
SOLUTION :
Note that H2O is a strong ionising solvent (protic) and a weaker nucleophile. Substrate is 2° halide and
aqueous medium serves as polarising (protic polar) solvent favouring SN1 path. This is an illustration of
solvolysis.

Illustration - 21 Identify various products obtained when 1 - Bromomethyl cyclohexene undergoes solvolysis
in the presence of C2H5OH. Propose a proper mechanism and identify the type of paths (mechanism).
SOLUTION :
1-Bromomethylcyclohexene
(i) C2H5OH is a weakly polarising (protic polar) solvent which favours SN1 type of path giving carbocations as
intermediate. in slow (RDS) step.
..
(ii) C2H5 OH serves as a weak nucleophile in the fast step to give ethers as SN1 products.
Note that the carbocation formed is resonance stabilised (Allylic type).
Note : SN1 path (products) is usually competed by E1 path (products), since carbocations can loose a proton to
give alkene (E1) as product.
II :

Observe that :
1. Intermediate : I cannot loose proton.
2. Usually SN1 products are formed at normal room temperature. Here as a special case, E1 is very important
as a conjugated diene is formed which is highly stable (due to resonance).
3. If instead of C2H5OH, we use aqueous solution of KOH, the reaction will be faster and instead of ethers,
alcohols are formed as SN1 products. However E1 product will remain same.
Illustration - 22 Give the products (s) that can be formed in each of the following reactions. Also identify
the path (SN1, SN2, E1, or E2) in each case.
MeOH Me C  OH
(a) CH 3CH 2CH 2 Br  MeO   (b) CH 3CH 2CH 2 Br  Me3CO  
3

50 C 50 C
CH OH CH OH
(c)
3 
2  brom obutane  NaHS  (d) Et3C  Br  OH  
3 
50 C 50C
CH 3 OH Me C  OH
(e) Et3C  Br   (f) CH 3CH 2CH ( Br )CH 3  Me3CO  
3 
25 C 50C
SOLUTION :
(a) The substrate is a 1° halide. The attacking species is CH3O–, a strong base (but not a hindered one) and
a good nucleophile. So we should visualise an SN2 reaction mainly, and the major product should be
CH3CH2CH2 OCH3 .
A minor product might be CH3CH = CH2 by an E2 pathway.
(b) Again the substrate is a 1° halide, but the reagent is (CH3)3CO–, is a strong and hindered base. We should
expect, therefore, the major product to be CH3CH = CH2 by an E2 path, and a minor product to be
CH3CH2CH2OC(CH3)3 by an SN2 path. Note that here a -H is abstract which is not sterically hindered.
(c) The reactant is 2-bromobutane, a 2° halide, and one in which the leaving group is attached to a chiral centre.
The reagent is HS–, a strong nucleophile, but a weak base. We should expect mainly an SN2 reaction,
causing an inversion of configuration at the chiral centre and giving an inverted stereoisomer.
(d) The base/nucleophile is OH–, a strong base and a strong nucleophile. However, the substrate is a 3°halide;
therefore, we should not expect an SN2 reaction. The major product should be CH3CH = C(CH2CH3)2
via E2 reaction. At this higher temperature, and in the presence of a strong base, we should not expect an
appreciable amount of the SN1 product, CH3OC(CH2CH3)3, however we can expect the product :
CH 3CH = C(CH 2CH3 )2 via E1 also.

(e) This is solvolysis; the reagent is simply the solvent, CH3OH, which is a weak base (therefore, no E2
reaction) and a poor nucleophile. The substrate is tertiary (Therefore, no SN2 reaction). At this lower
temperature we should expect mainly an SN1 pathway leading to CH3OC(CH2CH3)3. A minor product, by
an E1 path would be : CH3CH = C(CH2CH3)2.
(f) Refer (b), (CH3 )3 CO  will abstract less hindered   H to give 1-Butene as major product (Anti-Saytzeiffs
product).
Illustration - 23 Find the product (A) and (B) :
SOLUTION :
At 0C , product will be controlled kinetically i.e. according to stability of intermediate,  1, 2-addition.
At 65C , product will be controlled thermodynamically i.e. according to the stability of products,  1, 4-
addition.

Illustration - 24 What are the major/minor products obtained in each of the following reactions. Also iden-
tify paths.
OTs
| CH 3 COOH OH
(a) CH 3CH 2  C H  CH 3  CH 3  COO    (b) Tert. pentyl bromide  
EtOH
HCl
(c) CH3CH  CH  CH  CHCH 3 
 (d)
SOLUTION :
(a) Note that substrate is 2° and CH3COO– is a weak base, so elimination is not possible. However CH3COO–
acts a good Nu– to give SN2 product as major. Also observe that TsO– , tosylate is a very good learing
group.
OTs O  CO  CH3
| SN 2 |
CH 3  CH 2  C H  CH3  CH3COO    CH3CH 2  C H  CH3  TsO
SN 2(Ester)
There may be minor, E2 product.

(b) Note that alc. KOH  OH as a base. Here, substrate is 3° and OH a good Nu and a good base, will give
E2 products (SN2 will not be possible due to steric factors at 3° –  – carbon)
CH3 CH3 CH3
| OH
 | |
CH 3  C  CH 2CH3   CH3  C  CHCH3  CH 2  C  CH 2CH3
| EtOH Major : Saytzeff Minor (Anti-Saytzeff)
E2
Br

H
(c) CH 3CH  CH  CH  CHCH 3 Visualise electrophilic addition in alkenes.

Cl

This is referred to as conjugate (E+) addition in dienes.

Note : If electromeric effect in diene occurs as follow, another (minor) addition product can be formed.
(d) Clearly it will follow SN1 path as C2H5OH is a polarising solvent and weak nucleophile.
CH3 CH3
| SN 1
|  CH3
 
CH 3  C  CH 2 Br   CH3  C  C H 2  CH 3  C  CH 2CH3
| | shift |
CH3 CH3 CH3
+ +
1°C : Less stable 3C : More stable
Accordingly 3° carbocation can give both SN1 (Major) and E1 (Minor) products.
(b) Dehydration of Alcohols

It can also be achieved via E1 or E2 paths.
E1 path :
Consider Dehydration in tertiary butyl alcohol
Step 1 : Formation of Oxonium ion :
In this reaction, first conc. H2SO4 gives a proton (H+). The electrophile (H+) attacks oxygen atom
(OH) containing lone pairs of electrons to form an unstable intermediate called as oxonium ion
(protonated alcohol).

Step 2 : Formation of Carbocation :

The oxonium ion (being unstable) loses a water molecule to give a carbocation.
Step 3 : Elimination of Proton :

This carbocation loses a proton to give an alkene at 170C.
An alkene is formed and water accepts a proton (H+) to give H3O+.

Note 1 :
 The important intermediate in this reaction is carbocation ion. So you have to check its stability, while
proposing the mechanism. In the above case, the carbocation ion formed is tertiary butyl carbocation,
which being a tertiary ion is highly stable (Recall the stability of carbonium ions). In other case, you have
to make proper rearrangements for the stability of carbonium ion.
For example consider Dehydration of the following alcohol :

In Dehydration of alcohols, Saytzeff rule is always obeyed, unlike in dehydrohalogenation.

Note 2 :
In alcohols having cycloalkyl radicals, ring expansion occurs and cycloalkenes are formed. For example
consider following dehydration.
What is major/minor product(s) ?
E2 path :
The E1 mechansim is clearly followed by secondary (2°) and tertiary (3°) alcohols as the corresponding
carbocations are stable and hence are formed. Primary alcohols do not prefer E1 path as the corresponding
(1°) carbocations are not formed, being poorly stable. These alcohols follow E2 dehydration as follows :
After protonation of –OH group (similar to E1 path) in step-1, a primary protonated alcohol reacts with the
conjugate base of mineral acid (HSO4–) by -elimination (similar to E2 elimination in halides by RO–).
H SO 
2 4  RCH CH O H  HSO 
RCH 2CH 2OH  2 2 2 4
[ Not neccessarily a saytzeff product]

Note :(i) E2 products always accomany SN2 products (just like in case of alkyl halides) since steric hinderance
is absent at 1° -carbon. HSO4– can attack ‘ – C’ to give alkyl sulphate ester.
(ii) In this reaction, we can also expect an ether to be formed if a second alcohol molecule makes an SN2
attack at 1° -carbon.
Hence acid-catalysed dehydration involving 1° alcohols is not a good method to prepare alkenes.
(iii) Alcohols cannot show E2 reactions with bases, as –OH will be a poor leaving group. So we use acid
catalysed dehydration (as above i.e., E1). But to prepare alkenes from 1° alcohols, E1 is not a good
method. So an alternative method is first convert alcohol to alkyl sulphonate and then carryout E2 with
sterically hindered base such as tert. butoxide
3 6 4p  CH  C H SO Cl
2  RCH CH O  Ts  HCl
RCH 2CH 2OH  2 2
Pyridine
Ts : tosyl  CH3 – C6H4 – SO2 –


RO /R OH
RCH 2CH 2OTs   RCH  CH 2  OTs
E2
(TsO– : Tosylate : a very good leaving group)
(R’ 3 alkyl group)
Note : Although dehydration of Primary Alcohols is an E2 reaction, the product in most of the cases is identical to
the product that could be obtained if a carbocation has been formed in an E1 reaction and then had rearranged.
This can be explained as per the following reaction mechanism :

Illustration - 25 What are the major and minor products obtained when the given
compound is dehydrated is presence of heated conc.H2SO4 ?
SOLUTION :
The six different Alkenes (A, B, C, D, E and F) are the possible products. The order of stability of these
alkenes is in order :
D > E > F> C > B >A Hence major is D and minor is E (second important product).
Note : (i) In such reaction i.e., involving carbocations, always visualise the most stable carbocation (visualise
rearrangement or ring expansion) and then proceed.
(ii) Usually endocyclic cycloalkenes are more stable, but watch for special case (as above) considering
stability via Hyperconjugation.
(iii) In 1 alcohols with   carbon being 3 or 4, E1 elimination occurs as follows. In such cases E2
can not occur due to steric factor or absence of   H .

IN - CHAPTER EXERCISE - E
1. Give the mechanistic symbols (SN 1,SN 2, E1, E 2) that are most consistent with each of the following
statements :
(A) Methyl halides react with sodium ethoxide in ethanol only by this mechanism.
(B) Unhindered primary halides react with sodium ethoxide in ethanol mainly by this mechanism.
(C) When cyclohexyl bromide is treated with sodium ethoxide in ethanol, the major product is formed by
this mechanism.
(D) The substitution product obtained by solvolysis of tert-butyl bromide in ethanol arises by this mecha
-nism.
(E) In ethanol that contains sodium ethoxide, tert-butyl bromide reacts mainly by this mechanism.
(F) These reaction mechanisms represent concerted processes.
(G) Reactions proceeding by these mechanisms are stereospecific.
(H) These reaction mechanisms involve carbocation intermediates.
(I) These reaction mechanisms are the ones most likely to have been involved when the products are
found to have a different carbon skeleton from the substrate.
(J) Alkyl iodides reacts faster than alkyl bromides in reactions that proceed by these mechanism.

Example - 1 Arrange the following in increasing order of stability on the basis of resonance :
(A) (i) (ii)
(iii) (iv)
 
(B) (i) C H 2  CH = CH  CH = O CH3 (ii) CH 2 = CH  C H  CH = O CH 2
 
(iii) C H 2  CH  CH = CH  O CH3 (iv) CH 2 = CH  C H  CH  O CH3
 
(C) (i) CH 2 = CH  CH = CH  CH 2 (ii) CH 2 = CH  CH  CH = CH 2
   
(iii) CH 2 = CH  CH  C H  CH 2 (iv) CH 2  CH = CH  C H  CH 2

(D) (i) CH 2 = CH  CH = CH  CH = CH 2 (ii) CH 2 = CH  CH  CH = CH  C H 2

(iii) CH 2  CH = CH  CH = CH  C H 2
SOLUTION :
(A) (i) < (iv) < (ii) < (iii)
In (iii) there is strong  M effect of NO 2 .
In (ii) and (iv)  I effect of Br and OCH3 are prominent.
In (i) delocalization due to only phenyl ring is there.
(B) (iii) < (iv) < (ii) < (i)
(i) and (ii) should have more stability as compared to (iii) and (iv) because of more number of covalent
bonds.
Also (i) has got 1 carbanion whereas (ii) has got 2 carbanion. Hence (ii) < (i)
In (iv), carbocation is close to oxygen hence it is more stable due to the lone pairs on oxygen.  (iv) > (iii).
(C) (ii) > (i) > (iii) > (iv)
(i) and (ii) should have greater stability as compared to (iii) and (iv) because of greater number of covalent
bonds.
Also (ii) has got 2 carbocation whereas (i) has 1 carbocation.
(iii) has unlike charges close to each other but (iv) has no such factor.
(D) (iii) < (ii) < (i)
(i) is most stable due to maximum number of covalent bonds.
(ii) has got 2 carbocation whereas (iii) has got 1 carbocation. Hence (ii) > (iii).
Example - 2 7-bromo-1, 3, 5-cycloheptatriene exists as ionic species in aqueous solution while 5-bromo-
1, 3-cyclopentadiene doesn’t ionise even in presence of Ag  (aq). Explain.
SOLUTION :
Example - 3 MATCH THE FOLLOWING :

Column 1 [Reactions] Column 2 [Type of reaction]
(A) (P) Electrophilic Substitution
(B) (Q) Free radical substitution
(C) (R) Electrophilic addition
(D) (S) Free radical addition
SOLUTION : [A-P] [B-Q] [C-R] [D-S]

Benzene is an aromatic compound and aromatic compounds undergoes electrophilic substitution reactions.
Cyclohexane is a saturated aliphatic hydrocarbon and it undergoes free radical substitution reaction in
presence of light.
1-Methyl cyclohexene is unsaturated hydrocarbon and it undergoes electrophilic addition reactions. But
addition of HBr in presence of peroxide takes place by free radical addition reaction mechanism.
Example - 4 MATCH THE FOLLOWING :

Column 1 [Reactions] Column 2 [Type of reaction]
(A) (P) Substitution reaction
(B) (Q) Elimination reaction
(C) (R) Addition reaction
(D) (S) Intramolecular reaction

(T) Rearrangement
SOLUTION : [A-P] [B-Q, T] [C-R] [D-P, S]
Derivative of benzene undergoes electrophilic substitution reactions. Alcohols on heating with conc. H2SO4
undergoes dehydration (elimination reaction). In this case alcohol is primary alcohol without -hydrogen
atom hence it dehydrated by E1 reaction through formation of carbocation. Primary carbocation formed
will rearrange to more stable 3carbocation.
Reduction of ketone is an addition reaction.
When attacking nucleophile and leaving group are part of same substrate then reaction is intramolecular
reaction.
Example - 5 Consider reactions 1 through 6. Those carbon atoms undergoing change, as part of a
functional group, are coloured. In the cases shown, each carbon atom has either been reduced or oxidized.
Your job is to identify the change in oxidation state that has occured for each of the colored carbons.
Br
2  CH CHBrCH Br
1. CH3CH  CH 2  3 2
2 6 1. B H
2. CH 3CH  CH 2 
 CH 3CH 2CH 2OH
2. H 2O2 , NaOH
NaBH
4  CH CH CH OH
3. CH3CH 2CH  O  3 2 2
Ag 
4. CH3CH 2CH  O 
 CH 3CH 2CO2 H
H 2O, pH  8
5. Heat
CH3COCH 2CO2 H  CH 3COCH 3  CO2
6. tautomerization
H 2C  C (OH )C2 H 5 
 H 3CCOC2 H 5
SOLUTION :
Addition of electronegative atom to carbon is oxidation. Removal of hydrogen atom from carbon is also
oxidation. While addition of hydrogen atom or removal of electronegative atom result in reduction of car-
bon. So in reaction :
(1) Both carbon atoms are oxidized (2) One is reduced, other is oxidized
(3) Carbon is reduced (4) Carbon is oxidized
(5) One is reduced, other is oxidized (6) One is reduced, other is oxidized
Example - 6 Explain why the doubly allylic alkyl halide (A) undergoes much more rapid solvolysis in
aqueous acetone than compound (B). Also then explain why compound (C). Which is also a doubly allylic
alkyl halide, is solvolytically inert.
(A) (B) (C)
SOLUTION :
Solvolysis reaction is nucleophilic substitution reaction in which both nucleophile and solvent are same
chemical species e.g. hydrolysis reaction. Generally solvolysis reactions of alkyl halides are proceed by
SN 1 reaction mechanism. The doubly allylic halide (A) easily undergoes solvolysis reaction because
allylic carbocation is resonance stabilized.
The compound (C) is also doubly allylic alkyl halide but it is solvolytically inert because on ionization it form
least stable anti-aromatic carbocation intermediate.
Example - 7
MATCH THE COLUMN :
Column 1 [Reactions] Column 2 [Reaction mechanism]
(A) (P) NGP
(B) (Q) SN 2
(C) (R) SN 1
(D) (S) Intramolecular nucleophilic

substitution
SOLUTION : [A-r][B-q, s][C-q][D-p,s]
Lone pair of electron on adjacent carbon atom of reaction centre stabilize carbocation so reaction proceed
by SN 1.
S N 2 reactions adjacent to groups are usually fast due to neighbouring group participation.
Observe the rearrangement in NGP.
SOLUTIONS TO REVIEW EXERCISE
1. If bonds formed by an atom are more or less than its valency, it has some charge called as formal charge.
Formal charge = Valence electrons in isolated atom – No. of bonds formed – No. of unshared electron
2. A, B and C are resonance forms of diazomethylene (CH 2 N 2 )
The structure (C) is least stable due to incomplete octet. But structure (B) is most stable because negative
charge is on more electronegative atom.
The structure (A) contains nucleophilic carbon atom while structuere (C) contains electrophilic carbon atom.
Both (A) and (B) have linear geometry while (C) has bent geometry. This is an example of how VSEPR can
fail when comparing resonance structures.
Self Study Course for IITJEE with Online Support Solutions 78

IN - CHAPTER EXERCISE - E
1. (A) Methyl halides are unhindred and react rapidly by the SN 2 mechanism.
(B) Sodium ethoxide is a good nucleophile and will react with unhindered primary alkyl halides by the
SN 2 mechanism.
(C) Cyclohexyl bromide is a secondary halide and will reacts with a strong base (sodium ethoxide)
predominatly by the E2 mechanism.
(D) The tertiary halide tert-butyl bromide will undergo solvolysis by the SN 1 mechanism.
(E) The presence of the strong base sodium ethoxide will cause the E2 mechanism to predominate.
(F) Concerted reactions are those that occur in a single step. The bimolecular mechanisms SN 2 and E2
represent concerted processes.
(G) In a stereospecific reaction, stereoisomeric reactants yield products that are stereoisomers of each
other. Reactions that occur by the SN 2 and E2 mechanisms are stereospecific.
(H) The unimolecular mechanisms SN 1 and E1, involve the formation of carbocation intermediates.
(I) Rearrangements are possbile when carbocations are intermediates in a reaction. Thus reactions occuring
by the SN 1 and E1 mechanisms are most likely to have a rearranged carbon skeleton.
(J) Iodide is a better leaving group than bromide, and alkyl iodides react faster than alkyl bromides by
any of the four mechanisms SN 1, SN 2, E1 and E2 .
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Vidyamandir Classes
My Chapter Notes

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Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Introduction to Organic Chemistry
Introduction to Organic Chemistry

STRUCTURAL FORMULAE Section - 1
We have already discussed that carbon has tetravalency and the formation of covalent bonds by it is explained
in terms of its electronic configuration and the hybridization of s and p orbitals. It may be recalled that
formation and shapes of molecules like Methane (CH4), Ethene (C2H4), and Ethyne (C2H2) were explained
in the terms of sp3, sp2, and sp hybridization of the respective carbon atoms.
Organic chemists use a variety of ways to represent structural formulae for an organic compound. The most
common types of representations are shown below.
Dot Structure (Lewis Structure)

This shows all of the valence electrons, For example, given below is the dot structure of n-propyl alcohol.
Writing dot structure is tedious and time consuming. The other representations are more convenient and are,
therefore, most often used.
Dash Structural Formula

Here, the pair of two electrons forming the covalent bond is represented by a dash. A single dash represents
a single bond, double dash is used for double bond and a triple dash represents a triple bond. The lone pair
of electrons on hetero-atoms like oxygen, nitrogen, sulphur, halogens, etc. may or may not be shown. Given
below is the dash structure of n-propyl alcohol.
Condensed Structural Formula

Condensed structural formulae are easier to write than dash formulae and, when we become familiar with
them, they will impart all the information that is contained in the dash structure. In the condensed formula, all
the atoms bonded to a carbon atom are written after ‘C’ in the same line but their bonds are shown.
Identical group are omitted by indicating their number as a subscript. The atoms or groups other than
hydrogen are written after the hydrogen atom.(in brackets)

Introduction to Organic Chemistry Vidyamandir Classes
Given below is the condensed formulae for n-propyl alcohol and isopropyl alcohol.
CH3(CH2)2OH n-Propyl alcohol
CH3CH(OH)CH3 Isopropyl alcohol
CH3(CH2)4CH3 n-Hexane
Note : The carbon atoms in organic compounds may also be

arranged in rings (Cyclic compounds). For example :
cyclopropane, whose structural formula is given alongside.
Bond-Line Formula
A very simplified formula called Bond-line formula can also be used to represent structures of organic
compounds. In this representation, the C and H atoms are not shown; the chain of carbon atoms is represented
by a zig-zag line. Each intersection of 2 or more lines (junction) and the end of a line represent a carbon
atom. Hetero-atoms (other than carbon and hydrogen) or functional groups are specifically written. Hydrogen
atoms necessary to fulfil the valence of carbon atoms is assumed to be present.
Bond line formulas are very frequently used for cyclic compounds.
Condensed formula Bond line formula
CH3CH 2CH3
CH3CH 2CH 2OH
CH3CH(OH)CH3

Multiple bonds are also included in bond-line formula. For example :
Condensed formula Bond line formula
Three-Dimensional Representation
None of the formulae that we have described so far conveys any information about how the atoms of a
molecule are arranged in space. There are several ways to represent the three dimensional structure of the
organic molecule on paper. For example: by using a solid and dashed wedge formula, the three dimensional
image of a molecule from a two dimensional picture can be perceived. In this representation, bonds that
project upwards out of the plane of the paper are indicated by a solid wedge , those that lie behind
the plane are indicated with a dashed wedge , and those bonds that lie in the plane of the paper are
indicated by a line ( ). Wedges are shown in such a way that the broad end of the wedge is towards the
observer. Generally, we only use three-dimensional formulae when it is necessary to convey information
about the shape of the molecule.
Wedge and Dash Representation

CLASSIFICATION OF ORGANIC COMPOUNDS Section - 2
Based upon the nature of carbon atom skeleton, the organic compounds have been classified into two
categories : Acyclic or Open Chain and Cyclic or Closed chain.

I. Open Chain or Acyclic Compounds : Compounds of carbon having open chain of carbon atoms,
branched or unbranched are called acyclic compounds.
Butane CH3 – CH2 – CH2 – CH3
Isopentane CH3  C H  CH 2  CH3
|
CH3
Open chain compounds are also known as aliphatic compounds since the earlier compounds of this class
were obtained either from animals or vegetable fats. (Greek, aliphatos  fats).
II. Cyclic or Closed Chain or Ring Compounds : Compounds of carbon having closed chain of
carbon as well as of other atoms are called cyclic compounds. Depending upon the constitution of the ring,
these are further divided into the following categories.
1. Homocyclic or carbocyclic compounds 2. Heterocylic compounds
1. Carbocyclic or Hom ocyclic Com pounds : Compounds of carbon having closed chain entirely made up
of carbon atoms are called carbocyclic or homocyclic compounds. These are further divided into two
groups.
(i) Alicyclic Compounds : Closed carbon chains except characteristic benzene ring, resembling in
properties with acyclic compounds. These include cycloalkanes, cycloalkenes and cycloalkadienes.
For e.g.,
(ii) Aromatic Compounds : Closed chain of only carbon atoms with alternate single and double bonds.
Benzene and its derivatives belong to this category. Some important examples of monocyclic, bicyclic
and tricyclic aromatic compounds are as follows.
(a) Monocyclic aromatic compounds :
(b) Bicyclic and Tricyclic aromatic compounds :

2. Heterocyclic compounds : Compounds of carbon having closed chain made up of carbon and other
atoms. The hetero atoms commonly found in these compounds are oxygen, nitrogen and sulphur and occa-
sionally, phosphorus, boron, silicon and some metal atoms like tin, selenium etc, may also be present.
Depending upon the chemical behaviour, these are further classified into the following two categories.
(i) Alicyclic heterocyclic compounds : Alicyclic compounds containing one or more heteroatoms in
their rings are called alicyclic heterocyclic compounds. For example:
(ii) Aromatic heterocyclic compounds : Aromatic cyclic compounds containing one or more het-
eroatoms in their molecules are called aromatic heterocyclic compounds. For example :
Note : An aliphatic compound burns with non-smoky flame (except CHCl3, CCl4). All aromatic compounds burn
with a smoky flame.
NOMENCLATURE OF ORGANIC COMPOUNDS Section - 3

The IUPAC (International Union of Pure and Applied Chemistry) has developed a systematic method of
naming organic compounds. This system gives a unique IUPAC name to every organic compound. However
before the IUPAC system came into existence, the trivial or common names for organic compounds were
used. These were based on their origin or certain properties. Some examples are as follows : (Please note
that the contents of following table are NOT to be memorised).
Compound Trivial Name Source of Compound
CH3OH Wood spirit Obtained by destructive distillation of wood
CH3OH Methyl alcohol Methu-spirit and hule-wood
NH2CONH2 Urea Obtained from urine
CH3COOH Acetic acid Obtained from Acetum-vinegar
(COOH)2 Oxalic acid Obtained from oxalis plant
HCOOH Formic acid Obtained from ants, in Latin Ants  Formicae.
C2H5OH Grain alcohol (Ethanol) Obtained by fermentation of grains.
6 Section
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These older names for organic compounds are still widely used by chemists and bio-chemists, and in com-
merce. For this reason it is necessary to learn the common names (Trivial Names) for some of the organic
compounds.
Trivial System Of Nomenclature

Classification of carbon atoms :
In trivial system of naming an organic compound, the carbon atoms of an alkane were classified on the basis
of the number of other carbon atoms attached to them, into four categories, viz., Primary carbon atoms,
Secondary carbon atoms, Tertiary carbon atoms and Quarternary carbon atoms.
Primary carbon atom : When a carbon atom is attached to one carbon atom, then it is primary carbon
atom or 1 carbon atom.
Secondary carbon atom : When a carbon atom is attached to two carbon atoms, then it is secondary
carbon atom or 2 carbon atom.
Tertiary carbon atom : When a carbon atom is attached to three carbon atoms, then it is tertiary carbon
atom or 3 carbon atom.
Quaternary carbon atom : When a carbon atom is attached to four carbon atoms, then it is quaternary
carbon atom or 4 carbon atom.
Consider following structure showing all four types of carbons.
Vinylic Carbon atom : Carbon atom of C = C is called as vinylic carbon atom.

Allylic Carbon atom : sp3 hybridized Carbon atom next to C = C is called as allylic carbon atom.
Benzylic Carbon atom : Carbon atom directly bonded to benzene ring is called as benzylic carbon atom.
Classification of Hydrogen atoms :

The hydrogen atoms of a sp3 carbon are classified on the basis of the carbon atoms to which they are
attached. A hydrogen atom attached to a primary carbon atom is a primary hydrogen atom, hydrogen atom
attached to a secondary carbon atom is secondary hydrogen atom and so forth. But there are no quaternary
hydrogen atoms as no hydrogen atom is attached to a quaternary carbon atom.

Note :
CH3
|
CH 3   CH 2  n  CH3 CH3  CH   CH 2  n  CH3 CH3  C   CH 2  n  CH3
 n  2 | |
CH3  n  0 CH3  n  0
Normal (n) stand for unbranched chain of carbon atoms. Iso indicate one CH3-side chain on second
carbon atom of the chain. Neo indicate two CH3-side chains on second carbon atom of the chain.
Note : Neopentane has only primary hydrogen atoms. Note : Isooctane has different structure.
CH3 CH 3 CH 3
| | |
CH 3  C  CH3 CH3  C  CH 2  CH  CH3
| |
CH3 CH 3
 - Carbon and  - Carbon atoms :

Carbon atom in the structure of compound to which a functional group (–OH, –CHO, Cl,. . . . . . . . . . etc.)
is attached is known as   carbon and the corresponding hydrogen is referred to as   hydrogen. The
carbon atom(s) adjacent to   carbon is known as   carbon(s).
   
C H3  C H 2  Cl C H3  C H 2  COOH
    
C H3  C H 2  CHO CH 3  C H 2  C H(Cl)  C H 3
 
H3 C  C  C H3 HCHO No  - Carbon and no  - Hydrogen
||
O
8 Section
Section 333
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IUPAC System of Nomenclature

The formal system of nomenclature used today is one proposed by the International Union of Pure and
Applied Chemistry (IUPAC). This system was first developed in 1892 and has been revised at regular
intervals to keep it up to date.The principle of IUPAC system is: Each different compound should have
a different name.
The IUPAC nomenclature involves the use of following terms :
1. Word root 2. Primary suffix 3. Secondary suffix 4. Prefix
1. Word Root : The word root represents the number of carbon atoms in the parent chain. For the
chains up to four carbon atoms special word roots are used whereas words (pent, hex, hept...etc.)
indicating the number of carbons in the chain are used for the compounds containing more than four
carbon atoms.
Some (straight) unbranched chains and their names :
Name Number of Structure Name Number of Structure

C -Atoms C -Atoms
Methane 1 CH4 Octane 8 CH3(CH2)6CH3
Ethane 2 CH3CH3 Nonane 9 CH3(CH2)7CH3
Propane 3 CH3CH2CH3 Decane 10 CH3(CH2)8CH3
Butane 4 CH3(CH2)2CH3 Undecane 11 CH3(CH2)9CH3
Pentane 5 CH3(CH2)3CH3 Dodecane 12 CH3(CH2)10CH3
Hexane 6 CH3(CH2)4CH3 Tridecane 13 CH3(CH2)11CH3
Heptane 7 CH3(CH2)5CH3 Tetradecane 14 CH3(CH2)12CH3

The word root of different carbon chains are obtained by leaving ‘ane’ from the name of the carbon
chain of the respective molecule. Some word roots are given below :
Chain Length Word Root Chain Length Word Root
C1 Meth  C7 Hept (a) 
C2 Eth  C8 Oct (a)
C3 Prop (a)  C9 Non (a) 
C4 But (a)  C 10 Dec (a)
C5 Pent (a)  C 11 Undec (a) 
C6 Hex (a)  C 12 Dodec (a) 
Note : Extra ‘a’ given in parenthesis is used only if the primary suffix (explained later) to be added to the word root
begins with a consonant (execpt y). In general, the word root for any carbon chain is alk.
2. Primary Suffix : Primary suffix is used to indicate saturation or unsaturation in the carbon chain.
While writing the name, primary suffix is added to the word root. Some of the primary suffixes are
given below in the following table.
Nature of Carbon Chain Primary Suffix
Saturated Carbon Chain ane
Unsaturated Carbon Chains
One C=C bond ene
Two C=C bonds diene
Three C=C bonds triene
One CC bond yne
Two CC bonds diyne

3. Secondary Suffix : Secondary suffix is used to indicate the functional group in the organic com-
pound. It is added to the primary suffix by dropping its terminal ‘e’. Secondary suffixes for various
functional groups are given in the following table.
Family of General Functional Secondary IUPAC name of

Compound Formula Group Suffix the family (Saturated)
Alcohols ROH OH ol alkanol
Thioalcohols RSH SH thiol alkanethiol
Amines RNH2 NH2 amine alkanamine
Aldehydes RCHO CHO al alkanal
Ketones RCOR >C=O one alkanone
Sulphonic Acids RSO3H SO3H sulphonic alkane sulphonic acid
Anhydrides CO)2O oic alkanoic anhydride
anhydride
Carboxylic acids RCOOH COOH oic alkanoic acid
Amides RCONH2 CONH2 amide alkanamide
Acid chlorides RCOCl COCl oyl alkanoyl chloride
Esters RCOOR COOR oate alkyl alkanoate
Nitriles RCN CN nitrile alkane nitrile
In addition to these some functional groups are represented as prefixes.They are discussed later
Note : (i) If the name of the secondary suffix begins with a consonant (except y), the terminal ‘e’ of the primary
suffix is retained while adding secondary suffix to it. For example : Thioalcohols have secondary
suffix thiol and thus ’e’ of ane should not be dropped, i.e., IUPAC name is Alkane thiol.
(ii) The terminal ‘e’ of primary suffix is also retained if some numerical prefixes like di, tri etc. are used
before the secondary suffix.

4. Prefix : The part of the name which appears before the word root is called prefix. Different prefixes are
used for different categories of groups present in molecule.
(i) Alkyl Groups : The univalent groups or radicals obtained by the removal of one H atom from a
molecule of paraffin are called alkyl groups. These alkyl groups have names that end in yl. The
symbol ‘R’ is often used to represent an alkyl group. Some alkyl groups with their prefixes are given
in the following table.
Alkane Alkyl Group Abbreviation Prefix
CH4 (Methyl) CH3  Me Methyl
C2H6 (Ethyl) CH3CH2  Et Ethyl
C3H8 (n  Propyl) CH3CH2CH2  nPr nPropyl
C3H8 (Isopropyl) CH3  C H  isoPr Isopropyl or

| (1  Methylethyl)
CH 3
C2H4 (Ethene) CH2= CH- - Vinyl (Ethenyl)
C3H6 (Propene) CH2= CH-CH2- - Allyl
C6H6 (Benzene) C6 H 5 - Ph- Phenyl

(ii) Some functional Groups are always indicated by prefixes instead of secondary suffixes. These with
their prefixes are given in the following table.
Functional Group Prefix Family IUPAC Name
-NO 2 Nitro R-NO2 Nitroalkane
-OR’ Alkoxy R-OR’ Alkoxyalkane
-Cl Chloro R-Cl Chloroalkane
-Br Bromo R-Br Bromoalkane
-I Iodo R-I Iodoalkane
-F Fluoro R-F Fluoroalkane
-N = O Nitroso R-NO Nitrosoalkane
O epoxy epoxyalkane

(iii) In polyfunctional compounds (compounds with more than one functional groups), one of the func-
tional groups is treated as principal functional group and is indicated by the secondary suffix whereas
other functional groups, treated as substituents, are indicated by the prefixes. The order of priority
among various functional groups to be treated as principal functional group has been discussed later in
this chapter. The prefixes for various functional groups are given in the following table.
Prefixes for functional groups in polyfunctional compounds
Functional Prefix Functional Prefix

Group Group
OH Hydroxy COOH Carboxy
CN Cyano COOR Carbalkoxy
NC Isocyano COX Haloformyl
CHO Formyl CONH2 Carbamyl
SH Mercapto NH2 Amino
SR Alkylthio =NH Imino
NHR alkylamino -NR2 dialkylamino
SO3H sulpho >C = O keto / oxo
Writing the IUPAC name of Organic Compounds :

While writing the IUPAC name of a compound word root, prefix, primary suffix, secondary suffix, follow
the order:
Prefix(es) + Word root + Primary suffix + Secondary suffix
The above arrangement is illustrated by the following examples :

Compound Prefix Word root P. suffix Sec. suffix IUPAC Name
CH 3  CH  CH 2  CH 2OH Methyl but an ol 3-Methylbutane-1-ol

|
CH3
CH3  C  CHOH Bromo prop en ol 2-Bromoprop-1-en-1-ol

|
Br
The Rules for naming Organic Compounds :

I. For Saturated Compounds
1. Selection of longest chain :
 The longest possible carbon chain is selected and the compound is named as derivative of hydrocar-
bon using word root.
The chain of 6 carbon atoms is selected.
 If more than one sets of longest possible chains are there, the selected longest chain should have :
(a) Maximum number of side chains or
(b) Minimum number of branched side chains
6 atoms chain with one side chain or one branched side chain is rejected.
6 atoms chain with two side chains or two unbranched side chains is
selected.
2. Numbering of selected chain :

The selected chain is numbered from one end to other. The numbers are called locants.
 Lowest number is assigned to first side chain (alkyl groups) or substituent group.
1 2 3 4 1 2 3 4 1 2 3 4 5
CCCC CCCC C C  C C  C
| |
Cl CH 3

 If two different alkyl groups are at same position from opposite ends, lowest number is given to the
one coming first in alphabetical listing.
7 6 5 4 3 2 1
C C C C C C C
| |
CH3 C2 H 5
Note that ethyl gets ‘3’ as the locant, not methyl.

 If two different substituents are at same position from opposite ends, lowest number is assigned in
order of their alphabets.
1 2 3 4 4 3 2 1
C C  C  C C C  C  C
| | | |
Cl I Cl Br
 If a substituent (such as halogen, or nitro group) and a side chain are at same position from opposite
ends, lowest number is assigned to substituents.
4 3 2 1
C C  C C
| |
CH3 I
 If more than two substituents and side chains are present, then the set of locants are compared term
by term, and that set is preferred which gets the least term at the first point of difference. This is the
lowest set of locants rule.
7 6 5 4 3 2 1
C C C C C  C C 2, 3, 6 is accepted.
| | | 2, 5, 6 is rejected.
CH3 CH3CH3
1 2 3 4 5
C  C C  C C 1, 2, 3, 5 is accepted.
| | | | 1, 3, 4, 5 is rejected.
Cl I CH3 Br
10 9 8 7 6 5 4 3 2 1 2, 7, 8 is accepted.
C  C  C C  C  C C  C  C C
1 2| 3 4 5 6 7 | 8| 9 10 3, 4, 9 is rejected.
C C C

3. Arrangement of prefixes :
 Alkyl nature of side chain or substituent group is identified and reported as prefix with its number
(locant) in hydrocarbon name in alphabetic order.
4 3 2 1
H3 C C H  C H  C H 3
| | 2-Bromo-3-chlorobutane
Cl Br
1 2 3 4
H 3 C H C H C  C H 3 2-Chloro-3-iodobutane
| |
Cl I
1 2 3 4 5
H3 C  H C  H C  C H 2  C H3 3-Chloro-2-methylpentane
| |
H 3C Cl
 If more than one similar alkyl chains or substituents are present, prefix names are modified by putting
di, tri....terms.
4 3 2 1
C H3  C H  C H  C H3 2, 3-Dimethylbutane
| |
CH 3 CH3
 If more than one similar alkyl groups or substituents are present at same position, their locant is also
repeated.
CH3
1 2| 3
H3C  C  CH3 2, 2-Dimethylpropane
|
CH3
 In case side chain is also branched, it is numbered from the carbon atom attached to main chain and
is generally written in brackets.
1 2 3 4 5 6 7 8
C H3  C H  C H 2  C H 2  C H  C H 2  C H 2  C H3 5-(1-Methylethyl)-2-methyl-octane
| 1|
CH 3 C H  CH3
2|
CH3

1 2 3 4 5 6 7 8
C H3  H 2 C C H 2  C H  C H 2  C H 2  C H 2  C H 3 4-(1, 1-Dimethylethyl)octane
|1 2
CH3  C H  C H3
|
CH3
II. For Unsaturated Hydrocarbons

1. Select the longest possible carbon chain having maximum number of unsaturated carbon atoms or maximum
number of double or triple bonds, even if prior rule is violated.
5 carbon atoms chain with two unsaturated carbons or one

double bond is selected.
2. Lowest number (locant) is assigned to first unsaturated carbon even if prior rule is violated.
1 2 3 4 1 2 3 4 1 2 3 4 5 6
C  C C  C C  C C  C C  C C  C  C C
|
CH3
3. In case of unsaturation suffix, name of unsaturation is used with hydrocarbon name, i.e.
C = C bond ane of hydrocarbon is replaced by ene.
C  C bond ane of hydrocarbon is replaced by yne.
4. In case of more than one double bonds we use di, tri etc. For example: diene or triene.
CH3 – CH = C = CH2 Buta-1, 2-diene
CH2 = CH – CH = CH2 Buta-1, 3-diene
5. If a compound contains both the unsaturations then compound is named as Alkenyne with numbering as
low as possible given to multiple bonds, following the lowest set of locant rule.
1 2 3 4 5
H C  C  C H  C H  C H3 Pent-3-en-1-yne
If there is a choice i.e. when the double bond and the triple bond are at the same distance from the two ends
then the double bond gets the preference over the triple bond in the numbering.
6 5 4 3 2 1
H C  C  C H 2  C H2  C H  C H 2 Hex-1-en-5-yne

III. For Functional Groups

1. Select the longest possible carbon chain having maximum number of functional groups even if prior rules are
violated, For example :
5 carbon chain inclusive of two functional groups is selected
2-ethylpentane-1, 4-diol
2. When the functional group itself contains a C atom, then the carbon atom of functional group is to be
included in deciding the longest carbon chain.
C – C – CN 3 carbon chain, i.e., C atom of cyanide is also included.
C – C – C – CHO 4 carbon chain, i.e., C atom of aldehyde is also included.
3. The lowest number (locant) is assigned to the functional group even if prior rules are violated.
5 4 3 2 1 1 2 3 4 5 5 4 3 2 1
C  C C  C C  OH C  C C C  C C  C C  C C
| | |
OH CH3 OH
4. The order for numbering a carbon chain, thus follows the order :
Functional Group then Unsaturation then Substituents and Side chains (or alkyl groups)
7 6 5 4 3 2 1 Lowest number to OH group.

C C C C C CC
|
OH
1 2 3 4 5 6 7
C C C C CCC OH is at equidistant from two ends and thus next low-
| est number to unsaturations.
OH
7 6 5 4 3 2 1 Lowest locant to OH group (not to double bond).
C  CCCCC C
|
OH
IUPAC names of some families of Organic Compounds :

1. Carboxylic Acids : The IUPAC name of acids is derived from the name of the corresponding alkane by
dropping the ending – e and putting the suffix – oic acid.

HCOOH CH3COOH
Methanoic acid Ethanoic acid
The position of the substituent is indicated by the usual numerals
4 3 2 1 5 4 3 2 1
H C  C  C H 2  C OOH H3 C  C  C  C H 2  C OOH
But-3-yn-1-oic acid Pent-3-ynoic acid
The cyclic acids cannot be named in this manner. To name them, the name
of the corresponding cycloalkane precedes the word carboxylic acid.
Cyclobutanecarboxylic acid
2. Aldehydes : Aldehydes have a hydrogen atom attached to the carbonyl group. The common name of an
aldehyde is derived from the corresponding carboxylic acid by dropping the suffix oic acid and adding the
suffix –a. For example :
HCOOH HCHO
Methanoic acid Methanal
4 3 2 1 5 4 3 2 1
H 2 C  C H  C H 2  C HO H C  C  C H  C H 2  C HO
|
CH 3
But-3-en-1-al 3-Methylpent-4-yn-1-al
3. Ketones : The suffix ane is changed to  one i.e. alkanone. The numbering commences from that end of the
chain which gives the lowest number to the carbonyl group. It is always necessary to prefix the name by a
number to specify the position of the carbonyl group.
O O
|| ||
C H3  C  C H3 C H3  C H 2  C  C H3
3 2 1 4 3 2 1
Acetone (Propan-2-one) Butan-2-one
O O
4 || ||
C H3  C H  C H 2  C  C H 3 C H3  C H  C H  C  C H3
5 | 3 2 1 5 4 3 2 1
CH3
4-Methylpentan-2-one Pent-3-en-2-one

4. Ethers : The common name of ethers is derived by naming the alkyl groups and adding the word ether. The
smaller group is written first.
C2H5OCH3 Methyl ethyl ether
C6H5OC(CH3)3 t-Butyl phenyl ether
The IUPAC nomenclature is rarely used. Ethers are named as Alkoxy Alkanes. The larger alkyl group is
chosen as the parent.
4 3 2 1 2
CH3OCH 2CH3 C H3  C H 2  CH  O  CH 3 C H 2  C O  CH 2CH3
1| |
CH3 3 CH3
Methoxy ethane 2  Methoxybutane 2  Ethoxy propene
In cyclic ethers, the oxygen atom is contained in a ring of carbon atoms. While numbering the cyclic group,
oxygen atom is always given number – 1. While naming a prefix Epoxy is added to the name of carbon
atoms in the cyclic chain.
5. Esters : In the IUPAC system the acid chain is used as the stem in naming the ester. The suffix –oate
replaces the –oic acid of carboxylic acids. It is necessary to number the substituent on the chain. The first
part of the name is derived from the alkyl group of the corresponding alcohol.
HCOOCH3 CH3COOCH3
Methylmethanoate Methylethanoate
4 3 2 1
CH3CH2COOC2H5 C H 2  C H  C H 2 C OOC 2 H5
Ethylpropanoate Ethylbut-3-en-1-oate
6. Amines : In the IUPAC system of nomenclature, amines are named similar to alcohols. The longest con-
tinuous carbon chain having max. no of amines determines the root name. The –e ending in the alkane
named is replaced by suffix - amine. A number is needed to specify the position of the substituents.
CH3CH2OH Ethanol
CH3CH2NH2 Ethanamine

4 3 2
C H 2  C H  C H 2  NH 2 But-3-en-2-amine
|
1 CH3
Secondary amines and Tertiary amines :

The name of any alkyl group bonded to nitrogen is preceded by an “N” (in Italic) to indicate that the group
is bonded to a nitrogen rather than to carbon.
H3C  CH 2  N H N-Methylethanamine
|
CH3
1 2
H3 C C H  N H  C H 2  CH 3 N-Ethylbutan-2-amine
|
3 C H2
|
4 CH3
H3C  CH 2  N  CH 2  CH3 N-Ethyl-N-methylethanamine

|
CH3
4 3 2
H3 C C H 2  C H  N  CH 2  CH3 N, N-Diethylbutan-2-amine
| |
1CH3 C H 2
|
CH3
All the substituents (regardless of whether they are attached to the nitrogen or to the parent hydrocarbon)
are listed in alphabetical order. The chain is numbered such that the functional group suffix gets the lowest
possible number.
7. Nitriles : While writing the IUPAC name, the cyano group takes the preference and its carbon atom is
numbered as 1, only suffix -nitrile is added to the name of parent hydrocarbon (including the carbon of
group).
3 2 1 3 2 1 5 4 3 2 1
C H3 C H 2 C N H3 C  C H  C N H 3 C C H  C H  C H  C N
| |
CH 3 CH3
Propanenitrile 2-Methylpropanenitrile 2-Methylpent-3-enitrile

Rules for IUPAC Nomenclature of Polyfunctional Compounds :

Organic compounds having polyfunctional groups are named as follows :
1. Principal functional group : When an organic compound contains two or more different functional
groups, one of the functional groups is selected as the principal functional group while all other groups (also
called the secondary functional groups) are treated as substituents. The choice of the principal functional
group is made on the basis of the following order of preference.
– COOH > – SO3H > – (CO) 2O > – COOR > – COX > – CONH 2 > – CN > – CHO >
> C = O > – OH > – phenol > – SH > – N H 2 > – OR > > –CC–
The secondary suffixes for these functional groups have already been listed before.
All the remaining functional groups such as halo (fluoro, chloro, bromo, iodo), nitroso (NO), nitro
(–NO2), and R (alkyl), C6H5 etc. are always treated as substituent group.
It may be noted that while writing the names of the polyfunctional compounds, the principal functional group
is indicated by adding the secondary suffix to the word root while the secondary functional groups are
indicated by adding suitable prefixes to the word root. The prefixes for secondary functional groups are
listed before.
2. Selecting the principal chain : While selecting the principal chain present in a polyfunctional compound
care should be taken that it must contain the principal functional group and the maximum number of second-
ary functional groups and multiple bonds, if any.
3. Numbering the principal chain : The principal chain present in a polyfunctional compound must be
numbered in such a way that the principal functional group gets the lowest possible number followed by
double bond, triple bond and the substituents, i.e.
Principal functional group > Double bond > Triple bond > Substituents.
4. Alphabetical order : The prefixes for the secondary functional groups and other substituents should be
placed in alphabetical order before the word root as explained earlier. If, however, two groups of the same
family (eg. halogens) occupy identical positions from either end of the parent chain, the lower number must
be given to the group whose prefix comes first in the alphabetical order. For example :
4 3 2 1
Cl C H 2 C H 2 C H 2 C H 2 Br 1–Bromo–4–chlorobutane (Correct)
1 2 3 4
Cl C H 2 C H 2 C H 2 C H 2 Br 4–Bromo–1–chlorobutane (Wrong)
The rest of the rules for numerical prefixes are the same as explained earlier.
If more than one kind of functional groups are present, the functional group placed above( in the order of
preference) decides suffix name.

CH3  C  COOH CH3  C  CH 2OH

|| ||
O O
2-Ketopropanoic acid 1-Hydroxypropan-2-one
O
||
CH3  C  CHO
|| CH3  C CH  CHO
|
O CH3
2-Ketopropanal 2-methyl-3-oxobutan-1-al
Naming of Alicyclic Compounds :

The nomenclature for alicyclic compounds is derived by putting another prefix ‘cyclo’ before the word root
of carbon atoms in ring. The suffixes ane, ene are written depending upon the nature of molecule, i.e.,
saturated (ane) or unsaturated (ene) for double bond.
-1, 1-Dimethylcyclopentane 1-Methylcyclohex-1-ene 1, 2-Dimethylcyclopent-1-ene
3-Methylcyclohex-1-ene 1, 3-Dimethylcyclohex-1-en
3-Bromocyclohex-1-ene Cyclohex-2-en-1-ol 3-Bromocyclohex-2-en-1-ol
Note : From above examples, we can see that substituted cycloalkanes are named as derivatives of parent
cycloalkanes. The substituted alkyl groups or functional groups around the ring from the point of greatest
substitution providing the lowest series of numbers.

Bicyclic Compounds : (This topic is for reference only, not in JEE syllabus).
Bicyclic compounds are compounds that contain two rings.
1. If the two rings share one carbon, the compound is a spirocyclic compound or simply spiro compound.
For example :
2. If the two rings share two adjacent carbons, the compound is a fused bicyclic compound.
3. If the two rings share more than two carbons, the compound is a bridged bicyclic compound.
Nomenclature of Bicyclic Compounds :

1. Bicyclic compounds are named by using the alkane name to designate the total number of carbons and the
prefix bicyclo or spiro to indicate the number of shared carbons.
2. Prefix spiro indicates one shared carbon and bicyclo indicates two or more shared carbons. The following
compound, for example, contains seven carbon atoms and is therefore, a bicycloheptane.

The carbon atoms common to both rings (Number of such carbons is either one in spiro or two in bicyclic)
are called bridgeheads and each carbon chain of atoms, connecting the bridgehead atoms is called a bridge.
3. After the prefix spiro or bicyclic comes brackets that contain numbers indicating the number of carbons in
each bridge. These are listed in order of decreasing bridge length. For example :
4. Numbering in bicyclic compounds starts at any one bridge head carbon and moves along the longest carbon
bridge to the next bridge head carbon. Continue along the next longest carbon bridge to return to the first
bridge head carbon so that the shortest bridge is numbered last.

Note : Number of rings in polycyclic compounds = (S - A+1) where ‘S’ is the number of single bonds in the ring
and A is the number of carbon atoms in the ring.
Some Prominent IUPAC Examples



Nomenclature of Aromatic Compounds :

Aromatic compounds are cyclic compounds which contain one or more benzene type rings. Benzene is the
simplest hydrocarbon of aromatic series which has a planar cyclic ring of six carbon atoms having three
double bonds in alternate positions as shown below :
kekule structures Resonance hybrid

The carbon atoms of benzene are numbered from 1 to 6 as shown above. The benzene ring is called the
nucleus and groups containing at least one carbon atom that too directly attached to benzene nucleus are
called side chains. Benzene forms only one mono substituted derivative. However, it can form three disub-
stituted derivatives; namely 1, 2 ; 1, 3 and 1, 4 derivatives or ortho (o), meta (m) and para (p) deriva-
tives respectively.
Some Important Aromatic Hydrocarbons :
Toluene Ethylbenzene Vinylbenzene(Stryene) Isopropyl benzene(Cumene)
Phenol Anisole Acetophenone Aniline
Benzaldehyde Salicylaldehyde Benzenesulphonic acid Benzoic acid

o-Xylene m-Xylene p-Xylene Mesitylene
o-Cresol m-Cresol p-Cresol Cyano benzene
Catechol Resorcinol Hydroquinol 1, 4-Benzouilone
Salicylic acid m-Toluidiene Methyl benzoate Phthalic acid
Isophthalic acid Terephthalic acid m-Toluic acid Anthranilic acid

Picric acid 2, 4, 6-Trinitrotoluene (TNT) Pyrogallol Aspirin
Cinnamic acid Benzophenone Naphthalene  -Naphthol
 -Naphthol Anthracene Phenanthrene Azzulene
Homologous Series : A homologous series is defined as a family or group of structurally similar organic
compounds all the members of which contain the same functional group, show a gradation in physical and
similarity in chemical properties and any two adjacent (or consecutive) members of which differ by a –CH2
group. For example: alkanes constitute a homologous series.
The first six members of this series are :
CH4 C2H6 C3H8 C4H10 C5H12 C6H14

Methane Ethane Propane Butane Pentane Hexane
These hydrocarbons can be represented by the same general formula, CnH2n+2 where n is the number of
carbon atoms. Further, any two adjacent members of this class differ by a CH2 group.
If a hydrogen atom from the above hydrocarbons is replaced by a hydroxyl group i.e., – OH, we get a new
homologous series. This homologous series is called alcohols. The different members of this series can be
represented by the general formula CnH2n+1 OH. The first four members of this series are :
CH3OH CH3CH2OH CH3CH2CH2OH CH3CH2CH2CH2OH

Methanol Ethanol Propan-1-ol Butan-1-ol
Some other homologous series are alkenes, alkynes, alkyl halides, ethers, aldehydes, ketones, amines,
esters and carboxylic acids etc.

Characteristics of a Homologous Series :

1. Each homologous series can be represented by a general formula. For example, CnH2n+1 COOH is the
general formula of carboxylic acids.
2. All the members of a given homologous series possess the same functional group. For example, the func-
tional group of alcohols is the hydroxyl group i.e., –OH group. Similarly, the functional group of aldehydes
is the aldehydic group i.e., –CHO and that of the ketones is the ketonic group, i.e., > C = O.
3. The successive members of a homologous series differ by a CH2 group or by 12 + 2  1 = 14 mass units.
4. The individual members of a homologous series can be prepared by the general methods of preparation
developed for that series.
5. The physical properties such as density, melting point, boiling point of the members of a homologous series
show a regular gradation with rise in molecular mass.
6. The chemical properties of the members of a homologous series are similar though the first member may
vary considerably from rest of the members.
Degree of Unsaturation (DU)

Degree of Unsaturation also known as “index of Hydrogen deficiency (IHD)” or “rings plus double bonds”
is helpful in Organic Chemistry while drawing Chemical structures.
For a compound with formula : CaHbNcOdXe where X is F, Cl, Br or I,
1
DU   2  2a  b  c  e  or DU  1 [2+ 2  No. of C atoms -No. of H atoms + No. of N atoms -
2 2
No. of Halide atoms]
Rules :
(i) Do not cout group 16 elements e.g. O, S etc. Remove them from the formula but count H-atoms
attached to them.
(ii) Each double bond, adds ‘one’ to DU.
(iii) Each triple bond, adds ‘two’ to DU.
(iv) Each ring adds ‘one’ to DU.
1
(i) C3H6 : DU   2  2  3  6  1  It contains a double bond OR a ring.
2

1
(ii) C5H8 : DU   2  2  5  8  2
2
 Two double bonds OR 1 triple bonds OR 2 rings OR 1 double bond and 1 ring.
(iii) DU = 6: as it contains 3 double bonds, 1 triple bond, and 1 ring.
1 1
(iv) C6 H12O6 : DU   2  2  6  12  1 (v) C6H12 N 2 Br2 : DU   2  2  6  12  2  2   1
2 2
(vi) DU = 1(One ring) (vii) : DU = 2 (Two combined rings)
(viii) : DU = 5 (4 double bonds + 1 ring)
(ix) : DU = 5 (4 double bonds + 1 ring)
Note: DU  4 doesn’t demand but suggest the possibility of an aromatic (benzene) ring.
Illustration - 1 Draw the condensed structures of following compounds. Also write their IUPAC name.
(i) tert-Butyl alcohol (ii) Isopropyl methyl ether (iii) sec-Butyl ethyl ketone
(iv) Phenyl methyl ether (v) Isopropyl isobutyrate (vi) sec-Butyl formate
(vii) Methyl vinyl ether (viii) Isopropyl benzene (ix) Dimethyl n-propyl amine
(x) Methyl n-propyl acetylene
SOLUTION :
OH
1 | 3
(i) C H3  2C  C H3 : 2-Methylpropan-2-ol
|
CH3

1 2
(ii) C H3  C H3  O  CH 3 : 2-Methoxypropane
|
CH3
3
1 2 3 4 5 6
(iii) C H3 C H 2  C C H  C H 2  C H 3 : 4-Methylhexan-3-one
|| |
O CH3
(iv) : Methoxybenzene ; (called as anisole :

trade name as IUPAC name)
O
3 2 ||1 1 2
(v) C H3  C H3  C  O  C H 2  C H3 : (1-Methylethyl) 2-methyl propanoate
| |
CH3 CH3
O
|| 1 2 3
(vi) H  C  O  C H  C H 2 C H3 : (1-Methylpropyl) methanoate
|
CH3
(vii) CH3 – O – CH = CH2 : Methoxyethene
(viii) : (2-propyl) benzene (or cumene)

or (1- Methylethyl) benzene.
(ix) CH3  N  CH3 : N, N-Dimethyl-1-propan - 1 - amine

|
C H3 C H 2 C H3
1 2 3
(x) CH 3  C  C  CH 2  CH 2  CH3 : Hex - 2 - yne

Illustration - 2 Draw the bond line structures for each of above compounds in Illustration - 1
SOLUTION :
(i) (ii) (iii)
(iv) (v) (vi)
(vii) (viii) (ix)
(x)
Illustration - 3
Give the IUPAC names of the following structures.
SOLUTION :
OH
4 | 2 1
1. C H3  3C H  C H 2  C OOC 2 H5 Ethyl 3-hydroxybutanoate
4 3 2 1
2. C H3  C H 2  C H 2  C OCl 2-Bromobutanoyl chloride
|
Br
6 5 4 3 2 1
3. H 2 C  C  C H 2  C H 2  C H 2 C OOH 2- Hydroxy-5-methylhex-5-enoic acid
| |
CH3 OH
4. N-Ethyl-N-methyl-2-methylpropan-1-amine

4 3 2 1
5. C H2  C  C H  C H3 3-Methylbut-3-ene-2-ol
| |
CH3 OH
O
|| 2 3
6. ph  O  C  C H 2  C H3 (phenyl) 2-methylpropanoate
|
CH3
7. 2-Methylbut-3-en-1-al
8. 4, 5-Dimethyloct-4-ene
9. 2-Methyl-3-Oxopentanoic acid
10. 2-Methoxybenzoic acid
11. 2, 2-Dimethylpropan-1-al
12. 2-Methylcyclohexan-1-one
13. 2, 3-Dimethylcyclohex-1-ene

3 2 1
14. ph  C H  C H  C OOH 3-Phenylprop-2-enoic acid
7 6 5 4 3 2 1
15. C H3  C H  C H  C H  C H 2  C H  C HO 6-Hydroxy-2-methoxyhept-4-en-1-al
| |
OH OCH3
1
C H3
|
16. C2 H5  NH  C H  C H 2 C H 3 N-Ethylbutan-2-amine
2 3 4
17. 2(N-Methylamino)propanoic acid
18. N-Ethyl-N-methylaniline
19. 2-Methylpropanamide
20. But-2-en-1-al
2
21. C2 H5  C H  COOCH3 Trival Name : (Dimethyl)--ethylmalonate
| IUPAC Name: (Dimethyl)-2-ethylpropan-1, 3-
COOH3 dioate
3
22. Methylenecyclopentane

IN-CHAPTER EXERCISE-A
1. Give the dash structures of the following :
(i) Isobutyl radical (ii) Neopentyl radical
(iii) tert-Pentyl radical (iv) sec-Butyl radical
(v) tert-butyl radical (vi) Benzyl radical
2. Give IUPAC name of following :
CH3
|
(i)  CH 3 3 C  COOCH 3 (ii)  CH 3 2 CH  CH  CH  CH  CH 2
|
CH3
(iii) CH 3  CH  CH 2COOH (iv)  CH3 2 CH  C  CH3 2

| |
Cl OH
(v) CH 3  CH 2  CH 2  CH  C 2 H5 (vi) CH3  CH 2  C  CH 2CH3

| ||
COOH CH 2
CH3
|
(vii)  CH3 2 CH  CH  C  CH 2 (viii)  CH3 2 CH  CH  CH  CH3 2
| |
CH  CH3 2 N  CH3
|
CH3
C 2 H5
| CH
(ix) CH 3  C  C  C  CH3  2 (x) CH 3  CH 2  CH  CH  O  CH  CH3
| | 3
| |
CH3 CH 3
CH3 C 2 H5
3. Give the structure of following aromatic compounds :

(i) o-Cresol (ii) p-Toludine (iii) m-Toluic acid
(iv) Benzoyl chloride (v) Benzo phenome (vi) Aniline
(vii) Benzoic anhydride (viii) Acetophenone (ix) Phenol
(x) Terephthalic acid

4. Give IUPAC name of following :
(i) CH 3  C  CH3  2 CH 2  CH  CH3 (ii) H3C  CH 2  CH 2  C  CH 2

| |
CH3 C2 H5
(iii) CH 2  C  C  CH 2 (iv) CH3  CH  CH  C  CH3

| | ||
CH3 CH3 O
(v) H  COO  CH  CH3 (vi) CH 2  CHCH 2  C6H 5

|
CH3

ISOMERISM IN ORGANIC COMPOUNDS Section - 4
Isomerism : The phenomenon of existence of two or more compounds possessing the same molecular
formula but different chemical and physical properties is known as isomerism. Such compounds are indi-
vidually referred to as isomers. For example : CH3CH2OH and CH3OCH3 are isomers of each other.
We have two types of isomerisms:
1. Structural Isomerism : There are also called as Constitutional Isomers.

2. Stereo Isomerism :
Types of isomerism :
Structural Isomerism :
In this type of isomerism, the compounds possessing same molecular formula differ in their properties due
to the difference in the linkages of atoms inside the molecule, i.e., due to the difference in their structure. For
example: CH3CH2OH and CH3OCH3. Both have the molecular formula C2H6O but they differ in their
structures (Ethanol has CCO linkage while Methoxymethane has COC linkage).
H H H H
| | | |
H  C  C O  H H  C O  C  H
| | | |
H H H H
Ethanol Methoxymethane

Structural isomers differ both in their physical as well as chemical properties.

Structural isomerism is classified into following six types.
1. Chain Isomerism : In this type of isomerism, the compounds possessing same molecular formula differ in
their properties due to the difference in the arrangement of carbon chain present in them. In one of them the
chain may be straight while in other the chain may be branched.
 Butane (C4H10) has two chain isomers :
CH3 – CH2 – CH2 – CH3 CH 3  C H  CH 3

|
CH3
n-Butane Isobutane
 Pentane (C5H12) has three chain isomers :

CH3
|
CH3CH2CH2CH2CH3 H3CH 2 C HCH3 CH3  C  CH3
| |
CH3 CH3
n-Pentane Isopentane Neopentane
 Butyl alcohol (Butanol) has a chain isomer :
CH3 – CH2 – CH2 – CH2OH CH 3  C H  CH 2OH

|
CH 3
n-Butyl alcohol Isobutyl alcohol
 1Butene has a chain isomer :
CH3 – CH2 – CH = CH2 CH3  C  CH 2

|
CH3
But-1-ene Isobutene
 Aromatic Compounds may also have chain isomers :
n-Propylbenzene Isopropylbenzene

2. Positional Isomerism : In this type of isomerism, the compounds possessing same molecular formula
differ in their properties due to the difference in the position of either the functional group or the multiple
bond or the branched chain attached to the main carbon chain. For example :
 Pentan-2-ol and Pentan-3-ol are the positional isomers :

CH3 – CH2 – CH2 – CH(OH) – CH3 CH3 – CH2 – CH(OH) – CH2 – CH3
Pentan-2-ol Pentan-3-ol
CH 3  CH 2  CH 2  C H 2
|
CH 2  OH
Pentan-1-ol
 Butene has two position isomers :

CH3 – CH2 – CH = CH2 CH3 – CH = CH – CH3
But-1-ene But-2-ene
 Methylpentane has position isomers :
CH 3  CH 2  CH 2  C H  CH3 CH 3  CH 2  C H  CH 2  CH3
| |
CH3 CH3
2-Methylpentane 3-Methylpentane
Note that the position isomers have same parent chain.
 In aromatic compounds, for example, in benzene ring three different positions are possible for a disubsti-
tuted product. They are 12 (called as ortho), 13 (called as meta), and 14 (called as para). Disubstituted
benzene has three positional isomers. For example :
 Cresol has three positional isomers.
3. Funct ional Isom erism : In this type of isomerism the compounds possessing same molecular formula
differ in their properties due to the difference in their functional group, i.e., the functional isomers differ in the
functional group present in them. For example :

 Alcohols (execept mehanol) have their isomeric ethers.

eg. Ethyl alcohol and Dimethyl ether having molecular formula of C2H6O are functional isomers :
CH3CH2OH H3COCH3
Ethanol Methoxymethane
 Aldehydes have isomeric ketones.

Propionaldehyde (Propanal) and Acetone (Propanone) are functional isomers:
CH3CH2CHO CH3COCH3
Propanal Propanone
Methanal, Ethanal, and Benzaldehyde have no isomeric ketones.

 An acid may be isomeric to an ester.
Propionic acid and Methyl acetate (Methyl ethanoate) are functional isomers:
CH3CH2COOH CH3COOCH3
Propanoic acid Methyl ethanoate
Only Methanoic acid cannot have its isomeric ester.

Note that sometimes an alkadiene may be isomeric with an alkyne. This is also called as functional isomer-
ism.
 Butyne is isomeric to Butadiene :
CH3  CH2 C  CH H2C = CH  CH = CH2
But-1-yne Buta-1, 3-diene
 Unsaturated alcohols are isomeric to Aldehydes :
H2C = CHOH CH3CHO
Vinyl Alcohol Acetaldehyde
 Unsaturated alcohols containing three or more carbon atoms are isomeric to Aldehydes as well as
Ketones :
CH2 = CH  CH2OH CH3CH2CHO CH3COCH3
Allyl alcohol Propionaldehyde Acetone

 Aromatic alcohols may be isomeric to Phenols :
 Primary, Secondary, and Tertiary amines of same molecular formula are functional isomers :
CH3CH2CH2NH2 CH3 NH C2H5 CH3  N  CH3

|
CH3
n-Propyl amine (1°) Ethyl methyl amine (2°) Trimethyl amine (3°)
4. Metamerism : In this type of isomerism the compounds possessing same molecular formula differ in their
properties due to the difference in alkyl groups present in them. Thus, the metamers differ only in the alkyl
groups present and they have same functional group, i.e., they belong to same homologous series. For
example :
 Diethyl ether (Ethoxyethane) and Methyl propyl ether (Methoxy propane) are the metamers :
C2H5  O  C2H5 CH3  O  C3H7
Ethoxy ethane Methoxy propane
 Diethylamine and Methylpropylamine are also the metamers :

C2H5  NH  C2H5 CH3  NH  C3H7
Diethyl amine Methyl propyl amine
 Metamers of 3 amines (C6H15N) :
C2 H 5  N  C 2 H 5 C3H 7  N  CH3 C 4H9  N  CH3

| | |
C 2 H5 C 2H 5 CH3
Triethyl amine Ethyl methyl propyl amine Dimethyl butyl amine
 Esters also show metamerism, n-Propyl formate has Ethyl acetate and Methyl propionate as its metamers.
HCOOC3H7 CH3COOC2H 5 CH3CH2COOCH3
n-Propyl formate Ethyl acetate Methyl propionate

5. Tautomerism : This is a special case of functional isomerism. In this type of isomerism two functional
isomers exist together in equilibrium. The two forms existing in equilibrium are called as tautomers. For
example :
 Consider tautomerism in Acetaldehyde (keto group) and Vinyl alcohol (enol group).
 H C = CHOH
CH3CHO  2
Acetaldehyde Vinyl alcohol
Out of the two tautomeric forms, generally the keto form is more stable and exists in larger proportion. The
equilibrium between the two forms is dynamic, i.e., if one form is somehow removed by a reaction, some of
the amount of the other form changes into the first form so that similar equilibrium exists again.
Due to the presence of keto and enol form this type of tautomerism is known as ketoenol tautomerism. It
is the most commonly observed type of tautomerism.
The keto-enol tautomerism is possible only in those Ketones and Aldehydes in which at least one -
hydrogen atom is present so that it may convert the carbonyl group to enol group.
 Consider the compound Acetone, it has two tautomers, one has a keto group and other has an enol group.
O OH
||  ||
 CH3  C  CH 2
CH3  C  C H3 
keto  form Enol  form
 Another example of ketoenol tautomerism is observed in 2-Butanone. It has two nol forms :
OH O OH
|  ||  |

CH 2  C  CH 2  CH3   H 3C  C  CH 2  CH3
H3 C  C C H 2  CH3 
Hence It is observed that (as above), if the -hydrogen atoms are present on both the carbons attached to
carbonyl group, it can have more than one enol. Thus, larger the number of different -hydrogens in a
ketone, more is the number of enols . In most of the cases, the keto form is more stable than the enol by
some 45-60 kJ/mol (11-14 kcal/mol). The main reason for this difference is that a carbon-oxygen double
bond is stronger than a carbon-carbon double bond.
Stabilized Enols :
Certain structural features can make the keto-enol equilibrium more favourable by stabilizing the enol form
such as extended conjugation, intramolecular H-bonding and aromatic characters etc.

The enol form is phenol, and the stabilization gained by forming an aromatic ring is more than enough to
overcome the normal preference for the keto form.
The 1, 3- arrangement of two carbonyl groups in -diketones leads to a situation in which the keto and the
enol forms are of comparable stability.
6. Ring chain isomerism : Compounds having the same molecular formula but possessing open chain and
cyclic structures are called ring chain isomers and the phenomenon is called ring chain isomerism. For
example:
 Alkenes are isomeric with Cycloalkanes :
CH 3CH = CH2
Propene
CH3CH2CH = CH2
But-1-ene
 Alkynes and Alkadienes are isomeric with Cycloalkenes :

CH3CH2C  CH CH2 = CH  CH = CH2
But-1-yne Buta-1, 3-diene

Stereo-isomerism :
The stereoisomerism is defined as the type of isomerism in which compounds possessing same molecular
formula and same structural formula, differ in their properties due to the difference in the arrangement in
space of their atoms in the molecule. Stereoisomers usually differ in some of their physical properties but
they may not differe much in their chemical properties.
In order to understand stereoisomerism, we need to familiarize ourselves with the following concepts.
Chirality
A molecule or any other object that cannot be superimposed onto its mirror image is said to be chiral, and
the phenomenon is known as chirality. Chirality arises from asymmetry in a molecule.
Objects and molecules that are super-imposable on their mirror images are achiral.
A test for chirality is to look for a plane of symmetry in the molecule. If there exists such a plane of symmetry
that divides the molecule into two identical halves, then such a molecule is achiral.
for e.g. n-butane is achiral while 2-chlorobutane is chiral.
CH3  CH  CH 2  CH3
|
Cl
Plane of symmety No plane of symmetry

n-Butane - ACHIRAL 2-Chlorobutane - CHILAR

Stereocentre-An-Asymmetric Carbon
A sp3 hybridised carbon atom that is bonded to four different substituents or groups (including hydrogen) is
a stereocentre.
;* stereocentre or chiral centre]
For example, consider Lactic acid (2-Hydroxy propanoic acid):
A molecule with only one stereocentre will be chiral, because such a molecule does not posses a plane of
symmetry and hence is non-super imposable on its mirror image.
Note: Molecules containing more than one stererocentre may or may not exhibit chirality depending on whether
they have a plane of symmetry and are superimposable on their mirror images or not.
Plane Polarized Light

Light is an electromagnetic wave, with oscillating electric and magnetic fields.
If we were to view a beam of ordinary light from one end, and if we could actually see the planes in which
the electrical oscillations were occuring, we would find that oscillations of the electric field were occuring in
all possible-planes, perpendicular to the direction of propagation. (The same would be true for magnetic
field)
Oscillations of the electric field of ordinary light occur in all possible planes,
perpendicular to the direction of propagation [Note that the direction of
propagation is perpendicular to the plane of paper].
When ordinary light is passed through a polarizer like Nicole prism, the light
that emerges from the polarizer is oscillating only in one plane. Such light is
called plane-polarized light. In the given figure, the plane of oscillation of the
electric field of plane-polarized light is vertical.

Optical Activity
It is found that some compounds have a tendency to rotate the plane of plane-polarised light i.e., when any
such compound is placed in the path of plane - polarised light, the compound rotates the plane of this light
by a certain angle. Such a rotation is known as optical rotation and the phenomenon is called as Optical
activity.
This optical rotation may be clockwise (+) or anti-clockwise (-). The molecules rotating the plane in clockwise
direction are termed as dextro-rotatory (d) or (+), while the molecules rotating the plane in anti-clockwise
direction are termed as laevo-rotatory (l) or (-). The instrument used to measure optical rotation is called as
Polarimeter.
Optical activity is a characteristic of chiral molecules only. We know that a chiral molecule is one that cannot
be superimposed on its mirror image. Such a molecule and its non-super imposable mirror image form a pair
of enantiomers.
Enantiomers rotate the plane of plane polarized light to the same extent but in opposite direction. i.e., one of
them is dextro-rotatory and the other is laevo-rotatory.
Consider 2-Chlorobutane, CH3-CH(Cl)-CH2CH3.
Whether a compound is dextro-rotatory or laevo-rotatory can only be determined experimently, and not by
merely looking at the 3-D structure of compound.
Another very common example is of Lactic Acid, CH3-CH(OH)-COOH.
Note: Any dissymmetric compound having non-superimposable mirror image is optically active compound.

Racemic mixture
An equimolecular mixture of (+) and () (i.e., d and l) forms of an optically active compound is not able
to rotate the plane of plane - polarised light because of the mutual cancellation. Such a mixture is known as
a racemic mixture or dl mixture or () mixture and is optically inactive. The phenomenon is called as
reacemisation. Thus, lactic acid can be said to be of three types, i.e. (+) lactic acid, () lactic acid, and ()
lactic acid.
Note:  Representation of a molecule in tetrahedral three dimensional shapes is a

little bit difficult. A simplified way to represent such molecules on plane of
paper is by using the Fischer projection formula. In a Fischer projection
formula, (+) lactic acid is represented as:
 Fischer projection formula can’t be rotated by 90o and can’t be lifted from
the plane of the paper.
The chiral carbon atom is represented by a point of intersection of a horizontal and a vertical line. Atoms or
groups attached with horizontal line are supposed to be coming forward above the plane of paper (i.e.,
towards the viewer) while the groups attached with vertical line are going back behind the plane of paper
(away from the viewer). Thus, the two enantiomers of lactic acid are represented as follows :
Compounds Containing Two Stereocentres

A useful rule gives the maximum number of stereoisomers of a compound. Total number of stereoisomers =
2n (only configurational), where n = number of stereocentres in the molecule. So, a molecule with 2
stereocentres can have a maximum of 22 = 4 stereoisomeric forms.
* *
Consider 2, 3-Dibromopentane, CH 3  CH  CH  CH 2CH3 has 4 stereoisomers as shown below..
| |
Br Br

 Enantiomers are non-super imposable mirror images.

 Diastereomers are non-super imposable non-mirror images.
Note that the pairs I & II and III & IV form pairs of Enantiomers (Optical Isomers).
And pairs I and III and I and IV and II and III etc. form pairs of diastereomers.
Meso Compounds and Diastereomers

A structure with two stereocentres does not always have four possible stereoisomers. Sometimes, there are
only three. Thiss happens because some molecules are achiral even though they contain stereocentres. To
understand this, let us consider the example of tartaric acid:
HOOC-CH(OH)-CH(OH)-COOH
Tartaric Acid has only three stereomers.
I and II are non-superimposable mirror images of each other (ENANTIOMERS).

If we look at structure III, it also has 2 stereocentres. But we can also note the presence of a plane of
symmetry in it. As described earlier, such a molecule is achiral, despite the presence of 2 stereocentres, and
it shall be imposable on its mirror image. Such an isomer, which has stereocentres, but the molecule is
overall Achiral is called a meso-isomer.
Note: Observe that in the case of 2, 3-Dibromopentane (above), there is no plane of symmetry in either of
stereomers.
Note: (i) The meso compound and its mirror image both represent a single configuration (i.e., one isomer)
(ii) The meso-isomer is optically inactive (achiral). In the meso-isomer, half part of the molecule gives
clockwise while the other half gives anti-clockwise rotation (due to a plane of symmetry), and thus,
because of internal compensation, the molecule is optically inactive. While the racemic mixture is not
able to show optical rotation because of external compensation, the meso form is not able to show
any rotation because of internal compensation.
(iii) The meso-tartaric acid is not the enantiomer of either I or II forms. The molecules (configurations)
which are not mirror images of one another are called diastereomers. The meso-tartaric acid is a
diastereomer of I and II forms of tartaric acid.

Geometrical Isomerism :
Consider the compound, 2-Buten-1, 4-dioic acid, HOOC CH = CH COOH. This compound can be
expressed in two different forms as follows:
Since free rotation about C = C Pi () bond is not allowed, these two geometries are non-inter convertible
and different. These are geometrical isomers of each other.
In Maleic acid, both  COOH groups are attached in the same direction, while in Fumaric acid, the two
 COOH groups are attached in opposite direction. The geometrical isomer in which the similar groups are
present in same direction (on the same side of double bond) is called as the cis isomer, while the one in
which similar groups are in opposite direction is called as the trans isomer. Geometrical isomerism is also
known as cistrans isomerism. Maleic acid is a cis isomer while Fumaric acid is the trans isomer.
 2Butene also exhibits geometrical isomerism :
 1, 2-Dichloroethene is another example of geometrical isomerism :
 Note that an organic compound having a bond may or may not show geometrical
isomerism.
If two similar groups (or atoms) are attached to same carbon atom(forming a double bond) in a
compound, then it does not show geometrical isomerism.
An organic compound having can have the following different forms :
I. cis-isomer trans-isomer

II. cis-isomer trans-isomer
Such compounds show geometrical isomerism and we can classify them as having cis and trans forms.
III.
Such compounds where 2 similar groups are attached to one carbon atom, do not show geometrical
isomerism.
Important Alkenes which do not show geometrical isomerism include Ethene (CH2= CH2), Propene (CH3CH
= CH2), 1-Butene(C2H5CH = CH2), Isobutene (Me2C = CH2) and Styrene(C6H5CH = CH2).
IV.
Such a pair of compound are geometrical isomers, but cannot be classified as cis-trans.
Note : cis form is comparatively less stable because of the mutual repulsion between the groups. Thus, Maleic acid
is less stable than Fumaric acid. Geometrical isomers differ in their physical properties and also in some of
their chemical properties. The trans form, being symmetrical has a zero dipole moment. Even in the cases
when the trans form is not symmetrical, it has a low dipole moment in comparison to the cis form. Since the
trans form is less polar, it is less soluble in water.
Also, being polar the cis isomer has comparatively higher boiling point. However, melting point of trans
isomer is higher because of better packing in crystal due to symmetry in molecule. Besides, the cis isomer
has higher heat of hydrogenation, heat of combustion, density, and refractive index. Accordingly, Fumaric
acid has higher melting point and is very sparingly soluble in water in comparison to Maleic acid.
Geometrical Isomerism in Cyclic Compounds :

In cyclic compounds the rotation about a C–C single bond is not free because of the rigidity caused by the
presence of other carbons of the ring which keep them tightly held. Thus, a disubstituted cyclic compound
(having the two substitutions at separate carbons) will exist as geometrical isomers. For example, consider
1, 2-Dimethylcyclopentane:

Other examples of Cycloalkanes and their derivatives showing Geometric Isomerism are illustrated below :
Conformational Isomerism :
Conformations are different spatial arrangements of a molecule that are generated by rotation about single
bonds. Conformational analysis is the study of how conformational factors affect the structure of a molecule
and its physical and chemical properties.
I. Conformational analysis of Ethane: Ethane is the simplest hydrocarbon that can have distinct
conformations. These two conformations are the staggered conformation and the eclipsed conformation.
In the staggered conformation, each C H bond of one carbon bisects an H C H angle of the
other carbon.
Some commonly used drawing of the staggered conformation of ethane.
In the eclipsed conformation, each C H bond of one carbon is aligned with a C H bond of the
other carbon. Some commonly used drawings of the eclipsed conformation of ethane.

Note: In a Newman projection (figure C), we sight down the C C bond, and represent the front carbon by a
point and the back carbon by a circle. Each carbon has three other bonds that are placed symmetrically
around it.
The structural feature that above mentioned figure illustrate is the spatial relationship between atoms on
adjacent carbons. Each H-C-C-H unit in ethane is characterized by a torsion angle or dihedral angle, which
is the angle between the H-C-C plane and the C-C-H plane. The dihedral angle is easily seen in a Newman
projection of ethane as the angle between C-H bonds of adjacent carbons.
Note: The staggered conformations have only gauche or anti-relationship between bonds on adjacent atoms. The
staggered and eclipsed conformation inter convert by rotation around the C-C bond, and do so very rapidly.
Note: Different conformations of the same compound are sometimes called conformers or rotamers. Of the two
conformations of ethane, the staggered is 12kJ/mol more stable than the eclipsed. The staggered conformation
is most stable conformations; the eclipsed is the least stable conformation.
Conformations in which the dihedral angle between adjacent bonds are other than 60o are said to have
torsional strain. Eclipsed bonds produce the most torsional strain; staggered bonds none.
Note: In principle ethane has an infinite number of conformations that differ by only tiny increments in their dihedral
angle. Not only is the staggered conformation more stable than the eclipsed, it is the most stable of all of the
conformations; the eclipsed is the least stable.

Figure: Potential energy diagram for rotation about the carbon-carbon bond in ethane
II. Conformational Analysis of Butane :

We consider conformations related by rotation about the bond between the middle two carbon (CH3CH2-
CH2CH3). Butane has four main conformations [two eclipsed type and two staggered type].
Unlike ethane, in which the staggered conformations are equivalent, two different staggared conformations
occur in butane.
The gauche conformation and anti-conformation both are staggered, so are free of torsional strain, but two
of the methyl hydrogens of the gauche conformations lie within 210 pm of each other. This distance is less
than the sum of their van der Waals radii (240 pm), and there is a repulsive force between them. The
destabilization of a molecule that results when two of its atoms are two close to each other is called van der
Waals strain, or steric hinderance and contributes to the total steric strain.

In the case of butane, van der Waals strain

makes t he gauche co nformation
approximately 0.8 kcal/mol less stable than
the anti.
Note: For ethane-1, 2-diol(ethylene glycol HO-CH2-

CH2-OH) gauche conformation is more stable than the
anti-conformation because of H-bonding in gauche
conformation.
III. Conformations of Higher alkanes:

Higher alkanes having unbranched carbon chain are, like butane, most stable in their all-anti conformations.
In depicting the conformations of higher alkanes it is often more helpful to look at them from the side rather
than end-on as in Newman projection. Viewed from this perspective, the most stable conformations of
pentane and hexane have their carbon “backbones” arranged in a zig-zag fashion as shown in the figure. All
the bonds are staggered, and the chain are characterized by anti-arrangement of C-C-C-C units.

Illustration - 4 Of the three conformations of propane shown, which one is the most stable? Which one is
the least stable? Why?
(A) (B) (C)
SOLUTION :
Conformation (A) is the most stable ; all its bonds are staggered. Conformation (C) is the least stable ; all its
bonds are eclipsed.
Illustration - 5 Sight down the C-2-C-3 bond, and draw Newman projection formulas for the :
(a) Most stable conformation of 2, 2-dimethyl butane.
(b) Two most stable conformations of 2-methyl butane.
(c) Two most stable conformations of 2, 3-dimethyl butane.
(d) One of the two staggered conformations of 2-methyl butane is more stable than the other. Which one
is more stable? Why?
SOLUTION :
(a) First write out the structural formula of 2, 2-dimethyl

butane in order to identify the substituent groups attached
to C-2 and C-3.
As shown in above structure C-2 bears three methyl groups, and C-3 bears two hydrogens and a
methyl group. The most stable conformation is the staggered one as shown below. All other staggered
conformations are equivalent to this one.

(b) The constitution of 2-methylbutane and its two most stable conformations are shown.
Both conformations are staggered. In one Newman projection (X), the methyl group at the back is
gauche to the two methyl groups in the front. In the other (Y), it is gauche to one and anti to the other.
(c) The hydrogen at C-2 and C-3 may be gauche to one another (P), or they may be anti (Q).
(d) The 2-methylbutane conformation with one gauche CH3.....CH3 and one anti CH3....CH3 relationship
is more stable than the one with two gauche CH3.....CH3 relationships. The more stable conformation
has less van der Waals strain.

Illustration - 6 Determine whether the two/three structures in each of the following pairs represent
constitutional (structural) isomers or different conformations of the same compound.
(a)
(b)
(c)
SOLUTION:
(a) By rewriting the structures in a form that shows the order of their atomic connections, it is apparent
that the two structures are constitutional (structural) isomers.
(b) Two compounds have the same constitution (structure); both are (CH3)2CHCH(CH3)2. The
Newman projections represent different staggered conformations of the same molecule ; in one the
hydrogens are anti to each other whereas in the other they are gauche. Both are different
conformations of 2, 3-dimethylbutane.

(c) I and II are constitutional isomers.

II and III are two Newman’s projection formula of
the same compound 3-Ethyl-2-methylpentane hence
these are same. II is Newman’s projection formula
about C-3-C-4 bond while III is Newman’s
projection formula about C-2-C-3 bond.
Illustration - 7 Write a structural formula for the most stable conformation of 2, 2, 5, 5-tetramethyl hexane
using Newman’s projection of conformation about C-3- C-4 bond.
SOLUTION :
The structural formula of compound is (CH3)3CCH2CH2C(CH3)3. Both
C-3 and C-4 have two hydrogens and a tert-butyl groups attached. The
most stable conformation has the large tert-butyl groups anti to each
other.
Illustration - 8 (a) Write Newman projections for the gauche and anti conformations of 1, 2-dichloro
ethane (Cl-CH2CH2-Cl).
(b) The measured dipole moment of ClCH2CH2Cl is 1.12 D. Which one of the following statements about
1, 2-dichloroethane is false?
(i) It may exist entirely in the anti-conformation
(ii) It may exist entirely in the gauche conformation.
(ii) It may exist as a mixture of anti and gauche conformations.

SOLUTION:
(a) The dihedral angle between chlorine substituents is 60o in
the gauche conformation and 180o in the anti conformation
of Cl-CH2-CH2-Cl.
(b) All the individual bond dipole moments cancel in the anti conformation of Cl-CH2-CH2-Cl, and this conformation
has no dipole moment. Because ClCH2CH2Cl has a dipole moment of 1.12 D, it can exist entirely in the
gauche conformation or it can be a mixture of anti and gauche conformations, but it cannot exist entirely in the
anti conformation. Statement I is false.
Conformers of Cyclohexane:
The cyclic compounds most commonly found in nature contain six-membered rings because carbon rings of
that size can exist in a conformation-called a chair conformer-that is almost completely free of strain.
Cyclohexane can also exist as a boat conformer, shown in figure like the chair conformer, the boat conformer
is free of strain. However, the boat conformer is not as stable because some of the bonds are eclipsed.
Order of Stability : Chair form > Twisted boat > Boat > Half chair.

IN-CHAPTER EXERCISE-B
1. Write structural formulae for each of the following :

(i) Three primary alcohols and one tertiary alcohol with the formula C4H8O
(ii) A secondary alcohol with the formula C3H6O
(iii) A cyclic ester with the formula C4H4O4
(iv) Two unsaturated dibasic acids with formula C4H4O4
2. Write all the isomers of the formula C5H10O2 and the select pair of one type of isomers.
3. Make tautomer of :
4. Write structure that correspond to the following description :

(i) four esters with the formula C4H8O2 (ii) Two aldehydes with the formula C4H8O
(iii) three ketones with the formula C5H10O (iv) a tertiary amine with the formula C4H11N

RESONANCE & AROMATICITY Section - 5
Resonance
When a molecule or ion can be represented by two or more structures which have the same arrangement of
atomic nuclei but differe in distribution of electrons, the phenomenon is called as Resonance. The various
structures are called contributing or resonating structures. None of these structures truly represents all
the properties fo that molecule or ion. The actual struture is a resonance hybrid of several contributing
structures.
It generally occurs when there is a conjugation of -bonds(alternate double-single-double bond arrangement)
known as conjugated system. It also takes place when there is double bond (C = C or C = O) alongwith
a group (G) present in the carbon chain having a lone pair.
Consider resonance in 1, 3-Butadiene (having a conjugated system):
 -electrons moves from first carbon atom to last carbon atom resulting in different structure.
Note that the relative atomic arrangement of four carbon atoms is same in both the structures (I)
and (II).
Resonance hybrid (actual structure) of butadiene is represented as follows (in square brackets) :
 Consider resonance in Benzene (C6H6) :
 Consider resonance in Vinyl Chloride : Observe that group having a lone pair i.e., Cl is in
conjugation with double (C = C).
The various resonating structures of chlororbenzene, aniline and nitrobenzene are illustrated in
following diagrams.


Rules for Resonance

1. No real existance of Resonance structures: Although the resonating structures have no real existence
of their own, these structures are useful because they allow us to describe molecules and ions for which a
single Lewis structure is inadequate. We write two or more Lewis structures, calling them resonating structures
or contributing structures. We connect these structures by double-headed arrows () , and we say that
the real molecule or ion is a hybrid of all of them.
2. While writing Resonance structures we are only allowed to move electrons: The relative positions
of the nuclie of the atoms must remains the same in all of the structures. Structure III is not a resonance
structure of I or II, in the given example, because in order to form it, we would have to move a hydrogen
atom and this is not permited :

Actually speaking, when we move electrons, we move only those of  bonds(as in the example above) and
those of non-bonding pairs (such as lone pairs).
3. All of the structures must be proper Lewis structures : We should not write structure in which carbon
has five bonds, for example:
This is not a proper resonance structure for methanol because carbon

has five bonds. Elements of the First major row of the periodic table
cannot have more than eight electrons in their valence shell.
4. Resonance Stabilisation: The energy of the actual molecule (Resonance hybrid) is lower than the energy
of any one of all the contributing structures. Hence the resonance hybrid is more stable form.
5. The more stable a structure is, the greater is its contribution to the hybrid.
For example, benzene is highly resonance stabilized because it is hybrid of the two equivalent forms that are
highly stable.
6. The following rules will help us in making decisions about the relative stabilities of resonance structures.
(a) The more covalent bonds a structure has, the more stable it is : This is because a covalent
bond lowers the energy of atoms. This means that out of the following two structures for 1, 3-
Butadiene, I is the most stable and hence imparts greater contribution to the stability of resonance
hybrid.
(b) Structure in which all of the atoms have a complete valence shell of electrons are especially
stable and make large contributions to the hybrid : In the following example, the structure II
makes a larger stabilizing contribution to the cation than the structure I because all of the atoms of
structure II have a complete valence shell.

Also note that structure II has more covalent bonds than structure I.
On the same pattern the structure II of the acyl carbonium ion is more stable than I
(c) Charge separation decreases stability : Separating opposite charges requires energy, hence the
structures in which opposite charges are separated have greater energy (lower stability) than those
that have no charge separation. This means that of the following two structures for vinyl chloride,
structure I makes a larger contribution because it does not have charge separation (This does not
mean that structure II does not contribute to the hybrid ; it just means that the contribution made by II
is smaller).
(d) Resonance contributors with negative charge on highly electronegative atoms are more
stable than ones with negative charge on less or nonelectronegative atoms : Conversly,
resonance contributors with positive charge on highly electronegative atoms are less stable than ones
with positive charge on nonelectronegative atoms.
 Observe the rules (c) and (d) above are illustrated beautifully in the following illustration:
Weakly stabilised by Resonance
Strongly stabilised by Resonance
Carboxylic acids (RCOOH) are less stable than carboxylate ions (RCOO-) because in carboxylic acids,
there is charge separatioin in one of the resonating structure.
Structures where formal charges don’t suit the electronegativity of the atom on which they rest, are less
stable e.g., consider the resonating structure of phenol.

Structure (i) and (ii) are more stable than the others. These are also known as kekule Structures.
Structures (iii), (iv) and (v) are less stable due to:
(a) charge separation (b) +ve charge over Oxygen atom
Illustration - 9 In each of the following pairs showing resonating structures, identify which is more stable
and why?
(A) (B)
(C) (D)
SOLUTION :
(A) I is more stable than II, because in II, the formal charge (-) is on carbon atom which does not suit
its electronegativity.
(B) II is more stable than I. In II, all atoms (except H-atom) have an octet, whereas in I, carbon has
sixet (incomplete octet).
(C) I is more stable than II, since in I all have complete octets.
(D) II is more stable than I because in the former, all the atoms have complete octet.
Aromatic , Anti-aromatic and Not Aromatic

Among planar, monocyclic, fully conjugated polyenes, only those possessing (4n + 2)electrons, where n
is a whole number, will have special stability ; that is, be aromatic.

Condition for a compound to be :

(i) Aromatic : Cyclic, Planar, Complete Conjugation, (4n + 2)e-s (n = 0, 1, 2,...)
(ii) Anti-aromatic : Cyclic, Planar, Complete Conjugation, 4n e-s ( n = 1, 2, ....)
(iii) Not-aromatic : Not cyclic OR Not Planar OR Not Completely Conjugated.
What is Complete Conjugation? Alternate single and double bonds. In other words, every Carbon has to be
sp2 hybridised.
Examples :
(a) : Cyclic, Planar but not completely conjugated. Carbon-(1) is sp3

hybridised.
 Compound is "Not aromatic"
(b) : Cyclic, Planar, Completely Conjugated. Carbon-(1) is sp2

hybridised as it is clear from its resonating structures
Now count the number of e-s in the compound as per the following rules:
(i) Each ‘=’ bond is counted as 2e-s (ii) Count the number of lone pairs.
Singly Bonded: Count as 2e-s
=1 : Check bonding of
atom with lone pair
If the number of lone pairs is: Doubly Bonded: Do not count
>1 : Count them as exactly one lone pair and
go back to the above condition corresponding
to 1 lone pair.
Number of e-s = 4(From 2 doouble bonds) + 2(one lone pair at C-1 and is single bonded)
= 6e-s  Compound is “ Aromatic”

(c) : Cyclic, Planar, Completely Conjugated (See Resonating Structure)

However, in anti-aromatic species delocation of  -electron does not
take place. i.e., they have conjugation but no delocalisation.
Now, count the number of p e-s : 4 (From 2 double bonds)
 Compound is “Anti-aromatic”
(d) : Cyclic, Planar, Completely Conjugated.

Now, count number of e-s : 2 (From I double bond)
 Compound is “Aromatic”
Note : Cyclopropenyl cation is smallest aromatic species.
(e) Pyridine : (C5H5N) :

Cyclic, Planar, Completely Conjugated.
6e-s (From 3 double bonds)
Note : ‘N’ has 1 lone pair and is doubly
bonded.
So, this will not be counted.
(f) Pyrrole : C4H4NH

4e-s (From 2 double bonds) + 2e-
s(From 1 lone pair)
Note : ‘N’ has 1 lone pair and is singly
bonded.
(g) Furan :
Number of e-s
= 4( From 2 double bonds) + 2(From 1
lone pair)

Note : ‘O’ has 2 lone pairs.Count only one lone pair.

(h) Cyclic, Planar, Completely Conjugated

Number of e-s = 2(From 1 double bond) + 2(From 1 lone pair) = 4
 Compound is “Anti-aromatic”
(i) Cyclic, Planar, Not Completely Conjugated.

 Compound is “Not Aromatic”
(j) Cyclic, Completely Conjugated.

Number of e-s = 6 (From 3 double bonds)
(k) Cyclo-Octateraene : Note: It has a tub shape structure

Cyclic, “Not Planar”, Completely Conjugated.
 Compound is “Not Aromatic”
(l) : Cyclic, Planar, Completely Conjugated.

Number of e-s = 4(From 2 double bonds)  Compound is “Anti-Aromatic”
 If a compound is Anti-aromatic, it is less stable than its open chain counter part i.e.,  electrons
conjugation adds de-stability to the compound, if it is anti-aromatic.
 If a compound is aromatic, it adds stability to the compound through  electrons delocalisation.
Note : There are thousands of aromatic compounds that are not monocyclic such as naphthalene, azzulene,
anthracene etc. are polycyclic aromatic hydrocarbons.

ORGANIC REACTIONS [BASICS] Section - 6

Organic compounds are covalent bonded. The carbon atom in these may be sp3, sp2 or sp hybridised.
Hydrocarbons are almost non-polar, but their derivatives containing functional group are polar covalent
compounds. To understand and visualise the mechanisms of organic reactions, first we must go into details
of various types of electrical effects that monitor the properties of various organic compounds. Then we
have to understand various types of Substrates (main organic compound) ; Intermediates formed from these
substrates ; the various types of Reagents and the Medium(solvent) in which organic reactions occur.
All organic reations can be classified into one of the following three categories for the purpose of understanding
reaction mechanisms :
(i) Substitution Reactions (ii) Addition Reactions (iii) Elimination Reactions
Above three categories of reactions may involve : Rearrangement, Cyclissation (Ring opening & Ring closing)
and stereo specific changes (involving optical and geometrical isomers), oxidation and reduction.
1. Substrate : It is the main organic compound acting as reactant and reacts with a reagent to give an new
organic compound as main product. Substrates in general are of two types :
Nucleophilic: The organic compounds which have “electron rich centre or area” are referred to as
nucleophilic in nature. They are acted upon by electron seeking reagents.
Alkenes, alkynes and benzene and its derivatives are some of such important substrates.
Electrophilic : The organic compounds which have “electron definicient centre or area” are referred to as
Electrophilic in nature. They are acted upon by electron rich reagents usually most of organic derivatives
containing functional groups act as electrophilic substrates. Organic Halides, Alcohols, Ethers, Aldehydes &
Ketones and Carboxylic Acids & Derivatives are some of the important electrophilic substrates.
 
Electrophilic centre  C  G
2. Reagents : Based on the attack by the type of attacking reagent, these are further categorised.
The main type of attacking reagents are:

(a) Nucleophile: Electron rich species, looking to attack a +vely charged centre (Electrophilic
substrate).These are classified as follows:
Charged : H  , OH  , RO  , CH 3 , X  , HS .......etc.
Neutral : Covalent compounds in which central atom has complete octet, has atleast one lone pair.

Ambident : Species having two nucleophilic centres, one is neutral (complete octet and has atleast
one lone pair of electrons) and other is charged (negative charge). They basically have
two nucleophilic sites / atoms.
(b) Electrophiles : Electron deficient species, looking to attack an electron rich site (Nucleophilic
substrate). These are classified as follows:
Charged : H+, X+, R+, .......etc, (X : Halogens except flourine)
Neutral : CO2, AlCl3, CS2 . . . . . . .etc.

(c) Free radicals : Atom or group of atoms with their valencies unsatisfied, looking to attack a place so
that they can satisfy their valencies. e.g., (alkyl)
3. Reaction Mechanism :
It gives detailed aspect of as to “How actually an organic reaction proceeds”. It depicts step-by-step
visualisation of an organic reaction.
Organic reactions always involve breaking and reforming of covalent bonds. A covalent bond can break
into two ways; In one of the ways, one of the fragments takes away the bonded electron pair (Heterolytic
cleavage) and in other, each fragment takes away one of the electrons of bond (Homolytic cleavage).
Such fragments are known as Reaction intermediates such as; C+ (carbocations), C-(carbanions) and C
free radicals).
I. Homolytic Fission:
Such type of fission occurs in gas phase or in non-polar solvents (i.e., absence of polarising solvents)
and is catalysed by free radical initiators. In such fission, free radicals are formed. Here the bond pair
is equally shared after the fission.
II. Heterolytic fission :

Such type of fission occurs in polarising solvents (such as H2O, alcohols and acids), catalysed by
acids or bases, greatly influenced by polarity of solvents. Here, the ions are formed. In an organic
compound such as R-G, two types of ions are formed.
(a) (R+ is known as carbocation)
(b) (R- is known as carbanion)

4. Electrical Effects:
For the detailed analysis of Reaction Mechanism, we have to first understand “Electrical Effects” existing in
the Organic Substrate and induced by External Reagents.
There are four kinds of Electrical Effects to be studied for the understanding of Reaction Mechanism.
I. Inductive Effect II. Resonance (Mesomeric ) Effect
III. Electromeric Effect IV. Hyperconjugation Effect
I. Inductive Effect (Polar nature of covalent bonds):

The displacement of an electron (shared) cloud along the carbon atom chain due to the presence of an
electron withdrawing (electron attracting) or electron realeasing (electron repelling) groups in the
carbon chain is known as Inductive Effect (I-effect).
 It is a permanent effect which is transmitted along the carbon-carbon chain.

(G : functional group)
But the effect is insignificant beyond teh third carbon atom.
 Any atom or group which attracts electrons more strongly than hydrogen is said to exert a negative
effect (-I effect) ; an atom or group which attracts electrons less strongly than hydrogen is said to exert
a positive inductive effect (+I effect).
Group producing -I effect : (All functional groups)

-NO2 > - CN  - SO3H > - CHO > - COOH > - F > - Cl > - Br > - I > - OH > - OR > - NH2
> HC  C - > CH2 = CH - > -C6H5 > - H
Note: (i) Alkynyl, vinyl and phenyl groups, because of sp and sp2 hybrid carbon atom exert weak-I effect.
Carbon atoms which are sp and sp2 hybridised are electronegative in character due to dominance of
‘s’ character over ‘p’ character. [50% ‘s’ character in ‘sp’ and 33% ‘s’ character in sp2 hybrid
carbon]
(ii) All such groups are called as Electron Withdrawing Groups (EWG).
Groups producing +I effect : (Only alkyl groups)

H - < D - < CH3 - < CH3CH2 - < CH3CH2CH2 - < (CH3)2CH - < (CH3)3C-
(1o) (1o) (2o) (3o)

Groups producing +I effect : (Only alkyl groups)

H - < D - < CH3 - < CH3CH2 - < CH3CH2CH2 - < (CH3)2CH - < (CH3)3C-
(1o) (1o) (2o) (3o)
Note: (i) All alkyl and cycloalkyl groups because of sp3 hybrid carbon atom exert +I effect. An sp3 hybrid
carbon atom is an electron releasing (donating) due to dominance of ‘p’ character over ‘s’ character.
[75% p character]
(ii) All these alkyl groups are called as: Electron Releasing Groups (ERG) or Electron Donating Group
(EDG).
II. Resonance (or Mesomeric) Effect:

When a molecule or ion can be represented by two or more structures which have the same arrangement
of atomic nuclei but differ in distribution of electrons, the phenomenon is called as Resonance. The
various structures are called contributing or resonating structures. None of these structures truly
represents all the properties of that molecule or ion. The actual structure is a resonance hybrid of
several contributing structures.
When multiple bonding is in conjugation with a functional group (G), then as per the electronic movement,
we can visualise resonance in two ways illustrated below.
+M effect (+R -effect) : When the movement of electrons starts from a particular group (G) towards the
carbon chain (C = C).
It takes place when group (G) has a lone pair or an extra electron (in an anion).

-M effect (-R-effect) : When the movement of electrons takes place towards a particular group (G) from
carbon chain (C = C).
or where G can be : -NO2, -C = O, -CN, -SO3H etc.
Note: In general, in the groups showing (-R/-M) effect, the

“attached atom” of the group is unsaturated with a more
electronegative atom e.g.
III. Electromeric Effect:

It is a temporary polarising effect and operates only in molecules having -electrons (i.e., multiple
bonded compounds) induced by the attacking reagents (nucleophiles & electrophiles) in a chemical
reaction.
 In presence of electrophiles (E+), -electrons shift to other carbon to make adjustment for the incoming
electrophile to be added.
Observe that E+ (electrophile) adds to the atom(group) where electrons are transferred. Such effect
is known as +E effect., when the transfer of electrons takes place towards the attacking reagent.

 In polar bonds, in presence of attacking reagents, a complete transfer of electron (one of e- pair) to
more electronegative atom takes place, e.g., in in presence of nucleophiles like R-, CN-,
HSO3-,  electrons shifts over to O.
Observe that CN- (nucleophile) adds to the atom (group) from where electrons are transferred. Such
effect is known as -E effect i.e., when the transfer of electrons takes place away from the attacking
reagent.
IV. Hyperconjunction Effect:
‘Baker and Nathan’ obeserved that alkyl groups (R) with at least one hydrogen (H) atom on the -
carbon, attached to an unsaturated carbon atom (i.e., having a -C = C - bond), or positive charge (as
in carbocation, C+) or odd electrons (as in free radicals, Co) are able to release electrons by a
mechanism quite similar to that of ‘electrometic effect’ (but it is a permanent effect).
This type of electron released by alkyl group is called as hyperconjugation. It involves delocalisation
of  and  bond orbitals (    conjugation). In structure (II), note that there is no definite bond
between carbon and one hydrogen atom, hence it is also known as No bond resonance,
 Greater the number of C-H bond at   carbon to the unsaturated system, greater will be the elec-
tron release and greater the hyperconjugation effect.
Hence electron release due to presence of three alpha (3 )  C H bonds in methyl groups is greater
than that by an ethyl group, in which there are only two alpha (2 )  C H bonds. Similarly, the effect
decrease in isopropyl group and further in tert-butyl group (no   C H bond ) .
increasing hyperconjugation effect and increasing +I effect
 Stability of Alkenes : Hyperconjugation explains the order of stability of alkenes. Propene is more
stable than ethene because in propene, there are three H-C hyperconjugated bonds and hence
  electrons of C-H bonds can delocalise over three different structures.

Hence greater the number of Methyl (each methyl group has 3  H ) groups, attached to doubly bonded
carbons, the more stable the alkene is
[more H-C bond on same carbon give greater effect]
increasing hyperconjugation and increasing stability
 Illustrating the Concept of Hyperconjugation :
The hyperconjugative stabilities of tert-butyl cation and 2-butene, respectively, are due to :
(A)   p (empty) and    * electron delocalisations
(B)    * and    electron delocalisations

(C)   p (filled) and    electron delocalisations
(D) p (filled)   * and    * electron delocalisations
Note :  * refers to  anti-bonding molecular orbitals.
Correct answer is (A)

Hyperconjugation is tert-butyl carbocation refers to delocalisation of s-electrons over the empty p-orbitals
of carbocation. In 2-butene, it refers to decalisation of   electrons over the  * orbitals of C = C.

5. Reaction Intermediates:
While understanding a reaction in detail (Reaction Mechanism), we have to visualise the overall reaction in
small steps. These steps involve various type of reaction intermediates, whose stability is the key to the
acceptance of a particular reaction mechanism (path). Most typically there are three kinds of intermediate:
Free Radicals Carbocations and Carbanions.
(a) Free Radicals :
An atom (or group of atoms) having an unpaired electron is called as Free Radical. These are formed
via homolytic fission.
(methyl and a halogen free radical is produced)
‘C’ of free radical (alkyl) is sp2 hybridised and hence the shape is planar,
having an unhybridised p-orbital containing an odd electron (Paramag-
netic in nature).
Tertiary alkyl free radicals are more stable than others. The stability of free
radicals follows the order:
The stability of free radicals is explained via hyperconjugation effect. In methyl free radical, there is
no hyperconjugation, as there is no -C-H bond.
Let us draw various hyperconjugation structure of ethyl radical.
Similarly a 2o radical is more stable than a 1o alkyl radical (as number of alpha H-atoms are increas-
ing, the hyperconjugation effect is increasing and hence stability increases).
Apart from alkyl free radicals, other important free radicals are :
Allyl and benzyl free radicals are highly stable due to resonance.

Note : Another kind of free radicals, Carbenes are also formed. Carbenes are neutral, divalent and highly reactive
intermediates.
Free radicals are formed with the help of free radicals generators such as : benzoyl peroxide, tert butyl
peroxide.
There are also some special type of intermediates such as Nitrene; and Benzyne;
(b) Carbocations:
The organic compounds which -carbon is electrophilic due to function attached to it, generally undergo
heterolytic cleavage to form carbocations as follows :
(C+ is known as carbocation)

‘C’ of carbocation (alkyl) is sp2 hybridised with one vacant unhybridised p-orbital. Hence the structure is
 
planar. Important carbocations include : Alkyl, allyl (CH 2  CH CH 2 ) and benzyl C6H 5 CH 2 ) .
The order of stability of carbocations is:
Stabilistions of carbocation is through +I effect and hyperconjugation effect.
 Electron releasing alkyl groups (R--  --- ) disperse +ve charge over carbon.
e.g. is more stable than

More is the number of -H attached to carbon atom having +ve charge, more is the number of
hyperconjugative structures. Hence more stable is carbocation.
Observe that 3o butyl carbocation has 9-H and hence more stable than 2o and 1o alkyl carbocations.

 Electron withdrawing (G--  -- - C  ) pulls electron density away from C+ carbon and hence stability of

carbocation decrease. G : CN -, CL, CHO, NO2 etc. e.g. CH 2  CH 2 CHO is more stable than
+
CH 3 CH  CHO
Stabilisation of carbocation is also takes place through resonance.
Allyl carbocation :
Benzyl carbocation :
Note: More is the number of resonating structures dispersing the +ive charge over carbon, more is the carbocation
  
stability e.g. Stability order follows : C6H 5  C  C6 H5  C6H5  C H  C6 H5  C H 2
|
C6 H 5
Order of stability of carbocation follows:

     
 CH3 3 C  C6 H5 C H2  CH3  CH  C H 2   CH3 2 C H  CH3 C H 2  C H3
 3  1  1  2  1
[tert  butyl  1o Benzyl  1o allyl  3o alkyl  2o alkyl  1o alkyl  methyl]
Also-Note : ;

Properties of carbocations :
(i) H3C H 2C  Nu  

 CH3CH 2 Nu (combination with a nucleophile)

(ii) H3C H 2C 
 CH 2  CH 2  H + (elimination of proton at high temperature or in pres
-ence of strong bases)
 In order to achieve stability (before above two properties), carbocations go through rearrangement
through shift of hydride ion (H-) or methide ion (CH 3 ) from adjacent carbon atom. Hence these shifts
are known as 1, 2-shifts.
(a) (2o is more stable)
(b) (3o is more stable)
(c) (3o is more stable)
(c) Carbanions : (C- is carbanions)

‘C’ of carbanions (alkyl) is sp3 hybridised, hence structure is pyramidal
with one of sp3 hybrid-orbital containing a pair of electrons.
e.g.
Stabilisation of carbanion (through -I effect)

 Electron-withdrawing group enhances stability whereas electron-releasing (R) group decreases sta-
bility.
 The stability of carbanions increases with increase in ‘s’ character (electron withdrawing).
An alkynide ion 50%‘s’(sp) A vinylic ion 33% ‘s’ (sp2) An alkyl ion 25% ‘s’ Character (sp3)

Stabilisation of carbanion (through resonance).

 Allyl carbanions is resonance stabilised.
 Carbanions are negatively charge particles acting as nucleophiles. Other important carbanions are
from carbonyl compounds, esters, nitro compounds.
These are resonance stabilised
 Anions in which negative charge is present on the carbon of aromatic system is known as aromtic
carbanions.
These are most stable carbanions.
cyclopentadienyl carbanion  rule and is aromatic.

It obeys Hukel
 Carbanions participate mainly in condensation reactions (to be studied later).
Note: (i) More is the number of resonating structure for a carbanion, more is its stability. e.g. consider the
stability order:
-CCl is more stable than -CF even though -I effect is more pronounced in the later and this is due to
(ii) 3 3
the formation of p-d back bonding between the unhybridised p-orbital of carbanion and empty d-
orbitals of Cl atom.

Illustration - 10 Arrange the following in increasing order of stability on the basis of resonance:
(A) (i) (ii) (iii) (iv)
(B) (i) (ii)
(iii) (iv)
SOLUTIONS :
(A) (i) < (iv) < (ii) < (iii)
In (iii) there is strong -M effect of -NO2.
In (ii) and (iv) -I effect of Br and -OCH3 are prominent.
In (i) delocalisation due to only phenyl ring is there.
(B) (ii) < (i) < (iii) < (iv)
(i) and (ii) should have greater stability as compared to (iii) and (iv) because of greater number of colvalent
bonds. Also (ii) has got 2o carbocation whereas (i) has 1o carbocation.
(iii) has unlike charges close (less charge separation) to each other but (iv) has no such factor.
Types of Reactions in Organic Chemistry :
Note : The detailed discussion of each of above reactions will be done later in Class XIIth in the chapter of
“Theoretical Organic Concepts”

QUALITATIVE & QUANTITATIVE ANALYSIS OF ORGANIC COMPOUNDS Section - 7
Qualitative Analysis:
Detection of functional groups is an important step in the analysis of organic compounds. It entirely depends
on the correct determination of the constituent elements.
Elemental Detection :
The elements present in organic compounds are carbon and hydrogen. In addition to these, they may also
contain oxygen, nitrogen, sulphur, halogens and phosphorus.
Detection of Carbon and Hydrogen:

Carbon and Hydrogen are detected by heating the compound with copper (II) oxide. Carbon present in the
compound with copper (II) oxide. Carbon present in the compound is oxidised to carbon dioxide (tested
with lime-water, which develops turbidity) and hydrogen to water (tested with anhydrous copper sulphate,
which turns blue).

C+ 2CuO 
 2 Cu+ CO2

2 H  CuO 
 Cu+ H 2O
CO2  Ca(OH) 2 
 CaCO3  + H 2O

5H 2O+ CuSO 4 
 Ca SO 4 .5 H 2O
White Blue
Detection of Other Eelements:

Nitrogen, sulphur, halogens and phosphorus present in an organic compound are detected by “Lassaigne’s
test”. The elements present in the compound are converted from covalent form into the ionic form by
fusing the compound with sodium metal. Following reaction take place :

Na+ C+ N 
 NaCN

2 Na+ S 
 Na 2 S

Na+ X 
 Na X  X = Cl, Br or I 
C, N, S and X come from organic compound.

Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the fused masses
by boiling it with distilled water. This extract is known as sodium fusion extract.

(A) Test for Nitrogen :

The sodium fusion extract is boiled with iron (II) sulphate and then acidified with concentrated sulphuric
acid. The formation of Prussian blue color confirms the presence of nitrogen. Sodium cyanide first
reacts with iron(II) sulphate and forms sodium hexacyanoferrate (II). One heating with concentrated
sulphuric acid some iron(II) ions are oxidised to iron (III) ions which react with sodium hexacyanoferrate
(II) to produce iron(III) hexacyanoferrate(II) (ferriferrocyanide) which is Prussian blue in colour.
(B) Test for Sulphur :

(a) The sodium fusion extract is acidified with acetic acid and lead acetate is added to it. A black
precipitate of lead sulphide indicates the presence of sulphur.
S2  + Pb2+ 
 PbS
(Black)
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour
further indicates the presence of sulphur.
S2  +[Fe(CN)5 NO]2  
 [Fe(CN)5 NOS]4
(Violet)
In case, nitrogen and sulphur both are present in an organic compound, sodium thiocyanate
is formed. It gives blood red colour and no Prussian blue since there are no free cyanide ions.
Na+ C+ N+ S 
 N aSCN
Fe3  SCN  
 [Fe(SCN)]2
Blood Red
If sodium fusion is carried out with excess of sodium, the thiocyanate decomposes to yield
cyanide and sulphide. These ions give their usual tests.
Na SCN 2 Na 
 NaCN+ Na 2S
(C) Test for Halogens :

The sodium fusion extract is acidified with nitric acid and then treated with silver nitrate. A white
precipitate, soluble in ammonium hydroxide shows the presence of chlorine, a yellowish precipitate,
sparingly soluble in ammonium hydroxide shows the presence of bromine and a yellow precipitate,
insoluble in ammonium hydroxide shows the presence of iodine.
X   Ag + 
 AgX

X represents a halogen -Cl, Br or I.

If nitrogen or sulphur is also present in the compound, the sodium fusion extract is first boiled with
concentrated nitric acid to decompose cyanide or sulphide of sodium formed during Lassaigne’s test.
These ions would otherwise interfere with silver nitrate test for halogens.
(D) Test for phosphorus :

The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in the
compound is oxidised to phosphate. The solution is boiled with nitric acid and then treated with
ammonium molybdate. A yellow colouration or precipitate indicates the presence of phosphorus.
Na3PO4 +3HNO3 
H3PO4 +3NaNO3
H3PO 4 +12(NH 4 )2 MoO4  21HNO3

Ammonium molybdate
  NH 4 3 PO4 .12 MoO3 + 21NH 4 NO3  12 H 2O


Ammonium phosphmolybdate
Quantitative Elemental Analysis :

After determining the constituent elements of an organic compound, the next step is to determine their
amounts by quantitative methods. The methods usually involve combutions, oxidation etc. of an organic
compound so that they may change into such inorganic compounds as can be estimated either by volumetric
or gravimetric method.
Estimation of Carbon and Hydrogen :

Liebig’s Combustion Method : A weighed amount of the compound is heated in a current of dry air
free from carbon dioxide or pure oxygen till the carbon of the compound changes to CO2 and hydrogen into
water. Carbon dioxide and water thus formed are trapped in a suitable apparatus and weighed.
C+ 2CuO 
CO2  2Cu
2 H+ CuO 
 H 2O+ Cu
The percentage composition is then calculated.

Calculation:
Let the weight of the sample = Wg
Let the weight of water formed = x g (Increase in weight of CaCl2 tube)
and let the weight of CO2 formed = y g (Increase in weight of potash bulb)

Since 44g of CO2 are formed from 12g of carbon.
12
 y g of CO2 are formed from  y g of carbon
14
Since 18 g of water are formed from 2g of hydrogen.
2 1
 x g of water are formed from  x g of hydrogen  x g of hydrogen
18 9
12
Now, Wg of the substance contains  y g of carbon
44
12  100 y
 100 g of the substance contains g carbon
44  W
x
Again W g of the substance contain g of hydrogen
9
100 x
 100 g of the substance contain g of hydrogen
9W
12  100 y
 Percentage of carbon 
44  W
100 x
and Percentage of hydrogen 
9W
Estimation of Nitrogen :
(i) Duma’s Method : In this method the organic compound is heated with copper oxide strongly.
Carbon, hydrogen and sulphur are oxidized to CO2, H2O and SO2 respectively, while nitrogen is set
free. These gases are passed through a nitrometer containing 30% KOH solution. Carbon dioxide
and sulphur dioxide are absorbed, steam condenses and nitrogen collects by the displacement of
KOH solution. From the volume of the collected nitrogen, the percentage of nitrogen is calculated.
y z
C x H y N z  CuO 
 x CO2 + H 2O+ N 2 + Cu
2 2
Calculation :
Let the weight of the sample = W g
Volume of moist N2 = Vcc
Room temperature = toC

Barometric pressure = P mm
Aqueous tension at toC = f mm
PV PV
We know, 1 1  2 2
T1 T2
( P  f )  V 760  V2
Or  V2  Volume of N2 at NTP 
(273  t ) 273
( P  f )  273  V
V2  cc
760  (273  t )
( P  f )  273  V
Volume of N 2 at NTP in cc 
760  (273  t )
Now, 22400 cc of N2 at NTP weigh 28 g.
( P  f )  273  V  28  P  f   273  V 
 at NTP weigh  g
760  (273  t )  760  22400  273  t  
28  P  f   273  V
W g of the substance contain g N2
760  22400  273  t 
28  P  f   273 V 100
 100g of the substance contains g
760  22400 W  273  t 
28 Volume of N 2 at NTP
Percentage of Nitrogen    100
22400 Weight of substance
(ii) Kjeldahl’s Method : The principle of this method is that when an organic compound containing
nitrogen is heated with concentrated sulphuric acid, the nitrogen is converted into ammonium sul-
phate. The resulting solution on treatment with excess of sodium hydroxide solution gives off ammo-
nia. Ammonia is then absorbed in excess of standard sulphuric acid. The amount of ammonia and
hence the amount of nitrogen is determined by finding the amount of acid neutralized by back titration
of the residual acid with a standard alkali solution. From this the percentage of nitrogen is calculated.
This method is not good for those nitrogen compounds which produce nitrogen gas N2 on heating
such as compound containing N in ring, nitro compounds, axo compounds etc.
Calculation :
Let the weight of the substance = Wg and let V cc of N acid is required to neutralize the ammonia
evolved.

 V cc of N acid = V cc of N NH3
1000 cc of N NH3 = 17 g of NH3 = 14 g of nitrogen
14
V cc of N NH3   V N  0.014 N V g
1000
100 0.014  N V 100

 Percentage of nitrogen = Weight of nitrogen  
Weight of subs tan ce W
Estimation of Halogen :
(i) Carius Method : The compound containing halogen is heated with fuming nitric acid in a sealed tube
(Carius tube) in presence of silver nitrate. Carbon and hydrogen present are oxidized to carbon
dioxide and water. The halogens react with silver nitrate to give the precipitate of silver halide. The
precipitate is collected, washed, dried and weighed.
Calculation :
Let the weight of the substance be W g.
Weight of the silver halide be y g.
Atomic weight of halogen

Weight of halogen   yg
Moleclar weight of silver halide
Atomic weight of halogen 100

 Percentage of halogen   y
Moleclar weight of silver halide W
Estimation of Sulphur :
The compound is heated with fuming nitric acid. Sulphur present is oxidized to sulphuric acid. Barium
chloride solution is added. The precipitate of barium sulphate is obtained. It is collected, washed, dried and
weighed.
% of Sulphur  Weight of BaSO4 Atomic weight of Sulphur

  100
Molecular weight of BaSO4 Weight of Organic compound
Silver Salt method for determining molecular weight of Organic acids :

This method on the fact that organic acids form insoluble silver salts which on ignition leave a residue to
metallic silver.
A small quantity of organic acid is treated with water or a suitable solvent and then a slight excess of
ammonia solution added. The solution is boiled to expel excess of ammonia. Excess of silver nitrate solution
is added to this solution when a white precipitated of insoluble silver salt is obtained. The precipitate is
filtered and washed successively with water, alcohol and ether and then dried in an air oven.

A known weight of the silver salt is taken in a weighed crucible and ignited till decomposition is complete.
The curcible is cooled and then weighed. Heating, cooling and weighing is continued till the final weight is
constant.
Calculation :
Weight of crucible + lid = W g
Weight of crucible + lid + silver salt = W 1 g
Weight of crucible + lid + residual silver = W2 g
Weight of silver salt = (W1 - W) g
And Weight of silver = (W2 - W) g
(W2 - W) g of silver is obtained from (W1 - W) g of silver salt.
108 g of silver is obtained from

 W1  W  108 g of silver salt.
 W2  W 
Equivalent weight of silver salt 

 W1  W  108
 W2  W 
But equivalent weight of acid = Equivalent weight of Ag salt - 108 + 1 = Equivalent weight of Ag salt -107
  W  W   108 
 Molecular weight of the acid   1  107   n (where n = basicity of the acid)
  W2  W  
Platinichloride method for determining molecular weight of Organic Bases :

Organic bases (e.g. amines) form insoluble salts known as platinichlorides when treated with
hydrochloroplatinic acid [H2PtCl6]. These salts are represented by the general formula B2H2PtCl6, where
B is one equivalent of the base. These salts on ignition leave a residue of metallic platinum.
The base is dissolved in HCl and a solution of platinic chloride PtCl4 is added. The yellow crystalline salt
that separateds out is filtered, washed and dried. A known weight of the dried salt is ignited in a crucible.
Calculation :
Let X1 g of the platinichloride leave on ignition X2 g of platinum
X2 g of Pt is left by X1 g of the slt on ignition.
 X 195 
195 g (At. weight of Pt) is left by  1  g of the salt on ignition.
 X2 
Molecular weight of the salt  X1  195

X2

Molecular weight of H 2 PtCl6  410
 X1 
 ×195   410
M  M H 2 PtCl6  X 2
Equivalent weight of base B  B2 H 2 PtCl6  
2 2
If the ascidity of the base is n, then
 X   n
Molecular weight of base   1 ×195   410  
 X 2   2
Illustration - 11 0.25 g of an organic compound on combustion gave 0.495 g of CO and 0.2025 g of H O.

2 2
Calculate the percentage of carbon and hydrogen in the compound.
SOLUTION :
Given weight of the substance = 0.25 g
Weight of CO2 formed = 0.495 g
Weight of H2O formed = 0.2025 g
44 g of CO2 are formed from 12g of carbon.
12
 0.495 g are formed from  0.495 of carbon
44
12  0.495
Now 0.25 g of the substance contains g carbon.
44
12  0.495  100
 100g of the substance contains  54.55 g
44  0.25
Since 18 g of H2O are formed from 2g of hydrogen.
2
 0.2025 g H2O are formed from  0.2025 g hydrogen
18
2  0.2025
Now, 0.25 g of the substance contains g hydrogen
18
2  0.2025  100
 100 g of the substance contains  9.09 g hydrogen
0.25  18
% of carbon = 54.55
% of hydrogen = 9.09

Illustration - 12 0.159 g of an organic compound gave 14.01 cc of nitrogen at 19oC and 719.5 mm pressure
by Duma’s method. Calcuate % of nitrogen in the organic compound. Given: Aqueous tension of water =
11.5 mm og Hg at 19oC.
SOLUTION :
Aqueous tension at 19oC = 11.5 mm
We know,
P1V1 P2V2

T1 T2
(719.5  11.5) 14.01 760  VN 2 at NTP

or 
(273  19) 273
708  14.01 273

VN 2 at NTP  cc
760  292
Now, 22400 cc of N2 at NTP weight 28g
28
 1cc of N2 at NTP weigh g
22400
708  14.01 273 28  708  14.01  273

 cc  g
760  292 22400  760  292
28  708 14.01 273

0.159 g of the compound contains g N2
22400  760  292
28  708  14.01 273 100

 100 g of the compound contains  9.60%
22400  760  292  0.159
Percentage of nitrogen = 9.60%
Illustration - 13 0.69 g of an organic compound after heating with concentrated sulphuric acid was dis-
tilled with excess of NaOH. Ammonia liberated was passed into 100 cc of N HCl solution. The excess of the
acid neutralized 80 cc of N NaOH. Calculate the percentage of nitrogen in the compound.
SOLUTION :
80 cc of N NaOH = 80 cc of N HCl = Volume of residual acid
Volume of acid neutralised = (100-80) cc of N HCl = 20 cc of N HCl = 20 cc of N NH3

Now, 1000 cc N NH3 = 14 g of nitrogen
14  20
20 cc N NH3  g of nitrogen
1000
14  20
0.69 g of the substance contains g of nitrogen
1000
14  20  100
 100 g of the substance contains  40
0.69 1000
 Percentage of nitrogen = 40 %
Illustration - 14 0.26 g of an organic compound on heating with fuming nitric acid and silver nitrate give
0.31 g of silver bromide. Calculate the percentage of bromine in the compound.
SOLUTION :
Now, AgBr 
 Br
or (108 + 80)g  80g

 188 g of AgBr give 80 g of bromine.
80
 0.31 g of AgBr give  0.31  0.1319 g bromine
188
Now, 0.26 g of the substance give 0.1319 g bromine.
 100 g of the substance gave
0.1319  100
 50.7
0.26
 Percentage of bromine = 50.7
Illustration - 15 0.40 g of an organic compound gave 0.60 g of barium sulphate after Carius method. Find
out the percentage of sulphur in the compound.
SOLUTION :
Since, BaSO4  S
233 g 32 g

233 g of BaSO4 gives 32 g of sulphur.
32
0.60 g of BaSO4, gives  0.60 g of sulphur = 0.082 g sulphur
233
0.082
 Percentage of sulphur   100  0.205%
40
Illustration - 16 0.167 g of teh silver salt of a monobasic organic acid left on ignition 0.108 g of silver.
Calculate the molecular weight of the acid.
SOLUTION :
Weight of Ag salt = 0.167 g and weight of Ag left = 0.108 g.
The weight of Ag salt that would leave 108 g of silver  0.167 108  167 g
0.108
Equivalent weight of the acid = 167 - 108 + 1 = 167 - 107 = 60

Molecular weight of the acid  60  1 (acidity) = 60
Illustration - 17 Calculate the molecular weight of a monobasic base, 0.298 g of whose platinichloride left
0.0975 g of platinum on ignition.
SOLUTION :
Weight of the platinichloride = 0.298 g (X1) and weight of platinum = 0.0975 g (X2)
0.298
 195  410
Equivalent weight of the base  0.0975 596  410 186
   93
2 2 2
Molecular weight of the base  931(acidity) = 93

Illustration - 18 A mono acid organic base on analysis gave the following results: 0.10 g of the base gave
0.28 g of CO2 and 0.075 g of water and 0.30 g of the base gave 31.32 ml N2 measured at 15oC and 760 mm,
0.30 g of the platinichloride left on ignition 0.093 g of platinum. What is the molecular formula of the base?
SOLUTION :
The molecular formula is derived as follows
(a) Calculation of % of elements
12 0.28
% of carbon    100  76.36%
44 0.10
2 0.075
% of hydrogen    100  8.33%
18 0.10
28 Volume of N 2 at NTP×100
% of nitrogen  
22400 Weight of organic compound
28  31.32  100
% of nitrogen   13.05%
22400  0.3
(b) Calculation of relative number of each atom :
76.36 8.33 13.05

C= = 6.36; H = = 8.33 and N = = 0.90
12 1 14
(c) Calculation os simplest ratio:
6.35 8.33 0.90

C 7;H  9 and N  l
0.90 0.90 0.90
(d) Determination of empirical formula :
It comes to be C7 H9 N , its empirical formula weight = 84 + 9 + 14 = 107
(e) Determination of molecules weight :

The molecular weight of the base is given by,
1 Weight % hexachloroplatinate salt 

B 195   410 
2 Weight % platinum 
1 195  0.3  1
B   410    629  410  109.5
2  0.093  2
B = 109.5

Molecular weight 109.5

n= = 1
Empirical weight 107
Hence, molecular formula = empirical formula = C7H9N
Illustration - 19 A sample of a gaseous hydrocarbon occupying 1.12 litre at NTP was completely burnt in
air and gave 2.2g of CO2 and 1.8 g of H2O. Calculate the weight of compound taken and volume of O2 at
NTP required for its burning. Also calculate the molecular formula of the hydrocarbon.
SOLUTION :
Volume evolved at NTP

Mole of compound 
22400 ml or 22.4 litres
1.12
  0.05 mol
22.4
2.2
Moles of CO2 produced   0.05 mol
44
1.8
Moles of H2O produced   0.10 mol
18
Suppose the hydrocarbon is Cx H y
 y y
Then C x H y   x   O2 
 CO2  H 2O
 4 2
 1 mole of Cx H y gives = 0.05 x mol of CO2
 0.05 x = 0.05
0.05
 x 1
0.05
y
Now, 1 mole of Cx H y gives  mol of H 2O
2
y
 0.05 mol of Cx H y will give = 0.05 mol of H 2O
2
y
0.05  0.10
2
 y=4

Hence, the hydrocarbon is CH4
16  1.12
Weight of 1.12 litre CH4 at STP   0.8 g
22.4
Also, CH 4 + 2 O2 
 CO 2 + 2 H 2O
1 mol of CH4 requires 2  32 g oxygen
 0.05 mol of CH4 requires 2  32  0.05  3.2 g CO2
CH4 requires O2 = 3.2 g
Illustration - 20 An organic compound, A containing C, H, N and O, on analysis gives 49.32 % carbon,

9.59% hydrogen and 19.18% nitrogen. A on boiling with NaOH gives off NH3 and a salt which on acidifica-
tion gives a monobasic nitrogen free acid B. The silver salt of B contains 59.67% silver. Deduce the structures
of A and B.
SOLUTION:
Percentage of oxygen = 100 - (49.32 + 9.59 + 19.18) = 21.91
Elements Percentage Atomic Relative No. of Simplest

composition weight atoms ratio
49.32 4.11
C 49.32 12  4.11 3
12 1.37
9.59 9.59
H 9.59 1  9.59 7
1 1.37
19.18 1.37
N 19.18 14  1.37 1
14 1.37
21.91 1.37
O 21.91 16  1.37 1
16 1.37
Hence empirical formula of A = C3H7NO

Because A, gives NH3 on boiling with NaOH, it can be an amide.

Now, silver salt of B, has 59.67 % silver.
 100  108 
Hence equivalent weight of acid     107  74
 59.67 
Molecular weight of monobasic acid = 74 1  74

Molecular formula of acid = C3H6O2
 Structural formula of acid B is C2H5COOH.
Molecular formula of amide = C3H7NO.
Hence structural formula of amide (A) is C2H5CONH2
IN - CHAPTER EXERCISE - A
CH3 CH3
| |
1. (i) CH3  C H  CH 2  (ii) CH3  C  CH 2  (iii) CH3CH 2  C 
| | |
CH3 CH3 CH3
CH3
|
(iv) CH 3CH 2  CH  (v) (iv) CH3 C
| |
CH3 CH3
CH3
3
| 1
2. (i) C H3  C 2  C OOCH3 (Methyl) 2, 2 - Dimethyl propanoate
|
CH3
CH3
6 5 4 | 2 1
(ii) C H3  C H  C H  C H  C H  C H 2 3, 4, 5 - trimethylhex - 1 - ene
| | 3
CH3 CH3
4 3 2 1
(iii) C H3  C H  C H 2 C OOH 3 - chlorobutanoic acid
|
Cl
CH3
4 3 2| 1
(iv) C H3  C H  C  C H3 2, 3 - Dimethyl butan - 2 - ol
| |
CH3 OH
5 4 3 2
(v) C H3  C H 2  C H 2  C H  CH 2CH3 2 - Ethyl pentanoic acid
|
1COOH
4 3 2
(vi) C H3  C H 2  C  CH 2CH3 2 – Ethyl but - 1 - ene
||
C H2
1
CH3
5 4 3 |
(vii) C H3  C H  C H  C  1CH 2 3 - (1 - Methylethyl) –2, 4 - dimethyl pent - 1 - ene
| | 2
CH3 C H  CH3
|
CH3
(viii) 3 – N, N - Dimethyl –2, 4 - dimethyl pentan - 3 - amine
(ix) 3 - Ethyl - 2, 4, 4 - trimethyl hex - 2 - ene
5 4 3 2
(x) C H3 C H 2  C H  C H  O  CH  CH3 2 - (1 - Methyl ethoxy) - 3 - methyl pentane
| | |
CH3 C H3 CH3
1
3. (i) (ii) (iii)
(iv) (v) (vi)
(vii) (viii) (ix)
(x)
CH3
1 2| 3 4 5
4. (i) C H3  C  C H 2  C H  C H3 2, 2, 4 - Trimethyl pentane
| |
CH3 CH3
5 4 3 2 1
(ii) C H3  C H 2  C H 2  C  C H 2 2 - Ethyl pent - 1 - ene
|
CH 2  CH3
CH 3
4 3 2| 1
(iii) C H2  C  C  C H 2 2, 3 - Dimethyl buta –1, 3 - diene
|
CH3
5 4 3 2 1
(iv) C H3  C H  C H  C – C H3 Pent - 3 - en - 2 - one
||
O
IN - CHAPTER EXERCISE - B
1
1. (A) CH 2  CH  CH 2  CH 2 OH
1
CH 3  CH  CH  CH 2OH
(B) C3H6O : (C) ; C4H4O4
(D) H  C  COOH (cis -) maleic acid and H  C  COOH (Trans -) fumaric acid; C4H4O4
|| ||
H  C  COOH HOOC  C  H
2.
3.
4. (A) CH3CH2COOCH3 ; CH3COOC2H5 ; H – COO – CH2CH2CH3 ; HCOO C H  CH3

|
CH3
(B) CH3CH2CH2CHO ; CH3  C H  CHO
|
CH3
O
||
(C) CH3COCH2CH2CH3 ; CH 3  CO  C H  CH3 ; CH3CH 2  C  CH 2  CH3
|
CH3
(D) CH 3  N  CH 2CH3
|
CH 3
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Hydrocarbons
Hydrocarbons
Hydrocarbons
ALKANES Section - 1
Hydrocarbons are the binary compounds of carbon and hydrogen only. Hydrocarbons occur in nature in
the form of coal, natural gas and petroleum. All the organic compounds (other than hydrocarbons) are
derived from hydrocarbons, by substituting hydrogen with a functional group or by adding a functional
group. Hydrocarbons are classified into two categories: Aliphatic hydrocarbons (open chains) and Cyclic
hydrocarbons (closed chains). Here, we will first study aliphatic type, which are further divided into Saturated
hydrocarbons (Alkanes) and Unsaturated hydrocarbons (Alkenes, Alkynes), and then cyclic hydrocarbons,
which are further divided into Cycloalkanes, Cycloalkenes and Aromatic Hydrocarbons.
ALKANES : [CnH2n + 2]
Alkanes form a homologous series, represented by a general formula : CnH2n+2. These have a tetrahedral
structure around carbon atom or one can say that all the carbon atoms in alkanes show sp3 type of
hybridisation. The important members of alkanes are: Methane (CH4), Ethane (CH3CH3), Propane
 CH3  C H  CH3 
(CH3CH2CH3), n-Butane (CH3CH2CH2CH3) and its isomer, Iso-butane  | .
 CH3 
 
Generally, alkanes are also represented as : RH, RCH3, R-R, R-R (where R and R are alkyl radical)
Preparation of Alkanes :
1. Reduction of Alkenes and Alkynes :
H
2 C H
Cn H 2n  n 2n  2
Ni/573 K
Alkane
2 2H
Cn H 2n  2  Cn H 2n  2
Pt or Ni/573 K
Alkane
This is known as Sabatatier-Sandern’s reaction.
Note : For the reduction of alkenes, and alkynes Pd – carbon/Ethanol at 25°C (50 atm) is generally used.
Pd  C/C H OH
2 5  CH
 CH3 2  C  CH 2 
  3 2 CHCH3
25 C, 50 atm
Isobutane

Hydrocarbons Vidyamandir Classes
2. From Alkyl Halides :

(a) By reducing Alkyl Halides :
Reducing agents : Zn + CH3COOH ; Zn + HCl ; Zn + NaOH ; ZnCu Couple ; Al  Hg amalgam.
RX + H2 
 RH + HX
Alkyl iodides are reduced by HI in red P under high temperature and pressure.
Re d P
RI + HI 

 RH + I2 (I2 is removed by P as : 2P + 3I2  
 2Pl3)
150 C, high pressure
(b) Wurtz Reaction :

It involves the condensation of two molecules of alkyl halide with Na and dry ether, to give sym-
metric alkanes
dry
2RI + Na   R – R + NaI
ether
If we start with RI and RI, we get mixture of alkanes. Hence it is not good method for unsymmetric
alkanes.
Note : Methane cannot be formed by this method.
Order of reactivity of alkyl halides RI > RBr > RCl > RF.
(c) Frankland Reaction :

RI + Zn + RI 
 R – R+ ZnI2
3. Reduction of Alcohols :
Re d P
ROH  2HI  RH  I2  H 2O
150C, high Pressure
4. Reduction of Aldehyde and Ketones :

Zn  Hg NH 2 NH 2
RCHO  2H 2   RCH3  H 2O RCH RCH3 + H 2O
HCl alc. KOH
Zn  Hg NH 2 NH 2
RCOR  2H 2   RCH 2 R  H 2O RCOR RCH 2 R + H 2O
HCl alc. KOH
This is known as Clemmensen’s Reduction. This know as Woff-Kishner’s Reduction.
5. From Carboxylic Acids :

(a) Reduction :
Re d P
RCOOH  6HI RCH3  2H 2O  3I2

(b) Decarboxylation :
It is obtained by heating sodium salts of carboxylic acids with sodalime (NaOH - CaO).
CaO
RCOONa  NaOH  RH  Na 2CO3

Note : In the product there is one carbon less than parent compound. So this reaction is an important method to
reduce a carbon atom in organic synthesis (known as Step-down method).
(c) Kolbe’s Electrolysis :

electrolysis
2CH3COONa  2H 2O 
 CH3  CH3  2CO 2  2NaOH  H2
 
(At Anode) (At Cathode)
6. From Grignard Reagent ( Alkyl magnesium halides, RMgX) :
Note : Any copound having acidic H atom(s), decomposes Grignard reagent.
7. By action of water on Aluminium and Beryllium Carbide :
 3CH 4  4Al  OH 3
Al4C3  12 H 2O 
 CH 4  2 Be  OH 2
Be 2C  4 H 2O 
Note : Only Methane is formed by this reaction.
8. Through formation of Lithium Dialkycuprates :

diethyl
RX  2Li  RLi  LiX
ether
2RLi  CuI 
 R 2CuLi  LiI
Lithium diakyl
cuprate
 Gilman 's Reagent 
Self Study Course for IITJEE with Online Support Section

Section 11 3
R 2CuLi  R 'X 
 R  R '  RCu  LiX
This is known as Corey House Synthesis
Note : (i) R can be 1°, 2°, 3° alkyl or aromatic group.

(ii) R should be 1° alkyl or 2° cycloalkyl group or even aromatic group.
Physical Properties of Alkanes :

The physical properties of alkanes such as boiling point, density and solubility depend upon the intermolecular
forces of attraction. The magnitude of these forces of attraction depend upon the surface area of contact
between adjacent molecules. Greater the surfae area, stronger are the forces of attraction.
1. Physical State : The normal alkanes C1 to C4 are colourless gases, C5 to C17 are colourless liquids and
from C18 onwards are colourless waxy solids.
2. Boiling Point : The boiling points of the unbranched alkanes show a regular increase with increasing
molecular weight. The increase is by 20 – 30°C for each –CH2 unit added to the chain. Branching of the
alkane chain, however, lowers the boiling point.
CH3
CH3 |
CH3CH2CH2CH2 -CH3 | CH 3  C  CH3
CH3  C H  CH 2CH3 |
CH3
n-Pentane Isopentane Neopentane
B.P. = 309 K B.P. = 301 K B.P. = 282.5 K
The explanation for these effects lies in the vander waals forces. With unbranched alkanes, as molecular
weight increases, so does molecular surface areas. With increasing surface area, the van der Waals forces
between molecules increase, therefore more energy is required to separate molecule from one another.
Branching in the chain, on the other hand, makes a molecule more compact, reducing its surface area. As a
result, the strength of the van der waals forces operating between the molecules decreases. This results in
the lowering the boiling point.(Observe the boiling points of isomericpentanes above)
3. Melting point : The melting points of alkanes do not follow a very smooth gradation with the increase of
molecular size. Alkanes with even number of carbon atoms have higher melting point than the next lower and
next higher alkanes having odd number of carbon atoms.

It is explained by the fact that alkanes with an odd number of carbon atoms have their end-carbon atoms on
the same side of the molecule and the even numbered carbon atoms alkanes have their end-carbon atoms
on the opposite sides of the molecules. Thus, alkanes with even number of carbon atoms pack closely in
such a manner as to permit greater inter molecular attraction and therefore have slightly higher melting point.
The more compact molecule, the more is the packing efficiency of a molecular solid. This results in higher
melting point. For example, neopentane when packed (in solid form) has a higher melting point as com-
pared to n-pentane (less effective packing due to open chain structure).
Name Formula B.P. (K) M.P. (K) Density
(as liquids)
Methane CH4 111.0 90.5 0.4240
Ethane CH3CH4 184.4 101.0 0.5462
Propane CH3CH2CH3 230.9 85.3 0.5824
n-Butane CH3(CH3)2CH3 272.4 134.6 0.5788
Isobutane  CH3 2 CH  CH3 261.0 114.7 -
n-Pentane CH3(CH2)3CH3 309.1 143.3 0.6264
Isopentane  CH3 2 CH  CH 2  CH 3 300.9 113.1 -
Neopentane  CH 3 3 C  CH3 282.5 256.4 -

3. Solubility : ‘Like dissolves like’ is the general rule of solubility. In the light of this rule, alkanes which are
predominantly non-polar are insoluble in polar solvents such as water, alcohol, etc. but are highly soluble in
non-polar solvents such as Petroleum either, Benzene, Carbon tetrachloride, etc.
4. Density : The density of alkanes increases with the increase in the molecular masses till the limiting value
of about 0.8 g cm3 is reached. This means that all alkanes are lighter than water.
Reaction of Alkanes :
Alkanes being saturated compounds undergo only substitution reactions, at C  H bond. The hydrogen atom is
replaced by other atom(s) such as : X-(halogens), NO2 (nitro), etc.
1. Halogenation :
Replacement of H-atom by X-atom (X = Cl, Br, I) in presence of UV light. The substitution reaction is
explained by free radical mechanism.
2 Cl /h 2 Cl / h
2  CHCl 
2 Cl / h Cl / h
CH 4  CH3Cl  CH 2Cl2  3  CCl4
The bromination is same as chlorination but it is relatively slow and high temperature favours it.
The iodination is reversible reaction :  CH3I + HI
CH4 + I2 
Note : HI is a reducing agent, so oxidising agents, such as HIO3, HNO3, HgO are used to oxidise HI.
5HI + HIO3 
 3H2O + 3 I2
Fluorination of alkanes is too vigorous to be controlled under ordinary conditions. Further-more, fluorina-
tion brings about extensive rupture of C  C and C  H bonds leading to a mixture of product. Alkyl
fluorides are more conveniently prepared indirectly by heating suitable chloroalkanes with inorganic fluo-
rides such as AsF3, SbF3, AgF, HgF2 etc. For example,
2 CH3CH 2 – Cl + Hg2F2 
 2 CH3CH2 – F + HgCl2
The above reaction is known as Swarts reaction.
Ease of halogenation : 3 H > 2H > 1H > CH4

Reactivity of X2 : F2 > Cl2 > Br2 > I2
The reactivity decreases with the electronegativity of the halogens.

Consider halogenation in Isobutane.

Cl
Cl2 , h
|
CH3  C H  CH3   CH3  C H  CH 2Cl  CH3  C  CH3
| 25 C | |
CH3 CH 3 CH3
(63%) (37%)
Br
Br2
|
CH3  C H  CH3   CH3  C CH 3
127C
| |
CH3 CH3
(99%)
The above reactions show that Bromine is less reactive toward alkanes (in general) than chlorine. But
bromine shows greater ability to identify among different types of hydrogen atom (i.e., primary, secondary
and tertiary). It gives exclusive replacement of tertiary hydrogen atom. Chlorine, on the other hand is less
selective than Bromine. Fluorine is even less selective than Chlorine and gives equal percentage of substituted
products. (We will discuss mechanism of this reaction later)
Note :  Laboratory chlorination of alkanes is often done with SO2Cl2 (sulphuryl chloride), instead of Cl2 and an
organic perioxide, ROOR is used as an indicator.
 During monchlorination, number of monochlorinated products formed are equal to number of different
types of hydrogen atoms in the alkane.
2. Nitration :
Lower members do not react with conc. HNO3 at ordinary temperatures but long chain members on
heating with HNO3 yield nitro-alkanes.
400C
C6H13  H  HONO2  C6H13 NO 2  H 2O
(vapour)
However, when a mixture of vapour of an alkane and nitric acid is heated at 400 - 450°C, nitroalkane is
formed readily. By this process lower as well as higher alkanes can be converted into nitroalkanes.
450C
CH 3  H  HONO 2  CH3 NO2  H 2O

(vapour)
In alkanes having two or more carbon atoms, there is always a possibility that the C - C bonds may break
at high temperature and a mixture of nitro alkanes is formed.
HNO
3  CH CH CH NO  CH  C H  CH  CH CH NO  CH NO
CH 3CH 2CH3  3 2 2 2 3 3 3 2 2 3 2
400 C |
NO2

3. Sulphonation :
Lower alkanes do not undergo sulphonation but higher member (from hexane onwards) are sulphonated
slowly when treated with fuming sulphuric acid at about 400°C.
SO
3
C6H13  H  HOSO3H  C6H13SO3H  H 2O
Hexane sulphonic acid
However lower members such as Propane, Butane, Pentane, etc., react with SO3 in vapour phase to form
Sulphonic acids.
4. Cracking : (Pyrolysis)
The decomposition of a compound by heat is called pyrolysis. The alkanes, on heating under high tempera-
ture in absence of air, are broken down into lower alkanes, alkenes and hydrogen during cracking of
alkanes,either rupture of carbon-hydrogen bonds or rupture of carbon-carbon bonds take place resulting in
the formation of mixture of lower alkanes, alkenes and hydrogen. The rupture of C – H bonds is catalysed
by oxide of Chromium, Vandium, Molybednum, etc., and the rupture of C – C bonds is catalysed by Silica,
Alumina, Zinc oxide, etc.
500C
C2 H 6   CH 2  CH 2  H 2
Cr O2 3
500C
C3H8   CH3CH  CH 2  H 2
Cr O 2 3
500C
C3H8   CH 2  CH 2  CH 4
Al2 O3
5. Reaction with Steam :

Ni
CH 4  H 2O   CO  3H 2
1273 K
6. Combustion :
(a) Complete Combustion :
CH4 + 2O2 
 CO2 + 2H2O
3n  1 
CnH2n + 2 +   nCO2 + (n + 1) H2O + heat
 O 2 
 2 
Note : Enthalpy of combustion increases with increase in number of carbon atoms in alkane. For isomeric alkane,
enthalpy of combustion decreases with increase in branching

(b) Incomplete Combustion : If the combustion of alkanes is carried out in limited supply of air or
oxygen, CO is produced along with unburnt carbon in the form of carbon black or soot.
2CH4  3O2 
 2CO  4 H2O
(limited)
CH 4  O 2 
 C  H 2O
(limited) Carbonblack
Carbon black is used in the preparation of black inks, paints, polishes etc.
(c) Catalyst Oxidation : Different prodcuts are formed under different conditions.
(i) When a mixture of methane and oxygen (9 : 1 by volume) at a pressure of 100 atm. is passed
through a copper tube at 573 K, methanol is formed.
100 atm. 573 K
2 CH 4  O2 
 2 CH3OH
Cu tube
Methane Methanol
(ii) When a mixture of methane and oxygen under pressure is passed over heated molybdenum
oxide, it is oxidised to methanal.
Mo O
2 3  HCHO  H O
CH 4  O2  2
 , pressure
Methane Methanal
(iii) Higher alkanes on oxidation in presence of silver oxide give carboxylic acids.
2 Ag O
2 R  CH3  3O 2  2 RCOOH  2 H 2O

Alkane Carboxylic acid
(iv) In presence of oxidising agents such as KMnO4, K2Cr2O7 etc.
CH3 CH3
| |
alk .
CH 3  C  H  (O)  CH3  C  OH
KMnO4
| |
CH3 CH3
Isobutane tert-Butyl alcohol
7. Aromatisation :
Cr O  Al O
2 3 2 3  C H (Benzene)  4 H
CH3   CH 2  4  CH3 
 6 6 2
600 C /15atm

8. Isomerization :
When n-alkanes are heated with anhydrous aluminium chloride and hydrogen chloride at 573 K under a
pressure of about 35 atm, they are converted into branched chain alkanes. For example,
CH 3
AlCl3 / HCl
|
(i) CH3CH 2CH 2CH3   CH3  C H  CH3
573K
Isobutane
CH3 CH3
AlCl3 / HCl
| |
(ii) CH 3  (CH 2 )4  CH3   CH 3  C H  CH 2CH 2CH3  CH3CH 2  C H  CH 2CH3

n - Hexane 2 - Methylpentane 3 - Methylpentane
Illustration - 1 Identify A, B, C, D.
SOLUTION :

ALKENES : [CnH2n] Section - 2
Alkenes form a homologous series, represented by a general formula : CnH2n. These have one C=C bond
or one can say that two carbon atoms (adjacent) in alkenes show sp2 type of hybridisation. The important
members of alkenes are: Ethene (CH2 = CH2), Propene (CH3 CH = CH2), 1-Butene (CH3CH2CH = CH3)
and its isomers, 2-Butene (CH3CH = CHCH3) and Iso-butene  CH3  C  CH 2  .
 | 
 CH 
 3 
Generally, alkenes are also represented as :
1. Terminal alkenes RCH = CH2, R2C = CH2
2. Non-terminal alkenes RCH = CHR, R2C = CHR, R2C = CR2 (where R : alkyl radical)
Preparation of Alkenes :
1. Dehydration of Alcohols :
The dehydration of alcohols is generally carried out in either of two ways :
(a) Heating the alcohol with conc. H2SO4 or H3PO3 to temperature as high as 170°C.
(b) Passing the vapours of alcohol over alumina (Al2O3) at 350 – 400°C.
RCH2CH2OH 
 RCH = CH2 (alkene) + H2O
Ease of dehydration is 3° alcohol > 2° alcohol > 1° alcohol.

Dehydration is governed by Saytzeff or Zaitsev rule i.e., the greater is number of alkyl groups attached to
doubly bonded ‘C’ atoms, the more stable is the alkene.
conc. H SO
2 4  CH CH  CHCH  CH CH CH  CH
CH 3CH 2  C H  CH3  3 3 3 2 2
| T 170C (80%) (20%)
OH
Order of Stability : R2C = CR2 > R2C = CHR > R2C = CH2 > RCH = CHR > RCH
= CH2 > CH2 = CH2
Note : If there are two geometric isomers, i.e., cis and trans isomers, then it is the trans isomer which is more
stable than the cis one.

2. Dehydrohalogenation of Alkyl Halides :

alc. KOH, 
CH3CH2CH 2 Br  CH3CH  CH 2
alc. KOH, 
CH 3CH 2  C H  CH3 
 CH3  CH  CH  CH3  CH 3  CH 2  CH  CH 2
| 2-Butene 1-Butene
Br (major) (minor)
Saytezeff prodcut Hoffmann product
The formation of less substituted alkene in an elimination reaction is called as a Hoffmann Elimination and
that of more substituted alkene as a Zaitsev Elimination or Saytzeff’s elimination.
Ease of dehydrohalogenation is in the order : 3° alkyl halide > 2° alkyl halide > 1° alkyl halide.
Ease of dehydrohalogenation for different halogens is in the order : Iodine > Bromine > Chlorine.
We can also used alkoxide ion, RO  , which acts as a strong base. The alkoxide ion abstracts a proton from
  carbon . Then dehydrohalogenation is known as   elimination or 1, 2  elimination.
CH3 CH3
| |
EtO
 CH3  C  EtOH  Br 
CH3  C  Br 
| Ethoxide ||
CH3 CH 2
Note : (i) In case of 1 RX, alkoxide (R’ O  ) does nucleophilic substitution of form ethers [R' O R].
(ii) By using alc. KOH [ KOH / ROH ], 1, 2,3 alkyl halides give elimination products.
3. By dehalogenation of Viccinal Halides :
CH 2BrCH 2Br  Zn 
 CH2  CH2  ZnBr2
4. Electrolysis of aqueous solution of sodium salts of dicarboxylic acids : (only for Ethene)
5. Cracking of Alkanes :
500C
C2 H 6  C2 H 4  H 2
Cr2 O3

500C
CH3CH 2CH3  CH3CH  CH 2  H 2
Cr2O3
6. Partial Hydrogenation of Alkynes :

The hydrogenation of alkynes to an alkene is brought about by the use of special catalysts. This is an
example of “Stereospecific reaction’’.
Note : Reaction that produce a particular stereoismers of the product is called as steroselective reaction.
(a) Using Lindlar catalyst (Pd/CaCO3 or Pd/BaSO4) in quinoline to give a cis alkene.
This is also called as syn addition, as two H-atoms are added to the same side.
This reaction can also be achieved by using Ni2B (called as P - 2 catalyst)
(b) Using Lithium (or Sodium) in NH3 (or in ethyl amine) at low temperature, gives trans alkene.
This is also called as anti addition, as two H-atoms are added to the opposite side of the bond.
Stability of Alkenes :
The reactivity of different types of alkenes in decreasing order is as follows : (As per heat of hydorgenation)
CH 2  CH 2  R  CH  CH 2  R  CH  CH  R  R 2 C  CH 2  R 2 C  CHR  R 2 C  CR 2
The heat of hydrogenation is always exothermic and experimentally it has been found that :

1
Stability of alkene  (i.e., higher is the heat of hydrogenation, higher is
Heat of hydrogenation reactivity and lower is the stability of an alkene)
Thus stability of alkenes in decreasing order is as follows :
R 2 C  CR 2  R 2 C  CHR  R 2 C  CH 2  RCH  CHR  RCH  CH 2  CH 2  CH 2

trans > cis
Physical Properties of Alkenes :

1. Physical state and smell : The first three members of the family, i.e., Ethene, Propene and Butene
are colourless gases. The next eleven members (C5  C15) are liquids while the higher ones are solids.
Except Ethene which has a pleasant smell, all other alkenes are odourless.
2. Melting points : The melting points of alkenes do not show regular gradation. However, the melting
points of alkenes are higher than those of the corresponding alkenes.
Amongst isomer of alkenes, trans-alkenes have higher melting points than their corresponding cis-
isomers.
3. Boiling points : The boiling points of alkenes, like alkanes, show a regular gradation with the increase
in the number of carbon atoms. Amongst the alkenes which show geometrical isomerism, cis-alkenes
have higher boiling points than the corresponding trans-isomers. This is due to the reason that cis-
alkenes being polar have stronger dipole-dipole interactions while trans-alkenes being non-polar (or
weakly polar) have weak induced dipole interactions.
4. Solubility : Alkenes like alkanes being either non-polar or weakly polar molecules are practically
insoluble in water and other polar solvents but are quite soluble in non-polar solvents such as benzene,
CCl4, petroleum ether, etc. and weakly polar solvents such as ether.
5. Density : The densities of alkenes, like those of alkanes, increase with the increase in molecular mass
till they have a limiting value of 0.89 g cm3. Thus, all alkenes are lighter than water.
Compound M.P. (°C) B.P. (°C) Density (g/mL)

Ethene –169 –104 0.384
Propene –185 –47 0.514
1-Butene - –6.3 0.595
cis-2-Butene –139 3.7 0.621
trans-2-Butene –106 0.9 0.604
1-Pentene –165 30 0.641
2-Methyl-1-butene –138 31 0.650

Reaction of Alkenes :
Alkenes undergo mainly addition reactions.
An addition that puts the part of AB on the same face of the reactant is called as syn addition.
The opposite of syn-addition is an anti-addition. An anti-addition puts the parts of AB on opposite faces
of reactants.
The addition reaction of alkenes are usually electrophilic addition.
Electrophile (E+) : An electron loving species looking for electron rich regions such as localised
pi   electron in alkenes and lakynees. Important Electrophiles :
H  , CI  , Br  , CH 3 etc.
Nucleophile (Nu) : A nucleus loving (electron rich) species looking to attack the electrophilic sites.
Important Nucleophiles : X  , OH  , OR  , CH 3 etc.

1. Addition of hydrogen halides (HX) :
The addition of HX to alkene is an electrophilic addition reaction. The reactivity order follows : HI > HBr
> HCl. The addition follows Markonikov’s rule. It states that in the addition of HX to an alkene, the
hydrogen atom adds to the carbon atom of the double bond that has the greater number of hydrogen atoms,
or the negative part of reagent adds to carbon having less number of hydrogen. The following examples
illustrate Markonikov’s addition.
(a) CH 2  CH  CH3  HI 
 CH3  C H  CH3  CH 3  CH 2  CH 2 I
|
I
2 - Iodopropane  Major  1 - Iodopropane  Minor 
(b) When 2-Methylpropene reacts with HI, the major product is tert. butyl iodide.
CH3 CH3
| |
CH3  C  C   HI 
 CH3  C  C   CH3  C H  C  I
| |
CH3 I
Major Minor
Anti Markonikov’s addition : When addition of HBr takes place in presence of perioxides (ROO
R or benzoyl peroxide), addition occurs in an anti-markonikov’s manner, i.e., Br is added to the carbon
having large number of H-atom.
ROOR
CH 3CH  CH 2  HBr 
 CH3CH 2CH 2Br
In presence of peroxides, free radical addition occurs in an anti-Markonikov’s fashion unlike the electrophillic
addition in above case (i.e., Markonikov’s addition).
Note : (i) Addition of HX in cycloalkenes also follows Markonikov’s addition.
(ii) Addition of HCl and HI in presence of perioxide follows Markonikov’s rule.

2. Addition of H2O :
The acid catalysed addition of H2O produces alcohols and follows Markonikov’s addition. The acids used
to catalyse the reaction are H2SO4 or H3PO4 (phosphoric acid).
CH3 CH 3
|  |
H
CH 3  C  CH 2  H 2O   CH 3  C  CH3
25C
|
OH
Isobutene tert. butyl alcohol
3. Addition of H2SO4 (cold and concentrated) :

Alkene react with cold concentrated H2SO4 to give alkyl hydrogen sulphates following Markonikov’s addi-
tion.
CH3  CH  CH 2  H  OSO3H 
 CH3  C H  OSO3H
cold |
CH3
Note : Alkyl hydrogen sulphates when boiled with water give alcohols. It is an irreversible reaction.
H O
2 
CH3  C H  OSO3H  CH3  C H  OH
boil
| |
CH3 CH3
Isopropyl hydrogen sulphate Isopropyl alcohol
4. Addition of Halogens (Cl2, Br2, I2) :

Alkenes decolourises Bromine water (Br2 in CCl4) following addition of Br2 across double bond. This
serves as a test of unsaturation. It follows anti-addition.
Cl
|
Low temp
CH3  CH  CH 2  Cl2  H3C  C H  C H 2  anti addition 
 anti addition  |
Cl
Viccinal dichloride

Note : (i) The addition of Br2 to cycloalkenes also follows anti-addition.
(ii) The addition of halogens to alkene is an anti-addition and provides an illustration for a stereoselective
and stereospecific reaction. For example, cyclohexene gives trans-1, 2-Dibromocyclohexane
(geometric isomer) is an example of stereoselective reaction. Consider addition of Br2 to cis and
trans-2- Butenes, which is an example of stereospecific reaction as the reactant (2-Butene) also
shows stereochemistry).
Note : The details of reaction mechanisms of all the addition reactions will be discuss later in the Chapter “Organic
Concepts”.
The above reaction, it is visulised as follows and remember the nature of product(s) : (Refer to the next
page)

5. Addition of halogen in aqueous solution :

When halogens are added in presence of H2O / THF (tetrahydrofuran) or NBS (N-bromo succinimide),
halohydrins are formed.
OH
| | | |
THF
 C  C   X 2  H 2O    C C
Alkene |
X
Halohydrins
The above reaction follows Markovnikov’s rule. It is an anti-addition reaction.
Note : (i) The cycloalkenes also reacts with aqueous Br2 to give anti-addition products.
(ii) In case of unsymmetrical alkene, halogen is added to the carbon atom with greater number of H-
atom, (i.e., Markonikov’s addition).
OH
|
H 2O or THF
CH 3  C  CH 2  Br2  CH3  C C H 2
| | |
CH3 H 3C Br

6. Oxymercuration - Demercuration :
An important method of formation of alcohols from alkenes. It occurs in two steps.
(i) Alkenes react with mercuric acetate Hg (CH3COO)2 or represented as, Hg (OAc)2 in a mixture of
THF and water to give a mercury compound.
O O
| | || | | ||
THF/ H2 O
 C  C   H 2O  Hg(O  C  CH3 ) 2    C  C   CH3  C  OH
| |
OH Hg  OAc
This step is known as Oxymercuration.
(ii) The mercury compound is reduced to alcohol with sodium borohydride.
| | NaBH 4 , OH
 | |
C  C     C  C   Hg  CH3  COO
| | | |
HO Hg  OAc HO H
Alcohol
The above reaction occurs in accordance with Markonikov’s addition. The ‘H’ becomes attached
to the carbon atom of the double bond with greater number of hydrogen atom.
H H H H
| | 1. Hg  OAc  /THF, H 2O | |
R  C  C  H  2 R  C  C H

2. NaBH 4 , OH | |
OH H
2 alcohol
Note : Observe that in the final product, OH comes from H 2O and H comes from NaBH 4 / OH  .
7. Hydroboration - Oxidation :
Hydrocration-oxidation serves as an important method for synthesis of alcohol 1 & 2  . It can be repre-
sented as :

H
| | | | |
 C  C  H  B  H 
  C  C
| | | |
H B H
|
H
Alkene Boron hydride Organoborane
Note : (i) The addition of boron hydride is syn-addition.

It is generally carried out by BH3 (boron hydride) B2H6 (diborane) in THF.
3 BH / THF
3CH 2  CH 2 
 (C2 H5 )3 B
Triethyl borane
3 BH /THF 3 CH CH  CH
2  (n  Pr) BH 
3 2  (n  Pr) B CH CH  CH
CH 3CH  CH 2 
 (n  Pr) BH 2  2 3
(ii) In each addition, the boron atom becomes attached to the less substituted carbon atom of double
bond and H is transferred from boron atom to the other carbon atom of double bond. Thus it
follows Anti-Markonikoff’s addition.
The organoboranes formed are oxidised and hydrolysed to alcohols by the addition of hydrogen
peroxides in an aqueous base.
H O
2 2  3ROH + Na BO H O2 2  3PrOH + Na BO
R 3B  3 3 (n  Pr)3 B  3 3
NaOH,25° C NaOH, 25°C
Note that alcohol formed is a primary alcohol (unlike that in Markonikov’s addition)
Consisder hydrobration and oxidation in 1-Methyl cyclopentene. It show syn-addition and anti-Markonikov’s
addition of H2O to alkene.
Note : Observe that in the final product, OH comes from H 2O 2 / OH  and H comes from BH 3 .
Note : Compare the alcohols formed above with those formed by Oxymercuration-Demercuration.

8. Hydroxylation of alkenes (Oxidation by cold alkaline KMnO4) :

The hydroxylation of alkene is brought about by alkaline KMnO4 or osmium tetraoxide (OsO4) to give 1, 2-
diols (or glycols).
| | KMnO 4
| |
 C  C     C  C (Vicinal alcohols or glycols)
OH  , cold | |
OH OH
| | 1. OsO 4 , pyridine
| |
 C  C     C  C (Vicinal alcohols or glycols)
2. NaHSO3 / H 2O
| |
OH OH
It represents syn-addition.
1. OsO , pyridine
4
CH 3  CH  CH 2   CH3  C H  C H 2
2. NaHSO3 / H 2 O
| |
OH OH
1, 2 - Propanediol
Note : Osmium tetra oxide, OsO4 gives a better yield than KMnO4. The hydroxylation like addition of Br2 is also
stereospecific. Consider hydroxylation in cis and trans isomeric alkenes.

9. Hydrogenation :
The hydrogenation of alkenes is a syn-addition, carried out by many reagents such as :
Na in liquid NH3 and alcohol ; H2, PtO2/CH3COOH ; H2/Ni at 573 K ; H2/Pd-Carbon in ethanol.
| | H2
| |
 C  C    C  C 
Ni (573K) | |
H H
This reaction also follows syn-addition rule.sheel

Consider hydrogenation in 1, 2-Dimethyl cyclohexene.
10. Oxidation of Alkenes :

(a) Oxidation by hot. conc. KMnO4 :
It gives acids or ketones depending upon structure of alkenes. The terminal alkenes gives acids
(ketones) and CO2, whereas non-terminal alkenes gives mixture of acids and ketones.
(O)
CH2  CH2 
 2CO2  2 H2O (HCOOH formed is oxidised further)
O
CH3CH  CH 2 
 CH3COOH  CO 2  H 2O
O
R  CH  CH  R 
 RCOOH  R 'COOH

O
CH 3  C  CHCH 3 
 CH3  C  O  CH3COOH
| |
CH 3 CH3
Note : Observe that the dialkylated side of double bond gives corresponding ketone.
Oxidation of cycloalkenes leads to the ring opening and gives dicarboxylic acids or keto acids.
(b) By Ozone (ozonolysis) :
Consider the ozonolysis of cycloalkenes :

Note : In ozonolysis, observe that we are using Zn/H2O or Pb/H2O or (CH3)2S which reduces the nascent oxygen
(O) given by ozonide.This is referred to as Reductive Ozonolysis. If Zn/H2O is not used, the product
aldehyde is oxidised to acid.
11. Alkylation :
CH3 CH3 CH3 CH3
| H2 SO4
| | |
CH3  C  CH 2  H  C  CH3   CH3  C H  CH 2  C  CH3  CH3  C  C  CH3
| | 0 10 C | | | |
CH3 CH3 CH3 CH3 CH3 CH3
 mixture of higher alkanes is formed 
12. Addition of oxygen :
13. Subst it ut ion in alkenes : (Partial Oxidation)

High temp.
CH 2  CH  CH3  X 2   CH 2  CH  CH 2 X  HX
or Low conc. X 2
Here, halogen replaces one of the hydrogen atoms of the methyl group. These hydrogen are allylic hydrogen
atom and hence the substitution is called as allylic substitution.
400 C  500 C
CH 2  CH  CH3  Cl2   CH 2  CH  CH 2Cl  HCl
gas phase
Allyl Chloride
Propene undergoes allylic bromination when it is treated with N-bromo succinimide (NBS) in CCl4 in
presence of perioxides or light.
NBS/CCl
4  CH  CH  CH Br
CH 2  CH  CH3  2 2
in ROOR or light
Allyl bromide
The mechanism is free radical substitution initiated by Br° (bromide free radical) to give intermediate allyl
radical which is stable. Consider allylic substitution in cyclohexene using NBS in CCl4.

Another intersting aspect of this reaction is that it also occurs in alkyl benzens.
14. Polymerisation :
High Temp
(i) n(CH 2  CH 2 )   (CH 2  CH 2  )n (Polyethene)
High pressure
(ii) Polymerization of substituted ethenes : A number of polymers can be obtained by using

substituted ethenes as monomers in place of ethene. For example,
 CH 2  C H  Polymerisation  CH 2  C H  
n |    | 
 Cl   Cl 
   n
Chloroethene 
Polyvinyl chloride PVC 
 Vinyl chloride 
n |    | 
 C H   C H 
 6 5  6 5 n
Styrene Polystrene
n |    | 
 CN   CN n
 
Acrylontrile or Polyacrylontrile(PAN)
vinyl cyanide
Polymerisation
n  CF2  CF2  
  CF2  CF2  n
Tetrafluoroethene Polytetrafluoroethene
 PTFE, Teflon 
Polyvinyl chloride (PVC) is used for making plastic bottles, syringes, etc. Polyacrylontrile is used for making
Orlon and Acrilan fibres used for making clothes, carpets and blankets.

Illustration - 2 Compound A (C6H13Cl)on treatment with hot alcoholic potassium hydroxide gave a
mixture of two isomeric alkense B and C, having formula C6H12. The mixture of (B) and (C), on ozonolysis,
furnished four compounds :
(i) CH3CHO (ii) C2H5CHO (iii) CH3COCH3 (iv) (CH3)2CHCHO
What are the structures of A, B and C ?
SOLUTION :
3 O
Alkenes C6H12 (B and C)  mixture of products
Zn  H 2 O
Try to draw the structures of alkenes (working backwards in ozonolysis reaction). Note that while joining
the products, keep in mind that on combining two products the sum of carbon atom must be six.
On carefully examining the products, alkenes B and C are :
3O
CH 3  C  CH  CH 2CH3  CH3COCH3  CH3CH 2CHO
|
CH3
O
3
and CH3  C H  CH  CH  CH3  (CH3 )2 CH  CHO  CH 3CHO
|
CH3
The structure of A must be :
alc.
CH3  C H  C H  CH2  CH3   CH3  C  CH  CH 2  CH3  CH3  C H  CH  CH  CH3
| | KOH,  | |
CH3 Cl CH3 CH3
(Major) (B) (Minor) (C)

Illustration - 3 Give the stucture of the major organic products form 3-Ethy-l-2-pentene form under
each of the following reaction conditions :
(A) HBr in the presence of peroxide (B) Br2/H2O (C) Hg(OAc)2/THF/H2O, NaBH4/OH–
SOLUTION :
Illustration - 4 A hydrocarbon X, C6H12 decolorizes bromine water and is oxidized to an acid Y by hot
acidic potassium permanganate solution. The acid Y can be resolved into two forms. Identify X and Y.
SOLUTION :
X is terminal alkene as it gives only Y.

Visualise the structure of Y (having a chiral centre) :
 O
 X is C2H5  C H  CH  CH 2 
 C2H5  CH  COOH Y
| |
CH3 CH3
Illustration - 5 Identify A, B, C, D. . . . .
SOLUTION :
Illustration - 6 Identify the products
SOLUTION :
Note that the dialkylated site in alkene give the same producer (Ketone) on oxidation and ozonolysis.

ALKYNES : [CnH2n – 2] Section - 3
Alkynes form a homologous series, represented by a general formula : CnH2n – 2. These have one C  C
bond or one can say that two carbon atoms (adjacent) in alkynes show sp type of hybridisation. The
important members of alkynes are: Ethyne (CH  CH), Propyne (CH3C  CH), 1-Butyne (CH3CH2C 
CH) and its isomer, 2-Butyne (CH3C  CCH3).
Generally, alkynes are also represented as :
1. Terminal alkynes RC  CH
2. Non-terminal alkynes RC  CR, RC  CR (where R : alkyl radical)
Preparation of Alkynes :
1. Dehydrohalogenation of Dihalides : (Gem and Vicinal)
Br
2  CH BrCH Br  alc 2  CH  CH NaNH
CH 2  CH 2  2 2  CH 2  CHBr 
KOH, 
Viccinal dihalide
alc.
CH3 CH Br2 
 CH  CH
KOH, 
Gem dihalides
If alcoholic KOH to be used, vinylic halides are formed, as it is unable to remove vinylic hydrogen. So
NaNH 2 Sodamide) is used to produce alkynes.
2. Dehalogenation of Tetrahalides :
Br Br Br Br
| | | |
Zn
H  C  C  H  Zn 
 H  C  C  H  CH  CH
| |
Br Br
3. By dehalogenation of haloform :
Trihaloderivative of methane is knwon as haloform  CHX3  .
Chloroform and Iodoform on heating with silver powder undergo dehalogenation to form ethyne.
Trihaloalkane  R  CX3 on heating with silver powder also undergo dehalogentation to form symmetrical
internal alkyne.

4. Kolbe’s electrolytic reaction :

Acetylene can be prepared by electrolysis of a concentrated solution of sodium or potassium salt of Maleic
acid or Fumaric acid. Thus,
This reaction is called Kolbe’s electrolytic reaction.
Note : On electrolysis of aqueous solution of Potassium succinate, we get Ethylene (C2H4) as a product at anode.
5. From Graphite :
Electric arc
2C  s   H 2  g  

 CH  CH (Only acetylene can be formed)
1000 C
6. From calcium carbide :

CaC2 + 2H2O 
 C2H2 + Ca (OH)2 (Only acetylene can be formed)

Note : (i) Calcium carbide is formed as follows :

2000C
CaCO3 
 CaO  CO2

2500C
CaO  C 
 CaC2  CO 
(ii) Carbides of Na, K, Ca, Mg, Ba are considered to be ionic and give acetylene with H2O.
(iii) However, carbides of Cu and Ag are covalent and hence do not give acetylene with H2O.
7. Higher alkynes from Lower alkynes :
2 NaNH , liq. NH
3  CH  CNa  R 'X
CH  CH   CH  C  R ' (Terminal alkynes)
excess 1.0 eq.
NaNH 2 , liq. NH3 R 'X

CH  CH   Na  C  C  Na   R ' C  C  R ' (Non-terminal Alkynes)
2.0 eq. excess
2 NaNH , liq. NH RX
3  R  C  C  Na  
R  C  CH   R  C  C  R  (Non-terminal alkynes)
1.0 eq
Note : R’ can only be 1o and 2o alkyl or cycloalkyl groups only.
Physical Properties of Alkynes:
1. Physical state : The first three members of this family (Ethyne, Propyne and Butyne) are colourless
gases, the next eight are liquids while the higher ones are solids.
2. Smell : All the alkynes are odourless. However acetylene has garlic smell due to the presence of
phosphine as impurity.
3. Melting and boiling points : The boiling points and melting points of alkynes are slightly higher
than those of the corresponding alkenes and alkanes. This is probably due to the reason that
because of the presence of a triple bond, alkynes have linear structures and hence their molecules
can be more closely packed in the crystal lattice as compared to those of corresponding alkenes
and alkanes.
Hydrocarbon Ethane Ethene Ethyne

M.P. (K) 101 104 191
B.P. (K) 184.5 171 198

4. Solubility : Alkynes like alkanes and alkenes being non-polar are insoluble in water but readily
dissolve in organic solvents such as petroleum ether, benzene, carbon tetrachloride etc.
5. Density : Densities of alkynes increase as the molecular size increases. However, they are all
lighter than water since their densities lie in the range 0.69  0.77 g/cm3.
Reactions of Alkynes :
1. Electrophillic Addition Reactions :
YX X Y
|| | |
XY XY
C  C     C  C     C C
| |
X Y
(a) Addition of Hydrogen :
H
2  CH  CH 
2  CH  CH H
CH  CH  2 2 3 3
Pt /573K Pt /573K
Read hydrogenation of alkynes in the preparation of alkenes.
(b) Addition of Halogens : (X = Cl, Br, I)
Cl Cl
2Cl2
| | BaCl2 , 
CH  CH   H C CH   CCl 2  CHCl
solvent
| | Westrosol
Cl Cl
Westron
(c) Addition of Halogen acids : (HX)

HBr
CH  CH  HBr 
 CH 2  CHBr   CH3  CHBr2 (Markonikov’s rule )
(d) Addition of Hypohalous acids(HOX) :

Similarly,
(e) Addition of water (H2O) is presence of acid :
Note : The addition of water to alkynes also follows Markonikow’s rule. The hydrogen atom become attached to
the carbon atom with the greater number of hydrogen atoms. Therefore, when higher terminal alkynes are
hydrated, ketones, rather than aldehydes are formed.
However, if the unsymmetrical alkyne is nonterminal, a mixture of two isomeric ketones is obtained
in which the methyl ketone predominates. In case of benzene ring, phenyl ketones is major product .
O O
HgSO4 / H2 SO4
|| ||
 CH3CH 2  C  C  CH3   CH3CH 2CH 2  C  CH3  CH3CH 2  C  CH3CH3
333 K
2 - Pentanone (Major) 2 - Pentanone (Minor)
(f) Addition of HCN :

CH CHHCN 
 CH2 = CHCN (Vinyl cyanide also known as acrylonitrile)
Note : Acrylonitrile is used in manufacture of BuNa-S rubber and Orlon fibre.
(g) Addition of Acetic acid (CH3COOH) :

(h) Addition of Arsenic trichoride (AsCl3) :

CH CClAsCl2 
 ClHC = CHAsCl2
(Lewisite, a poisonous gas)
2. Nucleophillic Addition reactions :
CH  CH  Nu  
 H C  C H
|
Nu
(Vinylic carbanion)
Vinylic Carbanion is formed which is more stable than vinylic carbonium ion.
Addition of Methanol :
3 CH O  K 
HC  CH  CH3OH 
 CH 2  CH  OCH3
Acetylene 433  473 K Methyl vinyl ether
Methyl vinyl ether is used for making polyvinyl ether plastics.
3. Oxidative - Hydroboration
3 BH ,THF 2 2 H O ,OH 
  CH3  CH  CH  3 B 
CH 3  C  CH 
 CH3 
BH3 ,THF H 2 O 2 , OH 
CH3  C  C  CH3 
  |  B 
 CH  CH  C  
 3 3
4. Acetylide Formation :
AgNO
3  Ag  C  C  Ag
CH  CH 
ammonical
silver Acetylide, (white ppt.)

Note : This reaction shows the acidity of terminal alkynes and serves as a test for terminal alkynes.
CuCl
2 Cu  C  C  Cu
CH  CH 
amm.
Copper Acetylide (Red ppt.)
5. Oxidation of Alkynes :
(a) Oxidation in Neutral KMnO4 :
KMnO , H O
4 2  CH  C  C  CH
CH 3  C  C  CH3  2 (O)  3 3
298  303 K
But-2-yne || ||
O O
 Butan-2, 3-dione 
(b) Oxidation with cold dilute alkaline KMnO4 :
Alkynes are readily oxidised by cold dilute alkaline KMnO4 solution to give dicarbonyl compounds.
In case of terminal alkynes,  CH part is oxidised to – COOH group while in case of non-terminal
alkynes, CR part is oxidised to R  C  O group, For example :
|
O
1. NaOH, KMnO 4
||
CH 3  C  CH  3(O)   CH3  C  COOH
298  303 K
Propyne 2-Oxopropanoic acid
2. H

O O
NaOH, KMnO 4
|| ||
CH 3  C  C  CH 3   CH3  C  C  CH3
298 303 K
Acetylene, however, under these conditions gives oxalic acid probably due to further oxidation of
the initially formed glyoxal.
4 KMnO , NaOH  2(O)

HC  CH  2(O)  OHC  CHO 
 HOOC  COOH

Acetylene 298  303 K Glyoxal H Oxalic acid
During this reaction, the pink colour of the KMnO4 solution is discharged and a brown precipitate
of manganese dioxide is obtained. This reaction is, therefore, used as a test for unsaturation under
the name Baeyer’s test.
(c) Oxidation by acidic KMnO4 (hot) :

KMnO
4  R  COOH  R 'COOH
R  C  C  R ' 

H , heat
Not that it is similar to the oxidation of alkenes.

6. Ozonolysis :
(a) For non-terminal alkynes :
O O
1. O3
|| ||
R  C  C  R '   R  C  C R '
2. Zn, H2O
Note : If, Zn or Pb is not used, then the product is mixture of acids.

O O
O3
|| ||
R  C  C  R   R  C  OH  R   C  OH
mixture of acids
(b) For terminal alkynes :

3 O
H  C  CH  OHC  CHO
Zn / H 2 O
 Glyoxal 
O
O3
||
R  C  CH  R  C  CHO
Zn /H 2 O
   alkyl glyoxal 
7. Polymerization Reactions of Alkynes :

Like alkenes, alkynes also undergo polymerization reactions. For example,
(a) When acetylene is passed through red hot iron tube, it rimerises to give benzene.
(b) In presence of nickel cyanide as catalyst and under high pressure, four moelcules of acetyrene
combine to form a tetramer called cycloocta-1, 3, 5, 7-tetraene.
(c) However, in presence of CuCl/NH4Cl, acetylene first gives vinylacetylene and then divinylacetylene.
Thus,

CuCl/ NH Cl
4  H C  C  CH  CH  HC  CH
2 HC  CH  2  H 2C  CH  C  C  CH  CH 2
CuCl/ NH 4 Cl
Acetylene Vinylacetylene Divinylacetylene
Vinylacetylene is widely used in the manufacture of chloroprene which is the starting material for the
synthetic rubber neoprene.
Cl
|
Markonikov 's
CH 2  CH  C  CH  HCl   CH 2  CH  C  CH 2
addition
Vinylacetylene  one mole  across C  C Chloroprene
(d) Under suitable conditions, polymerization of acetylene produces the linear polymer polyacetylene.
It is a high molecular weight conjuated polyene containing the repeating unit (CH = CH  CH =
CH)n. Under proper conditions, this material conducts electricity. Since polyacetylenes have much
higher conductance than metal conductors, these can be used to prepare lighter and cheapter batteries.
Acidic character of Alkynes :

(a) Formation of alkali metal acetylides :
475C
 2HC  C Na   H2
2 HC  CH  2Na 
Ethylne Sodium acetylide
(Acetylene)
Liq. NH
R  C  CH 3
 NaNH 2  R  C  C  Na   NH3
196 K
(A terminalalkyne) (An acetylide)
During these reactions, the acetylenic hydrogen is removed as a proton to form stable carbanions (acetylide
ions). Sodium acetylide is decomposed by water regenerating acetylene. This shows that water is a stronger
acid than acetylene and thus displaces acetylene from sodium acetylide.
HC  C Na   H 2O 
 HC  CH  NaOH
Acetylene
(b) Formation of heavy metal acetylides :

CH  CH  2  Ag  NH3 2  OH  
 AgC  CAg  2 H 2O  4NH3
Ethylne Tollen's reagent Silver acetylide
(White ppt.)


R  C  CH   Ag  NH3  2  OH  
 R  C  C  Ag  H 2O  2NH3
Tollen's reagent Silver acetylide
(White ppt.)

HC  CH  2 Cu  NH3 2  OH  
 CuC  C  Cu  H 2O  4NH3
Ethyne Copper acetylide
(Red ppt.)
Unlike alkali metal acetylides, silver and copper acetylides are not decomposed by water. They
can, however, be decomposed with dilute mineral acids to regenerate the original alkynes.
AgC  CAg  2 HNO3 

 HC  CH  AgNO3
Silver acetylide Acetylene
CuC  CCu  2 HCl 

 HC  CH  2CuCl
Cooper acetylide Acetylene
(c) Formation of alkynyl Grignard reagents :

Dry
HC  CH  RMgX 
 HC  CMgX  RH
Acetylene Grignard reagent ether Acetylenic Alkane
Grignard reagent
Dry
R '  C  CH  RMgX 
 R '  C  CMgX  RH
Terminal alkyne ether Alkynyl
Grignard reagent
Illustration - 7 How would convert acetylene to acetone ?
SOLUTION :
HC  CH  CH3COCH3
In such question, try to visulaise formation of CH3COCH3 . It is formed by hydration of CH3C  CH.
So now convert HC  CH to CH3C  CH.
NaNH  CH Br
3  HC  C  CH 
2  HC  C  N a  2 H O/ H  / Hg 2
HC  CH  3  CH3COCH3
1.0 eq
 via Tautomerism 

Illustration - 8
Identify A, B, C . . . . . . . . .
1.NaNH
2 A 
2  B  H
3 C  D O
(a) Me  C  CH 
2.EtBr Pd  BaSO 4 Zn / H 2 O
quinoline
(b)
1. NaNH (2.0eqv.)
2 2, 2 4C H Liq.Li Br /CCl
(c) HC  CH  A 
 B 
2. EtBr (2.0eqv.) NH3
SOLUTION :
(a)
(b)
(c)

CYCLOALKANES AND CYCLOALKENES Section - 4
These are closed chain hydrocarbons having CnH2n as general formula. These are isomeric to alkenes.
Cyclo propane or C3H6 or
Cyclo butane or C4H8 or
Cyclo pentane or C5H10 or
Cyclo hexane or C6H12 or
The bond angles in lower members, i.e., in cyclopropane and cyclobutane are quite different from normal
tetrahedral bond angle of 109.5°. Hence these are unstable as compared to higher member such as
cyclopentane and cyclohexane which have bond angles nearer to tetrahedral bond angles. The two small
cycloalkanes are said to have a ring strain due to bond deformation. This is referred to as Baeyer strain
theory. Due to this strain, cyclopropane and cyclobutane are highly reactive and tend to open their rings.
Cycloalkenes : These are isomeric to alkynes and alkadienes. Some important cycloalkenes are :
Cyclo propene or C3H4 or

Cyclo butene or C4H6 or
Cyclo pentene or C5H8 or
Cyclo hexene or C6H10 or
1-Methyl cyclopentene
1, 2-Dimethyl cyclohexene
Preparation of cycloalkanes and cycloalkenes :

1. Dehalogenation of iolated dibromides :
It is not a good method because of poor yield.
2. From diazomethane (CH2N2) :

Diazomethane or simple heating gives Carbene, : CH2, which adds to the double bond of alkenes to give
cyclopropane.

CH2 N2 
 : CH2  N 2

Note that the addition of : CH 2 (carbene) is sterospecific as 2-butene exist in cis and trans forms.
3. Simmon - Smith Reaction :

It is another method to form cyclopropane and its derivatives. Instead of diazomethane, di-iodomethane,
CH2I2 with Zn-Cu alloy in diethyl ether is used. The rest of the reaction is same as above.
4. Heating calcium/barium salts of dicarboxylic acids :

By heating barium salts of discarboxylic acids, cyclic ketones are formed, which on Clemmensen’s reduc-
tion (Zn-Hg/HCl) give cyclopentane, cyclohexanes and other higher derivatives.

5. Hydrogenation of benzene :
6. Diel - Alder Reaction :

It is an important reaction of conjugated dienes with double bonded compounds to form unsaturated cyclic
compounds. Let us take 1, 3Butadiene as conjugated diene and consider its reaction with some unsaturated
compounds such as Ethene and Vinyl alcohol. The unsaturated compounds are called as dienophiles. This
reaction proceed beacuse of formation of six membered cyclic transition state.
Note : (i)
‘G’ is preferably an electron withdrawing group (electronegative in nature) such as OH, NH2, 
CN, NO2, etc.
(ii) Each of the product can be hydrogenated to give a saturated compound.

Reaction of cycloalkanes :
1. Ring opening :
The ring of 5 carbons being stable does not open after reaction with hydrogen.
2. Chlorination :
3. Oxidation :
Note : Cyclobutane is opened in the presence of hydrogen and Ni. At ordinary temperatures, cyclobutanes resists
the action of halogens and hydrogen halides.
Reaction of Cycloalkenes :
The cycloalkenes show the reaction of alkenes. (Refer to the reaction of Alkenes). For a quick review of
the reactions, please go through the following page carefully. It shows all the typical reaction of alkenes
taking 1 - Methylcyclopentene as the substrate.


ALKADIENES Section - 5
Alkadienes are isomers of alkynes and cycloalkenes. These are classified in three categories.
(a) Hydrocarbons containing cumulated double bonds are called allenes or cumulated dienes.
CH2 = C = CH2 Propadiene C3H4
CH2 = C = CHCH3 Butadiene C4H6
(b) Those dienes which have an alternate system of double and single bonds are called conjugated
dienes.
CH2 = CH–CH = CH2 1, 3 Butadiene
CH 2  C CH  CH 2
| 2-Methyl-1, 3-Butadiene
CH3
1, 3-Cyclohexadiene
(c) In case, when two or more sp3 hybridised carbon atoms come in between the double bonds in
dienes, then they are called isolated dienes.
CH2 = CH2– CH2 – CH2 = CH2 1, 4-Pentadiene
Note : Conjugated dienes are most stable among dienes. They are stabilised due to resonance.
Preparation of Conjugate dienes :

1. From isolated dihalides
NaNH
2  CH  CH  CH  CH
C H 2  CH 2  CH 2  C H 2  2 2
| |
Cl Cl 1, 3 - Butadiene
NaNH
2  CH  CH  CH  CH  CH  CH  CH  CH  CH  CH
CH 3  C H  CH 2  CH 2  C H 2  3 2 2 2 2
| |
Cl Cl 1, 3 - Pentadiene (Major) 1, 4 - Pentadiene (Minor)

2. From isolated diols :
H SO
2 4  CH  CH  CH  CH  CH  CH  C  CH
CH3  C H  CH 2  C H 2  2 2 3 2
| | T 170C
OH OH 1, 3 - Butadiene (Major) 1, 2 - Butadiene (Minor)
H SO
2 4  CH  CH  CH  CH  CH  CH  CH  CH  CH  CH
CH3  C H  CH 2  CH 2  C H 2  3 2 2 2 2
| | T 170C
OH OH 1, 3 - Pentadiene (Major) 1, 4 - Pentadiene (Minor)
Reactions of Conjugate Dienes :

For the discussion of reactions of conjugated dienes we shall take 1, 3-Butadiene as an example.
1. Electrophillic Addition :
1, 3-Butadiene when reacts with HCl show unusual behaviour to give mixture of two products :
3-Chloro-1-butene (1, 2-addition product) and 1-Chloro-2-butene (1, 4-addition product)
(a) The formation of 1, 4-addition product is interesting.
HCl
CH 2  CH  CH  CH 2 
 CH3  C H  CH  CH 2  CH3  CH  CH  CH 2Cl
25 C |
Cl
(1, 2 - addition) (1, 4 - addition)
Note : Usually 1, 4-addition product is major.
(b) Addition of HBr to 1, 3-Butadiene takes place differently at different temperatures to give 1, 2-
addition and 1, 4-addition products as follows :
CH2 = CH – CH = CH2 + HBr 

(i) At – 80°C (Low temperature) :
CH3  C H  CH  CH 2  CH3  CH  CH  CH 2 Br
|
Br
(1, 2 - addition)(80%) (1, 4 - addition) (20%)

(ii) A 40°C (Near room temperature and above) :
CH3  C H  CH  CH 2  CH3  CH  CH  CH 2 Br
|
Br
(1, 2 - addition)(20%) (1, 4 - addition) (80%)
Note : At high temperatures, in case of HBr, 1, 2-addition product rearranges to give 1, 4-addition product.
(c) Addition of Br2 to 1, 3Butadiene also gives a mixture of 1, 2-addition and 1, 4-addition products.
Br2
(i) CH 2  CH  CH  CH 2   C H 2  C H  CH  CH 2  C H 2  CH  CH  CH 2 Br
15C
| | |
Br Br Br
 1, 3 - Butadiene  (1, 2 -addition) (54%) (1,4 - addition) (46%)
2 Br
(ii) CH 2  CH  CH  CH 2  1, 4  addition is major
T  27 C
2. Free radical addition :

In presence of perioxides, both 1, 2-addition product and 1, 4-addition products are formed. Consider
addition of BrCCl3 in presence of perioxide.
 Cl3C  CH 2  C H  CH  CH 2  Cl3C  CH 2  CH  CH  CH 2 Br
CH2 = CH – CH = CH2 + BrCCl3 
|
Br
(1, 2 -addition) (1, 4 - addition)
Note : Temperature dependency of products is similar to that HBr addition. Also refer to Diel - Alder reactions
(diense with alkenes) in cycloalkenes.
3. Reduction :
Catalytic hydrogenation of conjugated dienes in presence of H2/ Li gives a mixture of 1, 2-addition and 1, 4-
addition product with the 1, 4-addition products being major.
H H H H
H 2 / Li
| | | |
CH 2  CH  CH  CH 2   CH 2  C H  CH  CH 2  CH 2  CH  CH  CH 2
Buta - 1,3 - diene But - 1 - ene (Minor) But - 2 - ene (Major)
However, the chemical reduction of 1, 3-Butadiene with sodium in alcohol gives mainly the 1, 4-addition
product, i.e., But-2-ene.

Na /alcohol
CH 2  CH  CH  CH 2 
 CH3  CH  CH  CH3
1, 3-Butadiene But-2-ene
Under these conditions the isolated double bonds are not reduced. This suggests that dienes are much more
reactive than simple alkenes.
4. Polymerization :
Peroxides
n  CH 2  CH  CH  CH 2    CH 2  CH  CH  CH 2   n
Buta-1, 3-diene Polybutadiene
Since each repeating unit in polybutadiene contains a double bond, it may have either cis or trans-configu-
ration. Actually the polybutadiene polymer obtained by free-radical polymerisation has trans-configura-
tion.
 CH3 
Peroxides
n |  
 CH  C CH  CH 
 2 2
2-Methylbuta-1, 3-diene
(Isoprene)
 Cl   Cl 
Peroxides
n  |    | 
 CH  C CH  CH   CH  C  CH  CH  
 2 2  2 2 n
2-Chlorobuta-1, 3-diene Polychloroprene
(Chloroprene) (Neoprene)
Neoprene is an important substitute for natural rubber and is superior to natural rubber in being
more resistant to oil, gasoline and other organic solvents.
50 Section
Illustration - 9 Isomers A, B, C, and E have a common molecular formula C4H6. Identify A, B, C……as
per given instructions.
(a) A reacts with RMgBr to give a hydrocarbon.
(b) B reacts with Br2 to give a mixture of two products.
(c) C, an alicyclic compound, when oxidised by hot acidic KMnO4, gives a dicarboxylic acid whose
sodium salt on electrolysis gives an alkene, D. Also identify D.
(d) E is an alicyclic compound which is oxidized by hot KMnO4 to give 3-Oxo-1-butanoic acid.
SOLUTION :
C4H6 : can be alkyne, or alkadiene, or cycloalkene
(a) A should be terminal alkyne as it react with Grignard reagent.

 R MgBr
(A) CH3CH2C  CH  RH  CH3CH2C  C  MgBr
(b) B should be a conjugated diene as it gives a mixture of products.

Br
2  C H  C H  CH  CH  C H  CH  CH  C H
CH 2  CH  CH  CH 2  2 2 2 2
(B) | | | |
Br Br Br Br
(1, 2 - addition) (1, 4 - addition)
(c) D is clearly ethene as it is the only lakene

formed by Kolbe’s electrolysis.
(d)

Illustration - 10 Give the products.
(a) (b)
SOLUTION :
(a)
Note that aldehyde group is oxidised to acidic group
(b)

AROMATIC HYDROCARBONS Section - 6
Benzene : [C6H6]
Structure :
Its molecular formula is C6H6. This implies unsaturation in benzene. It shows addition reactions : addition of
3 molecules of Hydrogen, 3 moles of Cl2 and 3 moles of Ozone (like alkenes).
This leads to idea of three double bonds. However, benzene fails to give unsaturation test (i.e., Baeyer’s test
or decolouration of bromine water). Benzene also gives substitution reactions like halogenation, nitration
etc. (like alkanes). On addition of H2, benzene forms cyclohexane (a cyclic hydrocarbon) C6H12. Kekule
(1865) proposed following structure the basis of the structure of cyclohexane. But this structure fails to
explain ozonolysis of Xylene [C6H4  (CH3)2], a derivative of benzene. So benzene is found to be a
resonance hybrid of two Kekule structures :
This is supported by ozonolysis of o-Xylene, which gives a mixture of Glyoxal, Methyl glyoxal, Dimethyl
glyoxal which can not be explained by either of Kekule structures.
Now benzene is considered as resonance hybrid of two Kekule structures. Resonance imparts stability to
the benzene due to delocalisation of  electrons over entire benzene ring . Since  electrons are not concen-
trated in any specific region, addtion reaction (electrophillic) are not common is benzene. However, in
benzene electrophillic substitution reactions are common as they are stabilized by resonance stabilisation of
intermediate Carbonium ion. When a group is introduced in benzene nucleus (ring), only one product
(monosubstitued) is obtained. On the other hand, when a group of electrophillic nature is introduced in a
mono-substituted benzene, three different isomers are possible.
In the above sequence, nature of X (group over mono-substituted benzene) is responsible for the formation
of either ‘m’ or ‘o’ & ‘p’ derivatives.

Directive (orienting) influence of groups :

(a) o and p directing groups : These groups direct the incoming group predominantly to the ‘o’ &
‘p’ position. Some important groups are :
 NH 2 ;  NHR ;  ;
 OH  ;
 OR  ;  R
X
All of these groups exerts +M effect over benzene and tends to increase electron-density over
benzene and make benzene strongly nucleophillic towards electrophiles. These groups are called
activating groups. -I effect (elctronegative or electron withdrawing nature) of these groups is weaker
as compared to +M effect. Halogens exerts +M effect over benzene but their -I effect is very
powerful. Though they are o and p directing (+ M effect) but are de-activating in nature and hence
it is difficult to carry out electrophillic substitution in halo benzenes. Alkyl group (R) are o and p
directing due to hyperconjugation (to be discussed later).
(b) m-directing groups : These groups direct the incoming groups predomintly to m-positions. Some
of the important groups are :
O OH R H
|| || | |
 C  OH ;  S  O ; C  O ;  C  O ;  NO 2 ;  CCl3
||
O
All m-directing groups, (except CCl3) either possess a positive charge or the key atom of substituents
has an electronegative atom linked by a multiple bond. The benzene nucleus containing these groups
undergo strong –M, –I, effect such that the displacement of electron takes place away from the
benzene ring. These groups tends to deactivate the benzene ring and hence makes it less nucleophillic
towards electrophiles.These are called as de-activating groups. Benzene having these groups will
have greater difficulty in electrophillic substitution reactions.
Preparation of Benzene :
1. Decarboxylation of Sodium Benzoate :
2. From Chlorobenzene :

3. From Phenol :
4. From Sulphonic Acid :
5. Synthesis :
Red hot Fe tube
3C2 H 2  C6 H 6
6. From Benzene Diazonium Chloride :
7. Manufacture :
(a) n-hexane :
2 3 Al O  Cr O
2 3
CH3  CH 2 4 CH3 
600C, pressure
This is known as Hydroforming or catalytic Reforming or aromatisation
(b) Coal Tar :
fraction
Dry distillation 
 COAL  TAR  Ligt  oil  fraction 

of wood Distillation 80  170C
Physical properties of Arenes :

1. Benzene and its homologues containing upto eight carbon atoms are colourless liquids with charac-
teristic smell.
2. Due to large hydrophobic hydrocarbon part, arenes are not soluble in water but are soluble in
organic solvents.
3. The melting points and boiling points of arenes increase with increase in the molecular size due to
a corresponding increase in the magnitude of van der Waal’s forces of attraction. Amongst isomeric
arenes, i.e., o-, m- and p-Xylenes, the p-isomer is most symmetrical, has the highest melting point.

Reaction of Benzene :
When benzene is treated with bromine in carbon tetrachloride in the dark or with aqueous potassium in the
dark or with aqueous potassium permanganate or with dilute acids, none of the expected reactions (addition
reactions) occurs. Benzene does add hydrogen in the presence of finely divided nickel, but only at high
temperature and under high pressures.
Benzene does react with bromine except in the presence of catalyst such as ferric bromide. The interesting
aspect of this reaction is that benzene show substitution not addition (like alkenes).
Substitution :
FeBr
3  C H Br  HBr
C6H 6  Br2  6 5
Addition : Benzene does not show addition reaction of Br2 or H2 at all under normal conditions.
When benzene reacts with bromine, only one monobromobenzene is formed. That is, only one compound
with the formula C6H6Br is found among the products. Similarly, when benzene is chlorinated, only one
monochlorobenzene results.
Two possible explanations can be given for these observations. The first is that only one of the six hydrogen
atoms in benzene is reactive toward these reagents. The second is that all six hydrogen atoms in benzene are
equivalent, and replacing any one of them with a substituent results in the same product. From the concept
of Resonance we know all six carbon atom form equivalent C – C and C – H bonds. Hence this is the
correct explanation.
Structure of Benzene
The fact that the bond angles of the carbon atoms in the benzene ring are all 120strongly suggests that the
carbon atoms are sp2 hybridized. If we accept this suggestion and construct a planar six-membered ring
from sp2 carbon atoms, a representation like and shown in figure emerges. In this model, each carbon is sp2
hybridized and has a p-orbital available for overlap with p-orbitals of its neighbouring carbons. If we con-
sider favaourble overlap of these p-orbitals all around the ring, the result is the model shown in figure.
(a) Six sp2-hybridized carbon atoms are joined in a ring (each carbon also bears a hydrogen atom).
Each carbon has a p-orbital with lobes above and below the plane of the ring. Fig.(1)
Fig. (1)
(b) Overlap of the p-orbitals forming pi() bonds around the ring results in the delocalisation of pi()
electrons on the ring. [Refer to Fig.(2), (3), (4)]

Fig. (2)
Fig. (3)
Fig. (4)
The six  electrons are thus delocalised and can move freely about the six carbon nuclei, instead of any two
as shown in figure (4). The delocalised  electron cloud is attracted more strongly by the nuclei of the
carbon atoms than the electron cloud localised between two carbon atoms. Therefore, presence of delocalised
 electrons in benzene makes it more stable than the hypothetical cyclohexatriene. X-Ray diffraction data
reveals that benzene is a planar molecule. It also indicates that all the six C – C bond lengths are of the same
order (139 pm) which is intermediate between C – C single bond (154 pm) and C – C double bond (133
pm). This absence of pure double bond in benzene accounts for the reluctance of benzene to show addition
reactions under normal conditions, thus explaining the unusual behaviour of benzene.
1. Addition of Hydrogen (H2) :

2. Ozonolysis :
3. Oxidation :
Benzene is unreactive towards even strong oxidising agents such as : KMnO4/K2Cr2O7. However
in drastic conditions, it can be oxidised slowly to CO2 and H2O. It can be burned (i.e., combustion)
to give luminous and smoky flame.
(a) Controlled oxidation with air :
Benzene on oxidation with air at 773 K in presence of V2O5 as catalyst gives Maleic anhy-
dride.
(b) Oxidation of alkyl benzene :
Note : If R is a 3alkyl group, then it resists oxidation the benzene ring is destroyed.
3. Substitution Reactions :
Most important reactions of benzene are electrophillic substitution reactions. These are also denoted as SE
reactions.

Elecrophiles :
  +
Cl+ (Chloronium ion), N O 2 (Nitronium ion), SO3 (Sulphur trioxide), R (Carbonium ion), R  C  O
(Acylium ion).
(a) Halogenation :
 FeCl4  Cl
FeCl3  Cl2 
Note : (i) In iodination, oxidising agents like HNO3 or HIO3 are used to oxidise HI, a reducing agent.
(ii) In presence of sunlight and absence of halogen carriers (i.e., AlCl3, FeBr3, etc), benzene adds three
molecules of chlorine to form Benzene hexachloride (BHC) or Gammexane.
h
C6 H 6  3Cl2 
 C6 H6 Cl6
It may be noted that this is an addition reaction, not a substitution reaction.
(b) Nitration :

 HSO 4  H O NO 2 
HNO3  H 2SO 4   NO2  H 2O
Base Acid |
(Nitrating mixture) H
(c) Sulphonation :
H 2S2O7 
 SO3 + H 2SO4
electrophile
(d) Introduction of alkyl and acyl groups in presence of Catalysts : AlCl3, FeCl3, SbCl3 (acting
as Lewis acids) or protonating agents like HF, H2SO4, H3PO4 etc. These are known as Friedal
Craft reactions.

(i) Alkylation :
 AlCl4 
RCl  AlCl3  R (alkyl carbonium)
Electrophile
Note : The above reaction can be achieved with :
(a) An alcohol in HF or dil H2SO4 (b) An alkenne in HF or dil. H 2SO 4 (at low temperature)
(a)
(b)
Obseve that 3 carbon is attached to the ring.

While during alkylation, we expect formation of polyalkylated products as alkyl groups are o- and p-directing and
activating
(ii) Acylation :
O
||
RCOCl  AlCl3 
 R C  AlCl4

Acylium ion is Electrophile

The above two reaction are called as Acctylation and Benzoylation respectively.
Some Friedal Craft acylation are shown below :
The above reaction is also known as Gatterman - Koch reaction.
Note : (i) Aryl and vinylic halides cannot be used in Friedal craft reactions as they do not form carbocations
easily.
(ii) In substituted benzenes, Friedal Craft reactions gives poor yield when electron withdrawing (de-
activating) groups are present on the ring. These include :
O
||
 NO 2 , CN  ,  COOH,  C  R,  CCl3 ,  SO3H
(iii) In Friedal craft alkylation. most stable carbocation (from alkyl halide or alkene) determines the final
substitution product.

It does not give npropyl benzene since CH3 – C HCH3 , being a 2° carbocation is more stable

than CH3CH 2CH 2 1  .
* The detailed mechanism of SE reaction will be discussed later in the chapter “Organic Concepts”.
(iv) Intramolecular Friedal Craft reactions of - & - alkyl alkanoic acid or alkanoyl chlorides give
cyclic products.
4. Dehydrogenation :
Toluene :
Preparation of Toluene :
1. Friedal craft alkylation :

2. From dialkyl cuprates :

 CH3 2 CuLi  C6 H 5I 
 C6H 5  CH 3  LiI  CH 3Cu
Reactions :
1. Oxidation :
(a)
(b)
This is also known as Etard reaction.
2. Substitution :
(a) Side chain substitution :

(b) CH3 group being o and p directing directs incoming electrophile to o and p position :
3. Addition Reactions :

Illustration - 11 One of the benzene ring of [4] phenylene undergoes catalytic hydrongation readily under
conditions usually used for ordinary alkenes, but the other benzene ring do not. Identify which of these two
reaction correctely represent product of hydrogenation of [4] phenylen ?
I.
II.
(A) Only I (B) Only II (C) Both I and II (D) None
SOLUTION
Reaction I correctly represent product of hydrogenation of [4]-phenylen beacuse of loss in anti-aromatic

characters of all four memebered rings.

Illustration - 12 Which is the major product of the following

intramolecular F.C. acylation reaction ?
SOLUTION
Enolic form is more stable than keto form due to more aromatic characters in enolic form.

Example - 1
Give the structure of A, B and C (explanation are not required) :
(i) A (C4H8) which adds on HBr in the presence and in the absence of peroxide to give same product,
C4H9Br
(ii) B (C4H8) which when treated with H2O/H2SO4 gives C4H10O which cannot be resolved into optical
isomers.
(iii) C (C6H12), an optically active hydrocarbon which on catalytic hydrogenation gives an optically
inactive compound C6H14.
SOLUTION :
(i) A: CH3CH = CHCH3 symmetric alkenes give same product.
OH
H 2O
|
(ii) B: CH3  C  CH 2 
 CH 3  C  CH3 ; optically inactive (No chiral centre)
| H |
CH3 CH3
H H
| H 2 / Pt
|
(iii) C: CH3  C*  CH  CH 2 (active)   CH3  C  C2 H5
|  |
C 2H 5 C 2 H5
(* : Chiral centre)
optically inactive (No chiral centre)
Example - 2
An organic compound E (C5H8) on hydrogenation gives compound F (C5H12). Compound
E on ozonolysis gives formaldehyde and 2-ketopropanal. Deduce the structure of compound E.
SOLUTION : In such questions, by working backwards we join :
Note : Since 2-ketopropanal has two keto groups, hence there must be 2 moles of HCHO.
O
O3
||
(E)  2HCHO  CH3  C  CHO  E is :
Zn  H2 O
Self Study Course for IITJEE with Online Support Subjective Solved Example 67
Example - 3 The hydrocarbon, A adds one mole of hydrogen in the presence of a platium catalyst to
form neo-hexane. When A is oxidised vigorously with KMnO4, a single carboxylic acid, B is isolated. Give the
structures of A and B.
SOLUTION :
CH3
|
Hence A is : CH3  C  CH  CH 2
|
CH3
CH3
|
Clearly B is : CH3  C  COOH
|
CH3
Example - 4 What are product A, B and C in the following rection ?
2 H (O)

 A 
 B  C
Lindlarcatalyst
SOLUTION : Visualise the structure of given compound as follows :
Example - 5 Identify the products A, B and C and the reagent R in the following reactions :
alc. KOH 2 H O
(i) (CH 3 )2 C  CH 2CH 3  A (ii) HC  CH 
 2
B
| H / Hg
Cl
(iii) R
A 
BC
SOLUTION :
CH3 CH3
| RO |
(i) CH3  C  C HCH 3  CH3  C  CHCH3 (Saytzeff’s product)
| | (A)
Cl H
H O Tautomerises
2 

(ii) HC  CH   CH 2  CHOH 
 CH3CHO
 2
H / Hg
(B)
CH3
| R
(iii) CH 3  C  CHCH3  CH3CHO  (C)
R is clearly O3/Zn-H2O and (C) is acetone (CH3COCH3)

CH3
| O3
CH 3  C  CHCH 3   CH3CHO  (CH 3 )2 C  O
Zn /H 2 O
(A) (B) (C)
Example - 6 De-hydro-bromination of two compounds A and B gives the same compound C. C

regenerates A and B when reacts with HBr in the presence and absence of peroxide respectively. The hydrolysis
of A and B gives isomeric products D and E respectively. C when reacts with benzene in presence of H+ ions
gives 1, 1-Diphenylethane. Identify the compounds A to E.
SOLUTION : Visualizing the flow chart of the question as follows.
Recall Friedal Craft alkylation
 C is an alkene containing a – C = C – bond, hence C is vinyl benzene. C :
As per given reactions in question :
A: B: D: E:
Example - 7 An organic compound A, C5H9Br de-colourises bromine water and alk. KMnO4. It gives
B, C5H11Br when treated with H2, Pd-carbon in methanol. The reaction of A with NaNH2 gives C with the
evolution of NH3. C does not react with sodium but reacts with Lindlar catalyst to give D. It also reacts with
Na/liquid NH3 to give E. Both D and E are isomers. Identify the compounds A to E with proper reasoning.
SOLUTION :
Visualizing the flow chart of the question as follows :
Hydrocarbons
Since D and E are isomers obtained by partial hydrogenation of ‘C’ (C : an alkyne) from two different
reagents, D and E must be geometric isomers with molecular formula C5H10. “Check this as follows”
NaNH 2
(A) C5H9 Br  C5H8  NH3  Br 
(Dehydrobro min ation)
2H
C(C5H8 )   C5H10 (D and E)
The alkene with molecular formula, C5H10 showing geometric isomerism is only 2-Pentene
[CH3CH = CHC2H5]
Hence the compound (C) is 2-Pentyne (Non-terminal alkynes do not react with Na).
A can be :
CH 3 C  CH  C 2 H5 or CH3CH  C  C 2H5
| |
Br Br
Both will give 2-Pentyne with NaNH2.

Accordingly B can be :
CH 3 C H  CH  C2 H5 or CH3CH 2  C HC 2 H5
| |
Br Br
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Vidyamandir Classes Stoichiometry- II
Stoichiometry - II
Analysis of Redox Reaction
There are two ways of analysing and solving the stoichiometric problems based on redox reactions :
(a) One is to balance the redox reaction and then approach the problem like a simple balanced chemical
equation using the concept of moles (Application of mole concept as done earlier).
(b) Second, use the concept of gram equivalents (or milli equivalents) as used in neutralisation.
Here gmeq. (or meq) of oxidising agent = gmeq. (or meq) of reducing agent.
First we will learn how to analyse a given redox reaction and different methods used for
balancing it. Then as the chapter progress, you will learn how to proceed while solving
numerical problems based on the redox analysis.
OXIDATION - REDUCTION Section - 1
Oxidation is a process that involves the loss of electrons by the atoms or ions.
Reduction is a process that involves the gain of electrons by the atoms or ions.
Any reaction, in which the electrons are exchanged between atoms or ions, represents simultaneous pro-
cess of oxidation and reduction and is called as a Redox Reaction.
In a Redox Reaction, the species that loses electron (i.e., gets oxidised) is known as reducing agent or
reductant, (since it causes reduction of other species), the species which accepts electrons from reductant
(i.e., gets reduced) is known as oxidising agent or oxidant (as it causes oxidation of other species).
Mg + Zn2+ 
 Mg2+ + Zn is a redox reaction.
Oxidation : Mg0  Mg2+ + 2e


Reduction : Zn2+ + 2e  Zn0


Mg causes reduction of Zn2+, so it is Reductant.
Zn2+ causes oxidation of Mg, so it is Oxidant.
Note : A redox reaction involves two half reactions: Oxidation half reaction and Reduction half reaction

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Now, a new concept of Oxidation Number and Oxidation State is being introduced in order to study
oxidation and reduction reactions (redox reactions) in a much better way.
Oxidation Number (O.N.) : It refers to the total charge on all atoms of same kind in a compound.
Oxidation State (O.S.) : It refers to the charge per atom of all atoms of same kind in a compoun.
Oxidation state, many a times, is alos referred to as Oxidation Number (Refer to NCERT Book).
This means, oxidation number of an element in a compound is equal to oxidation state of that element
multiplied by total atoms of that element in particular compound.
(i) In ionic compounds, it is simply the charge on corresponding cation and anion which is expressed as
oxidation state of that partiular element. For example, oxidation state of potassium and chlorine in
potassium chloride (KCl) is simply +1 and –1 respectively as KCl is treated as K+ Cl–.
Refer to following examples where oxidation states are written above the atoms : .
+2 –1 +2 –2 +3 –1 +2 –2 +1 –1 +1+6 –2
MgCl2 CaS AlCl3 CaO NaF K2SO4
Note : (a) In MgCl2 and AlCl3, -1 is the oxidation state of Cl atom and its oxidation number is -2 and -3
respectively.
(b) In each of the cases, the sum of oxidation number of all atoms of all kinds is equal to zero (as the
compound is neutral).
(ii) In Covalent Compounds, it is not so easy to assign oxidation state of an atom. In order to simplify
the concept, we are going to define a set of rules which would enable us to assign oxidation state to
every element in any compound.
Rules for Assigning Oxidation State (O.S.) and Oxidation Number (O.N.) :
1. Any element in free state is assigned an oxidation state of zero (0). For example: O.S. of H, P, S, O,
Fe, Br, in H2, P4, S8, O2, Fe, Br2 is equal to 0.
2. The oxidation state of any cation or anion (of form A+ or B ) is equal to the magnitude of its charge.
For example: O.S. of Ca in Ca2+ = +2, O.S. of Al in Al3+ = +3, O.S. of Cl in Cl = 1 and so on.
3. (a) The algebraic sum of the oxidation number of all atoms in a neutral compound is equal to 0.
(b) The algebraic sum of the oxidation numbers of all atoms in an ion (like PO34 etc.) is equal to
the charge on the ion.

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4. The oxidation states of Alkali Metals (Group IA) is +1 in all of their compounds and that of Alkaline
Earth elements (Group IIA) is +2 in all of their compounds.
5. Hydrogen in almost all of its compounds is assigned an oxidation state of +1. The exception occurs
when hydrogen forms compounds with strong metals (metallic hydrides). For example : KH, NaH,
MgH2, CaH2 etc. In all of these, the oxidation state of hydrogen is 1.
6. Oxygen in almost all of its compounds is assigned an oxidation state of 2. In a class of compounds,
Peroxides, oxidation state of oxygen is 1, for example : H2O2, Na2O2 etc. Another exception is
1
OF2, where O.S. is +2. O2F2, where O.S. is +1 and KO2 in which O.S. is  .
2
7. Fluorine is most electronegative element and is assigned an O.S. of 1, in all its compounds. For
other halogens, O.S. is generally 1 except when they are bonded to a more electronegative halo-
gen or oxygen. O.S. of iodine in IF7 is +7, O.S. of chlorine in KClO3 is +5.
Concept of Fractional Oxidation States :

Fractional oxidation state is the average oxidation state of the element under examination and it means
that the element for which fractional oxidation state is realised is present in different oxidation states.
Structure of the species C3O2, Br3O8 and S4O62 reveal the following bonding situations :
The elements marked with asterisk in the above examples are exhibiting different oxidation state from the
rest of the atoms of the same element in each of the species. This means that in C3O2, two carbon atoms are
present in +2 oxidation state each, whereas the third one is present in zero oxidation state and the average
is 4/3. Likewise in Br3O8, each of the two terminal bromine atoms are present in +6 oxidation state and the
middle bromine is present in +4 oxidation state and the average is 16/3. In the same manner, in the species
S 4 O 62  is 2.5, whereas the reality being +5, 0, 0 and +5 oxidation number respectively for each sulphur..
Fe3O4, Mn3O4, Pb3O4 are some of the other examples of the compounds, which are mixed oxides having
the metal in fractional oxidation state. However, the oxidation states may be in fraction as in O 2 and O 2
where it is +1/2 and 1/ 2 respectively..
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Section 3
Using all these rules, we can now assign oxidatizon states to almost all the elements in various compounds
and ions.
Try Yourself : Find the oxidation state of atoms (written in bold) in the following compounds.
SiO2, OF2, KClO3, HClO4, NH4+, Hg2O, Pb3O4, MnO2, C3H6Cl2, BO33, K2MnO4, Cr2O3,
CrO2Cl2, Mg3N2, N2O5, MgSiO3, Na2S2O3, S4O62, CaC2, H2C2O4, NH4NO3
Analysis of a Redox Reaction

Consider the following Redox Reaction :
CuSO4 + Pb  
 PbSO4 + Cu
1. Assign oxidation state to each atom.

+2 +6 2 0 +2 +6 2 0
Cu S O4 + Pb 
 Pb S O4 + Cu
Note : (i) O.S. of S, O remains same, i.e., neither of the two is oxidised or reduced (by inspection).
(ii) O.S of Pb and Cu2+ has changed from left to right.
Rewriting the equation as two equations (oxidation and reduction) as follows :
Reduction : Cu2+ + 2e 

 Cu0 (gaining 2e)
Oxidation :  Pb2+ + 2e
Pb0  (losing 2e)
Note : (i) O.S of Pb has increased from 0 to +2.

(ii) O.S of Cu2+ has decreased from +2 to 0.
We can now re-define oxidation and reduction as follows :

Oxidation is an increase in oxidation state and Reduction is a decrease in oxidation state.
Note : Pb is oxidised and causes the reduction of Cu2+. Pb is called as reductant. Cu2+ is reduced and causes the
oxidation of Pb. Cu2+ is called as oxidant.
Now an important aspect at this stage is to learn “How to balance the redox reactions”. So first we will learn
balancing the Redox Reactions.
4 Section
Balancing of Redox Reactions

For balancing of Redox Reactions, two methods are generally adopted :
(A) Oxidation Number Method
(B) Ion Electron (Half-Reaction) Method
(A) Oxidation Number Method :

While balancing a given reaction by this method, following steps are to be followed :
1. Assign oxidation state to each element (atom) on both sides of the equation and identify which
element has been oxidised and which reduced.
2. Write two oxidation and reduction reactions (two half reactions) separately involving only atoms.
Now balance the atoms on both sides of equation in each half reaction.
3. Balance charge on both sides by adding electrons to whichever side is deficient in electrons. (i.e.,
negative charge)
4. Add two half reactions together. How ? In doing this we want electrons to cancel from both sides. For
this, multiply the equations by appropriate coefficients so that number of electrons produced in oxidation
reaction equals to that used up in reduction reaction.
5. Now compare this balanced equation with original unbalanced equation. Here, notice whether the
given equation is a molecular equation or an ionic equation.
6. For molecular equation, to balance Oxygen (O) and Hydrogen (H), add required water to the side
deficient in H and check for Oxygen atoms on both sides. (They will be equal on both sides)
7. For ionic equation, apart from balancing O and H atoms, charge needs to be balanced. It depends
upon the medium in which the reaction is taking place : Acidic (containing H+ ions or any acid) or
Alkaline (containing OH ions or any base).
(a) In Acidic medium, count total charge on both sides and balance it by adding H+ ions to the
required side (i.e., to the side deficient in +ve charge). Finally add enough water molecules to
balance H and O atoms to the required side.
(b) In Basic medium, balance the charge by adding OH ions to the side with excess of +ve charge
and finally add required number of H2O molecules to the appropriate side to balance O and H.
(B) Ion Electron (Half-Reaction) Method

1. Identify the oxidation and reduction half reactions and write them separately in ionic form. Note that,
write whole of ion in half reaction (unlike the oxidation number method where only atoms undergoing
the change of state were taken).

Stoichiometry-
Stoichiometry-IIII Vidyamandir Classes
For example : Mn in MnO4 in acidic medium generally goes to MnSO4 or Mn2+
Write it like this : MnO4 

 Mn2+ (and not as Mn7+ 
 Mn2+ )
2. Balance each half reaction separately. This is done accordingly to the following procedure.
3. Balance all the atoms of both reactions except O and H.
4. Now first balance O and H atoms (unlike in first method) depending upon the medium of reaction.
Acidic Medium :
To balance O atoms add same number of water (H2O) molecules to the side deficient in O atoms.
MnO4 
 Mn2+ (acidic medium)
Illustration - 1 MnO4 
 Mn2+ + 4 H2O
Now to balance H atoms, add as many H+ ions required to the side deficient in H atoms (generally it is
equal to double the number of water molecules added to the other side while balancing O atoms).
MnO4 + 8 H+ 
 Mn2+ + 4 H2O
Basic Medium :
To balance O atoms, add same number of H2O molecules to the side having excess of O atoms and add the
double the number of OH ions to the other side (i.e., to the side deficient in O atoms).
NO3  
 NH4+ (basic medium)
NO3 + 3 H2O   NH4+ + 6 OH


Now to balance H atoms (if required), add same number of OH ions to the side in excess of H atoms and
then add same number of water molecules to the other side (i.e., the side deficient in H atoms).
NO3 + 3 H2O + 4 H2O 

 NH4+ + 6 OH + 4 OH
NO3 + 7 H2O 
 NH4+ + 10 OH
5. Now add electrons to the side deficient in negative charge in order to balance the charge on both
sides.
MnO4 + 8 H+ + 5e  
 Mn2+ + 4 H2O
NO3 + 7 H2O + 8e 

 NH4+ + 10 OH
These are balanced half reactions in acidic and basic medium respectively.
6 Section
Vidyamandir Classes Stoichiometry- IIII
Stoichiometry-
6. Now add two half reactions together in such a manner that electrons from both sides cancel. So
multiply by coefficients so that number of electrons produced in oxidation equals the number of electrons
used in reduction (as done in oxidation number method step – 4).
Note : In this method we don’t have to calculate oxidation states as done in first method.
Illustration - 1 Balance the following reaction by Oxidation number and Ion electron method.
KMnO4 + H2SO4 + K2C2O4 

 MnSO4 + CO2 + K2SO4
SOLUTION :
Oxidation Number Method :
Follow the steps given below to balance the 2 Mn7+ + 5 C23+ 
 2 Mn2+ + 10 C4+
reaction given above :
Now compare this balanced equation with the
Assign O.S. to the atoms which are oxidised or molecular unbalanced equation as follows.
reduced. Note that O.S of O, K, H, S are same
on both sides. This is done by oral inspection. 2 KMnO4+ 5 K2C2O4 
 2 MnSO4+10 CO2
We’ll consider O.S of Mn and C on both sides. As the charge is balanced, now balance ‘K’ atoms
+7 +3 on both sides by adding 6 K2SO4 on right.
KMnO4 + H2SO4 + K2C2O4
2 KMnO4 + 5 K2C2O4 

 +2 +4
2 MnSO4 + 10CO2 + 6K2SO4

 MnSO4 + CO2
Now to balance SO42 ions on both sides, add
Write two half reactions and balance the atoms as 8H2SO4 on left.
follows.
2 KMnO4 + 5 K2C2O4 + 8 H2SO4 

(a) Mn7+ 
 Mn2+ (reduction)
2 MnSO4 + 10 CO2 + 6 K2SO4
(b) C23+ 
 2 C4+ (oxidation)
Finally add 8 H2O on right to balance O and H
Balance the charge by adding 5e to left of (a) and atoms to get balanced equation.
2e to the right of (b).
2 KMnO4 + 5 K2C2O4 + 8 H2SO4  
(a) Mn7+ + 5e 
 Mn2+ (reduction) 2 MnSO4 + 10 CO2 + 6 K2SO4 + 8 H2O
(b)  2 C4+ + 2 e
C23+  (oxidation)
Note : You can always make a final check by counting O
atoms on both sides.
Add two half reactions after multiplying (a) by 2
and (b) by 5 in order that electrons cancel from
both sides.

Stoichiometry-
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Ion Electron Method :

First write the given equation in Ionic form having Add 5e in LHS (Note : each e is equivalent to a
ions with Central atom (which has undergone a charge of –1).
change in Oxidation State).
MnO4 + 8H+ + 5e 
 Mn2+ + 4H2O . . . .(i)
 2 2+
MnO4 + C2O4  Mn + CO2

Oxidation :
Note that O and H atoms attached to the Central
atom (shown in bold), have to be retained. C2O42 
 CO2
Now, write the Oxidation and Reduction half and Following the same procedure as above, we have
balance them as shown : :
Reduction :
(i) Balance C atoms : C2O42  
  2 CO2
MnO4 
 Mn
2+
(ii) Balance O atoms : Already balanced.
(i) First, make sure that the element (iii) Balance H atoms : No H atom.
undergone a change in Oxidation State is
balanced. (iv)   2 CO2 + 2e . . . .(ii)
C2O42  
(ii) Balance O atoms by adding 4 H2O on Multiply equation (i) by 2 and (ii) by 5 to balance
right hand side (RHS). the electrons transfer and add to get :
MnO4 
 Mn2+ + 4H2O 2 MnO4+ 5 C2O42 + 16 H+  

(iii) Now, RHS has excess of 8 H atoms. Add 2 Mn2+ + 10 CO2 + 8 H2O
8H+ on left hand side (LHS). Note, the Using the above balanced equation, convert it to
medium is acidic due to the presence of its corresponding given Neutral equation to get :
H2SO4.
2 KMnO4 +5 K2C2O4+ 8H2SO4 
 + 2+
MnO4 + 8H  
 Mn + 4H2O 2MnSO4 + 10 CO2 + 8H2O
(iv) Note, now O and H is balanced. Balance Now, K (12 atoms on LHS) and SO42 (6 atoms
the charge on both sides. on LHS) is unbalanced. Add 6 K2SO4 on RHS to
On LHS : Charge is 1  (1) + 8  (+1) get the final equation as :
= +7
2 KMnO4 + 5 K2C2O4 + 8 H2SO4  
On RHS : Charge is 1  (+2) + 4  (0) 2 MnSO4 + 10 CO2 + 6 K2SO4 + 8H2O
= +2
Note : At the later stages, you will find that it is Ion electron method which is more important.

Illustration - 2 Balance the following reaction by oxidation number method.
CrO42 + I 
 Cr3+ + IO3 (in alkaline or basic medium)
SOLUTION :
Proceeding on the pattern of last illustration On adding (a) and (b) we get :
+6 1 +3 +5
2 Cr6+ + I 
 2 Cr3+ + I5+
(i) CrO42 + I 
 Cr3+ + IO3 On comparing with given reaction
(ii) (a) Cr6+ 
 Cr3+
2 CrO42 + I 
 2 Cr3+ + IO3
(Reduction : decrease in O.S.) Note that the given reaction is ionic, so first of all
charge needs to be balanced. Balance charge by
(b) I 
  I5+
adding OH ions (in basic medium).
(Oxidation : increase in O.S.) A charge of 5 on left and +5 on right side means
add 10 OH ions to the right side of the equation.
(iii) (a) Cr6+ + 3e 
 Cr3+
2 CrO42 + I 
 2 Cr3+ + IO3 + 10 OH
 
 5+ 
(b) I I + 6e
Finally add 5 H2O molecules on the left to bal-
(iv) (a) [ Cr + 3e6+  
 Cr ] × 2 3+ ance H and O and get the balanced equation.
(b) [ I 
 I5+ + 6e ] × 1 2 CrO42 + I + 5 H2O 

2 Cr3+ + IO3 + 10 OH
Illustration - 3
Balance the following reaction in acidic medium.
CuS + NO3 
 Cu2+ + S8 + NO
SOLUTION :
Proceeding on the same pattern of last illustration (b) N5+ + 3e 
 N2+
2 +5 0 +2
(iv) 24 CuS + 16 NO3 
 3 S8 + 16 NO
 2+
(i) CuS + NO3  
 Cu + S8 + NO
Add 24 Cu2+ ions on right side to balance Cu
before balancing the charge.
(ii) (a) 8 S2 
 S80 (Oxidation)
24 CuS + 16 NO3  

(b) N5+  
 N2+ (Reduction)
24 Cu2+ + 3 S8 + 16 NO
(iii) (a) 8 S2 
 S80 + 16e

Stoichiometry-
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A charge of 16 on left and +48 on right means,

24 CuS + 16 NO3 + 64 H+ 

add 64 H+ ions to the left (acidic). Finally add 32
H2O on right to balance H and O atom s. 24 Cu2+ + 3 S8 + 16 NO + 32 H2O
Illustration - 4 Complete and balance the following in acidic medium.
Ag+ + AsH3 
 H3AsO3
SOLUTION :
+1 3 +3 (b) Ag + 1e  
 Ag
Ag+ + AsH3 
 H3AsO3 As3 + 6 Ag  
 As3 + 6 Ag
(a) As3 
 As3 (Oxidation) AsH3 + 6 Ag 
 6 Ag + H3AsO3
Now balance charge by adding 6 H on right
(b)  Agx
Ag  x=?
side and finally add 3 H2O on left side.
Clearly, (b) must be a reduction, so x must be 0,
as x can’t be ve for Ag (Silver being metal). AsH3 + 6 Ag + 3 H2O 

(a)  As3 + 6e

As3  6 Ag + H3AsO3 + 6 H+
Illustration - 5 Balance the following by ion-electron method in basic medium.
NO3 + Zn 
 Zn2 + NH +
4
SOLUTION :
Two half reactions are : NH4+ + 6 OH + 4OH
Balancing the charge :
(a) NO3 
 NH4+
NO3 + 8e + 7 H2O 


(b) Zn 
 Zn2+
NH4 + 10 OH
+
First balance ‘O’ atoms in basic medium.

(b)  Zn2+ + 2e
Zn 
(a) NO3 + 3 H2O 
 NH4+ + 6 OH
Now overall reaction is :
Balancing H atoms in basic medium
4 Zn + NO3 + 7 H2O 

NO3 + 3H2O + 4 H2O 
 4 Zn2+ + NH4+ + 10 OH
10 Section
Stoichiometry-
Illustration - 6 Balance the following by ion-electron in acidic medium.
 IO3 + Cl
ClO3 + I2 
SOLUTION :
Two half reactions are : 5 ClO3 + 3 I2 + 3 H2O  
5 Cl + 6 IO3 + 6 H+
(a) ClO3 
 Cl
(b) I2 
 IO3
Balancing them separately :
 IO3
I2 
ClO3 
 Cl
 2 IO3+ 12 H+
I2 + 6 H2O 
ClO3 + 6 H+ 
 Cl + 3 H2O
 2 IO3 + 10e + 12
I2 + 6 H2O 
ClO3 + 6 e + 6 H+ 
 Cl + 3 H2O +
H
Balancing electrons in two half reactions, and
adding we get :
Illustration - 7 Balance the following by ion-electron method. (Acidic medium)
Mn2+ + S2O8 2 
 MnO4 + HSO4
SOLUTION :
Two half reactions are :  2 MnO4
2 Mn2+ + 5 S2O82 + 8 H2O 
+ 
+ 6 H + 10 HSO4
(a)  MnO4
Mn2+ 
(b) S2O82 
 HSO4
Balancing these two half reactions :
S2O82 + 2 H+ + 2e 
 2 HSO4
 MnO4 + 5e + 8 H+
Mn2+ + 4 H2O 
Adding the two equations, we have the balanced
equation.
Illustration - 8 Balance the following by ion-electron method. (Basic medium)
 I + CrO42
Cr(OH)3 + IO3 
SOLUTION :
Two half reactions are : (b) IO3 
 I
Balancing O atoms
(a) Cr(OH)3 
 CrO42

(a) Cr(OH)3 + 2 OH 

 CrO42 + H2O Balancing the charge
(b) IO3 + 3 H2O 

 I + 6 OH (a) Cr(OH)3 + 5 OH 
CrO42 + 4 H2O + 3e
Balancing H atoms
(b) IO3 + 3 H2O + 6e 
 I + 6 OH
  

(a) Cr(OH)3 + 2 OH + 3 OH
Adding (a) and (b), we get :’
CrO42 + H2O + 3 H2O
2 Cr(OH)3 + IO3 + 4 OH  
(b) IO3 + 3 H2O  
 I + 6 OH
2 CrO4 + I+ 5 H2O
2
Illustration - 9 Which of the following are examples of disproportionation reactions ?
(a) Ag(NH3)2+ + 2H+ 

 Ag+ + 2NH4+ (b) Cl2 + 2OH 
 ClO + Cl + H2O
(c) CaCO3 
 CaO + CO2 (d) 2HgO 
 2Hg + O2
(e) Cu2O + 2H+ 

 Cu + Cu2+ + H2O (f) CuS + O2 
 Cu + SO2
(g)  Cu + Cu2+ + 4Cl + 2H+

2HCuCl2 + dilute with H2O 
(h) 2H2O2 
 2H2O + O2
SOLUTION :
What is the criteria for a disproportionation reaction ?
A reaction in which same atom is oxidised and reduced at the same time is called as a disproportionation
reaction. Observing very carefully among the above reactions, we note that (b), (e), (g) and (h) are
disproportionation reactions.
Illustration - 10 H SO acts as an oxidising agent, a dehydrating agent and an acid. Among the each of
2 4
following reactions, which behaviour is shown by H2SO4 ?
(a) C6H12O6 + H2SO4(conc.) 

 6C + 6H2O
(b) 5 H2SO4 (conc.) + 4 Zn 

 H2S + 4 Zn2+ + 4 SO42 + 4H2O
(c)  Zn2+ + H2 + SO42

H2SO4 (dil) + Zn 
(d)  Zn2+ + CO2 + SO42 + H2O

H2SO4 (dil) + ZnCO3 

SOLUTION :
(a) As a dehydrating agent since it simply removes water from glucose.
(b) H2SO4 (S in +6 state)   H S (S in 2 state), i.e., acid is reduced. So it acts as an oxidising agent.
2
(c) All strong acids liberate H2 with an active metals like Zn (i.e., it is reduced) unless SO42 is reduced. In this
case, H+ is reduced to H2. So it acts as an oxidising agent. We can also call it as an acidic property.
(d) Simply an acid.
Illustration - 11 Balance the following reaction by ion-electron method. (Acidic medium)
As2S3 + NO3 
 S + NO2 + AsO43
SOLUTION :
This is a very special case of redox reac-  3 S + 6e
(ii) 3 S2 
tion.
Now add the two equations to get :
Note that, the given reaction involves two oxi-
dations and one reduction. Proceed carefully as
follows. (a) 2As3+ + 3S2 + 8H2O 
 2AsO43 + 3S +
16H+ + 10e
(a) Two half reactions (oxidation) are :
Now balance oxidation half reaction and pro-
(i) As3+ 
 AsO43 ceed as usual.
(ii) S2 
 S (b) NO3 + 2H+ + 1e 
  NO2 + H2O
Adding the two reactions
(b) Reduction half reaction : NO3  
  NO2
First balancing these two half reductions : As2S3 + 10 NO3 + 4H+ 
3
2 AsO4 + 10 NO2 + 3S + 2H2O
(i) 2As3+ + 8H2O 
 2AsO43 + 16
H+ + 4e
Note : In above type of cases, take total change in oxidation number (increase or decrease) for cross multi plica-
tion while adding oxidation and reduction half reactions. For example, in the given case, 10e1s are lost per
mole of As2S3.

IN - CHAPTER EXERCISE - A
1. Indicate the species which are oxidized and reduced in the following reactions.
(i) CN  + OCl   N 2 + HCO3 + Cl 
(ii) C6 H5OH + O3  CO 2 + H 2O + O 2
(iii) I  + O3  O 2 + I 2
(iv) S2 O32   Cl2  HSO 4  Cl 

(v) C ZnO  Zn  CO
2. Write balanced ionic half equations ( oxidation and reduction) for each of the following reactions.
(i) Te(s)  NO3 (aq)  TeO 2 (s)  NO(g)
(ii) H 2 O 2 (aq)  Fe 2+ (aq)  Fe 3+ (aq)  H 2O(l )
(iii) Mn(s)  NO3 (aq)  Mn 2+ (aq)  NO 2 (g)
(iv) Mn 3+ (aq)  MnO 2 (s)  Mn 2+ (aq)

3. Balance the following half-reactions in acidic medium.
(i) VO2+ (aq)  V 3+ (aq)
(ii) NO3 (aq)  NO 2 (g)
(iii) IO 3 (aq)  I3 (aq)

4. Balance the following half-reactions in basic medium.
(i) CrO 24  (aq)  Cr(OH) 4 (aq)
(ii) Bi3+ (aq)  BiO3 (aq)
(iii) ClO (aq)  Cl (aq)

5. Write balanced net ionic equations for the following reaction in basic solution.
(i) MnO 4 (aq)  IO3 (aq)  MnO 2 (s)  IO 4 (aq)
(ii) Cu(OH)2 (s)  N 2H 4 (aq)  Cu(s)  N 2 (g)
(iii) Fe(OH) 2 (s)  CrO 42  (aq)  Fe(OH)3 (s)  Cr(OH) 4 (aq)
(iv) H 2 O 2 (aq)  ClO 4 (aq)  ClO 2 (aq)  O 2 (g)

6. Write balanced redox reactions for each of the following reactions.

(i) H 2O 2 (aq) reduces Cr2O 72  (aq) to green coloured Cr3+ (aq) in acidic medium
(ii) H 2O 2 (aq) Oxidises Mn 2+ (aq) to MnO 2 in basic medium
(iii) Sn 2+ (aq) reduces IO 4 ( aq ) to I (aq) and is oxidized to Sn 4+

(iv) A purple solution of aqueous potassium permanganate (KMnO 4 ) reacts with aqueous
2
sodium sulphite (Na 2SO3 ) in basic solution to yield the green manganate ion MnO 4 and  

2
sulphate ion SO4 . 
(v) Potassium dichromate (K 2Cr2O7 ) reacts with hydroiodic acid (HI ) to produce potassium iodide,
chromium (III) iodide and solid iodine, I2 (s).
7. Balance the following chemical reactions. ( It is better to use ion electron method )
(i) CuO + NH3  Cu+ N 2 + H 2O (ii) HI + HNO3  I2 + NO  H 2O
(iii) P4 + H 2 O  PH 3 + H 2PO 2  H + (iv) H 2S SO 2  S + H 2O
(v) CN   MnO 4  H 2O  MnO 2  CNO   OH 
(vi) [Fe(CN) 6 ]3  + N 2 H 4 + OH   [Fe(CN) 6 ]4   N 2 + H 2O
(vii) C2 H 5 OH+ MnO 4  CH 3COO  + MnO 2 + H 2O+ OH 
(viii) P + H + + NO  + H O  H PO  + NO
4 3 2 2 4
(dil)
(ix) HS + HSO3  S2 O 32  + H 2 O
(x) Fe3+ + NH 2 OH  Fe2+ + N 2O+ H  (xi) O2 + H 2O  OH  + O2

(superoxide ion)
(xii) IO 3 + HSO3  I  + H + + SO 42  (xiii) I  + IO3 + H +  H 2 O+ I 2

(xiv) Fe2S3 + H 2O + O2  Fe(OH)3 +S
(xv) IBr+ BrO 3 + H 2 O  IO 3 + Br  + H +
(xvi) CrI3 + H 2O 2 + OH   CrO 42  + IO 4 + H 2O
(xviii) H 2 O 2 + H + + Fe2+  H 2O+ Fe3+
(xviii) As 2S3 + MnO 4 + H +  H 3AsO 4 + Mn 2+ + S

ANALYSIS BASED ON MOLE CONCEPT Section - 2
Let us now solve some numerical problems based on the analysis of redox reactions. In such type of applications
based problems, first we have to create a chemical equation and then balance it. And then proceed as per the given
problem, using Mole concept.
Illustration - 12 Find the amount of Iron pyrites (FeS ) which is sufficient to produces enough SO on
2 2
roasting (heating in excess of O2) such that (SO2) completely decolourises a 1L solution KMnO4 containing
15.8 g/L of it.
The equation are : FeS2  O2 

 Fe2O3  SO2 and KMnO4  SO2 
 MnSO4  H 2 SO4  K 2 SO4
SOLUTION :
 1.0 L of KMnO4 contains 0.1 moles
First calculate the amount of SO2 required to
declourise 15.8 g/L of KMnO4 solution. For this 5
you need to balance the following chemical Hence moles of So2 required = (0.1)
2
reaction.
= 0.25
KMnO 4  SO2 
 To calculate the amount of pyrites, we have to
MnSO 4  H 2SO4  K 2SO 4 balance the reaction :
Proceeding in the manner as given in above FeS2  O2 

 Fe2 O3  SO2
illustrations, we have balanced equation as :
Balancing the reaction (using Hit and Trial
2 KMnO 4  5SO 2  2H 2 O 
 Method) we have
2 MnSO 4  2H 2SO 4  K 2SO 4
4FeS2  11O2 
 2Fe2 O3  8SO2
Now, using our understanding to solve a
From stoichiometry of roasting, we have :
typical stoichiometric problems, we can solve
this problem as follows : 8 moles of SO2  4 moles of FeS2
From stoichiometry of balanced equation, we 4
have: 0.25 moles of SO2  (0.25) moles of FeS2
8
2 moles of KMnO4  5 moles of SO2
= 0.125 moles of FeS2
Calculate moles in 15.8 g/L of KMnO4 :
 mass of FeS2 = 0.125  120 = 15 gm
Using : Strength (g/L) = M M0
15.8
Molarity = = 0.1 M
158

Illustration - 13 20 mL of a solution containing 0.2 gm of impure sample of H O reacts with 0.316 gm of

2 2
KMnO4 in presence of H2SO4 as per following reaction.
KMnO4  H2O2  H 2SO4 

 MnSO4  O2  H2O
(a) Find the purity of H2O2 solution (b) Calculate the volume of dry oxygen evolved at 27C and at 750
mm Hg.
SOLUTION :
0.17
First write a complete balanced the reaction :  % age purity of H2O2 = 100
0.2
2 KMnO4 + 5 H2O2 + 3H2SO4 
 = 85 %
2 MnSO4 + K2SO4 + 5 O2 + 8 H2O Now : 2 moles of KMnO4  5 moles of O2
From the balanced reaction, we have : 5 0.316
Moles of O2 produced = 
5 moles of H2O2  2 moles of KMnO4 2 158
0.316 = 5  103
Moles of KMnO4 =
158 Using PV = nRT we have :
5 0.316
 Moles of H2O2 required =  nRT 5×103 ×0.0821×300
2 158 V= =
P 760 / 760
5 0.316
Grams of H2O2 =  34 = 0.17 gm = 0.123 L = 123 mL
2 158
Illustration - 14
Calculate the amount of SeO32  in a solution on the basis of given analysis. 20 mL of M/
60 KBrO3 was added to a sample of SeO32  . The bromine evolved was removed and the excess of KBrO3 was
titrated with 5.1 mL of M/25 solution of NaAsO2 . The reactions involved are : [ASe = 79 gm/mol]
 SeO42   Br2  H 2O and BrO3  AsO2  H 2O 

SeO32   BrO3  H    Br   AsO43  H 
SOLUTION :
In this problem, find the exact amount of KBrO3 Balancing the two equations
used for SeO32- (in the first equation) by
calculating the excess of KBrO3 with the help (i) 5 SeO32   2BrO3  2H  

of second equation.
5 SeO 24   Br2  H 2O

(ii) BrO3  3AsO 2  3H 2O 

  1 
   20   0.068  0.265 m.moles
Br   3AsO34  6H   60 
From equation (i) :
From the equation (ii) :
2 m.moles of K BrO3  5 m.moles of SeO32 
3 m.moles of AsO 2  1 m.moles of excess of
KBrO3 0.265 m.moles of KBrO3  5/2 (0.265)
m.moles
1 
  5.1 m.moles of AsO 2  5/2 (0.265)  127 mg
25
Mass of SeO32  = 84.13 mg = 0.08413 g
1 5.1
  (= 0.0628) m.moles of excess of
3 25
KBrO3 m.moles of KBrO3 used in equation (i)
Illustration - 15 1.0 gms of AgNO is dissolved in 50 mL of water. It is titrated with 50 mL of KI solution.

3
The Agl precipitated is filtered off. The excess of KI in the filtrate is titrated with M/10 KIO3 in presence of 6
M HCl till all I- is converted to ICl. It requires 50 ml of M/10 KIO3 solution. 20 mL of same KI solution requires
30 mL of M/10 KIO3 under same conditions. Determine the percentage of AgNO3 in the sample.
The reaction involved is : KIO3  KI  HCl 

 ICl  KCl  H 2O
SOLUTION :
The problem considers three experiments : First of all you must balance the equation
involved in experiments 2 and 3. (Note that the
(i) 1.0 gm AgNO3 (50 mL) + 50 mL of KI
reaction is same in both cases)
(M = ?)
I  
 I   2e 
AgNO3 + KI 
 AgI + KNO3
(ii) Excess of KI + 50 mL of M/10 KIO3 in IO3  6H   4e 
 I  3H 2O
6M HCl
 The overall balanced equation is :
KI  KIO3  HCl 
 ICl  KCl  H 2O.
2I   IO3-  6H  
 3I  3H 2O
(iii) Tod determine the molarity of KI (say M)
20 mL KI (original) + 30 mL of M/10  2 m.moles of KI  1 m.moles of KIO3
KIO3
18 Section
Using the above stoichiometry, first find the This gives us initial m.moles of KI in 50 mL
excess of KI and then molarity of KI volume taken initially.
 m.moles of KIO3 used  1/10  50  Initial m.moles of KI = (6/20)  50 = 15
=5
 m. moles of KI used for AgNO3
1 m mole of KIO3  2 m. moles of
= 15 – 10 = 5
KI
Now, 1 m.mole of KI  1 m.mole of AgNO3
 5 m.moles of KIO3  10 m.moles of
KI (excess)  m.moles of AgNO3 = 5
 m.moles of KIO3 used for titrating 20 g
mL KI  1000  5  g  0.85 gram
170
= 1/10  30 = 3
or % AgNO3 = 85%
 m.moles of KI = 6 = M  20
(mass of sample = 1gm)
 M = 6/20
IMP. Not n-factro of KBrO3 in illustration-14 and that of KI in illustration-15 is different in two redox reactions.
It is advised to use concept of mole in such case as done above

Vidyamandir Classes
CONCEPT OF GRAM EQUIVALENTS Section - 3
In the method of gram-equivalents (milli-equivalents), there is no need to balance a redox reaction. For
example, let us consider a typical redox reaction (consisting of two reactants and two main products):
X + Y 
 A + B
Reducing Oxidising
agent agent
According to concept of gram equivalent (or meq) ;
1 gm.eq. of X  1 gm. eq. of Y  1 gm eq. of A  1 gm eq. of B
or meq. of an oxidising agent = meq. of a reducing agent
g g
Note : gm.eq. = and meq = meq   1000
E E
Now to understand the method of gram-equivalents more clearly, let us understand the following illustrations
very carefully.

What volume of a deci-normal solution of K2Cr2O7 is required to oxidise 1.0 gm of Tin (Sn) in pres-
ence of HCl to its highest oxidation state ?
The involved reaction is :
K2Cr2O7 + Sn + H+ 
 Sn4+ + Cr3+(The highest oxidation state of Sn is +4, so SnCl4 will be formed here)
Here, Sn is a reducing agent (RA) and K2Cr2O7 is an oxidant (OA).
So applying the concept of gram-equivalent, we have : gm.eq of OA (K2Cr2O7) = gm.eq of RA (Sn)
g
Using the definition : N VL  , we get :
E
1 1 119
 VL  ; ESn  where x = electron transfer / mol (also known as valence or n-factor)
10 ESn x
 Sn4+ + 4e
Sn   x=4
V 1 40
   V= = 0.336 L = 336 mL
10 119 / 4 119
20 Section
Vidyamandir Classes Stoichiometry-
Stoichiometry- IIII
 g 
Note : From definition of gram-equivalents  gmeq.   N VL  , it is very clear that, we must be very confident
 E 
about the concept of equivalent weight (E), for an oxidising or reducing agent. So first let us learn intricacies
of the concept of equivalent weight for an oxidant(s) and reductant(s) in detail.
Equivalent Weight (E) of Oxidant and Reductant :

The equivalent weight of an oxidising or reducing agent is defined as :
M0
Equivalent weight = E 
x
where M0 = molecular mass ; x = number of electrons transferred (loss or gain) by one mole of oxidising or
reducing agent as given by their balanced ionic half reaction.

 FeSO4 (Ferrous Sulphate)
As reducing agent : As an oxidising agent :
Fe2+ 
 Fe3+ + 1e Fe2+ + 2e 
 Fe + le–
1 mole of e’s are transferred/ mole of FeSO4, so x = 1  x=2
M 152 M 152
 E FeSO   = 152  E FeSO  
4 x 1 4 x 2
Note : FeSO4 (ferrous sulphate) acts both as an oxidant and as a reductant
 H2C2O4 (Oxalic acid) or C2O42 (Oxalate ion)
As reducing agent only
 2 CO2 + 2e or H2C2O4 

C2O42   2 CO2 + 2 H+ + 2 e
90
x = 2 or E H 2C 2O4 
2
134 128
Note : E Na C O  ; E CaC 2O 4  as nfactor for C2O42 is always 2
2 2 4 2 2
Sodium oxalate Calcium oxalate

 SO2 (Sulphur Dioxide)

As reducing agent
 SO42 + 4H+ + 2e

SO2 + 2H2O 
64
x=2  ESO 2 
2
 HI (Hydrogen Iodide)
As reducing agent only
2HI 
 I2 + 2H+ + 2e  2 mole of e’s / 2 mole of HI
2 128
x= = 1 (for 1 mole of HI)  EHI =
2 1
 Fe2(SO4)3 (Ferric sulphate)  Na2S2O3 (Sodium Thiosulphate)

As oxidising agent only As reducing agent in acidic medium
Fe3+ + 1e  
  Fe2+
 S4O62 + 2e
2 S2O32 
Since 1 mole of Fe2(SO4)3  2 moles of x = 2/2 = 1 for 1 mole of Na2S2O3
Fe3+
 x = 2 for 1 mole of Fe2(SO4)3 158
 E 
Na 2S2 O3 / H  1
400
 E Fe SO    K2Cr2O7 (Potassium Dichromate)
2 4 3 2
As oxidising agent only
 KMnO4 (Potassium Permanganate)
Cr2O72 + 6e + 14 H+  

As oxidising agent in acidic medium
2 Cr3+ + 7 H2O
MnO4 + 8H+ + 5e 
 Mn2+ +
4H2O 294
x = 6  E K 2Cr2O7 
6
158
x=5  E  
KMnO 4 / H 5  MnO2 (Managanese dioxide)
As oxidising agent in strong alkaline As oxidising agent in acidic medium
medium
MnO2 + 4H+ + 2e 
 Mn2+ + 2 H2O
MnO4 + 1e 
 MnO42
158 87
x = 1  E KMnO4  x = 2  E MnO2 
1 2
22 Section
As oxidising agent in dilute alkaline As reducing agent in alkaline medium

medium
S2O32 + 10OH 
 2SO42 + 5H2O + 8e
 
MnO4 + 2H2O + 3e 
 MnO2 + x=8

4 OH
158
 E Na 
x = 3  158 2S2O3 /OH

8
E 
KMnO 4 /OH  3
Note : From the above case, you should observe carefully that the equivalent weight depends upon medium.
 HNO3 (Nitric Acid) As oxidising agent (dil. HNO3)

As oxidising agent (conc. HNO3)
NO3 + 4 H+ + 3e 
 NO + 2 H2O
NO3 + 2H+ + 1e 
  NO2 + H2O x=3
x=1
63
 E HNO3 (dil)   21
63 3
 E HNO3 (conc.)   63
1
Note : Equivalent weight depends on dilution for HNO3.
Try to Calculate ‘E’
(a)  NH4+
HNO3 (very dilute)  (b) HNO3 (cold dilute) 
 NH2OH
Note : Some substance act both as OA (oxidants) and reductans (RA) in different reactions. Like FeSO4, H2O2,
HNO2 etc
H2O2 (Hydrogen Peroxide) as OA : H2O2 + 2H+ + 2e 

 2H2O
as RA :   O2 + 2H+ + 2e
H2O2 
FeSO4(Ferrous Sulphate) as OA : Fe2+ + 2e  

 Fe
as RA :   Fe3+ + 1e
Fe2+  
HNO2(Nitrous Acid) as OA : HNO2 + H+ e 

 NO + H2O
as RA :   NO3 + 3H+ + 2e

HNO2 + H2O 
Some other type of oxidants and reductants are also given below.

 (NH4)2 Cr2O7 
 N2 + Cr2O3
(Ammonium Dichormate)
RA : NH 4 
 N2 OA : Cr2O72  
 Cr2O3
 FeC 2O 4  Fe3+ + CO 2
 Ferrous Oxalate 
RA : Fe2+ 
 Fe3+ + 1e– ; C2O42  
  2CO2 + 2e–  x = 3
Note : In FeC2O4 both cations and anions are oxidised.
  I– + IO3–
I2  (disproportionation reaction)
OA :  2I– ;
I2  RA :   IO3–
I2 
(same compound as OA/RA)
Note : Some compounds act as Acids and RA or OA in separate experiments.

 as acid  x  2  as acid  x  1
  as acid  x  1

H2C2O4 ; HNO3 ; NaHC2O4

 as RA  x  2  as OA  x  1, 3, 6, 8
  as RA  x  2 

Illustration - 16 Complete and balance the following.
(a) H2O2 + I2  
 I + ?? (b) H2O2 + Sn2+ 
 Sn4+ + ??
(c) MnO42 + H+ 
 Mn2+ + ?? (d) NO2 + H2O 
 NO + ??
SOLUTION :
(a) I2 is reduced to I, so H2O2 must be  I + O2
H2O2 + I2 
oxidised, i.e., it acts as a reducing agent.
Hence final product will be O2 gas. The balanced equation will be :
The complete chemical equation is :  2I+ O2 + 2H+

H2O2 + I2 
24 Section
Stoichiometry-
(b) Sn2+   Sn4+, i.e., Sn2+ is oxidised. (c) MnO42 is reduced to Mn2+, i.e it is act-
So H2O2 acts as an oxidising agent, which ing as an oxidising agent. Now H+ is al-
means it must be reduced to H2O. ready in the maximum oxidation state, so
MnO42 must also be reduced to Mn7+
H2O2 + Sn2+ 
 Sn4+ + H2O state i.e. MnO4 will be formed. Hence it
The balanced equation will be : is a case of disproportionation reaction.
 Mn2+ + MnO4
MnO42 + H+ 
2+
H2O2 + Sn + 2H + 
 Sn4+ + 2H2O
The balanced equation will be :
Important Note :
5 MnO42 + 8H+
H2O2 is chemical species acting both as a re-
ducing agent and as an oxidising agent.  Mn2+ + 4MnO4 + 4H2O
 
as oxidant
H 2O 2  H 2O (d) NO2 (+4 state) disproportionate (like in
as reductant last case) to NO (+2 state) and NO3
 O2
(+5 state).
NO2 + H2O  NO + NO3
The balanced equation will be :
 NO + 2NO 3 
3 NO 2 +H 2 O 
+2 H+
Equivalent weight of a compound undergoing disproportion :

Let a compound ‘A’ contains an ion ‘X’ undergoing disproportionation.
Effective molecular weight of A

Then, EA = Equivalent weight of A =
Number of e transfer
 Total weight of A in   Total weight of A in 

where Effective molecular weight of A =   
 Oxidation half reaction   Re duction half reaction 
1. When number of e- transfer are in oxidation and reduction half reactions
Illustration the concept :

H2O2 undergoes disproportionation in ocidic medium given by the following reaction :
H 2O2 
 H 2O  O 2

Stoichiometry-
Stoichiometry - IIII Vidyamandir Classes
Oxidation half reaction : H2O2 

 O2 + 2H+ + 2e- [2e- transfer] …(i)
Reduction half reaction : H2O2 + 2H+ + 2e- 

 2H2O [2- transfer] …(ii)
Thus, Effective molecular mass of H2O2 = M H 2O2  M H 2O 2  2M H 2O2

from  i  from  ii 
2M H 2O2
 E H 2 O2   34
2
2. When number of e- transfer are different in oxidation and reduction half reaction
Br2 undergoes disproportionation in basic medium given by the following reaction:
Br2  OH  
 Br   BrO3  H 2O
Oxidation half reaction : Br2 + 12OH– 

 2BrO3– + 6H2O + 10e– [10e– transfer] …(i)
Reduction half reaction : Br2 + 2e– 

 2Br– [2e– transfer] …(ii)
Now, Effective molecular mass of Br2 = M Br2  5M Br2  6M Br2

from  i  from ii 
Note : 5M Br2 is taken because we have to equalize the number of electrons in both oxidation reduction.
6M Br2
Thus, E Br2   0.6 M Br2  96
10
10
This means n-factor of Br2 is
6
Note : However, we should use “Mole concept” while solving problems based on such ractions.
Illustration - 17 1.0 gram of a sample of H O solution containing y% H O by weight requires y mL of

2 2 2 2
KMnO4 solution for complete titration under acidic condition. Find the molarity of KMnO4 solution.

SOLUTION :  y 
1  
This question involves a redox reaction between  100   1000
meq of H2O2 =
EH O
H2O2 (RA) and KMnO4 (OA). Let us apply 2 2
the concept of gram (milli) equivalents to solve
 34 
this problem.  E H 2 O2  2 
 
i.e., meq of H2O2 = meq of KMnO4
meq of KMnO4 = N (y)
Let us find n-factor (valence factor) of H2O2
and KMnO4 as follows.  y 
1  
 100   1000  N(y) 10
 N =
MnO4 + 8H+ + 5e  
  Mn2+ + 4H2O 17 17
 O2 + 2H+ + 2e
and H2O2   N
And Molarity = ; x = 5 for KMnO4/H+
x = 5 for KMnO4 and x = 2 for H2O2 x
10 / 17 2
 M =  = 0.117
5 17
Illustration - 18 A solution of KMnO /H+ containing 3 gm/L is used to titrate H O solution containing 2
4 2 2
gm/L. What volume of KMnO4 will be required to react with 20 mL of H2O2 solution ? Also find the strength
of H2O2 in terms of available oxygen.
SOLUTION :
It is also called as volume strength of H2O2.
This redox reaction is a typical one.
Volume strength is the volume of O2 given out
strength 3 15 at S.T.P. by 1 volume solution of H2O2.
N KMnO 4   
E 158 / 5 158
2H2O2  
  2H2O + O2
strength 2
N H 2O2  
E 17 2 mol H2O2  1 mol of O2  22.4 L of O2
Now using equation of titration 1 mol H2O2  1/2 mol of O2  11.2 L of O2

per 1.0 L
meq. of OA = meq of RA
 1 M H2O2  11.2 vol of O2 at STP
 NOAVOA = NRAVRA (meq = NVcc)
or 1N H2O2  5.6 vol of O2
15 2
V  20 In the present question :
158 17
2 2
 V = 24.8 mL N H2O2   5.6 = 0.66 L of O2
17 17
What is strength in terms of available
oxygen ? It is written as : 0.66 vol H2O2

Stoichiometry
Stoichiometry-- IIII Vidyamandir Classes
Try yourself : Express the volume strength of H2O2 sample if 100 cc of H2O2 solution were diluted with
100 cc of water. 10 cc of this diluted solution required 20 cc of M/50 KMnO4 in presence
of H2SO4 for complete titration. [Ans : 2.24 vol H2O2]
Illustration - 19 1.25 gm of a sample of bleaching power (CaOCl2) is dissolved in 100 mL of water. 25 mL

of it are treated with KI solution. The iodine so liberated required 12.5 mL of M/25 hypo solution (Na2S2O3 /
H+) for complete titration. Find the percentage of available chlorine from the sample of bleaching powder.
SOLUTION :
CaOCl2 
 Cl2  meq of Cl2 in 100 mL = (0.5  4)
g
Cl2 + 2 KI 
 I2 + 2 KCl   1000 = 2
E
I2 + 2 Na2S2O3  
 2 NaI + Na2S4O6 (Cl2 + 2e  
 2Cl ; E = 71/2)
2 71
  S4O62 + 2e ; x = 1)
(2 S2O32  g  = 0.071 gms
1000 2
In 25 ml sample : % available chlorine
meq of Cl2 in bleaching powder g Cl 2 0.071
=  100   100  5.68 %
= meq of I2 liberated = meq of hypo solution g CaOCl2 1.25
 1 
meq of Hypo = NVcc  1    12.5  0.5
 25 
 meq of Cl2/ 25ml. = 0.5
Try yourself : 5.0 gm of CaOCl2 is dissolved in water to make 500 mL solution. 20 mL of it is acidified
with acetic acid and treated with KI solution. The iodine liberated required 20 mL of M/
10 Na2S2O3 solution. Find the percentage of available chlorine. [Ans: 35.5%]
Illustration - 20
50 ml of an aqueous solution of H2O2 was titrated with an excess of KI solution in dilute
H2SO4, the liberated iodine required 20 ml of 0.1 N Na2S2O3 solution for complete reaction.Calculate volume
strength of H2O2 solution.
SOLUTION :
Both the chemcial equations involved in the H2O2 + KI + H2SO4 

problem are typical redox reactions.
I2 + H2O + K2SO4 . . . (i)

Stoichiometry- IIII
and I2 + 2 Na2S2O3 
 2 NaI + Now, 1 N H2O2 solution = 5.6 vol. of O2
Na2S4O6 . . . (ii)
1 1
Now : meq. of I2 = meq. of Na2S2O3 (in eq (ii))  N H 2O 2 solution  5.6 
25 25
 meq. of I2 = 20  0.1 = 2 = 0.224 vol of O2
and meq. of H2O2 = meq. of I2 (in eq (i))  Volume Strength of H2O2 solution
2 1 = 0.224 vol.
N H 2O2  VH  2  N H2O2  
2O 2 50 25
Note : In above two problems, Na2S2O3 is used as reducing agent (very common and important reductant). You
must remember its action in acidic and basic both, though acidic medium (hypo solution) is more important.
H OH 
 S4 O 6 2 
Na 2S2O3  ; Na 2S2O3  SO 42 
Example - 1 A polyvalent metal weighing 0.1 gm and having atomic weight of 50 reacted with dilute
H2SO4 to give 44.8 mL of hydrogen at STP. The solution containing the metal in this Lower oxidation state,
was found to require 60 mL of 0.1 N KMnO4 solution for complete oxidation. What are valencies of metal ?
SOLUTION :
 Mx+ + xe, i.e., oxidation sate
Thus, M 
Metal (M) + H2SO4 
 H2 is +2
Now M2+ will acquire higher oxidation state
44.8 when oxidized by KMnO4
44.8 mL H2 at STP  moles of H2
22400
M2+ 
 M2 + n + ne-
Now, meq of M = meq of H2
meq of M2+ = meq of KMnO4
+ 
Note : For Hydrogen 2H + 2e 
 H2
0.1
Meq of H2 = 2  m.moles of H2 1000  0.1 60  n 3
50 / n
0.1  44.8  So oxidation state of M is M 2  n  M 5
  2  x 2
50 / x  22400 
Hence the possible valencies are + 2, + 5.
Stoichiometry
Example - 2 Hydroxylamine (NH2OH) reduces Fe3+ as per following reaction :
NH 2OH  Fe3 
 N2O  H 2O  Fe2 
Fe2+ produced is estimated by titration with KMnO4. A 10 mL sample of NH2OH is diluted to 1000 mL, 50 mL
of this diluted sample is boiled with excess of Fe3+ solution. The resulting solution required 12 mL of 0.02 M
KMnO4 for complete oxidation. Determine the strength of NH2OH.
SOLUTION :
Consider 50 mL sample : Now meq. of NH2OH in original 10 mL = 24
(meq. remain same on dilution)
NH 2OH  Fe3 
 Fe 2   N 2O
Now find grams of NH 2 OH using
meq of NH2OH  meq of Fe3+  meq of Fe2+
g
2+ 1000  24
Now meq of Fe ions are calculated by titrating E
it against KMnO4.
meq of Fe2+ = meq of KMnO4  N 2O  H 2O  4H   4e
2 NH 2OH 
Now for calculating meq. of KMnO4, convert
4
molarity (M) into normality (N). Now, x  for 1 mole of NH2OH
2
N = xM = 5  0.02 = 0.10 N
33
 E NH 2OH 
x  5; MnO4 
 5e 
 Mn 2
 2
meq of Fe2+ in 50 mL sample = 0.10  12 24   33 / 2 

 g  0.396
= 1.2 = meq of NH2OH 1000
meq of NH2OH in 1000 mL sample 10 mL sample  0.396 grams
= 1.2  20 = 24  1000 mL  39.6 grams

 Strength of NH2OH = 39.6 g/L
Stoichiometry- IIII
Example - 3 A sample of Pyrolusite (MnO2) weighs 0.5 gm. To this solution 0.594 gm of As2O3 and a
dil. acid are added. After the reaction has ceased, As3+ in As2O3 is titrated with 45 mL of M/50 KMnO4
solution. Calculate the % age of MnO2 in pyrolusite.
SOLUTION :
 Mn2+ + AsO43
MnO2 + As2O3  meq of excess As2O3 = meq of KMnO4
0.5 gm 0.594 gm = 45 [1/50  5 ] = 4.5
For excess of As2O3 :

MnO4 + 5e + 8H+  
  Mn2+ + 4 H2O
(x = 5)
As2O3 + MnO4 
 Mn2+ + AsO43
Note that the number of electron transfer for
E AS2O3 = ? As2O3  As2O3 in two reactions is same.
 AsO43
so meq. of As2O3 used for MnO2 = 12  4.5
 2AsO43 + 10 H+ +
(As2O3 + 5H2O  = 7.5

4e ) meq of MnO2 = 7.5
For 1 mole of As2O3, x = 4 g
  1000 = 7.5
87 / 2
198
 E AS2O3 =
4 (MnO2 + 4H+ 
 Mn2+ + 2H2O ; x = 2)
0.594  g = 0.326
meq of As2O3 taken = 1000  12
198 / 4
0.326
% MnO2 =  100  65.25%
0.5
Example - 4 1 gm of Fe2O3 solid of 55.2 % purity is dissolved in acid and reduced by heating the
solution with Zn dust. The resultant solution is cooled and made upto 100 mL. An aliquot of 25 mL of this
solution, requires 17 mL of 0.0167 M solution of an oxidant. Calculate the number of electrons taken up by
the oxidant in the above reaction.
SOLUTION :
 Fe2+ 
Fe2O3 + Zn   100 mL solution Now meq of Fe2+ in 25 mL = meq of oxidant
25 mL sample 17 mL of 0.0167 M of an = [ 0.0167  n]  17 [N = xM]
oxidant.
meq of Fe2+ in 100 mL = [ 0.0167  n  17 ]  4
Let ‘n’ be the number of electrons taken up by
Also meq of Fe2O3 = meq of Fe2+ in 100 mL
oxidant
Stoichiometry
 x = 2 for 1 mole of Fe2O3

0.552
meq of Fe2O3 =  1000
E 160
 E Fe2 O3   80
= (0.0167  68 ) n 2
EFe2O3 = ?  0.552 
 n =   1000   (0.0167 × 68) = 6
 80 
1 mole of Fe2O3  2Fe3+ ; Fe3+ + 1e–  Fe2+
 Electrons taken by oxidant = 6
Example - 5 An equal volume of a reducing agent is titrated separately with 1 M KMnO4 in acid,
neutral and alkaline media. The volumes of KMnO4 required are 20 mL in acid, 33.4 mL in neutral and 100
mL in alkaline media. Find out he oxidation state of manganese in each reduction product. Give the balanced
equations for all three half reactions. Find out the volume of 1 M K2 Cr2O7 consumed, if the same volume of
the reducing agent is titrated in an acid medium.
SOLUTION :
Let meq of RA = P (Since equal volume of RA Balanced half reaction are :
is used in all cases, meq in each case are
same.) (a) MnO4  5e 
 Mn 2 
1 M KMnO4 (in acidic medium)
7
(a) Mn O 4  xe  H  
 Mn 7  x (b) MnO4 1e 
 Mn 6
volume of KMnO4 = 20 mL (in alkaline medium)
7 (c) MnO 4  3e  
 Mn 4
(b) Mn O4  ye   OH  
 Mn 7 y
(in neutral medium)

volume of KMnO4 = 100 mL
Now this mean P = 100
7
(c) Mn O4  ze  
 Mn 7  z meq of RA = meq of K 2Cr2O7
volume of KMnO4 = 33.4 mL
meq of KMnO4 = meq of Ra in each case  Cr O
2 7
2
 14 H   6e 
 2Cr 3  7H 2O 
(a) P = x 1 20 [N = xM] 100  6 1 V
(b) P = y 1100 100

 V = 16.67
6
(c) P = z 1 33.4
 20 x = 100 y = 33.4 z Note : Dil. Alkaline KMnO 4 should be

considered as neutral KMnO4
 x : y : z  5: 1 : 3
Stoichiometry- IIII
Example - 6 20 mL of a solution containing oxalic acid and sulphuric acid on titration with 0.05 N
NaOH required 40 mL of the base. 20 mL of same solution on titration with 0.02 N KMnO4 required 50 mL of
KMnO4. Determine the strength of oxalic acid and H2SO4.
SOLUTION :
In this problem, two type of titrations viz :  2  x  2  y  meqof NaOH= 40  0.05  2
Neutralisation and Redox are involved. Note that
in both cases, the volume of sample is same,  x+y=1
i.e., mmoles of two constituent are same in both. In second titration, only H2C2O4 (being reducing
Let x = mmoles of H2C2O4 and y = mmoles of agent) reacts with KMnO4.
H2SO4 in first titration, both H2C2O4 and H2SO4
 2  x = meq of KMnO4 = 50  0.02  1
react with base (as acids). [n-factor of both
being 2 due to 2H+ per mole in each].
 H C O 
 CO 2  2H   2e  
 2 2 4 
Note : In the above reaction H2SO4 also reacts with KMnO4 but in the same reaction with H2C2O4 so the meq. of
H2SO4 should not be added separately.  H C O  KMnO  H SO 

 Mn 2   CO 2 
 2 2 4 4 2 4

Hence x = y = 0.5 mmoles
g H 2 C2 O 4 g H 2SO 4
 1000  0.05 Similarly, 1000  0.05
M H 2 C2 O 4 M H 2SO 4
 g  0.045 gm  g  0.049 gm
0.045 0.049
Strenght of H2C2O4 =  2.25 g / L Strengh of H2SO4 =  2.45 g / L
20 / 1000 20 / 1000
Stoichiometry
Example - 7 The neutralization of a solution of 1.2 gm of mixture of H2C2O4. 2H2O and KHC2O4.H2O
and same impurities which are neutral, consumed 40.0 mL of 0.25 N NaOH. On the other hand on titration
with KMnO4 in acidic medium, 0.4 gm of mixture required 40.0 mL of 0.125 N KMnO4. Find the molar ratio
of the components.
SOLUTION :
Note that the mass of two samples is different in 2. Rdox reaction with KMnO4 :
tow titrations.
meq of H2C2O4.2H2O + meq of KHC2O4. H2O
Let x = mmoles of H2C2O4. 2H2O
= meq of KMnO4
and y = mmoles of KHC2O4. H2O in 0.4 g
sample 2  x  2  y  0.125  40
So mmoles of oxalic acid in 1.2gm sample = 3x

 HC 2O4 
 2 CO 2  H   2e ; x  2 
and mmoles of bioxalate in 1.2 gm sample = 3y  
 and C O 2   
 2CO2  2e ; x  2 
 2 4 
1. Neutralisation with NaOH :
meq of H2C2O4. 2H2O + meq of KHC2O4. H2O  x + y = 2.5 ... (ii)
= meq of NaOH 5 5
Solve for x and y to get : x  and y 
6 3
2  3 x  1 3y  0.25  40
 x:y=1:2
[oxalic acid has 2 H+ ions while bioxalate has only
1 H+]
10
 2x  y  ...(i)
3
Example - 8 A sample of Fe2(SO4)3 and FeC2O4 was dissolved in H2SO4 . 40 mL of N/16 KMnO4 were
required for complete oxidation. After oxidation, the mixture was reduced by Zn/H2SO4 . On again oxidation
by same KMnO4, 60 mL of it were required. Calculate the ratio of millimoles of Fe2(SO4)3 and FeC2O4.
SOLUTION :
Let m.moles of Fe2(SO4)3 = x Fe2+ 
 Fe3+ + 1e-
and m.moles of FeC2O4 = y y mmol FeC2O4  y mmol Fe2+  y meq Fe2+
Fe3+ + 1e- 
 Fe2+
C2O 42  
 2CO 2  2e
x mmole Fe2 (SO4)  2x mmol meq Fe3
y mmol C2O 42   2y meq C2O 42 
meq Fe3
Stoichiometry- IIII
In the first titration In the second titration

meq of KMnO4 = meq of Fe2+ + meq of So total meq of Fe2+ = 2x + y
C2O 42  meq of KMnO4 = meq of Fe2+
1/16  60 = (2x + y)
1/16  40 = y + 2y (Fe3+ will not be oxidised
further) 60 70
 2x  y   x
 y = 40/48 16 48
Zn reduces whole of Fe3+ (Fe3+ : original and Ratio of millimoles = x : y = 7 : 4
Fe3+ from FeC2O4) to Fe2+
Example - 9 A 4:3 molar mixture of Cu2S and CuS was titrated with 200 mL of 0.75 M KMnO4 in acidic
medium producing SO2, Cu2+ . The SO2 was boiled off and the excess of MnO4 was titrated with 175 mL of
1 M Fe2+ solution. Find the moles of CuS and Cu2S in the original mixture.
SOLUTION :
Note that in Cu2S, both Cu2+ and S2- will get  meq of Cu2S + meq of CuS = 575 ….(ii)
oxidize
Oxidation of Cu2S
Let x = mmoles of Cu2S ; y = mmoles of CuS
Cu 2 
 2Cu 2   2e
x 4
   3 x  4 y …(i)
y 3
S2  
 SO 2  6e
Now, first find excess of KMnO4
1 mole of Cu2S  8e  n- factor = 8
2 3 
Fe 
 Fe  1e  x 1
Oxidation of Cus
and MnO 4  5e  
 Mn 2   x  5
S2  
 SO 2  6e
meq of Fe2   11 175 175 1 mole of CuS  6e   n – factor = 6

 excess meq. of KMnO4 = 175
Using (ii), x  8  y  6  575
Now, meq of KMnO4 taken
= 200  (0.75  5) = 750 4 
  . y   8  y  6  575 [Using (i)]
3 
 meq of KMnO4 used for Cu2S and CuS
 x = 46 mmoles and y = 34.5 mmoles
= 750 – 175 = 575 meq.
Stoichiometry
Example - 10 25 mL of a solution of ferric alum Fe2(SO4)3. (NH4)2SO4.24 H2O containing 2.41 gm of

salt was boiled with iron then the reaction Fe + Fe2(SO4)3   3Fe(SO4) take place. The un-reacted iron
was filtered off and the solution was treated with 0.1 N KMnO4 in acidic medium. What is the titre value (vol.
of KMnO4) of KMnO4 ? If Cu had been used in place of iron, what would have been titre value ?
SOLUTION :
Fe  Fe 2  SO4  3 
 3FeSO 4  V = 75 mL
 Titre value = 75 mL
1 mole of Fe 2  SO4 3  3 moles of FeSO 4
If Cu were used in place of Fe
1 mole of Fe 2  SO4 3 .  NH 4 2 SO 4 .24H 2O
Cu  Fe2  SO 4 3 
 2FeSO 4  CuSO4
1 mole 2 mole
 1 mole of Fe 2  SO4 3
(only FeSO4 react with KMnO4)
2.41
moles of salt  2.41 mole of Fe 2  SO4 3
9.64 964 2.41 2.41
mol Fe 2  SO4 3  2  mole FeSO4
964 964
3  2.41
 moles of FeSO4 . meq of FeSO4  meq of KMnO4
964
Now, meq of FeSO 4  meq of KMnO 4 .  2  2.41 

   11000  0.1 V
 964 
 3  2.41 
  1000  0.1 V  V = 50 mL
 964 
 Titre value = 50 mL
 Fe 2
 Fe3  1e ; x 1
 
Example - 11 A solution of 0.2 gm of a compound containing cupric and oxalate ions or titration with
0.02 M potassium permanganate in presence of sulphuric acid consumes 22.6 mL of the oxidant. The resultant
solution is neutralised with sodium carbonate, acidified with dil. acetic acid and treated with excess of KI.
The iodine liberated required 11.3 mL of 0.05 M sodium thiosulphate solution for reduction. Find the mole
rate of two ions. Also write down the balanced redox reactions involved in the above titrations.
SOLUTION :
Cu2+ ion can not be oxidised, so only C2O42- 5C 2O42   2MnO 4 16H  

will be oxidised by KMnO4.
2Mn 2   10C O 2  8H 2
Stoichiometry- IIII
2 millimoles of MnO 4  5 millimoles of 2 millimoles of S2O32   1 millimoles of I2
C2 O42  ions (0.05  11.3)mmole S2O32  
0.02  22.6 m . m o l e s o f MnO 4  5 / 2 1 / 2(0.05  11.3) mmol of I2

 0.02  22.6 m.moles = 1.13 m.moles of
= 0.2825 mmole I2
oxalate ions
Also, 1 mmol I 2  2 mmol Cu 2 
Important :
Cu 2   KI 
 Cu  (not Cu 0 ) 0.2825 m.mol I 2  2  0.2825 mmol Cu 2 
2Cu 2   2I 
 I2  2Cu  = 0.565 mmol Cu2+
2
and I2  2S2O32  
 2I   S4O62  C2 O 4 1.13
So, mole ratio of  2
Cu 2  0.565
Example - 12 25 ml solution containing 6.35 g/L of K H3(C2O4)2 .2H2O required V1 ml of 0.1 N NaOH
and V2 ml of 0.1 N KMnO4 in two separate titrations. Calculate V1 and V2
SOLUTION :
KH3(C2O4)2 . 2H2O : M0 = 254 gm/mol (b) meq of compound (as RA) = meq of
KMnO4
(a) meq of compound (as acid)  meq of
NaOH 25  NRA = V2  0.1
25  Na = V1  0.1 S 6.35
where N RA    0.10
E 254 / 4
S 6.35
 where Na    0.075
E 254 / 3 25  0.1
 V2   25ml
[Note : 3 acidic Hydrogens] 0.1
25  0.075 [Note : n - factor = 4 due to 2 mole of C2 O 42  ]

 V1   18.75 ml
0.1
Stoichiometry-- IIII
Stoichiometry Vidyamandir Classes
Example - 13 Three solution, each 100 ml containing 0.3 M Ag2S2, 4.5M NaOH and 4.5M H2O2 respectiley
were mixed to form AsO43- and SO42- as products.
(i) Give a balanced redox equation.
(ii) Calculate the molarity of each species left at the end of the reaction.
(iii) If the above solution is allowed to stand for sometime, what volume of O2 will be collected at STP ?
SOLUTION :
(i)  AsO43  H 2O  SO42 

Given: As 2S3  NaOH  H 2O2 
Oxidation : As32 16OH  

 2AsO34  8H 2O  4e  ...(i)
S32   24OH  
 3SO42   12H 2O  24e ...(ii)
Adding (i) and (ii), we ger : As32  S32   40OH  

 2AsO34  3SO42   20H 2O  28e ...(iii)
  As2S3 
Reduction : H 2O 2  2e  
 2OH  ...(iv)
Multiply (iii) by 1 and (iv) by 14 and add to get :
As2S3  12OH   14 H 2O2 

 2 AsO34  3SO42   20 H 2O
(ii) Initial mmoles of As 2S3  0.3100  30; Initial mmole of NaOH  4.5 100  450
Initial mmoles of H 2O2  4.5 100  450;
It is clear form the balanced equation and mmoles of reactants that As 2S3 is the limiting regent.
90
moles of NaOH left = 450  12  30  90  M NaOH   0.3M
300
30
mmoles of H 2O 2 left  450 14  30  30  M H 2O2   0.1M
300
60
mmoles of AsO 34 formed  2  30  60  M   0.2 M
AsO34 300
Stoichiometry- IIII
90
mmoles of SO 24  formed  3  30  90  M   0.3M
SO24  300
600
mmoles of H 2O formed  20  30  60  MH2O  2M
300
(iii) If a H 2O 2 solution is allowed to stand, it decomposes to give O2 and H 2O 2 .
1
H 2O 2 
 H 2O  O 2
2
1
Thus, mmoles of O2 formed  30   15
2
or, volume of O2 at STP 15  22.4 103 L  0.336 L [ 1 mole of O2 at STP  22.4 L]
Stoichiometry
Stoichiometry-- IIII Classes
Vidyamandir Classes
THINGS TO REMEMBER
1. In a typical redox reaction : X  Y 

AB
meq. of an oxidising agent = meq. of a reducing agent
 g 
2. From definition of gram-equivalents  gmeq.   N VL  , it is very clear that, we must be very confident
 E 
about the concept of equivalent weight (E), for an oxidising or reducing agent.
 The equivalent weight of an oxidising or reducing agent is defined as :
M0
Equivalent weight = E 
x
where M0 = molecular mass ; x = number of electrons transferred (loss or gain) by one mole of
oxidising or reducing agent as given by their balanced ionic half reaction.
3. Variable equivalent weight : Equivalent weight may be variable in many cases. It may depend upon the
medium (acidic/basic) ; dilute/concentrated solution ; whether a reagent is acting as an oxidant or reductant ;
whether a reagent is acting as an oxidant or an acid ; whether a reagent is acting reductant or an acid.
4. A reaction in which same atom is oxidised and reduced at the same time is called as a disproportion-
ation reaction. And the equivalent weight of a compound undergoing disproportionation is :
Effective molecular weight of compound

E 
Number of e  transfer
 Total weight in   Total weight in 

where Effective molecular weight =    
 Oxidation half reaction   Re duction half reaction 
5. Volume strength is the volume of O2 given out at S.T.P. by 1 volume solution of H2O2.
1 M H2O2  11.2 vol of O2 at STP or 1N H2O2  5.6 vol of O2
6. Avoid use of concept of meq in following cases. (Non-typiccal Redox reactions).

H
(a) KMnO4  HCl 
 Cl2  MnCl2  KCl (b) KIO3  KI 
 I2
(c) KMnO4 
 KMnO4  MnO2
7. If a reagent (oxidant or reductant) shows different equivalent weights in two different redox reactions in
a given problem then apply concept of meq carefully. In fact it is advised to use the mole concept in such
cases. (Refer to Illustration 14 & 15)
40 Things
Things to
to Remember
Remember Self Study Course for IITJEE with Online Support
SOLUTION - IN-CHAPTER EXERCISE - A
1. (i) CN  
 N 2  HCO3 and OCl 
 Cl
(Both C and N areoxidised) (Re duced)
(ii) O3 
 O2 and C6 H5OH 
 CO 2
Reduced Oxidised
(iii) I 
 I2 and O3 
 O2
Oxidised Re duced
(iv) S2O32  
 HSO4 and Cl2 
 Cl
Oxidised Re duced
(v) C 
 CO and ZnO 
 Zn
Oxidised Re duced
2. (i) Te(s)  NO3 (aq.) 

 TeO 2 (s)  NO(g)
 TeO 2 (s)  4H   4e

Oxidation : Te(s)  2H 2O  ; Reduct ion :
NO3 (aq.)  4H   3e 

 NO(g)  2H 2O
(ii) H 2O 2 (aq.)  Fe 2 (aq.) 

 Fe3 (aq.)  H 2O()
Oxidation : Fe 2  (aq.) 
 Fe3 (aq.)  e  ; Reduct ion :
H 2O 2 (aq.)  2H   2e 
 2H 2O()
(iii) Mn(s)  NO3 (aq.) 

 Mn 2  (aq.)  NO 2 (g)
 Mn 2  (aq.)  2e 
Oxidation : Mn(s)  ; Reduct ion :
NO3 (aq.)  2H   1e  
 NO 2 (g)  H 2O()
(iv) Mn 3 (aq.) 
 MnO2 (s)  Mn 2  (aq.) (Disproportionation Rxn.)
Oxidation : Mn 3 (aq.)  2H 2O 
 MnO 2 (s)  4H   e  ; Reduction :
Mn 3  (aq.)  e  
 Mn 2  (aq.)
Self Study Course for IITJEE with Online Support Solution-INE 41

3. (i) VO2  (aq.) 

 V3 (aq.)  VO2  (aq.)  2H   e 
 V3 (aq.)  H 2O
(ii) NO3 (aq.) 

 NO2 (g)  NO3 (aq.)  2H   e 
 NO2  H 2O
(iii) IO3 (aq.) 

 I3 (aq.)  3IO3  18H  18e 
 I3  9H 2O
4. (i) CrO24  (aq.) 

 Cr(OH)4 (aq.)  CrO24  (aq.)  4H 2O  3e 
 Cr(OH)4  4OH
(ii) Bi3 (aq.) 

 BiO3 (aq.)  Bi3 (aq.)  6OH 
 BiO3 (aq.)  3H 2O  2e
(iii) ClO (aq.) 

 Cl (aq.)  ClO (aq.)  H 2O  2e 
 Cl (aq.)  2OH 
5. (i) MnO4 (aq.)  IO3 (aq.) 

 MnO 2 (s)  IO 4 (aq.)
Re duction : MnO 4 (aq)  2H 2O  3e   MnO2 (s)  4OH 

Oxidation : IO3 (aq.)  2OH    IO 4 (aq.)  H 2O  2e 
________________________________________________
2MnO4  3IO3  H 2O 
 2MnO 2  3IO 4  2OH 
(ii) Cu(OH) 2 (s)  N 2H 4 (aq.) 

 Cu(s)  N 2 (g)
Oxidation : N 2 H 4 (aq.)  4OH   N 2 (g)  4H 2O  4e

Re duction : Cu(OH) 2 (s)  2H 2O  2OH   2e   Cu(s)  4OH   2H 2O
_________________________________________________________
2Cu(OH)2 (s)  N 2H 4 (aq.) 
 2Cu(s)  N 2 (g)  4H 2O
(iii) Fe(OH)2 (s)  CrO 42  (aq.) 

 Fe(OH)3 (s)  Cr(OH)4 (aq.)
Oxidation : Fe(OH) 2 (s)  OH    Fe(OH)3 (s)  e

Re duction : CrO 24  (aq.)  4H 2O  3e  
 Cr(OH) 4  4OH 
_________________________________________________________
3Fe(OH)2  CrO 42  (aq.)  4H 2O 
 3Fe(OH)3  Cr(OH) 4  OH 
(iv) H 2O 2 (aq.)  ClO4 (aq.) 

 ClO2 (aq.)  O2 (g)
Oxidation : H 2O2 (aq.)  2OH    O 2 (g)  2H 2O  2e 

Re duction : ClO4 (aq.)  2H 2O  4e   ClO2 (aq.)  4OH 
____________________________________________________
2H 2O2 (aq.)  ClO 4 (aq.) 
 2O2 (g)  ClO 2 (aq.)  2H 2O
42 Solution-INE Self Study Course for IITJEE with Online Support

6. (i) H 2O 2 (aq.)  Cr2O72  (aq.) 

 Cr 3 (aq.)  O2 (g)
Oxidation: H 2O2 (aq.)   O2 (g)  2H   2e 

Re duction : Cr2O72  (aq.)  14H   6e  
 2Cr 3 (aq.)  7H 2O
________________________________________________
Cr2O72  (aq.)  3H 2O2  8H  
 2Cr 3  3O2  7H 2O
(ii) H 2O 2 (aq.)  Mn 2  (aq.) 

 MnO 2 (s)  H 2O
Oxidation : Mn 2  (aq.)  4OH  

 MnO 2 (s)  2H 2O  2e
Re duction : H 2O2 (aq.)  2e  
  2OH 
_______________________________________________
Mn 2  (aq.)  H 2O2 (aq.)  2OH  
 MnO 2  2H 2O
(iii) Sn 2  (aq.)  IO4 (aq.) 

 I (aq.)  Sn 4  (aq.)
Oxidation : Sn 2  (aq.) 
 Sn 4  (aq.)  2e
Re duction : IO 4 (aq.)  8H   8e  
 I (aq.)  4H 2O
_____________________________________________________
4Sn 2  (aq.)  IO4 (aq.)  8H  
 4Sn 4  (aq.)  I   4H 2O
(iv) MnO4 (aq.)  SO32  (aq.) 

 MnO42  (aq)  SO42  (aq.)
Oxidation : SO32  (aq.)  2OH   SO 42  (aq.)  H 2O  2e 

Re duction : MnO 4 (aq.)  e   MnO42  (aq.)
_______________________________________________________________
SO32 (aq.)  2MnO4 (aq.)  2OH  
 SO 42  (aq.)  2MnO 42  (aq.)  H 2O
(v) Cr2O72  (aq.)  HI (aq.) 

 CrI3 (aq.)  I2 (g)  KI
Oxidation : 2HI(aq.)   I 2 (aq)  2H   2e 

Re duction : Cr2O72  (aq.)  14H   6e    2Cr 3  7H 2O
______________________________________________________
Cr2O72  (aq.)  6HI(aq.)  8H  
 2Cr 3 (aq.)  3I 2 (g)  7H 2O

7. (i) CuO  NH3 

 N 2  Cu  H 2O
Oxidation : 2NH3   N 2  6H   6e

Re duction:CuO  2H   2e    Cu  H 2 O
________________________________
3CuO  2NH3 
 3Cu  N 2  3H 2O
(ii) HI  HNO3 
 I2  NO  H 2O
Oxidation : 2HI   I 2  2H   2e

Re duction : HNO3  3H   3e    NO  2H 2O
__________________________________
6HI  2HNO3 
 3I 2  2NO  4H 2O
(iii)  PH3  H 2 PO2  H 

P4  H 2O 
Oxidation : P4  8H 2O   4H 2PO 2  8H   4e

Re duction :P4  12H   12e   4PH 3
_______________________________________
 4PH3  12H 2 PO 2  12H 
4P4  24H 2O 
(iv) H 2S  SO 2 
 S  H 2O
 S  2H   2e
Oxidation : H 2S 
Re duction : SO 2  4H   4e 
 S  2H 2O
_____________________________
2H 2S  SO 2 
 3S  2H 2O
(v) CN   MnO4  H 2O 
 MnO 2  CNO   OH 
Oxidation : CN   2OH  
 CNO  H 2O  2e
Re duction : MnO 4  2H 2O  3e 
 MnO2  4OH 
_______________________________________________
3CN   2MnO 4  H 2O 
 3CNO  2MnO 2  2OH 
(vi) [Fe(CN)6 ]3  N 2 H 4  OH  

 [Fe(CN)6 ]4   N 2  H 2O

Re duction :[Fe(CN)6 ]3  e  

 [Fe(CN) 6 ]4 
Oxidation : N 2 H 4  4OH  
 N 2  4H 2O  4e 
______________________________________________________
4[Fe(CN)6 ]3  N 2 H 4  4OH  
 4[Fe(CN) 6 ]4  N 2  4H 2O
(vii) C2 H5OH  MnO 4 

 CH3COO  MnO2  H 2O  OH 
Oxidation : C2 H5OH  5OH    CH3COO  4H 2O  4e 

Re duction : MnO4  2H 2O  3e 
 MnO 2  4OH 
_______________________________________________________
3C 2H5OH  4MnO4 
 3CH3COO  4MnO2  4H 2O  OH 
(viii) P4  H   NO3 (dil)  H 2O 

 H 2PO 4  NO
Oxidation : P4  16H 2O   4H 2PO4  24H   20 e

Re duction : NO3  4H   3e  NO  2H 2O
______________________________________________
3P4  20NO3  8H 2O  8H  
 12H 2 PO 4  20NO
(ix) HS  HSO3 

 S2O32   H2O
Oxidation : HS  3H 2O   S2O32   8H   8e 

Re duction : 2HSO3  4H   4e   S2O32  3H 2O
____________________________________
2HS  4HSO3 
 3S2O32   3H 2O
(x) Fe3  NH2OH 

 Fe2   N 2O  H 
Oxidation : 2NH 2OH   N 2O  H 2O  4H   4e 

Re duction : Fe3  e 
 Fe 2
_____________________________________________
4Fe3  2NH 2OH 
 4Fe 2   N 2O  H 2O  4H 
(xi) O2  H 2O 
 OH   O2

Oxidation : O 2 
 O 2  e
Re duction:O2  2H 2O  3e 
 4OH 
___________________________
4O 2  2H 2O 
 3O 2  4OH 
(xii) IO3  HSO3 

 I  H  SO42 
Oxidation : HSO3  H 2O   SO42   3H   2e 

Re duction: IO3  6H   6e   I  3H 2O
_________________________________
IO3  3HSO3   3SO 42   I  3H 
(xiii) I  IO3  H  
 I 2  H 2O
Oxidation : 2I   I 2  2e 
Re duction : 2IO3  12H   10e  
 I 2  6H 2O
________________________________
IO3  5I  6H  
 3I2  3H 2O
(xiv) Fe2S3  H2O  O2 

 Fe(OH)3  S
Oxidation : S2 
 S  2e 
Re duction :O 2  2H 2O  4e  
 4OH 
_______________________________
O2  2S2   2H 2O 
 2S  4OH 
 2Fe2S3  3O2  6H 2O 

 4Fe(OH)3  6S
(xv) IBr  BrO3  H 2O 

 IO3  Br   H 
Oxidation : I  3H 2O   IO3  6H   4e

Re duction : BrO3  6H   6e  Br   3H 2O
_______________________________________
3I  2BrO3  3H 2 O 
 3IO3  2Br   6H 
 3IBr  2BrO3  3H 2O 
 3IO3  5Br   6H 
(xvi) CrI3  H 2O 2  OH  
 CrO42  IO4  H 2O

Oxidation : CrI3  32OH    CrO 42   3IO 4  16H 2O  27e

Re duction : H 2O 2  2e  
 2OH 
_________________________________________________
2CrI3  27H 2O2  10 OH  
 2CrO 42  6IO4  32H 2O
(xvii) H 2O 2  Fe2   H  
 H 2O  Fe3
Oxidation : Fe 2  
 Fe3  e 
Re duction: H 2O 2  2H   2e  
 2H 2O
___________________________________
2Fe 2   H 2O2  2H  
 2Fe3  2H 2O
(xviii) As2S3  MnO4  H 2O  H  

 H3AsO 4  Mn 2   S
Oxidation : As 2S3  8H 2O   2H3AsO 4  3S  10H   10e 

Re duction : MnO 4  8H   5e   Mn 2   4H 2O
______________________________________________
As 2S3  2MnO 4  6H  
 2H3AsO4  3S  2Mn 2 

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Vidyamandir Classes Atomic Structure

DISCOVERY OF CATHODE RAYS & POSITIVE RAYS SECTION - 1B

Self Study Course for IITJEE with Online Support Section 1 1

MODELS OF ATOM SECTION - 2A

Observations of the Rutherford’s experiment :

2 Section 2 Self Study Course for IITJEE with Online Support

Failure of Rutherford’s Model

Self Study Course for IITJEE with Online Support Section 2 3

NATURE OF CHARACTERISTICS OF RADIANT ENERGY SECTION - 2B

4 Section 2 Self Study Course for IITJEE with Online Support

The Quantum Theory of Radiation

6 Section 2 Self Study Course for IITJEE with Online Support

Self Study Course for IITJEE with Online Support Section 2 7

NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK

ATOMIC SPECTRA OF HYDROGEN AND BOHR’S MODEL SECTION - 3

Region Spectral line n m

8 Section 3 Self Study Course for IITJEE with Online Support

In Hydrogen atom spectra :

Self Study Course for IITJEE with Online Support Section 3 9

Note : Atomic number  Number of protons on the nucleus = Z

Also, according to Bohr’s postulate of quantization of angular momentum, we have :

Using the value of rn in the expression of En, we get :

Self Study Course for IITJEE with Online Support Section 3 11

vn = 2.18  106 (1/n) m/s

What does the negative electron energy (En) means ?

12 Section 3 Self Study Course for IITJEE with Online Support

Self Study Course for IITJEE with Online Support Section 3 13

ENERGY LEVELS OF HYDROGEN ATOM SECTION - 4

Note : For H-atom, Z = 1 ; He+ ion, Z = 2 and Li2+, Z = 3

14 Section 4 Self Study Course for IITJEE with Online Support

Self Study Course for IITJEE with Online Support Section 4 15

  = 4.872  107 m = 4872 Å

16 Section 4 Self Study Course for IITJEE with Online Support

  1 / v  1 /15222.22  6.569  10 5 cm  6569 Å

Drawbacks of Bohr model :

Self Study Course for IITJEE with Online Support Section 4 17

18 Section 4 Self Study Course for IITJEE with Online Support

E  (2  6.023 1023 )  3.03 10 19 J

Self Study Course for IITJEE with Online Support Section 4 19

WAVE NATURE OF PARTICLES SECTION - 5

20 Section 5 Self Study Course for IITJEE with Online Support

 The new theory still defines a definite energy to an orbital in an atom

circumference of the orbit

Illustrating the concept :

Self Study Course for IITJEE with Online Support Section 5 21

(b) For an electron, p = m v

p = 0.1 % of p = 1.82  1027 Kg m/s

22 Section 5 Self Study Course for IITJEE with Online Support

CONCEPT OF QUANTUM NUMBERS SECTION - 6

Introduction to Quantum Mechanics

Equation of Quantum Mechanics :

What is a wave function (  ) ?

Self Study Course for IITJEE with Online Support Section 6 23

Designation of An Electron in an Orbital

(i) Principal Quantum Number (n) :

For example : n = 1 (K shell) has only one subshell ( = 0)

We can create the following notation :

24 Section 6 Self Study Course for IITJEE with Online Support

Note : Number of orbitals in a sub-shell  Number of possible orientations of an orbital.

Note the conventions :

Self Study Course for IITJEE with Online Support Section 6 25

There is an orbital angular momentum associated with an electron in a subshell given by :

Difference between Orbit and Orbital :

26 Section 6 Self Study Course for IITJEE with Online Support