Complete Notes of Puc First Year

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Content:
Unit 1: Some Basic Concepts of Chemistry
Unit 2: Structure of Atom
Unit 3: Classification of Elements and Periodicity in Properties
Unit 4: Chemical Bonding and Molecular Structure
Unit 5: States of Matter
Unit 6: Thermodynamics
Unit 7: Equilibrium
Unit 8: Redox Reactions
Unit 9: Hydrogen
Unit 10: The s-Block Elements
Unit 11: The p-Block Elements
Unit 12: Organic Chemistry – Some Basic Principles and Techniques
Unit 13: Hydrocarbons
Unit 14: Environmental Chemistry

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1 Basic concepts of Chemistry

Matter is defined as anything that occupies the pace and has mass. This matter
can exist in three physical states i.e., solid (which is having definite shape and definite
volume), liquid (which is having definite volume but not shape) gas (which is not having
neither definite volume nor definite shape).
Matter at macroscopic level it is classified into two types i.e., mixtures and pure
substance.
Mixture: It is defined as the matter in which the components are present at any ratio
and their composition is variable. The mixture is further classified into two types i.e.,
homogeneous mixture and heterogeneous mixture.
Homogeneous mixture is the one where the components are completely mixed
with each other and its composition is uniform throughout. Example: sugar in water,
salt in water etc.
Heterogeneous mixture is the one where the components are not completely
mixed with each other and its composition is not uniform throughout. Example: salt and
sugar, grains and pluses.
Pure substances: It is defined as the matter in which the components are present in the
fixed ratio and their composition is not variable. The pure substances are further
classified into two type i.e., elements and compounds.
Elements are defined as the pure substances which consist of only one type of
particles. These particles may be atoms or molecules. Molecules are formed by the
combination of two or more atoms. Example: hydrogen molecule, oxygen molecules,
nitrogen molecules. Etc.
Compounds are defined as the pure substances which consist of two or more
different elements. Example water, ammonia, carbon dioxide etc.
Properties of matter: The properties of the matter is classified into two types i.e.,
Physical properties: It is the property which is measurable or observed without

changing the identity of the substance. Example: length, weight, colour, etc
Chemical properties: It is the property which measurable or observed with the

change of identity of the substance. Example: acidic, basic and combustibility.
International system of units (SI): The SI system has seven base units which are
fundamental scientific quantities. These are
Length ― meter ― m Mass ― kilogram ― kg
Temperature ― kelvin ― K amount of substance ― mole ― mol
Luminous intensity ― candala ― cd current ― amper ― A
Time ― second ― s
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Mass: It is amount of matter present in substance. It is the constant quantity. It is

determined in the laboratory by using analytical balance.
Weight: it is amount of matter present in substance along with force exerted on it by

gravity. It is variable because variation due to change in the gravity from place to place.
Density: it is the amount of mass of the substance per unit volume. Its SI unit is kg/m3.
Temperature: This physical quantity is measure using three different scales i.e.,
Degree Celsius scales (0C), degree fahrenheit scale (0F) and kelvin scale. The
temperature on two scales are related to each other
Fahrenheit scale and degree Celsius scale: 0F = (9/5)0C + 32
Degree Celsius scale and kelvin scale: K = 0C + 273.15
Scientific notation: It is the exponential notation in which any number can be

represented in the form of N x 10n, where “N” is a number called digit which varies
between 1.00 ---- to 9.999---- and “n” is exponent having positive or negative values.
Significant figures: It is the meaningful digits which are known with certainty.
Rules to determining the significant figures:
1. All non – zero digits are significant.

2. Zeroes proceeding to first non – zero digit are not significant.
3. Zeros between two non – zeros digits are significant.
4. Zeroes at the end or right of a number are significant provided they are on the
right side of the decimal point.
5. Counting numbers of objects have infinite significant figures as these are
exact numbers and can be represented with writing infinite number of zeros
after placing a decimal.
Precision: The closeness of various measurements for the same quantity.
Accuracy: The agreement of a particular value of the true value of the result.
Rules for rounding off the numbers:
1. If the right most digits are to be removed is more than 5, the preceding
number is increased by one.
2. If the right most digits are to be removed is less than 5, the preceding number
is not changed.
3. If the right most digits are to be removed is 5, then preceding number is not
changed if it is an even number but it is increased by one if it is odd number.
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Dimensional analysis: The method of converting units from one system to other. It is
also called factor label method or unit factor method. Example: 30 min is equal to 30 x
60 = 1800 s.
LAWS OF CHEMICAL COMBINATIONS
Law of conservation of mass: The matter can neither be created nor destroyed. This
law is given by Antoine Lavoisier.
Law of definite proportions or Law of definite composition: A given compound

always contains exactly the same proportion of elements by weight. This law is given by
Joseph Proust.
Law of multiple proportions: If two elements can combine to form more than one
compound, the masses of one element that combine with a fixed mass of other element,
are in the ratio of small whole numbers. This law is given by Dalton.
Gay’s Lussac’s law of gaseous volumes: When gases combine or are produced in a
chemical reaction they do so in a simple ratio by volume provide all gases are at same
temperature and pressure. This law is given by Gay Lussac.
Avogadro Law: Equal volumes of gases at the same temperature and pressure should
contain equal number of molecules. This law was given by Avogadro.
Dalton’s atomic theory:
Postulates:
1. Matter consists of individual atoms

2. All the atoms of a given elements have identical properties including identical
mass. Atoms of different elements differ in mass.
3. Compounds are formed when atoms of different elements combine in a fixed
ratio.
4. Chemical reactions involve reorganisation of atoms. i.e., atoms neither created
nor destroyed in a chemical reaction.
Atomic mass unit: It is defined as a mass exactly equal to 1/12th the mass of one
carbon – 12 atoms. One amu value is 1.66056 x 10 – 24 g. This amu is replaced by ‘u’
which is known as unified mass.
Molecular mass: It is the sum of atomic masses of the elements present in the
molecule.
Formula mass: Sum of the atomic masses of all the elements present in the formula
unit. Example: the formula mass of NaCl is 23 + 35.5 = 58.5u
Mole: It is defined as the amount of substance that contains as many particles or

entities as there are atoms in exactly 12g of the C – 12 isotope.
Molar mass: The mass of one mole of substance in gram.
Empirical formula: It is the formula which represents the simplest whole number ratio
of various atoms present in a compound. Example: empirical formula of benzene is CH,
water is H2O
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Molecular formula: it is the formula which represents the exact number of different
types of atoms present in the molecule of a compound.
Limiting reagent: The reactant which gets consumed completely during the reaction to
form product.
Concentration of the solution: The amount of substances present in its given volume.
The following are the units used to express the concentration of the solutions
1. Mass percent : (mass of solute x 100)  (mass of solution)
Mass of solute
Mass per cent = X 100
Mass of solution
2. Mole fraction: It is the ratio of number of moles of a particular component to
the total number of moles of solutions.
No. of mole of solute

Mole Fraction =
No. of mole of solution
3. Molarity: The number of moles of solute in one litre of the solution.
wb x 1000
No. of mole of solute
Molarity = =
Volume of solution in litre Mbx given voluem of solution
4. Molality: The number of moles of solute present in one kilogram of solvent.
No. of mole of solute wb x 1000

Molality = =
Mass of solvent in kilogram Mbx W A
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2 Structure of Atom
 Atomic theory of matter was proposed by John Dalton in 1808.

 Fundamental particles: electrons, protons and neutrons.
 First fundamental particles discovered were electrons.
 Presence of electrons was reported by Faraday in 1830 during his electrolysis
experiment.
 The name electron was coined by Stoney in 1891.
 J.J. Thomson discovered the electron by using discharge tube or cathode tube
experiment in 1896.
 Cathode tube or discharge tube was construed by William Crooke.
 Cathode ray tube experiment:
When a very high voltage about 10,000 volts is
applied between the two electrodes, no electric discharge
occurs until the part of the air has been pumped out of
the tube. When the pressure of the gas inside the tube is
less than 1 mm, a dark space appears near the cathode
and thread like lines are observed in the rest of 0.01 mm
Hg it fills the whole tube. The electric discharge passes
between the electrodes and the residual gas in the tube
begins to glow. These rays which proceed from the cathode and move away from it at
right angle in straight lines are called cathode rays.
Properties of cathode rays:
 They travel in straight lines away from the cathode and produce shadow of the
object placed in their path.
 The rays carry a negative charge.
 These rays can also be easily deflected by an electrostatic field.
 The rays can exert mechanical pressure showing that these consist of material
particle which are moving with kinetic energy.
 The produce fluorescence when they strike the glass wall of the discharge
tube.
 Cathode rays produce x-rays when they strike a metallic plate.
 These rays consist of material particle whose e/m resembles with electron.
 These rays emerge normally from the cathode and can be focused by using a
concave cathode.
 Charge to mass ratio of electron:(e/me ratio)
o J.J. Thomson determined the value of e/me ratio as 1.758820 x 1011 C/kg,
by using cathode ray tube in 1897, by applying electrical and magnetic field
perpendicular to each other as well as to the path of electrons.
o Experiment: when only electric field is applied
the cathode rays will deflect and hits the screen
at the point A, where as only magnetic field is
applied the cathode rays will deflect and hits
the screen at the point B, when both the fields
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are applied perpendicular to each other and adjusted such that the cathode
rays will hits the point C on the screen.
o J.J. Thomson argued that the deflection of the rays will depends on
 The magnitude of the negative charge on the particles, i.e., higher
the charge more will be the deflection.
 The mass of the particles i.e., lighter the mass greater will be the
deflection.
 The strength of the electrical and magnetic field i.e., the deflection is
more if the voltage of the electric current is high or the strength of
the magnetic filed is high.
 Charge on the electron: R.A Millikan devised a method to find out the charge of the
electron i.e., oil drop method and the value is found to 1.6 x 10 – 19 C, but today
value of the electron found to be 1.6022 x 10 – 19 C.
 Mass of the electron: the mass of the electron is determined by combining the
charge of the electron which is determined by Millikan and e/m ratio by Thomson
i.e.,
e
 1.7588201011 Ckg 1
m
e 1.6022 10 19 C
m 
1.7588201011 Ckg 1 1.7588201011 Ckg 1
 m  9.1094 10 31 kg
 Discovery of protons is done by Goldstein by modifying the cathode ray tub in

which electrical discharge is carried out. These positive charged rays are known as
canal rays.
 Characteristics of canal rays or positive rays:
o These rays travel in a straight line in a direction opposite to the cathode.
o These are deflected by electric as well as magnetic field in the way
indicating that they are positively charged
o The charge to mass ratio (e/m) of positive particles varies with the nature
of
o the gas placed in the discharge tube
o Positive rays are produced from the ionization of gas and not from anode
electrode
o Positive rays are deflected in electric field. This deflection shows that these
are positively charged so these are named as protons given by Rutherford.

Discovery of neutrons: In 1933, James Chadwick identified a new particle
obtained from the bombardment of beryllium by α-particles. It had a unit mass and
carried no charge. It was named “Neutron”. 4Be9 + 2He4  6C12 + 0n1
Properties Electron Proton Neutron
Discovery J.J. THOMSON GOLDSTEIN JAMES CHADWICK
Chare
relative to –1 +1 0
the proton
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Charge 1.6022 X 10 – 19 C 1.6022 X 10 – 19 C 0
Mass 9.101 X 10 – 31 kg 1.67262 X 10 – 27 kg 1.67495 X 10 – 27 kg
Mass
relative to 1 1836 1839
the electron
Spin ½ ½ ½
o Atomic number: number of protons present in the nucleus of an atom.

o Mass number: the total number of protons and neutrons in an atom
o Isotopes: are different atoms of the same element having same atomic number
but different number of neutrons, i.e., mass number
o Isobars: are the atoms of different elements having same mass number but
different number of protons i.e., atomic number.
o Isotones: are atoms of different elements having same number of neutrons.
o Isodiapheres are atoms having same difference in number of neutrons and
protons.
Atomic modes
J. J. Thomson model of atom [plum pudding model]
He got Noble prize for theoretical explanation of structure of an atom in 1906.
He proposed a spherical shape model for an atom which is having approximately 10–10m
radius, where the positive charge is uniformly distributed and electrons are embedded
into it in such a manner as to give the most stable electrostatic arrangement.
The important feature of this model is that the mass of the atom is assumed to be
uniformly distributed over the atom.
This model explains only neutrality of the atom but other properties are not
explained.
Rutherford’s nuclear model of atom [ -

particle scattering experiment]
Rutherford and his students were led

to find out that, in an atom the nucleus is
present at the center but not whole, by
performing an experiment called gold foil  -
particle scattering experiment.
In this experiment they bombarded a thin sheet of gold foil

with high speed  - particles, and got the following observations,
o Most of the - particles went straight without suffering any deflection.

o A few of the - particles got deflected through small angles.
o A very few did not pass though the foil at all but suffered large deflection or even
came back in more or less the direction from which they have incidences.
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The following conclusions were drawn from the above observations on the basis of
scattering experiments; he proposed the model of the atom which is as follows
o Rutherford atomic model was similar to the solar system, the nucleus
representing the sun and revolving electrons as planets. The electrons are
therefore, generally referred to as planetary electrons.
o An atom consists of a heavy positively charged nucleus where all the protons and
neutrons are present which are collectively called as nucleons. The whole mass of
the atom is contributed by these nucleons. The magnitude of the positive charge
on the nucleus is different for different atoms.
o The volume of the nucleus is very small and is only a minute fraction of the total
volume of the atom. Nucleus has a diameter of the order of 10 – 12 to 10 – 13 cm
and the atom has a diameter of the order of 10 – 8 cm.
o There is an empty space around the nucleus called extra nuclear part, in which
electrons are present. The numbers of electrons are equal to number of protons.
This extra nuclear part is responsible to the volume of the atom, which is 1015
times the volume of the nucleus.
o The electrons revolve round the nucleus in closed orbits with high speed. The
centrifugal force acting on the revolving electrons is being counterbalanced by the
force of attraction between the electrons and the nucleus.
Demerits of Rutherford atomic model
An electron revolving around the nucleus gets accelerated towards the

nucleus. According to the electromagnetic theory, an accelerating charged particle
must emit radiation, and lose energy. Because of this loss of energy, the electron
would slow down, and will not be able to withstand the attraction of the nucleus. As
a result, the electron should follow a spiral path, and ultimately fall into nucleus. If it
happens then the atom should collapse in about 10-8 second. But, this does not
happen: atoms are stable.
o This model of atom does not say anything about the arrangement of
electrons in an atom.
o If the electrons lose energy continuously, the observed spectrum should be
continuous but the act ual observed spectrum consists of well defined lines
of definite frequencies, which is not explained by this model.
Quantum theory:
 This theory was proposed by Max Planck’s, after reporting this famous
experiment called black body radiation in 1900 which shows that light has as
dual character, i.e., particle and wave nature.
 He gave the Quantum Theory of Radiation to explain electromagnetic radiation
and energy.
 The of main features of this theory is
 Radiant energy is emitted or absorbed discontinuously in the form of small
packet energy called quanta.
 Each quantum of energy is associated with a definite amount of energy, in the
case of light; the quantum of energy is called photon.
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 The amount of energy associated with a quantum of radiation is proportional
to the frequency of the radiation. E  , or E = h, where h = Planck’s constant
whose value is 6.63 x 1034J/s or 3.99 x 10 – 13 kJs/mol,
 The total amount of energy emitted or absorbed by a body will be some whole
number multiple of the quantum i.e., E = nh, where n = 1,2,3,------.
 The energy associated with a quantum of radiation depends inversely on its
wavelength.
Black body radiation: the ideal body which emits and absorbs radiations of all
frequencies, is called black body, the radiations emitted by these black body is know as
black body radiation. The exact frequency distribution of the emitted radiation from a
black body depends only on its temperature, i.e., at a given temperature, the intensity of
radiation emitted increases with decrease of wavelength, reaches a maximum value at a
given wavelength and then starts decreasing with further decrease of wavelength.
Photoelectric effect:
 This effect is explained by H. Hertz in 1887.

 The phenomenon of ejection of electrons from the
surface of metal when light of suitable frequency
strikes is known as photoelectric effect. The ejected
electrons are called photoelectrons.
 The metals which show the photoelectric effect are
Potassium, cesium, rubidium.
 Experimental results observed for the experiment of
photoelectric effect observed by Hertz:
o When beam of light falls on a metal surface electrons are ejected
immediately i.e., there is not time lag between light striking metal surface
and ejection of electrons.
o Number of electrons ejected is proportional to intensity or brightness of
light.
o Threshold frequency: (0): it is the minimum frequency of a metal below
which photoelectric effect is not observed.
o If frequency of light is less than the threshold frequency there is no
ejection of electrons no matter how long if falls on surface or how high its
intensity is.
 Photoelectric work function (W0): the minimum energy required to eject
electrons. W0 = h0
 Energy of the ejected electrons: h( - 0) = ½ meV2
Spectrum:
 When a light is passed through a prism, it splits into a series of coloured bands.
 Types of spectrums:
o Continuous spectrum: the spectrum which consists of all the
wavelengths.
o Line spectrum or atomic spectrum: a spectrum in which only specific
wavelengths are present.
 It is used to study the electronic structure of an element.
 Each element produces characteristic lines which are used in
chemical analysis to identify unknown atoms.
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 Robert Bunsen first person used line spectrum to identify the
elements.
o Emission spectrum: the spectrum of radiation emitted by a substance
that has absorbed energy.
o Absorption spectrum: the spectrum obtained when radiation is passed
through a sample of material. The sample radiation of certain
wavelengths. The wavelengths which are absorbed are missing and come
as dark lines.
 The study of emission or absorption spectra is referred as spectroscopy.
Electromagnetic spectrum:
 When electrically charged particle movies under acceleration, alternating

electrical and magnetic fields are produced and transmitted. These fields are
transmitted in the forms of waves called electromagnetic waves or electromagnetic
radiation.
 It is a continuous spectrum.
 It consists of a range of electromagnetic radiations arranged in the order of
increasing wavelengths or decreasing frequencies.
 It extends from radio waves to gamma rays.
 Properties of electromagnetic radiations

o The oscillating electric and magnetic fields produced by oscillating charged
particles are perpendicular to each other and both are perpendicular to the
direction of propagation of the wave.
o Electromagnetic waves do not require medium and can move in vacuum.
o They are many types of electromagnetic radiations, which differs one
another in wavelength. These constitute is known as electromagnetic
spectrum.
o Different kinds of units are used to represent electromagnetic radiation.
o All electromagnetic radiations travel with the speed of the light i.e., 3 x 108
m/s.
 Electromagnetic radiations are characterized by frequency () and wavelength ().
o Frequency (): number of waves that pass a given point in one per second.
SI unit hertz.
o Wavelength (): it is the distance between peaks of two successful crusts.
SI unit is meter (m).
o Wave number: ( ): the number of wavelengths per unit length or
reciprocal of wavelength. SI unit is m – 1.
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Hydrogen atom spectrum:
 It is the emission type of spectrum.

 Production of spectrum: when an electric discharge is passed through gaseous
hydrogen, it will break up into the hydrogen atoms. The hydrogen atom get
energized and go into an excited state, these excited atoms while returning back
to ground state emits bluish the light. When this light is passed through a prism,
a discontinuous line spectrum consisting of several sharp lines is obtained.
Spectral Lines for atomic hydrogen:
Series n1 n2 Spectral Region
Lyman 1 2, 3, 4, 5 Ultraviolet
Balmer 2 3, 4, 5 … Visible
Paschen 3 4, 5 … Infrared
Brackett 4 5, 6 … Infrared
Pfund 5 6, 7… Infrared
 Balmer given an expression on which the characteristic of line are studied on the
basis of wave number, which obeys the following equation
1 1
  RH  2
 2  Where RH is known as Rydberg constant whose value is
 n1 n2 
109,677cm – 1, n1 and n2 are the integers.
Bohr’s model of hydrogen atom
 An electron in the hydrogen atom can move around the nucleus in a circular path
of fixed radius and energy. These paths are called orbits or energy levels. These
orbits are arranged concentrically around the nucleus.
 As long as an electron remains in a stationary orbit, it does not lose or gain
energy and its energy remains constant.
 When transition occurs between two stationary states that differ in energy, the
frequency of the radiation absorbed or emitted can be calculated.
 An electron can move only in those orbits for which its angular momentum is an
integral multiple of h/2, i.e., mevr = nh/2, where n = 1,2,3, -----
Merits of Bohr’s model of hydrogen atom
 Stationary states for electron are numbered in terms of Principal Quantum

numbered as n=1, 2, 3…
 For hydrogen atom: The radii of the stationary states is expressed as rn = n2a0
where a0= 52.9 pm
 Energy of stationary state En = – RH (1/n2), where RH = 2.18 x 10 – 18 J (Rydberg
constant), n = 1,2,3 -----
 For ions containing only one electron En = –2 .18 x 10 – 18 (Z2/n2)J, where Z =
atomic number. The radii by the expression is rn = 52.9n2/Z pm.
 It is also possible to calculate the velocities of electrons moving in these orbits,
i.e., the magnitude of velocity of electron increases with increase of positive
charge on the nucleus and decreases with increase of principal quantum number.
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Bohr’s explanation of line spectrum of hydrogen
According to one of the postulates of Bohr’s, when a electron observes the energy it will
moves from lower principal quantum number to higher quantum number, while coming
back it emits the radiation, therefore the energy gap between the two orbits are given by
E = Ef - Ei
But we known that En = – RH (1/n2)
R   
R  1 1 
Therefore, E =  2 H    2 H    R H  2  2 
 n  n 
 f   ni   f ni 
where RH = 2.18 x 10 – 18, but the frequency () associated with the absorption and
emission of the photo can be evaluated by using equation.
 = E/h
Where h = Planck’s constant whose value is 6.63 x 1034J/s,
Therefore
 RH  1 1   2.18  10 18  1 1 
      2
h  n2 n2  6.63  10 34 n 2 
 f i   f ni 
 1 1  
15  1 1 
  3.29  1015   or   3 . 29  10  Hz
 n2 n2   n2 n2 
 f i   i f 
In terms of wave number
  1   1   
  1   3.29  10
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RH   1   1.09677  10 7  1  1 m 1
  
C C  n2 n2  3  10 8 n 2 2  n 2 2 
 i f   i nf   i nf 
In case of absorption spectrum nf>ni and the term in the parenthesis is positive and
energy is absorbed. On the other hand in case of emission spectrum n i>nf E is negative
and energy is released.
Limitations of Bohr’s model of atom
 Bohr’s model failed to account for the finer details of the hydrogen spectrum. For
instance splitting of a line in the spectrum into two closely spaced lines.
 Bohr’s model was also unable to explain spectrum of atoms containing more than
one electron.
 Bohr’s model was unable to explain Zeeman Effect i.e. splitting of spectral line in
presence of magnetic effect.
 Bohr’s model also failed to explain Stark effect i.e. splitting of spectral line in
presence of electric field.
 Bohr’s model could not explain the ability of atoms to form molecules by chemical
bonds.
 It ignores the dual behavior of matter.
 It contradicts Heisenberg’s uncertainty principle.
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Dual nature of matter:
 de Broglie proposed that matter exhibits dual behaviour i.e., matter shows both
particle and wave nature. According to him, every objet in motion has a wave
character. Wavelengths of macroscopic objects cannot be detected but for
microscopic particles it can be detected. This is because for microscopic objects,
the mass is less. Since mass and wavelength are inversely proportional to each
other, the wavelength will be more. But for macroscopic objects, the mass is
large. Therefore, wavelength will be two short to be detected.
o de Broglie equation:  = h/m = h/
 Heisenberg’s uncertainty principle: it states that it is impossible to determine
simultaneously, the exact position and exact momentum i.e., velocity of an
electron.
o Heisenberg’s uncertainty equation: x. p = h/4, or x  = h/4m
o The main significance of this principle is the existence of definite paths or
trajectories of electrons and other similar particles.
Quantum mechanical model of atom:
Classical mechanics is based on Newton’s law of motion. It successfully describes

the motion of macroscopic particles but fails in the case of microscopic particles,
because this concept ignores the concept of dual behaviour of matter especially for sub –
atomic particles and the Heisenberg’s uncertainty principle.
Quantum mechanics is a theoretical science that deals with the study of the
motions of the microscopic objects that have both observable wave like and particle like
properties. When quantum mechanics is applied to macroscopic objects the results are
the same as those from the classical mechanics.
This quantum mechanics takes into account the de Broglie concept of dual
nature and Heisenberg’s uncertainty principle, Schrodinger described the motion of
electron in three dimension spaces in terms of a mathematical equation called
Schrodinger wave equation.
 2  2  2 8 2 m
   ( E  V )  0
x 2 x 2 x 2 h2
The wave function  is the amplitude function of the particle wave and 2 is the
measure of the probability of finding an electron in a volume element xyz.
Or Hˆ   E
Where Ĥ is the Hamiltonian operator, E is the total energy of the system, 

represents the wave function which is the amplitude of the electron wave.
When Schrodinger equation is solved for the hydrogen atom, the solution gives
the possible energy levels the electron and the corresponding wave function/s of the
electron associated with each energy level. Out of the possible values, only certain
solutions are permitted. Each permitted solution is highly significant as it corresponds
to a definite energy state. Thus, we can say that energy is quantized.
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Orbitals and Quantum numbers:
o Orbital: the region of space around the nucleus where the probability of finding
an electron is maximum.
o Quantum numbers: there are a set of four quantum numbers which specify the
energy, size, shape and orientation of an orbital.
o Principal quantum number:(n):
 It determines the size and to a large extent the energy of the orbital,
i.e., the total number of orbitals in a shell = n 2, and maximum
number of electrons = 2n2.
 It can have positive integer values 1,2,3 and so on.
 It also identifies the shell, i.e., K,L,M etc.
 As the value of ‘n’ increases, the energy also increases. Hence, the
electron will be located far away from the nucleus.
o Azimuthal quantum number:(l)
 It identified the sub shell and the three dimensional shape of the
orbital.
 It also determines the number of sub shells or sub levels in a shell.
Total number of sub shells in a particular shell is equal to the value
of n, i.e., l = (n – 1) where n = 1,2, 3----
 Each sub shell corresponding to different values of l are represented
by different symbols i.e.,
l = 0 denoted by‘s’ ,l = 1 denoted by ‘p’
l = 2 denoted by‘d’, l = 3 denoted by ‘f’
Note: it is also called orbital angular momentum or sub subsidiary quantum

number.
o Magnetic quantum number:(m)

 It gives information about the spatial orientation of the orbital with
respect to standard set of co – ordinate axis.
 For any sub – shell (defined by ‘l’ value) 2l + 1 values of orientation
are possible.
o Spin quantum number:(s)
 It refers to orientation of the spin of the electron. It can have two
values + ½ and – ½, + ½ identifies the clock wise spin and – ½
identifies the anti – clock wise spin.
Overe all quantum number
Number of
Quantum numbers
quantum states
Principal Azimuthal Magnetic

Spin quantum In the
quantum quantum quantum In the
number sub
number number number coat
shell
n l=(n – 1 ) m = (2l+1) s
1 0 (s) 0 + ½ and - ½ 2 2
2 0 (s) 0 2
16
1(p) –1 0 + 1 + ½ and - ½ 6 10
0 (s) 0 2
3 1(p) –1 0 + 1 + ½ and - ½ 6
18
2 (d) –2, –1, 0 +1, +2 10
0
0 (s) 2
–1 0 + 1
1(p) 6
4 –2, –1, 0 +1, +2 + ½ and - ½
2 (d) 10 32
–3,–2, –1, 0 +1,
3 (f) 14
+2, +3
Note:
o An orbital is identified by the set of three quantum numbers i.e., principal,

Azimuthal and magnetic quantum number.
o An electron is identified by a set of four quantum numbers, i.e., principal,
Azimuthal, magnetic and spin quantum number.
Sub shell notation or shapes of atomic orbitals:
o Notation of a sub shell is written as the

principal quantum number followed by the symbol
of the respective sub shell.
o The orbital wave function  for an electron
in an atom has no physical meaning. It is simply a
mathematical function of the coordinate of the
electron.
o Plots of the orbital wave function (r),
and probability density 2(r) vs distance ‘r’ of
the electron from the nucleus for ‘1s’ orbital.
o For 1s orbital the probability density
is maximum at the nucleus and it decreases
sharply as we move away from it(which is not possible).Hence plot of
probability density 2(r) Vs distance r of the electron from the nucleus was
drawn as shown below.
o Plots of the orbital wave function (r), and probability density 2(r) vs
distance ‘r’ of the electron from the nucleus for ‘2s’ orbital.
o For 2s orbital the probability density is maximum at the nucleus and it
decreases sharply as we move away from it(which is not possible). Hence,
plot of probability density 2(r) Vs distance r of the electron from the
nucleus was drawn as shown below.
o For 2s orbital, the probability density first decreases sharply to zero and
again starts increasing. After reaching small maxima it decreases again
and approaches zero as the value of r increases further.
Nodal surface: The region where this probability density function reduces to zero is
called nodal surfaces or simply nodes.
17
Charge cloud diagrams: In these diagrams, dots represent the electron probability
density. The density of the dots in a region represents electron probability density in
that region.
Boundary surface diagram: In this representation, a boundary surface or contour

surface is drawn in space for an orbital on which the value of probability density Y2(r) is
constant. However, for a given orbital, only that boundary surface diagram of constant
probability density is taken to be good representation of the shape of the orbital which
encloses a region or volume in which the probability of finding the electron is very high,
say, 90%.
Shapes of orbitals:
Radial nodes: Radial nodes occur when the probability density wave function for the
electron is zero on a spherical surface of a particular radius. Number of radial nodes = n
–l–1
Angular nodes: Angular nodes occur when the probability density wave function for the
electron is zero along the directions specified by a particular angle.
Number of angular nodes = l
Total number of nodes = n – 1
Degenerate orbitals: Orbitals having the same energy are called degenerate orbitals.
The stability of an electron in a multi electron system is because of:
o The repulsive interaction of the electrons in the outer shell with the electrons in
the inner shell.
o The attractive interactions of electron with the nucleus.
These attractive interactions increase with increase of positive charge (Ze) on the
nucleus.
o The stability of an electron in multi-electron atom is because total attractive

interactions are more than the repulsive interactions.
Shielding effect or screening effect: Due to the presence of electrons in the inner
shells, the electron in the outer shell will not experience the full positive charge on the
18
nucleus. So, due to the screening effect, the net positive charge experienced by the
electron from the nucleus is lowered and is known as effective nuclear charge.
o Effective nuclear charge experienced by the orbital decreases with increase of

azimuthal quantum number (l).
o Orbitals have different energies because of mutual repulsion between electrons in
a multi- electron atom.
o Orbitals with lower value of (n+l) are filled first as they have lower energy.
o If two orbitals have the same value of (n+l) then orbital with lower value of n will
have lower energy.
o Energies of the orbitals in the same subshell decrease with increase in atomic
number.
Filling of electrons:
The filling of electrons into the orbitals of different atoms takes place
according to Aufbau principle ,Pauli’s exclusion principle, the
Hund’s rule of maximum multiplicity
o Aufbau Principle: In the ground state of the atoms, the

orbitals are filled in order of their increasing energies. The
order in which the orbitals are filled is as follows:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d, 6p, 7s...
o It is based on (n+ l) rule. It states that the orbital with lower value of (n+l) has
lower energy.
o Pauli Exclusion Principle: No two electrons in an atom can have the same set of
four quantum numbers. Only two electrons may exist in the same orbital and
these electrons must have opposite spin.
o Hund’s rule of maximum multiplicity: Pairing of electrons in the orbitals
belonging to the same subshell (p, d or f) does not take place until each orbital
belonging to that subshell has got one electron each i.e., it is singly occupied.
Electronic configuration of atoms:
The electronic configuration of different atoms can be represented in two ways.
sapbdc ...... notation: In the first notation, the subshell is represented by the
respective letter symbol and the number of electrons present in the subshell is
depicted, as the super script, like a, b, c, ... etc. The similar subshell represented
for different shells is differentiated by writing the principal quantum number
before the respective subshell.
Orbital diagram: In the second notation, each orbital of the subshell is represented by a
box and the electron is represented by an arrow a positive spin or an arrow a negative
spin.
Stability of completely filled and half filled sub shells:
o Symmetrical distribution of electrons

o Exchange energy
19
Classification of elements and

3 periodicity in properties
Dobereiner’s Law of Triads: Johann Dobereiner in 1829 classified similar elements
into group of three or triads such that atomic weight of the central element was the
arithmetic mean of the atomic weights of the other two members of the triad.
Example Li (7) Na(3) K (39) → (7 + 39)  2 = 23
Ca(40) Sr (88) Ba(137) → (40 + 137)  88.5
Cl (35.5) Br (80) I (127) → (35.5 + 127) 2 = 80
John Newland’s law of octaves: The law states that “The elements when arranged in
order of their increasing atomic weights, every eight element has properties
similar to the first element like eight note of the musical scale”.
Example: Element Li Be B C N O F
At. Wt 7 9 11 12 14 16 19
Element Na Mg Al Si P S Cl
23 24 27 28 31 32 35.5
Limitations of Newland’s law of octaves: The law was applicable for only lighter
elements having atomic weights up to 40. Moreover, with the discovery of noble gases,
the eight element no longer remains a similar element.
Mendeleev’s Periodic table:
Mendeleev’s periodic law states “The properties of elements are periodic functions of
their atomic weights”.
Significance of Mendeleev’s periodic table:
1. Periodic table proved very useful in systematic study of element and their
compounds
2. Prediction of discovery of new elements
Mendeleev had left some gaps for elements yet to be discovered. He even
predicted the properties of such elements. Example: the elements
Scandium, Gallium and Germanium were not known at the time. He left
blank spaces for the and named them as eka born, eka aluminium and eka
silicon.
3. Mendeleev’s periodic table has helped in correcting the atomic weights in doubtful
cases.
Limitations of Mendeleev’s periodic table
1. The position of hydrogen atom is undecided

2. Position of isotopes of an element could not be explained.
20
Modern periodic table:
In 1913, Moseley proposed that atomic number is a more fundamental property of an

element that its atomic weight. The modern periodic law states “The physical and
chemical properties of elements are the periodic functions of their atomic
number”.
Long form of the periodic table has seven horizontal rows called periodic and eighteen
vertical columns called groups.
Number of elements in different periods:
Principal Orbitals
Electrons to be Number of
Periodic valence shell being
accommodated elements.
(n) filled up
First 1 1s 2 2
Second 2 2s2p 8 8
Third 3 3s3p 8 8
Fourth 4 4s3d4p 18 18
Fifth 5 5s4d5p 18 18
Sixth 6 6s4f5d6p 32 32
Seventh 7 7s5f6d7p 32 32
Classification of elements into s,p,d and f blocks
1. s – block elements: the elements in which the last electron enters the s –
subshell of their outermost energy level. Since s – subshell has only one orbital
which can accommodate only two electrons; therefore there are two groups of s –
block elements.
a. Group – I → alkali metals → ns1
b. Group – II → alkaline earth metals → ns2
c. General outershell configuration of s – block elements is ns 1 – 2
d. General characteristics of s – block elements:
i. They are soft metals
ii. They have low melting point and boiling point
iii. They show oxidation states of +1 and +2
iv. They are highly electropositive
v. They are good reducing agents (give electrons for reduction)
2. p – block elements: The elements in which the last electron enters the p sub
shell of their outermost energy level. Since, p sub shell can accommodate six
electrons. There are six groups of p – block elements. These are
a. Group – 13 → boron family – ns2np1
b. Group – 14 → carbon family – ns2np2
c. Group – 15 → oxygen family – ns2np3
d. Group – 16 → nitrogen family – ns2np4
e. Group – 17 → halogen family – ns2np5
f. Group – 18 → noble gases family – ns2np6
g. General outer shell configuration of p – block elements is ns2np 1 – 6
h. General characteristics of p – block elements:
i. They contain both semi – metal and non – metal
ii. They show variable oxidation states
iii. They are highly electronegative
iv. They form ionic as well as covalent compounds
21
Note: the elements s and p block are called Representative elements.
3. d - Block elements: The elements in which last electron enter the d – sub shell of
the penultimate energy level. Since d – sub shell has five orbitals, can
accommodate then electrons. General outer shell electronic configuration of d –
block elements (n – 1 )d 1 – 10 ns0 – 2 . Since the properties of these elements are
midway between s and p block elements, they are called transition elements.
a. first transition series contains ten elements from Scandium (Sc) to Zinc
(Zn)
b. second transition series contains ten elements from Yttrium (Y) to
cadmium (Cd)
c. third transition series contains ten elements from Lanthanium (La),
Hafnium (Hf) to mercury (Hg)
d. fourth transition series contains ten elements from Actinium (Ac),
Rutherfordiun (Rf) to Copernicium (Cn)
General characteristics of d – block elements
1. They are hard, malleable (converted into sheets) and ductile (drawn into
wires)
2. They have high melting and boiling point
3. They show variable oxidation states
4. They from coloured complexes
5. They exhibit paramagnetsim
6. They show catalytic properties
4. f – block elements: The elements in which the last electrons enters the f – sub
shell of the antipenltimate energy level. They general outermost electronic
configuration is (n – 2)f 1 – 14 (n – 1)d 0 -1 ns2. They consist of two series of
elements, each contain fourteen elements. In the first series, the filling of electron
takes place in the 4f sub shell. The elements of first series follow Lanthanum,
hence they are called Lanthanoids [cerium to lutetium). The elements of second
series follow Actinium, hence they are called actinoids. In the second series the
filling of electrons takes place in the 5f sub shell. The two series of elements are
called inner transition elements.
General characteristics of f – block element:
1. They are heavy metals

2. They have generally high melting and boiling points
3. They show variable oxidation states
4. Their compounds are generally coloured
5. They have high tendency to form complexes.
Periodicity: the periodical repetition of elements with similar properties after certain
regular intervals when the elements are arranged in order of increasing atomic number
is called periodicity.
Cause of periodicity: The physical and chemical properties are related to the
arrangement of electrons in their atom. The cause of periodicity in properties is due to
the repetition of similar outer most shell electronic configuration after certain regular
intervals. The important periodic properties are
22
1. Atomic radius
2. Ionisation enthalpy
3. Electron gain enthalpy
4. Electronegativity.
Atomic radius: It is defined as the distance between the centre of the

nucleus and outer most shell of electrons.
+ Atomic radius
Covalent radius: It is defined as the half of the distance between the H H

nuclei of two covalently bonded atoms of the same elements in a
molecule. Example: the bond length between two atoms in a hydrogen + 74pm
+
molecule is 74pm. therefore the covalent radius of hydrogen atom is
74/2 = 37pm. Covalent
radius
Metallic radius: It is defined as half of the inter nuclear distance between two adjacent
atoms in a metallic lattice.
Cation and anion: the removal of electron from an atom results in the formation of
cation whereas gain of an electron leads to an anion.
Ionic radius: It is defined as the distance between the nucleuses of an ion at a point up
to which the nucleus has influence on its electron cloud.
Radius of cation is always smaller than that of atom – give reason: a cation is
smaller than its parent atom because it has less number of electrons while its nuclear
charge remains the same. Hence size decreases due to greater force of attraction by the
nucleus on the electron. Example atomic radius of Na is 186pm where as its ionic
radius Na+ is 95pm.
Radius of anion is always larger than that of the atom – give reason: The size of an
anion will be larger that that of the parent atom because anion is formed by the addition
of electrons. Since the nuclear charge remains unchanged size of ion increases due to
less force of attraction by the nucleus on the electrons. Example atomic radius of
fluorine (F) is 64pm where as fluoride ion (F – ) is 136pm.
Isoelectronic species: Some atoms and ions which contain the same number of
electrons.
Example N3 –, O 2 – ,F –,Ne,Na+,Mg2+,Al3+ these species will have 10 electrons. Among

isoelectronic species, cation with greater positive charge will have smaller radius and
anion with greater negative charge will have the larger radius. Therefore in isoelectronic
species in the increasing order of their radii is Al3+< Mg2+ < Na+ < F – < O2 –.
Variation of atomic radius in the periodic table:
The atomic radius increases down the group because the number of principle shells
increases on moving down in the group and the distance between nucleus and
outermost shell increases. As a result the effective nuclear charge on the outermost
electron decreases and size of atom increases.
The size of atoms decreases along the period because electrons are added to the
orbitals of same shell. As a result the effective nuclear charge on the outermost electron
increases and size of atom decreases.
23
Ionization enthalpy: It is defined as “the amount of energy required in removing an
outermost electron from an isolated gaseous atom in its ground state”. This energy
is measured in the units of kJ/mol. X + I.E → X+ + e –
Factors affecting ionisation enthalpy:
1. Atomic radius: the larger the atomic size, lesser the ionization enthalpy and vice
versa.
2. Effective nuclear charge: ionization enthalpy increases with increases in the
effective nuclear charge.
3. Screening or shielding effect: In multi – electron atoms, 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 electrons in the inner shells tend to
shield outer electrons from the attractive force of the nucleus. This repulsive force
left by the valence electrons from the electrons present in the inner shells is
called screening or shielding effect. As the screening effect increases, the I.E
decreases.
4. Half filled or completely filled orbitals: The half filled and completely filled
orbitals give extra stability to an atom. As a result, ionisation enthalpy is high.
5. Penetration effect of electrons: In multi – electron atom, the electron of the s –
orbital has the maximum probability of being found near nucleus and this
probability goes on decreasing in case of p,d and f orbitals of the same shell.
Thus, within the same shell the penetration effect decrease in the order s > p > d
> f. Therefore, ionisation enthalpy is maximum to remove an electron from s –
orbital and minimum for f – orbital.
Variation of ionization enthalpy:
Ionization enthalpy increases across a period due to decrease in atomic size and
decrease on moving down in a group due to increase in atomic size.
Nitrogen has greater ionization enthalpy than oxygen. Give reason: this is because
nitrogen has half filled electronic configuration which is more stable. Therefore nitrogen
is have more ionization enthalpy than oxygen.
Electron gain enthalpy: It is defined as “the amount of energy released when an

electron is added to the outermost orbit of an isolated gaseous atom. X + e - → X –
Electron gain enthalpy decreases down the group due to increase in atomic size
and increases along a period from left to right due to decreases in atomic size and
effective nuclear force on the additional electron increases, as a result attraction by the
nucleus for an additional electron increases.
Fluorine has less electron gain enthalpy than chlorine: due to small size of fluorine
atom, adding an electron to the 2p orbital leads to a greater repulsion, hence less energy
is released compared to chlorine. The element with highest gain enthalpy is chlorine.
Electronegativity: it is the measure of the ability of an atom in a chemical compound to

attract shared electrons to itself. Fluorine is the most electronegative element.
Variation of electronegativity in the periodic table: It decreases down the group due
to increase in atomic size. This is due to decrease in effective nuclear charge. As a
result, the capacity of attracting the electrons pair decreases. Electronegativity increase
across a period due to decrease in atomic size.
24
Periodic trends in chemical properties:
Periodicity of valence:
Valence is the most characteristic property of the elements. The electrons present in the
outermost shell of an atom called valence electrons and the number of these electrons
determine the valence. In case of s and p block elements, the valance of an atom is
generally equal to either the number of valence electrons or equal to 8 – number of
valence electrons.
Group 1 2 13 14 15 16 17 18
Valence electrons 1 2 3 4 5 6 7 8
Valence 1 2 3 4 5,3 6,2 7,1 8,0
Periodic trends in valence of elements as shown by the formulas of their

compounds
Group 1 2 13 14 15 16 17 18
Formula of hydrides LiH CaH2 B2H6 CH4 NH3 H2O HCl there are
already stable
NaH AlH3 SiH4 PH3 H2S HBr
BH3 is not formed because it is an abnormal bond.
Formula of oxides Li2O MgO B2O3 CO2 N2O3 SO3 Cl2O7
Na2O CaO Al2O3 SiO2 N2O5
P2O3
Anomalous properties of second period elements:
Some elements of the second period show similarities with the elements of the third
period diagonally to each other. This similarity in property of elements placed diagonally
to each other is called diagonal relationship.
Example group 1 group 2 group 13 group 14
Second period Li Be B C
Third period Na Mg Al Si
Lithium resembles magnesium, beryllium resembles aluminium, boron resembles

silicon.
The anomalous behaviour of these elements is due to their small size, large
charge/radius (also known as polarising power) high electronegativity, absence of d –
orbitals.
Metals: Elements of group – 1, group – 2, d – block elements and f – block elements are
metallic in nature. They have low ionization enthalpy and lose electrons easily to form
cation. They are electropositive in nature. They have high melting and boiling points.
They are good conductors of heat and electricity. They are malleable and ductile. They
25
are solid at room temperature except mercury. Metallic property increases down the
group and decreases across a period.
Non – metals: Elements of group 13 to 18 are mostly non – metals. They have high
ionisation enthalpy and high electronegativity. They are poor conductors of heat and
electricity. Non – metals are solids or gases at room temperature. Most non – metals
solids are brittle, non – metallic property or character increases across a period and
decreases down the group.
Metalloids: A few elements like silicon, germanium, arsenic, antimony, tellurium, shows
properties of metals as well as non – metals. They are called metalloids or semi – metals.
Notation of IUPAC nomenclature of elements:
Digit 0 1 2 3 4 5 6 7 8 9
Name Nil Un bi tri Quad pent hex spet oct Enn
Abbreviation N U b t Q p h s o e
Nomenclature of elements with atomic number above 100
Atomic IUPAC official IUPAC

Name Symbol
number name symbol
101 Unnilunium Unu Mendelevium Md
102 Unnilbium Unb Nobelium No
103 Unniltrium Unt Lawrencium Lr
104 Unnilquadium Unq Rutherfordium Rf
105 Unnilpentium Unp Dubnium Db
106 Unnilhexium Unh Seaborgium Sg
107 Unnilseptium Uns Bohrium Bh
108 Unniloctium Uno Hassium Hs
109 Unnilennium Une Meitnerium Mt
110 Ununnillium Unn Darmstadtium Ds
111 Unununnium Uuu Rontgenium Rg
112 Ununbium Unb Copernicium Cn
113 Ununtrium Uut Nihonium Nh
114 Ununquadium Uuq Flerovium Fl
115 Ununpentium Uup Moscovium Mc
116 Ununhexium Uuh Livermorium Lv
117 Ununseptium Uus Tennessine Ts
118 Ununoctium Uuo Oganesson Og
26
Chemical Bonding and

4 Molecular Structure
The attractive force which holds various constituents particles i.e., atoms, ions or
molecules together in different chemical species is called a chemical bond.
The following are the theories or concepts which explains why constituent
particles will
undergo chemical bonding
1. Kossel—Lewis approach.
2. Valence shell electron pair repulsion theory [VSEPR]
3. Valence band theory [VBT]
4. Molecular orbital theory. [MOT]
Kossel—Lewis approach to chemical bonding: In 1916 developed an important theory

of chemical combination between atoms known as electronic theory of chemical
bonding. According to this, atoms can combine either by transfer of valence electrons
from one atom to another or by sharing of valence electrons in order to attain their octet
state i.e., stable outer shell configuration of eight electrons (noble gas configuration).
This is known as octet rule.
Lewis symbols: It is the simple notations to represent valence electrons in an atom.

The main significance of Lewis symbols is to represents the number of valence electrons
in an atom which help to calculate the common or group valence of the element which is
equal to the number of dots in Lewis symbols or eight minus the number of dots of
valence electrons.
The following are some examples of representing Lewis symbols of few elements or
compounds.
27
Limitations of octet rule-
1. 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- LiCl
,BeCl2 , BCl3
2. Odd-electron molecules: In molecules with an odd number of electrons like nitric

oxide, NO and nitrogen dioxide, the octet rule is not satisfied for all the atoms.
3. 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. Some
of examples of such compounds are: PF5, SF6.
4. This theory does not account for the shape of molecules.
Formal charge: The formal charge on an atom in polyatomic molecule or ion may be
defined as the difference between the number of valence electrons of that atom in an
isolated or free state and the number of electrons assigned to that atom in the Lewis
structure. The formula for formal charge is
Formal charge = [total no. of valence electrons in the free atom] - [ total no. of lone pair
electrons] - 1/2 [total no. of shared electrons]
Calculate the formal charge for ozone molecule:
The formal charge ‘O’ atom marked 1 = 6—2—1/2 (6) = +1
The formal charge ‘O’ atom marked 2 = 6—4—1/2 (4) = 0
The formal charge ‘O’ atom marked 3 = 6—4—1/2 (6) = —1
The lowest energy structure is the one with the smallest formal charges on the atoms.
The formal charge is a factor based on a pure covalent view of bonding in which
electrons pairs are shared equally by neighbouring atoms.
Electrovalent bond or Ionic Bond: The chemical bond as result of transfer of electron
from one atom (electropositive) to another atom (electronegative). Ionic bonds will be
formed more easily between elements with
comparatively low ionization enthalpies and
elements with comparatively high negative value of
electron gain enthalpy. Most ionic compounds have
cations derived from metallic elements and anions
from non-metallic elements.
28
Factors for formation of ionic bond
1. Low ionization enthalpy of electropositive atom
2. High negative electron gain enthalpy of the electronegative atom
3. High lattice enthalpy of the ionic compound formed.
Covalent bond: The bond formed between two atoms by mutual sharing of electrons
between them so as to complete their octets or duplets. When two atoms share one
electron pair they are said to be joined by single bond. If two atoms share two
electron pairs of electrons, the covalent bond between them is called double bond.
If two atoms share three electron pairs of electrons, the covalent bond between
them is called triple bond.
Favorable conditions for formation of covalent bond:
1. High ionization enthalpy of combining elements.
2. Nearly equal electron gain enthalpy and equal electro– negativity of combining
elements.
3. High nuclear charge and small atomic size of combining elements.
Covalency: The number of electrons contributed by an atom to the shared paired

(bonded pair) during the formation of covalent bond.
Example:
1. In the formation of Cl2 molecule, the covalency of each Cl atoms is one.
2. In the formation of O2 molecule, the covalency of each O atoms is two.
3. In the formation of N2 molecule, the covalency of each N atoms is three.
Bond parameters:
Bond length is defined as the equilibrium distance between the nuclei of two bonded
atoms in a molecule. The bond length is measured by spectroscopic, X—ray
diffraction and electron—diffraction techniques. It is expressed in pico—meter [pm]
or in A0.
Covalent radius: It is measured as the radius of an atom’s core which is in contact

with the core of an adjacent atom in a bonded situation.
van der Waals radius: It represents the overall size of the atom which includes its
valence shall in a non bonded situation.
29
Bond Angle: It is defined as the angle between the orbital containing bonding electron
pairs around the central atom in a molecule/complex ion. It gives some idea
regarding the distribution of orbital around the central atom in a molecule/complex
ion and hence it helps us in determining its shape
Bond enthalpy: It is defined as the amount of energy required to break one mole of
bonds of a particular type between two atoms in a gaseous state. The unit of bond
enthalpy is kJ mol–1
Bond Order : The Bond Order is given by the number of bonds between the two atoms
in a
molecule. E.g.: Bond Order of O2= 2. With increase in bond order, bond enthalpy
increases and bond length decreases. If two or more molecules or ions are having
same bond order them they are called as isoelectronic molecules or ions.
Example F2 and O22— which are having bond order one, N2, CO and NO+ are
isoelectronic because they have same bond order of 3.
Resonance: According to the concept of resonance, whenever a single Lewis structure

cannot describe a molecule accurately, a number of structures with similar
energy, positions of nuclei, bonding and the non- bonding pairs of electrons are
taken as the canonical structures of the hybrid which describes the molecule
accurately.
Characteristics of resonance:
1. Resonance stabilizes the molecule, as the number of resonating structures

increases, the stability also increases.
2. Resonance changes the bond length
3. The difference in energy between the actual structure and the most stable
canonical structure is called resonance energy. Greater the resonance energy,
stable will be the molecules.
Polarity of bonds: In case of heteronuclear molecules like HCl, the shared pair of
electron between the two atoms gets displaced more towards chlorine since the
electronegativity of chlorine is far greater than that of hydrogen. The resultant
covalent bond is called a polar covalent bond.
Non—polar bond: When a covalent bond is formed between two similar atoms, the
shared pair of electrons is equally attracted by the two atoms, so that electron
pair is exactly between the two nuclei.
30
Dipole moment: As a result of polarization, the molecule possesses the dipole moment
which can be defined as the product of charge and the distance between the centers
of positive and negative charge. It is usually designated by a Greek letter = µ‘.
Mathematically, it is expressed as follows: Dipole moment (µ ) = charge (Q) X
distance of separation (r). The SI unit for dipole moment is Debye (1D) whose
value is 1D = 3.33564 x 10—30C m. The dipole moment is a vector quantity i.e., it has
both magnitude and direction.
Factors on which dipole moment of diatomic molecules depends:
1. The individual bond dipoles
2. The spatial arrangement of bonds.
Reasonable type
1. The dipole moment of BeF2 is zero: because the two equal bond dipoles are acting
in opposite directions which cancel each other.
2. The dipole moment of BF3 is zero: because the resultant of any two bond dipoles is
equal and opposite of the third one.
3. The dipole moment of NH3 (4.9 x 10 –30Cm) is higher than NF3(0.8 x 10—30Cm): This
is because in NH3, the orbital dipole is due to the lone pair is in the same direction as
the resultant dipole moment of the three N—H bonds, where as in NF3, the orbital
dipole is in the opposite direction to the resultant dipole moment of the three N—F
bonds, where by dipole moments gets partially cancelled.
Fajans Rules: The partial covalent character of ionic bonds was explained by Fajans in
terms of the following rules.
1. The smaller the size of the cation and the larger the size of anion, the greater the
covalent character of an ionic bond.
2. The greater the charge on the cation, greater the covalent character of the ionic bond
3. For cations of the same size and charge, the ion with electronic configuration (n—
1)dnns0 is more polarizing than the ion with a noble gas configuration (ns2np6).
Valence Shell Electron Pair Repulsion Theory [VSEPR]
This theory was proposed by Sidgwick and Powell and later modified by Nyholm and
Gillespie . The main postulates of this theory are:
1. The shape of the molecule depends on the number of valence shell electron pairs
around the central atom.
2. The valence shell electron pairs repel each other.
3. In order to reduce the repulsion, the electron pairs stay at maximum distance.
4. Presence of lone pairs of electron cause distortion in the expected geometry of the
molecule.
31
5. The repulsion between two lone pairs of electrons is different from those between two
bond pairs or between a lone pair and bond pair. The repulsion decreases in the
order lone pair—lone pair > lone pair—bond pair > bond pair—bond pair.
6. As the angle between the electron pairs increases, the repulsion decreases.
According to this theory the molecules are broadly classified into two type
1. Molecules containing only bond pairs of electrons
2. Molecules containing both bond pairs and lone pairs of electrons.
The geometry of the molecules containing only bond pairs of electrons on the
basis of VSEPR theory
Types of Total no. of Bond angle Shape Example Structure

molecule VSEPs
AB2 2 1800 Linear BeCl2, HgCl2
AB3 3 1200 Planar triangle BF3, BCl3
AB4 4 1090 28’ Tetrahedron CH4, NH4+
AB5 5 1200 and 900 Trigonal PCl5

bipyramid
AB6 6 900 Octahedron SF6

32
The geometry of the molecules containing both bond pairs and lone pairs of electrons on
the basis of VSEPR theory.
No. of No. of non Arrangement

Molecular
bonding pair bonding pair of electron Shape Examples
type
of electrons of electrons pair
AB2F Two One Bent SO2, O3
Trigonal
AB3F Three One NH3
pyramidal
AB2F2 Two Two Bent H2O
AB4F Four One Sea – saw SF4
AB3F2 Three Two T –shape ClF3
Square
AB5F Five One BrF5
pyramid
Square
AB4F2 Four Two XeF4
planar
Shape of ammonia molecule on the basis of VSEPR theory:
In ammonia, the central atom N has five valence electrons.

Among these electrons, three are used for the formation of
bonds with hydrogen atoms and the remaining two electrons
stay as lone pairs. So there are four VSEPs. Hence the
expected shape of the molecule is tetrahedral, but due to the
presence of lone pairs, the shape is distorted to Trigonal bipyramid with bond angle of
1070
Shape of water molecules by VSEPR theory:
In water, the central atom O has six valence electrons. Two of them are used for
the formation of bonds with hydrogen atoms and the remaining four electrons stay
as lone pairs. So there are four VSEPs. Hence the expected shape of the molecules
is tetrahedral, but due to the presence of two lone pairs of electrons, the shape is
distorted bent or angular or inverted ’v’ shaped with bond angle 104.50.
33
Orbital overlapping: The important characteristics of orbital overlapping are
1. A covalent bond is formed by the overlapping of half filled atomic orbitals present in
the valence shell of atoms.
2. The overlapping orbitals should contain electron with opposite spin.
3. As a result of overlapping, the electrons get paired and a stable covalent bond is
formed.
4. The strength of a covalent bond depends on the extent of overlapping. The greater the
extent of overlapping, the stronger will be the covalent bond formed.
The overlapping of atomic orbitals can be happened in two ways :
1. Axial overlapping orbitals: the overlapping of atomic orbitals takes place along inter
nuclear axis which leads to formation of strong bond called sigma bond.
2. Lateral overlapping of orbitals: The overlapping of atomic orbitals takes place along
perpendicular to the inter nuclear axis which leads to formation of weak bond called
pi bond.
Sigma bond Pi—bond

Overlapping of atomic orbitals take Overlapping take place perpendicular
place along inter nuclear axis to the inter nuclear axis
Strong bond Weak bond
This bond form along with sigma
This bond form without pi—bond
bond
This bond is formed when orbitals s– This bond is formed when orbitals
s, s—p, p—p overlaps. p—p overlaps.
Hybridization: The process of inter mixing atomic orbitals having slightly different
energies to form new orbitals having equivalent energy and identical shape. The new
orbitals formed are called hybrid orbitals.
Characteristics of hybridization:
1. The number of hybrid orbitals formed is equal to the number of atomic orbitals
undergo hybridization.
2. The hybrid orbitals are always equivalent in energy and with identical shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.
4. They hybrid orbitals are directed to some fixed positions in space. So the type of
hybridization gives the shape of the molecule.
34
Important conditions of hybridization:
1. The orbitals present in the valence shell of the atom are hybridized.
2. The orbitals undergoing hybridization should have almost equal energy.
3. Promotion of electrons is not an essential condition before hybridisation.
4. Completely filled orbitals of valence shell can also take part in hybridisation.
sp3 hybridization of methane molecule (CH4)
In methane the central atom is “C” with electronic configuration of

1s22s22p2. during bond formation, one of the electron of 2s orbital is
shifted to 2p orbital, thereby showing the tetra covalency for carbon
1s22s12px12py12pz1 showing sp3 type of hybridization. These orbitals are
directed to the four corners of regular tetrahedron with bond angle of
109028’. Each of these sp3 orbitals of carbon overlap with 1s orbitals of
hydrogen to form C—H bond. In this structure, s—character is 25% and p—character is
75%.
sp3 hybridization of ethane molecule (C2H6)
In ethane each carbon atom undergoes sp3 type of hybridization, out of four sp3 orbitals,
one of each C atom overlap axially to C—C sigma band and remaining there sp3 orbitals
of each carbon atom overlap with 1s orbitals of hydrogen atom to form six C—H sigma
bonds.
sp3 hybridization of ammonia molecule (NH3)
In ammonia the central atom is nitrogen having the electronic

configuration 1s22s22p3. the one s—orbital and three p— orbitals of N
undergo sp3 hybridization to form four sp3 hybrid orbitals is occupied by a
lone pair and the other three sp3 hybrid orbitals overlap with 1s orbital of
hydrogen to form three N—H bonds. Due to the greater repulsion between
lone pair and bond pairs, the shape is distorted to pyramidal and the bond angle
becomes 1070.
sp3 hybridization of water molecule (H2O)
In water the central atom is oxygen having the electronic configuration

1s22s22p4. Now the one s—orbital and three p—orbitals of oxygen undergo sp3
hybridisation to form four sp3 hybrid orbitals. Two of these sp3 hybrid
orbitals are occupied by lone pairs and the other two sp3 hybrid orbitals
overlap with 1s orbital of hydrogen to form two O—H bonds. Due to the greater
repulsion between lone pairs, the shape is distorted to angular shape or bent structure
or inverted ’v’ shape and the bond angle becomes 104.50.
35
sp2 hybridization of boron trichloride molecule (BCl3)
In boron trichloride the central atom is Boron has the electronic

configuration 1s22s22p1. in the excited state, one of the 2s electrons is
promoted to vacant 2p orbital. So the configuration becomes 2s1 2p2. now
one s—orbital and two p—orbitals undergo hybridisation. The three
hybrid orbitals formed overlap with 2p orbitals of Cl to form three B—Cl
bonds. Since the hybridization is sp2 the shape of the molecule is planar triangular with
bond angle 1200.
sp2 hybridization of ethene molecule (C2H4):
In ethene, each C atom undergoes sp2 hybridisation. Out of the three sp2 hybrid orbitals,
one of each C atom overlaps axially to form a C—C sigma bond, the
remaining two sp2 hybrid orbitals of each C overlap with the 1s orbital
of H to form four C—H sigma bonds. Now each C atom has one
unhybridized p—orbital with overlaps laterally to form a pi bond. Thus
there are five sigma bonds and one pi bond in ethene with bond angle is 1200.
sp hybridization of ethyne molecule (C2H2)
In acetylene, each C atom undergoes sp hybridization. Out of the two sp hybrid orbitals,
one of each C overlaps axially to form a C—C sigma bond. The
remaining two sp hybrid orbitals of each C overlap with the 1s
orbital of H to form two C—H sigma bonds. Now each C atom has
two unhydridizde p—orbitals, which overlap laterally to form two pi
bonds. Thus the molecule has linear shape with bond angle of
1800. Here there are three sigma bonds and two pi bonds in ethyne.
sp hybridization of beryllium dichloride molecule (BeCl2)
In BeCl2 the central atom Be has the electronic configuration 1s22s2.

in the excited state, one of the 2s electrons is promoted to 2p level.
So the configuration becomes 1s22s12p1. Now one s—orbital and one
p—orbital undergo sp hybridisation to form two new sp hybrid
orbitals. Each of these hybrid orbitals overlaps with 2p orbitals of Cl to form two Be—Cl
bonds. So the shape of the molecule is linear with bond angle 1800.
sp3d hybridization of phosphorus pent chloride molecule (PCl5)
In PCl5 the central atom is phosphorus, whose electronic configuration is

1s22s22p63s23p3 . To satisfy the penta valency of phosphorus, one of the 3s
electron is promoted to 3d orbital, thereby one 3s, three 3p and one 3d orbitals
are involved to form the five sigma bonds to show sp3d hybridization by directing
the five orbitals to the corners of Trigonal bipyramid with the bond angle of 1200 and
900.
36
sp3d2 hybridization of sulphur hexafluoride molecule (SF6)
In SF6 the central sulphur atom has the ground state outer electronic
configuration [Ne]3s23p4. In the excited state one electron each from 3s
and 3p orbitals are promoted to 3d level. Now one 3s—orbital, three
3p—orbital and two 3d—orbtials undergo sp3d2 hybridization. These
hybrid orbitals overlap with p—orbitals of fluorine atoms to form six S—
F sigma bonds. SF6 is octahedral geometry with bond angle of 900.
Molecular orbital theory [MOT]: This theory was developed by F. Hund and R. S.
Mulliken. The important postulates of this theory are:
1. The electrons in a molecule are present in the various molecular orbitals as the
electrons of atoms are present in the various atomic orbitals.
2. The atomic orbitals of comparable energies and proper symmetry combine to form
molecular orbitals.
3. In a molecular orbital it is influenced by two or more nuclei depending upon the

number of atoms in the molecule.
4. The number of molecular orbital formed is equal to the number of combining atomic
orbitals. When two atomic orbitals combine, two molecular orbitals are formed. One
is known as bonding molecular orbital while the other is called antibonding
molecular orbital
5. The bonding molecular orbital has lower energy and hence greater stability than the
corresponding antibonding molecular orbital
6. Just as the electron probability distribution around a nucleus in an atom is given by

an atomic orbital, the electron probability distribution around a group of nuclei in a
molecule is given by a molecular orbital
7. The molecular orbitals like atomic orbitals are filled in accordance with the aufbau
principle obeying the Pauli’s exclusion principle and the Hund’s rule
Formation of molecular orbitals—Linear Combination of Atomic Orbitals theory

(LCAO): Molecular orbitals are formed by the combination of atomic orbitals by an
approximate method known as Linear combination of atomic orbital. According to this
theory, the combinations of atomic orbitals take place by addition and subtraction of
wave functions of atomic orbitals. The MO formed by the addition of A.Os is called the
bonding molecular orbital (BMO) and by the subtraction of A.Os is called the anti—
bonding molecular orbital (ABMO). The electron density in a BMO is located between the
nuclei of the bonded atoms. So the repulsion between the nuclei is very low. Therefore a
BMO always possess lower energy than the combining AOs. While in the case of an
ABMO, most of the electron density is located away from the space between the nuclei.
There is a nodal plane between the nuclei and hence the repulsion between the nuclei is
high. So an ABMO possess higher energy than the combing AOs. ABMO is denoted by
using an asteric (*) mark.
37
Conditions for the combination of atomic orbitals to form molecular orbitals.
1. The combining AOs must have the same or nearly the same energy.
2. The combining AOs must have the same symmetry about the molecular axis.
3. The combining AOs must overlap to the maximum extent.
The electronic configuration, bond order, magnetic property and energy level
diagram:
Hydrogen molecule (H2):
1. Electronic configuration : σ1s2 σ*1s
2. Bond order = 1/2 [Nb—Na] = 1/2 (2—0) = 1
3. Magnetic property: It is diamagnetic in nature due to absence of unpaired electrons

in the orbitals.
4. Energy level diagram: An energy level diagram for the combination of two atomic
orbitals of hydrogen to form the MOs in the hydrogen molecule.
Helium molecule (He2):
1. Electronic configuration: σ1s2 σ*1s2
2. Bond order = 1/2 [Nb—Na] = 1/2 (2—2) = 0. Since the B.O is zero, helium molecule
does not exist.

in the orbitals.
orbitals of to form the MOs in the He molecule.
Lithium molecule (Li2):
1. Electronic configuration: σ1s2 σ*1s2 σ2s2 σ*2s
2. Bond order = 1/2 [Nb—Na] = 1/2 (4—2) = 1.

in the orbitals.
orbitals of to form the MOs in the lithium molecule.
Carbon molecule (C2):
1. Electronic configuration: σ1s2 σ*1s2 σ2s2 σ*2s2 π2px2 = π2py2
2. Bond order = 1/2 [Nb—Na] = 1/2 (6—2) =2.

38
in the orbitals.
orbitals of to form the MOs in the carbon molecule.
Oxygen molecule (O2):
1. Electronic configuration : σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 [π2px2 = π2py2][π*2px1 = π*2py1]
2. Bond order = 1/2 [Nb—Na] = 1/2 (10—6) =2.
3. Magnetic property: It is paramagnetic in nature due to presence of unpaired

electrons in the anti bonding molecular orbitals.
orbitals of to form the MOs in the oxygen molecule.
Hydrogen bond: The weak attractive force between hydrogen atom of one molecule and
electronegative atom like F, O or N of the same or different molecule is termed as
hydrogen bond. It is weaker than a covalent bond but stronger than van der Waal’s
force.
Types of hydrogen bond:
1. Inter molecular hydrogen bond: it is the hydrogen bond formed by hydrogen

atom of one molecule and the electronegative atom of another molecule. Example
HF, H2O.
2. Intra molecular Hydrogen bond: it is the hydrogen bond formed by hydrogen

atom of one molecule and the electronegative atom of same molecule. Example:
o—nitrophenol.
Cause for hydrogen bonding: When hydrogen is bonded to a strongly electronegative

atom X, the shared electron pair is shifted more towards X. so hydrogen atom gets a
slight positive charge (δ+) and the electronegative atom gets a slight negative charge (δ—).
This results in the formation of polar molecule. The electrostatic force of attraction
between these polar molecule is called as H bond.
39
5 State of Matter
INTERMOLECULAR FORCES: Intermolecular forces are the forces of attraction and

repulsion between interacting particles (atoms and molecules). Attractive intermolecular
forces are known as van der Waals forces. These forces include dispersion forces or
London forces, dipole-dipole forces, and dipole-induced dipole forces. A particularly
strong type of dipole-dipole interaction is hydrogen bonding.
1) Dispersion Forces or London Forces: Atoms and non-polar molecules are

electrically symmetrical and have no dipole moment. But in an atom, at a particular
moment, the nucleus is shifted towards one side and the electrons, to the other side.
So a temporary dipole (momentarily dipole) is created. This results in the
development of instantaneous dipole on the adjacent atom for a very short time.
These temporary dipoles of atoms attract each other. This force of attraction between
temporary dipoles is termed as London forces or dispersion forces. These forces are
important only at short distances.
2) Dipole - Dipole Forces: Dipole-dipole forces act between the molecules possessing
permanent dipole (polar molecules). These molecules interact with the neighbouring
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. E.g.: HCl
Dipole–Induced Dipole Forces: This type of attractive forces operates between the polar
molecules and the non-polar molecules. 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. The attraction between these
molecules is termed as dipole – induced dipole force.
Thermal energy:
1. It is the energy of a body which arises due to the motion of the atoms /molecules
present in it.
2. It is directly proportional to the temperature of the substance.
3. It is the measure of the average kinetic energy of the particles of the matter
4. It is also responsible for the moment of the particles, which is known as thermal
motion of the particles.
Intermolecular forces and thermal interactions: The physical state of the matter
depends mainly on two factors i.e., intermolecular forces and thermal energy.
40
1. When molecular interactions are very weak, molecules will not combined to form
liquid or solid until the thermal energy is reduce by decreasing the temperature.
2. Gases do not liquefied only by compression, even though the molecular interactions
are maximum. But when the thermal energy of the molecule is reduced by lowering
the temperature, the gases are easily liquefied.
Gaseous state: It is the one of the physical state of matter which is characterized as
follows
1. They are highly compressible
2. They exert pressure equally in all directions.
3. They have lower density than solids and liquids.
4. They don’t have fixed volume and shape but takes the shape of the container by
occupying volume of the container.
5. They mix evenly and completely in all proportions without any mechanical aid.
Gas laws:
1) Boyle’s Law (Pressure – Volume Relationship): It states that at “constant

temperature, the volume of a fixed mass of gas is inversely proportional to its
pressure”.
Mathematically, P α 1/V or P = k x 1/V,
where k is the proportionality constant. Or, PV = k, a proportionality constant
Note: The value of proportionality constant ‘k’ which depends on the following factors
1. The amount of the gas.
2. Temperature of the gas.
3. The units in which p and V are expressed.
Consider a fixed amount of gas at constant temperature T. Let V1 & P1

are its initial volume and pressure respectively. Let the gas undergoes expansion, so
that its final volume and pressure becomes V2 and P2. Then according to Boyle’s law,
P1V1 = P2V2
Graphical representation of Boyle’s law:
When a graph of pressure vs volume is draw at different temperature

for a given mass of gas, then value of ‘k’ for each curve is different,
41
because it varies with temperature. It should be noted that higher volume of the gas is
doubled if the pressure is halved at a given temperature.
The curve of pressure vs volume at different constant temperature is known as

isotherm.
When p vs 1/V is drawn we get a straight line passing through origin, but at high
pressure, gases deviate from the Boyle’s law and such conditions a straight line will not
obtained in the graph.
Derive a relationship between pressure and density of a gas using Boyle’s law:
From Boyle’s law p = k/V ————(1) From definition of density d = m/V ———
—(2)
From equation (1) V = k/p, therefore substituting the value of ‘V’ in equation (2) we get
d = (m/k)p = k’p i.e, d  p
From the above equation it is clear that density of the gas is directly proportional to
pressure
Charles’ Law: The law states that “at constant pressure, the volume of fixed
mass of a gas is directly proportional to its absolute temperature”.
Derivation for Charles’ law: Charles’ and Gay Lussac’s independently identified that
for every rise in one degree of temperature, the volume of the gas increased by 1/273.15
times the original volume of the gas at 00C.
If V0 is the volume of the gas at 00C and Vt is the volume at t0C, then
—————-(1)
If Tt = 273.15 + t and T0 = 273.15, then the above equation (1) becomes

i.e., V  T i.e., Charles law is provide.
Note:
1. Kelvin temperature scale: It is the scale which uses to measure the

temperature in Kelvin whose value starts from the value of 273.15.
2. Kelvin temperature scale is also called as Thermodynamic scale or

Absolute temperature scale.
42
3. Absolute zero: It is the lowest hypothetical or imaginary temperatures at which gases
are occupy zero volume. The value of absolute zero is —273.150C.
4. Isobar: These are the line obtained when a graph is drawn between volume vs
temperature.
5. All gases obey Charles’ law only at very low pressure and high temperature.
6. For a given gas at any pressure, when a graph of volume and temperature is draw, we
always gets the straight line which extending to zero volume, each line intercepts the
temperature axis at—273.150C and slope of lines at different pressure are different.
Gay Lussac’s law (Pressure—temperature Relationship)
The law states that “ at constant volume, pressure of a fixed amount of a gas varies
directly with the temperature”.
P α T when V = constant.
The graphical lines obtained when pressure vs temperature is
drawn at constant molar volume is known as isochore.
Avogadro Law (Volume—Amount Relationship)
The law states that “equal volumes of all gases under the same conditions of
temperature and pressure contain equal number of molecules”.
V α n when T and P are constant.
Note:
1. The number of molecules in one mole of gas is found to be 6.022 x 1023 which is
known as Avogadro constant.
2. Standard temperature and pressure i.e., STP conditions means 273.15K (00C) and 1
bar (105Pa)
3. The volume occupied by any gas at STP conditions is known as Molar volume, whose
value is equal to 22.71098L/mol.
Ideal gas equation: The combining three basic laws into form a single equation which
is known as ideal gas equation. i.e., from
Boyle’s law: at constant temperature P α 1/V
Charles’ Law: at constant pressure VαT

43
Avogadro law: at constant pressure and temperature V α T
Therefore: V α nT/P => V = RnT/P => PV = nRT
Where R is called as universal gas constant and equation is called as ideal gas equation.
Calculation of the value of universal gas constant using ideal gas equation.
𝑃𝑉 10 × 22.7 × 10
𝑅= = = 8.314𝐽𝐾 𝑚𝑜𝑙
𝑛𝑇 1 × 273.15
Note:
1. At STP conditions used earlier (0 °C and 1 atm pressure), value of R is 8.20578 × 10–2
L atm K–1 mol–1.
2. Equation of state: Ideal gas equation is a relation between four variables and it
describes the state of any gas.
3. Combined gas law: If temperature, volume and pressure of a fixed amount of gas vary
from T1, V1 and p1 to T2, V2 and p2 then we can write
𝑝 𝑝
=
𝑇 𝑇
Density and Molar Mass of a Gaseous Substance
Consider the ideal gas, with ‘n’ number of moles of gas occupying a volume of V dm3 at
STP condition. Therefore the ideal gas equation is
PV = nRT
But n = m/M where ’m’ is the mass of the gas and ’M’ is the molar mass of the gas,
therefore
Where‘d’ is the density of the gas, at STP conditions i.e., molar mass of the gas is
directly proportional to density of the gas.
Dalton’s law of partial pressure: The law states that “ the total pressure
exerted by the mixture of non-reactive gases is equal to the sum of the partial
pressures of individual gases” . pTotal = p1+p2+p3+......(at constant T, V)
Note:
1. Partial pressure: In a mixture of gases, the pressure exerted by the individual gas
44
2. Aqueous tension: Pressure exerted by saturated water vapour.
3. Pressure of dry gas can be calculated by subtracting vapour pressure of water from
the total pressure of the moist gas which contains water vapours
“pDry gas = pTotal – Aqueous tension” .
Partial pressure in terms of mole fraction:
Let us consider three gases, A, B and C are enclosed in the volume V at a

temperature T. if pA, pB and pC are the partial pressures of exerted by the individual
gases respectively.
Applying the ideal gas equation PV = nRT we have
Therefore partial pressure of gas A =
Partial pressure of gas B =
Partial pressure of gas C =
According to Dalton’s law of partial pressure, total pressure of the gaseous mixture is
given by
pTotoal = pA + pB + pC
Therefore
Divide the partial pressure of gas A by total pressure of the gases mixture we get
Therefore
Kinetic theory of gases: The following are the postulates of kinetic theory of
gases i.e.,
1. All the gases are made out of tiny particles with a tiny mass known as molecules.
2. All molecules will travel in straight line motion.
3. All gas molecules will have elastic type of collisions.
4. The total pressure of the gas is equal to number of collisions of the gas molecules
5. There is no intermolecular force of attraction between the gas molecules.
6. The volume occupied by the individual gas molecules is negligible as compared with
total volume occupied by the gas.
45
7. The kinetic energy of the gas is directly proportional to absolute temperature.
Ideal and Real gases:
Ideal gas: It a hypothetical gas which obeys PV = nRT equation under all conditions.
Real gas: It a gas which obeys PV = nRT equation under certain conditions.
Note:
1. Real gases deviates from Ideal gas behavior under high pressure and low temperature.
2. Real gases behavior as Ideal gas under low pressure and pressure temperature.
3. Hydrogen gas and Helium gas are considered to be reference ideal gases where as all
other gases are considered to be real gases.
van der Waal’s equation for real gases:
van der Waal’s tries to explain why the real gases deviates from the ideal gas behavior
by make two corrections in the assumption of kinetic theory of gases i.e.,
1. There is no force of attraction between the molecules of a gas — Pressure

correction.
2. Volume of the molecules of a gas is negligible small in comparison to the space

occupied by the gas — Volume correction
Pressure correction: It has been seen that at high pressure
1. Gas molecules come close to each other and develops the intermolecular force
attraction between them.
2. The molecules do not strike the walls of the container with full impact because these
are dragged back by the other molecules due to molecular attractive forces, thereby
the effect of pressure exerted by the molecules on the walls of the container is lower
than the pressure exerted by the ideal gas. Therefore Where ‘a’
is constant
Volume correction: The volume occupied by the molecule also becomes significant
because instead of moving in volume V, these are now restricted to volume (V—nb)
where ‘nb’ is approximately the total volume occupied by the molecule.
Therefore taking these conditions for pressure and volume the ideal gas equation
can be written as Where ‘a’ and ‘b’ are constants.
46
Note:
1. The value of ’a’ is the measure of magnitude of intermolecular attractive forces within
the gas.
2. The value of ’a’ is independent of temperature and pressure.
3. The real gas shows ideal gas behaviour only when pressure approaches zero.
Compressibility factor (Z):
1. It is the factor which is used to measure the deviation of real gases from the ideal
behaviour.
2. Compressibility factor is defined as the ratio of product of pV and nRT.
3. Significance of compressibility factor (Z)
a. if Z = 1, then the gas behaviour as ideal gas under all temperature and
pressure
b. if Z >1, the gases are difficult to compress, at high pressure
c. if Z < 1, at intermediate pressures.
d. The compressibility factor is the ratio of actual molar volume of a gas to the
molar volume of it, if it were an ideal gas at that temperature and pressure.
Boyle’s temperature or Boyle’s point:
1. Definition: The temperature at which a real gas obeys ideal gas law over an
appreciable range of pressure.
2. The value of Boyle’s point depends on the nature of the gas.
3. Above Boyle’s point: The real gases shows positive deviation from ideal behaviour
and compressibility factor value is greater than one (Z >1) where forces of attraction
between the molecules are very feeble.
4. Below Boyle’s point: The real gases first show decrease in value of Z with increasing
in pressure, reaches to minimum value and increases in pressure the value of Z
increases continuously.
47
Liquid State:
1. It is the one of the physical state of matter where the intermolecular forces are
stronger than gaseous state.
2. They doesn’t have definite shape.
3. They have definite volume because molecules do not separate from each other.
4. Vapour pressure: The vapor pressure of a liquid is the equilibrium pressure of a

vapor above its liquid that is, the pressure of the vapor resulting from evaporation of
a liquid above a sample of the liquid (or solid) in a closed container. This vapour
pressure is temperature dependent physical quantity.
5. Boiling point: The temperature at which vapour pressure of liquid is equal to the
external pressure.
6. Normal boiling point: The temperature at which a liquid gets boiled when pressure is
1 atm.
7. Standard boiling point: The temperature at which a liquid gets boiled when pressure
is 1 bar.
Note:
1. Standard boiling point of the liquid is slightly lower than the normal boiling point,
because 1 bas pressure is slightly less than 1 atm.
2. Standard boiling point of water is 99.60 C where as normal boiling point of water is
1000C.
3. The liquids at high altitudes boil at lower temperature than at sea level because at
higher altitude atmospheric pressure is low.
4. Pressure cooker is used for cooking food on hills because water boils at low
temperature.
5. In hospitals surgical instruments are sterilized in autoclaves in which boiling point of

water is increased by increasing the pressure above the atmospheric pressure by
using a weight covered the vent.
48
Surface tension:
1. Definition: It is the force acting per unit length perpendicular to the line drawn on
the surface liquid.
2. Its SI units of it is N/m. It is denoted by Greek letter γ.
3. Surface energy: The energy required to increase the surface area of a liquid by one
unit. Its dimensions are J/m3.
4. The magnitude of the surface tension depends on the intermolecular forces of

attraction i.e., if intermolecular forces of attraction is more, surface tension of the
liquid is also more.
5. Surface tension of a liquid also depends on temperature i.e., if the temperature is

increased, the kinetic energy of the molecules also increased due to which
effectiveness of intermolecular attraction decreases, thereby surface tension of the
liquid decreases.
Reasons for following properties:
 Mercury drops as spherical in shape: This is because when surface area is minimum,
then lowest will be energy for a liquid, thereby Hg drops takes the shape of spherical.
 Glass edges becomes smooth on heating: On heating the glass melts and the surface of
the liquid tends to take the rounded shape at the edges, which makes the edges of
glass to become smooth on heating. This process is called fire polishing of glass.
 Liquids tends to rise in the capillary: This is due to surface tension.
 Liquids wets the things/objects: This is due to spreading of liquid across their surfaces
as a thin film.
 Moist soil grams are pulled together: This is due to surface area of thin film of water is
reduced.
 On the surface, droplets are slightly flattened by the effect of gravity, but in gravity free
environments drops are perfectly spherical in nature.
Viscosity:
1. Definition: It is the measure of resistance to flow of the liquid which arises due to the
internal friction between layers of fluid as they slip past one another while liquid
flows.
49
2. Laminar flow of liquid: It is the flow of liquid in which there is a regular gradation of
velocity in passing from one layer to the next layer.
3. It should be remembered that, if a particular layer of liquid is flowing, then the layer
above this layer will accelerates its flow and the layer below this retards its flow.
4. Hydrogen bond and van der Waals forces causes the liquid to show the property
called viscosity.
5. Glass is said to be an example for extremely viscous liquid.
6. Viscosity of liquids decreases with increase in the temperature: Because at high

temperature molecules have high kinetic energy which reduces the intermolecular
forces between the layers, thereby each layer slip past one another between the
layers.
7. Derivation to find out the force required to maintain the flow of layers of the
liquid:
If the velocity of the layer at a distance ‘dz’ is changed by a value ‘du’ then velocity
gradient is given by ‘du/dz’.
But force between the layers is proportional to the area of contact of layers (A)
and velocity gradient of the layer (du/dz) i.e.,
Where is called as proportionally constant i.e., Coefficient of viscosity .
Coefficient of viscosity which is defined as “ the force when velocity gradient is unity
and are of contact is unit area”. It is also a measure of viscosity. The SI unit of
coefficient of viscosity is (newton second per square meter) Ns/m2 or
(pascal second) Pa s. The cgs units of coefficient of viscosity is ‘poise’.
[1 poise = 1 g /cm s = 10—1 kg/m s]
Andrews curves for CO2 gas
Thomas Andrews ( 1869 ) studied the behaviour of gases. The results showing p – V
isotherms for CO2 ( a real gas ) at different temperatures are summarized in Fig..These
isotherms exhibit the following features :
50
1. At low temperature, there are three distinct regions :
 At very low pressures, the curve AB resembles the Boyle’s curve. At point B the volume
decreases rapidly due to liquefaction.
 The portion BC corresponding to one value of pressure is parallel to V- axis and

represents the equilibrium of gas with liquid. Different points represent different
proportions of gas and liquid. This region is called the liquefaction region and at
point C the gas is completely converted into liquid.
 The portion CD corresponds to the liquid state and shows that the increase in pressure
produces a very small decrease in volume. This curve rises almost vertically.
2. With increase in temperature the length of the liquefaction region decreases until it
reduces to a point P at critical temperature Tc ( 31.1o C for CO2 ). The isotherm at this
temperature is called critical isotherm and the point P is called critical point.
3. The isotherms above Tc are rectangular hyperbola and approximates to the isotherms
for ideal gas . In this region, the matter always exists in gaseous state and the gas
cannot be liquefied.
Kinetic energy and molecular speeds:
As the gas molecules are moving in the container can have

the collisions either walls of the container or other gas molecules
makes it to change their direction with change in speed and
redistribution of energy. Thereby speed and energy of gas
molecules not same at any instant. Hence the speed of the gas
molecules is obtained will be average value of speed of molecules.
If u1, u2 …. un are the speed of individual molecules of the gas containing ‘n’
number of molecules then the average speed is given by
Maxwell and Boltzmann have shown that actual distribution of molecular speeds
depends on two factors i.e., (a) temperature and (b) molecular mass of a gas.
51
Effect of speed of gas molecules with change in
temperature: When a graph of number of molecules vs
molecular speed is drawn at to different temperatures T1 and T2
shows that number of molecules possessing very high and very
low speed is very small. The maximum in the curve represents
speed possessed by maximum number of molecules. This speed
is called most probable speed Ump . On increasing the
temperature most probable speed also increases. The speed
distribution curve broadens at higher temperature shows the number of molecules
moving at higher speed increases.
Speed distribution depends upon mass of molecules: At the give temperature gas
molecules with heavier mass have slower speed than lighter gas molecules. Example: at
the given temperature, nitrogen molecules have higher value of most probable speed
than the chlorine molecules which is shown in the graph.
Kinetic energy of the gas molecules:
We known that kinetic energy of a particles is
If we want to know average translational kinetic energy for the movement of a gas
particles in a straight line, we require the value of mean of square of speeds, of all
molecules. This is represented as follows:
Root mean square speed: [rms speed]: The mean square speed is the direct measure of
the average kinetic energy of gas molecules. If we take the square root of the mean of the
square of speeds then we get a value of speed which is different from most probable
speed and average speed. This speed is called root mean square speed, the expression of
it is as follows
Relationship between root mean square speed, average speed and most probable speed
The ratio between the three speeds is given below:

52
6 Thermodynamics
 Thermodynamics is an experimental science based on a small number of
principles that are generalizations made from experience.
 It is concerned only with macroscopic or large scale properties of matter and it
makes no hypotheses about the small scale or microscopic structure of matter.
 From the principles of thermodynamics one can derive general relations between
such quantities as coefficients of expansion, compressibility, specific heat
capacities, heats of transformation, and magnetic and dielectric coefficients,
especially as these are affected by temperature.
 The principles of thermodynamics also tell us which of these relations must be
determined experimentally in order to completely specify all the properties of the
system.
 Thermodynamics is complementary to kinetic theory and statistical
thermodynamics.
 Thermodynamics proves relationships between physical properties of any system
once certain measurements are made.
 It has been seen that all the chemical and physical processes are accompanied by
either evolution or absorbed the heat.
 This branch is governed by following laws i.e., zero, first, second and third law.
 It has been seen that thermodynamics is basically have the following objectives
1. To predict the flexibility of a process under a given set of conditions
2. To predict whether a reaction is spontaneous or not.
3. It always concerned only with the initial and final state of the system but
not on the molecular structure and kinetic energy.
BASIC CONCEPTS OF THERMODYNAMICS:
1. System: it is a part of universe which is under thermodynamical study.

2. Boundary: it is an imaginary line which separates system from the surrounding
3. Surrounding: it a part of universe which is not under thermodynamical study
4. Universe: system + boundary + surrounding.
TYPES OF SYSTEMS:
Open system: a system from which amount of the substance and energy is
exchangeable to surroundings. Example: hot water in an open conical flask
Closed system: a system only energy is exchangeable to surrounding but not the mass
of the substance. Example: hot water in a closed conical flask
Isolated system: A system in which either mass of the substance or energy can be
exchangeable to surrounding. Example: Hot water in conical flask enclosed into a
sealed thermos flask
Properties of systems:
The properties of thermodynamical system is associated with bulk behaviour of

matter which is called observable properties or macroscopic properties of the system,
which is classified into two types
53
Intensive or intrinsic property: Property which do not depend upon the quantity of
matter present in the system. Example: Temperature, density, concentration, specific
heat, viscosity, pressure, refractive index, surface tension, boiling point freezing point,
melting point.
Extensive property: Property which depends upon the quantity of matter present in the
system. Example: Mass, number of moles, energy, volume, free energy, enthalpy,
entropy, internal energy.
State of a system and state variables:
The concept of state of a system and state variables is very important in the study
of thermodynamics.
 Thermodynamical state: “a system is said to be in a particular state when all its

measurable properties have fixed values”.
 State variables or state functions: “the factors which are necessary to be
specified in order to define a particular state of a system”. These variables will
posses a remarkable property i.e., “the change in the value of a state function
depends only upon the initial state and final state of the system and is
independent upon the manner in which the change has been carried out”.
Examples: temperature, pressure, volume, internal energy, enthalpy, entropy,
free energy etc.
TYPES OF THERMODYNAMICAL PROCESS:
Thermodynamical process or process means an operation which brings about changes

in the state of a system.
This thermodynamical process is classified into following types.
Type of process Definition

Isothermal process Any process which is carried out at constant temperature
Any process in which no heat is exchanged between the
Adiabatic process
system and the surroundings
Isobaric process The process which is carried out at constant pressure.
Isochoric process The process which is carried out at constant volume.
The initial and final state of system is same after
Cyclic process
undergoing several steps.
A process which is carried out infinitesimally slowly in
such a way that each step remains in equilibrium with the
Reversible process
previous step and the process could be reversed at any
stage.
A process which is carried out in such a way that each
Irreversible process step is not in equilibrium with the previous step and the
process could not be reversed at any stage.
54
CONCEPT OF HEAT AND WORK
The exchange of energy between a system and its surroundings can take place in a
variety of ways. Among these, heat and work are the important modes of transference of
energy.
Heat (q): The form of energy exchanged between a system and the surroundings when
the two are at different temperatures. The unit of heat is Calories or joule.
Sign convention: Heat absorbed by the system q = is positive.
Heat liberated by the system q is negative.
Work (w): The work which is said to have done if the point of application of a force is
displaced in the direction of force. i.e., force x displacement.
The unit of work is Calories or joule.
Sign convention: Work done on the system w = is positive
Work done by the system w = is negative
Note:
In general work is expressed as the product of two factors an intensity factor and a
capacity factor. If there is no opposing force, then the motion itself produces no work.
On the other hand, in the absence of motion, even the strongest opposing force cannot
generate any work.
Work done = intensity factor x capacity factor.
There are many kinds of work, some of these which are used in thermodynamics are
o Electrical work: the work is said to be done when an electric current flows
through a circuit. If the potential difference causing the flow of current is E volts
(intensity factor) and the quantity of electricity that flows in a given time is Q
coulombs (capacity factor) then
Electric work (W) = EMF x quantity of electricity = E Q = EIt joule.
o Pressure – Volume work (Mechanical work): this type of work is said to be done,
if gases are compressed or expand.
 The system and the surroundings are in thermal equilibrium
 The volume of the system changes i.e, the number of moles of gaseous
reactants is different from the number of moles of gaseous products.
 The pressure remains constant.
Internal energy: it is defined as “sum total of different forms of energies like kinetic
energy, potential energy, nuclear energy, chemical energy etc. associated with the
molecules. It is denoted by U or E.
Internal energy of the substance depends upon
(i) Nature of substance

(ii) Pressure
(iii) Temperature etc.
It should be remembered that internal energy of the substance can not be
measured directly because translational energy, rotational energy, vibrational energy
nuclear energy can not be measured easily. Therefore internal energy is calculated by
55
considering the difference between the internal energies of products and reactants i.e.,
U = Up – UR, where Up is internal energy of products and UR is the internal energy of
reactants.
Note:
1. if U <0 i.e, negative value or UP < UR the reaction is exothermic in nature

2. if U >0 i.e, positive value or UP > UR the reaction is endothermic in nature
3. A unit of internal energy is joule in SI system.
4. Internal energy is a state function
5. It is an extensive property.
First law of thermodynamics:
 This law was proposed by Mayer and Helmholtz in 1840.

 This law was guided by the law of conservation of energy.
 It is based upon experimental observations and human experience.
This law can be stated in any one of the following ways:
 Energy can neither by created nor destroyed by any physical or chemical

changes. However, one form of energy can be changed into equivalent amount of
the other form.
 The sum of all the forms of energies is isolated system is constant.
 It is impossible to construct a perpetual motion machine i.e., a machine which
works without consuming energy.
 The total sum of mass and energy is constant in the universe though these are
inter convertible.
Mathematical form of first law
Consider a system having internal energy, U1 suppose heat ‘q’ is supplied to the
system. Thus its energy increases from U1 to U1 + q. further suppose that work (w) is
done on the system. As a result, its internal energy further increases and becomes equal
to U2. Here U2 is the energy of the final state thus
U2 = U1 + q + w  U2 – U1 = q + w  U = q + w
Change in internal energy = heat added to the system + work done on the system
If internal energy does not change i.e., U = 0 then q + w = 0  q = - w
i.e., when U = 0 heat absorbed by a system is equal to negative of work done on the
system or equal to work done by the system.
If the process is such that work done by the system is only pressure – volume work,
then
w = - PV  U = q - PV
If the process takes place at constant volume V = 0, then PV = 0 then U = qV. i.e.,
56
“Change in internal energy, U is equal heat (qV) absorbed or evolved at constant
volume and constant temperature”
Free expansion: expansion of a gas in vacuum i.e., P expansion = 0. it should be noted that
no work is done during free expansion of an ideal gas whether the process is reversible
or irreversible.
Enthalpy [H]  Heat content of the system. H = U + PV
1. it is state function
2. it is an extensive property
3. the change of the enthalpy is given by H = U + PV for solids and liquide
4. The change of the enthalpy is give by H = U + nRT for gaseous state.
5. By convention if heat is liberated by the system H = - ve valued and if heat is
absorbed by the system then H = +ve valued is taken.
Spontaneity of the system: any process which takes places on it own or small
initiation is required to start the process. Example: melting of ice, resting of iron etc.
Non spontaneity of the system: any process which takes place with the help of
external aid. Example: condensation of vapours.
Criterion for spontaneity of the system:
1. decreasing in enthalpy i.e., H = - ve value

2. increasing in entropy i.e., S = +ve value
Entropy [S] it is the measure of randomness or disorder ness of the system.
1. It is a state function i.e., value of this quantity will depends on the initial and final
state of the system.
2. It is an extensive property.
3. Entropy of the system changes with the change in the physical state.
4. For a solid entropy is zero where as for vapours it is maximum.
Gibb’s free energy: [G] : it is defined as G = H – TS.
1. It is an extensive property
2. It is a state function.
3. if G <0 the system is said to be spontaneous
4. if G > 0 the system is said to be non – spontaneous
5. if G = 0 the system is said to be equilibrium state.
6. Change in Gibb’s free energy: G = H - TS
7. Standard Gibb’s free energy change: G0 = H0 - TS0
8. Relationship between standard Gibb’s free energy change and equilibrium
constant G0 = - 2.303RTlogKp where R = gas constant T = temperature Kp =
equilibrium constant.
57
Heat capacity
This heat appears as a rise in temperature of the system in case of heat absorbed
by the system. The increase of temperature is proportional to the heat transferred
q=coeff×ΔT
The magnitude of the coefficient depends on the size, composition and nature of
the system. We can also write it as q = CΔT the coefficient, C is called the heat
capacity.
Thus, we can measure the heat supplied by monitoring the temperature rise, provided
we know the heat capacity. When C is large, a given amount of heat results in only a
small temperature rise. Water has a large heat capacity i.e., a lot of energy is needed to
raise its temperature. C is directly proportional to amount of substance. The molar heat
capacity of a substance, Cm = C/n, is the heat capacity for one mole of the substance
and is the quantity of heat needed to raise the temperature of one mole by one degree
celsius (or one kelvin). Specific heat, also called specific heat capacity is the quantity of
heat required to raise the temperature of one unit mass of a substance by one degree
celsius (or one kelvin). For finding out the heat, q, required to raise the temperatures of
a sample, we multiply the specific heat of the substance, c, by the mass m, and
temperatures change, ΔT as
q = C× m ×ΔT =CΔT
The relationship between Cp and CV for an ideal gas
At constant volume, the heat capacity, C is denoted by CV and at constant

pressure, this is denoted by Cp. Let us find the relationship between the two.
We can write equation for heat, q
At constant volume as qV = CVΔT =ΔU
At constant pressure as qp = CpΔT =ΔH
The difference between Cp and CV can be derived for an ideal gas as:
For a mole of an ideal gas, ΔH = ΔU + Δ(PV ) = ΔU + Δ(RT) = ΔU + RΔT
∴ ΔH= ΔU+RΔT
On putting the values of ΔH and ΔU, we have
CpΔT = CVΔT + RΔT
Or CpT - CvT = RT or Cp – CV = R

58
MEASUREMENT OF ΔU AND ΔH: CALORIMETRY
We can measure energy changes associated with chemical or physical processes

by an experimental technique called calorimetry. In calorimetry, the process is carried
out in a vessel called calorimeter, which is immersed in a known volume of a liquid.
Knowing the heat capacity of the liquid in which calorimeter is immersed and the heat
capacity of calorimeter, it is possible to determine the heat evolved in the process by
measuring temperature changes. Measurements are made under two different
conditions:
i) at constant volume, qV
ii) at constant pressure, qp
(a) ΔU measurements
For chemical reactions, heat absorbed at constant

volume, is measured in a bomb calorimeter. Here, a steel
vessel (the bomb) is immersed in a water bath. The whole
device is called calorimeter. The steel vessel is immersed
in water bath to ensure that no heat is lost to the
surroundings. A combustible substance is burnt in pure
dioxygen supplied in the steel bomb. Heat evolved during
the reaction is transferred to the water around the bomb
and its temperature is monitored. Since the bomb
calorimeter is sealed, its volume does not change i.e., the
energy changes associated with reactions are measured
at constant volume. Under these conditions, no work is
done as the reaction is carried out at constant volume in
the bomb calorimeter. Even for reactions involving gases,
there is no work done as ΔV = 0. Temperature change of
the calorimeter produced by the completed reaction is
then converted to qV, by using the known heat capacity
of the calorimeter with the help of equation.
(b) ΔH measurements
Measurement of heat change at constant pressure

(generally under atmospheric pressure) can be done in a
calorimeter. We know that ΔH = qp (at constant p) and,
therefore, heat absorbed or evolved, qp at constant
pressure is also called the heat of reaction or enthalpy of
reaction, ΔrH.
In an exothermic reaction, heat is evolved, and

system loses heat to the surroundings. Therefore, qp will
be negative and ΔrH will also be negative. Similarly in an
endothermic reaction, heat is absorbed, qp is positive and
ΔrH will be positive.
59
Thermo chemical equations
A balanced chemical equation together with the value of its ΔrH is called a thermo
chemical equation. We specify the physical state (along with allotropic state) of the
substance in an equation. For example: C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O( l): ΔrHΘ =
-1367 kJ mol-1
Enthalpy of the reactions:
In a chemical reaction, reactants are converted into products and is represented

by, Reactants → Products
The enthalpy change accompanying a reaction is called the reaction enthalpy. The
enthalpy change of a chemical reaction, is given by the symbol ΔrH
ΔrH = (sum of enthalpies of products) – (sum of enthalpies of reactants)
Standard enthalpy of reactions: one atmospheric pressure at 250C
Standard enthalpy of fusion [Hfus0]: The enthalpy change that accompanies melting of
one mole of a solid substance in standard state. Example: H2O(s) → H2O( l); ΔfusHΘ =
6.00 kJ mol−1
Standard enthalpy of vaporization or molar enthalpy of vaporization ΔvapHΘ:

Amount of heat required to vaporize one mole of a liquid at constant temperature and
under standard pressure (1bar). Example: H2O(l) → H2O(g); ΔvapHΘ = + 40.79kJ mol-1.
Standard enthalpy of sublimation, ΔsubHΘ: The change in enthalpy when one mole of a
solid substance sublimes at a constant temperature and under standard pressure
(1bar). Example: Solid CO2 or ‘dry ice’ sublimes at 195K with ΔsubHΘ=25.2 kJ mol-1.
Standard enthalpy of formation ΔfHΘ: The standard enthalpy change for the formation
of one mole of a compound from its elements in their most stable states of aggregation.
Example: H2 (g) + ½O2 (g) → H2O(1) ΔfHΘ = -285.8 kJ mol−1.
Standard enthalpy of combustion (symbol : ΔcHΘ): The enthalpy change per mole (or
per unit amount) of a substance, when it undergoes combustion and all the reactants
and products being in their standard states at the specified temperature. Example:
C4H10 (g) + 13/2 O2 (g) → 4CO2(g) + 5H2O(1); ΔcHΘ = -2658.0 kJ mol−1
Enthalpy of atomization, ΔaHΘ. It is the enthalpy : Change on breaking one mole of

bonds completely to obtain atoms in the gas phase. Example: H2(g) → 2H(g); ΔaHΘ =
435.0 kJ mol-1
Enthalpy of Solution ΔsolHΘ ): Enthalpy of solution of a substance is the enthalpy
change when one mole of it dissolves in a specified amount of solvent. Example: KNO3 +
H2O  KNO3; H =+58kJ/mol.
Hess’s Law of Constant Heat Summation: If a reaction takes place in several steps
then its standard reaction enthalpy is the sum of the standard enthalpies of the
intermediate reactions into which the overall reaction may be divided at the same
temperature.
60
Lattice Enthalpy
The lattice enthalpy of an ionic compound is the enthalpy change which occurs
when one mole of an ionic compound dissociates into its ions in gaseous state.
Na+Cl-(s) → Na+(g) + Cl-(g) ; ΔlatticeHΘ = +788 kJmol-1
Since it is impossible to determine lattice enthalpies directly by experiment, we use an

indirect method where we construct an enthalpy diagram called a Born-Haber Cycle
Let us now calculate the lattice enthalpy of Na+Cl-(s) by following steps given below:
1. Na(s)→ Na(g) , sublimation of sodium metal, ΔsubHΘ =
108.4 kJ mol−1
2. Na(g)→Na+(g) + e−1(g) , the ionization of sodium
atoms, ionization enthalpy ΔiHΘ = 496 kJ mol−1
3. 1/2 Cl2 (g) → Cl(g), the dissociation of chlorine, the
reaction enthalpy is half the bond dissociation
enthalpy.½ ΔbondHΘ = 121kJ mol−1
4. Cl(g) + e−1(g) → Cl-(g) electron gained by chlorine
atoms. The electron gain enthalpy, ΔegHΘ = -348.6 kJ
mol−1.
61
7 Equilibrium
 Chemical equilibrium: a reaction is said to be at equilibrium state when the rate of
forward reaction is same as the rate of backward reaction. Or in a reaction if rate of
change of concentration of reactants is same as the rate of change of concentration of
products. Equilibrium state in a reaction is shown by double half arrows i.e., .
 Equilibrium mixture: the mixture in which the reactants and products in the
equilibrium state.
 Equilibrium can be established for both physical processes and chemical reactions if it
is performed in a closed container.
 Equilibrium state is said to be dynamic in nature: when the reaction is carried out
in a closed vessel at a particular temperature products are formed. i.e., the
concentrations of the reactants keep on decreasing, while those of products
concentration keep on increasing for some time after which there is no change in the
concentrations of either the reactants or products. i.e., the rates of the forward and
reverse reactions become equal.
Let us consider a general reaction i.e., A + B C + D which is carried out in a
closed vessel at a temperature. At initial state it is seen that concentration of reactant
are more and products is zero. When time processed the concentration of reactants
decreases and products formation takes place and at the same time decomposition of
products takes place to form reactants, here the rate of forward reaction decreases and
back ward reaction increases, a stage reaches where the rate of backward reaction is
equal to rate of forward reaction.
 Based on the extent to which the reactions proceed, the state of chemical equilibrium
is a chemical reaction is classified into three groups.
o The reactions that proceed nearly to completion and only negligible concentrations
of the reactants are left.
o The reactions in which only small amounts of products are formed and most of the
reactants remain unchanged at equilibrium stage.
o The reactions in which the concentrations of the reactants and products are
comparable, when the system is in equilibrium.
 Equilibrium in physical processes: This type of equilibrium is divided into following

types
 Phase transformation processes
 Dissolution of Solid or Gases in Liquids
 Phase transformation processes:

 Solid – liquid equilibrium  when ice and water are kept in a perfectly insulated
thermos flask at 273K under one atmospheric pressure are said to be at
equilibrium state i.e., at the boundary between ice and water, molecules from the
liquid water collide against ice and adhere to it and some molecules of ice escape
into liquid phase due to which the mass of ice and water do not change with time
and the temperature remains constant.
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 For any pure substance at atmospheric pressure, the temperature at
which the solid and liquid phases are at equilibrium is called the normal
melting point or normal freezing point of the substance.
 Liquid – vapour equilibrium  Take a transparent box carrying a U-tube with

mercury (manometer). Drying agent like anhydrous calcium chloride is placed for a
few hours in the box. After removing the drying agent, a watch glass containing
water is quickly placed inside the box. It will be observed that the mercury level in
the right limb of the manometer slowly increases and finally attains a constant
value, that is, the pressure inside the box increases and reaches a constant value.
Also the volume of water in the watch glass decreases. Initially there was no water
vapour inside the box. As water evaporated the pressure in the box increased due
to addition of water molecules into the gaseous phase inside the box.
At equilibrium: rate of evaporation= rate of condensation H2O(l)
H2O (vap)
 For a pure liquid at atmospheric pressure (1.013 bar) the temperature

at which the liquid and vapours are at equilibrium is called boiling point of
the liquid.
 At high altitude the boiling point decreases because at high altitudes
vapour pressure decreases.
 At equilibrium the pressure exerted by the liquid molecules at a given
temperature remains constant and is called the equilibrium vapour pressure
of liquid or vapour pressure of liquid.
 Vapour pressure of liquid increases with temperature.
 Different liquids will have different vapour pressure.
 Higher the vapour pressure more will be the volatility of the liquid and
have low boiling point.
 Solid – vapour equilibrium  Let us now consider the systems where solids
sublime to vapour phase. If we place solid iodine in a closed vessel, after sometime
the vessel gets filled up with violet vapour and the intensity of colour increases with
time. After certain time the intensity of colour becomes constant and at this stage
equilibrium is attained. Hence solid iodine sublimes to give iodine vapour and the
iodine vapour condenses to give solid iodine. The equilibrium can be represented
as, I2(solid) I2 (vapour)
Equilibrium Involving Dissolution of Solid or Gases in Liquids
 Solids in liquids: this type of equilibrium is seen in the saturated solutions i.e.,
a solution in which no more solute can be dissolved at a given temperature is
known as saturated solution. Here dynamic equilibrium exists between the
solute molecules in the solid state and in the solution.
Example: Dissolve only a limited amount of sugar in a given amount of
water at room temperature. a dynamic equilibrium exits between the solute
molecules in the solid state and in the solution:
Sugar (solution Sugar (solid),

63
i.e., the rate of dissolution of sugar = rate of crystallisation of sugar.
The dynamic nature of equilibrium between aqueous solution of sugar and

crystallization of sugar has been confirmed with the help of radioactive sugar. A
drop some radioactive sugar is added into saturated solution of non-radioactive
sugar, then after some time radioactivity is observed both in the solution and in
the solid sugar. Initially there were no radioactive sugar molecules in the solution
but due to dynamic nature of equilibrium, there is exchange between the
radioactive and non-radioactive sugar molecules between the two phases. The
ratio of the radioactive to nonradioactive molecules in the solution increases till it
attains a constant value.
 Gases in liquids There is equilibrium between the molecules in the gaseous

state and the molecules dissolved in the liquid under pressure i.e., when a soda
water bottle is opened, some of the carbon dioxide gas dissolved in it fizzes out
rapidly. The phenomenon arises due to difference in solubility of carbon dioxide
at different pressures.
CO2(gas) CO2(in solution)
This equilibrium is governed by Henry’s law, which states that the mass
of a gas dissolved in a given mass of a solvent at any temperature is
proportional to the pressure of the gas above the solvent.
The dissolution of gases in a solvent decreases with increase of temperature.

The soda water bottle is sealed under pressure of gas when its solubility in water
is high. As soon as the bottle is opened, some of the dissolved carbon dioxide gas
escapes to reach a new equilibrium condition required for the lower pressure,
namely its partial pressure in the atmosphere.
General Characteristics of Equilibria Involving Physical Processes
 Equilibrium is possible only in a closed system at a given temperature.

 Both the opposing processes occur at the same rate and there is a dynamic but
stable condition.
 All measurable properties of the system remain constant.
 When equilibrium is attained for a physical process, it is characterized by
constant value of one of its parameters at a given temperature.
 The magnitude of such quantities at any stage indicates the extent to which the
reaction has proceeded before reaching equilibrium.
EQUILIBRIUM IN CHEMICAL PROCESSES ñ DYNAMIC EQUILIBRIUM
LAW OF CHEMICAL EQUILIBRIUM AND EQUILIBRIUM CONSTANT
 A mixture of reactants and products in the equilibrium state is called an

equilibrium mixture.
 Maximillian Guldberg and Peter Waage in 1864 proposed an equilibrium
equation between equilibrium mixture which is known as equilibrium constant
expression. This equation is called as law of mass action.
 Law of mass action  at given temperature, the rate of reaction is directly
proportional to active masses of the reactants. An active mass of the reactants
means molar concentration of the reactants.
64
Derivation for equilibrium equation:
Let us consider a general reversible reaction: A + B C + D where ‘A’ and ‘B’ are
the reactants, ‘C’ and ‘D’ are the products in the balanced chemical equation. By
applying the law of mass action
Rate of forward reaction (Rf)  [A][B] or Rf = kf[A][B] --------(i) where kf is the equilibrium
constant for forward reaction
Rate of backward reaction (Rb) [C][D] or Rb = kb[C][D]------(ii) where kb is the equilibrium

constant for back ward reaction
At equilibrium, the rate of forward reaction = rate of back ward reaction i.e., Rf = Rb
kf[A][B] = kb[C][D] kf [C ][ D]
Kc  
kb [ A][ B]
Where Kc is the equilibrium constant and the expression is called the equilibrium
constant expression.
 in general if aA + bB cC + dD then the equilibrium constant expression is

given as K c  k f  [C ] [ D]
c d
a b
kb [ A] [ B]
i.e., equilibrium law or law of chemical equilibrium can be stated as ‘at a given
temperature, the product of concentrations of the reaction products raised to
the respective stoichiometric coefficient in the balanced chemical equation
divided by the product of concentrations of the reactants raised to their
individual stoichiometric coefficients has a constant value’.
 Note: Equilibrium constant for the reverse reaction is the inverse of the
equilibrium constant for the reaction in the forward direction. K1 = 1/K2
HOMOGENEOUS EQUILIBRIA
It is the equilibrium state exists between the all the reactants and all the
products which are at same phase.
N2(g) + 3H2(g) 2NH3(g),
In the above reaction, all the reactants and all the products are in the same or
homogeneous phase.
HETEROGENEOUS EQUILIBRIA
Equilibrium in a system having more than one phase is called heterogeneous

equilibrium.
Example:
o The equilibrium between water vapour and liquid water in a closed

container. H2O(l) H2O(g)
o The equilibrium between a solid and its saturated solution, Ca(OH)2 (s) +
(aq) Ca2+ (aq) + 2OH–(aq)
 Heterogeneous system always involves either liquid or solid state.
65
 The equilibrium constant of liquid or solid is taken as constant because it is
independent of amount of the substance present.
 It must be remembered that in heterogeneous equilibrium pure solids or liquids
must be present (however small it may be) for the equilibrium to exist, but their
concentrations or partial pressure do not appear in the expression of the
equilibrium constant.
Equilibrium Constant in Gaseous Systems [Kp]
The reactions involving gases, the equilibrium constant is expressed in terms of partial
pressure. K p  k f  ( PC ) ( PD )
c d
a b
kb ( PA ) ( PB )
Relationship between Kp and Kc
Consider a general reaction aA(g) + bB(g) cC(g) + dD(g)
By applying law of mass action, the equilibrium constant for the gaseous reaction is
( PC )c ( PD ) d
given by K p 
( PA )a ( PB )b
We know, for ideal gas equation pV = nRT  p = (n/V)RT
But number of moles per volume (n/V) is concentration of the substance, therefore p
= cRT, i.e., p = [gas]RT
i.e., at constant temperature, the pressure of the gas is proportional to its

concentration i.e., p  [gas]
Therefore
( PC )c ( PD )d [C ]c [ D]d RT 
( cd )
[C ]c [ D]d c d
Kp    RT (cd )( ab)  [C ] a[ D]b RT n  K c RT n
[ A] [ B ] RT 
a b ( ab )
( PA ) ( PB ) a b a
[ A] [ B ]b
[ A] [ B ]
n
i.e., K p  K c ( RT )
∆n = (number of moles of gaseous products) – (number of moles of gaseous

reactants) in the balanced chemical equation.
 Note
o It is necessary that while calculating the value of Kp, pressure should be
expressed in bar as standard state is 1bar. We have known 1pascal,
Pa=1Nm–2, and 1bar = 105 Pa
o When n = 0  Kp = Kc example 2HI(g) H2(g) + I2(g)
o When n < 0 i.e., negative value  Kp< Kc example N2(g) + 3H2(g)
2NH3(g)
o When n > 0 i.e., positive value  Kp> Kc example PCl5(g) PCl3(g) +
Cl2(g)
Units of Equilibrium Constant
 The value of equilibrium constant Kc can be calculated by substituting the

concentration terms in mol/L and for Kp partial pressure is substituted in Pa,
66
kPa, bar or atm. This results in units of equilibrium constant based on molarity
or pressure, unless the exponents of both the numerator and denominator are
same.
 The numerical value of equilibrium constant depends on the standard state
chosen. Thus, in this system both Kp and Kc are dimensionless quantities but
have different numerical values due to different standard states.
Important features of equilibrium constants;
1. Equilibrium constant is applicable only when concentrations of the reactants

and products have attained their equilibrium state.
2. The value of equilibrium constant is independent of initial concentrations of
the reactants and products.
3. Equilibrium constant is temperature dependent having one unique value for a
particular reaction represented by a balanced equation at a given
temperature.
4. The equilibrium constant for the reverse reaction is equal to the inverse of the
equilibrium constant for the forward reaction.
5. The equilibrium constant K for a reaction is related to the equilibrium
constant of the corresponding reaction, whose equation is obtained by
multiplying or dividing the equation for the original reaction by a small
integer.
APPLICATIONS OF EQUILIBRIUM CONSTANTS---Equilibrium constant used to:
1. Predict the extent of a reaction on the basis of its magnitude,

2. Predict the direction of the reaction, and
3. Calculate equilibrium concentrations.
Predicting the Extent of a Reaction
 The numerical value of the equilibrium constant for a reaction indicates the
extent of the reaction formation.
 Equilibrium constant does not give any information about the rate at which the
equilibrium is reached.
 The magnitude of Kc or Kp is directly proportional to the concentrations of
products i.e., higher the value of K implies that concentrations of the product is
more i.e., forward reaction takes places where as lower the value of K implies that
concentration of reactant is high i.e., back ward reaction takes place.
o If Kc > 103 the reaction proceeds nearly to completion i.e., products
concentration is more.
o If Kc < 10 – 3 the reaction proceeds rarely i.e., products concentration
is less
o If Kc value lies between 10 – 3 to 103 then appreciable concentrations
of both reactants and products are present.
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Predicting the Direction of the Reaction: To predict the direction the reaction
proceeds i.e., either towards products side or reactants side which is decided by a
quantity known as reaction quotient (Q). i.e.,
 If Qc > Kc the reaction will proceed in the direction of reactants i.e., reverse
reaction can takes place.
 If Qc< Kc the reaction will proceed in the direction of products i.e., forward
reaction can takes place.
 If Qc= Kc the reaction is at equilibrium state.
Calculating Equilibrium Concentrations: In case of a problem in which we know the

initial concentrations but do not know any of the equilibrium concentrations, the
following three steps shall be followed:
 Step 1. Write the balanced equation for the reaction.

 Step 2. Under the balanced equation, make a table that lists for each substance
involved in the reaction:
o The initial concentration,
o The change in concentration on going to equilibrium, and
o The equilibrium concentration.
In constructing the table, define x as the concentration (mol/L) of one of the
substances that reacts on going to equilibrium, then use the stoichiometry of the
reaction to determine the concentrations of the other substances in terms of x.
 Step 3. Substitute the equilibrium concentrations into the equilibrium

equation for the reaction and solve for x.
 Step 4. Calculate the equilibrium concentrations from the calculated value of
x.
 Step 5. Check your results by substituting them into the equilibrium
equation.
RELATIONSHIP BETWEEN EQUILIBRIUM CONSTANT (K), REACTION QUOTIENT

(Q) AND GIBBS ENERGY (G)
G = G0 + (RT)lnQ
o G is Gibbs free energy change

o G0 is standard Gibbs free energy change
o K is equilibrium constant
o Q is reaction quotient.
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But we known that
 The value of Kc for a reaction does not depend on the rate of the reaction.
 If G < 0, reaction is spontaneous i.e., proceeds towards forward direction
 If G > 0, reaction is non – spontaneous i.e., reaction hardly takes place
 If G = 0, reaction is at equilibrium state.
At equilibrium G = 0 and Q = Kc, therefore the above equation becomes
G0 = - RTln(Kc)  ln(Kc) = - G0/RT
Taking antilog on both sides

0
Kc = e  G / RT
Using this equation the spontaneity of the reaction can be determined in terms of G0 value.
 If G0 < 0, i.e., negative value, then - G0/RT becomes positive value i.e., Kc > 1
therefore reaction is spontaneous.
 If G0 < 0, i.e., positive value, then - G0/RT becomes negative value i.e., Kc < 1
therefore reaction is non - spontaneous.
FACTORS AFFECTING EQUILIBRIA:
The effect of the physical parameters shows the change in the equilibria of the reactions,
this is explained on the basis of a principle called Le Chatelieris principle, which states that “a
change in any of the factors that determine the equilibrium conditions of a system will
cause the system to change in such a manner so as to reduce or to counteract the effect
of the change”. This principle is applicable to all physical and chemical equilibria.
The following factors which affects the state of equilibrium of a reaction
 Concentration of reactants or products

 Pressure
 Temperature
 Inert gas atmosphere
 Catalyst
 Concentration Change: When the concentration of any of the reactants or products in a

reaction at equilibrium is changed, the composition of the equilibrium mixture changes
so as to minimize the effect of concentration changes.
o If the concentration of reactants are increased or concentration of products are
decreased the equilibrium shifts toward products side i.e., reaction becomes
spontaneous. Here Qc values becomes less than Kc.
o If the concentration of reactants are decreased or concentration of products are
increased the equilibrium shits toward reactants side i.e., reaction becomes non –
spontaneous. Here Qc values becomes more than Kc.
Effect of Concentration change-- An experiment
Consider a equilibrium reaction
Fe3+(aq)+ SCN–(aq) [Fe(SCN)]2+(aq)

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yellow colourless deep red
A reddish colour appears on adding two drops of 0.002 M potassium

thiocynate solution to 1 mL of 0.2 M iron (III) nitrate solution due to the formation
of [Fe (SCN)]2+. The intensity of the red colour becomes constant on attaining
equilibrium. This equilibrium can be shifted in either forward or reverse directions
depending on our choice of adding a reactant or a product.
 Pressure Change--- A pressure change obtained by changing the volume which can
affect the yield of products in case of a gaseous reaction because the total number of
moles of gaseous reactants and total number of moles of gaseous products are different.
o If n is negative, then increasing in pressure favors the forward direction
i.e., product formation increases and vise versa.
o If n is positive, then increasing in pressure favors the backward direction
i.e., product decomposes to form reactants and vise versa.
o If n = 0 there is no effect of pressure on the reaction.
Note:
 In applying Le Chatelier’s principle to a heterogeneous equilibrium the

effect of pressure changes on solids and liquids can be ignored because the
volume (and concentration) of a solution/liquid is nearly independent of
pressure.
 Shifting of equilibrium constant due to change in pressure is because of
change in the volume of the contents, i.e., P 1/V at constant temperature.
 Inert Gas Addition: If the volume is kept constant and an inert gas such as argon is
added which does not take part in the reaction, the equilibrium remains undisturbed. It
is because the addition of an inert gas at constant volume does not change the partial
pressures or the molar concentrations of the substance involved in the reaction. The
reaction quotient changes only if the added gas is a reactant or product involved in the
reaction.
 Temperature Change: Temperature changes affect the equilibrium constant and rates
of reactions. In general, the temperature dependence of the equilibrium constant
depends on the sign of ∆H for the reaction.
o If reaction is exothermic, increasing of temperature favors the backward reaction
where as decreasing in the temperature favors the forward reaction.
o If reaction is endothermic, increasing of temperature favors the forward reaction
where as decreasing in the temperature favors the backward reaction.
o The equilibrium constant for an exothermic reaction (negative ∆H) decreases as
the temperature increases.
o The equilibrium constant for an endothermic reaction (positive ∆H) increases as
the temperature increases.
Note:
Whenever equilibrium is disturbed by a change in the concentration, pressure or

volume, the composition of the equilibrium mixture changes because the reaction
70
quotient, Qc no longer equals the equilibrium constant, Kc. However, when a change in
temperature occurs, the value of equilibrium constant, Kc is changed.
 Effect of a Catalyst:
o A catalyst increases the rate of the chemical reaction by making available a new
low energy pathway for the conversion of reactants to products.
o It increases the rate of forward and reverse reactions that pass through the same
transition state and does not affect equilibrium.
o Catalyst lowers the activation energy for the forward and reverse reactions by
exactly the same amount.
o Catalyst does not affect the equilibrium composition of a reaction mixture. It does
not appear in the balanced chemical equation or in the equilibrium constant
expression.
Note: If a reaction has an exceedingly small K, a catalyst would be of little help.
IONIC EQUILIBRIUM IN SOLUTION
o Michael Faraday classified the substances into two categories based on their ability to
conduct electricity.
o Electrolytes: The substances conduct electricity in their aqueous solutions. Example:
aqueous solution of salt, acid and bases.
o Non – electrolytes: The substance does not conduct electricity in their aqueous
solutions. Example: aqueous solution of sugar, urea, etc.
o Strong electrolytes: Electrolytes which ionized almost completely when dissolved in
water. Example: aqueous solution of strong acids, strong bases and salts.
o Weak electrolytes: Electrolyte which ionized partially when dissolved in water.
Example: aqueous solution of weak acids, and weak bases.
o Ionic equilibrium: it is the equilibrium conditions exist between ions and the unionized
molecules in an aqueous solution.
ACIDS, BASES AND SALTS
Acids are the substances which are sour in taste, turns blue litmus paper to red and
o
liberate dihydrogen gas when reacts with metals.
o Bases are the substances which are bitter in taste, turns red litmus paper to blue and
have soapy in nature.
o A salt is the product obtain when acid reacts with base.
o Dissociation refers to the process of separation of ions in water already existing as such
in the solid state of the solute.
o Ionization corresponds to a process in which a neutral molecule splits into charged ions
in the solution.
Arrhenius Concept of Acids and Bases--According to this theory
o “Acids are substances which dissociates in water to give hydrogen ions”.

o “Bases are substances which dissociates in water to give hydroxyl ions”.
o Limitations of Arrhenius concept:
o Any substance is acid or base only with dissolves in water to give H + ions or
OH – ions.
o It will not give any account for the basicity of substances like ammonia
According to this theory the strength of the acid and base can be decided based on the ability of
donating H+ ions and OH – ions in water, i.e., a strong acid which is capable of is one which
71
dissociates completely into H+ when dissolved in water, where as strong base is one which
dissociates completely into OH – ions when in water.
The Bronsted-Lowry Acids and Bases: [proton donor acceptor theory]
o Acid is a substance that is capable of donating a hydrogen ion H+

o Bases are substances capable of accepting a hydrogen ion, H+.
i.e., Acids are proton donors and bases are proton acceptors.
o Conjugate acid – base pair: acid – base pair that differs by only proton.
o It may be noted that conjugate acid has one extra proton and each conjugate base
has one less proton in comparison with the given species.
o If the acid is strong in nature then its conjugate base is weak base and vice versa.
o “Water acts as both acid and base i.e., it is an amphoteric in nature” this
nature can be explained as follows
Consider the example of dissolution of NH3 in H2O represented by the following
equation:
The basic solution is formed due to the presence of hydroxyl ions. In this reaction,
water molecule acts as proton donor and ammonia molecule acts as proton acceptor and
are thus, called Lowry-Brönsted acid and base, respectively. In the reverse reaction, H+ is
transferred from NH4+ to OH–. In this case, NH4+ acts as a Bronsted acid while OH– acted
as a Brönsted base.
Consider the example of ionization of hydrochloric acid in water. HCl(aq) acts as an

acid by donating a proton to H2O molecule which acts as a base.
It can be seen in the above equation, that water acts as a base because it accepts the
proton. The species H3O+ is produced when water accepts a proton from HCl. Therefore,
Cl– is a conjugate base of HCl and HCl is the conjugate acid of base Cl–. Similarly, H2O is a
conjugate base of an acid H3O+ and H3O+ is a conjugate acid of base H2O. It is interesting
to observe the dual role of water as an acid and a base. In case of reaction with HCl water
acts as a base while in case of ammonia it acts as an acid by donating a proton.
Hydronium and Hydroxyl Ions-- Hydrogen ion by itself is a bare proton with very small size
(~10–15 m radius)
And intense electric field, binds itself with the water molecule at one of the two available lone
pairs on it giving H3O+. This species has been detected in many compounds (e.g., H3O+Cl–) in
72
the solid state. In aqueous solution the hydronium ion is further hydrated to give species like
H5O2+, H7O3+ and H9O4+. Similarly the hydroxyl ion is hydrated to give several ionic species like
H3O2–, H5O3–and H7O4– etc.
Lewis Acids and Bases (electron donor and acceptor theory): according to this theory
 “Acid is a species which accepts electron pair”. Example: H2O, NH3,

 “Base is a species which donates an electron pair”. Example: AlCl3, Co3+, Mg3+
Example: Let us consider a reaction of electron deficient species BF3 with NH3.
BF3 does not have a proton but still acts as an acid and reacts with NH3 by accepting its
lone pair of electrons. The reaction can be represented by, BF3 +:NH3 →BF3:NH3
The Ionization Constant of Water and its Ionic Product: as we known that water acts as both
acid and base in the presence of base and acid respectively. But in pure water one H2O molecule
donates proton and acts as an acid and another water molecule accepts a proton and acts as a
base at the same time. Therefore following equilibrium exists: H2O(l) + H2O(l) 
H3O (aq) + OH (aq)
+ –
Therefore the dissociation constant is represented by,
[ H 3O  ][OH  ]
K
[ H 2O ]
The concentration of water is omitted from the denominator as water is a pure liquid and its
concentration remains constant. [H2O] is incorporated within the equilibrium constant to give a
new constant, Kw, which is called the ionic product of water. Therefore,
Kw = [H+][OH–]
It has been experimentally found that at 298K the [H+] is 1.0 x 10 – 7M , and, as dissociation of
water produces equal number of H+ and OH– ions, the concentration of hydroxyl ions, [OH–] =
[H+] = 1.0 × 10–7 M. therefore, the value of Kw at 298K,
Kw = [H+][OH–] = (1 × 10–7)2 = 1 × 10–14 M2
Note:
 The value of Kw is temperature dependent

 The density of pure water is 1000g/L, molar mass is 18.0 g/mol, therefore molarity of
pure water is 55.55M
 The ratio of dissociated water to that of undissoicated water is 10 – 7 /55.55 = 1.8 x 10 – 9
i.e., equilibrium lies towards undissoicated water.
73
 Distinguish between acidic, neutral and basic aqueous solutions by the relative values
of the H3O+ and OH– concentrations is : Acidic: [H3O+] > [OH– ] Neutral: [H3O+] = [OH– ]
Basic : [H3O+] < [OH–]
The pH Scale
 pH scale: it is a logarithmic scale used to express the concentration of hydonium ion in

terms of molarity.
 The pH of a solution is defined as the negative logarithm to base 10 of the activity
 
aH  of hydrogen ion.
 In dilute solutions (< 0.01 M), activity of hydrogen ion (H+) is equal in magnitude to
molarity represented by [H+].
 
 It should be noted that activity has no units and is defined as: aH  = [H+] / mol L–1.
 From the definition of pH, we can write the expression pH = - log a  = H
– log ([H+]/mol L
) –
 At 298K the [H+] of pure water is 10 – 7 M, therefore its pH = 7, it is neutral in nature,

where as for acidic solution the pH < 7, and for basic solution the pH > 7.
 The concept of p[H] was first introduced by Danish chemist Søren Peder Lauritz
Sørensen at the Carlsberg Laboratory in 1909[3] and revised to the modern pH in 1924 to
accommodate definitions and measurements in terms of electrochemical cells.
Show that pKw = pH + pOH = 14 at 298K:
We know that at 298K Kw = [H+][OH–] = (1 × 10–7)2 = 1 × 10–14,
Taking negative logarithm on both sides,
– log (Kw ) = – log ( [H+][OH–]) = – log (1 × 10–14)
= – log ( [H+]) +(– log [OH–]) = – log ( 1) + – log (10 – 14 )
pKw = pH + pOH = 14 i.e., pH + pOH = 14 at 298K
Note
 Kw value changes with the temperature; therefore pH of the solution is also changes but
it is vary small and it will be ignored.
 pKw is a very important quantity for aqueous solutions and controls the relative
concentrations of hydrogen and hydroxyl ions as their product is a constant.
 Measurement of pH of a solution is very essential as its value should be known when
dealing with biological and cosmetic applications.
 The pH of a solution can be found roughly with the help of pH paper that has different
colour in solutions of different pH.
 Now a days greater accuracy pH meters are used to calculate pH of the solutions. pH
meter is a device that measures the pH-dependent electrical potential of the test
solution within 0.001 precision.
pH of some solutions:
o Milk of magnesia  10
o Egg white, sea water  7.8
o Human blood  7.4
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o Milk  6.8
o Human saliva  6.4
o Black coffee  5.0
o Soft drinks   3.0
o Lemon juice   2.2
o Gastric juice   1.2
o Lime water   10.5
o Tomato juice   4.2
Ionization Constants of Weak Acids

Consider a weak acid HX that is partially ionized in the aqueous solution. The equilibrium can
be expressed by:
HX(aq) + H2O(l)  H3O+(aq) + X–(aq)
Initial concentration (M) c 0 0
Let ‘’ be the extent of ionization Change (M) c c c
Equilibrium concentration (M) (c-c) c c
Here, c = initial concentration of the undissoicated acid, HX at time, t = 0.  = extent up to

which HX is ionized into ions.
The equilibrium constant for the dissociation of weak acid is
[ H 3O  ][ X  ] [c ][c ] c 2 2
Ka   
[ HX ] [c  c ] c(1   )
c 2
Ka 
(1   )
 Ka is called the dissociation or ionization constant of acid HX.

 At a given temperature T, Ka is a measure of the strength of the acid HX.
 Larger the value of Ka stronger the acid.
 Ka is a dimensionless quantity with the understanding that the standard state
concentration of all species is 1M.
 pKa = – log (Ka)
Ionization of Weak Bases
Consider a weak base MOH that is partially ionized in the aqueous solution. The equilibrium
can be expressed by:
MOH(aq)  M+(aq) + OH–(aq)
Initial concentration (M) c 0 0
Let ‘’ be the extent of ionization Change (M) c c c

75
Equilibrium concentration (M) (c-c) c c
Here, c = initial concentration of the undissoicated base, HX at time, t = 0.  = extent up to

which MOH is ionized into ions.
The equilibrium constant for the dissociation of weak base is
[ M  ][OH  ] [c ][c ] c 2 2

Kb   
[ MOH ] [c  c ] c(1   )
c 2
Kb 
(1   )
 Kb is called the dissociation or ionization constant of acid MOH.

 At a given temperature T, Kb is a measure of the strength of the base MOH.
 Larger the value of Kb stronger the acid.
 Kb is a dimensionless quantity with the understanding that the standard state
concentration of all species is 1M.
 pKb = – log (Kb)
Relation between Ka and Kb
 Kw = Ka x Kb
 The equilibrium constant for a net reaction obtained after adding two reactions equals
the product of the equilibrium constants for individual reactions. Knet reaction = K1 + K2 +
K3 + ----
 Consider base – dissociation equilibrium reaction : B(aq)+ H 2O (l)  B+ (aq) + OH – (aq)
[ BH  ][OH  ]
Kb 
[ B]
Since concentration of water remains constant, its concentration is omitted. Multiplying and
[ BH  ][OH  ][ H  ] K w
dividing the above expression by [H+] we get K b  
[ B ][ H  ] Ka
K w  K a  Kb
Taking negative logarithm of both sides of the equation, then pK values of the conjugate acid
and base are related to each other by the equation:
pK w  pK a  pK b
Di- and Polybasic Acids and Di- and Polyacidic Bases
 Polybasic or polyprotic acid: acids having more than one ionizable proton per molecule.
Example: oxalic acid, sulphuric acid, phosphoric acid etc.
 Polyacidic or polyhydroxic base: acids having more than one ionizable hydroxylic per
molecule. Example: barium hydroxide, ferric hydroxide etc.
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 These polybasic acids will ionizes in respective steps depends upon how many ionizable
protons are present per molecule, for example: if an acid H2X is said to be ionized in two
steps i.e.,
H2X (aq)  H+ (aq) + HX – (aq)
HX – (aq)  H+(aq) + X2 – (aq)
The corresponding equilibrium constants for the steps are as follows
[ H  ][ HX  ]
For Step – 1: equilibrium constant: K1  Step – 2: equilibrium constant:
[H 2 X ]
[ H  ][ X 2  ]
K2 
[ HX  ]
Where K1 and K2 are first and second ionization constants for the acid H2X
 These Polyacidic base will ionizes in respective steps depends upon how many ionizable
hydroxylic groups are present per molecule, for example: if an acid B(OH) 2 is said to be
ionized in two steps i.e.,
B(OH)2 (aq)  BOH+ (aq) + OH – (aq)
BOH + (aq)  B+2(aq) + OH – (aq)
The corresponding equilibrium constants for the steps are as follows
[ BOH  ][OH  ]
For Step – 1: equilibrium constant: K a1  Step – 2: equilibrium constant:
[ B (OH ) 2 ]
[ B 2  ][OH  ]
K a2 
[ BOH  ]
Where K a1 and K a 2 are first and second ionization constants for the base B(OH) 2
 Note:
o For a polybasic acids the higher the order of ionization constant K a 2 , than the
smaller order of ionization constant K a1 : this because it is very difficult to
remove a positively charged proton from a negative ion due to electrostatic
forces of attraction.
Factors affecting acid strengths: the strength of the acid depends on two factors i.e., strength
and polarity of H – A bond.
 If the energy required breaking the H – A bond is low implies that H – A bond is weak,
which shows that the acid is stronger in nature.
 If the H – A bond becomes more polar, cleavage of the bond becomes easier, thereby
increasing the acidity of the acid.
 Note:
o The acidic strength of acid increases as we move down the group in the
periodic table, because of the increasing the size of the atoms decreases the
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strength of the bond. i.e., “the acidic strength of HF < HCl < HBr < HI”.
Similarly H2S is more acidic than H2O.
o The acidic strength of the acid increases as we move from left to right of the
period in the periodic table, because of the increasing of the polarity of the
bond i.e., electronegativity between the atoms. i.e., the acidic strength of CH4 <
NH3 < H2O < HF.
o In the periodic table the acidic nature increases down the group due to decreasing
the strength of H – A bond, where as along the period the acidic nature increases
from left to right due to increasing in polarity of H – A bond.
Common Ion Effect in the Ionization of Acids and Bases
 Common ion effect: it is defined as “the phenomenon of shifting in equilibrium position

on adding a substance that provides more of an ionic species already present in the
dissociation equilibrium”. Or “the phenomenon of suppressing the ionization of weak
electrolyte by the addition of strong electrolyte having same type of ion”.
Example: Consider the dissociation of acetic acid whose equilibrium state is represented
as:
CH3COOH(aq)  H+(aq) + CH3COO – (aq)
Ka = [CH3COO – ][H+] / [CH3COOH]
Addition of acetate ions to an acetic acid solution results in decreasing the

concentration of hydrogen ions, [H+]. Also, if H+ ions are added from an external source
then the equilibrium moves in the direction of undissociated acetic acid i.e., in a
direction of reducing the concentration of hydrogen ions, [H+].
Hydrolysis of Salts and the pH of their Solutions
 Salt: “it is a product formed by the neutralization reaction between acid and base”.
Example: HCl + NaOH  NaCl + H2O
 Hydrolysis: “the process of interaction between water molecules and cations/anions or

both”.
 It should be noted that the ionized salt in water exists as hydrated ions or interact
with water to reform acids or bases i.e., to form acidic solution or basic solutions.
So, the pH of the solution changes due to ionization of salt in water.
o If a salt of strong acid and strong base is dissolved in water the pH of the solution
remains neural i.e., 7 this is because these salts get hydrated but not undergo
hydrolysis.
o If a salt of weak acid and strong base i.e., CH3COONa is dissolved in water the pH
of the solution become more than 7 and solution becomes basic in nature this is
because acetate ion formed will hydrolysis with water and forms undissoicated
acetic acid with the liberation of OH – ions in the solution, thereby OH – 1 ion
concentration of solution increases.
CH3COONa + H2O(l)  CH3COOH + Na+ + OH –
o If a salt of strong acid and weak base i.e., NH4Cl is dissolved in water the pH of
the solution become less than 7 and solution becomes acidic in nature this is
because NH4+ ion formed will hydrolysis with water and forms undissoicated
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ammonium hydroxide (NH4OH) with the liberation of H+ ions in the solution,
thereby H+ ion concentration in the solution increases.
NH4Cl (s)+ H2O (l)  NH4OH(aq) + H+ (aq)+ Cl – (aq)
o If a salt of weak acid and weak base i.e., ammonium acetate (CH3COONH4) is
dissolved in water the change in the pH value can be determined by
experimentally, this is because both the ions i.e., acetate ion and ammonium ion
undergo hydrolysis with water forming partially dissociated acetic acid and
ammonium hydroxide i.e., the degree of hydrolysis of salt of weak acid and weak
base is independent of the concentration of the solution. thereby the extent of
dissociation of salt tells the nature of the resulting solution, which can be known
by using the formula
pH = 7 + ½ (pKa – pKb)
Where pKa is the strength of the weak acid and pKb is the strength of weak
base at the given temperature.
NOTE: for a salt of weak acid and weak base
 If pKb > pKa or pKa < pKb then the solution is acidic in nature
 If pKb < pKa or pKa > pKb then the solution is basic in nature.
 If pKb = pKa then the solution is neutral
Buffer solutions:
 Definition: The solutions which resist the change in pH on dilution or with the addition of
small amounts of acid or base.
 Buffer action: The ability of the solution to resist the change in pH value.
 The pH of the required buffer solutions can be prepared by knowing pK a value of acid
and pKb value of base and by taking the controlled ratio of salt and acid or salt and
base molar concentrations.
 Type of buffer solutions:
o Acidic buffer: obtained by mixing weak acid with its salt of strong base. Example :
Acetic acid + sodium acetate its pH value is 4.75
o Basic buffer: obtained by mixing weak base with its salt of strong acid. Example:
Ammonium hydroxide + ammonium chloride. Its pH value is 9.25
o Neutral buffer: obtained by mixing salt of weak acid with salt of weak base.
Example:
SOLUBILITY EQUILIBRIA OF SPARINGLY SOLUBLE SALTS
 Solubility means the ability of the solute to dissolve in solvent to form a solution.
 Solubility of the solute depends on number of factors, among them the important factors
are
o Lattice enthalpy of the salt
o Solvation enthalpy of the salt
o Temperature
o Lattice enthalpy of the salt: if the ion – solvent interactions force is more than ion
– ion interaction of slat, then salt is easily soluble in solvent if not it is slightly or
sparingly soluble in solvent.
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o Solvation enthalpy of the salt: higher the solvation enthalpy of solvent i.e.,
more amount is energy is released to break the lattice energy of the salt, salt is
soluble in solvent if not it is insoluble. In general polar solvent solvation enthalpy is
greater so most of the slats soluble, where as in non – polar solvent solvation
enthalpy is less thereby slats, are insoluble.
NOTE: As a general rule, for a salt to be able to dissolve in a particular solvent its
solvation enthalpy must be greater than its lattice enthalpy.
Temperature: as the temperature is increased the solubility of the solute in solvent

o
also increases.
Classification of salts on the basis of their solubility: based on this salts are broadly
classified into three categories
o Category I : Soluble  Solubility > 0.1M

o Category II :Slightly soluble if  0.01M<Solubility< 0.1M
o Category III: Sparingly Solubility if < 0.01M
Solubility Product Constant
Let us consider a sparingly soluble salt MX in contact with its saturated aqueous solution,
then the equilibrium between the undissolved solid and the ions in a saturated solution can be
represented as
MX(s)  M + (aq) + X – (aq)
The equilibrium constant for the above equation is given as
[ M  ][ X  ]
K
[ MX ]
K [ MX ]  [ M  ][ X  ]
But for a pure solid the concentration remains constant therefore, K sp  [ M  ][ X  ] , where Ksp is
called solubility product constant. If ‘S’ is the molar solubility of Salt at equilibrium then for
the above expression K sp  [ M  ][ X  ] = [S][S] = S2.
But we known that salt may give different number of ions on dissolution in water therefore,
If a solid salt M x p X y q with the molar solubility ‘S’ of the salt at equilibrium then its solubility
product constant is given by
K sp  [ M p  ]x [ X q  ] y  [ xS ]x [ yS ] y  x x y y S ( x y )
1
 K  x y
S   x spy 
x y 
NOTE:
o If solubility product (Ksp) of barium sulphate at 298K is 1.1 × 10–10, means that for solid
barium sulphate in equilibrium with its saturated solution, the product of the
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concentrations of barium and sulphate ions is equal to its solubility product constant.
If molar solubility of barium sulphate is S, then
1.1 × 10–10 = (S)(S) = S2 or S = 1.05 × 10–5.
Thus, molar solubility of barium sulphate is equal to 1.05 × 10–5 mol L–1.
o The term Ksp in equation is given by Qsp

o When the concentration of one or more species is not the concentration under
equilibrium. Obviously under equilibrium conditions Ksp = Qsp but otherwise it gives the
direction of the processes of precipitation or dissolution.
Common Ion Effect on Solubility of Ionic Salts
We known that Ksp = Qsp when
o The concentration of any one of the ions is increased in the solution, then it combines
with opposite charged ion and salt will be precipitated in accordance with Le – Chatelier’s
principle. Or
o The concentration of one of the ions is decreased; more salt will dissolve to increase the
concentration of both the ions.
Note:
o To a saturated solution of NaCl when HCl gas is passed through it, NaCl get
precipitated due to increased in concentration (activity) of chloride ion in the
solution due to dissociation of HCl, thus we get pure sodium chloride.
o The common ion effect is also used for almost complete precipitation of a particular
ion as its sparingly soluble salt, with very low value of solubility product for
gravimetric estimation.
 Example: the precipitation of silver ion as silver chloride, ferric ion as ferric
hydroxide or hydrated ferric oxide and barium ion as barium sulphate for
quantitative estimations.
o The solubility of salts of weak acids increased at lower pH values, because of the
concentration of anion decreased due to its protonation which in turn increased the
solubility of the salt so that Ksp = Qsp . to prove this we have to satisfy two equilibria
simultaneously i.e.,
Ksp = [M+] [X–], and HX(aq) H+ (aq) + X−(aq); Therefore
[ H  ][ X  ] Ka [X ] [ H  ] [ HX ]
Ka  i.e.,  or 
[ HX ] [ H  ] [ HX ] [K a ] [ X  ]
[H  ] [ HX ] [ H  ]  [ K a ] [ HX ]  [ X  ]
Adding ‘1’ on both sides we get 1   1 or 
[Ka ] [X ] [Ka ] [X ]
Ka [X ]
Now, again taking inverse, we get  f  and it can be seen that ‘f’
[H  ]  Ka [ HX ]  [ X  ]
decreases as pH decreases.
If S is the solubility of the salt at a given pH then Ksp = [S] [f S] = S2 {Ka / (Ka + [H+])} and S =
{Ksp ([H+] + Ka ) / Ka }1/2.
Therefore, solubility S increases with increase in the [H+] or decrease in pH.

81
82
8 Redox Reactions
Introductions:
Redox reactions are the one of the important category of chemical reactions which deals
with change of one kind of matter into the other. These reactions are found extensive uses in
pharmaceutical, biological, industrial, metallurgical and agricultural areas. The importance of
these reactions is that burning of different types of fuels for obtaining energy for domestic,
transport and other commercial purposes, electrochemical processes for extraction of highly
reactive metals and non-metals, manufacturing of chemical compounds like caustic soda,
operation of dry and wet batteries and corrosion of metals fall within the purview of redox
processes. It also considered that hydrogen economy i.e., use of liquid hydrogen as fuel and
development of ‘Ozone Hole’ are redox phenomenon.
OXIDATION AND REDUCTION REACTIONS

A redox reaction involves oxidation and reduction processes.
CLASSICAL IDEA OF REDOX REACTIONS –

DEFINITION
Oxidation
In terms of oxygen: the addition of oxygen to an element or a compound. Example:
2Mg(s) + O2(g) → 2MgO(s)
2Fe (s) + 3O2 (g) 2Fe2O3(s)
S(s) + O2 (g) → SO2(g)
In terms of hydrogen: removal of hydrogen from an element or a compound. Example:
CH4 (g) + 2O2 (g) → CO2(g) + 2H2O(l)
2H2S(g) + O2(g) → 2S(s) + 2H2O(l)
In terms of electronegative element: the addition of electronegative element to substance.

Example:
Mg(s) + F2(g) → MgF2(s)

Mg(s) + Cl2 (g) → MgCl2 (s)
Mg(s) + S(s) → MgS(s) (8.7)
In terms of electropositive element: the removal of electropositive elements. Example
2K4[Fe(CN)6](aq) + H2O2(aq) →2K3[Fe(CN)6](aq) + 2KOH(aq)
Reduction
In terms of oxygen: the removal of oxygen from an element or a compound. Examples
2 HgO (s) + heat  2Hg(l) + O2 (g)
In terms of hydrogen: the addition of hydrogen to an element or a compound. Example
CH2 = CH2(g) + H2(g) → H3C-CH3(g)

83
In terms of electronegative element: removal of electronegative element from the substance.
Example: when Zn reacts with HCl to form hydrogen gas
Zn + 2HCl  ZnCl2 + H2
In terms of electropositive element: addition of electropositive element to substance or
compound. Example: addition of mercury to mercuric chloride
2HgCl2(aq) + SnCl2(aq) → Hg2Cl2(s)+SnCl4(aq)
Redox – reactions
Oxidation: removal or loss of electron from an element: Zn  Zn2+ + 2e –
Reduction: addition or gain of electron to an element: Cu2+ + 2e –  Cu

Zn + Cu2+  Zn2+ + Cu
In above reaction Zn will losses two electrons to from Zn2+ thereby it is undergoing oxidation
where as Cu2+ ions gains two electrons to from Cu metal i.e., reduction. These two reactions take
place simultaneously; such reactions are known as Redox reactions.
Redox reaction is defined as the reaction where both reduction and oxidation a reaction takes
place simultaneously.
Oxidising agent: it is the species which undergo reduction by accepting the electrons.
Reducing agent: it is the species which undergo oxidation by losing the electrons.
Consider the reaction i.e., Zn + Cu2+  Zn2+ + Cu

In this reaction Zn losses the electron i.e., undergo oxidation thereby it is called reducing agent
where as Cu2+ gains the electrons i.e., undergo reduction thereby it is called oxidising agent.
Note: in general metals acts as oxidising agents by losing the electrons where as non – metals
acts as reducing agents by gaining electrons.
Problems
In the reactions given below, identify the species undergoing oxidation and reduction:
(i) H2S(g) + Cl2(g) → 2HCl(g) + S(s)
(ii)3Fe3O4(s) + 8Al(s) → 9Fe(s) + 4Al2OM3(s)
(iii) 2Na(s) + H2(g) → 2NaH (s)
(iv) 2Na(s) + Cl2(g) → 2NaCl(s)
(v) Mg(s) + O2(g) →MgO(s)
OXIDATION NUMBER
The apparent charge possessed by an atom is known as oxidation number or is a complete
transfer of electron from a less electronegative atom to a more electronegative atom.
Oxidation number denotes the oxidation state of an element in a compound ascertained

according to a set of rules formulated on the basis that electron in a covalent bond belongs
entirely to more electronegative element.
84
Rules For The Calculation Of Oxidation Number. These rules are:
1. In elements, in the free or the uncombined state, each atom bears an oxidation number of
zero. Evidently each atom in H2, O2, Cl2, O3, P4, S8, Na, Mg, Al has the oxidation number
zero.
2. the oxidation number of ions is equal to the charge on the ion. I.e., Na + ion oxidation
number is +1, Mg2+ ion is +2, Fe3+ ion is +3, Cl – ion is – 1.
3. the oxidation number of alkali metal is +1 and alkali earth metals is +2
4. The oxidation number of oxygen in oxide state is – 2. Peroxide is – 1 and superoxide is -
½.
5. The oxidation number of hydrogen is +1, except in metal hydrates is – 1.
6. In all its compounds, fluorine has an oxidation number of – 1.
7. The algebraic sum of the oxidation number of all the atoms in a compound must be zero.
In polyatomic ion, the algebraic sum of all the oxidation numbers of atoms of the ion must
equal the charge on the ion.
Note:
 The oxidation number of oxygen in F2O is +2 and F2O2 is +1
 Halogens except fluorine can show positive oxidation number with attached to
highly electron negative element i.e, fluorine or oxygen.
 The example of oxygen to shown – ½ oxidation state is K2O.
STOCK NOTATION:
 Alfred stock as developed a method of writing the oxidation number state of metals which
is latter on called as stock notation of oxidation number.
 Stock notation of metals oxidation state can be written by putting a Roman numeral
representing the oxidation number in parenthesis after the symbol of the metal in the
molecular formula.
Example: FeO, Fe2O3, CuI, CuO, MnO and MnO2 stock notation can be written as follows
FeO Fe(II)O, Fe2O3 Fe2(III)O3, CuI Cu(I)I,
CuO Cu(II)O, MnO Mn(II)O, MnO2 -Mn(IV)O2.
The idea of oxidation number has been invariably applied to define oxidation, reduction,
oxidising agent (oxidant), reducing agent (reductant) and the redox reaction.
Definition of Oxidation and Reduction In Terms Of Oxidation Number
Oxidation: An increase in the oxidation number of the element in the given substance.
Reduction: A decrease in the oxidation number of the element in the given substance.
Oxidising agent: A reagent which can increase the oxidation number of an element in a given
substance. These reagents are called as oxidants also.
Reducing agent: A reagent which lowers the oxidation number of an element in a given
substance. These reagents are also called as reductants.
Redox reactions: Reactions which involve change in oxidation number of the interacting species.
Types of Redox Reactions

Redox reactions are classified into four types
 Combination reaction
 Decomposition reactions
 Displacement reactions
 Disproportionation reactions
85
Combination reactions: A combination reaction may be denoted in the manner:

A+B→C
Either A and B or both A and B must be in the elemental form for such a reaction to be a redox
0 0 4  2
reaction. Example: C (s)  O 2 ( g )  C O 2 ( g )
Decomposition reactions
Decomposition reactions are the opposite of combination reactions. Precisely, a decomposition
reaction leads to the breakdown of a compound into two or more components at least one of
which must be in the elemental state. Examples:
1 5 2 1 1 0
2 K Cl O 3 ( s ) 


2 K Cl ( s )  3 O 2 ( g )
NOTE: all decomposition reactions are not redox reactions. For example, decomposition of
2 4 2 2 2 4 2
calcium carbonate is not a redox reaction. Ca C O 3 ( s ) 

Ca O ( s )  C O 2 ( g )
Displacement reactions In a displacement reaction, an ion (or an atom) in a compound is

replaced by an ion (or an atom) of another element. It may be denoted as:
X + YZ → XZ + Y
Displacement reactions fit into two categories: metal displacement and non-metal displacement.
(a) Metal displacement:

A metal in a compound can be displaced by another metal in the uncombined state. Examples
2 4 2 0 0 2 4 2
Cu S O 4 ( aq )  Zn ( s )  Cu ( s )  Zn S O 4 ( aq )
In each case, the reducing metal is a better reducing agent than the one that is being reduced
which evidently shows more capability to lose electrons as compared to the one that is reduced.
(b) Non-metal displacement: The non-metal displacement redox reactions include hydrogen
displacement and a rarely occurring reaction involving oxygen displacement. All alkali metals
and some alkaline earth metals (Ca, Sr, and Ba) which are very good reluctant , will displace
hydrogen from cold water.
0 1 2 1 2 1 0
2 Na ( s )  2 H 2 O(l )  2 Na O H (aq )  H 2 ( g )
1 2 0 1 1 0
2 H 2 O (l )  2 F 2 ( g )  4 H F (aq)  O 2 ( g )
Disproportionation reactions
In a disproportionation reaction an element in one oxidation state is simultaneously oxidised and
reduced. One of the reacting substances in a disproportionation reaction always contains an
element that can exist in at least three oxidation states. The element in the form of reacting
substance is in the intermediate oxidation state; and both higher and lower oxidation states of
that element are formed in the reaction.
1 1 1 2 0
2 H 2 O 2 (aq)  2 H 2 O(l )  O 2 ( g )
0 2 1  1 2  1  1 2
Cl 2 ( g )  2 O H (aq)  Cl O (aq)  Cl  H 2 O
86
Balancing of Redox Reactions
Two methods are used to balance chemical equations for redox processes.
 First methods is based on the change in the oxidation number of reducing agent and the
oxidising agent
 Second method is based on splitting the redox reaction into two half reactions – one
involving oxidation and the other involving reduction.
Oxidation Number Method:

In writing equations for oxidation-reduction reactions, just as for other reactions, the
compositions and formulas must be known for the substances that react and for the products
that are formed. The oxidation number method is now best illustrated in the following steps:
Rules to balance the redox reactions based on oxidation number method:
Balance the following equations by using oxidation number method
in acidic medium
Step 1: The skeletal ionic equation is:
Step 2: Assign oxidation numbers for Cr and S

6 4 3 6
Cr 2 O7 2 ( aq )  S O3 2 ( aq )  Cr ( aq )  S O 42  ( aq )
This indicates that the dichromate ion is the oxidant and the sulphite ion is the reductant.
Step 3: Calculate the increase and decrease of oxidation number, and make them equal:
6 4 3 6
Cr 2 O 7 2 ( aq )  3S O 3 2 ( aq )  2 Cr ( aq )  3S O 42  ( aq )
Step 4: As the reaction occurs in the acidic medium, and further the ionic charges are not equal
on both the sides, add 8H+ on the left to make ionic charges equal
6 4 3 6
Cr 2 O7 2 ( aq )  3S O3 2 (aq )  8 H   2 Cr ( aq )  3S O42  (aq )
Step 5: to balance the oxygen atoms add water to right hand side
6 4 3 6
Cr 2 O7 2 ( aq )  3S O3 2 ( aq )  8 H   2 Cr ( aq )  3S O42  ( aq )  4 H 2O
Balance the following equations by using oxidation number method

MnO4 (aq )  Br  (aq )  MnO2 ( s )  BrO3 (aq) in acidic medium
Step 1: The skeletal ionic equation is:

MnO4 (aq)  Br  (aq)  MnO2 ( s )  BrO3 (aq)
Step 2 : Assign oxidation numbers for Mn and Br the oxident and bromide ion is the reductant.
7 2 1  4 2 5 2
Mn O 4 ( aq )  Br ( aq )  Mn O 2 ( s )  Br O 3 ( aq )
87
Step 3: Calculate the increase and decrease of oxidation number, and make the increase equal
to the decrease.
7 2 1 4 2 5 2
2 Mn O 4 ( aq)  Br ( aq)  2 Mn O 2 ( s)  Br O 3 (aq)
Step 4: As the reaction occurs in the basic medium, and the ionic charges are not equal on both
sides, add 2 H+ ions on the right to make ionic charges equal.
2 MnO4 ( aq)  Br  (aq )  2MnO2 ( s)  BrO3 (aq)  2OH 
Step 5: the hydrogen atoms are balanced by add appropriate number of water molecules on the
right side to achieve balanced redox change.
2MnO4 (aq)  Br  (aq)  H 2O  2MnO2 ( s)  BrO3 (aq)  2OH 
Half Reaction Method:

In this method, the two half equations are balanced separately and then added together to give
balanced equation.
Rules to balance the redox reaction by half reaction or ion electron method:
1. Separate the oxidizing and the reducing agents.

2. Write down one half – equation for the oxidizing agent changing into its reduce form.
3. Write down the other half equation showing the reducing agent changing into its oxidized
form.
4. Balance the atoms other than H and O for each half reaction by adjusting coefficients. If
necessary
5. Balance the oxygen atoms on the two sides by adding H2O to the side deficient in oxygen.
6. Balance the hydrogen atoms on the two sides by adding H+ to the side deficient in
hydrogen.
7. Equalize the charge on both sides by adding electrons to the side deficient in negative
charge.
8. If the reaction proceeds in basic solution, add enough OH – on both sides of the half –
reaction to get the of H+ appearing there. Combine H+ and OH – to give H2O and remove
H2O duplication.
9. Add these two balanced half – reactions in such a way that the electrons appearing on the
right of one half – reaction and on the left of the other cancel. For this each half – reaction
will be multiplied by some appropriate number before addition.
Balance the following redox equation by using half reaction method:

Fe 2 (aq )  Cr2O72 (aq)  Fe 3 (aq )  Cr 3 (aq ) in acidic medium
Step 1: Produce unbalanced equation for the reaction in ionic form:
Fe 2 (aq)  Cr2 O72 (aq)  Fe 3 (aq)  Cr 3 (aq)
Step 2: Separate the equation into half-reactions:
2  2 3  3
Oxidation half reaction: Fe ( aq )  Fe ( aq )
6 2 2  3 3
Reduction half reaction: Cr 2 O 7 ( aq )  Cr (aq )
88
Step 3: multiply the oxidation reaction by ‘1’ and reduction half reaction by ‘2’ to balance Fe2+
and Cr3+ ions.
2 2  3 3
Oxidation half reaction:  Fe (aq)  Fe (aq)   1 Fe ( aq)  Fe ( aq)
2 2 3 3 
 
 
6 2 2  3 3
Reduction half reaction:  Cr   2Cr 2 O 7 (aq)  2Cr (aq )
6 2 3 2 3
 2 O 7 ( aq )  Cr ( aq )   2
 
Step 4: since the reaction occurs in acidic medium add H2O to right side to balance O atoms and
H+ to left side to balance H atoms.
6 2 2  3 3
2Cr 2 O 7 (aq)  14H   2Cr (aq)  7 H 2 O(l )

Step 5: Add electrons to one side of the half reaction to balance the charges.
2 2 3  3
Fe (aq)  Fe (aq)  e 
6 2 2  3 3
2Cr 2 O 7 (aq)  14 H   6e   2Cr (aq)  4 H 2 O(l )

To balance the numbers of electrons multiply the oxidation half reaction with ‘6’
2 2  3 3
6 Fe (aq)  6 Fe (aq)  6e 
Step 6: We add the two half reactions to achieve the overall reaction and cancel the electrons on
each side. This gives the net ionic equation as :
6 Fe 2  ( aq )  Cr2 O72  ( aq )  14 H  ( aq )  6 Fe 3 (aq )  2Cr 3 ( aq )  7 H 2 O (l )
Balance the following redox equation by using half reaction method:
MnO4 (aq)  I  (aq)  MnO2 ( s)  I 2 ( s) in basic medium
Step 1: First we write the skeletal ionic equation
MnO4 (aq)  I  (aq)  MnO2 ( s)  I 2 ( s )
Step 2: The two half-reactions are:
1 0
Oxidation half reaction: I ( aq )  I 2 ( aq )
7 2 4 2
Reduction half reaction: Mn O 2 ( aq )  Mn O 2 ( s )
1 0
Step 3: To balance the ‘I’ atoms in the oxidation half reaction, 2 I (aq)  I 2 (aq)
Step 4: To balance the O atoms and H in the reduction half reaction and oxidation reactions
respectively, we add two water molecules on the right and H+ on left side:
7 2 4 2
Mn O 2 ( aq )  4 H  ( aq )  Mn O 2 ( s )  2 H 2 O (l )
As the reaction takes place in a basic solution, therefore, for four H + ions, we add four OH-ions to
both sides of the equation:
7 2 4 2
Mn O 2 ( aq )  4 H  ( aq )  4OH  ( aq )  Mn O 2 ( s )  2 H 2 O (l )  4OH  ( aq )
Replacing the H+ and OH- ions with water, the resultant equation is:
7 2 4 2
Mn O 2 ( aq)  2 H 2 O(l )  Mn O 2 ( s )  4OH  (aq)

Step 5: In this step we balance the charges of the two half-reactions in the manner depicted as:
1 0
2 I (aq )  I 2 (aq )  2e 
7 2 4 2
Mn O 2 (aq)  2 H 2 O(l )  3e   Mn O 2 ( s )  4OH  ( aq)
Multiply the oxidation half-reaction by 3 and the reduction half-reaction by 2 to equate the
number of electrons.
89
 1 0

1 0

 2 I (aq)  I 2 (aq)  2e   3  6 I (aq)  3I 2 (aq)  6e ----- (1)
 
 Mn O 2 ( aq )  2 H O (l )  3e   Mn O 2 ( s )  4OH  (aq )   2
7 2 4 2
 2
 ------(2)
7 2 4 2
 2 Mn O 2 ( aq )  4 H 2 O (l )  6e   2 Mn O 2 ( s )  8OH  ( aq )
Step 6: Add equation (1) and (2) two half-reactions to obtain the net reactions after cancelling
electrons on both sides.
2MnO4 (aq)  6 I  (aq)  4 H 2 O(l )  2MnO2 ( s)  3I 2 ( s )  8OH  (aq)
Redox Reactions as the Basis for Titrations

In redox systems, the titration method can be adopted to determine the strength of a
reductant/oxidant using a redox sensitive indicator. The usage of indicators in redox titration is
illustrated below:
 In one situation, the reagent itself is intensely coloured, e.g., permanganate ion, MnO 4-.
Here MnO4- acts as the self indicator. The visible end point in this case is achieved after
the last of the reductant (Fe2+ or C2O42-) is oxidised and the first lasting tinge of pink
colour appears at MnO4 - concentration as low as 10-6 mol dm-3 (10-6 mol L-1). This
ensures a minimal ‘overshoot’ in colour beyond the equivalence point, the point where the
reductant and the oxidant are equal in terms of their mole stoichiometry.
 If there is no dramatic auto-colour change (as with MnO4- titration), there are indicators
which are oxidised immediately after the last bit of the reactant is consumed, producing a
dramatic colour change. The best example is afforded by Cr2O72-, which is not a self-
indicator, but oxidises the indicator substance diphenylamine just after the equivalence
point to produce an intense blue colour, thus signalling the end point.
 There is yet another method which is interesting and quite common. Its use is restricted
to those reagents which are able to oxidise I - ions, say, for example, Cu(II): 2Cu2+(aq) + 4I-
(aq) → Cu2I2(s) + I2(aq)
This method relies on the facts that iodine itself gives an intense blue colour with starch
and has a very specific reaction with thiosulphate ions (S 2O32-), which too is a redox
reaction: I2(aq) + 2S2O32-(aq)→2I-(aq) + S4O62-(aq) I2, though insoluble in water, remains in
solution containing KI as KI3. On addition of starch after the liberation of iodine from the
reaction of Cu2+ ions on iodide ions, an intense blue colour appears. This colour
disappears as soon as the iodine is consumed by the thiosulphate ions. Thus, the end-
point can easily be tracked and the rest is the stoichiometric calculation only.
Limitations of Concept of Oxidation Number As you have observed in the above discussion,
the concept of redox processes has been evolving with time. This process of evolution is
continuing. In fact, in recent past the oxidation process is visualised as a decrease in electron
density and reduction process as an increase in electron density around the atom(s) involved in
the reaction.
90
REDOX REACTIONS AND ELECTRODE
PROCESSES
We observed if zinc rod is dipped in copper sulphate

solution. The redox reaction takes place and during
the reaction, zinc is oxidised to zinc ions and copper
ions are reduced to metallic copper due to direct
transfer of electrons from zinc to copper ion.
During this reaction heat is also evolved. Now we

modify the experiment in such a manner that for the
same redox reaction transfer of electrons takes place
indirectly. We can do that by making a separation
between Zn metal and copper sulphate solution.
Preparation of salt bridge----
We connect solutions in two beakers by a salt bridge (a U-tube containing a solution of

potassium chloride or ammonium nitrate usually solidified by boiling with agar agar and later
cooling to a jelly like substance).
Significance of salt bridge------
This provides an electric contact between the two solutions without allowing them to mix
with each other.
We know that the flow of current is possible only if there is a potential difference between
the copper and zinc rods known as electrodes here.
The potential associated with each electrode is known as electrode potential.
If the concentration of each species taking part in the electrode reaction is unity (if any
gas appears in the electrode reaction, it is confined to 1 atmospheric pressure) and further the
reaction is carried out at 298K, then the potential of each electrode is said to be the Standard
Electrode Potential.
By convention, the standard electrode potential (E0 of hydrogen electrode is 0.00 volts).
The electrode potential value for each electrode process is a measure of the relative tendency of
the active species in the process to remain in the oxidised/reduced form. A negative E0 means
that the redox couple is a stronger reducing agent than the H+/H2 couple. A positive E0 means
that the redox couple is a weaker reducing agent than the H+/H2 couple.
The standard electrode potentials are very important and we can get a lot of other useful
information from them.
91
9 Hydrogen
Introduction:
 It is the first element in the periodic table.

 Discovery of hydrogen  Scientists had been producing hydrogen for years before it was
recognized as an element. Written records indicate that Robert Boyle produced hydrogen
gas as early as 1671 while experimenting with iron and acids. Hydrogen was first
recognized as a distinct element by Henry Cavendish in 1766.
 Discovery of isotopes of hydrogen  Deuterium discovered in 1932, Tritium discovered in
1934.
 Symbol  H
 Atomic number  1
 Atomic mass or mass number  1.008amu
 Electronic configuration  1s1
 Isotopes  Hydrogen or protium, Deuterium and Tritium.
 Number of protons, electrons and neutrons  1, 1 and 0 in hydrogen, 1, 1, 1 in
deuterium and 1, 1, 2 in tritium.
 Protium is present in the large amount in earth curst; deuterium is next where as tritium
is one part for every 108 parts of protium.
 Tritium is the radioactive isotope of hydrogen.
 Density  0.09g/L
 Melting point  13.96K
 Boiling point  20.39K
 Meaning of hydrogen  It is a Greek word ‘hydro and genes’ means ‘water forming’
 Physical state at room temperature  Colourless, odorless, tasteless lightest and
combustible gas
 Oxidation state  +1, - 1
 Ionization energy 13.598 eV
 Uses of dihydrogen gas:
92
o In the synthesis of ammonia by Haber’s process
o In the hydrogenation of fats and oils
o In the manufacturing of bulk organic compounds particularly methanol.
o In the manufacturing of metal hydrides.
o In the preparation of hydrogen chloride.
o In the reduction of metal oxides to metal in metallurgical processes.
o Liquid hydrogen is used to study the properties of semiconductors.
o The combination of liquid hydrogen and liquid oxygen in it used as rocket fuel.
o Atomic hydrogen and oxy – hydrogen torches are used for welding and cutting of
metals.
o In the form of fuel cells, dihydrogen gas is used to generate electrical energy.
 Position of hydrogen atom in the periodic table: the position of the hydrogen atom in
the periodic table is uncertainty because of its electronic configuration and reactivity, i.e.,
its electronic configuration is 1s1 shows that it belongs to alkali metals where as its
reactivity to form diatomic molecules shows that it belongs with halogens. More or less it
behaviour as alkali metal by donating one electron, forming oxides, halides and
sulphides, where as it behaviour as halogens by having very high ionization enthalpy and
not possessing metallic character under normal conditions and low reactivity than
halogens.
In fact, it is also seen that, hydrogen differs from alkali metals as well as halogens
because by loosing one electron resulting its ionic radii approximately equal to 1.5 x 10 – 3
pm size which is extremely smaller than atomic or ionic radii, thereby formation of free H +
is not so easy and it is always associated with other atoms or molecules, which is the
unique property of the hydrogen only, thereby it is suggested that it should be kept
separately in the periodic table.
 Preparation of dihydrogen
o Laboratory preparation: When diluted hydrochloric acid or aqueous alkali is
treated with granulated zinc dihydrogen is obtained. Zn + 2HCl  ZnCl2 + H2,
Zn + 2NaOH (aq)  Na2ZnO2 + H2
o Commercial production of dihydrogen:
 Electrolysis of acidified water using platinum electrodes
Electrolysis
2H2O(l) 2H2 (g) + O2(g)
Traces of
 When steam is passed over hydrocarbons (methane) at high temperature

i.e., around 1270K in the presence of catalyst dihydrogen is obtained.
Cn H2n + 2 + nH2O 1270
 K
 nCO + (2n + 1)H2
C H4 + H2O 1270
 K
 CO + 2H2
 Coal gasification: it is the method of preparation of ‘water gas’ or

‘synthesis gas’ or ‘syngas’ by passing steam over coal at high temperature
i.e., 1270K. Reaction:
C(s) + H2O(steam)  CO(g) + H2 (g) 
 Water gas shift reaction: it is the method of increasing the production of

dihydrogen gas by reacting water gas with steam and carbon dioxide is
removed by scrubbing by sodium arsenite solution. Reaction: CO(g) +
H2O(steam)  CO2 (g)+ H2(g)
93
NOTE:
 Water gas or synthesis gas or syngas is nothing but mixture of carbon monoxide and
dihydrogen gas
 77% of the production of dihydrogen is obtained from petrochemicals, 18% from
coal, 4% from electrolysis of aqueous solutions and 1% from other sources.
 Chemical properties:
The cleavage of the H – H bond requires large amount of energy i.e., around 5000K and
more or less it always undergo three types of reactions i.e., (1) it looses an electron to give
H+, (2) it gains an electron to give H – 1 and (3) shares the electrons to form a single
covalent bond
o Reaction with halogens: it reacts with halogens to form corresponding hydrogen

halides. H2 + X2  2HX
o Reaction with oxygen: it reacts with dioxygen to form water which is an exothermic
reaction 2H2 + O2  2H2O
o Reaction with nitrogen: it reacts with nitrogen to form ammonia
N2 + 3H2 (Fe/Mo at 200atm/4500C)  2NH3
HYDROGEN PEROXIDE (H2O2)

 Hydrogen peroxide is an important chemical used in pollution control treatment of
domestic and industrial effluents.
 It is almost a colourless liquid.
 Molecular formula  H2O2

 Its melting point 272.4K
 Its boiling point 423K
 It is water soluble in all proportions and forms a hydrate i.e., H2O2.H2O whose melting
point is 221K
Note: A 30% solution of H2O2 is marketed as ’100 volume’ hydrogen peroxide. It means that one
millilitre of 30% H2O2 solution will give 100 V of oxygen at STP. Commercially, it is marketed as
10 V, which means it contains 3% H2O2.
Preparation
 Acidifying barium peroxide and removing excess water by evaporation under reduced
pressure gives hydrogen peroxide.
BaO2.8H2O(s)+ H2SO4(aq)→ BaSO4(s)+H2O2(aq)+8H2O(l)
Structure of hydrogen peroxide:
 It is having non – planar structure.

 Structure of H2O2 in gas phase: structure of H2O2 in solid phase
94
Chemical Properties It acts as an oxidising as well as reducing agent in both acidic and
alkaline media. Simple reactions are described below.
 Oxidising action in acidic medium: PbS(s)+ 4H2O2(aq)→ PbSO4(s)+4H2O(l)
 Reducing action in acidic medium: 2MnO4-+6H++5H2O2→ 2Mn2++8H2O+ 5O2
 Reducing action in basic medium: I 2+ H2O+2OH-→ 2I-+2H2O+ O2
Storage of hydrogen peroxide: it is observed that H2O2 decomposes slowly on exposure
to light.
2H2O2(l) → 2H2O(l) +O2(g)
 Hydrogen peroxide is not stored in glass container because the traces of alkali metal
present in the glass will catalysis the decomposition of hydrogen peroxide.
 Therefore, it is stored in wax-lined glass or plastic vessels in dark. Urea can be added as a
stabiliser. It is kept away from dust because dust can induce explosive decomposition of
the compound.
Uses of hydrogen peroxide:

 Its wide scale use has led to tremendous increase in the industrial production of H 2O2.
 In daily life it is used as hair bleach and as a mild disinfectant. As an antiseptic it is sold
in the market as perhydrol.
 It is used to manufacture chemicals like sodium perborate and per-carbonate, which are
used in high quality detergents.
 It is used in the synthesis of hydroquinone, tartaric acid and certain food products and
pharmaceuticals (cephalosporin)
 It is employed in the industries as a bleaching agent for textiles, paper pulp, leather, oils,
fats, etc.
 It is also used in Environmental (Green) Chemistry. For example, in pollution control
treatment of domestic and industrial effluents, oxidation of cyanides, restoration of
aerobic conditions to sewage wastes, etc.
HEAVY WATER, D2O

It is extensively used as a moderator in nuclear reactors
It is in exchange reactions for the study of reaction mechanisms.
It is used for the preparation of other deuterium compounds, i.e., C 2D2, Ca(OD)2, D2SO4, 3CD4,
4Al(OD)3
DIHYDROGEN AS A FUEL
Dihydrogen releases large quantities of heat on combustion.
Hydrogen economy: In this view Hydrogen Economy is an alternative. The basic principle of
hydrogen economy is the transportation and storage of energy in the form of liquid or gaseous
dihydrogen. Advantage of hydrogen economy is that energy is transmitted in the form of
dihydrogen and not as electric power. It is for the first time in the history of India that a pilot
project using dihydrogen as fuel was launched in October 2005 for running automobiles. Initially
5% dihydrogen has been mixed in CNG for use in four-wheeler vehicles. The percentage of
dihydrogen would be gradually increased to reach the optimum level.
Nowadays, it is also used in fuel cells for generation of electric power. It is expected that
economically viable and safe sources of dihydrogen will be identified in the years to come, for its
usage as a common source of energy.
95
HYDRIDES
Dihydrogen, under certain reaction conditions, combines with almost all elements, except
noble gases, to form binary compounds, called hydrides. If ‘E’ is the symbol of an element then
hydride can be expressed as EHx (e.g., MgH2) or EmHn (e.g., B2H6).
The hydrides are classified into three categories:
(i) Ionic or saline or salt like hydrides example:
(ii) Covalent or molecular hydrides
(iii) Metallic or non-stoichiometric hydrides
Ionic or Saline Hydrides

These are stoichiometric compounds of dihydrogen formed with most of the s-block elements
which are highly electropositive in character. Example: LiH, BeH2 and MgH2, BeH2 MgH2
Covalent or Molecular Hydride

Dihydrogen forms molecular compounds with most of the p-block elements. Examples are CH4,
NH3, H2O and HF.
Molecular hydrides are further classified according to the relative numbers of electrons and
bonds in their Lewis structure into:
 Electron-deficient Example Diborane (B2H6), hydride of 13th group elements
 Electron-precise Example: CH4, hydride of 14th group elements
 Electron-rich hydrides. Example NH3, H2O,HF hydride of 15th to 17th group
elements
Metallic or Non-stoichiometric (or Interstitial) Hydrides

These are formed by many d-block and f-block elements. Example: LaH2.87, YbH2.55, TiH1.5-1.8,
ZrH1.3-1.75, VH0.56, NiH0.6-0.7, PdH0.6-0.8etc.
WATER
Structure of Water
In the gas phase water is a bent molecule with a bond
angle of 104.5°, and O-H bond length of 95.7 pm.
It is a highly polar molecule.
Its orbital overlap picture in water is shown in Fig.
In the liquid phase water molecules are associated
together by hydrogen bonds.
Structure of Ice
Ice has a highly ordered three dimensional hydrogen bonded structure
Examination of ice crystals with X-rays shows that each oxygen atom is
surrounded tetrahedrally by four other oxygen atoms at a distance of 276
pm.
Hydrogen bonding gives ice a rather open type structure with wide holes.
These holes can hold some other molecules of appropriate size
interstitially.
Hard and Soft Water
Hard water Soft water

96
It contains calcium and magnesium It doesn’t contains calcium and
salts of bicarbonates, chloride and magnesium salts of
sulphate bicarbonates, chloride and
sulphate
It will not give lather with soap It will give lather with soap
It give scum/precipitate with soap It will not give scum/precipitate
with soap
Hard water forms scum/precipitate with soap because it contains sodium stearate reacts with
hard water to precipitate out Ca/Mg stearate.
2C17H35COONa(aq) + Ca2+/Mg2+  (C17H35COO)2Ca
It is, therefore, unsuitable for laundry. It is harmful for boilers as well, because of deposition of
salts in the form of scale. This reduces the efficiency of the boiler. The hardness of water is of two
types:
Hardness of the water is of into two types (i) temporary hardness and (ii) permanent
hardness
Temporary hardness Permanent hardness

It contains calcium and magnesium It contains calcium and magnesium
salts of bicarbonates. salts of chloride and sulphate
It can be removed by boiling or by It can not be removed by boiling or
adding lime to it by adding lime to it.
97
10 s – Block Elements
Introduction:
s – Block elements: valency electrons end in the s – sub orbital


Its electronic configuration is[noble gas] ns1 – 2

It contains two groups i.e., group 1 and 2 are known as alkali metals and alkali earth
metals respectively.

Alkali metals having electronic configuration [noble gas] ns1. They have the oxidation
state is +1.

Alkali earth metals. [Noble gas] ns2. They have the oxidation state is +2

As moving down the group ionization enthalpy decreases because their atomic radii
increases so that valency electrons and loosely attracted by the nucleus.

The metallic character and reactivity increases down the group because ionization energy
will decreases along the group.

Except beryllium and lithium forms covalent bond where as all other elements a forms
ionic compound because of it’s smaller in size of anion and high polarizing power.
ALKALI METALS:
 First group elements are called alkali metals. The members of this group are Lithium,
Sodium, Potassium, Rubidium, Caesium and Francium.
 Alkali metals are called so because they form hydroxides on reaction with water which are
strongly alkaline i.e., basic in nature.
 Occurrence: Among alkali metals sodium and potassium are abundant, lithium,
rubidium and caesium lower abundance, where as francium is highly radioactive whose
half life period is 21 minutes.
Physical properties:
 Nature: These metals are silvery white, soft and light in nature.
 Electronic configuration : [Noble gas]ns1 where n = 2,3,4,5,6,7
 Electropositive nature: These elements are highly electropositive in nature because of
loosely held s – electrons in the outermost valence shell, so in nature they always found in
combined form.
 Oxidation state: They always show +1 oxidation state i.e., always they form monovalent,
because of the presence of one electron in the valence shell and by loosing it they show
noble gas configuration.
 Ionization Enthalpy:The ionization enthalpies of the alkali metals are considerably low
and decrease down the group from Li to Cs. This is because the effect of increasing size
outweighs the increasing nuclear charge, and the outermost electron is very well screened
from the nuclear charge.
 Hydration Enthalpy: The hydration enthalpies of alkali metal ions decrease with increase
in ionic sizes. Li+> Na+ > K+ > Rb+ > Cs+. Li+ has maximum degree of hydration and for this
reason lithium salts are mostly hydrated, e.g., LiCl· 2H2O
 Atomic radii and ionic radii: lithium to caesium atomic radii and ionic radii increases
because of increasing of number of shells around the nucleus, and ionic radii is always
less than the atomic radii of the parent atom.
98
 Density: these elements will have lower density and along the group density increases.
Potassium is having lower density that sodium because of abnormal increase of its atomic
size.
Element Lithium Sodium Potassium Rubidium Caesium
Density/gm 0.53 0.97 0.86 1.53 1.90

–3
 Melting and boiling points: they have low m.p and b.p indicates weak metallic bounding
due to the presence of only one valence electron in the valence shell.
 Flame colouration: these metals and metal salts will be characteristic colour to the
oxidizied flame. This is because, when the metal or its salt is heated the outer most
electron absorbs the energy and exited to the higher energy level and when comes back to
the ground state they emit the radiation which falls in the visible region of the light which
impact the colour to the flame. Caesium and potassium are used as electrodes in
photoelectric cells.
Element Lithium Sodium Potassium Rubidium Caesium
Flame Crimson Yellow Violet Reddish Blue

colour red violet
Chemical properties:
All the alkali metals are highly reactive elements since they have a strong tendency to lose
the single valence s – electron to form unipositive ions having inert gas configuration. This
reactivity of alkali metals is due to
 Low ionization enthalpies

 High negative values of standard electrode potentials.
 Strong tendency to lose the single valence electron to get noble gas
configuration.
1. Reducing property: Alkali metals with have the tendency to loose the valency electrons
readily because of their lower ionization enthalpies. Therefore alkali metals will show very
good reducing property as we move down the group because ionization enthalpy will
decreases down the group. Thereby their reducing character or reactivity of alkali metals
a. In the gaseous state increases from Li to Cs. Li < Na < K < Rb < Cs.
b. In the aqueous solutions shows the reducing sequences of Na < K < Rb < Cs < Li.
 Note: Lithium is very strong reducing agent in aqueous solution because of its low
standard electrode potential i.e., - 3.04 volts, its smallest ionic size and highest
enthalpy of hydration.
2. Reaction with Water: due to low standard electrode potential values, the reactivity with
water increases violently from Li to Cs forming metal hydroxides with the liberation of
dihydrogen gas. 2M + 2H2O  2MOH + H2 + energy.
 Note: Lithium is reactive with water low standard electrode potential i.e., - 3.04
volts, its smallest ionic size and highest enthalpy of hydration.
3. Reactivity towards dihydrogen: The alkali metals react with dihydrogen at about 673K
(lithium at 1073K) to form hydrides. All the alkali metal hydrides are ionic solids with
high melting points. 2M + H2  2MH
4. Reactivity towards halogens: The alkali metals readily react vigorously with halogens to
form ionic halides, 2M + X2  2MX
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 Note: lithium halides are covalent to some extent because of the high
polarisation capability of lithium ion. The high polarisation capability of Li+ ion is
due to very small in size and has high tendency to distort electron cloud around the
negative halide ion.
 Due to large size of anion which can be easily distorted, therefore among halides,
lithium iodide is the most covalent in nature.
 The distortion of electron cloud of the anion by the cation is called polarisation
character.
5. Reducing nature: The alkali metals are strong reducing agents, because of their high
negative E0 values. Lithium being the most and sodium the least powerful reducing
agent.
 Note With the small size of lithium ion, lithium has the highest hydration enthalpy
which accounts for its high negative E0 value and its high reducing power.
6. Solutions in liquid ammonia: The alkali metals dissolve in liquid ammonia giving deep
blue solutions which are conducting in nature. 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 liquid ammonia solutions of alkali metals are paramagnetic in nature
 These solutions on standing for a period of time slowly liberate hydrogen resulting
in the formation of amide.
M+ (ammonium solution) + e – + NH3 (liquid)  MNH2 (ammonium solution) + ½ H2(g)
 In the concentrated ammonium solution of alkali metals are bronze colour and
diamagnetic in nature.
7. Reaction with air: The alkali metals tarnish in dry air due to the formation of their
oxides which in turn react with moisture to form hydroxides. They burn vigorously in
oxygen forming oxides. Lithium forms monoxide, sodium forms peroxide, the other
metals form superoxides. The superoxide O2 – ion is stable only in the presence of
large cations such as K, Rb, Cs.
4 Li + O2  2Li2O (oxide)
2Na + O2 Na2O2 (peroxide)
M + O2  MO2 (superoxide) (M = K, Rb, Cs)
In all these oxides the oxidation state of the alkali metal is +1. Lithium shows exceptional
behaviour in reacting directly with nitrogen of air to form the nitride, Li 3N as well.
Because of their high reactivity towards air and water, they are normally kept in
kerosene oil.
Uses of Alkali Metals
a. Lithium: Mainly used to make alloys.

i. Along with lead is used in preparing white metal which in turn used for the
making of bearings of motor engines.
ii. Along with aluminium used to prepare parts of aircraft.
iii. Along with magnesium used to prepare armour plates.
iv. It is used in thermonuclear reactions.
v. It is used to make electrochemical cells.
b. Sodium:
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i. It is used to make alloys of lead which in turn used to make Tetraethyl
lead (TEL) and Tetramethyl lead (TML) which is used as anti knowing
additives for petrol.
ii. Liquid sodium metal is used as a coolant in fast breeder nuclear reactors.
iii. Sodium peroxide is used as an oxidizing agent in inorganic chemistry.
c. Potassium: Mainly used biological systems
i. Potassium chloride is used as a fertilizer.
ii. Potassium hydroxide is used in the manufacture of soft soap.
iii. It is used as an excellent absorbent of CO2
iv. It is also used in devising photoelectric cells.
d. Caesium: Mainly used in devising photoelectric cells.
GENERAL CHARACTERISTICS OF ALKALI METALS:
Oxides and hydroxides: When alkali metals are subjected to combustion depending upon their
stability oxides, peroxides and superoxide are formed.
 Lithium on combustion with air generally forms oxides but for some extent it also forms
peroxide.
4Li + O2  2Li2O some extent 2Li + O2  Li2O2
 Sodium on combustion with air generally forms peroxides but for some extent it also
forms superoxide. 2Na + O2  Na2O2 some extent Na + O2 NaO2
 Potassium, Rubidium and Caesium on combustion with air always forms superoxide.
K + O2  KO2(postassium superoxide); Rb + O2 RbO2(rubidium superoxid);
Cs + O2  CsO2(caesium superoxide)
Note:
1. The stability of the peroxide or superoxide of alkali metals increases with

increasing of their metal ion size because of lattice energy effects.
2. Oxides and peroxides are colourless in their pure form.
3. Superoxides are either yellow or orange in colour.
4. Superoxides are generally paramagnetic in nature.
Alkali metal hydroxides are formed when oxides or peroxides or superoxide of alkali
metals are subjected to hydrolysis using H 2O.
M2O + H2O  2M+ + 2OH – 1
M2O2 + 2H2O  2M+ + 2OH – 1 + H2O2
2MO2 + 2H2O  2M+ + 2OH – 1 + H2O2 + O2
 The oxides and the peroxides are colourless when pure, but the superoxides are
yellow or orange in colour.
 The superoxides are also paramagnetic.
 Sodium peroxide is widely used as an oxidising agent in inorganic chemistry
Alkali Halides
 The alkali metal halides, MX, (X=F,Cl,Br,I) are all high melting, colourless crystalline
solids.
 Preparation of alkali metal halides: when the appropriate oxide, hydroxide or carbonate
is treated with aqueous hydrohalic acid (HX) we get corresponding alkali metal halides.
101
 All alkali metal halides have high negative enthalpies of formation.
o The Δf H0 values for fluorides become less negative as we go down the group, whilst
the reverse is true for Δf H0 for chlorides, bromides and iodides. For a given metal Δf
H0 always becomes less negative from fluoride to iodide.
 Melting point: The melting and boiling points always follow the trend: fluoride > chloride
> bromide > iodide.
 All these halides are soluble in water. The low solubility of LiF in water is due to its high
lattice enthalpy whereas the low solubility of CsI is due to smaller hydration enthalpy of
its two ions. Other halides of lithium are soluble in ethanol, acetone and ethyl acetate;
LiCl is soluble in pyridine also.
Salts of Oxo-Acids
 Oxo-acids are those in which the acidic proton is on a hydroxyl group with an oxo
group attached to the same atom e.g., carbonic acid, H2CO3 (OC(OH)2; sulphuric acid,
H2SO4 (O2S(OH)2).
 The alkali metals form salts with all the oxo-acids.
 They are generally soluble in water and thermally stable.
 Their carbonates (M2CO3) and in most cases the hydrogencarbonates (MHCO3) also are
highly stable to heat.
 As the electropositive character increases down the group, the stability of the carbonates
and hydorgencarbonates increases. Lithium carbonate is not so stable to heat; lithium
being very small in size polarises a large CO3 2– ion leading to the formation of more stable
Li2O and CO2. Its hydrogencarbonate does not exist as a solid.
ANOMALOUS PROPERTIES OF LITHIUM
The anomalous behaviour of lithium is due to the :
(i) exceptionally small size of its atom and ion, and
(ii) high polarising power (i.e., charge/ radius ratio).
As a result, there is increased covalent character of lithium compounds which is responsible

for their solubility in organic solvents. And lithium shows diagonal relationship to magnesium .
Points of Difference between ‘Lithium and other Alkali Metals’
 Lithium is much harder. Its m.p. and b.p. are higher than the other alkali metals.
 Lithium is least reactive but the strongest reducing agent among all the alkali metals. On
combustion in air it forms mainly monoxide, Li 2O and the nitride, Li3N unlike other alkali
metals.
 LiCl is deliquescent and crystallises as a hydrate, LiCl.2H2O whereas other alkali metal
chlorides do not form hydrates.
 Lithium hydrogencarbonate is not obtained in the solid form while all other elements form
solid hydrogen carbonates.
 Lithium unlike other alkali metals forms no ethynide on reaction with ethyne.
 Lithium nitrate when heated gives lithium oxide, Li2O, whereas other alkali metal nitrates
decompose to give the corresponding nitrite.
4LiNO3  2Li2O + 4NO2 + O2
2NaNO3  2NaNO2 + O2
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 LiF and Li2O are comparatively much less soluble in water than the corresponding
compounds of other alkali metals.
Diagonal relationship: The first elements of Group 1 and Group 2 respectively exhibit some
properties which are different from those of the other members of the respective group. In these
anomalous properties they resemble the second element of the following group. This type of
diagonal similarity is commonly referred to as diagonal relationship in the periodic table.
Example: lithium shows diagonal relationship to magnesium and beryllium to aluminium.
The diagonal relationship is due to the similarity in ionic sizes and /or
charge/radius ratio of the elements.
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:
 Both lithium and magnesium are harder and lighter than other elements in the respective
groups.
 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, Li 3N and Mg3N2, by
direct combination with nitrogen.
 The oxides, Li2O and MgO do not combine with excess oxygen to give any superoxide.
 The carbonates of lithium and magnesium decompose easily on heating to form the oxides
and CO2. therefore solid hydrogencarbonates are not formed by lithium and magnesium.
 Both LiCl and MgCl2 are soluble in ethanol.
 Both LiCl and MgCl2 are deliquescent and crystallise from aqueous solution as hydrates,
LiCl·2H2O and MgCl2·8H2O.
SOME IMPORTANT COMPOUNDS OF SODIUM
Industrially important compounds of sodium include sodium carbonate, sodium hydroxide,

sodium chloride and sodium bicarbonate.
Sodium Carbonate (Washing Soda), Na2CO3·10H2O “Solvay Process”
 Principle: it is prepared by passing CO2 to a concentrated solution of sodium chloride

saturated with ammonia, where ammonium carbonate followed by ammonium
hydrogencarbonate is formed.
2NH3 + H2O + CO2  (NH4)2CO3
(NH4)2 CO3 + H2O + CO2  2NH4HCO3
NH4HCO3 + NaCl  NH4Cl + NaHCO3
Sodium hydrogencarbonate crystal separates which is on heating gives sodium carbonate.
2NaHCO3  Na2CO3 + CO2 + H2O
Note:
103
 Recovery of some raw material--In this process NH3 is recovered when the solution
containing NH4Cl is treated with Ca(OH)2. Calcium chloride is obtained as a by-product.
2NH4Cl + Ca(OH)2  2NH3 + CaCl2 + H2O
 Solvay process cannot be extended to the manufacture of potassium carbonate because

potassium hydrogencarbonate is too soluble to be precipitated by the addition of
ammonium hydrogencarbonate to a saturated solution of potassium chloride.
 In this process, advantage is taken of the low solubility of sodium hydrogencarbonate
whereby it gets precipitated in the reaction of sodium chloride with ammonium
hydrogencarbonate.
Properties:
 It is a white crystalline solid

 It has 10 molecules of water as water of crystallization i.e. decahydrate, Na2CO3·10H2O.
 It is readily soluble in water.
Chemical Properties--On heating, the decahydrate loses its water of crystallization to form
monohydrate. Above 373K, the monohydrate becomes completely anhydrous and changes to a
white powder called soda ash.
Na2CO3. 10H2O at 375K  Na2CO3. H2O + 9H2O
Na2CO3. H2O above 375K  Na2CO3+ H2O
Carbonate part of sodium carbonate gets hydrolysed by water to form an alkaline solution.
Uses:
(i) It is used in water softening, laundering and cleaning.
(ii) It is used in the manufacture of glass, soap, borax and caustic soda.
(iii) It is used in paper, paints and textile industries.
(iv) It is an important laboratory reagent both in qualitative and quantitative analysis.
Sodium Chloride, NaCl
The most abundant source of sodium chloride is sea water which contains 2.7 to 2.9% by mass
of the salt.
Extraction of NaCl from sea water---To obtain pure sodium chloride, the crude salt is dissolved
in minimum amount of water and filtered to remove insoluble impurities. The solution is then
saturated with hydrogen chloride gas. Crystals of pure sodium chloride separate out.
Calcium and magnesium chloride, being more soluble than sodium chloride, remain in solution.
Physical Properties
104
 Sodium chloride melts at 1081K.
 It has a solubility of 36.0 g in 100 g of water at 273 K. The solubility does not increase
appreciably with increase in temperature.
Uses :
(i) It is used as a common salt or table salt for domestic purpose.
(ii) It is used for the preparation of Na2O2, NaOH and Na2CO3.
Sodium Hydroxide (Caustic Soda), NaOH
Preparation Sodium hydroxide is generally prepared commercially by the electrolysis of sodium

chloride in Castner-Kellner cell. A brine solution is electrolysed using a mercury cathode and a
carbon anode. Sodium metal discharged at the cathode combines with mercury to form sodium
amalgam. Chlorine gas is evolved at the anode.
Cathode reaction: Na+ + e – 1 + Hg  Na – amalgam
Anode reaction: Cl – 1  ½ Cl2 + e –
The amalgam is treated with water to give sodium hydroxide and hydrogen gas.
2Na – amalgam + 2H2O  2NaOH + 2Hg + H2
Physical Properties
 Sodium hydroxide is a white, translucent solid.

 It melts at 591 K.
 It is readily soluble in water to give a strong alkaline solution.
 Crystals of sodium hydroxide are deliquescent.
 The sodium hydroxide solution at the surface reacts with the CO2 in the atmosphere to
form Na2CO3.
Uses: It is used in
(i) The manufacture of soap, paper, artificial silk and a number of chemicals,
(ii) In petroleum refining,
(iii) In the purification of bauxite,
(iv) In the textile industries for mercerising cotton fabrics,
(v) For the preparation of pure fats and oils, and
Sodium Hydrogencarbonate (Baking Soda), NaHCO3 or sodium bicarbonate
Sodium bicarbonate is known as baking soda because it decomposes on heating to

generate bubbles of carbon dioxide (leaving holes in cakes or pastries and making them
light and fluffy).
Preparation--Sodium bicarbonate is made by saturating a solution of sodium carbonate with

carbon dioxide. The white crystalline powder of sodium bicarbonate, being less soluble, gets
separated out.
105
Na2CO3 + H2O + CO2  2NaHCO3
Uses
 Sodium bicarbonate is a mild antiseptic for skin infections.

 It is used in fire extinguishers.
BIOLOGICAL IMPORTANCE OF SODIUM AND POTASSIUM:
Sodium ions are found primarily on the outside of cells, being located in blood plasma and
in the interstitial fluid which surrounds the cells. These ions participate in the transmission of
nerve signals, in regulating the flow of water across cell membranes and in the transport of
sugars and amino acids into cells. Sodium and potassium, although so similar chemically, differ
quantitatively in their ability to penetrate cell membranes, in their transport mechanisms and in
their efficiency to activate enzymes. Thus, potassium ions are the most abundant cations within
cell fluids, where they activate many enzymes, participate in the oxidation of glucose to produce
ATP and, with sodium, are responsible for the transmission of nerve signals.
ALKALINE EARTH METALS
 These are group 2 elements.

 Elements are beryllium, magnesium, calcium, strontium, barium and radium.
 The first element beryllium differs from the rest of the members and shows diagonal
relationship to aluminium.
 Electronic Configuration These elements have two electrons in the s -orbital of the
valence shell. Their general electronic configuration may be represented as [noble gas]
ns2.
 The compounds of these elements are also predominantly ionic.
 Atomic and Ionic Radii: The atomic and ionic radii of the alkaline earth metals are
smaller than those of the corresponding alkali metals in the same periods. This is due to
the increased nuclear charge in these elements. Within the group, the atomic and ionic
radii increase with increase in atomic number.
 Ionization Enthalpies: The alkaline earth metals have low ionization enthalpies due to
fairly large size of the atoms. Since the atomic size increases down the group, their
ionization enthalpy decreases The first ionisation enthalpies of the alkaline earth metals
are higher than those of the corresponding Group 1 metals. This is due to their small size
as compared to the corresponding alkali metals. It is interesting to note that the second
ionisation enthalpies of the alkaline earth metals are smaller than those of the
corresponding alkali metals.
 Hydration Enthalpies The hydration enthalpies of alkaline earth metal ions decrease
with increase in ionic size down the group. Be2+> Mg2+ > Ca2+ > Sr2+ > Ba2+ The hydration
enthalpies of alkaline earth metal ions are larger than those of alkali metal ions. Thus,
compounds of alkaline earth metals are more extensively hydrated than those of alkali
metals, e.g., MgCl2 and CaCl2 exist as MgCl2.6H2O and CaCl2· 6H2O while NaCl and KCl do
not form such hydrates.
Physical Properties
 These elements are silvery white, lustrous and relatively soft but harder than the alkali
metals. Beryllium and magnesium appear to be somewhat greyish.
106
 The melting and boiling points of these metals are higher than the corresponding alkali
metals due to smaller sizes. The trend is, however, not systematic, because of the low
ionization enthalpies, they are strongly electropositive in nature.
 The electropositive character increases down the group from Be to Ba.
 Flame colour: these elements shows the characteristic colour to the flame i.e., due to this
detection of these elements is easy and also depending upon the colour intensity the
amount of these elements are estimated by photometry method.
o Calcium shows brick red
o Strontium shows crimson red
o Barium apple green colour
In flame the electrons are excited to higher energy levels and when they drop back
to the ground state, energy is emitted in the form of visible light.
The electrons in beryllium and magnesium are too strongly bound to get excited by
flame. Hence, these elements do not impart any colour to the flame.
 The alkaline earth metals like those of alkali metals have high electrical and thermal
conductivities which are typical characteristics of metals.
Chemical Properties
The alkaline earth metals are less reactive than the alkali metals. The reactivity of these elements
increases on going down the group.
Reactivity with air:
Beryllium:
 Beryllium is kinetically inert to oxygen because of the formation of an oxide film on its
surface.
 Beryllium on ignition with air burns brilliantly to give BeO and Be3N2
Magnesium
 Magnesium is kinetically inert to oxygen because of the formation of an oxide film on its
surface.
 Magnesium is more electropositive and burns with dazzling brilliance in air to give MgO
and Mg3N2.
Calcium, Strontium and Barium:
 Calcium, strontium and barium are readily attacked by air to form the oxide and nitride.
Reaction with water:
 Beryllium and magnesium are kinetically inert to water because they form an oxide film
on its surface.
 Calcium, strontium and barium react with water to form hydroxides.
 The reactivity will increases vigorously from top to bottom of the series.
107
Reactivity towards the halogens:
 All the alkaline earth metals combine with halogen at elevated temperatures forming their
halides.
M + X2  MX2 where X = F, Cl, Br, I
 Thermal decomposition of (NH4)2BeF4 is the best route for the preparation of BeF2,
 BeCl2 is conveniently made from the oxide. BeO + C + Cl 2 at 600 – 800K  BeCl2 + CO
Reactivity towards hydrogen:
 All the elements except beryllium combine with hydrogen upon heating to form their
hydrides, MH2.
 BeH2, however, can be prepared by the reaction of BeCl 2 with LiAlH4.
2BeCl2 + LiAlH4  2BeH2 + LiCl + AlCl3
Uses
Beryllium:
 It is used in the manufacture of alloys. Copper-beryllium alloys are used in the

preparation of high strength springs. Metallic beryllium is used for making windows of X-
ray tubes.
Magnesium
 Magnesium-aluminium alloys being light in mass are used in air-craft construction.

 Magnesium (powder and ribbon) is used in flash powders and bulbs, incendiary bombs
and signals. A suspension of magnesium hydroxide in water (called milk of magnesia) is
used as antacid in medicine.
 Magnesium carbonate is an ingredient of toothpaste.
Calcium
 It is used in the extraction of metals from oxides which are difficult to reduce with carbon.
 Calcium having high reactivity with oxygen and nitrogen at elevated temperatures has
often been used to remove air from vacuum tubes.
Barium
 It is having high reactivity with oxygen and nitrogen at elevated temperatures, have often
been used to remove air from vacuum tubes
Radium
 Radium salts are used in radiotherapy, for example, in the treatment of cancer.
ANOMALOUS BEHAVIOUR OF BERYLLIUM
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 subsequently.
 Beryllium has exceptionally small atomic and ionic sizes and thus does not compare well
with other members of the group.
108
 Because of high ionisation enthalpy and small size it forms compounds which are
largely covalent and get easily hydrolysed.
 Beryllium does not exhibit coordination number more than four as in its valence shell
there are only four orbitals. The remaining members of the group can have a coordination
number of six by making use of d-orbitals.
 The oxide and hydroxide of beryllium, unlike the hydroxides of other elements in the
group, are amphoteric in nature.
Diagonal Relationship between Beryllium and Aluminium
The ionic radius and charge/radius ratio of beryllium ion (Be2+) is nearly the same as that
of aluminium ion (Al3+), therefore beryllium resembles aluminium in some ways. Some of the
similarities are:
 Like aluminium, beryllium is not readily attacked by acids because of the presence of an
oxide film on the surface of the metal.
 Beryllium hydroxide dissolves in excess of alkali to give a beryllate ion, [Be(OH)4]2– just as
aluminium hydroxide gives aluminate ion, [Al(OH)4]–.
 The chlorides of both beryllium and aluminium have Cl– bridged chloride structure in
vapour phase. Both the chlorides are soluble in organic solvents and are strong Lewis
acids. They are used as Friedel Craft catalysts.
 Beryllium and aluminium ions have strong tendency to form complexes, BeF42–, AlF63–.
SOME IMPORTANT COMPOUNDS OFCALCIUM
Calcium Oxide or Quick Lime, CaO
 Preparation It is prepared on a commercial scale by heating limestone (CaCO3) in a rotary

kiln at 1070-1270 K.
The carbon dioxide is removed as soon as it is produced to enable the reaction to

proceed to completion.
Physical Properties--Calcium oxide is a white amorphous solid. It has a melting point of 2870
K.
Chemical Properties- On exposure to atmosphere, it absorbs moisture and carbon dioxide.
The addition of limited amount of water breaks the lump of lime. This process is called
slaking of lime. Quick lime slaked with soda gives solid sodalime.
Uses:
109
(i) It is an important primary material for manufacturing cement and is the cheapest form of
alkali.
(ii) It is used in the manufacture of sodium carbonate from caustic soda.
(iii) It is employed in the purification of sugar and in the manufacture of dye stuffs.
Calcium Carbonate, CaCO3
Calcium carbonate occurs in nature in several forms like limestone, chalk, marble etc.
Preparation--It can be prepared by passing carbon dioxide through slaked lime
Note
Excess of carbon dioxide should be avoided since this leads to the formation of water
soluble calcium hydrogencarbonate.
Uses:
 It is used as a building material in the form of marble and in the manufacture of quick lime.
 Calcium carbonate along with magnesium carbonate is used as a flux in the extraction of
metals such as iron.
 Specially precipitated CaCO3 is extensively used in the manufacture of high quality paper.
 It is also used as an antacid, mild abrasive in tooth paste, a constituent of chewing gum,
and filler in cosmetics.
Calcium Sulphate (Plaster of Paris), CaSO4·½ H2O (hemihydrate of calcium sulphate)--
Preparation--It is a. It is obtained when gypsum, CaSO4·2H2O, is heated to 393 K.
2(CaSO4.2H2O)  2(CaSO4).H2O + 3H2O
Above 393 K, no water of crystallisation is left and anhydrous calcium sulphate, CaSO4 is
formed. This is known as ‘dead burnt plaster’. It has a remarkable property of setting with
water. On mixing with an adequate quantity
of water it forms a plastic mass that gets into a hard solid in 5 to 15 minutes.
Uses:
 The largest use of Plaster of Paris is in the building industry as well as plasters.
 It is used for immoblising the affected part of organ where there is a bone fracture or sprain.
 It is also employed in dentistry, in ornamental work and for making casts of statues and
busts.
BIOLOGICAL IMPORTANCE OF MAGNESIUM AND CALCIUM
An adult body contains about 25 g of Mg and 1200 g of Ca compared with only 5 g of iron and
0.06 g of copper. The daily requirement in the human body has been estimated to be 200 – 300
110
mg. All enzymes that utilise ATP in phosphate transfer require magnesium as the cofactor.
The main pigment for the absorption of light in plants is chlorophyll which contains magnesium.
About 99 % of body calcium is present in bones and teeth. It also plays important roles in
neuromuscular function, interneuronal transmission, cell membrane integrity and blood
coagulation. The calcium concentration in plasma is regulated at about 100 mgL–1. It is
maintained by two hormones: calcitonin and parathyroid hormone. Do you know that bone is not
an inert and unchanging substance but is continuously being solubilised and redeposited to the
extent of 400 mg per day in man? All this calcium passes through the plasma.
111
11 P – BLOCK ELEMENTS
p – Block Elements
General characteristics of p – block elements
Its electronic configuration is [noble gas] ns 2p1 – 6

These block elements are called as representative elements or main group elements.
It contains six groups i.e., group 13 and 18.
13th group elements are called boron family, 14th group elements are called carbon family,
and 15th group elements are called nitrogen family elements.
 16th group elements are called chalcogens. i.e., oxygen family elements.
 17th group elements are called halogens.
 16th and 17th group elements are highly negative electron gain enthalpies and readily add
one or two electrons respectively to attain the stable noble gas configuration.
 18th group elements are called noble gases. With the exception of helium, these elements
have ns2 np6 electronic configuration in the outermost shell. Helium has 1s 2
configuration.
 In this block non – metallic character increases as from left to right across the period.
 Metallic character increases down the group.
 The maximum oxidation state shown by p – block element is equal to the total number of
valence electrons i.e., the sum of the s – and p – electrons.
 The oxidation state of these elements increases from left to right side, i.e., 13th to 18th
group.
 This block element contains metals, metalloids, non – metals, natural radioactive elements
and non – radioactive elements.
 In case of 13th, 14th, 15th, group elements, the group oxidation state is the most stable
state for the lighter elements in the group. However, the oxidation state two units less
than the group oxidation state become progressively more stable for the heavier elements
in each group. “The occurrence of oxidation states two units less than the group
oxidation states are is known as inert pair effect”.
 The ionization enthalpy, electro negativities increases from left to right and decreases from
top to bottom.
 The compounds formed between non – metals, generally form covalent bond because of
small difference in their electro negativities.
 The non – metal oxides are acidic or natural whereas metal oxides are basic in nature.
General electronic configuration and oxidation states of p – block elements
Group 13 14 15 16 17 18
General ns2np6
electronic ns2np1 Ns2np2 ns2np3 ns2np4 ns2np5
configuration [1s2 for He]
First member
of the group
B C N O F He
Group
oxidation state
+3 +4 +5 +6 +7 +8
Other
+1 +2, - 4 +3, - 3 +4, +2, - 2 +5,+3+1,-1 +6, +4, +2
oxidation state
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Anomalous behavior of first member of each group in p – block elements
The first member of p – block differs from the remaining members of the their corresponding
group due to
1. Small in their atomic size

2. High ionization enthalpy
3. High electronegative nature
4. Absence of d – orbitals
First member of the p – block Other members of the p –block
elements elements
Due to smaller in These elements forms covalent These elements forms ionic bonds,
atomic size bond co – ordinate bonds
Due to absence of These elements restricts their These elements covalence is more
d – orbitals maximum covalence of four than four
These elements forms p - p These elements forms d - p

Due to smaller in bonds bonds or d - d bonds.
size and absence of
d – orbitals The stability of the molecules of
The molecules are more stable
these compounds less
Having the same The coordination number of The coordination number of these
oxidation state these elements are low elements are higher
THIRTEEN GROUP ELEMENTS

BORON FAMILY MEMBERS
Electronic
Atomic configuration Atomic
Element Symbol
number mass
ns2np1
Boron B 4 [He]2s22p1 10.81
Aluminium Al 31 [Ne]3s23p1 26.98
Gallium Ga 31 [Ar]3d104s24p1 69.72
Indium In 49 [Kr]4d105s25p1 114.82
Thallium Ti 81 [Xe]4f145d106s26p1 204.38
 Atomic radii:
o Increases from boron to thallium due to increase in the number of orbitals.
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o This increases in atomic radii is not uniform, i.e., gallium while have less atomic
size than aluminum because of presence of 3d orbitals, which is having poor
screening effect for the outer electrons from the increased nuclear charge.
 Ionization enthalpy:
o Decreases from boron to thallium due to increase in the atomic size.
o This decreases is not uniform
 regular decreases is seen from B to Al due to increase in atomic size
 Al to Ga increases due to poor screenings ability of d – electrons,
 In to Ti increases due to poor screening ability of f – electrons.
 Electronegativity: decreases from B to Al and then increases marginally due to
discrepancies in atomic size of the elements.
o Boron is non – metal, black and hard solid, with high M.P due to strong crystalline
lattice.
o Other elements are soft metals with low M.P. and high electrical conductivity.
o Ga is having low melting point i.e., 303K exists as liquid in summer and high boiling
point of 2676K used for measuring high temperature.
o Density of these elements increase from B to Ti
 Oxidation states:
o Due to smaller in size, sum of first three ionization enthalpies high Boron forms
covalent compounds and prevents to show +3 oxidation states.
o Due to having low ionization enthalpy Al shows +3 oxidation state i.e. high
electropositive metal.
o Presence of d and f – orbitals screening effect decreases due to increasing in nuclear
charge thereby ‘ns’ electrons are tightly hold by the nucleus i.e., inner pair effect, Ga,
In and Ti shows predominately +1 oxidization state than +3 states.
o +1 oxidation state is more ionic than +3 oxidation state.
 Chemical trend:
o Lewis acid nature: The trivalent states of these elements in compounds behave as
Lewis acid because of electron deficiency, i.e., these elements will have only six
electrons, thereby they accepts lone pair of electrons to fulfill the octet state. It has
been seen that Lewis acid nature i.e., tendency to accept electrons decreases from B to
Ti.
Example:
 BF3 easily accepts electrons from NH3 to change its structure from planar
to tetrahedral
 AlCl3 becomes more stable due to having tetrahedral structure by forming
dimer.
o The trivalent states of these elements in compounds have the covalent bond which is
hydrolysed when dissolved in water.
 The trichlorides of these compounds get hydrolysed in water to tetraaqua
complexes having tetrahedral structure where the metal is having sp3 of
hybridization.
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 AlCl3 get hydrolysed in water to form hexaaqua complexes having
octahedral structure where the Al is having sp3d2 type of hybridization.
Reactions of aluminium:
 With air:
o Aluminium when exposed to air forms a thin layer of aluminum oxide which will
protects the inner metal.
o When aluminium is burnt in air it forms aluminium oxide (Al 2O3) with oxygen and
aluminium nitrides with nitrogen. The oxide of aluminium is amphoteric in nature
i.e., behaves as acid and also base.
2Al (s) + 3O2 (g) + heat  2Al2O3 (s)
2Al (s) + N2(g) + heat  2AlN(s)
 With acid:
o With dil. HCl: it liberates dihydrogen gas when reacts with dil. HCl by forming
AlCl3.
2Al(s) + 6HCl(diluted)  2AlCl3 + 3H2
o With conc. HCl: it renders passive due to formation of protective oxide layer on the
surface. Therefore conc. HCl can be transported using Al cans.
 With alkali:
o Aluminium reacts with alkali solution i.e., NaOH aqueous solution to from sodium
tetrahydroxoaluminate(III) complex with the liberation of dihydrogen gas.
2Al(s) + 2NaOH(aq) + 6H 2O  2Na[Al(OH)4] (aq) + 3H2
ANOMALOUS BEHAVIOR OF BORON:
Boron shows anomalous behavior i.e., some different characteristics compare with other
members of the group this is because of the following regions
 Smaller in atomic size

 Absence of d – suborbital
 High ionization enthalpy
 High electronegativity
o Due to smaller in size, boron behaves very strong Lewis acid as compared with
other elements.
o Due to absence of d – orbital it shows its maximum covalence of four, where as
other elements shows more than four.
o Except boron other elements will form dimers to satisfy the octet state by accepting
electrons from halogens forming halogen bridged molecules.
o The tri halides of all elements undergo hydrolysis in water to form either
tetrahedral or octahedral structured compounds where as boron will not form it.
COMPOUNDS OF BORON
o Borax  Na2B4O7.10H2O or Na2[B4O5(OH)4]. 8H2O

o Orthoboric acid  H3BO3
o Diborane  B2H6
Borax:
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o With water: borax dissolves in water to form alkaline solution due to formation of
orthoboric acid. Na2B4O7 + 7H2O  2NaOH + 4H3BO3
o Action of heat: when borax is heated, it swells up due to loss of a water molecule and
further heating turns into a transparent liquid which gets solidified into glass like
material known as borax bead.
Na2B4O7.10H2O + heat  Na2B4O7 (sodium metaborate)
Na2B4O7 + heat  2NaBO2 + B2O3 ( Boric anhydride)
Orthobroic acid:
o Preparation: when aqueous solution is subjected to acidify by using HCl, orthobroic acid
is obtained. Na2B4O7 + 2 HCl + 5H2O  2NaCl + 4H3BO3
o Physical properties:
o It is a crystalline white solid
o It is having soapy touch.
o It is sparingly soluble in water but soluble in hot water.
o It is having a layer structure in which planar BO3 units are joined by hydrogen
bonds.
o It acts as Lewis acid i.e., it will accepts the lone pair of electrons from hydroxyl
ion when treated with water. B(OH)3 + H2O  [B(OH)4] – + H3O+.
o Action of heat: when it is heated above 370K it forms metaboric acid which on
further heating forms boric oxide.
B(OH)3 + heat  HBO2 + H2O
2HBO2 + heat  B2O3 + H2O
Diborane:
o Preparation: when boron triflouride is treated with LiAlH4 in diethyl ether, diborane is
formed. 3BF3 + 3LiAlH4  2B2H6 + 3LiF + 2AlF3
o Properties:
o It is colourless highly toxic gas with b.p 180K.
o Action with air:
 It catches fire spontaneously upon exposure to air.
 When it burns in air releases enormous amount of energy to form boron tri
oxide. B2H6 + 3O2  B2O3 + 3H2O; ∆H = - 1976 kJ/mol
o Action with water: when diborane is treated with water it readily undergoes
hydrolysis to form boric acid. B2H6 + 6H2O  2B(OH)3 + 6H2
o Action with ammonia: [formation of borazine i.e.,
inorganic benzene]
When diborane is treated with ammonia it forms B2H6.2NH3.
This compound on heating, liberates hydrogen and forms
borazine i.e., B3N3H6 which is known as inorganic benzene.
3B2H6 + 6NH3  3[BH2(NH3)2]+[BH4] –
3[BH2(NH3)2]+[BH4] – + heat  2B3N3H6 + 12H2
o Structure of borazine or inorganic benzene

Uses of Boron:
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o Boron fibers are used in making bullet proof vest.
o It is used in composite material for aircraft.
o Boron – 10 isotopes is used as protective shields and control rods in nuclear
industries.
o Borax and boric acid is used for manufacturing of heat resistant glasses i.e.,
pyrex glass, glass – wool and fibre glass.
o Borax is used as flux for soldering metals.
o An aqueous solution of orthboric acid is used as the mild antiseptic.
Uses of Aluminium:
o It is used to make packing materials.

o It is used to make utensils
o It is used to make wires, tube rods, and plates.
o It is used to make the body of airplanes
14TH GROUP ELEMENTS

Electronic
Atomic configuration Atomic
Element Symbol
number mass
ns2np2
Carbon C 6 [He]2s22p2 12.01
Silicon Si 14 [Ne]3s23p2 28.09
Germanium Ge 32 [Ar]3d104s24p2 72.60
Tin Sn 50 [Kr]4d105s25p2 118.71
Lead Pb 82 [Xe]4f145d106s26p2 207.2
o Ionization enthalpy: in general ionization enthalpy decreases from carbon to lead but
this is not in uniform manner i.e., from carbon to silicon in decreases where as from
silicon to tin there is small decreases the slight increase from tin to lead due to poor
screening effect of completely filled d and f orbital electrons.
o Electronegativity: due to small in atomic size these elements will have high
electronegative nature which decreases from carbon to tin, but tin and lead shows almost
same electronegativity.
o Covalent radius: over all covalent radius increases from carbon to lead but it is not in
uniform way i.e., covalent radius increases from carbon to silicon, but silicon to lead there
is small increases of covalent radius is seen due to the presence of complete d and f
orbitals.
o Oxidation state:
o the common oxidation states of these elements are +4 and +2
o carbon shows the negative oxidation state
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o Since the sum of the first ionization enthalpies are high +4 oxidation state these
compounds form covalent bonds.
o In heaver elements i.e., Ge, Sn and Pb, +2 oxidation states will increase due to inert
pair effect.
o Carbon and silicon shows +4 oxidation states, Ge shows stable +4 oxidation state to
some extent it also show +2 oxidation state. Tin shows both +2 and +4 oxidation
states, where as lead shows +2 oxidation state as stable and +4 stable is less
stable.
o Due to availability of d orbitals some compounds exceeds the oxidation state more
than +4.
o Reactivity of the compounds:

o Reactivity towards oxygen:
 The elements of this group when burnt in air forms monoxides and dioxides.
 General formula for monoxide is MO and dioxide is MO2.
 Higher oxidation states of these elements are acidic in nature.
 Among dioxides
 CO2, SiO2 and GeO2 are acidic in nature.
 SnO2, PbO2 are amphoteric in nature i.e., behaves as acid and base
 Among monoxides:
 CO is neutral
 GeO is acidic in nature
 SnO and PbO are amphoteric in nature.
o Reactivity with water:

o Carbon, silicon, germanium will not reacts with water may be due to their stable
nature.
o Tin reacts with water to form dioxide with the liberation of dihydrogen gas.
Sn + 2H2O  SnO2 + 2H2
o Lead also cannot affect by water it may be due to the formation a protective oxide
film on it.
ANOMALOUS BEHAVIOUR OF CARBON
Carbon shows anomalous behaviour with the other members of the group is due to
o Smaller in atomic size

o High ionization enthalpy
o High electronegativity
o Absence of d – orbitals
 Carbon shows maximum covalence of four, where as other elements shows
more than four due to availability of d – orbitals
 Carbon can able to form p - p multiple bonds with itself or with other
atoms of small size and high electronegativity. Where as heavier elements
cannot form p - p because of their large atomic orbital size and default to
overlap.
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 Due to strong C – C bond carbon can bond with other carbon atoms
either to form linear structure or ring structures; this property is known as
catenation property. This property wills decreases as we move down the
group.
Allotropes of carbon:
 Carbon atom shows very good allotropic nature due to catenation and p - p bond
formation.
 Carbon shows three types of allotropic forms (i) graphite (ii) diamond and (iii) fullerenes
 Graphite and diamond are the crystalline allotropic form of carbon where as fullerenes
are the amorphous.
STRUCTURE OF DIAMOND
 It is a crystalline allotropic form of carbon.
 Carbon atom in this form shows sp3 type of hybridization.
 The bond length i.e., C – C bond length is 154pm.
 It contains directional covalent bonds throughout the lattice.
 It is very hard due to strong tetrahedral bonding of C – C.
 Due to absence of lone pair of electrons it is bad conductor of electricity.
 It is thermodynamically stable one so its heat of formation is zero
 Uses:
o It is used to cut the hard substances i.e., diamond, glass etc.
o It is used in jeweler ornaments
o In making dyes
o In manufacture of tungsten filaments for electric light bulbs.
STRUCTURE OF GRAPHITE:
 It is a crystalline allotropic form of carbon.
 Carbon atom in this form shows sp2 type of hybridization.
 It is having layered type of structure.
 The layers are held by van der Waal’s force of attraction with distance of 340pm.
 Each layer is carbon atoms are present in the form of hexagonal rings; there each
carbon atom is having three sigma bonds with three different carbon atoms.
 The bond length i.e., C – C bond length with in the layer is 141.5pm.
 Due to layered nature it is soft and slippery in nature it is used as lubricant in
machines running at high temperature.
 Each carbon atom is having one unpaired electrons, due to delocalization of these
electrons graphite is good conductor of electricity.
 Heat of formation is 1.9kJ/mol
STRUCTURE OF FULLERENES
 Fullerenes are of two types C60 and C70.
 These are the purest form of carbon due to non dangling bonds.
 It is having cage like structure having soccer ball shape therefore it is called
Buckminsterfullerene.
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 It contains 20 six membered rings, and 12 five membered rings in its structure.
 Each six membered ring is fussed to either six membered ring or five membered ring,
where as five membered ring is fussed to only six membered ring.
 All carbon atoms in fullerenes is having sp2 type of hybridization, with three sigma bonds
attached to three carbon atoms, the remaining electron at each carbon atom is
delocalized in the molecular orbitals, which in turn gives aromatic character to the
molecules.
 The ball shaped molecule has 60 vertices and each one is occupied by one carbon atom
and it also contains both single and double bonds with C – C distances of 143.5 pm and
138.3pm respectively.
 The heat of formation is 38.1kJ/mol
USES OF CARBON
1. Graphite is used an electrodes in batteries and industrial electrolysis.
2. Activated charcoal due to more porous nature used in adsorbing poisonous gases
and also in water filters to remove organic contaminators and in air conditioning
system to control odour.
3. Carbon black used in black paints, black ink filler in automobile tyres.
4. Coke is used as a fuel and largely as a reducing agent in metallurgy.
5. Diamond is used in jewellery.
COMPOUNDS OF CARBON
Carbon monoxide:
 Preparation:
o From formic acid: [HCOOH]: formic acid on dehydration using conc. H2SO4 at
373K carbon monoxide is obtained.
HCOOH + conc. H2SO4 at 373K  CO + H2O
o From air: when air is passed over hot coke at 1273K we get a mixture of CO and N 2
gas. This mixture is known as producer gas.
2C(s) + O2 + 4N2  2CO + 4N2
 Properties:
o Reducing property:
 When it is heated with Fe2O3 reduces it to iron, at 7100C,
Fe2O3 + 3CO  2Fe + 3CO2
 When it is heated with ZnO reduces it to zinc, at 1627K,

ZnO + CO  2Zn + CO2
 Carbon monoxide is poisonous because it easily combines with iron which is present in
haemoglobin forming ferrous carbonyl complex which will prevents haemoglobin in the red
blood corpuscles from carrying oxygen round the body and ultimately resulting in death.
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 Metal carbonyl complex formation: due the presence of lone pair of electrons on
carbon which can easily donated to metal at normal temperature, thereby forms more
stable metal carbonyl complexes.
 Uses: it is having very high reducing property; so many metals are reduced using it from
their metal oxides.
CARBON DIOXIDE:
 Laboratory preparation: when calcium carbonate is treated with dil. HCl, calcium chloride
is formed with the liberation of carbon dioxide.
CaCO3 + 2HCl  CaCl2 + H2O + CO2
 Properties:
o Dibasic nature: it reacts with water and forms carbonic acid H2CO3, which is a
weak dibasic acid, which dissociates in two ways to liberate the protonated water.
H2CO3 (aq) + H2O (l)  HCO3 – (aq) + H3+O
HCO3 – (aq) + H2O (l)  CO3 – 2 (aq)+ H3+O
o Photosynthesis: it is the process of preparing food (glucose) by the plants by using

CO2 in the presence of sun light.
6CO2 + 12H2O + hv/chlorphyll  C6H12O6.
o Dry ice: solid carbon dioxide is known as dry ice, which is obtained by sudden
expansion of liquid CO2.
 Uses:
o Gaseous CO2 is used to carbonate soft drinks.
o Solid CO2 i.e., dry ice is used as refrigerant for ice – cream and frozen food.
o It is used as fire extinguisher due to its heavy and non – supporter of combustion
nature.
o For some extent it is used in the manufacturing of urea.
Important compounds of silicon:
Silicon dioxide: (SiO2)
– It is known as silica.
– Quartz, cristobalite and tridymite are some forms of silica.
– Structure of silica:
o It is a covalent three – dimensional network solid, where each silicon atom is
bonded to four oxygen atoms in a tetrahedral manner. Each oxygen atom is
attached to two silicon atoms. The crystal of silica is a giant structured molecule
with eight membered ring containing alternative silicon and oxygen atoms as shown
in the diagram.
o Reactions of silica:
 Reaction with NaOH: it reacts with NaOH to form sodium silicate with the liberation
of water. 2NaOH + SiO2  NaSiO3 + H2O
 Reaction with HF: it reacts with HF forming silicone tetrafluoride:
SiO2+ 4HF  SiF4 + 2H2O
 Uses
 Quartz is extensively used as a piezoelectric material which is used in radio,
television, mobile radio communications, and accurate clocks makings.
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 Silica gel is used as a drying agent and as a support for chromatographic
materials and catalysts.
 Kieselghur, an amorphous form of silica is used in filtration plants.
Silicones
– It is a linear polymer with the repeating unit ( R2SiO ).
– It is prepared when dimethyldichorosilane is subjected to hydrolysis followed by
condensation polymerization
(CH3)2SiCl2 + 2H2O  (CH3)2Si(OH)2 + 2HCl
This polymer is terminated when reacted with (CH3)3SiCl
– Uses: it is used as sealant, greases electrical insulators and water proofing of fabriecs. It is
also used in surgical and cosmetic plants.
Silicates
– Basic unit: the basic unit is SiO4 – 4 where silicon atom is bounded to four oxygen atoms
in tetrahedron fashion.
– When silicates units are linked together, they form chain, ring, sheet or three dimensional
structures.
– Negative charge on silicate structure is neutralized by positively charged metal ions.
– Examples: feldspar, zeoliltes, mica and asbestos.
Zeolites –
Example: ZSM – .5, Hydrated zeolites
Uses:
– ZSM – 5 used to convert alcohols directly into gasoline

– Hydrated zeolites used as ion exchanges in softening of hard water.
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Organic Chemistry – Some Basic

12 Principles and Techniques
INTRODUCTION:
Berzilius, a Swedish chemist proposed that a ‘vital force’ was responsible for the
formation of organic compounds.
F. Wohler synthesised an organic compound, urea from an inorganic compound,
ammonium cyanate.
NH4CNO  NH2CONH2
The pioneering synthesis of acetic acid by Kolbe (1845) and that of methane by
Berthelot (1856) showed conclusively that organic compounds could be
synthesised from inorganic sources in a laboratory.
STRUCTURAL REPRESENTATIONS OF ORGANIC COMPOUNDS:
Complete, Condensed and Bond-line Structural Formula:
The Lewis structures, however, can be simplified by representing the two-electron
covalent bond by a dash (–). Such a structural formula focuses on the electrons
involved in bond formation. A single dash represents a single bond, double dash is
used for double bond and a triple dash represents triple bond. Lonepairs of
electrons on heteroatoms (e.g., oxygen, nitrogen, sulphur, halogens etc.) may or
123
may not be shown. Such structural representations are called complete
structural formulas.
Ex: CH4 , C2H4 , C2H6 etc can be represented as
These structural formulas can be further abbreviated by omitting some or all of the
dashes representing covalent bonds and by indicating the number of identical
groups attached to an atom by a subscript. The resulting expression of the
compound is called a condensed structural formula. Thus, ethane, ethene, ethyne
and methanol can be written as:
For further simplification, organic chemists use another way of representing the
structures, in which only lines are used. In this bond-line structural representation
of organic compounds, carbon and hydrogen atoms are not shown and the lines
representing carbon-carbon bonds are drawn in a zig-zag fashion. The only atoms
specifically written are oxygen, chlorine, nitrogen etc. The terminals denote methyl
(–CH3) groups (unless indicated otherwise by a functional group), while the line
junctions denote carbon atoms bonded to appropriate number of hydrogen
required to satisfy the valence of the carbon atoms.
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Wedge formula for CH4

Classification of organic compounds
The organic compounds have been broadly classified into four main types, they are
1) Aliphatic compounds 2) Aromatic compounds
3) Alicyclic compounds 4) Hetero cyclic compounds
1) Aliphatic compounds:
Open chain carbon compounds (which may be either straight chain or
branched chain compounds) are called as aliphatic compounds.
Examples: CH4 , CH3—CH3 , CH2=CH2 , all alkanes, all alkenes and all alkynes.
Methane Ethane Ethene
2) Aromatic compounds:
Aromatic compounds are those compounds which contain at least one
benzene ring in them.
Examples;
OH
CH3 NH2
Benzene Toluene Phenol Aniline Naphthalene

125
3) Alicyclic compounds:
These are the compounds contain ring of three or more carbon atoms and
resemble aliphatic compounds in their characteristics.
Examples:
4) Heterocyclic compounds:
Heterocyclic compounds are those compounds which have the ring structure
where one or more carbon atoms of the ring are replaced by some other
(hetero) atom.
Examples:
N
O H S c
Furan Pyrrole Thiophene Pyridine
Functional group:
An atom or group of atoms which determine the properties of an organic
compound is called as a functional group.
Most of the organic compounds mainly contain two parts in them
a) Highly reactive part called as ‘functional group’
b) A skeleton of carbon and hydrogen atoms which is called as alkyl or aryl group.
Examples: CH3—CH2—OH CH3—CH2—CHO
Alkyl group Functional group Functional group
Functional group Family Common
examples
Alkenes R—CH=CH—R
—OH Alcohols R—OH
Aldehydes
Ketones
Carboxylic acids
—NH2 Amines R—NH2

ethers R—O—R
—NO2 Nitroalkanes R—NO2

126
Homologous series:
A series of closely related organic compounds which can be represented by a
general formula is called as homologous series.
Examples: Alkanes they obey general formula CnH2n+2 where n=1,2,3,…..
Alkanes Alcohols
Molecular Name Molecular formula Name
formula
CH4 CH3—OH Methyl
Methane alcohol
CH3—CH3 CH3—CH2—OH Ethyl alcohol
Ethane
CH3—CH2—CH3 CH3—CH2—CH2— Propyl alcohol
Propan OH
e
Characteristics of homologous series:

1. All the members of a series can be represented by the general formula.
2. Two successive members differ in their molecular formula by –CH 2 group.
3. They have almost identical chemical properties.
4. Physical properties like melting point, boiling point, density, solubility etc
gradually varies with increase in molecular mass.
5. The members of particular series can be prepared almost by identical methods.
Nomenclature of organic compounds;

The term nomenclature indicates naming of organic compounds. Two types of
systems are known for naming they are (1) Trivial or common names (2) IUPAC
system
1. Trivial names or common names.
In the early stages of development of organic chemistry, the organic compounds
were named after the source from which they were prepared.
For example acetic acid (CH3—COOH) was derived from acetum (Latin; acetum
means vinegar). Similarly, the name formic acid (HCOOH) was obtained from
formicus ( means red ants) because compound was obtained by the distillation of
red ants.
IUPAC system:
With the rapid growth of organic chemistry, large numbers of organic compounds
were discovered. Chemist felt that it is impossible to give common names to such a
large number of organic compounds. In the year 1957, the International Union
of Pure and Applied Chemistry (IUPAC) evolved a scheme for giving systematic
127
names to organic compounds on the basis of structure. This system is called
IUPAC system and is used all over the world.
The IUPAC name of a compound contains three parts namely word root, suffix
and prefix.
1. Word root:
It indicates the number of carbon atoms in the longest possible continuous carbon
chain also known as parent chain. The word roots used for different length of
carbon chain are shown below.
Number of carbon Word root
atoms in the parent chain
1 Meth
2 Eth
3 Prop
4 But
5 Pent
6 Hex
7 Hept
8 Oct
9 Non
10 Dec
2) Suffix: It is again divided into two types i) Primary suffix and ii) Secondary suffix
i) Primary suffix: It is used to indicate the degree of saturation or unsaturation in
the main chain. It is added immediately after the word root.
Type of carbon chain Primary suffix General name
Saturated (all C-C bonds) -ane Alkane
Unsaturated: ( C=C ) -ene Alkene
Unsaturated: (C≡C) -yne Alkyne
(ii) Secondary suffix: It is used to indicate the main functional group in the
organic compound and is added immediately after the primary suffix.
Class of organic Functional Secondary
compound group suffix
Alcohols —OH -ol
Aldehydes —CHO -al
Ketones -one
Carboxylic acids —COOH -oic acid

Esters —COOR -oate
128
Acid amides —CONH2 -amide
Amines —NH2 -amine
Cyanides —CN -nitrile
Note: While naming compounds the terminal ‘e’ is dropped from the primary
suffix if the secondary suffix begins with a vowel ( a,e,i,o,u or y)
3) Prefix: The prefix is used to indicate the side chains, substituents and low priority
groups (which are considered as substituents). The prefix may be added
immediately before the word root. Generally there exist two type prefixes namely
primary prefix and secondary prefix. Primary prefix is used to distinguish cyclic
from acyclic compounds. Secondary prefix is a group added before the word root to
indicate a side chain or substituent.
Some of the prefixes are given below.
Substituent Prefix Substituent Prefix
group group
—F Fluoro —CN Cyano
—Cl Chloro —R Alkyl
—Br Bromo —CH3 Methyl
—I Iodo —C2H5 Ethyl
—NO2 Nitro —OR Alkoxy
—NH2 Amino —OCH3 Methoxy
—OH Hydroxy —NC Isocyano
Thus the complete systematic IUPAC name can be represented as:
Secondary prefix + Primary prefix + Word root + Primary suffix + secondary
suffix
IUPAC rules for naming compounds:
Rule: 1) Longest chain rule:
The longest continuous chain of carbon atoms (which may or may not be straight)
is first chosen. This chain is called parent chain. This is named by using correct
word root depending on the number of carbon atoms present in it and suffix.
(Note; The longest continuous carbon chain containing as many functional groups,
double bonds, triple bonds, side chains and substituents as possible is to be
selected as parent chain.)
Examples:
Molecule IUPAC name
CH4 Methane [Meth (root word)+ ane (suffix)]
CH3—CH3 Ethane (Eth + ane)
CH3—CH2—CH3 Propane ( Prop+ ane)
CH3—CH2—CH2—CH3 Butane ( But + ane)
Illustration:
129
Here the maximum number of carbon atoms in a chain is 4, therefore root word is
given as but. Being alkane the suffix is –ane. Hence the name becomes Butane.
But there is methyl group which is not included in the parent chain. This
becomes substituent group.
The substituent group is named as prefix. While writing the name of the
substituent group its position on the parent chain is mentioned. Hence the name
becomes 2-methylbutane.
Note:we should start the numbering in such a way that the substituent should
gate least number. The number used to specify the position of the substituent
group called locant.
Rule: 2) Lowest number or lowest sum rule:
The parent chain is numbered in such a way that substituent group should get
minimum number. If more than one substituent group is present then the sum of
the locants must be minimum.
Rule: 3) Presence of identical groups:
If more than one identical substituent group are present, it is indicated as di, tri,
etc. The positions of the substitution are separated by commas.
Illustration: 1: Consider the naming of organic compound
Let the parent carbon chain be numbered in two different ways starting from one
of the ends. Thus
2-Methylpentane (Correct) 4-Methylpentane (Incorrect)

(a) (b)
Here numbering order (a) is selected because the substituent methyl group gets
minimum number. Hence the name becomes 2-methylpentane, where the
numbering
(b) is wrong because it is against to rule 2.
130
Illustration 2:
Consider the naming of
The parent chain can be numbered in the following two ways.
2,4-Dimethylhexane (correct) 3,5-Dimethylhexane ( incorrect)

(a) (b)
Here two methyl groups are present as substituent groups. In the numbering (a)
the sum of the locants is 2+4=6 and in the numbering (b) it is 3+5=8. Hence
numbering order (a) is selected which gives minimum sum of the locants. So the
name becomes 2,4-Dimethylhexane.
Rule 4: Arrangement of prefixes:
If the different substituent groups are present their prefixes must be arranged
according to the alphabetical order. The prefixes di, tri, etc. are not considered
while arranging the groups in the alphabetical order.
Illustration:
The name of the molecule becomes 4-Ethyl-2-methylhexane and not 2-Methyl-4-

ethylhexane.
If two different alkyl groups are located at the equivalent positions, then
numbering of the chain is done in such a way that the alkyl group which comes
first in alphabetical order gets the lower position. For example if ethyl and methyl
groups are present at the equivalent positions, then carbon bearing ethyl group
should get the lower number as illustrated in the following example:
3-Ethyl-2-methylhexane
Some more illustrative examples are;

Molecule IUPAC
131
3-Methylheptane
Prefix: methyl Word root: hept Primary suffix: ane
Prefix:2,4-dimethyl Word root: hex Primary suffix: 2,4-Dimethylhexane

ane
2, 3, 5-Trimethylheptane
Prefixes: 2,3,5-Trimethyl Word root: hept Primary
suffix: ane
2, 2,3-Trimethylpentane
Prefix: 2,2,3-Trimethyl Word root: pent Primary
suffix: ane
Nomenclature of the compounds with functional group:

While naming of the organic compound containing functional group first of all the
functional group is identified and appropriate suffix is selected. In the next step
the longest chain of carbon atoms containing functional group is selected and then
it is numbered in such a way that functional group should get lowest possible
number. The name of the functional group is indicated as suffix.
Note: If functional group itself contains carbon atom in it then lowest number is
given to that group. In the case the functional group does not contain carbon
atom, then the carbon atom of the parent chain attached to the functional group
should get the lowest possible number.
The name of the organic compound is then arrived at by arranging prefixes along
with their positions as follows:
Prefixes-word root-primary suffix-secondary suffix
Nomenclature of bifunctional compounds.

If more than one functional group is present in the molecule then a functional
group is chosen on the basis of priority list. The name of the main functional
group ( I e. the functional group with higher priority also called as principal
functional group) is given as suffix. Where all other functional groups are given as
prefixes.
132
The numbering of the parent chain containing functional groups is done in
such a way that the functional group of higher priority gets the lower number.
The order of priority of various functional groups is given as follows.
Carboxylic acids (-COOH) > esters (-COOR) > acid chlorides (-COCl) > amides
(-CONH2) > nitriles (-CN) > isocyanides (-NC) > aldehydes (-CHO) > ketones (-
CO) > alcohols (- OH) > amine (- NH2) > alkenes (> C = C <) > alkynes > ethers
> halo (Br,Cl,F,I) > nitro (- NO2) > alkyl
Fun. -COOH -COOR - CN - CHO -CO- -OH - NH2

group
Suffix oic aicd oate cyanide al one ol amine
Prefix Car Carbal Cyano Formyl Keto hydrox Amino
boxy koxy Or Oxo Or y
Oxo
Illustration: 1:
3-Hydroxybutan-2-one
According to the order of prefernce –CO gets priority over –OH group. Therefore
numbering given in such a way that keto group sholud get the least noumber.
Hence the name should end end with suffix –one and –OH group is named as the
prefix hydroxy. Therefore the name is 3-Hydroxybutan-2-one.
Some more examples:
Isomerism:
Two or more compounds having the same molecular formula but different
physical and chemical properties are called isomers and this phenomenon is
known as isomerism.
There are two types of isomerism.
1) Structural isomerism 2) Stereo isomerism
1) Structural isomerism:
Two or more compounds with same molecular formula, but different
structural formulae
133
(i.e. differing in arrangement of atoms in molecules) exihibit structural
isomerism.
Stuctural isomerism is further divided into three types namely:
a) Chain isomerism b) Position isomerism
c) Functional isomerism d) Metamerism
(a) Chain isomerism:
Compounds with same molecular formula but diffenet numbers of carbon
atoms in the parent chain show chain isomerism.
Example:
CH3—CH2—CH2—CH3 and CH3—CH—CH3
|
Butane CH3
2-Methylpropane (iso-butane)
CH3—CH2—CH2—CH2—CH3 and
CH3—CH—CH2—CH3
Pentane |
CH3
2-Methylbutane
CH3—CH2—CH2—OH and
CH3—CH—OH
Propan-1-ol |
CH3
1-Methylethanol
(b) Position isomerism:

Compounds with same molecular formula and same carbon chain length but
differ in the position of the functional group or substituent show position
isomerism.
Example:
CH3—CH2—CH2—CH2—OH and CH3—CH2—CH—CH3
|
Butan-1-ol OH
Butane – 2 –ol
CH3—CH2—CH=CH2 and CH3—CH=CH—CH3

But-1-ene But – 2 – ene
(c) Functional isomerism:
Compounds having same molecular formula, but different functional groups
show functional isomerism.
CH3—O—CH3 and CH3—CH2—OH
Methoxy methane Ethyl alcohol
CH3—CO—CH3 and CH3—CH2—CHO
Propanone (Acetone) Propanal
(d) Metamerism :
It arises due to different alkyl chains on either side of the functional groups in the
molecule.
134
Ex: C4H10O represents methoxypropane (CH3OC3H7) and ethoxy ethane
(C2H5OC2H5)
Stereoisomerism:
The compounds that have the same constitution and sequence of covalent bonds
but differ in relative positions of their atoms or groups in space are called
stereoisomers. This special type of isomerism is called as stereoisomerism and can
be classified as geometrical and optical isomerism.
FUNDAMENTAL CONCEPTS IN ORGANIC REACTION MECHANISM:
In an organic reaction, the organic molecule (also reffered as substrate) reacts with
an appropriate attacking reagent and leads to the formation of one or more
intermediate (s) and finally products(s).
attacking reagent
Organic molecule intermediate products
biproducts
Displacement of electrons in covalent bonds:

During chemical reaction the bonding electrons of the reacting molecule are either
completely or partially displaced. This type of displacement of electrons is called
electronic effect. These are 3 types
(a) Inductive effect (I effect):
Consider halogen atom attached to carbon atom. Since halogen is more electro – ve
than carbon, it attracts the shared pair of electrons towards itself & hence
becomes partially –ve& carbon becomes partially +ve.

CH 3  X  
The permanent displacement of bonded pair of electrons towards the more
electronegative atom as a result of higher electronegativity of one atom compared
to another is known as inductive effect.
These are 2 types
(i) –ve Inductive effect (-I effect)
The inductive effect where the electron displacement takes place towards the
substituent group is called – I effect. Some of the group having – I effect are in the
order.
- NO2> -F > -Br> -Cl> -I > -C6H5
(ii) +ve inductive effective effect where the electron displacement takes place away
from the substituent group is called +I effect. Some of the groups having + I effect
are
(CH3)3C> - (CH3)2CH > - C2H5 > - CH3
(b) Mesomeric effect or Resonance effect.(-M or -R effect).:
It is a permanent effect by which molecule becomes polar by the delocalization of
the electrons & lone pair of electrons. This effect is observed in those molecules
which have conjugated double bonds & in compounds containing both ‘  ’ & lone
pair of electrons. These are 2 types
135
(i)– M or – R effect
An atom or group of atoms is said to have –M or –R effect if electron displacement
takes place towards it.
Eg-Some of the group having – M effect are – CHO & - SO 3H, - CN etc
+ -
CH2=CH - CH=CH - CH=O C H2 - CH=CH - CH=CH - O
(ii) + M or + R effect
An atom or group of atoms is said to have +M effect if the direction of electron
displacement takes place away from it. Some groups having +M effect are Cl, Br, I,
NH2, OH etc.
.. + + + ..
NH2 NH2 NH2 NH2 NH2
- -
-
Eg-
(c) Electromeric effect:
The complete transfer of shared pair of  electrons of multiple bonds from l atom
to another in presence of attacking agent is called electromeric effect.
There are 2 types
(I) +E effect
Here there is movement of electrons towards the attacking agent.
H H H
+ + H
H
C = CH + H C -C
Eg- H
H
(ii) -E effect:
Here electron displacement takes place away from attacking agent.
H H
- -
CN + C=O CN - C - O
Eg- H
H
Hyper conjugation effect:
It involves the conjugation between sigma electrons with pi electrons of the
adjacent multiple bond or empty p orbital adjacent carbon atom.
In this effect the delocalization of sigma electrons of C – H bond of an alkyl
group directly attached to an atom of unsaturated system or to an atom with
an unshared p orbital takes place.
This effect is also called no bond resonance effect. Larger the number of hyper
conjugative structures higher the delocalization of electron pairs and greater the
stability of the compound.
e.g. C2H5 , C2H5o , CH3  CH2  Cl2
Homolytic cleavage or homolytic fission:
136
In this type of fission, each fragment formed as a result of cleavage of covalent
bond gets one electron each from the shared bond pair electrons.
sunlight
. .
Ex: Cl - Cl Cl - Cl
An atom or group of atoms containing odd number of electrons or unpaired

electron is called free radicals.
Heterolytic fission:
In this type of cleavage both the bond pair of electrons of the covalent bond is
taken away by electron withdrawing fragment. An atom or molecule which loses
the electron becomes positively charged species and which gains the electron
become negatively charged species.
Ex: CH3 – Br  CH3+ + Br-
H – Cl  H+ + Cl-
Reaction intermediate :
Carbocation:
A reaction intermediate formed by heterolytic fission of a covalent bond which
contains positively charged carbon with three bond pair electrons (sextet electrons)
is called carbocation.
Ex: CH3 – Br  CH3+ + Br-
methyl carbocation
The carbocation is classified into primary, secondary and tertiary based on the
carbon atom bearing the positive charge.
Ex:
H H H CH3
+ + + +
H C H3C C H3C C H3C C
H H H3C CH3
methyl primary secondary tertiary

carbocation carbocation carbocation carbocation
The carbocations are electron deficient containing six electrons. The carbocations
have trigonal planar shape as positively carbon in sp2 hybridized.
Orbital structure of carbocation:
H
120o C+ H
H
Stability of the carbocations: The carbocations are stabilized in the presence of
electron releasing groups. Alkyl group directly attached to positively charged
carbon stabilize the carbocation due to inductive and hyperconjugation effect.
Greater the number of α – hydrogen atoms higher be the stability of carbocations.
As the stability of the carbocation increases its reactivity decreases.
137
The order of the relative stability of tertiary (3o), secondary (2o) and primary
(1o)carbocations are given by,
H H H CH3
+ + + +
H C H3C C H3C C H3C C
H H H3C CH3

carbocation carbocation carbocation carbocation
Carbanion:
A reaction intermediate formed by heterolytic fission of a covalent bond which
contains one negatively charged carbon with eight electrons in its valence shell is
called carbaion.
Ex: CH3 – MgI  CH3- + MgI+

OH- + H – CH2 – CHO  C H2 – CHO + H2O
The carbocation is classified into primary, secondary and tertiary based on the
carbon atom bearing the negative charge.
Ex:
H CH3 CH3 CH3
H C- H C- H3C C- H3C C-
H H H CH3
carbanion carbanion carbanion carbanion
Structure of carbanion: carbanions are electron rich with complete octet structure
(8 electrons). The carbon atom carrying negative charge in carbanion is sp3
hybridized with lone pair of electrons. Due to the presence of lone pair of electrons,
the shape of the molecule changes from tetrahedral to pyramidal in carbanion.
sp3 .. lone pair of electrons
orbital
C-
H H
H
orbital structure of methyl carbanion.
Stability of carbanions:
Alkyl group bonded to negatively charged carbon increases the intensity of
negative charge due to +I effect and stabilize the carbanion. Therefore the stability
of alkyl carbanion is
138
H CH3 CH3 CH3
H C- > H C- > H3C C- > H3C C-
H H H CH3
carbanion carbanion carbanion carbanion
The order of the reactivity of carbanions is given by 3o < 2o < 1o < CH3 –.
Free radicals:
An atom or group of atoms containing odd or unpaired electrons is called free
radical. These are formed by the homolytic cleavage of covalent bond. This
cleavage of bond is initiated by the action of heat light or a reagent.
sunlight . .
Ex: Cl - Cl Cl - Cl
.
R – H + Cl.  CH3 + HCl
The freeradical is classified into primary, secondary and tertiary based on the
carbon atom bearing the unpaired electron.
H CH3 CH3 CH3
H C H C H3C C H3C C
H H H CH3
free radical free radical free radical free radical
Stability of the free radicals:

The relative stability of alkyl free radicals is explained on the basis of
hyperconjugation and inductive effects. The more number of alkyl group attached
to carbon atom carrying unpaired electron, higher is the delocalization and hence
more stable is the alkyl radical. The relative stability of the stability of free radical
is given by ,
H CH3 CH3 CH3
H C < H C < H3C C < H3 C C
H H H CH3
free radical free radical free radical free radical
The reactivity of the free radicals of 1o , 2o ,and 3o free radicals are given by,
1o free radical > 2o free radical > 3o free radical.
Electrophiles and nucleophiles: the organic reactions proceed by the attack of
highly reactive reagents on the substrate molecule. These reagents are classified
into two groups.
139
Electrophiles:
The electron deficient molecules or positively charged ions are called electrophiles.
These are capable of accepting one electron pair from substrate molecules. These
act as Lewis acids.
Ex: H+ , Cl+ , Br+ , NO2+ , etc (positive electrophiles)
SO3 , BF3 , AlCl3 , etc ( neutral electrophiles)
Nucleophiles:
The electron rich molecules or negatively charged ions are called nucleophiles.
These have capacity to donate the electrons. hence these are also called as Lewis
bases.
Ex: Cl- , Br- , OH- , NH2- etc (negatively charged nucleophiles)
H2O, NH3, RSH, etc (neutral nucleophiles, since in the given examples O , N , S
contain lone pair of electrons. )
METHODS OF PURIFICATION OF ORGANIC COMPOUNDS:

Once an organic compound is extracted from a natural source or synthesised in
the laboratory, it is essential to purify it. Various methods used for the
purification of organic compounds are based on the nature of the compound and
the impurity present in it.
The common techniques used for purification are as follows:
i)Sublimation (ii) Crystallisation (iii) Distillation (iv) Differential extraction and (v)
Chromatography
Sublimation:
On heating, some solid substances change from solid to vapour state without
passing through liquid state. The purification technique based on the above
principle is known as sublimation and is used to separate sublimable compounds
from nonsublimable impurities.
Crystallisation:
Compound and the impurities in a suitable solvent. The impure compound is
dissolved in a solvent in which it is sparingly soluble at room temperature but
appreciably soluble at higher temperature.
The solution is concentrated to get a nearly saturated solution. On cooling the
solution, pure compound crystallises out and is removed by filtration. The filtrate
(mother liquor) contains impurities and small quantity of the compound. If the
compound is highly soluble in one solvent and very little soluble in another
solvent, crystallisation can be satisfactorily carried out in a mixture of these
solvents. Impurities, which impart colour to the solution are removed by
adsorbing over activated charcoal.
140
Distillation:
This important method is used to separate (i) volatile liquids from nonvolatile
impurities and (ii) the liquids having sufficient difference in their boiling points.
Liquids having different boiling points vaporise at different temperatures. The
vapours are cooled and the liquids so formed are collected separately. Chloroform
(b.p 334 K) and aniline (b.p. 457 K) are easily separated by the technique of
distillation. The liquid mixture is taken in a round bottom flask and heated
carefully. On boiling, the vapours of lower boiling component are formed first.
The vapours are condensed by using a condenser and the liquid is collected in a
receiver. The vapours of higher boiling component form later and the liquid can be
collected separately.
Differential Extraction:
When an organic compound is present in an aqueous medium, it is separated by
shaking it with an organic solvent in which it is more soluble than in water. The
organic solvent and the aqueous solution should be immiscible with each other so
that they form two distinct layers which can be separated by separatory funnel.
The organic solvent is later removed by distillation or by evaporation to get back
the compound.
Chromatography:
Chromatography is an important technique extensively used to separate mixtures
into their components, purify compounds and also to test the purity of
compounds. In this technique, the mixture of substances is applied onto a
stationary phase, which may be a solid or a liquid. A pure solvent, a mixture of
solvents, or a gas is allowed to move slowly over the stationary phase. The
components of the mixture get gradually separated from one another. The moving
phase is called the mobilephase.
I. Adsorption Chromatography:
Adsorption chromatography is based on the fact that different compounds are
adsorbed on an adsorbent to different degrees. Commonly used adsorbents are
silica gel and alumina. When a mobile phase is allowed to move over a stationary
phase (adsorbent), the components of the mixture move by varying distances over
the stationary phase.
(a) Column Chromatography:
Column chromatography involves separation of a mixture over a column of
adsorbent (stationary phase) packed in a glass tube.
The column is fitted with a stopcock at its lower
soluble in the organic solvent, a very large end. The
mixture adsorbed on adsorbent is placed on the top of
the adsorbent column packed in a glass tube. An
appropriate eluant which is a liquid or a mixture of
liquids is allowed to flow down the column slowly.
141
Depending upon the degree to which the compounds are adsorbed, complete
separation takes place. The most readily adsorbed substances are retained near
the top and others come down to various distances in the column
(b) Thin Layer Chromatography:

TLC involves separation of substances of a mixture over a thin layer of an
adsorbent coated on glass plate . A thin layer (about 0.2mm thick) of an adsorbent
(silica gel or alumina) is spread over a glass plate of suitable size. The plate is
known as thin layer chromatography plate or chromaplate.
The solution of the mixture to be separated is applied as a small spot about 2 cm
above one end of the TLC plate. The glass plate is
then placed in a closed jar containing the eluant.
eluant rises up the plate, the components of the
mixture move up along with the eluant to different
distances depending on their degree of adsorption
and separation takes place. The relative adsorption
of each component of the mixture is expressed in terms of its retardation factor i.e.
Rf value
Rf = Distance moved by the substance from base line (x) / Distance moved by
the solvent from base line (y)
II. Partition Chromatography:

Partition chromatography is based on continuous differential partitioning of
components of a mixture between stationary and mobile phases. Paper
chromatography is a type of partition chromatography. In paper chromatography,
a special quality paper known as chromatography paper is used. Chromatography
paper contains water trapped in it, which acts as the stationary phase. A strip of
chromatography paper spotted at the base with the solution of the mixture is
suspended in a suitable solvent or a mixture of solvents. This solvent acts as the
mobile phase. The solvent rises up the paper by capillary action and flows over the
spot. The paper selectively retains different components according to their
differing partition in the two phases. The paper strip so developed is known as
chromatogram. The spots of the separated coloured compounds are visible at
different heights from the position of initial spot on the chromatogram.
QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS:

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:
142
Carbon and hydrogen are detected by heating 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).
Detection of Other Elements:
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 reactions take place:
Na + C + N → NaCN 2Na + S → Na2S Na + X → Na X
(X = Cl, Br or I) C, N, S and X come from organic compound.
Test for Nitrogen:
The sodium fusion extract is boiled with iron(II) sulphate and ferric chloride and
then acidified with concentrated sulphuric acid. The formation of Prussian blue
colour confirms the presence of nitrogen.
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.
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a
violet colour further indicates the presence of sulphur.
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.
If sodium fusion is carried out with excess of sodium, the thiocyanate decomposes
to yield cyanide and sulphide. These ions give their usual tests.
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.
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.
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.
QUANTITATIVE ANALYSIS:
143
The percentage composition of elements present in an organic compound is
determined by the methods based on the following principles:
Carbon and Hydrogen by Leiligs method:
Both carbon and hydrogen are estimated in one experiment. A known mass of an
organic compound is burnt in the presence of excess of oxygen and copper(II)
oxide. Carbon and hydrogen in the compound are oxidised to carbon dioxide and
water respectively.
The mass of water produced is determined by passing the mixture through a
weighed U-tube containing anhydrous calcium chloride. Carbon dioxide is
absorbed in another U-tube containing concentrated solution of potassium
hydroxide. These tubes are connected in series The increase in masses of calcium
chloride and potassium hydroxide gives the amounts of water and carbon dioxide
from which the percentages of carbon and hydrogen are calculated. Let the mass
of organic compound be m g, mass of water and carbon dioxide produced be m1
and m2 g respectively;
12  m2  100
•Percentage of carbon 
44  m
2  m1  100
Percentage of Hydrogen 
18  m
Nitrogen:
There are two methods for estimation of nitrogen: (i) Dumas method and (ii) Kjeldahl’s
method.
(i) Dumas method: The nitrogen containing organic compound, when heated with
copper oxide in an atmosphere of carbon dioxide, yields free nitrogen in addition to
carbon dioxide and water.
CxHyNz + (2x + y/2) CuO → x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu
Traces of nitrogen oxides formed, if any, are reduced to nitrogen by passing the gaseous
mixture over a heated copper gauze. The mixture of gases so produced is collected over
an aqueous solution of potassium hydroxide which absorbs carbon dioxide. Nitrogen is
collected in the upper part of the graduated tube
Let the mass of organic compound = m g,
Volume of nitrogen collected = V1 mL ,
Room temperature = T1K
144
Where p1 and V 1 are the pressure and volume of nitrogen, p1 is different from
the atmospheric pressure at which nitrogen gas is collected. The value of p 1 is
obtained by the relation;
p1= Atmospheric pressure – Aqueous tension ,
22400 mL N2 at STP weighs 28 g.
28  V
V mL N 2 at STP weighs  g
22400
28  V  100
Percentage of nitrogen 
22400  m
Kjeldahl’s method:
The compound containing nitrogen is heated with concentrated sulphuric acid.
Nitrogen in the compound gets converted to ammonium sulphate. The resulting
acid mixture is then heated with excess of sodium hydroxide. The liberated
ammonia gas is absorbed in an excess of standard solution of sulphuric acid. The
amount of ammonia produced is determined by estimating the amount of
sulphuric acid consumed in the reaction. It is done by estimating unreacted
sulphuric acid left after the absorption of ammonia by titrating it with standard
alkali solution. The difference between the initial amount of acid taken and that
left after the reaction gives the amount of acid reacted with ammonia.
Organic compound + H2SO4 → (NH4)2SO4  Na2SO4 +2NH3 +2H2O
2NH3 + H2SO4 → (NH4)2SO4
1.4  Basicity of acid  (VM)H2SO4
Percentage of N =
mass of
Halogens:
Carius method: A known mass of an organic compound is heated with fuming
nitric acid in the presence of silver nitrate contained in a hard glass tube known as
Carius tube, in a furnace. Carbon and hydrogen present in the compound are
oxidised to carbon dioxide and water. The halogen present forms the
corresponding silver halide (AgX). It is filtered, washed, dried and weighed.
Let the mass of organic compound taken = m g
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of X
atomic mass of X  m1g
Mass of halogen in m1g of AgX 
molecular mass of AgX
atomic mass of X x m1 X 100
Percentage of halogen 
Molecular mass of AgX x m
Sulphur:
145
A known mass of an organic compound is heated in a Carius tube with sodium
peroxide or fuming nitric acid. Sulphur present in the compound is oxidised to
sulphuric acid. It is precipitated as barium sulphate by adding excess of barium
chloride solution in water. The precipitate is filtered, washed, dried and weighed.
The percentage of sulphur can be calculated from the mass of barium sulphate.
Let the mass of organic compound taken = m g and the mass of barium sulphate
formed = m1g
1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur
m1 g BaSO4 contains 32  m1 / 233 g sulphur
Percentage of sulphur= 32  m1  100 / 233  m
Phosphorus:
A known mass of an organic compound is heated with fuming nitric acid where
upon phosphorus present in the compound is oxidised to phosphoric acid. It is
precipitated as ammonium phosphomolybdate, (NH 4)3 PO4.12MoO3, by adding
ammonia and ammonium molybdate. Alternatively, phosphoric acid may be
precipitated as MgNH4PO4 by adding magnesia mixture which on ignition yields
Mg2P2O7.
Let the mass of organic compound taken = mg, and
mass of ammonium phosphomolybdate = m1g.
Molar mass of phosphorus (NH4)3PO4.12MoO3 = 1877g.
31  m1  100
Percentage of phosphorus =
1877  m
If phosphorus is estimated as Mg2P2O7
62  m1  100
Percentage of phosphorus =
222  m
146
13 HYDROCARBONS
The term ‘hydrocarbon’ is self-explanatory which means compounds of carbon and hydrogen
only. Hydrocarbons play a key role in our daily life. You must be familiar with the terms ‘LPG’
and ‘CNG’ used as fuels. LPG is the abbreviated form of liquified petroleum gas whereas CNG
stands for compressed natural gas.
CLASSIFICATION:
Hydrocarbons are of different types. Depending upon the types of carbon-carbon bonds
present, they can be classified into three main categories –
(i) Saturated (ii) Unsaturated and (iii) Aromatic hydrocarbons.
(i) Saturated hydrocarbons: It contains carbon-carbon and carbon-hydrogen single
bonds. If different carbon atoms are joined together to form open chain of carbon atoms
with single bonds, they are termed as alkanes.If carbon atoms form a closed chain or a
ring, they are termed as cycloalkanes.
(ii) Unsaturated hydrocarbons: It contain carbon-carbon multiple bonds – double bonds,
triple bonds or both.
(iii) Aromatic hydrocarbons: These are the special type of cyclic compounds.
ALKANES:
The general formula of alkanes is CnH2n+2.
Nomenclature:
1. Straight chain Alkanes: The name Alkane compounds are based on their chain
structure, and end with suffix ‘-ane’ and carrya prefix indicating the number of
carbonatoms present in the chain (except from CH4to C4H10, where the prefixes are
derived from trivial names).
147
Example:
Molecular formula IUPAC name Trivial name
CH4 Methane methane
C 2 H6 Ethane ethane
C 3 H8 Propane propane
C4H10 Butane n-butane
C5H12 Pentane n-pentane
2. Branched chain Alkanes: In a branched chain compound small chains of carbon atoms
are attached at one or more carbon atoms of the parent chain. The small carbon chains
(branches) are called alkyl groups.
Name of some Alkyl groups:
Alkyl group formula Name of Alkyl group
-CH3 Methyl
-C2H5 Ethyl
-C3H7 Propyl
-C4H9 Butyl
-C5H11 Pentyl
Example:
Molecular Structural formula IUPAC name Trivial name
formula
CH3
C4H10 2-methylpropane isobutane
H3C CH CH3
CH3
C5H12 2-methylbutane isopentane
H3C CH CH2 CH3
CH3
C5H12 H3C C CH3 2,2-dimethylpropane neopentane
CH3
Isomerism:
Alkanes exhibits structural isomerism. Compounds having same molecular formula but
different structural formula are called as structural isomers and the phenomenon is
called as Structural isomerism.
Example:
1. n-butane and isobutene: Molecular formula of these compounds is C4H10.
CH3
H3C CH2 CH2 CH3 & H3C CH CH3
butane(n - butane) 2-methylpropane (iso-butane)
2. n-pentane, isopentane and neopentane. Molecular formula is C5H12.
148
CH3 CH3
H3C CH2 CH2 CH2 CH3 H3C CH CH2 CH3 H 3C C CH3
pentane 2-methylbutane CH3
(n-pentane) (isopentane) 2,2-dimethylpropane
(neopentane)
Exercise:
Write structures of different chain isomers of alkanes corresponding to the molecular
formula C6H14.
CH3 CH3
H3C CH2 CH2 CH2 CH2 CH3 H3C CH2 CH2 CH CH3 H3C CH2 CH CH2 CH3
hexane 2-methylpentane 3-methylpentane
CH3
H3C CH CH CH3 H3C CH2 C CH3
CH3 CH3 CH3
2,3-dimethylbutane 2,2-dimethylbutane
1. Alkanes are almost non-polar molecules because of the covalent nature of C-C and C-H
bonds and due to very little difference of electronegativity between carbon and hydrogen
atoms.
2. They possess weak van der Waals forces. Due to the weak forces, the first four members,
C1 to C4 are gases, C5 to C17 are liquids and those containing 18 carbon atoms or more
are solids at 298 K.
3. They are colourless and odourless.
4. What do you think about solubility of alkanes in water based upon nonpolar nature of
alkanes? It is generally observed that in relation to solubility of substances in solvents,
polar substances are soluble in polar solvents, whereas the non-polar ones in non-polar
solvents i.e., like dissolves like.
5. Boiling point (b.p.) data of different alkanes clearly reveals that there is a steady increase
in boiling point with increase in molecular mass. This is due to the fact that the
intermolecular van der Waals forces increase with increase of the molecular size or the
surface area of the molecule.
6. With increase in number of branched chains, boiling point decreases. The molecule
attains the shape of a sphere. This results in smaller area of contact and therefore weak
intermolecular forces between spherical molecules, which are overcome at relatively lower
temperatures.
Preparation:
1. From unsaturated hydrocarbons:
Dihydrogen gas adds to alkenes and alkynes in the presence of finely divided catalysts
like platinum, palladium or nickel to form alkanes. This process is called hydrogenation.
149
(i) From Alkenes:
Pt / Pd / Ni
R CH CH2 + H2 R CH2 CH3
Alkene Alkane
Example:
1. Ethene reacts with dihydrogen in the presence of platinum or palladium or nickel as
catalyst to form ethane.
Pt / Pd / Ni
H2C CH2 + H2 H3C CH3
ethene ethane
2. Propyne reacts with dihydrogen in the presence of platinum or palladium or nickel as
catalyst to form propane.
Pt / Pd / Ni
H3C CH CH2 + H2 H3C CH2 CH3
prop-1-ene propane
(ii) From Alkynes:
Pt / Pd / Ni
R C CH + 2 H2 R CH2 CH3
Alkyne Alkane
Example:
1. Ethyne reacts with dihydrogen in the presence of platinum or palladium or nickel as
HC CH + 2 H2 Pt / Pd / Ni H3C CH3
ethyne ethane
2. Propyne reacts with dihydrogen in the presence of platinum or palladium or nickel as
catalyst to form propane.
H3C C CH + 2 H2 Pt / Pd / Ni H3C CH2 CH3
prop-1-yne propane
2. From alkyl halides:
(i) Reduction: Alkyl halides (except fluorides) onreduction with zinc and dilute
hydrochloric acid give alkanes.
Zn, H+
R CH2 X + H2 R CH3 + HX Where X = Cl, Br, I (except F)
Alkyl halide Alkane
Example:
1. Chloromethane on reduction with zinc and dilute hydrochloric acid give methane.
Zn, H+
H3C Cl + H2 CH4 + HCl
Chloromethane methane
(methyl chloride)
2. Chloroethane on reduction with zinc and dilute hydrochloric acid give ethane.
Zn, H+
H3C CH2 Cl + H2 H3C CH3 + HCl
Chloroethane ethane
(ethyl chloride)
150
3. Chloropropane on reduction with zinc and dilute hydrochloric acid give propane.
Zn, H+
H3C CH2 CH2 Cl + H2 H3C CH2 CH3+ HCl
Chloropropane propane
(propyl chloride)
(ii)Wurtz reaction: Alkyl halides on treatment with sodiummetal in dry ethereal (free
from moisture) solution give higher alkanes. This reactionis known as Wurtz reaction
and is used for the preparation of higher alkanes containing even number of carbon
atoms.
dry ether
R X + 2 Na + X R R R + 2 NaX
Alkyl halide Alkyl halide Alkane
Example:
1. Bromomethane reacts with sodium metal in the presence of dry ether to form ethane
and sodium bromide.
H3C Br + 2 Na + Br CH3 dry ether H3C CH3 + 2 NaBr
Bromomethane Bromomethane ethane
(methyl bromide) (methyl bromide)
2. Bromoethane reacts with sodium metal in the presence of dry ether to form butane and
sodium bromide.
H5C2 Br + 2 Na + Br C2H5 dry ether H5C2 C2H5 + 2 NaBr
Bromoethane Bromoethane butane
(ethyl bromide) (ethyl bromide)
3. From carboxylic acids by Kolbe’s electrolytic method:

An aqueoussolution of sodium or potassium salt of a carboxylic acid on electrolysis gives
alkanecontaining even number of carbon atomsat the anode.
2CH3COONa + 2H 2O 
Electrolysis
 CH 3 - CH 3 + 2CO 2 + H 2 + 2NaOH
Sodium acetate ethane
1. Substitution reactions: These reactions in which hydrogen atoms of alkanes are
substituted are known as substitution reactions. One or more hydrogen atoms of alkanes
can be replaced by halogens, nitro group and sulphonic acid group. Lower alkanes do not
undergo nitration and sulphonation reactions.
(i) Halogenation: It takes place either at higher temperature (573-773 K) or in the
presence of diffused sunlight or ultraviolet light.
Example: Chlorination of methane.
Methane reacts with excess of chlorine gas in the presence of diffused sunlight to form a
mixture of chloromethane, dichloromethane, trichloromethane and tetrachloromethane.
CH 4 + Cl2 
hυ
 CH3Cl  HCl
methane chloromethane
CH Cl + Cl2  CH 2Cl 2  HCl

3
hυ
chloromethane dichloromethane
151
CH Cl 2 2 + Cl2  hυ
CHCl 3  HCl
dichloromethane trichloromethane
CHCl3 + Cl 2 
hυ
 CCl 4  HCl
trichloromethane tetrachloromethane
Mechanism:
(i) Initiation: The reaction is initiated by homolysis of chlorine molecule in the presence
of light or heat.
h
Cl Cl homolysis
Cl + Cl
Chlorine free radicals
(ii) Propagation: Chlorine free radical attacks the methane molecule and takes the
reaction in the forward direction by breaking the C-H bond to generate methyl free radical
with the formation of H-Cl.
h
(a) CH4+ Cl CH3 + HCl
methane methyl free
radical
The methyl radical thus obtained attacks the second molecule of chlorine to form CH 3 – Cl
with the liberation of another chlorine free radical by homolysis of chlorine molecule.
(b) CH3 + Cl Cl h H3C Cl + Cl
methyl free methyl Chlorine free
radical chloride radicals
The chlorine and methyl free radicals generated above repeat steps (a) and (b) respectively
and thereby setup a chain of reactions. The propagation steps (a) and (b) are those which
directly give principal products, but many other propagation steps are possible and may
occur.
(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:
(a) Cl +
Cl Cl Cl
CH3 + Cl H3C Cl
CH3 + CH3 H3C CH3 chloromethane
(b) c)
Methyl free radicals ethane
Though in (c), CH3– Cl, the one of the products is formed but free radicals are consumed
and the chain is terminated. The above mechanism helps us to understand the reason for
the formation of ethane as a byproduct during chlorination of methane.
2. Combustion:
Alkanes on heating in the presence of air or dioxygen are completely oxidized to carbon
dioxide and water with the evolution of large amount of heat.
Example:
1. Combustion of methane:
152
CH + 2 O2 
4  CO 2
0
+ 2 H 2O , Δ c H = -890 kJmol -1
methane Carbondioxide
2. Combustion of butane:
13
C4 H10 + O 2 
 4 CO 2 + 5 H 2O , Δ c H 0 = -2875.84 kJmol-1
butane 2 Carbondioxide
3. Controlled oxidation:
Alkanes on heating with a regulated supply ofdioxygen or air at high pressure and in the
presence of suitable catalysts give a variety ofoxidation products.
Example:
(1)When methane is heated with dioxygen (air) at 523 K under 100 atm pressure in the
presence of copper as catalyst methanol is formed.
2 CH 4 + O 2 
Cu / 523 K / 100 atm
 2 CH 3OH
methane methanol
(2)When methane is heated withdioxygen (air) in the presence of Mo2O3 as catalyst,

methanal (formaldehyde) is formed.
CH 4 + O 2 
Mo 2 O3

 HCHO + H 2O
Methane Methanal
4. Aromatization:
n-Alkanes having six or more carbon atoms on heating to 773K at 10-20 atmospheric
pressure in the presence of oxides of vanadium, molybdenum or chromium supported
over alumina get dehydrogenated and cyclised to benzene and its homologues. This
reaction is known as aromatization or reforming.
CH3
Cr2O3 or V2O5 or
H2C CH3 Mo2O3
773 K , 10 - 20 atm
H2C CH2
CH2
n - hexane Benzene
5. Pyrolysis: Higher alkanes on heating to higher temperature decompose into lower
alkanes, alkenes etc. Such a decomposition reaction into smaller fragments by the
application of heat is called pyrolysis or cracking.
Example:
(1)n-hexane on pyrolysis yields a mixture of hexene, dihydrogen, butene, ethane, ethene,
propene, and methane.
C6H12 + H2
773 K
C6H14 C4H8 + C2H6
C3H6 + C2H4 + CH4
(2)Dodecane (C12H26), a constituent of kerosene oil on heating to 973K in the presence of

platinum, palladium or nickel gives a mixture of heptane and pentene.
C12H26 Pt /973
Pd / Ni
K
C7H16 + C5H10 + other
Dodecane Heptane Pentene products
153
Conformations:
 Alkanes contain carbon-carbon sigma (σ) bonds. Electron distribution of the sigma
molecular orbital is symmetrical around the internuclear axis of the C–C bond which
is not disturbed due to rotation about its axis.
 This permits free rotation about C–C single bond. This rotation results into different
spatial arrangements of atoms in space which can change into one another.
 Such spatial arrangements of atoms which can be converted into one another by
rotation around a C-C single bond are called conformations or conformers or
rotamers.
 Alkanes can thus have infinite number of conformations by rotation around C-C single
bonds. However, it may be remembered that rotation around a C-C single bond is not
completely free. It is hindered by a small energy barrier of1-20 kJ mol–1 due to weak
repulsive interaction between the adjacent bonds. Such a type of repulsive interaction
is called torsional strain.
Conformations of ethane:
 Ethane molecule (C2H6) contains a carbon – carbon single bond with each carbon atom
attached to three hydrogen atoms.
 Considering the ball and stick model of ethane, keep one carbon atom stationary and
rotate the other carbon atom around the C-C axis.
 Thisrotation results into infinite number of spatial arrangements of hydrogen atoms
attached to one carbon atom with respect to the hydrogen atoms attached to the other
carbon atom. These are called conformational isomers(conformers).
 Thus there are infinite number of conformations of ethane. However, there are two
extreme cases. One such conformation in which hydrogen atoms attached to two
carbons are as closed together as possible is called eclipsed conformation and the
other in which hydrogens are as far apart a spossible is known as the
staggeredconformation.
 Any other intermediate conformation is called a skew conformation. It may be
remembered that in all the conformations, the bond angles and the bond lengths
remain the same.
 Eclipsed and the staggered conformations can be represented by Sawhorse and
Newman projections.
1. Sawhorse projections of ethane:

H
H
H
H H H H
H
H H H H
Eclipsed conformation of ethane Staggered conformation of ethane
Sawhorse projections of ethane
2. Newman projections of ethane:

154
Angle of rotation or angle of
tortion or dihedral angle
HH H
H H
H H H H
H H
H
Eclipsed conformation of ethane Staggered conformation of ethane
Newman’s projections of ethane
Relative stability of conformations:

 In staggered form of ethane, the electron clouds of carbon-hydrogen bonds are as far
apart as possible. Thus, there are minimum repulsive forces, minimum energy and
maximum stability of the molecule.
 On the other hand, when the staggered form changes into the eclipsed form, the
electron clouds of the carbon – hydrogen bonds come closer to each other resulting in
increase in electron cloud repulsions.
 The repulsive interaction between the electron clouds, which affects stability of a
conformation, is called torsionalstrain.
 Magnitude of torsional strain dependsupon the angle of rotation about C–C bond. This
angle is also called dihedral angle or torsional angle.
 Of all the conformations of ethane, the staggered form has the least torsional strain
and the eclipsed form, the maximum torsional strain.
 It has not been possible to separate and isolate different conformational isomers of
ethane.
ALKENES:
Alkenes are unsaturated hydrocarbons containing at least one double bond. The general
formula of alkenes is CnH2n.
Alkenes are also known as olefins (oil forming) since the first smember, ethylene or ethene
(C2H4) was found to form an oily liquid on reaction with chlorine.
Nomenclature:
For nomenclature of alkenes in IUPAC system, the longest chain of carbon atoms
containing the double bond is selected. Numbering of the chain is done from the end
which is nearer to the double bond. The suffix ‘ene’ replaces ‘ane’ of alkanes.
Example:
H 2C CH2 Ethene ethylene
CH2 = CH – CH3 1- propeneor prop-1-ene propylene
155
H 3C CH2 CH CH2 1-buteneor but-1-ene 1-butylene
H 3C CH CH CH 3 2-buteneor but-2-ene 2-butylene
H3C CH 2 CH2 CH CH2 1-penteneor pent-1-ene 1-pentene
H 3C CH 2 CH CH CH 3 2-penteneor pent-2-ene 2-pentene
Structure of Double Bond in ethene:
 Carbon-carbon double bond in ethene consists of one strong sigma (σ) bond due to
head-on overlapping of sp2 hybridised orbitals and one weak pi (π) bond obtained by
lateral or sideways overlapping of the two 2p orbitals of the two carbon atoms.
 The double bond is shorter in bond length (134 pm) than the C–C single bond (154
pm). pi (π) bond is a weaker bond due to poor sideways overlapping between the two
2p orbitals.
 Strength of the double bond is greater than that of a carbon-carbon single bond in
ethane.
s   s
sp2 sp2
2 2
sp sp
sp2 sp2
 
s s
Orbital picture of ethene depicting  bonds only
p-p ( -bond)
 -colud 121.7o
H H H H
H H
o
C C 110 pm C C 116.6
C C
H H
H H H H
134 pm
(a) (b) (c)
Orbital picture of ethene showing formation of (a)  -bond, (b)  -cloud and (c) bond angles and
bond lengths
Geometrical isomerism:
Doubly bonded carbon atoms have to satisfy the remaining two valences by joining with
two atoms or groups.
If the two atoms or groups attached to each carbon atom are different, they can be
represented by
YX C = C XY like structure. YX C = C XY can be represented in space in the following two
ways:
156
X Y Y X
C C
C C
X Y X Y
cis -isomer trans -isomer
Structure (a) Structure (b)
 In (a), the two identical atoms i.e., both the X or both the Y lie on the same side of the
double bond but in (b) the two X or two Y lie across the double bond or on the opposite
sides of the double bond.
 This results indifferent geometry of (a) and (b) i.e. disposition of atoms or groups in
space in the two arrangements is different. Therefore, they are stereo isomers.
 The stereoisomers of this type are called geometrical isomers.
 The isomer of the type(a), in which two identical atoms or groups lie on the same side of
the double bond is called cis isomer and the other isomer of the type(b), in which
identical atoms or groups lie on the opposite sides of the double bond is called trans
isomer .
 Due to different arrangement of atoms or groups in space, these isomers differ in their
properties like melting point, boiling point, dipole moment, solubility etc.
Example for geometrical isomers: (CH3 – CH = CH – CH3)
cis-2-butene and trans-2-butene:
  
H3C CH3 H3C H

C C C C
   
H H H CH3
cis-2-butene trans-2-butene
 = 0.33 D =0D
 Cis form of alkene is found to be more polar than the trans form.
 For example, dipole moment of cis-but-2-ene is 0.33 Debye, whereas, dipole moment of
the transform is almost zero or it can be said thattrans-but-2-ene is non-polar.
 This can be understood by drawing geometries of the two forms as shown in the figure.
 It is clear that in the trans-but-2-ene, the two methyl groups are in opposite directions,
Therefore, dipole moments of C-CH3 bonds cancel, thus making the trans form non-
polar.
Alkenes as a class resemble alkanes in physical properties, except in types of isomerism
and difference in polar nature.
157
 The first three members are gases, the next fourteen are liquids and the higher ones
are solids.
 Ethene is a colourless gas with a faint sweet smell. All other alkenes are colourless and
odourless, insoluble in water but fairly soluble in nonpolar solvents like benzene,
petroleum ether.
 They show a regular increase in boiling point with increase in size i.e., every – CH2
group added increases boiling point by 20–30 K.
 Straight chain alkenes have higher boiling point than isomeric branched chain
compounds.
Preparation:
1. From alkynes:
Alkynes on partial reduction with calculated amount of dihydrogen in the presence of
palladised charcoal partially deactivated with poisons like sulphur compounds or
quinoline give alkenes. Alkenes thus obtained are having cisgeometry. Partially
deactivated palladised charcoal is known as Lindlar’s catalyst. However, alkynes on
reductionwith sodium in liquid ammonia form trans alkenes.
(a) Synthesis of cis – but-2-ene: 2-butyne on partial reduction with calculated amount of
dihydrogen in the presence of palladised charcoal partially deactivated with quinoline give
cis-2-butene.
H3C CH3
Pd / C C C
H3C C C CH3 + H2
but-2-yne H H
cis -but-2-yne
Alkynes on partial reduction with calculated amount of dihydrogen in the presence of
palladised charcoal partially deactivated with poisons like sulphur compounds or
quinoline give alkenes. Alkenes thus obtained are having cis geometry.
Partially deactivated palladised charcoal is known as Lindlar’s catalyst.
(b)2-butyne on partial reduction with sodium in liquid ammonia form trans-2-butyne.
H3C H
Na / liquid NH3
H3C C C CH3 + H2 C C
but-2-yne H CH3
trans -but-2-yne
2. From alkyl halides:
Alkyl halides (R-X)on heating with alcoholic potash (potassium hydroxide dissolved in
alcohol, say, ethanol) eliminate one molecule of halogen acid to form alkenes. This
reaction is known as dehydrohalogenation. It is an example for β-elimination reaction.
H H H H
  alc. KOH
H C C H C C

H X H H
X = Cl, Br, I Alkene
158
Nature of halogen atom and the alkyl group determine rate of the reaction. It is
observed that for halogens, the rate is: iodine > bromine > chlorine, while for alkyl groups
it is: tert> secondary > primary.
Example:
1. When ethyl bromide is heated with alcoholic KOH, ethene is formed.
C2 H 5 Br + KOH (alc) 

 C 2 H 4 + KBr
bromoethane ethene
(Ethyl bromide)
2. When 2-chloropropane is heated with alcoholic KOH, 1-propene is formed.

Cl
alc. KOH
H3C CH CH3 H3C CH CH2 + KCl

1-propene
3. From vicinal dihalides:
Dihalides in which two halogen atoms are attached to two adjacent carbon atoms are
known as vicinal dihalides.
Vicinal dihalides on treatment with zinc metal lose a molecule of ZnX2 to form an alkene.
This reaction is known as dehalogenation.
Example:
1.When 1,2-dibromoethane is treated with zinc metal, ethene is formed.
H2C CH2 + Zn H2C CH2 + ZnBr2
Br Br ethene
1,2 -dibromoethane
4. From alcohols by acidic dehydration:
Alcohols on heating with concentrated sulphuric acid form alkenes with the elimination of
one water molecule. Since a water molecule is eliminated from the alcohol molecule in the
presence of an acid, this reaction is known as acidic dehydration of alcohols. This
reaction is also the example of β-elimination reaction since –OH group takes out one
hydrogen atom from the β-carbon atom.
Example:
1. When ethanol is heated with concentrated sulphuric acid, dehydration takes place to
form ethene.
H H
Conc. H2SO4
H C C OH H2C CH2 + H2O

H H ethene
ethanol
1. Addition of dihydrogen:
159
Alkenes add up one molecule of dihydrogen gas in the presence of finely divided nickel,
palladium or platinum to form alkanes. (method of preparation of alkanes from
unsaturated hydrocarbons)
Example:
Ethene reacts with dihydrogen in the presence of platinum or palladium or nickel as
Pt / Pd / Ni
H2C CH2 + H2 H3C CH3
ethene ethane
2. Addition of halogens:
Halogens like bromine or chlorine add up to alkene to form vicinal dihalides. However,
iodine does not show addition reaction under normal conditions. The reddish orange
colour of bromine solution in carbon tetrachloride is discharged when bromine adds up to
an unsaturation site. This reaction is used as a test for unsaturation.
Example:
When bromine is added to ethene in the presence of carbon tetrachloride as solvent, 1,2-
dibromoethane is formed.
Br Br
CCl4
H2C CH2 + Br - Br HC CH
ethene 1,2 - dibromoethane
3. Addition of hydrogen halides:
Hydrogen halides (HCl, HBr,HI) add up toalkenes to form alkyl halides. The order of
reactivity of the hydrogen halides isHI > HBr > HCl.
Example:
1. Addition reaction of HBr to symmetrical alkenes:
Addition reactions of HBr to symmetrical alkenes (similar groups attached to double
bond) take place by electrophilic addition mechanism.
Example:
Ethene reacts with HBr to form Bromoethane.
CH 2 =CH 2 + HBr 
 CH 3 -CH 2 -Br
ethene bromoethane
2. Addition reaction of HBr to unsymmetrical alkenes (Markovnikov Rule):

Markovnikov rule: The rule states that negative part of the addendum (adding molecule)
gets attached to that carbon atom which possesses lesser number of hydrogen atoms.
Example:
When HBr is added to 1-propene, 2-bromopropane is formed as a majour product.
160
Br
H3C CH CH3 Majour product
2 -bromopropane
H3C CH CH2 + H-Br
1 -propene
H3C CH2 CH2 Br Minor product
1 -bromopropane
Mechanism:
Step1: HBr dissociates to form H+ and Br -.
HBr 
 H + + Br -
Step 2: H+attacks the double bond of 1-propene to form carbocation as shown below:
H
+
H3C C CH3
20 carbocation
H3C CH CH2 + H+
1 -propene H
+
H3C CH2 C
H
10 carbocation
The secondary carbocation is more stable than the primary carbocation.

Step 3: The 20 carbocation is attacked by Br– ion to form 2-bromopropane.
H Br
+ -
H3C C CH3 + Br H3C CH CH3
20 carbocation 2 -bromopropane
3. Anti Markovnikov addition or peroxide effect or Kharash effect:

In the presence of peroxide like benzoyl peroxide, addition of HBr to unsymmetrical
alkenes like propene takes place contrary to the Markovnikov rule to give 1-
bromopropane. This happens only with HBr but not with HCl and Hl.
Br
(C6H5CO)2O2
H2C CH CH3 + HBr H2C CH2 CH3
1-propene 1-bromopropane
4. Addition of water:
In the presence of a few drops of concentrated sulphuric acid alkenes react with water to
form alcohols, in accordance with the Markovnikov rule.
Example:
1.Addition of water to ethene in the presence of few drops of concentrated sulphuric acid
gives ethanol.
e
2.Addition of water to propene in the presence of few drops of concentrated sulphuric acid
gives 2-propanol.
161
OH
H+
H2C CH CH3 + H2O H3C CH CH3
1-propene 2-propanol
5. Baeyer’s oxidation:
Alkenes on reaction with cold, dilute, aqueous solution of potassium permanganate
(Baeyer’s reagent) produce vicinal glycols. Decolourisation of KMnO4solution is used as a
test for unsaturation.
Example:
Ethene on reaction with cold,dilute, aqueous solution of potassium permanganate
produces ethane-1, 2 – diol (ethylene glycol or glycol)
HO OH
Aq. KMnO4
H2C CH2 + H2O + (O) 273 K CH2 CH2
ethene ethane-1,2-diol
(Glycol)
6. Ozonolysis:
Ozonolysis of alkenes involves the addition of ozone molecule to alkene to form ozonide,
and then cleavage of the ozonide by Zn-H2O to smaller molecules.
This reaction is highly useful in detecting the position of the double bond in alkenes or
other unsaturated compounds.
R O R
Zn, H2O
R CH CH R + O3 C C 2 RCHO
Alkene H O O H
Ozonide
Example:
1.Ethene on reaction with ozone followed by addition Zn-H 2O gives formaldehyde.
H O H
Zn, H2O
H2C CH2 + O3 C C 2 HCHO
Ethene Methanal
H O O H (formaldehyde)
Ozonide
2.Propene on reaction with ozone followed by addition Zn-H2O gives methanal
(formaldehyde) and Ethanal (acetaldehyde).
H O CH3
Zn, H2O
H2C CH CH3 + O3 C C HCHO + CH3CHO
Propene Methanal Ethanal
H O O H
Ozonide (formaldehyde) (Acetaldehyde)
7. Polymerisation:
Polythene is obtained by the combination of large number of ethene molecules at high
temperature, high pressure and in the presence of a catalyst. The large molecules thus
obtained are called polymers. This reaction is known as polymerisation. The simple
compounds from which polymers are made are called monomers.
162
Example:
When ethene molecules are heated to high temperature in the presence of suitable
catalyst at high pressure, polythene is formed.
high temp. / pressure
n ( H2C CH2 ) ( CH2 CH2 ) n
Catalyst
ethene Polythene
Uses:
1.Polymers are used for the manufacture of plastic bags, squeeze bottles, refrigerator
dishes, toys, pipes, radio and T.V. cabinets etc.
2.Polypropene is used for the manufacture of milk crates, plastic buckets and other
moulded articles.
ALKYNES:
Alkynes are also unsaturated hydrocarbons. They contain at least one triple bond
between two carbon atoms. The number of hydrogen atoms is still less in alkynes as
compared to alkenes or alkanes. Their general formula is CnH2n–2.
The first stable member of alkyne series is ethyne which is popularly known as acetylene.
Nomenclature:
In common system, alkynes are named as derivatives of acetylene. In IUPAC system, they
are named as derivatives of the corresponding alkanes replacing ‘ane’ by the suffix ‘yne’.
The position of the triple bond is indicated by the first triply bonded carbon.
Example:
HC ≡ CH Ethyne Acetylene
HC ≡ C – CH3 Propyne Methylacetylene
HC ≡ C – CH2 – CH3 1-butyne or but-1-yne Ethylacetylene
H3C – C ≡ C – CH3 2-butyne or but-2-yne Dimethylacetylene
HC ≡ C – CH2 – CH2-CH3 1-pentyne or pent-1-yne propylacetylene
H3C – C ≡ C – CH2 -CH3 2-pentyne or pent-2-yne Ethylmethylacetylene
Isomerism:
Alkyne exhibits structural isomerism namely position isomerism and chain isomerism a
type of.
Example:
1.butyne shows position isomerism:

The two isomers are
(i) but-1-yne → HC ≡ C – CH2 – CH3and
(ii) but-2-yne → H3C – C ≡ C – CH3
Since these two compounds differ in their structures due to the position of the triple
bond, they are known as position isomers.
2.pentyne shows position and chain isomerism.
163
The structural isomers of pentyne are
(i) pent-1-yne → HC ≡ C – CH2 – CH2-CH3
(ii) pent-2-yne → H3C – C ≡ C – CH2 -CH3
(iii) 3-methylbut-1-yne → H3C CH C CH
CH3
Compound (i) and (ii) are position isomers.
Compound (i) and (ii), compound (ii) and (iii) are chain isomers.
Structure of Triple Bond:
Ethyne is the simplest molecule of alkyne series. Ethyne consist of
1.Two carbon atom of ethyne are sp hybridises.
2.Totally 3 sigma bonds are present in ethyne, i.e.,
(a) One Carbon-carbon sigma (σ) bond is obtained by the head-on overlapping of
the two sp hybridised orbitals of the two carbon atoms.
(b)The remaining one sp hybridised orbital of each carbon atom undergoes
overlapping along the inter nuclear axis with the 1s orbital of each of the two
hydrogen atoms forming two C-H sigma bonds.
3.H-C-C bond angle is of 180°and C≡C bond length is shorter 120 pm.
4.Each carbon has two unhybridised p orbitals which are perpendicular to each other as
well as to the plane of the C-C sigma bond. The 2p orbitals of one carbon atom are
parallel to the 2porbitals of the other carbon atom, which undergo lateral or sideways
overlapping to form two pi (π) bonds between two carbon atoms.
5.The strength of C≡C bond (bond enthalpy 823 kJ mol-1) is more than those of C=C bond
(bond enthalpy 681 kJ mol–1) and C–C bond (bond enthalpy 348 kJ mol–1).
6.Electron cloud between two carbon atoms is cylindrically symmetrical about the inter
nuclear axis. Thus, ethyne is a linear molecule.


1s sp sp sp sp 1s H C C H
  


Formation of sigma and pi - bonds in Ethyne
Preparation:
1. From calcium carbide:
164
Ethyne is prepared by treating calciumcarbide with water.
CaC 2 + 2H 2O 
 Ca(OH) 2 + C 2 H 2
Calcium carbide ethyne
Note: Calcium carbide is prepared by heating quick lime with coke.


CaO + 3C   CaC 2 + CO
Quick lime Calcium carbide
Quick lime can be obtained by heating limestone as shown in the following reactions:

CaCO3   CaO + CO2
Lime stone Quick lime
2. From vicinal dihalides:

Vicinal dihalides on treatment with alcoholic potassium hydroxide undergo
dehydrohalogenation. One molecule of hydrogen halide is eliminated to form alkenyl
halide which on treatment with sodamide gives alkyne.
Example:
When 1,2-bibromoethane is heated with alcoholic KOH, 1-bromoethene is formed, which
upon on treatment with sodamide gives ethyne.
H H H
NaNH2
H2C C H + KOH (alc.) - KBr, - H2O C C -NaBr, -NH3
HC CH
Br Br H Br Ethyne
1,2-dibromoethane 1-bromoethene
1. Acidic character of ethyne:
Sodium metal (Na) is a strong base reacts with ethyne to form monosodium ethynide
(sodium acetylide) with the liberation of dihydrogen gas, which further reacts with sodium
metal to form disodium ethynide with the liberation of dihydrogen.
1
Na + H-C  C-H  Δ
 H-C  C- Na  + H 2 
ethyne Monosodium ethynide 2
1
Na + H-C  C- Na   Δ
 Na + - C  C- Na  + H 2 
Monosodium ethynide Disodium ethynide 2
2. Addition reactions:
Alkynes contain atriple bond, so they add up, two molecules of dihydrogen, halogen,
hydrogen halides etc. Addition reaction takes place according to Markovnikov’s rule.
(i) Addition of dihydrogen:
Alkynes consume two moles of H2 to form alkanes in the presence of Pt / Pd / Ni as
catalyst.
Example:
Ethyne consumes two moles of dihydrogen in the presence of Pt / Pd / Ni as catalyst to
form ethane.
165
Pt / Pd / Ni Pt / Pd / Ni
HC CH + H2 H2C CH2 + H2 H3C CH3
Ethyne Ethene Ethane
(ii) Addition of halogens:
Two moles of halogens in CCl4adds to alkynes form tetrahaloalkanes alkanes.
Example:
Two moles of Br2in CCl4adds to ethyne to form 1,1,2,2-tetrabromoethane.
Br Br Br Br
CCl4 CCl4
HC CH + Br2 HC CH + Br2 Br CH CH Br
Ethyne 1,2-dibromoethene 1,1,2,2-tetrabromoethane
(iii) Addition of hydrogen halides:

Two molecules of hydrogen halides (HCl, HBr, HI) add to alkynes to form gem dihalides (in
which two halogens are attached to the same carbon atom)
Example:
Two moles of HBr adds to ethyne to form 1,1-dibromoethane.
Br
HC CH + HBr H2C CH Br + HBr H3C CH Br
Ethyne 1-bromoethene 1,1-dibromoethane
(iv) Addition of water:

One molecule of water adds to alkynes on warming with mercuric sulphate and
dilutesulphuric acid at 333 K to form carbonyl compounds.
Example:
One molecule of water adds to ethyne on warming with mercuric sulphate and
dilutesulphuric acid at 333 K to form ethanal.
H O
Hg2+ / H+ Isomerisation
HC CH + H2O 333 K
H2C C O H H3C C H
Ethyne Ethenol Ethanal
(v) Polymerisation
(a) Linear polymerisation: Under suitable conditions, linear polymerisation of ethyne
takes place to produce polyacetylene or polyethyne which is a high molecular weight
polyene containing repeating units of(CH = CH – CH = CH )
CH  CH  ( CH  CH ) n
acetylene polyacetylene
(b) Cyclic polymerisation:
Ethyne on passingthrough red hot iron tube at 873K undergoes cyclic polymerization.
Three molecules polymerise to form benzene.
CH
HC CH Redhot iron tube
873 K
or
HC CH
CH
166
AROMATIC HYDROCARBON:
These hydrocarbons are also known as ‘arenes’. Since most of them possess pleasant
odour (Greek; aroma meaning pleasant smelling), the class of compounds was named as
‘aromatic compounds’. Most of such compounds were found to contain benzene ring.
Aromatic compounds containing benzene ring are known as benzenoids and those not
containing a benzene ring are known as non-benzenoids.
Examples: Benzene, Toluene, Naphthalene, and Biphenyl etc.
Nomenclature and Isomerism:

1.For IUPAC nomenclature of substituted benzene compounds, the substituent is placed
as prefix to the word benzene.
2.When two hydrogen atoms in benzene are replaced by two similar or different
monovalent atoms or groups, three different position isomers are possible. They are
named as substituted benzene.
3.The positions of the substituent in indicated by numbers.
4.Common names of substituted benzenes with positions 1, 2 or 1, 6 is known as the
ortho(o–), the 1, 3 or 1, 5 as meta (m–) and the 1, 4 as para (p–) disubstituted compounds.
Example:
1. Methylbenzene (Toluene) 3. 1,3-dimethylbenzene (m – xylene)
CH3 CH3
CH3
2.1,2-dimethylbenzene (o – xylene) 4.1,4-dimethylbenzene (p – xylene)
CH3
CH3
CH3
CH3
Structure of benzene:
Benzene was isolated by Michael Faraday in1825. The molecular formula of benzene,
C6H6, indicates a high degree of unsaturation.
Kekule structures:
1.Benzene was found to be a stable molecule and found to form a triozonide which
indicates the presence of three double bonds.
167
2.Benzene was further found to produce one and only one mono substituted derivative
which indicated that all the six carbon and six hydrogen atoms of benzene are identical.
3.On the basis of this observation August Kekule in 1865 proposed the following
structure for benzene having cyclic arrangement of six carbon atoms with alternate single
and double bonds and one hydrogen atom attached to each carbon atom.
H
H C H
C C
or
C C
H C H
H
4.The Kekule structure indicates the possibility of two isomeric 1, 2-dibromobenzenes. In
one of the isomers, the bromine atoms are attached to the doubly bonded carbon atoms
whereas in the other, they are attached to the singly bonded carbons.
Br Br
Br Br
5.However, benzene was found to form only one ortho disubstituted product. This
problem was overcome by Kekule by suggesting the concept of oscillating nature of double
bonds in benzene as given below.
Resonance and stability of benzene:

1. According to Valence Bond Theory, the concept of oscillating double bonds in benzene is
now explained by resonance.
2. Benzene is a hybrid of various resonating structures. The two structures, A and B given
by Kekule are the main contributing structures. The hybrid structure is represented by
inserting a circle or a dotted circle in the hexagon as shown in (C). The circle represents
the six electrons which are delocalised between the six carbon atoms of the benzene ring.
A B C
3. The six π electrons are thus delocalised and can move freely about the six carbon nuclei,
instead of any two as shown in the above structure. The delocalised π 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 π electrons in
benzene makes it more stable.
168
Aromaticity:
Benzene was considered as parent ‘aromatic’ compound. Now, the name is applied to all
the ring systems whether or not having benzene ring, possessing following characteristics.
(i)Planarity
(ii)Complete delocalisation of the π electrons in the ring
(iii)Presence of (4n + 2) π electrons in the ring
Wheren is an integer (n = 0, 1, 2 . . .).
This is often referred to as Huckel Rule.
Example:
1.Aromatic compounds with n = 1 and 6π-electrons.
..
-
Benzene Cyclopentadienyl
anion
2.Aromatic compound with n = 2 and 10π electrons.
Napthalene
Arenes are characterised by electrophilic substitution reactions. However, under special
conditions they can also undergo addition and oxidation reactions.
Addition reactions:
1. Addition of dihydrogen:
Under vigorous conditions, i.e., at high temperature and/ or pressure in the presence of
nickel catalyst, hydrogenation of benzene gives cyclohexane.
+ 3 H2 Ni

Benzene Cyclohexane
2. Addition of chlorine molecule:

Under ultra-violet light, three chlorine molecules add to benzene to produce benzene
hexachloride, C6H6Cl6 which is also called gammaxane.
Cl
Cl Cl
+ 3Cl2 UV
500 K
Cl Cl
Benzene
Cl
Benzene hexachloride
(BHC)
Electrophilic substitution reactions:

Important Electrophilic substitution reactions of benzene:
1. Halogenation (chlorination) 2. Friedel Craft’s Reaction (alkylation reaction)
169
3. Nitration 4. Sulphonation
1. Halogenation (chlorination) reaction:
Benzene reacts with chlorine in the presence of halogen carrier like ferric chloride (FeCl 3)
or Anhy. AlCl3 to form chlorobenzene.
Cl
Anhy.AlCl3
+ Cl2 + HCl
chlorobenzene
If excess of Cl2 is used in the presence of Anhy. AlCl3hexachlorobenzene will be formed.

Cl
Cl Cl
Anhy.AlCl3
+ 6 Cl2 + 6 HCl
Cl Cl
Cl
hexachlorobenzene
Mechanism of monochlorination of benzene:

1. Formation of electrophile Cl+: Chlorine reacts with Anhy. AlCl3 to form the electrophile,
Cl+.
Cl Cl + AlCl3 Cl+ + [AlCl4]-

Cloronium ion
2. Attack of electrophile on benzene: The electrophile, Cl+ attacks the benzene ring to
form carbocation and it is resonance stabilized.
H H H
Cl H Cl H Cl Cl
+ +
C H H C
+ Cl+ +
+
C
H
3. Elimination of a proton: The resonance hybrid loses a proton to AlCl4- to form

Chlorobenzene.
Cl
H Cl
+
H C
+ [AlCl4]- + HCl + AlCl3
Friedel-Craft`s alkylation reaction:

Benzene reacts with alkyl halides in the presence of anhydrous aluminium chloride
catalyst to form Alkyl benzene.
R
Anhy.AlCl3
+ R-Cl + HCl
Alkylbenzene
Example: Benzene reacts with methyl chloride in the presence of anhydrous AlCl 3 catalyst
to form toluene.
170
CH3
+ CH3-Cl Anhy.AlCl3 + HCl
Toluene
Mechanism:
1. Formation of electrophile: Methyl chloride reacts with anhydrous aluminium chloride to
form the electrophile, CH3+.
H3C Cl + AlCl3 CH3+ + [AlCl4]-
2. Attack of electrophile on benzene: The electrophile, CH3+ attacks the benzene ring to
H H H
CH3 H CH3 H CH3 CH3
+ +
C H H C
+ CH3+ +
+
C
H
3. Elimination of a proton: The carbocation loses a proton to AlCl4-form toluene.
CH3
H CH3
+
H C
3. Friedel-Craft`s acylation reaction: Benzene reacts with acyl halides in the presence of
anhydrous aluminium chloride catalyst to form Acyl benzene.
O
R C
O
Anhy.AlCl3
+ R C Cl + HCl
Acylbenzene
Example:
1. Benzene reacts with acetyl chloride in the presence of anhydrous AlCl3 catalyst to form
acetophenone.
O
H3C C
O
Anhy.AlCl3
+ H3C C Cl + HCl

Accetophenone
2. Benzene reacts with acetic anhydride in the presence of anhydrous AlCl3 catalyst to
form acetophenone and acetic acid.
O
H3C C
Anhy.AlCl3
+ (CH3CO)2O + CH3COOH

Accetophenone
Mechanism for conversion of benzene to acetophenone on reaction with acetyl chloride:

1. Formation of electrophile: Methyl chloride reacts with anhydrous aluminium chloride to
form the electrophile, CH3CO+.
171
O O
H3C C Cl + AlCl3 H3C C
+
+ [AlCl4]-
2. Attack of electrophile on benzene: The electrophile, CH3CO+ attacks the benzene ring to
O O O O
H H H
C CH3 H C CH3 H C CH3 C CH3
O + +
C H H C
+ C+ CH +
3
C+
H
3. Elimination of a proton: The carbocation loses a proton to AlCl4-form acetophenone.

O O
H C CH3 H3C C
+
H C
4. Nitration of benzene: Benzene reacts with a mixture of conc. HNO3 and conc. H2SO4
(nitrating mixture) at 323 -333 K to form nitrobenzene.
NO2
Conc. H2SO4
+ HNO3 (conc.) + H2O
323 - 333 K
nitrobenzene
Mechanism:
1. Formation of electrophile: Conc. HNO3 reacts with conc. H2SO4 to form the electrophile
NO2+ (nitronium ion).
HNO3 + H2SO4 NO2+ + HSO4- + H2 O
2. Attack of electrophile on benzene: The electrophile NO2+ attacks the benzene ring to
H H H
NO2 H NO2 H NO2 NO2
+ +
C H H C
+ +
NO2 +
+
C
H
3. Elimination of a proton: The carbocation loses a proton to yield nitrobenzene.

H NO2 NO2
+
H C
+ HSO4- + H2SO4
4. Sulphonation of benzene: Benzene on heating with fuming sulphuric acid (oleum –

H2S2O7) to form benzene sulphonic acid.
172
SO 3H
+ H2SO4(SO3) + H2 O

Fuming
sulphuric acid Benzene
Sulphonic acid
Directive influence of a functional group in mono substituted benzene:

1. When mono substituted benzene is subjected to further substitution, three possible
disubstituted products are not formed in equal amounts.
2. Two types of behaviour are observed. Either ortho and para products or meta product is
predominantly formed.
3. The product obtained depends on the nature of the substituent already present in the
benzene ring and not on the nature of the entering group. This is known as directive
influence of substituents.
Ortho and para directing groups:
1. The groups which direct the incoming group to ortho and para positions are called ortho
and para directing groups.
Examples: –OH, –NH2, –NHR, –NHCOCH3, –OCH3, –CH3, –C2H5, etc.
(electron releasing substituents)
2. The electron density is more on o – and p – positions. Hence, the substitution takes place
mainly at these positions.
3. Ortho-para directing groups activates the benzene ring for the attack by an electrophile
and hence they are called as ring activators.
4. In the case of aryl halides, halogens are moderately deactivating. Because of their strong
– I effect, overall electron density on benzene ring decreases. It makes further substitution
difficult. However, due to resonance the electron density on o– and p– positions is greater
than that at the m-position. Hence, they are also o– and p– directing groups.
-OH group as example for ortho and para directing group:
Phenol is resonance hybrid of following structures:
.. .. + .. + .. + ..
:OH O H O H O H OH
..
:- -:
..-
1. It is clear from the above resonating structures that the electron density is more ono –
and p – positions.
2. Hence, the substitution takes place mainly at these positions. However, it may be noted
that –I effect of – OH group also operates due to which the electron density on ortho and
para positions of the benzene ring is slightly reduced. But the overall electrondensity
increases at these positions of the ring due to resonance.
3. Therefore, –OH group activates the benzene ring for the attack by an electrophile.
Meta directing group:
173
1. The groups which direct the incoming group to meta position are called meta directing
groups. Examples:–NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H, etc.(electron
withdrawing substituents).
2. The electron density on benzene ring decreases making further substitution difficult,
therefore these groups are also called ‘deactivating groups’.
3. The electron density on o– and p– position is comparatively less than that at meta
position. Hence, the electrophile attacks on comparatively electron rich meta position
resulting in meta substitution.
–NO2 group as example for meta directing group:
Nitrobenzene is a resonance hybrid of the following structures.
.. - .. - .. - ..
O O O O O O O O
.. : .. : .. : O
.. : O
..
N N N N N
+ +
1. Nitro group reduces the electron density in the benzene ring due to its strong–I effect.
2. The electron density on benzene ring decreases.
3. In the resonance structures, ortho and para positions are having + charges but no charge
on meta positions in any of the resonance structures.
4. Electron density is relatively more on the meta position than at ortho and para positions.
Hence electrophilic substitution tales place at meta position.
CARCINOGENICITY AND TOXICITY:

1. Benzene and polynuclear hydrocarbons containing more than two benzene rings fused
together are toxic and said to possess cancer producing (carcinogenic) property.
2. Such polynuclear hydrocarbons are formed on incomplete combustion of organic
materials like tobacco, coal and petroleum.
3. They enter into human body and undergo various biochemical reactions and finally
damage DNA and cause cancer.
4. Some of the carcinogenic hydrocarbons are:
CH3
CH3
1,2-Benzanthracene 9,10-dimethyl 1,2-Benzanthracene 1,2-Benzpyrene
174
14 Environmental Chemistry
It is the branch of science which deals with the chemical changes in the environment. It
includes our surroundings as air, water, soil, forest etc.
• Environmental Pollution: It is the effect of undesirable changes in our surroundings that
have harmful effects on plants, animals and human beings.
• Pollutants: A substance, which causes pollution, is known as pollutant. Pollutants can be
solid, liquid or gaseous substances. Present in higher concentration, it can be produced due to
human activities or natural happenings.
175
• Troposphere: The lowest region of atmosphere, in which the human beings along with other
organisms live, is called troposphere. It extends to the height of about 10 km from the sea level.
It contains air, water vapours, clouds etc. The pollution in this region is caused by some
poisonous gases, smoke fumes, smog etc.
• Stratosphere: It extends from height of 10 to 50 km above the sea level. Ozone and some other
gaseous substances present in this region are responsible for the pollution.
• Tropospheric Pollution: Pollution in this region is caused by the presence of undesirable
gaseous particles like oxides of sulphur, nitrogen and carbon, hydrocarbons along with solid
particles like dust, mist, fumes, smoke etc.
• Oxides of Sulphur
These are produced when coal containing sulphur is burnt.
It is also produced during volcanic eruptions.

Harmful effects:
(i) It is poisonous to both animals and plants.
(ii) A very high concentration of S02 may cause respiratory diseases e.g., asthma, bronchitis,
emphysema in human beings.
(iii) It causes irritation to the eyes, resulting in tears and redness.
(iv) Its high concentration leads to the stiffness of flower buds.
(v) Particulate matter present in the air can catalyse the formation of sulphur trioxide from
sulphur dioxide.
• Oxides of Nitrogen
Main oxides of nitrogen are nitric oxide (NO) and nitrogen dioxide (NO2).
Major Sources:
(i) Lightning discharge results in the combination of N2 and 02 to form NO.
(ii) Combustion of gasoline in automobilies, burning of hydrocarbons and coal etc.
Harmful effects:
Nitric oxide itself is not harmful to human beings, but it is very unstable and changes to nitrogen
dioxide which is toxic in nature. These effects are as follows:
(i) It reacts with Ozone (03) present in the atmosphere and thus decrease the density of Ozone.
(ii) It affects the respiratory system and damages the lungs.
176
(iii) Higher concentrations of N02 damage the leaves of plants and retard the rate of
photosynthesis.
(iv) It causes cracks in rubber.
(v) Nitrogen dioxide is also harmful to various textile fibres and metals.
• Hydrocarbons
Incomplete combustion of fossil fuel in industry and thermal power plants and the exhaust of
automobiles release hydrocarbons into the atmosphere constantly causing pollution.
Harmful Effects:
(i) They cause cancer.
(ii) Methane is one of the greenhouse gases.
(iii) They harm plants in various ways like breakdown of tissues, shedding of leaves etc.
• Oxides of Carbon
Carbon dioxide: 0.03% C02 is present in air by Volume.
Major Sources:
(i) By burning of fossil fuels.
(ii) By the decomposition of limestone during the manufacture of cement.
(iii) Emitted during volcanic eruptions.
(iv) C02 is released into the atmosphere by respiration.
Harmful effects:
Deforestation and burning of fossil fuel increases the C02 level which is mainly responsible for
global warming.
Carbon Monoxide: Carbon Monoxide is a colourless and odourless gas.
Major Sources:
(i) Released by the automobile exhaust.
(ii) Incomplete combustion of coal, fire wood, petrol etc.
(iii) By the dissociation of C02 at high temperature.
Harmful effects:
(i) It binds to haemoglobin to form carboxyhaemoglobin which is more stable than oxygen-
haemoglobin complex. Its concentration in blood when reaches to 3-4%, the oxygen carrying
capacity of blood is greatly reduced.
The oxygen deficiency, results into headache, weak eyesight, nervousness etc.
(ii) It has harmful effects on plants when its concentration is (100 ppm or more).
• Global Warming and Greenhouse Effect
Greenhouse Effect:
Some gases like carbon dioxide, methane, ozone, water vapours, CFCs have the capacity to trap
some of the heat radiations that are released from the earth or from sun. These gases are known
as greenhouse gases and the effect is called greenhouse effect. This leads to global warming.
177
Consequences of global warming:
(i) It leads to melting of polar ice caps and flooding of low lying areas all over the earth.
(ii) Global rise in temperature increases the incidence of infectious diseases like dengue, malaria,
yellow fever, sleeping sickness etc.
• Acid Rain
When the pH of the rain water drops below 5.6, it is known as acid rain.
Normal rain is slightly acidic due to dissolution of atmospheric carbon dioxide in water.
Oxides of nitrogen and sulphur released as a result of combustion of fossil fuels dissolve in water
to form nitric acid and sulphuric acid.
Harmful Effects of Acid Rain:

(i) It has harmful effects on trees and plants as it dissolves and washes away nutrients needed
for their growth.
(ii) It has very bad effect on aquatic ecosystem.
(iii) Acid rain damages buildings and other structures made of stone or metal. Taj Mahal in India
has been affected by acid rain.
• Particulate Pollutants
Viable Particulates: They are minute living organisms that are dispersed in the atmosphere.
e.g., bacteria, fungi) moulds, algae etc.
Non Viable Particulates:
(i) Smoke: It is the mixture of solid and liquid particles formed during combustion of organic
matter,
Example: Cigarette smoke, smoke from burning of fossil fuel.
(ii) Dust: Composed of fine solid particles (over 2gm in diameter).
It is produced during crushing, grinding and attribution of solid particles.
(iii) Mist: These are produced due to the spray of liquids like herbicides and pesticides over the
plants. They travel through air and form mist.
(iv) Fumes: They are generally released to the atmosphere by the metallurgical operations and
also by several chemical reactions.
Harmful Effects of Particulate Pollutants:
(i) Fine particles less than 5 microns penetrate into the lungs. Inhalation of such particles can
lead to serious lung diseases including lung cancer.
178
(ii) Suspended particles of bigger size can hinder the sun rays from reaching the earth
surface. This can lower the temperature of earth and make the weather foggy.
• Smog
This is the common form of air pollution which is combination of smoke and fog.
Smog exists in two types:
(i) Classical Smog: Occurs in cool humid climate. It contains smoke, fog and sulphur dioxide. It
is also called as reducing smog.
(ii) Photochemical Smog: This type of smog result from the action of sunlight on unsaturated
hydrocarbons and nitrogen oxides released by the vehicles and industries. It has high
concentration of oxidising agents and is therefore, called as oxidising smog.
Formation of Photochemical Smog
Harmful effects of photochemical smog:

(i) It can cause cough, bronchitis, irritation of respiratory system etc.
– To control this type of pollution the engines of the automobiles are fitted with catalytic
converters to check the release of both oxides of nitrogen and hydrocarbons in the atmosphere.
– Some plants like Vitis, Pinus, Juniparus, Quercus, Pyrus can metabolise nitrogen
oxide and therefore, their plantation can be done.
• Stratospheric Pollution
Formation of Ozone: Ozone in the stratosphere is produced by UV radiations. When UV –
radiations act on dioxygen (02) molecules, Ozone is produced.
Ozone is thermodynamically unstable and decomposes to molecular oxygen. Thus there exists an
equilibrium between production and decomposition of Ozone molecules.
Depletion of Ozone layer: Ozone blanket in the upper atmosphere prevent the harmful UV
radiations from reaching earth.
179
But in recent years, there have been reports of depletion of this layer due to presence of
,certain chemicals in the stratosphere. Chlorofluorocarbons (CFCs), nitrogen oxides, chloride,
CCl4 etc. are the chemicals responsible for depletion.
Chlorofluorocarbons dissociate in the presence of light gives chlorine free radicals which catalyse
the conversion of ozone into oxygen.
Effects of the depletion of Ozone layer:
(i) This leads to many diseases like skin cancer, sunburn, ageing of skin, cataract etc.
(ii) UV radiations can kill many phytoplanktons, damage the fish productivity.
(iii) It can decrease moisture content of the soil by increasing the evaporation of surface water.
(iv) UV radiations can damage paints and fibres, causing them to fade faster.
• Water Pollution
Presence of undesirable materials in water which is harmful for the human beings and plants is
known as water pollution. Normal properties of the water can be changed by the presence of
these foreign materials.
Causes of Water Pollution:

(i) Pathogens: Pathogens are the bacteria and the other organisms that enter water from
180
domestic sewage and animal excreta.
Human excreta contain bacteria such as Escherichia coli and Streptococcus faecalis. It causes
gastrointestinal diseases.
(ii) Organic Wastes: Organic matter such as leaves, grass, trash etc. can pollute water.
– Excessive growth of phytoplankton within water also pollute water.
– Large numbers of bacteria in water can consume oxygen dissolved in water by decomposing
organic matter present in water.
– If the concentration of dissolved oxygen in water is below 6 ppm, the growth of fish gets
inhibited.
– If too much of organic matter is added to water, all the available oxygen is used up. This can
cause the death of the aquatic life.
• BOD (Biochemical Oxygen Demand)
It is defined as the amount of oxygen required by bacteria for the breakdown of the organic
matter present in a certain volume of a sample of water.
The amount of BOD in water is a measure of the amount of organic material in the water. Clean
water has BOD value of less than 5 ppm.
Highly polluted water could have a BOD value of 17 ppm or more.
• Chemical Pollutants
(i) Industrial Wastes: Chemical reactions carried in the industrial units also pollute water to a
great extent. For example, lead, mercury, nickel, cobalt etc. These chemicals give very bad effect
to the groundwater and waterbodies are polluted due’ to the chemical reactions known as
leaching.
Organic chemicals like petroleum products also pollute many sources of water e.g., major oil
spills in oceans.
(ii) Pesticides: These are mostly chlorinated hydrocarbons, organophosphates and metallic salts
etc. They dissolve in water to small extent and pollute it. Since all the pesticides are toxic in
nature, they are injurious to both plants and animals.
(iii) Polychlorinated biphenyls (PCBS): These are the chemical compounds used as fluids in
transformers and capacitors. These are released in atmosphere as vapours. They mix with rain
water and thus contaminate the water.
(iv) Eutrophication: The process in which algae like organisms reduce dissolved oxygen in water
is called as eutrophication. It is harmful for aquatic life.
• International Standards for Drinking Water
Fluoride: Concentration of fluoride up to 1 ppm or 1 mg dm -3, is not harmful for human
beings if it is used as drinking water. The F~ ions make the enamel on teeth much harder by
converting hydroxyapatite [3Ca3(P04)2- Ca(OH)2] the enamel on the surface of the teeth, into much
harder fluorapatite, [3Ca3(P04)2- CaF2]. Concentration of F~ above 2 ppm causes brown mottling
of teeth. Excess of fluoride is harmful to bones also.
181
Lead: Upper limit concentration of lead in drinking water is about 50 ppm. Lead can damage
kidney, lever, reproductive system etc.
Sulphate: At moderate level it is harmless but excess is harmful.
Nitrate: The maximum limit of nitrate should be 50 ppm. Excess nitrate in drinking water can
cause diseases such as methemoglobinemia (blue baby syndrome).
Chemical Oxygen Demand (COD): Water is treated with K2Cr207 in acidic medium to oxidise
polluting substance which cannot be oxidised by microbial oxidation. The remaining is
determined by back titration with suitable reducing agent.
From the concentration of K2Cr207 consumed, the amount of O2 used in the oxidation is
calculated.
• Soil Pollution—Sources of Soil Pollution

Pesticides: It can be classified as:
(i) Insecticide: The most common insecticides are chlorinated hydrocarbons like DDT, BHC etc.
As they are not much soluble in water, they stay in the soil for long time. They are ‘ absorbed by
the soil and contaminate root crops like radish, carrot etc.
(ii) Herbicides: These are the compounds used to control weeds, namely, sodium chlorate
(NaCl03) and sodium arsenite (Na3As03) are commonly used herbicides but arsenic compounds,
being toxic are no longer preferred.
Fungicides: Organo-mercury compounds are the most common fungicides. Its dissociation in
soil produces mercury which is highly toxic and harmful for the crops. i Industrial Waste: It has
seen that most of the industrial wastes are thrown into water or dumped into the soil. These
industrial wastes contain huge amounts of toxic chemicals which are mostly non-bidegradable.
For example, metal processing industries, mining cement, glass industries, petroleum industry
etc., fertilizer industry produce gypsum.
The disposal of non-biodegradable industrial solid waste is not done by suitable methods i and
cause many serious problems.
Strategies to control environmental pollution:
(i) The improper disposal of wastes is one of the major causes of environmental I degradation.
The management of wastes is very important.
(ii) All domestic wastes should be properly collected and disposed.
• Green Chemistry
Green Chemistry is a way of thinking and is about utilising the knowledge and principles of
chemistry that would control the increasing environmental pollution.
Green chemistry in day-to-day life:
(i) Dry-Cleaning of clothes and laundary: Replacement of halogenated solvent like (CCl4) by liquid
C02 which is less harmful to groundwater.
Hydrogen peroxide (H202) is used for the purpose of bleaching clothes.
182
(ii) Bleaching of Paper: In place of chlorine H202 is used for the bleaching of paper,
(iii) Synthesis of Chemicals: Ethahal (CH3CHO) is prepared by step oxidation of ethene. Such as,
• Environmental pollution: It is the effect of undesirable changes in the surroundings that have
harmful effects on plants, animals, and human beings.
• Troposphere: The lowest region of atmosphere which extends up to the height of 10 km from
sea level in which man and other living organism exists.
• Stratosphere: It is above troposhere between 10 to 50 km above the sea level.
• Acid rain: It is caused by the presence of oxides of sulphur and nitrogen and C02 in the
atmosphere. The pH of the rain drops below 5.6, and it becomes acidic.
• Greenhouse gases: Some gases like carbon dioxide, methane, ozone, water vapours, CFCs
have the capacity to trap some of the heat radiations from the earth or from the sun. This leads
to global warming.
• Eutrophication: When phosphate ion increases in water it increases the growth of algae which
consume the dissolved oxygen in water consequently aquatic life is adversely affected. This
results in loss of biodiversity and the phenomenon is known as Eutrophication.
• COD (Chemical Oxygen Demand): It is calculated as the amount of oxygen required to oxidise
the polluting substances. It is measured by treating the given sample of water with an oxidising
agent, generally K2Cr207in the presence of dil. H2S04.

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1

Unit 2: Structure of Atom

Unit 3: Classification of Elements and Periodicity in Properties

Unit 4: Chemical Bonding and Molecular Structure

Unit 5: States of Matter

Unit 8: Redox Reactions

Unit 10: The s-Block Elements

Unit 11: The p-Block Elements

Unit 12: Organic Chemistry – Some Basic Principles and Techniques

Unit 13: Hydrocarbons

Unit 14: Environmental Chemistry

1 Basic concepts of Chemistry

Physical properties: It is the property which is measurable or observed without

Chemical properties: It is the property which measurable or observed with the

Length ― meter ― m Mass ― kilogram ― kg

Temperature ― kelvin ― K amount of substance ― mole ― mol

Luminous intensity ― candala ― cd current ― amper ― A

Mass: It is amount of matter present in substance. It is the constant quantity. It is

Weight: it is amount of matter present in substance along with force exerted on it by

Fahrenheit scale and degree Celsius scale: 0F = (9/5)0C + 32

Degree Celsius scale and kelvin scale: K = 0C + 273.15

Scientific notation: It is the exponential notation in which any number can be

Rules to determining the significant figures:

1. All non – zero digits are significant.

Precision: The closeness of various measurements for the same quantity.

Rules for rounding off the numbers:

LAWS OF CHEMICAL COMBINATIONS

Law of definite proportions or Law of definite composition: A given compound

Dalton’s atomic theory:

1. Matter consists of individual atoms

Mole: It is defined as the amount of substance that contains as many particles or

Molar mass: The mass of one mole of substance in gram.

1. Mass percent : (mass of solute x 100)  (mass of solution)

No. of mole of solute

4. Molality: The number of moles of solute present in one kilogram of solvent.

No. of mole of solute wb x 1000

 Atomic theory of matter was proposed by John Dalton in 1808.

Properties of cathode rays:

 Discovery of protons is done by Goldstein by modifying the cathode ray tub in

Properties Electron Proton Neutron

Discovery J.J. THOMSON GOLDSTEIN JAMES CHADWICK

Mass 9.101 X 10 – 31 kg 1.67262 X 10 – 27 kg 1.67495 X 10 – 27 kg

o Atomic number: number of protons present in the nucleus of an atom.

J. J. Thomson model of atom [plum pudding model]

He got Noble prize for theoretical explanation of structure of an atom in 1906.

Rutherford’s nuclear model of atom [ -

Rutherford and his students were led

In this experiment they bombarded a thin sheet of gold foil

o Most of the - particles went straight without suffering any deflection.

Demerits of Rutherford atomic model

An electron revolving around the nucleus gets accelerated towards the

 This effect is explained by H. Hertz in 1887.

 When electrically charged particle movies under acceleration, alternating

 Properties of electromagnetic radiations

 It is the emission type of spectrum.

Series n1 n2 Spectral Region

Bohr’s model of hydrogen atom