Contents

Some basic concepts of chemistry ............................................................................................. 1

Structure of atom ..................................................................................................................... 10

Classification of elements and periodicity in properties ......................................................... 36

Chemical bonding and molecular structure ............................................................................ 42

States of matter ....................................................................................................................... 58

Thermodynamics ..................................................................................................................... 78

Equilibrium ............................................................................................................................. 88

Redox reaction ...................................................................................................................... 107

Hydrogen ............................................................................................................................... 116

The s-block elements ............................................................................................................ 126

The p-block elements ............................................................................................................ 141

Organic chemistry: some basic principle and technique ....................................................... 152

Hydrocarbons ........................................................................................................................ 182

Environmental chemistry ...................................................................................................... 205

 Some Basic Concepts of Chemistry

Chemistry plays an important role in meeting human needs for food, health care products and
other materials aimed at improving the quality of life.

❖ DEVELOPMENT OF CHEMISTRY
● Chemistry was not studied for its own sake, rather it came up as a result of search for
two interesting things:
i. Philosopher’s stone (Paras) which would convert all baser metals e.g., iron and copper
into gold.
ii. ‘Elexir of life’ which would grant immortality.
● Chemistry developed mainly in the form of Alchemy and Iatrochemistry during 1300-
1600 CE. Modern chemistry took shape in the 18th century Europe, after a few
centuries of alchemical traditions which were introduced in Europe by the Arabs.
● Atharvaveda (1000 BCE) mentioned some dye stuff, the material used were turmeric,
madder, sunflower, orpiment, cochineal and lac. Some other substances having tinting
property were kamplcica, pattanga and jatuka.
● Recipes for hair dying were made from plants, like indigo and minerals like iron power,
black iron or steel and acidic extracts of sour rice gruel.
● Excavations at Taxila indicate that ink was used in India from the fourth century.
Colours of ink were made from chalk, red lead.
● Acharya Kanda, born in 600 BCE, originally known by the name Kashyap, was the first
proponent of the ‘atomic theory’.
● All substances are aggregated form of smaller units called atoms (Paramãnu), which
are eternal, indestructible, spherical, suprasensible and in motion in the original state.
He explained that this individual entity cannot be sensed through any human organ.
● Extreme reduction of particle size is termed as nanotechnology.
● Charaka Samhita describes the use of bhasma of metals in the treatment of ailments.

❖ IMPORTANCE OF CHEMISTRY
● Many lifesaving drugs such as cisplatin and taxol, are effective in cancer therapy and
AZT (Azidothymidine) used for helping AIDS victims, have been isolated from plant
and animal sources or prepared by synthetic methods.
● Safer alternatives to environmentally hazardous refrigerants like CFCs
(chlorofluorocarbons), responsible for ozone depletion in the stratosphere, have been
successfully synthesised.

❖ NATURE OF MATTER
Anything which has mass and occupies space is called matter.
❖ States of Matter
● Matter can exist in three physical states viz. solid, liquid and gas.
● Solids have definite volume and definite shape.

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 ● Liquids have definite volume but do not have definite shape. They take the shape
of the container in which they are placed.
● Gases have neither definite volume nor definite shape. They completely occupy the
space of the container in which they are placed.

❖ Classification of Matter:

● A mixture may be homogeneous or heterogeneous. In a homogeneous mixture, the

components completely mix with each other, and its composition is uniform
throughout. In heterogeneous mixtures, the composition is not uniform throughout and
sometimes the different components can be observed.
● Pure substances have fixed composition, whereas mixtures may contain the
components in any ratio. Constituents of pure substances cannot be separated by simple
physical methods
● Hydrogen and oxygen are gases, whereas the compound formed by their combination
i.e., water is a liquid. Hydrogen burns with a pop sound and oxygen is a supporter of
combustion, but water is used as a fire extinguisher.

⮚ PROPERTIES OF MATTER AND THEIR MEASUREMENT

❖ Physical and chemical properties
o Physical properties can be measured or observed without changing the identity or
the composition of the substance e.g., colour, odour, melting point, boiling point,
density, etc.
o The measurement or observation of chemical properties requires a chemical change
to occur like composition, combustibility, reactivity with acids and bases, etc.
❖ Measurement of physical properties
● Earlier, two different systems of measurement, English System and the Metric
System were being used.
● Each modern industrialised country, including India, has a National Metrology
Institute (NMI), which maintains standards of measurements. This responsibility
has been given to the National Physical Laboratory (NPL), New Delhi. This

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 laboratory establishes experiments to realise the base units and derived units of
measurement and maintains National Standards of Measurement.
❖ The International System of Units (SI)
● The International System of Units (in French Le Systeme International d’Unités —
abbreviated as SI) was established by the 11th General Conference on Weights and
Measures (CGPM from Conference Generale des Poids et Measures).
● The SI system has seven base units. These units pertain to the seven fundamental
scientific quantities.

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 ● The SI system allows the use of prefixes to indicate the multiples or submultiples
of a unit.

❖ Mass and Weight

o Mass of a substance is the amount of matter present in it, while weight is the force
exerted by gravity on an object.
o The mass of a substance is constant, whereas, its weight may vary from one place to
another due to change in gravity.
❖ Volume
o Volume is the amount of space occupied by a substance. It has the units of (length)3.
1 L = 1000 mL, 1000 cm3 = 1 dm3
o In the laboratory, the volume of liquids or solutions can be measured by graduated
cylinder, burette, pipette, etc.
o A volumetric flask is used to prepare a known volume of a solution.

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❖ Density
o Density of a substance is its amount of mass per unit volume. Its SI unit is kg m–3.
Mass
Density =
Volume
o Density of a substance tells us about how closely its particles are packed. If density is
more, it means particles are more closely packed.
❖ Temperature
o There are three common scales to measure temperature — °C (degree celsius), °F
(degree fahrenheit) and K (kelvin). Here, K is the SI unit.
F = ( C ) + 32
9
5
K = C + 273
o Temperature below 0 °C (i.e., negative values) are possible in Celsius scale but in
Kelvin scale, negative temperature is not possible.

❖ UNCERTAINTY IN MEASUREMENT
❖ Scientific Notation
o Problem of handling extremely large/small numbers is solved by using scientific
notation for such numbers, i.e., exponential notation in which any number can be
represented in the form N × 10n, where n is an exponent having positive or negative
values and N is a number (called digit term) which varies between 1.000... and 9.999....
o While performing mathematical operations on numbers expressed in scientific
notations, the following points are to be kept in mind:
o Multiplication and Division follow the same rules which are there for exponential
numbers.

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 o For Addition and Subtraction, first the numbers are written in such a way that they have
the same exponent. After that, the coefficients (digit terms) are added or subtracted as
the case may be.

❖ Significant Figures
o Significant figures are meaningful digits which are known with certainty.
o All non-zero digits are significant.
o Zeros preceding to first non-zero digit are not significant. Such zero indicates the
position of decimal point.
o Zeros between two non-zero digits are significant.
o Zeros at the end or right of a number are significant provided they are on the right side
of the decimal point.
o The terminal zeros are not significant if there is no decimal point
o In addition and subtraction of significant figures, the result cannot have more digits to
the right of the decimal point than either of the original numbers.
o In multiplication and division of significant figures, the result must be reported with no
more significant figures as are there in the measurement with the few significant
figures.
o Precision refers to the closeness of various measurements for the same quantity.
Accuracy is the agreement of a particular value to the true value of the result.

❖ LAWS OF CHEMICAL COMBINATIONS

● Law of Conservation of Mass: It states that matter can neither be created nor
destroyed. This law was given by Antoine Lavoisier in 1789.
● Law of Definite Proportions: This law was given by a French chemist, Joseph Proust.
He stated that a given compound always contains exactly the same proportion of
elements by weight. Proust worked with two samples of cupric carbonate — one of
which was of natural origin and the other was synthetic. He found that the composition
of elements present in it was same for both the samples.
● Law of Multiple Proportions: This law was proposed by Dalton in 1803. According
to this law, if two elements can combine to form more than one compound, the masses
of one element that combine with a fixed mass of the other element, are in the ratio of
small whole numbers.
● Gay Lussac’s Law of Gaseous Volumes: This law was given by Gay Lussac in 1808.
He observed that when gases combine or are produced in a chemical reaction, they do
so in a simple ratio by volume provided all gases are at same temperature and pressure.
Gay Lussac’s discovery of integer ratio in volume relationship is actually the law of
definite proportions by volume.
● Avogadro Law: Equal volumes of gases at the same temperature and pressure should
contain equal number of molecules. Avogadro made a distinction between atoms and
molecules.

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❖ DALTON’S ATOMIC THEORY
Idea that matter is composed of small indivisible particles called ‘atomio’ (meaning,
indivisible), dates back to the time of Democritus, a Greek Philosopher (460–370 BC). In
1808, Dalton published ‘A New System of Chemical Philosophy’, in which he proposed
the following:
● Matter consists of indivisible atoms.
● All the atoms of a given element have identical properties including identical mass.
● Atoms of different elements differ in mass.
● Compounds are formed when atoms of different elements combine in a fixed ratio.
● Chemical reactions involve reorganization of atoms. These are neither created nor
destroyed in a chemical reaction.
● Dalton’s theory could not explain the laws of gaseous volumes.
● It could not provide the reason for combining of atoms.

❖ ATOMIC AND MOLECULAR MASSES

❖ Atomic mass
● One atomic mass unit is defined as a mass exactly equal to one twelfth the mass of one
carbon - 12 atom.
● 1 amu = 1.66056×10–24 g
● Mass of an atom of hydrogen = 1.0078 amu
● The mass of oxygen – 16 = 15.995 amu.
● At present, ‘amu’ has been replaced by ‘u’, which is known as unified mass.

❖ Average Atomic mass

● Many naturally occurring elements exist as more than one isotope. When we take into
account the existence of these isotopes and their relative abundance (per cent
occurrence), the average atomic mass of that element can be computed.
● In the periodic table of elements, the atomic masses mentioned for different elements
represent their average atomic masses.

❖ Molecular mass
● Molecular mass is the sum of atomic masses of the elements present in a molecule.
● It is obtained by multiplying the atomic mass of each element by the number of its
atoms and adding them together.

❖ Formula Mass
● For substance which exist as ions - the formula, such as NaCl, is used to calculate the
formula mass instead of molecular mass as in the solid-state sodium chloride does not
exist as a single entity.

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❖ MOLE CONCEPT AND MOLAR MASSES
● One mole contains exactly 6.02214076 × 1023 elementary entities. This number is the
fixed numerical value of the Avogadro constant, NA, when expressed in the unit mol–1
and is called the Avogadro number.
● The mole of a substance always contains the same number of entities, no matter what
the substance may be.
● One mole is the amount of a substance that contains as many particles or entities as
there are atoms in exactly 12 g (or 0.012 kg) of the 12C isotope.
● The mass of a carbon–12 atom was determined by a mass spectrometer and found to be
equal to 1.992648 × 10–23 g.
● The mass of one mole of a substance in grams is called its molar mass. The molar mass
in grams is numerically equal to atomic/molecular/ formula mass in u.

❖ PERCENTAGE COMPOSITION
mass of the element in compound
 100
● Mass % of an element = molar mass of compound
● An empirical formula represents the simplest whole number ratio of various atoms
present in a compound whereas the molecular formula shows the exact number of
different types of atoms present in a molecule of a compound.

❖ STOICHIOMETRY AND STOICHIOMETRIC CALCULATIONS

● The word ‘stoichiometry’ is derived from two Greek words — stoicheion (meaning,
element) and metron (meaning, measure).
● All the reactants and the products which are gases in a reaction are indicated by letter
(g) in the brackets next to its formula. Similarly, in case of solids and liquids, (s) and
(l) are written respectively.
● A balanced equation is: CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
According to the above chemical reaction –
o One mole of CH4(g) reacts with two moles of O2(g) to give one mole of CO2(g) and
two moles of H2O(g)
o One molecule of CH4(g) reacts with 2 molecules of O2(g) to give one molecule of
CO2(g) and 2 molecules of H2O(g)
o 22.7 L of CH4(g) reacts with 45.4 L of O2(g) to give 22.7 L of CO2(g) and 45.4 L
of H2O(g)
o 16 g of CH4(g) reacts with 2×32 g of O2(g) to give 44 g of CO2(g) and 2×18 g of
H2O(g).

❖ Limiting Reagent
o The reactant, which gets consumed first, limits the amount of product formed and is,
therefore, called the limiting reagent.

❖ Reactions in Solutions

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o The concentration of a solution or the amount of substance present in its given volume
can be expressed as –
mass of solute
1. Mass per cent or weight per cent (w/w%) =  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 the solution.
No. of moles of A nA
Mole fraction of A= =
No. of moles of solution nA + nB
3. Molarity: It is defined as the number of moles of the solute in 1 litre of the solution.
It is denoted by M.
No. of moles of solute
Molarity ( M ) =
Volume of solution in litres
4. Molality: It is defined as the number of moles of solute present in 1 kg of solvent.
It is denoted by m.
No. of moles of solute
Molality ( m ) =
Mass of solvent in kg

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 Structure of Atom

⮚ Introduction:
● Atoms are the fundamental building blocks of matter.
● The word ‘atom’ has been derived from the Greek word ‘a-tomio’ which means
‘uncuttable’ or ‘non-divisible’.

⮚ Dalton’s atomic theory:

● In 1808 John Dalton proposed a theory, called Dalton’s atomic theory, which explains
the law of conservation of mass, law of constant composition and law of multiple
proportions.
● However, it failed to explain the results of many experiments like why substances like
glass or ebonite when rubbed with silk or fur generate electricity.
● In 1830, Michael Faraday's electrolysis experiment suggested the particulate nature of
electricity.

⮚ Discovery of Electron:
● Cathode ray discharge tube experiment:
(i) In the mid 1850s Faraday and other scientists began to study electrical discharge
in partially evacuated tubes, known as cathode ray discharge tubes.

A cathode ray discharge tube

(ii) A cathode ray tube is made of sealed glass containing electrodes.
(iii) The electrical discharge through the gases was observed at very low pressures and
at very high voltages, current started flowing through a stream of particles
moving in the tube from the negative electrode(cathode) to the positive electrode
(anode).
(iv) These were called cathode rays or cathode ray particles.
(v) The flow of current from cathode to anode was further checked by making a hole
in the anode and coating the tube behind anode with phosphorescent material zinc
sulphide.
(vi) When these rays, after passing through anode, strike the zinc sulphide coating, a
bright spot is developed on the coating.

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 A cathode ray discharge tube with perforated tube
❖ Results:
i. Cathode rays start from the cathode and move towards the anode.
ii. These rays themselves are not visible but their behaviour can be observed with the
help of certain kinds of materials which glow when hit by them.
(Television picture tubes are cathode ray tubes)
iii. In the absence of an electrical or magnetic field, these rays travel in straight lines.
iv. In the presence of an electrical or magnetic field, the behaviour of cathode rays are
similar to that expected from negatively charged particles, suggesting that the
cathode rays consist of negatively charged particles, called electrons.
v. The characteristics of cathode rays (electrons) do not depend upon the material of
electrodes and the nature of the gas present in the cathode ray tube.

❖ Conclusion:
Electrons are the basic constituent of all the atoms.

⮚ e/m ratio of electron:

i. In 1897, British physicist J.J. Thomson measured the ratio of electrical charge (e) to
the mass of electrons (m) by using a cathode ray tube and applying electrical and
magnetic fields perpendicular to each other as well as to the path of electrons.

The apparatus to determine the charge to the mass ratio of electron

ii. When only electric field is applied, the electrons deviate from their path and hit the
cathode ray tube at point A

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 iii. Similarly when only a magnetic field is applied, an electron strikes the cathode ray
tube at point C.
iv. By carefully balancing the electrical and magnetic field strength, it is possible to bring
back the electron to the path which is followed in the absence of electric or magnetic
field and they hit the screen at point B.
v. Deviation of the particles from their path in the presence of electrical or magnetic
field depends upon:
(a) The magnitude of the negative charge on the particle. (greater the magnitude of
the charge on the particle, greater is the interaction with the electric or magnetic
field and thus greater is the deflection).
(b) The mass of the particle (lighter the particle, greater the deflection).
(c) The strength of the electrical or magnetic field. (the deflection of electrons from
its original path increases with the increase in the voltage across the electrodes, or
the strength of the magnetic field).
vi. e/m = 1.758820 × 1011 C kg–1
where m is the mass of the electron in kg and
e is the magnitude of the charge on the electron in coulomb (C).
vii. Since electrons are negatively charged, the charge on electrons is –e.

⮚ Millikan’s oil drop experiment:

i. In 1914, R.A. Millikan devised a method known as oil drop experiment, to determine
the charge on the electrons.
ii. In this method, oil droplets in the form of mist, produced by the atomiser, were
allowed to enter through a tiny hole in the upper plate of the electrical condenser.
iii. The downward motion of these droplets was viewed through the telescope, equipped
with a micrometer eyepiece.
iv. By measuring the rate of fall of these droplets, Millikan was able to measure the mass
of oil droplets.
v. The air inside the chamber was ionized by passing a beam of X-rays through it.
vi. The electrical charge on these oil droplets was acquired by collisions with gaseous
ions.
vii. The fall of these charged oil droplets can be retarded, accelerated or made stationary
depending upon the charge on the droplets and the polarity and strength of the voltage
applied to the plate.
viii. By carefully measuring the effects of electrical field strength on the motion of oil
droplets.

❖ Conclusion:
i. The magnitude of electrical charge, q, on the droplets is always an integral
multiple of the electrical charge,e, that is, q = n e, where n = 1, 2, 3... .

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 The Millikan oil drop apparatus for measuring charge ‘e’. In chamber, the forces acting on oil drop are:
gravitational electrostatic due to electrical field and a viscous drag force when the oil drop is moving.
ii. The charge on the electron was found to be – 1.6 × 10–19 C.
iii. The mass of the electron was determined by combining these results with
Thomson’s value of e/m ratio.
Mass of electron = 9.1094×10–31 kg.

⮚ Discovery of proton:
● Electrical discharge carried out in the modified cathode ray tube led to the discovery of
canal rays carrying positively charged particles.
● The characteristics of these positively charged particles are listed below.
i. Mass of positively charged particles depends upon the nature of gas present in the
cathode ray tube.
ii. The charge to mass ratio of the particles depends on the gas from which these
originate.
iii. Some of the positively charged particles carry a multiple of the fundamental unit of
electrical charge.
iv. The behaviour of these particles in the magnetic or electrical field is opposite to
that observed for electrons.
● The smallest and lightest positive ion was obtained from hydrogen and was called
proton.

⮚ Discovery of neutron:
● Neutrons were discovered by Chadwick (1932) by bombarding a thin sheet of beryllium
by α-particles. Mass of a neutron is slightly greater than that of protons emitted.

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⮚ Thomson Model of Atom/Plum Pudding/Raisin Pudding or Watermelon Model of
an atom (proposed in 1898):
● He proposed that an atom possesses a spherical shape (radius approximately 10–10 m in
which the positive charge is uniformly distributed.
● The electrons are embedded into it in such a manner as to give the most stable
electrostatic arrangement

Thomson model of atom

● It explained the overall neutrality of the atom.

❖ Radioactivity:
● In 1895 Wilhalm Röentgen showed that when electrons strike a material in the
cathode ray tubes, they produce rays which can cause fluorescence in the
fluorescent materials placed outside the cathode ray tubes, he named the radiation
as X-rays.
● X-rays are not deflected by the electric and magnetic fields and have a very high
penetrating power and are of very short wavelength.
● Henri Becqueral observed that there are certain elements which emit radiation on
their own and named this phenomenon as radioactivity and the elements known as
radioactive elements.
● It was observed that three kinds of rays i.e., α, β- and γ-rays are emitted.
● Rutherford found that α-rays consist of two units of positive charge and four units
of atomic mass. (α- particles combine with two electrons to yield helium gas)
● Beta-rays are negatively charged particles similar to electrons.
● γ-rays are high energy radiations like X-rays, are neutral in nature and do not consist
of particles.
Order of penetrating power: α-particles < β-rays (100 times that of α–particles) < γ-
rays (1000 times of that α-particles).
❖ Rutherford’s famous α–particle scattering experiment:

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 Rutherford’s scattering experiment
● A stream of high energy α–particles from a radioactive source was directed at a thin
foil (thickness ∼ 100 nm) of gold metal.
● The thin gold foil had a circular fluorescent zinc sulphide screen around it.
● Whenever α–particles struck the screen, a tiny flash of light was produced at that
point.

❖ Observations:
i. Most of the α–particles passed through the gold foil undeflected.
ii. a small fraction of the α–particles was deflected by small angles.
iii. a very few α–particles (∼1 in 20,000) bounced back, that is, were deflected by
nearly 180°.

❖ Conclusion:
i. Most of the space in the atom is empty as most of the α–particles passed through
the foil undeflected.
ii. A few positively charged α–particles were deflected. The deflection must be due
to enormous repulsive force showing that the positive charge of the atom is not
spread throughout the atom as Thomson had presumed. The positive charge has to
be concentrated in a very small volume that repelled and deflected the positively
charged α–particles.
iii. The volume occupied by the nucleus is negligibly small as compared to the total
volume of the atom. The radius of the atom is about 10–10 m, while that of the
nucleus is 10–15 m.

Schematic molecular view of the gold foil

⮚ Rutherford’s nuclear model of an atom:

i. The positive charge and most of the mass of the atom was densely concentrated in an
extremely small region. This very small portion of the atom was called the nucleus by
Rutherford.
ii. The nucleus is surrounded by electrons that move around the nucleus with a very high
speed in circular paths called orbits.

15
 iii. Electrons and the nucleus are held together by electrostatic forces of attraction.

⮚ Atomic number, Mass number:

● The number of protons present in the nucleus is equal to atomic number (Z ).
Atomic number (Z) = number of protons in the nucleus of an atom = number of
electrons in a neutral atom.
● Protons and neutrons present in the nucleus are collectively known as nucleons.
● The total number of nucleons is termed as mass number (A) of the atom.
● mass number (A) = number of protons (Z) + number of neutrons (n)
A
● Elements can be represented as Z X.

⮚ Isotopes and Isobars:

● Atoms with identical atomic numbers but different atomic mass numbers are known as
Isotopes.
1 2 3
For example: 1 H , 1 H , and 1 H .
● All the isotopes of a given element show the same chemical behaviour.
● Isobars are the atoms with the same mass number but different atomic numbers.
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For example: 6 C and 14
7 N .

⮚ Drawbacks of Rutherford Model:

● When a body is moving in an orbit, it undergoes acceleration even if it is moving with
a constant speed in an orbit because of changing direction.So an electron in the nuclear
model is under acceleration.
According to the electromagnetic theory of Maxwell, charged particles when
accelerated should emit electromagnetic radiation (This feature does not exist for
planets since they are uncharged).
Therefore, an electron in an orbit will emit radiation, the energy carried by radiation
comes from electronic motion. The orbit will thus continue to shrink.
Thus electrons in only 10–8 s will spiral into the nucleus. But this does not happen.
Thus, the Rutherford model cannot explain the stability of an atom.
● Another serious drawback of the Rutherford model is that it says nothing about
distribution of the electrons around the nucleus and the energies of these electrons.

⮚ Bohr’s Theory:
● Neils Bohr improved the model proposed by Rutherford and two developments played
a major role in the formulation of Bohr’s model of atom.
i. Dual character of the electromagnetic radiation which means that radiation possess
both like and particle like properties, and
ii. Experimental results regarding atomic spectra.

⮚ Wave Nature of Electromagnetic Radiation:

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● James Maxwell (1870) suggested that when an electrically charged particle moves
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.
● In earlier days light was supposed to be made of particles (corpuscules).
● Maxwell was again the first to reveal that light waves are associated with oscillating
electric and magnetic character

The electric and magnetic field components of an electromagnetic wave. These components have the same
wavelength, frequency, speed and amplitude, but they vibrate in two mutually perpendicular planes.

❖ Properties of electromagnetic waves:

i. 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.
ii. Unlike sound waves or waves produced in water, electromagnetic waves do not
require medium and can move in vacuum.
iii. There are many types of electromagnetic radiation, which differ from one another
in wavelength (or frequency). These constitute electromagnetic spectrum

(a) The spectrum of electromagnetic radiation. (b) Visible spectrum. The visible region is only a small part
of the entire spectrum .

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 ❖ Characteristic of electromagnetic radiations:
i. Frequency: It is defined as the number of waves that pass a given point in one
Second. The SI unit for frequency (ν) is hertz (Hz, s–1),
ii. Wavelength: It is the distance between two adjacent crest or trough. SI unit of
wavelength is meter (m)
iii. Speed: In vacuum all types of electromagnetic radiations, regardless of wavelength,
travel at the same speed, i.e., 3.0 × 108 m s–1 (2.997925 × 108 m s–1, to be precise).
This is called speed of light and is given the symbol ‘c‘.
iv. The frequency (ν ), wavelength (λ) and velocity of light (c) are related by the
equation. c = ν λ
v. Wavenumber: It is defined as the number of wavelengths per unit length. Its units
are reciprocal of the wavelength unit, i.e., m–1.
However, the commonly used unit is cm–1 (not SI unit).
● Electromagnetic radiation explains phenomenon such as diffraction(bending of wave
around an obstacle) and interference (combination of two waves of the same or different
frequencies) but fails to explain
i. The nature of emission of radiation from hot bodies (black -body radiation)
ii. Ejection of electrons from metal surface when radiation strikes it (photoelectric
effect)
iii. variation of heat capacity of solids as a function of temperature
iv. Line spectra of atoms with special reference to hydrogen.

⮚ Black Body Radiation:

● Hot objects emit electromagnetic radiation over a wide range of wavelengths.
● At high temperatures, an appreciable proportion of radiation is in the visible region of
the spectrum.
● As the temperature is raised, a higher proportion of short wavelength (blue light) is
generated.

❖ For example:
▪ When an iron rod is heated in a furnace, it first turns to dull red and then
progressively becomes more and more red as the temperature increases.
▪ As this is heated further, the radiation emitted becomes white and then becomes
blue as the temperature becomes very high. This means that red radiation is most
intense at a particular temperature and the blue radiation is more intense at another
temperature.
▪ This means intensities of radiations of different wavelengths emitted by the hot
body depend upon its temperature.
▪ Objects made of different materials and kept at different temperatures emit different
amounts of radiation.
▪ Also, when the surface of an object is irradiated with light (electromagnetic
radiation),a part of radiant energy is generally reflected as such, a part is absorbed

18
 and a part of it is transmitted. The reason for incomplete absorption is that ordinary
objects are imperfect absorbers of radiation.
▪ An ideal body,which emits and absorbs radiations of all frequencies uniformly, is
called a black body and the radiation emitted by such a body is called black body
radiation. (No such body exists. Carbon black approximates fairly closely to black
body) A good physical approximation to a black body is a cavity with a tiny hole,
which has no other opening. Any ray entering the hole will be reflected by the cavity
walls and will be eventually absorbed by the walls.
▪ A black body is also a perfect radiator of radiant energy.
▪ Furthermore, a black body is in thermal equilibrium with its surroundings. It
radiates same amount of energy per unit area as it absorbs from its surrounding in
any given time.
▪ The amount of light emitted (intensity of radiation) from a black body and its
spectral distribution depends only on its temperature.

Also, as the temperature increases,the maxima of the curve shifts to short wavelength.

⮚ Photoelectric Effect:
● In 1887, H. Hertz performed an experiment in which electrons (or electric current) were
ejected when certain metals (for example potassium, rubidium, caesium etc.) were
exposed to a beam of light. The phenomenon is called the Photoelectric effect.

19
 Equipment for studying the photoelectric effect. Light of a particular frequency strikes a clean metal surface inside
a vacuum chamber. Electrons are ejected from the metal and are counted by a detector that measures their kinetic
energy.
● The results observed in this experiment were:
i. The electrons are ejected from the metal surface as soon as the beam of light
strikes the surface, i.e. there is no time lag between the striking of a light beam
and the ejection of electrons from the metal surface.
ii. The number of electrons ejected is proportional to the intensity or brightness of
light.
iii. For each metal, there is a characteristic minimum frequency, ν0 (also known as
threshold frequency) below which photoelectric effect is not observed. At a
frequency ν > ν0, the ejected electrons come out with certain kinetic energy. The
kinetic energies of these electrons increases with the increase of frequency of the
light used. According to the latter, the energy content of the beam of light depends
upon the brightness of the light. In other words, the number of electrons ejected and
kinetic energy associated with them should depend on the brightness of light. It has
been observed that though the number of electrons ejected does depend upon the
brightness of light, the kinetic energy of the ejected electrons does not.

● Einstein (1905) was able to explain the photoelectric effect using Planck’s quantum
theory of electromagnetic radiation, when a photon of sufficient energy strikes an
electron in the atom of the metal, it transfers its energy instantaneously to the electron
during the collision and the electron is ejected without any time lag or delay. Greater
the energy possessed by the photon, greater will be the transfer of energy to the electron
and greater the kinetic energy of the ejected electron.
Since the striking photon has energy equal to hν and the minimum energy required to
eject the electron is hν0 (also called work function, W0), then the difference in energy
(hν – hν0 ) is transferred as the kinetic energy to the photoelectron.
Kinetic energy of the ejected electron = hv = hv0 + ½ mv2
where m is the mass of the electron and v is the velocity associated with the ejected
electron.
Lastly, a more intense beam of light consists of a larger number of photons,
consequently the number of electrons ejected is also larger as compared to that in an
experiment in which a beam of weaker intensity of light is employed.

⮚ Planck’s Quantum Theory:

● Planck assumed that radiation could be subdivided into discrete chunks of energy.
● He suggested that atoms and molecules could emit or absorb energy only in discrete
quantities and not in a continuous manner.
● He gave the name quantum to the smallest quantity of energy that can be emitted or
absorbed in the form of electromagnetic radiation.
● The energy (E ) of a quantum of radiation is proportional to its frequency (ν ) and is
expressed as E = hυ
h = Planck’s constant = 6.626×10–34 J s.

20
⮚ Dual Behaviour of Electromagnetic Radiation:
● The particle nature of light could explain the black body radiation and photoelectric
effect satisfactorily and the wave behaviour of light could account for the phenomena
of interference and diffraction.
● Thus light possesses both particle and wave-like properties, i.e., light has dual
behaviour.
● Depending on the experiment, we find that light behaves either as a wave or as a
stream of particles.
● Whenever radiation interacts with matter, it displays particle-like properties in contrast
to the wavelike properties (interference and diffraction), which it exhibits when it
propagates

⮚ Atomic spectra:
● Continuous spectrum: When a ray of white light is passed through a prism, the wave
with shorter wavelength bends more than the one with a longer wavelength. Since
ordinary white light consists of waves with all the wavelengths in the visible range, a
ray of white light is spread out into a series of coloured bands called spectrum. The
light of red colour which has the longest wavelength is deviated the least while the
violet light, which has the shortest wavelength is deviated the most. Such a spectrum is
called a continuous spectrum. Continuous because violet merges into blue, blue into
green and so on. (similar spectrum to rainbow).
● Emission spectrum: When electromagnetic radiation interacts with matter, it may
absorb energy and reach a higher energy state. With higher energy, these are in an
unstable state. For returning to their normal energy state, the atoms and molecules emit
radiation in various regions of the electromagnetic spectrum. The spectrum of radiation
emitted by a substance that has absorbed energy is called an emission spectrum. To
produce an emission spectrum, energy is supplied to a sample by heating it or irradiating
it and the wavelength(or frequency) of the radiation emitted, as the sample gives up the
absorbed energy.
● Absorption spectrum: A continuum of radiation is passed through a sample which
absorbs radiation of certain wavelengths. The missing wavelength which corresponds
to the radiation absorbed by the matter, leaves dark spaces in the bright continuous
spectrum.

21
 (a) Atomic emission. The light emitted by a sample of excited hydrogen atoms (or any other element) can be
passed through a prism and separated into certain discrete wavelengths. Thus an emission spectrum, which
is a photographic recording of the separated wavelengths is called as line spectrum. Any sample of
reasonable size contains an enormous number of atoms. Although a single atom can be in only one excited
state at a time, the collection of atoms contains all possible excited states. The light emitted as these atoms
fall to lower energy states is responsible for the spectrum. (b) Atomic absorption. When white light is passed
through unexcited atomic hydrogen and then through a slit and prism, the transmitted light is lacking in
intensity at the same wavelengths as are emitted in (a) The recorded absorption spectrum is also a line
spectrum and the photographic negative of the emission spectrum.

❖ Note:
The emission spectra of atoms in the gas phase do not show a continuous spread of
wavelength from red to violet, rather they emit light only at specific wavelengths with
dark spaces between them. Such spectra are called line spectra or atomic spectra. Each
element has a unique line emission spectrum, which is used in chemical analysis to
identify unknown atoms in the same way as fingerprints are used to identify people.

⮚ Line Spectrum of Hydrogen:

● When an electric discharge is passed through gaseous hydrogen, the H2 molecules
dissociate and the energetically excited hydrogen atoms produced emit electromagnetic
radiation of discrete frequencies.
● The hydrogen spectrum consists of several series of lines named after their discoverers.
● Lines of the hydrogen spectrum obey the following formula:

The value 109,677 cm–1 is called the Rydberg constant for hydrogen
The first five series of lines that correspond to n1= 1, 2, 3,4, 5 are known as Lyman,
Balmer, Paschen, Bracket and Pfund series respectively.
The Spectral Lines for Atomic Hydrogen

22
 Transitions of the electron in the hydrogen atom (The diagram shows the Lyman, Balmer and Paschen series
of transitions)

⮚ BOHR’S MODEL FOR HYDROGEN ATOM

● Bohr’s model for hydrogen atom is based on the following postulates:
i. The electron in the hydrogen atom can move around the nucleus in a circular path
of fixed radius and energy. These paths are called orbits, stationary states or
allowed energy states. These orbits are arranged concentrically around the
nucleus.
ii. The energy of an electron in the orbit does not change with time. However, the
electron will move from a lower stationary state to a higher stationary state when
the required amount of energy is absorbed by the electron or energy is emitted

23
 when the electron moves from higher stationary state to lower stationary state.
The energy change does not take place in a continuous manner.
iii. The frequency of radiation absorbed or emitted when transition occurs between
two stationary states that differ in energy by ∆E, is given by

where E1 and E2 are the energies of the lower and higher allowed energy states
respectively. This expression is commonly known as Bohr’s frequency rule.
iv. The angular momentum of an electron in a given stationary state can be expressed
as in equation

n = 1,2,3.....
Thus an electron can move only in those orbits for which its angular momentum is
integral multiple of h/2π that is why only certain fixed orbits are allowed.

● According to Bohr’s theory for hydrogen atom:

a) The stationary states for electrons are numbered n = 1,2,3..........
These integral numbers are known as Principal quantum numbers.
b) The radii of the stationary states are expressed as:

where a0 = 52,9 pm. Thus the radius of the first stationary state, called the Bohr
orbit, is 52.9 pm.
c) The most important property associated with the electron, is the energy of its
stationary state. It is given by the expression

where RH is called Rydberg constant and its value is 2.18×10–18 J.

When the electron is free from the influence of the nucleus, the energy is taken as
zero, i.e. n = ∞ and is called an ionized hydrogen atom. When the electron is
attracted by the nucleus and is present in orbit n, the energy is emitted and its
energy is lowered. That is the reason for the presence of negative sign in the
energy equation.
d) Bohr’s theory can also be applied to the ions containing only one electron, similar
to that present in hydrogen atom. For example, He+ Li2+ , Be3+ and so on.
e) It is also possible to calculate the velocities of electrons moving in these orbits.
Vn = 2.165 x 106 (Z/n) m/s

24
⮚ Explanation of Line Spectrum of Hydrogen:
● Energy is absorbed if the electron moves from the orbit of smaller Principal quantum
number to the orbit of higher Principal quantum number, whereas the Energy is emitted
if the electron moves from higher orbit to lower orbit.
The energy gap between the two orbits is given as

⮚ Limitations of Bohr’s Model:

● It fails to account for the finer details (doublet, that is two closely spaced lines) of the
hydrogen atom spectrum.
● This model is also unable to explain the spectrum of atoms other than hydrogen,
● Bohr’s theory was also unable to explain the splitting of spectral lines in the presence
of a magnetic field (Zeeman effect) or an electric field (Stark effect).
● It could not explain the ability of atoms to form molecules by chemical bonds.

⮚ Dual Behaviour of Matter:

25
 ● de Broglie in 1924 proposed that matter, like radiation, should also exhibit dual
behaviour i.e., both particle and wavelike properties.
● This means that just as the photon has momentum as well as wavelength, electrons
should also have momentum as well as wavelength.

where m is the mass of the particle, v its velocity and p its momentum.
● It needs to be noted that according to de Broglie, every object in motion has a wave
character.
● The wavelengths associated with ordinary objects are so short (because of their large
masses) that their wave properties cannot be detected.
● The wavelengths associated with electrons and other subatomic particles (with very
small mass) can however be detected experimentally.

⮚ Heisenberg’s Uncertainty Principle:

● Werner Heisenberg, a German physicist in 1927, stated the uncertainty principle which
is the consequence of dual behaviour of matter and radiation.
● It states that it is impossible to determine simultaneously, the exact position and exact
momentum (or velocity) of an electron.

where ∆x is the uncertainty in position and ∆px (or ∆vx) is the uncertainty in
momentum (or velocity) of the particle. If the position of the electron is known with a
high degree of accuracy (∆x is small), then the velocity of the electron will be
uncertain [∆(vx) is large].
● On the other hand, if the velocity of the electron is known precisely (∆(vx) is small),
then the position of the electron will be uncertain (∆x will be large).
● One of the important implications of the Heisenberg Uncertainty Principle is that it
rules out the existence of definite paths or trajectories of electrons and other similar
particles.
● The effect of Heisenberg Uncertainty Principle is significant only for motion of
microscopic objects and is negligible for that of macroscopic objects.
● In the case of a microscopic object like an electron on the other hand. ∆v.∆x obtained
is much larger and such uncertainties are of real consequence.
● It, therefore, means that the precise statements of the position and momentum of
electrons have to be replaced by the statements of probability that the electron has at a
given position and momentum. This is what happens in the quantum mechanical model
of atom.

26
⮚ Reasons for the Failure of the Bohr Model:
● In the Bohr model, an electron is regarded as a charged particle moving in well defined
circular orbits about the nucleus. The wave character of the electron is not considered
in the Bohr model.
● Further, an orbit is a clearly defined path and this path can completely be defined only
if both the position and the velocity of the electron are known exactly at the same time.
This is not possible according to the Heisenberg uncertainty principle.

⮚ QUANTUM MECHANICAL MODEL OF ATOM:

● The branch of science that takes into account the dual behaviour of matter is called
quantum mechanics.
● Quantum mechanics is a theoretical science that deals with the study of the motions of
microscopic objects that have both observable wave-like and particle-like properties.
● For a system (such as an atom or a molecule whose energy does not change with time)
the Schrödinger equation is written as H ψ = Eψ where H is a mathematical operator
called Hamiltonian.
● Solution of this equation gives E and ψ.
● When the Schrödinger equation is solved for a hydrogen atom, the solution gives the
possible energy levels the electron can occupy and the corresponding wave function(s)
(ψ) of the electron associated with each energy level. These quantized energy states and
corresponding wave functions which are characterized by a set of three quantum
numbers (principal quantum number n, azimuthal quantum number l and magnetic
quantum number ml ) arise as a natural consequence in the solution of the Schrödinger
equation.
● When an electron is in any energy state, the wave function corresponding to that energy
state contains all information about the electron. Such wave functions of hydrogen or
hydrogen like species with one electron are called atomic orbitals. Such wave functions
pertaining to one-electron species are called one-electron systems.
● The probability of finding an electron at a point within an atom is proportional to the
|ψ|2 at that point.

⮚ Orbitals and Quantum Numbers:

● Orbit and orbital are not synonymous.
● An orbit, as proposed by Bohr, is a circular path around the nucleus in which an electron
moves.
● An atomic orbital, on the other hand, is a quantum mechanical concept and refers to the
one electron wave function ψ in an atom. It is characterized by quantum numbers.

⮚ Principal quantum number:

● The principal quantum number ‘n’ is a positive integer with value of n = 1,2,3..

27
 ● The principal quantum number determines the size and to large extent the energy of the
orbital.
● The principal quantum number also identifies the shell.
● With the increase in the value of ‘n’, the number of allowed orbital increases and are
given by n2.
● All the orbitals of a given value of ‘n’ constitute a single shell of atom.

⮚ Azimuthal quantum number:

● Azimuthal quantum number ‘l’ is also known as orbital angular momentum or
subsidiary quantum number.
● It defines the three dimensional shape of the orbital.
● For a given value of n, l can have n values ranging from 0 to n – 1.
● For a given value of n, the possible value of l are : l = 0, 1, 2, .......... (n–1).
● Each shell consists of one or more subshells or sub-levels. The number of subshells in
a principal shell is equal to the value of n.

⮚ Magnetic quantum number:

● Magnetic orbital quantum number ‘ml’ gives information about the spatial
orientation of the orbital.
● ml = 2l+1
● For l = 0, the only permitted value of ml = 0, [2(0)+1 = 1] i.e one s orbital.
● For l = 1, ml can be –1, 0 and +1 [2(1)+1 = 3], three p orbitals.

⮚ Electron spin quantum number (ms):

28
 ● An electron spins around its own axis.
● Spin angular momentum of the electron is a vector quantity, and can have two
orientations relative to the chosen axis.
● These two orientations are distinguished by the spin quantum numbers ms which can
take the values of +½ or –½. These are called the two spin states of the electron and are
normally represented by two arrows, ↑ (spin up) and ↓ (spin down). Two electrons that
have different ms values (one +½ and the other –½)

⮚ Shapes of Atomic Orbitals:

● The square of the wave function (i.e.,ψ2) at a point gives the probability density of the
electron at that point.
● It may be noted that for 1s orbital the probability density is maximum at the nucleus
and it decreases sharply as we move away from it.
● On the other hand, for 2s orbital the probability density first decreases sharply to zero
and again starts increasing. After reaching a small maxima it decreases again and
approaches zero as the value of r increases further.
● The region where this probability density function reduces to zero is called nodal
surfaces or simply nodes.

⮚ s-orbital:
● s-orbitals are spherical in shape.
● Probability of finding the electron at a given distance is equal in all directions.

29
 ● It is also observed that the size of the s orbital increases with increase in n i.e. 4s > 3s
> 2s > 1s and the electron is located further away from the nucleus as the principal
quantum number increases.

⮚ p orbital:
● p orbital consists of two sections called lobes that are on either side of the plane that
passes through the nucleus.
● The probability density function is zero on the plane where the two lobes touch each
other.
● The size, shape and energy of the three orbitals are identical.
● They differ however, in the way the lobes are oriented. Since the lobes may be
considered to lie along the x, y or z axis, they are given the designations 2px , 2py , and
2pz .

⮚ d orbital:
● The five d-orbitals are designated as dxy , dyz , dxz , dx2 –y2 and dz2.
● The shapes of the first four d-orbitals are similar to each other, whereas that of the fifth
one, dz2, is different from others, but all five 3d orbitals are equivalent in energy.

30
 ● The orbitals having the same energy are called degenerate.

Boundary surface diagrams of the five 3d orbitals.

⮚ Energies of Orbitals:
● The energy of an electron in a H atom = 1s < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d =
4f
● In multi-electron atoms, electrons are filled as per (n + l) rule.
● The lower the value of (n + l) for an orbital, the lower is its energy. If two orbitals have
the same value of (n + l), the orbital with lower value of n will have the lower energy.

⮚ Aufbau Principle:
● In the ground state of the atoms, the orbitals are filled in order of their increasing
energies.

31
⮚ Pauli Exclusion Principle:
● No two electrons in an atom can have the same set of four quantum numbers.
● Pauli exclusion principle can also be stated as : “Only two electrons may exist in the
same orbital and these electrons must have opposite spin.”
● The maximum number of electrons in the shell with principal quantum number n is
equal to 2n2.

⮚ 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.

32
⮚ Electronic Configuration of Atoms:

33
⮚ Stability of Completely Filled and Half Filled Subshells:
● In certain elements such as Cu, or Cr, where the two subshells (4s and 3d) differ slightly
in their energies, an electron shifts from a subshell of lower energy (4s) to a subshell of
higher energy (3d), provided such a shift results in all orbitals of the subshell of higher
energy getting either completely filled or half filled.
● The valence electronic configurations of Cr and Cu, therefore, are 3d5 4s1 and 3d10 4s1
respectively and not 3d4 4s2 and 3d9 4s2. It has been found that there is extra stability
associated with these electronic configurations.

34
Wavelength-intensity relationship

35
 Classification Of Elements and Periodicity in Properties
Dobernier triads:
● Classified elements into a group of three called triads.
● Arranged elements in triads in increasing order of atomic weight and the weight of the
central element is equal to Arithmetic mean of other two elements.

Triad-1 Li (wt: 7) Na (wt: 23) K (wt: 39)

Traid-2 Ca (wt: 40) Sr (wt: 88) Ba (wt: 137)

Traid-3 Cl (wt: 35.5) Br (wt: 80) I (Wt: 127)

Law of octaves:
● Every 8th element had similar properties as that of the first element when all the
elements were arranged in the increasing order of atomic weights.
● True only till Calcium.

Lother Meyer curve:

● Plotted physical properties like volume, Melting point and boiling point against
atomic weights and found a periodically repeating pattern.
Mendeleev’s periodic table:
● Arranged elements in horizontal rows and vertical columns of the table in order of
their increasing atomic weights in such a way that the elements with similar properties
occupy the same vertical column.
● Relied on similarities in empirical formulas and properties of the compounds formed
by the elements.
● Few elements did not fit in the classification if atomic weight was strictly followed so
he ignored atomic weight order and placed elements based on similar properties. Eg:
Iodine with lower weight than tellurium (Group VI) is placed in group VII.
● Gaps were left at few positions accounting to the fact that there are undiscovered
elements.
Modern periodic table:
● Henry mosley plotted graphs and observed following points:

❖ v Vs atomic mass : Non linear

❖ v Vs atomic number : Linear/ straight line plot.

36
 ● Modern periodic law: The physical and chemical properties are periodic functions of
their atomic numbers.
● Horizontal rows: Periods, Vertical columns: Groups
● Elements with similar outer electron configuration are arranged in the same group.
● Total : 7 periods, 18 groups (Numbered 1 to 18 as newer notation and IA, IIA ...VIIA,
VIII, IB, IIB,...VIIB)
● 2,8,8,18,18,32 are the number of elements in each period from 1 to 6 respectively.
The 7th is still incomplete.
● 14 elements of 6th and 7th period are placed below in separate rows.

● Classified into 4 blocks s,p,d,f based on the orbital which the last electron enters.
S-block:
● Group-1: Alkali metals, Group 2: Alkaline earth metals.
● Outermost electronic configuration: ns2
● Predominantly form ionic compounds except Li and Be
● Group-1: Easily form +1 ion, Group-2: Easily form +2 ions
P-block:
● From group:13-18
● Group-16: chalcogens, Group-17: Halogens, Group-18: Noble gases.
● s and p block together call as representative elements.
● Outermost electronic configuration: ns2np(1-6)
d block elements (Transition elements):
● From group: 3-12
● Outer electronic configuration: (n-1)d1-10 ns0-2
● Have variable valency, variable oxidation states, form coloured ions etc.
● Zn, Cd, Hg having (n-1)d10ns2 do not show properties of transition elements.

37
 ● Form bridge between active s-block metals and less active 13,14 group elements and
thus called as transition elements.
f block elements (inner-transition elements):
● Group: 3
● The two rows placed in the bottom are called f-block elements.
● The first row (Ce-Lu) is called lanthanoids
● The second row (Th-Lr) is called actinoids
● Outermost electronic configuration: (n-2)f1-14 (n-1)d0-1 ns2.
● Radioactive in nature
● Elements after uranium are called transuranium metals

Determination of period and group number of elements:

● Period number: Max principal quantum number
● Group: s block - no. of valence electron
p block - 10 + no. of valence electron
d block – ns + no. of (n – 1) d electrons
f block – III B
Nomenclature of the elements with Z > 100:
● IUPAC nomenclature:

● Eg:
Z = 101 : Name - Unnilunium, Symbol - Unu
Z = 102 : Name - Unnilbium, Symbol - Unb

38
 Z = 110 : Name - Ununnilium, Symbol - Uun

Atomic radius
● Determination of atomic radius is tough because the electronic cloud around the
nucleus doesn’t have a sharp boundary. Thus we approximately measure size by
knowing the distance between atoms in a combined state.
● Types of atomic radius:
❖ Covalent radius: Half the internuclear distance between covalently bonded
atoms.
❖ Metallic radius: Half the internuclear distance separating the metal cores in the
metallic crystal
❖ Vanderwaal radius: Half the internuclear distance between noble gas atoms
bound together by vanderwaal force
❖ Covalent radius < Metallic radius < Vanderwaal radius
● General atomic trend:
❖ Along group: Increases from T (top) → B (bottom) as number of shells increase
❖ Along period: Decreases form L → R as the last electron adds to same shell
effective nuclear charge increases
● Exception:
❖ d- block:
▪ Along the period, show exceptions due to interplay between effective nuclear
charge and interatomic repulsions.
▪ Very low radius gap between 5th and 6th period elements due to poor
shielding effect of f electrons.
❖ Noble gases have exceptionally high radius due to van der waal radius
❖ p-block: Due to poor shielding effect of d and f electrons there are exceptions
along the group. Eg: In group-13 the size of Al is greater than Ga.
Ionic radius:
● Order: Cation size < Atomic size < Anion size
Eg: Na+ < Na, Cl- > Cl
● For isoelectronic species: If Z/e (Atomic number to electron) ratio increases size
decreases
Ionisation enthalpy (IE):
● The energy required to remove an electron from an isolated gaseous atom in its
ground state.
X ( g ) → X + ( g ) + e − IE1

X + ( g ) → X 2+ ( g ) + e − IE2
Equal to enthalpy change of the reaction. Always positive since its endothermic
● Variation of IE1:
❖ Group: decreases from T → B as the size increases

39
 ❖ Period: Increases from L → R as Zeff increases. But due to half filled and fully
filled stability of few elements like Be, N etc they show higher IE than expected.
Eg: Along period-2 : Li < Be > B < C < N > O < F < Ne
● Exceptions: Based on the half filled stability, Zeff, shielding effect there are many
exceptions throughout the periodic table.
Electron gain enthalpy:
● The enthalpy change when an electron is added to a neutral gaseous atom.

● May be endothermic or exothermic based on element.

Eg: Enthalpy change of halogens is negative whereas, for noble gases it highly
positive
● More negative electron gain enthalpy => more energy released => more affinity to the
electron (More electron affinity).
● Variation:
❖ Group: Less negative from T → B i.e electron affinity decreases
❖ Period: More negative from L → R i.e electron affinity increases
● Exceptions: Less systematic than IE
❖ Electron affinity of Cl > F, S > O due to very small size of F, O and higher
repulsions when an electron is added.
● Cl is the element with highest electron affinity.
Electronegativity (EN):
● Ability of an atom in a chemical compound to attract shared electrons to itself is
called Electronegativity.
● 2 scales used to measure EN: Pauling scale (mostly used) and Mulliken scale.
❖ Pauling scale: EN is a relative term and depends on the atoms attached. Fluorine
is assigned with arbitrary highest value i.e 4.
❖ Mulliken scale: Assumes EN is absolute.
● Variation:
❖ Group: Decreases from T → B
❖ Period: Increases from L → R
● Application:
❖ Metallic elements => Low EN, Strong tendency to lose electrons.
❖ Non-Metallic elements => High EN, Strong tendency to gain electrons.
PERIODIC TRENDS IN CHEMICAL PROPERTIES:
Oxidation and reduction:
● Oxidation: Loss of electrons, Reduction: Gain of electrons.
● Oxidising agent: Reduces itself and oxidises the other element, Reducing agent:
Oxidises itself and reduces the other element.
● Trend:
❖ Group: Reducing nature increases or tendency to get oxidised increases
❖ Period: Oxidising nature increases or the tendency to get reduced increases.

40
 ● Strongest oxidising agent is F.

PERIODIC TRENDS IN CHEMICAL REACTIVITY:

● High reactivity at the two extremes and low in between as the the left extreme the
metallic nature is high and at the right extreme nonmetallic behaviour is high.
● Metallic oxides (Extreme left) => Basic in nature ie in water they form base
● Non metallic oxides (Extreme right) => Acidic in nature ie in water they form acid
● Eg:
Na2O + H2O → 2NaOH
Cl2O7 + H2O → 2HClO4
● Oxides in between are amphoteric (reacts with both acid and base) or neutral (do not
react with acid or base).

41
 Chemical Bonding and Molecular Structure

➢ Chemical bonding and molecular structure

The attractive force which holds various constituents (atoms, ions, etc.) together in different
chemical species is called a chemical bond.

➢ KÖSSEL-LEWIS APPROACH TO CHEMICAL BONDING:

• Lewis pictured the atom in terms of a positively charged ‘Kernel’ (the nucleus plus the
inner electrons) and the outer shell that could accommodate a maximum of eight
electrons.
• Lewis postulated that atoms achieve the stable octet when they are linked by chemical
bonds.
➢ Lewis Symbol:
Only the outer shell electrons take part in chemical combination and they are known as valence
electrons.

According to octet rule, the atoms can combine either by transfer of valence electrons from one
atom to another (gaining or losing) or by sharing of valence electrons in order to have an octet
in their valence shells.
The negative and positive ions are stabilized by electrostatic attraction.The bond formed was
termed as the electrovalent bond.

When two atoms share one electron pair they are said to be joined by a single covalent bond.

➢ Lewis Representation of Simple Molecules:

The Lewis dot structures provide a picture of bonding in molecules and ions in terms of the
shared pairs of electrons and the octet rule.
The total number of electrons required for writing the structures are obtained by adding the
valence electrons of the combining atoms.

42
➢ Formal Charge:
The formal charge of an atom in a 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.

➢ Limitations of the Octet Rule:

1. The incomplete octet of the central atom

2. Odd-electron molecules

3. The expanded octet

43
 4. The octet rule is based upon the chemical inertness of noble gases. However, some
noble gases (for example xenon and krypton) also combine with oxygen and fluorine
to form a number of compounds like XeF2, KrF2, XeOF2 etc.,
5. This theory does not account for the shape of molecules.
6. It does not explain the relative stability of the molecules being totally silent about the
energy of a molecule.
➢ IONIC OR ELECTROVALENT BOND:
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.
Ionic compounds in the crystalline state consist of orderly three-dimensional arrangements of
cations and anions held together by coulombic interaction energies.
The crystal structure of sodium chloride, NaCl (rock salt), for example is shown below.

➢ Lattice Enthalpy:
The Lattice Enthalpy of an ionic solid is defined as the energy required to completely separate
one mole of a solid ionic compound into gaseous constituent ions.
➢ BOND PARAMETERS:
• Bond Length:
Bond length is defined as the equilibrium distance between the nuclei of two bonded
atoms in a molecule.
Covalent and van der Waals radii of chlorine are depicted below:

44
• Bond Angle:
The angle between the orbitals containing bonding electron pairs around the central
atom in a molecule/complex ion.

• 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.

• Bond Order:
In the Lewis description of covalent bond, the Bond Order is given by the number of
bonds between the two atoms in a molecule. Isoelectronic molecules and ions have
identical bond orders; for example, F2 and O2 2– have bond order 1. N2, CO and NO+
have bond order 3.

45
➢ Resonance Structures:
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 non-bonding pairs of electrons are taken as the canonical structures of the hybrid which
describes the molecule accurately.

➢ Polarity of Bonds:
In reality no bond or a compound is either completely covalent or ionic.
As a result of polarisation, the molecule possesses the dipole moment (depicted below) which
can be defined as the product of the magnitude of the charge and the
distance between the centres of positive and negative charge.

➢ Dipole moment of NH3 vs NF3

➢ Dipole moments of some molecules are shown in the Table below.

46
➢ VSEPR THEORY:
This theory provides a simple procedure to predict the shapes of covalent molecules.
• The main postulates of VSEPR theory are as follows:
1. The shape of a molecule depends upon the number of valence shell electron pairs
(bonded or nonbonded) around the central atom.
2. Pairs of electrons in the valence shell repel one another since their electron clouds
are negatively charged.
3. These pairs of electrons tend to occupy such positions in space that minimise
repulsion and thus maximise distance between them.
4. The valence shell is taken as a sphere with the electron pairs localising on the
spherical surface at maximum distance from one another.
5. A multiple bond is treated as if it is a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.
6. Where two or more resonance structures can represent a molecule, the VSEPR
model is applicable to any such structure.
• The repulsive interaction of electron pairs decrease in the order:
Lone pair (lp) –Lone pair (lp) > Lone pair (lp) –Bond pair (bp) > Bond pair (bp) –Bond
pair (bp)
These repulsion effects result in deviations from idealised shapes and alterations in
bond angles in molecules.

47
48
49
➢ VALENCE BOND THEORY:
The valence bond theory is based on the knowledge of atomic orbitals, electronic
configurations of elements, the overlap criteria of atomic orbitals, the hybridization of
atomic orbitals and the principles of variation and superposition.
• Orbital Overlap Concept:
The formation of a covalent bond between two atoms results by pairing of electrons
present in the valence shell having opposite spins.
• Overlapping of Atomic Orbitals:
When orbitals of two atoms come close to form bond, their overlap may be positive,
negative or zero depending upon the sign (phase) and direction of orientation of
amplitude of orbital wave function in space

• Types of Overlapping and Nature of Covalent Bonds:

❖ Sigma(𝞼) bond: formed by the end to end (head-on) overlap of bonding orbitals
along the internuclear axis.

50
 ❖ pi(𝝅) bond:
Sidewise overlapping consists of two saucer type charged clouds above and below
the plane of the participating atoms

➢ HYBRIDISATION:
To explain the characteristic geometrical shapes of polyatomic molecules like CH4, NH3
and H2O etc.,
The atomic orbitals combine to form a new set of equivalent orbitals known as hybrid
orbitals. Unlike pure orbitals, the hybrid orbitals are used in bond formation. The
phenomenon is known as hybridisation
• Salient features of hybridisation:
1. The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridised.
2. The hybridised orbitals are always equivalent in energy and shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.
4. These hybrid orbitals are directed in space in some preferred direction to have
minimum repulsion between electron pairs and thus a stable arrangement.
Therefore, the type of hybridisation indicates the geometry of the molecules.

• Types of Hybridisation:
There are various types of hybridisation involving s, p and d orbitals.
❖ sp hybridisation: Each sp hybrid orbitals has 50% s-character and 50% p-
character.
E.g. BeCl2 molecule.

51
❖ sp2 hybridisation: 33.3 % s-character and 66.6 % p-character in each sp2 hybrid
orbital.
E.g. BCl3 molecule

❖ sp3 hybridisation:
25% s-character and 75% p-character in each sp3 hybrid orbital.
E.g. CH4 molecule, H2O and NH3

52
 ❖ Other Examples hybridised molecules:

➢ MOLECULAR ORBITAL THEORY:

• Salient features:
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.

53
 3. While an electron in an atomic orbital is influenced by one nucleus, in a molecular
orbital it is influenced by two or more nuclei depending upon the number of atoms
in the molecule. Thus, an atomic orbital is monocentric while a molecular orbital is
polycentric.
4. The number of molecular orbital forms 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
(LCAO):
The molecular orbital 𝝈 formed by the addition of atomic orbitals is called the bonding
molecular orbital while the molecular orbital 𝝈* formed by the subtraction of atomic
orbital is called antibonding molecular orbital.

➢ Conditions for the Combination of Atomic Orbitals:

1. The combining atomic orbitals must have the same or nearly the same energy.
2. The combining atomic orbitals must have the same symmetry about the molecular axis.
3. The combining atomic orbitals must overlap to the maximum extent.
• Types of Molecular Orbitals:

54
 Molecular orbitals of diatomic molecules are designated as 𝝈 (sigma), 𝝅 (pi), 𝛅 (delta),
etc.
sigma(𝝈) molecular orbitals are symmetrical around the bond-axis while pi (𝝅)
molecular orbitals are not symmetrical.
• Energy Level Diagram for Molecular Orbitals:
For O2 and F2

• The increasing order of energies of various molecular orbitals for O2 and F2 is given
below:

• The increasing order of energies of various molecular orbitals for Li2, Be2, B2, C2, and
N2 is given below:

55
➢ Electronic Configuration and Molecular Behaviour:
• Bond order:
Bond order (b.o.) is defined as one half the difference between the number of electrons
present in the bonding and the antibonding orbitals.

• Magnetic nature:
If all the molecular orbitals in a molecule are doubly occupied, the substance is
diamagnetic (repelled by magnetic field). However if one or more molecular orbitals
are singly occupied it is paramagnetic (attracted by magnetic field), e.g., O2 molecule.

➢ BONDING IN SOME HOMONUCLEAR DIATOMIC MOLECULES:

H2 molecule:

He2 molecule:

Li2 molecule:
Bond order =1
C2 molecule:

O2 molecule:

➢ MO occupancy and molecular properties for B2 through Ne2.

56
➢ HYDROGEN BONDING:
Hydrogen bond can be defined as the attractive force which binds the hydrogen atom of
one molecule with the electronegative atom (F, O or N) of another molecule.
• There are two types of H-bonds
(i) Intermolecular hydrogen bond
(ii) Intramolecular hydrogen bond

57
 States of Matter

● Bulk properties of matter are the properties associated with a collection of a large
number of atoms, ions or molecules.
○ an individual molecule of a liquid does not boil but the bulk boils.
○ Collection of water molecules have wetting properties; individual molecules do not
wet.
● Chemical properties of a substance do not change with the change of its physical state;
but the rate of chemical reactions do depend upon the physical state.

➢ INTERMOLECULAR FORCES
● Intermolecular forces are the forces of attraction and repulsion between interacting
particles (atoms and molecules). It does not include the ionic and covalent bonds.
● Attractive intermolecular forces are known as van der Waals forces, in honour of Dutch
scientist Johannes van der Waals (1837- 1923).
● Attractive forces between an ion and a dipole are known as ion-dipole forces and these
are not van der Waals forces.

➢ Dispersion Forces or London Forces

● Atoms and nonpolar molecules are electrically symmetrical and have no dipole moment
because their electronic charge cloud is symmetrically distributed.
● A dipole may develop momentarily even in such atoms and molecules.
● Instantaneous or transient dipoles distort the electron density of the other atom which
is close to it and as a consequence a dipole is induced in that atom.
● The temporary dipoles attract each other.

58
 ● This force of attraction was first proposed by the German physicist Fritz London, and
for this reason it is known as London force.
● Another name for this force is dispersion force.
● These forces are always attractive.
● Interaction energy is inversely proportional to the sixth power of the distance between
two interacting particles (i.e., 1/r6 where r is the distance between two particles)
● These forces are important only at short distances (~500 pm) and their magnitude
depends on the polarisability of the particle.

➢ Dipole - Dipole Forces

● Dipole-dipole forces act between the molecules possessing permanent dipoles.
● Ends of the dipoles possess “partial charges” (shown by Greek letter delta (δ)) which
are always less than the unit electronic charge (1.6 × 10–19 C)
● The polar molecules interact with 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.
● The interaction energy is inversely proportional to distance between polar molecules.
○ Dipole-dipole interaction energy between stationary polar molecules (as in solids)
is proportional to 1/r3.
○ Interaction energy between rotating polar molecules is proportional to 1/r6, where r
is the distance between polar molecules.

59
 ● Besides dipole dipole interaction, polar molecules can interact by London forces also.
Thus the cumulative effect is that the total of intermolecular forces in polar molecules
increase.

➢ Dipole–Induced Dipole Forces

● This type of attractive forces operate between the polar molecules having permanent
dipole and the molecules lacking permanent dipole.
● Permanent dipole of the polar molecule induces dipole on the electrically neutral
molecule by deforming its electron cloud.

● Interaction energy is proportional to 1/r6 where r is the distance between two molecules.
● Induced dipole moment depends upon the dipole moment present in the permanent
dipole and the polarisability of the electrically neutral molecule.
● Molecules of larger size can be easily polarized. High polarisability increases the
strength of attractive interactions.
● Cumulative effects of dispersion forces and dipole-induced dipole interactions exists.

➢ Hydrogen bond
● This is a special case of dipole-dipole interaction.
● This is found in the molecules in which highly polar N–H, O–H or H–F bonds are
present. However, species such as Cl– may also participate in hydrogen bonding
● Energy of the hydrogen bond varies between 10 to 100 kJ mol–1.
● Hydrogen bonds are a powerful force in determining the structure and properties of
many compounds, for example proteins and nucleic acids.
● Strength of the hydrogen bond is determined by the coulombic interaction between the
lone-pair electrons of the electronegative atom of one molecule and the hydrogen atom
of another molecule.

➢ Repulsive intermolecular forces

● Molecules also exert repulsive forces on one another.
● When two molecules are brought into close contact with each other, the repulsion
between the electron clouds and that between the nuclei of two molecules comes into
play.
● Magnitude of the repulsion rises very rapidly as the distance separating the molecules
decreases.

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 ● This is the reason that liquids and solids are hard to compress. In these states molecules
are already in close contact; therefore they resist further compression; as that would
result in the increase of repulsive interactions.

➢ THERMAL ENERGY
● It is the energy of a body arising from motion of its atoms or molecules.
● Directly proportional to the temperature of the substance.
● It is the measure of average kinetic energy of the particles of the matter and is thus
responsible for movement of particles. This movement of particles is called thermal
motion.

➢ INTERMOLECULAR FORCES vs THERMAL INTERACTIONS

● Intermolecular forces tend to keep the molecules together but thermal energy of the
molecules tends to keep them apart.
● Three states of matter are the result of balance between intermolecular forces and the
thermal energy of the molecules.
● When molecular interactions are very weak, molecules do not cling together to make
liquid or solid unless thermal energy is reduced by lowering the temperature.
○ Gases do not liquify on compression only, although molecules come very close to
each other and intermolecular forces operate to the maximum.
○ When thermal energy of molecules is reduced by lowering the temperature; the
gases can be very easily liquified.

➢ THE GASEOUS STATE

● This is the simplest state of matter.
● We spend our life in the lowermost layer of the atmosphere called the troposphere,
which is held to the surface of the earth by gravitational force.
○ The thin layer of atmosphere is vital to our life.
○ It shields us from harmful radiations and contains substances like dioxygen,
dinitrogen, carbon dioxide, water vapour, etc.
● Only eleven elements exist as gases under normal conditions.

61
➢ Physical properties of gases
● Gases are highly compressible.
● Gases exert pressure equally in all directions.
● Gases have much lower density than the solids and liquids.
● The volume and the shape of gases are not fixed. These assume the volume and shape
of the container.
● Gases mix evenly and completely in all proportions without any mechanical aid.
● Simplicity of gases is due to the fact that the forces of interaction between their
molecules are negligible.

➢ THE GAS LAWS

● The first reliable measurement on properties of gases was made by Anglo-Irish
scientist Robert Boyle in 1662. The law which he formulated is known as Boyle’s
Law.
● Later on attempts to fly in air with the help of hot air balloons motivated Jaccques
Charles and Joseph Lewis Gay Lussac to discover additional gas laws.
● Contribution from Avogadro and others provided a lot of information about the
gaseous state.

➢ Boyle’s Law (Pressure - Volume Relationship)

● At constant temperature, the pressure of a fixed amount (i.e., number of moles n) of
gas varies inversely with its volume.
● This is known as Boyle’s law.
● Mathematically-
p ∝ 1/V ⇒ p = k1 (1/V)
k1 is the proportionality constant whose value depends upon the amount of the gas,
temperature of the gas and the units in which p and V are expressed.
● On rearranging, we obtain -
pV = k1
It means that at constant temperature, the product of pressure and volume of a fixed
amount of gas is constant.
● If a fixed amount of gas at constant temperature T occupying volume V1 at pressure
p1 undergoes expansion, so that volume becomes V2 and pressure becomes p2, then
according to Boyle’s law:
p1V1 = p2V2 = constant

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● Two conventional ways of graphically presenting Boyle’s law –

Graph of pressure, p vs. Volume, V of a gas at different temperatures.

● The value of k1 for each curve is different because for a given mass of gas, it varies
only with temperature.
● Each curve corresponds to a different constant temperature and is known as an
isotherm (constant temperature plot).
● Higher curves correspond to higher temperatures.

Graph of pressure of a gas, p vs. (1/V)

● It is a straight line passing through the origin.
● However at high pressures, gases deviate from Boyle’s law and under such conditions
a straight line is not obtained in the graph.
● In a quantitative manner prove that gases are highly compressible because when a
given mass of a gas is compressed, the same number of molecules occupy a smaller
space. This means that gases become denser at high pressure.
● A relationship can be obtained between density and pressure of a gas by using Boyle’s
law:

63
 ● This shows that at a constant temperature, pressure is directly proportional to the
density of a fixed mass of the gas.

➢ Charles’ Law (Temperature - Volume Relationship)

● For a fixed mass of a gas at constant pressure, volume of a gas increases on increasing
temperature and decreases on cooling.
● For each degree rise in temperature, volume of a gas increases by (1/273.15) of the
original volume of the gas at 0°C.

● New temperature scale called the Kelvin temperature scale or Absolute

temperature scale is defined based on the above relationship.
○ t°C on new scale is given by T = 273.15 + t and 0°C will be given by T0 =
273.15
● Degree sign is not used while writing the temperature in absolute temperature scale,
i.e., Kelvin scale.
● The Kelvin scale of temperature is also called Thermodynamic scale of temperature
and is used in all scientific works.
● If the temperature is used in kelvin, we can write general expression of Charles’ law
as -

● The value of constant k2 is determined by the pressure of the gas, its amount and the
units in which volume V is expressed.
● The mathematical expression for Charles’ law states that pressure remaining constant,
the volume of a fixed mass of a gas is directly proportional to its absolute
temperature.
● For all gases, at any given pressure, the graph of volume vs temperature (in celsius) is
a straight line and on extending to zero volume, each line intercepts the temperature
axis at – 273.15°C. Slopes of lines obtained at different pressure are different but at
zero volume all the lines meet the temperature axis at – 273.15°C.

64
 ● Each line of the volume vs temperature graph is called isobar.
● The volume of the gas at – 273.15°C will be zero. This means that gas will not exist.
In fact all the gases get liquified before this temperature is reached.
● The lowest hypothetical or imaginary temperature at which gases are supposed to
occupy zero volume is called Absolute zero.
● All gases obey Charles’ law at very low pressures and high temperatures.

➢ Gay Lussac’s Law (Pressure-Temperature Relationship)

● The mathematical relationship between pressure and temperature was given by Joseph
Gay Lussac and is known as Gay Lussac’s law.
● At constant volume, pressure of a fixed amount of a gas varies directly with the
temperature.
● Mathematically,

● Pressure vs temperature (Kelvin) graph at constant molar volume is shown. Each line
of this graph is called isochore.

65
➢ Avogadro Law (Volume - Amount Relationship)
● In 1811 Italian scientist Amedeo Avogadro tried to combine conclusions of Dalton’s
atomic theory and Gay Lussac’s law of combining volumes which is now known as
Avogadro law.
● Equal volumes of all gases under the same conditions of temperature and pressure
contain equal numbers of molecules.
● As long as the temperature and pressure remain constant, the volume depends upon
the number of molecules of the gas or in other words amount of the gas.
● Mathematically we can write
V ∝ n (where n is the number of moles of the gas)
⇒ V = k4 n
● Standard temperature and pressure (STP): 273.15 K (0°C) temperature and 1 bar
(i.e., exactly 105 pascal) pressure. These values approximate freezing temperature of
water and atmospheric pressure at sea level.
● One mole of each gas at standard temperature and pressure (STP) will have the same
volume. At STP the molar volume of an ideal gas or a combination of ideal gases is
22.71098 L mol–1.
● Standard ambient temperature and pressure (SATP), conditions are also used in
some scientific works. SATP conditions means 298.15 K and 1 bar (i.e., exactly 105
Pa).
● At SATP (1 bar and 298.15 K), the molar volume of an ideal gas is 24.789 L mol–1.
● On rearranging the avogadro’s law we can also conclude - The density of a gas is
directly proportional to its molar mass.

● A gas that follows Boyle’s law, Charles’ law and Avogadro law is called an ideal gas.
Such a gas is hypothetical.
● It is assumed that intermolecular forces are not present between the molecules of an
ideal gas.
● Real gases follow these laws only under certain specific conditions when forces of
interaction are practically negligible. In all other situations these deviate from ideal
behaviour.

➢ IDEAL GAS EQUATION

● The three laws (Boyle’s, Charles’, Avogadro’s) can be combined together in a single
equation which is known as the ideal gas equation.
pV = nRT
● R is called gas constant. It is the same for all gases. Therefore, it is also called
Universal Gas Constant.
● This equation will be applicable to any gas, under those conditions when behaviour of
the gas approaches ideal behaviour.
● The value of R depends upon units in which p, V and T are measured. Volume of one
mole of an ideal gas under STP conditions (273.15 K and 1 bar pressure) is 22.710981
L mol–1. Value of R for one mole of an ideal gas can be calculated under these
conditions.

66
 R = 8.314 J K–1 mol–1
● According to the previous definition of STP - temperature of 0°C (273.15 K), but a
slightly higher pressure of 1 atm (101.325 kPa), One mole of any gas of a combination
of gases occupies 22.413996 L of volume at STP.
● The value of R as per previous definition is 0.0820578 L atm K–1 mol–1.
● Ideal gas equation is a relation between four variables and it describes the state of any
gas, therefore, it is also called the equation of state.
● Combined gas law –

➢ Density and Molar Mass of a Gaseous Substance

● On rearrangement of ideal gas equation, we get the relationship for calculating molar
mass of a gas –

➢ Dalton’s Law of Partial Pressures

● The law was formulated by John Dalton in 1801.
● The total pressure exerted by the mixture of non-reactive gases is equal to the sum of
the partial pressures of individual gases.
● In a mixture of gases, the pressure exerted by the individual gas is called partial
pressure.
● Mathematically, pTotal = p1 + p2 + p3 + ..... .(at constant T, V)
pTotal is the total pressure exerted by the mixture of gases and p1, p2, p3 etc. are partial
pressures of gases.
● Gases are generally collected over water and therefore are moist. Pressure exerted by
saturated water vapour is called aqueous tension. Aqueous tension of water at
different temperatures is given in Table.

● 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 also.
pDry gas = pTotal – Aqueous tension

➢ Partial pressure in terms of mole fraction

● Using a combination of ideal gas equation and Dalton’s law of partial pressures, we
get the relationship -
partial pressure of a gas = total pressure × mole fraction
pi = ptotal 𝜒i

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 pi and 𝜒i are partial pressure and mole fraction of ith gas respectively.

➢ KINETIC MOLECULAR THEORY OF GASES

● A theory is a model (i.e., a mental picture) that enables us to better understand our
observations.
● The theory that attempts to elucidate the behaviour of gases is known as kinetic
molecular theory.

➢ Assumptions or postulates of the kinetic molecular theory of gases

● Gases consist of a large number of identical particles (atoms or molecules) that are so
small and so far apart on the average that the actual volume of the molecules is
negligible in comparison to the empty space between them. They are considered as
point masses.
○ This assumption explains the great compressibility of gases.
● There is no force of attraction between the particles of a gas at ordinary temperature
and pressure.
○ The support for this assumption comes from the fact that gases expand and occupy
all the space available to them.
● Particles of a gas are always in constant and random motion.
○ If the particles were at rest and occupied fixed positions, then a gas would have had
a fixed shape which is not observed.
● Particles of a gas move in all possible directions in straight lines. During their random
motion, they collide with each other and with the walls of the container.
○ Pressure is exerted by the gas as a result of collision of the particles with the walls
of the container.
● Collisions of gas molecules are perfectly elastic. This means that the total energy of
molecules before and after the collision remains the same. There may be exchange of
energy between colliding molecules, their individual energies may change, but the sum
of their energies remains constant.
○ If there were loss of kinetic energy, the motion of molecules will stop and gases
will settle down. This is contrary to what is actually observed.
● At any particular time, different particles in the gas have different speeds and hence
different kinetic energies.
○ This assumption is reasonable because as the particles collide, we expect their speed
to change. Even if initial speed of all the particles was same, the molecular
collisions will disrupt this uniformity. Consequently, the particles must have
different speeds, which go on changing constantly.
○ It is possible to show that though the individual speeds are changing, the
distribution of speeds remains constant at a particular temperature.
● If a molecule has variable speed, then it must have a variable kinetic energy. Under
these circumstances, we can talk only about average kinetic energy. In kinetic theory it
is assumed that average kinetic energy of the gas molecules is directly proportional to
the absolute temperature.
○ It is seen that on heating a gas at constant volume, the pressure increases. On heating
the gas, kinetic energy of the particles increases and these strike the walls of the
container more frequently thus exerting more pressure.

68
 ● Kinetic theory of gases allows us to derive theoretically, all the gas laws. Calculations
and predictions based on kinetic theory of gases agree very well with the experimental
observations and thus establish the correctness of this model.

➢ BEHAVIOUR OF REAL GASES: DEVIATION FROM IDEAL GAS BEHAVIOUR

● To test how far the relation pV = nRT reproduces the actual pressure - volume -
temperature relationship of gases we plot pV vs p plot of gases –

a plot of pV vs p for real gas and ideal gas constructed from actual data for several
gases at 273 K.
● Two types of curves are seen.
○ In the curves for dihydrogen and helium, as the pressure increases the value of pV
also increases.
○ The second type of plot is seen in the case of other gases like carbon monoxide
and methane. In these plots first there is a negative deviation from ideal
behaviour, the pV value decreases with increase in pressure and reaches to a
minimum value characteristic of a gas. After that pV value starts increasing. The
curve then crosses the line for ideal gas and after that shows positive deviation
continuously.
● We can conclude - Real gases do not follow ideal gas equation perfectly under all
conditions.
● Deviation from ideal behaviour also becomes apparent when pressure vs volume plot
is drawn –

69
 Plot of pressure vs volume for real gas and ideal gas
● At very high pressure the measured volume is more than the calculated volume. At
low pressures, measured and calculated volumes approach each other.
● It is found that real gases do not follow Boyle's law, Charles law and Avogadro law
perfectly under all conditions.
● We find that two assumptions of the kinetic theory do not hold good. These are -
○ There is no force of attraction between the molecules of a gas. If this assumption
is correct, the gas will never liquify. However, we know that gases do liquify
when cooled and compressed. Also, liquids formed are very difficult to compress.
This means that forces of repulsion are powerful enough and prevent squashing of
molecules in tiny volumes.
○ Volume of the molecules of a gas is negligibly small in comparison to the space
occupied by the gas. If this assumption is correct, the pressure vs volume graph of
experimental data (real gas) and that theoretically calculated from Boyle's law
(ideal gas) should coincide.

➢ Van der Waals equation

● Real gases show deviations from ideal gas law because molecules interact with each
other.
● At high pressures molecules of gases are very close to each other. Molecular
interactions start operating. At high pressure, molecules do not strike the walls of the
container with full impact because these are dragged back by other molecules due to
molecular attractive forces. This affects the pressure exerted by the molecules on the
walls of the container.
● Thus, the pressure exerted by the gas is lower than the pressure exerted by the ideal
gas.

Here, a is a constant.

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 ● Repulsive interactions are short-range interactions and are significant when molecules
are almost in contact. This is the situation at high pressure. The repulsive forces cause
the molecules to behave as small but impenetrable spheres.
● The volume occupied by the molecules 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 molecules themselves. Here, b is a
constant.
● Having taken into account the corrections for pressure and volume, we can rewrite
ideal gas equation as -

- It is known as van der Waals equation.

- n is the number of moles of the gas.
- Constants a and b are called van der Waals constants and their value depends on
the characteristic of a gas.
● At very low temperatures, intermolecular forces become significant. As the molecules
travel with low average speed, these can be captured by one another due to attractive
forces.
● Real gases show ideal behaviour when conditions of temperature and pressure are
such that the intermolecular forces are practically negligible. The real gases show
ideal behaviour when pressure approaches zero.

➢ Compressibility factor
● The deviation from ideal behaviour can be measured in terms of compressibility
factor Z, which is the ratio of product pV and nRT. Mathematically -

○ For ideal gas Z = 1 at all temperatures and pressures.

○ For gases which deviate from ideality, the value of Z deviates from unity.

Variation of compressibility factor for some gases

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 ➔ At very low pressures all gases shown have Z ≈1 and behave as ideal gas.
➔ At high pressure all the gases have Z > 1. These are more difficult to compress.
➔ At intermediate pressures, most gases have Z < 1.
● Gases show ideal behaviour when the volume occupied is large so that the volume of
the molecules can be neglected in comparison to it.
● The temperature at which a real gas obeys ideal gas law over an appreciable range of
pressure is called Boyle temperature or Boyle point.
○ The Boyle point of a gas depends upon its nature.
○ Above their Boyle point, real gases show positive deviations from ideality and Z
values are greater than one. The forces of attraction between the molecules are very
feeble.
○ Below Boyle temperature real gases first show decrease in Z value with increasing
pressure, which reaches a minimum value. On further increase in pressure, the value
of Z increases continuously.
● Significance of Z -

From this equation we can see that 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.
➢ LIQUEFACTION OF GASES
● Liquids may be considered as continuation of the gas phase into a region of small
volumes and very high molecular attraction.
● First complete data on pressure - volume - temperature relations of a substance in both
gaseous and liquid state was obtained by Thomas Andrews on carbon dioxide.
● He plotted isotherms of carbon dioxide at various temperatures –

Isotherms of carbon dioxide at various temperatures

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➢ Observations -
● At high temperatures isotherms look like that of an ideal gas and the gas cannot be
liquified even at very high pressure.
● At 30.98°C carbon dioxide remains gas upto 73 atmospheric pressure. At 73
atmospheric pressure, liquid carbon dioxide appears for the first time. The temperature
30.98°C is called critical temperature (TC) of carbon dioxide.
○ Critical temperature (TC) is the highest temperature at which liquid state of
substance is observed. Above this temperature it is gas.
○ Volume of one mole of the gas at critical temperature is called critical volume (VC)
and pressure at this temperature is called critical pressure (pC).
○ The critical temperature, pressure and volume are called critical constants.
● Further increase in pressure above 73 atm at 30.98°C simply compresses the liquid
carbon dioxide and the curve represents the compressibility of the liquid. The steep line
represents the isotherm of liquid. Even a slight compression results in a steep rise in
pressure indicating very low compressibility of the liquid.
● Below 30.98 °C, the behaviour of the gas on compression is quite different -
○ At 21.5 °C, carbon dioxide remains as a gas only upto point B. At point B, liquid
of a particular volume appears. Further compression does not change the pressure.
Liquid and gaseous carbon dioxide coexist and further application of pressure
results in the condensation of more gas until the point C is reached. At point C, all
the gas has been condensed and further application of pressure merely compresses
the liquid as shown by the steep line. A slight compression from volume V2 to V3
results in steep rise in pressure from p2 to p3.
● A point under the dome-shaped area represents the existence of liquid and gaseous
carbon dioxide in equilibrium.

➢ Conclusions -
● Gases should be cooled below their critical temperature for liquefaction. Critical
temperature of a gas is the highest temperature at which liquefaction of the gas first
occurs.
● Liquefaction of permanent gases (i.e., gases which show continuous positive deviation
in Z value) requires cooling as well as considerable compression.
○ Compression brings the molecules in close vicinity and cooling slows down the
movement of molecules therefore, intermolecular interactions may hold the closely
and slowly moving molecules together and the gas liquifies.
● There is continuity between the gaseous and liquid state. The term fluid is used for
either a liquid or a gas to recognise this continuity.
● a liquid can be viewed as a very dense gas.
● Liquid and gas can be distinguished only when the fluid is below its critical temperature
and its pressure and volume lie under the dome, since in that situation liquid and gas
are in equilibrium and a surface separating the two phases is visible.In the absence of
this surface there is no fundamental way of distinguishing between two states.
● At critical temperature, liquid passes into gaseous state imperceptibly and continuously;
the surface separating two phases disappears.
● A gas below the critical temperature can be liquified by applying pressure, and is
called vapour of the substance.

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 ● Critical constants for some common substances are given in Table

➢ LIQUID STATE
● Liquids have definite volume because molecules do not separate from each other.
● However, molecules of liquids can move past one another freely, therefore, liquids can
flow, can be poured and can assume the shape of the container in which these are stored.

➢ Vapour Pressure
● If an evacuated container is partially filled with a liquid -
○ Initially the liquid evaporates and pressure exerted by vapours on the walls of the
container (vapour pressure) increases.
○ After some time it becomes constant, an equilibrium is established between liquid
phase and vapour phase.
● Vapour pressure at equilibrium stage is known as equilibrium vapour pressure or
saturated vapour pressure.
● Process of vapourisation is temperature dependent; the temperature must be mentioned
while reporting the vapour pressure of a liquid.
● The temperature at which vapour pressure of liquid is equal to the external pressure is
called boiling temperature at that pressure.
● At 1 atm pressure boiling temperature is called normal boiling point. If pressure is 1
bar then the boiling point is called the standard boiling point of the liquid.
● Standard boiling point of the liquid is slightly lower than the normal boiling point
because 1 bar pressure is slightly less than 1 atm pressure.
○ The normal boiling point of water is 100°C (373 K), its standard boiling point is
99.6°C (372.6 K)
● At high altitudes atmospheric pressure is low. Therefore liquids at high altitudes boil at
lower temperatures in comparison to that at sea level. Since water boils at low
temperature on hills, the pressure cooker is used for cooking food.
● 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 covering the vent.
● Boiling does not occur when liquid is heated in a closed vessel. As the temperature
increases more and more molecules go to the vapour phase and the density of vapours
rises. At the same time liquid becomes less dense. It expands because molecules move
apart.
● When the density of liquid and vapours becomes the same; the clear boundary between
liquid and vapours disappears. This temperature is called critical temperature.

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➢ Surface Tension
● Observed phenomena -
○ drops of mercury form spherical bead instead of spreading on the surface.
○ particles of soil at the bottom of the river remain separated but they stick together
when taken out.
○ a liquid rises (or falls) in a thin capillary as soon as the capillary touches the surface
of the liquid.
● A molecule in the bulk of liquid experiences equal intermolecular forces from all sides.
The molecule, therefore, does not experience any net force.
● For the molecule on the surface of liquid, net attractive force is towards the interior of
the liquid, due to the molecules below it. Since there are no molecules above it.

● Liquids tend to minimize their surface area. The molecules on the surface experience a
net downward force and have more energy than the molecules in the bulk. Therefore,
liquids tend to have a minimum number of molecules at their surface.
● If the surface of the liquid is increased by pulling a molecule from the bulk, attractive
forces will have to be overcome. This will require expenditure of energy.
● The energy required to increase the surface area of the liquid by one unit is defined as
surface energy. Its dimensions are J m–2.
● Surface tension is defined as the force acting per unit length perpendicular to the line
drawn on the surface of liquid.
○ It is denoted by the Greek letter γ (Gamma).
○ It has dimensions of kg s–2 and in SI units it is expressed as N m–1.
● The lowest energy state of the liquid will be when surface area is minimum. Spherical
shape satisfies this condition, that is why mercury drops are spherical in shape.
○ This is the reason that sharp glass edges are heated to make them smooth. On
heating, the glass melts and the surface of the liquid tends to take the rounded shape
at the edges, which makes the edges smooth. This is called fire polishing of glass.
● Liquids wet the things because they spread across their surfaces as thin film.
● Moist soil grains are pulled together because the surface area of the thin film of water
is reduced.

75
 ● Surface tension gives stretching properties to the surface of a liquid. On a flat surface,
droplets are slightly flattened by the effect of gravity; but in the gravity free
environments drops are perfectly spherical.
● The magnitude of surface tension of a liquid depends on the attractive forces between
the molecules.
○ When the attractive forces are large, the surface tension is large.
○ Increase in temperature increases the kinetic energy of the molecules and
effectiveness of intermolecular attraction decreases, so surface tension decreases as
the temperature is raised.

➢ Viscosity
● Viscosity is a measure of resistance to flow which arises due to the internal friction
between layers of fluid as they slip past one another while liquid flows.
● When a liquid flows over a fixed surface, the layer of molecules in the immediate
contact of the surface is stationary.
● The velocity of upper layers increases as the distance of layers from the fixed layer
increases. This type of flow in which there is a regular gradation of velocity in passing
from one layer to the next is called laminar flow.
● If we choose any layer in the flowing liquid, the layer above it accelerates its flow and
the layer below this retards its flow.

● If the velocity of the layer at a distance dz is changed by a value du then velocity

gradient is given by the amount (du/dz).
● A force is required to maintain the flow of layers. This force is proportional to the
area of contact of layers and velocity gradient i.e.

- ‘η’ is proportionality constant and is called coefficient of viscosity.

- (du/dz) is velocity gradient; the change in velocity with distance.
- A is the area of contact.
● Viscosity coefficient is the force when velocity gradient is unity and the area of contact
is unit area. Thus ‘η’ is a measure of viscosity.
● SI unit of viscosity coefficient is 1 newton second per square metre (N s m–2) = pascal
second (Pa s = 1 kg m–1s–1).
● In cgs system the unit of coefficient of viscosity is poise (named after great scientist
Jean Louise Poiseuille).
1 poise = 1 g cm–1s–1 = 10–1 kg m–1s–1
● Greater the viscosity, the more slowly the liquid flows.
● Hydrogen bonding and van der Waals forces are strong enough to cause high viscosity.

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● Glass is an extremely viscous liquid. It is so viscous that many of its properties resemble
solids
○ The flow of glass can be experienced by measuring the thickness of window panes
of old buildings. These become thicker at the bottom than at the top.
● Viscosity of liquids decreases as the temperature rises because at high temperature
molecules have high kinetic energy and can overcome the intermolecular forces to slip
past one another between the layers.

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 Thermodynamics

⮚ Chemical energy stored by molecules is

● Released as heat during chemical reactions when a fuel like methane, cooking gas or
coal burns.
● Used to do mechanical work when a fuel burns in an engine
● Used to provide electrical energy through a galvanic cell
⮚ The study of these energy transformations forms the subject matter of thermodynamics.
⮚ Laws of thermodynamics
● Deal with energy changes of macroscopic systems involving a large number of
molecules
● Doesnt deal in how and the rate of energy transformations
● Is based on initial and final states of a system undergoing the change
● Apply only when a system is in equilibrium or moves from one equilibrium state to
another equilibrium state.
⮚ System is part of the universe in which observations are made.
⮚ Remaining universe constitutes the surroundings.
⮚ The universe = The system + The surroundings.
⮚ Practically surroundings are that part which can interact with the system.

⮚ The wall that separates the system from the surroundings is called boundary. It can be real
or imaginary.
⮚ At boundary energy and matter exchange occurs.
⮚ Types of the System
● The open System exchanges energy and matter both with the surrounding. The presence
of reactants in an open beaker is an example of an open system.

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 ● Closed System exchanges only energy with the surroundings. The presence of reactants
in a closed vessel made of conducting material e.g., copper or steel is an example of a
closed system.

● In an isolated system, there is no exchange of energy or matter. The presence of

reactants in a thermos flask or any other closed insulated vessel is an example of an
isolated system.

⮚ The state of a thermodynamic system is described by its measurable or macroscopic (bulk)

properties.
⮚ State variables or state functions depend only on the state of the system and not on how it
is reached.
⮚ State of the surroundings can never be completely specified.
⮚ To define the state all properties are not necessary - only a certain number of properties can
be varied independently and the number depends on the nature of the system.
⮚ Internal Energy represents the total energy of the system.
● It may be chemical, electrical, mechanical or any other type of energy.

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⮚ Internal energy, U, may change, when
● Heat passes into or out of the system,
● Work is done on or by the system,
● Matter enters or leaves the system.
⮚ Internal energy, U, of the system is a state function.
⮚ Types of processes:
● Isothermal process: T = Constant
dT = 0
∆T = 0
● Isochoric process: V = Constant
dV = 0
∆V = 0
● Isobaric process: P = Constant
dP = 0
∆P = 0
● Adiabatic process: q = 0
Heat exchange with the surrounding = 0 (zero)

⮚ J. P. Joule was able to show that a given amount of work done on the system, no matter
how it was done (irrespective of path) produced the same change of state
⮚ Work is positive when work is done on the system.
⮚ Work done by the system will be negative.
⮚ Exchange of energy, which is a result of temperature difference is called heat, q
● q is positive, when heat is transferred from the surroundings to the system
● q is negative when heat is transferred from system to the surroundings
⮚ ∆U = q + w is mathematical statement of the first law of thermodynamics
● It states that energy of an isolated system is constant.
● Also known as the law of conservation of energy
⮚ Absolute value of thermodynamic property energy eg. U cannot be defined

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 ● Only the changes in the internal energy, ∆U of the system is defined
⮚ Thermodynamic work consider only mechanical work i.e., P-V work

● Work done when compressed by constant Pex (in single step) is equal to the shaded area
w = force × distance = Pex . A .l
= Pex . (–∆V) = – Pex ∆V = – Pex (Vf – Vi)
● The negative sign of this expression is required to obtain conventional sign for w
● If the pressure changes in number of finite steps work will be summed over all the steps
i.e − ∑ p V∆

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 ● If the pressure changes such that it is always infinitesimally greater than the pressure
of the gas

pV-plot when pressure is not constant and changes in infinite steps (reversible conditions)
during compression from initial volume, Vi to final volume, Vf . Work done on the gas is
represented by the shaded area.
⮚ A process or change is said to be reversible
● If a change is brought out in such a way that the process could, at any moment, be
reversed by an infinitesimal change.
● If the process proceeds infinitely slowly by a series of equilibrium states.
● System and the surroundings are always in near equilibrium with each other.
⮚ Processes other than reversible processes are known as irreversible processes.
⮚ We can relate work to internal pressure of the system under reversible conditions
Vf

Wrev = −  pin dV
Vt

⇒ p = nRT/V
At constant temperature, Wrev = – 2.303 nRT log (Vf/Vi)
⮚ Free expansion: Expansion of a gas in vacuum (pex = 0) is called free expansion.
● No work is done during free expansion of an ideal gas whether the process is
reversible or irreversible.
⮚ ∆U =q − pex ∆V
If (∆V = 0), then,∆U = qV
subscript V in qV denotes that heat is supplied at constant volume.
⮚ Isothermal and free expansion of an ideal gas
● W = 0 as Pex = 0
● q = 0 as joules calculated
● ∆U=0

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⮚ Applying ∆U = q + w
● Isothermal irreversible: ∆U = 0, q = –w = pex (Vf – Vi)
● Isothermal reversible: ∆U = 0, q = –w = – 2.303 nRT log (Vf/Vi)
● Adiabatic change: q = 0, ∆U = Wad
⮚ Enthalpy (H, greek word meaning heat content)
● When the system is under conditions of constant pressure, the energy of the system is
called enthalpy.
● H = U + pV
● ∆H = ∆U + P∆V
● p ∆V = ∆ng RT (∆ng refers to the number of moles of gaseous products minus the
number of moles of gaseous reactants)
● ∆H = ∆U + ∆ngRT
● ∆H = Qp, heat exchanged at constant pressure
● ∆H = –ve (exothermic reaction
● ∆H = +ve (endothermic reaction)
⮚ Extensive property depends on the quantity or size of matter present in the system.
● Example: m, V, U, H, heat capacity(C), etc.
⮚ Properties which do not depend on quantity or size of matter are known as intensive
properties.example temperature, density, pressure etc.

● Molar property is an extensive property. examples: molar volume, Vm and molar heat
capacity, Cm.
⮚ Heat Capacity(C) is the quantity of heat needed to raise the temperature of system by one
degree celsius.
● q = C × ∆T
● A large heat capacity means a lot of energy is needed to raise its temperature.
⮚ The molar heat capacity (Cm) = C/ n
● Is the heat capacity for one mole of the substance .
● Is the quantity of heat needed to raise the temperature of one mole by one degree
celsius
● q = nCm∆T

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⮚ Specific heat, also called specific heat capacity (S) = C/m
● Is the quantity of heat required to raise temperature of unit mass of substance by one
degree celsius
● q = mS∆T
⮚ Cp – CV = R (both are molar heat capacity)
⮚ ∆H and ∆U are measured in coffee cup calorimeter (constant pressure condition) and
bomb calorimeter (constant volume condition) respectively.

⮚ First law of thermodynamics is about the relationship between heat absorbed and work
done on or by a system.
● It puts no restrictions on the direction of heat flow
● Flow of heat is unidirectional from higher T to lower T
● All natural processes will proceed spontaneously in one direction only.
● Example, a gas expanding to fill the available volume
● Example, burning carbon in oxygen gives carbon dioxide.
⮚ A spontaneous process is an irreversible process and may only be reversed by some
external agency.
⮚ Enthalpy as Criterion for Spontaneity
● Phenomenon like flow of water downhill or fall of a stone on to the ground (both
spontaneous process)
● There is a net decrease in potential energy.
● By analogy, we may state a chemical reaction is spontaneous in exothermic direction,
because decrease in energy takes place.

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 Enthalpy diagram for exothermic reactions

⮚ But endothermic reactions are also spontaneous

⮚ Therefore decrease in enthalpy may be a contributory factor for spontaneity, but it is not
true for all cases.
● A case in which ∆H = 0, but still the process is spontaneous
● Example diffusion of two gases into each other in a closed isolated container

● In isolated systems, there is always a tendency for the system's energy to become
more disordered or chaotic and this could be a criterion for spontaneous change!

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⮚ Entropy denoted as S, is a measure of the degree of randomness or disorder in the system
● Greater the disorder in an isolated system, the higher is the entropy
● For chemical reaction, this entropy change is due to rearrangement of atoms or ions
from one pattern (in the reactants) to another (in the products)
● Decrease of regularity in structure would mean increase in entropy
● The crystalline solid state is the state of lowest entropy (most ordered)
● Gaseous state is state of highest entropy
● Entropy is a state function and ∆S is independent of path.
● Heat (q) has randomising influence on the system as it increases molecular motions
● ∆S is directly proportional to q
● Distribution of heat also depends on the temperature at which heat is added to the
system.
● Heat added at lower temperature causes greater randomness than same quantity of
heat added at higher temperature
● ∆S is inversely proportional to the temperature
● ∆S = qrev /T (6.18)
⮚ The total entropy change ( ∆Stotal) for the system and surroundings of a spontaneous
process is given by ∆Stot=∆Ssys+∆Ssurr >0.
⮚ For a system in equilibrium, the entropy is maximum, and the change in entropy, ∆S = 0
● Entropy for spontaneous process increases till it reaches maximum
● At equilibrium the change in entropy is zero
⮚ For reversible and irreversible expansion for an ideal gas, under isothermal conditions
● ∆U = 0
● But ∆Stotal is not zero for irreversible processes.
● ∆U does not discriminate between reversible and irreversible processes, whereas ∆S
does.
⮚ Neither decrease in enthalpy nor increase in entropy alone can determine the direction of
spontaneous change for systems.
● Hence New thermodynamic function the Gibbs energy or Gibbs function, G, is
defined.
⮚ G = H – TS
● Gibbs function, G is an extensive property and a state function
● At constant temp(isothermal) ∆Gsys= ∆Hsys – T∆Ssys
● ∆Gsys= –T∆Stotal
● ∆G gives a criteria for spontaneity at constant pressure and temperature.
● If ∆G is negative (< 0), the process is spontaneous.
● If ∆G is positive (> 0), the process is non spontaneous.
⮚ Second law of thermodynamics states that an increase in entropy of isolated systems is
the natural direction of a spontaneous change.

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⮚ The entropy of any pure crystalline substance approaches zero as the temperature
approaches absolute zero. This is called the third law of thermodynamics.
● Because there is perfect order in a crystal at absolute zero
● Theoretical arguments and practical evidences have shown that entropy of solutions
and supercooled liquids is not zero at 0 K
● It permits the calculation of absolute values of entropy of pure substance from thermal
data alone
● Standard entropies can be used to calculate standard entropy changes by a Hess’s law
type of calculation
⮚ Free energy change (∆G) of a chemical reaction allows:
i. Prediction of the spontaneity of the chemical reaction.
ii. Prediction of the useful work that could be extracted from it.
⮚ The criterion for equilibrium
A + B ⇌ C + D;
is ∆rG = 0
∆rG0 = – RT ln K or ∆rG0 = – 2.303 RT log K
⮚ For strongly endothermic reactions,
● ∆rH0 may be large and positive.
● Value of K will be much smaller than 1
● and the reaction is unlikely to form much product.
⮚ In case of exothermic reactions,
● ∆rH0 is large and negative,
● and ∆rG0 is likely to be large and negative too.
● K will be much larger than 1
⮚ Effect of Temperature on Spontaneity of Reactions

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 Equilibrium

• Equilibria involving O2 molecules, and the protein hemoglobin play a crucial role in the
transport and delivery of O2 from our lungs to our muscles. Similar equilibria involving
CO molecules and hemoglobin account for the toxicity of CO.

• Chemical equilibrium relates to such a state when the reactants, as well as products, will
no longer undergo any further change. In such a case, the rate of forward and backward
reaction remains the same.

• Types of chemical reactions based on extent to which it proceeds -

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

• Solid-Liquid Equilibrium
o Ice and water kept in a perfectly insulated thermos flask at 273 K and the
atmospheric pressure are in equilibrium state.
o The mass of ice and water do not change with time and the temperature remains
constant.
o Equilibrium is dynamic. The intense activity can be noticed at the boundary
between ice and water.
o Molecules from the liquid water collide against ice and adhere to it and some
molecules of ice escape into liquid phase. There is no change of mass of ice and
water, as the rates of transfer of molecules from ice into water and of reverse
transfer from water into ice are equal at atmospheric pressure and 273 K.
o 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
o The rate of evaporation is constant.
o The rate of increase in vapour pressure decreases with time due to condensation of
vapour into water.
o The equilibrium is attained when rate of evaporation= rate of condensation.
o At equilibrium the pressure exerted by the water molecules at a given temperature
remains constant and is called the equilibrium vapour pressure of water (or just
vapour pressure of water).
o Vapour pressure of water increases with temperature.

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 o The liquid which has a higher vapour pressure is more volatile and has a lower
boiling point.
o Time taken for complete evaporation of a volatile liquid depends on (i) the nature
of the liquid, (ii) the amount of the liquid and (iii) the temperature.
o It is not possible to reach equilibrium in an open system.
o For any pure liquid at one atmospheric pressure (1.013 bar), the temperature at
which the liquid and vapours are at equilibrium is called normal boiling point of the
liquid.
o Boiling point of the liquid depends on the atmospheric pressure. It depends on the
altitude of the place, at high altitude the boiling point decreases.
• Solid – Vapour Equilibrium
o Colour of solid iodine – Violet. If we place solid iodine in a closed vessel, after
some time 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.
o Solid iodine sublimes to give iodine vapour and the iodine vapour condenses to
give solid iodine.
• Equilibrium Involving Dissolution of Solid in Liquids
o If we make a thick sugar syrup solution by dissolving sugar at a higher temperature,
sugar crystals separate out if we cool the syrup to the room temperature.
o A saturated solution is when no more of solute can be dissolved in it at a given
temperature.
o The concentration of the solute in a saturated solution depends upon the
temperature.
o In a saturated solution, a dynamic equilibrium exits between the solute molecules
in the solid state and in the solution.
o If we drop some radioactive sugar into saturated solution of non-radioactive sugar,
then after some time radioactivity is observed both in the solution and in the solid
sugar. The ratio of the radioactive to non-radioactive molecules in the solution
increases till it attains a constant value.
• Equilibrium Involving Dissolution of Gases in Liquids
o Henry’s law: 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.
o Solubility of gas in liquid decreases with increasing temperature.
o 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. This is how the soda water in bottle
when left open to the air for some time, turns ‘flat’.
• General Characteristics of Equilibria Involving Physical Processes
o Equilibrium is possible only in a closed system at a given temperature.
o Both the opposing processes occur at the same rate and there is a dynamic but stable
condition.

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 o All measurable properties of the system remain constant.
o When equilibrium is attained for a physical process, it is characterised by constant
value of one of its parameters at a given temperature.

o The magnitude of such quantities at any stage indicates the extent to which the
physical process has proceeded before reaching equilibrium.

➢ Equilibrium in Chemical Processes – Dynamic Equilibrium

● Reversible reaction - These reactions can occur both in forward and backward
directions.
A+B C+D
● When the rates of the forward and reverse reactions become equal, the concentrations
of the reactants and the products remain constant. This is the stage of chemical
equilibrium.

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 • Chemical reactions reach a state of dynamic equilibrium in which the rates of forward
and reverse reactions are equal and there is no net change in composition.
• If we mix two separate mixture having two different equilibriums achieved -
N 2 + 3H 2 2 NH 3 and N 2 + 3D2 2 ND3 , we find that at equilibrium
ammonia and all deuterium containing forms of ammonia (NH3, NH2D, NHD2 and
ND3) and dihydrogen and its deutrated forms (H2, HD and D2) are present. Thus proves
the dynamic nature of chemical equilirbium.
• Equilibrium can be attained from both sides.

➢ Law of Chemical Equilibrium and Equilibrium Constant

● Based on experimental studies of many reversible reactions, the Norwegian chemists
Cato Maximillian Guldberg and Peter Waage proposed law of mass action in 1864.
● In the early days of chemistry, concentration was called “active mass”.
● Equilibrium Law or Law of Chemical Equilibrium - 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.
The equilibrium constant for a general reaction,
a A + b B ⇌ c C + d D is expressed as,
Kc = [C]c [D]d / [A]a [B]b
where [A], [B], [C] and [D] are the equilibrium concentrations of the reactants and
products and Kc is the equilibrium constant. The subscript ‘c’ indicates that Kc is
expressed in concentrations of mol L–1.
● Equilibrium constant for the reverse reaction is the inverse of the equilibrium constant
for the reaction in the forward direction.

91
 H 2 (g) + I 2 (g) 2HI(g)
K c = [HI] / [H 2 ][I 2 ]
2

The equilibrium constant for the reverse reaction,

2HI(g) ⇌ H2 (g) + I2 (g), at the same temperature is,
K′ c = [H2] [I2] / [HI]2 Thus, K′c = 1/Kc
● If we change the stoichiometric coefficients in a chemical equation by multiplying
throughout by a factor, than equilibrium constant must be raised by the same power as
the multiplying factor.
1 H (g) + 1 I (g) HI(g)
2 2 2 2

The equilibrium constant for the above reaction is given by

➢ Homogeneous Equilibria
In a homogeneous system, all the reactants and products are in the same phase. Examples–
• N2 ( g ) + 3H 2 ( g ) 2 NH3 ( g )
• CH3COOC2 H5 ( aq ) + H 2O ( l ) CH 3COOH ( aq ) + C2 H 5OH ( aq )
Fe3+ ( aq ) + SCN − ( aq ) Fe ( SCN ) ( aq )
2+
•
➢ Equilibrium Constant in Gaseous Systems
• For reactions involving gases, equilibrium constant is expressed in terms of partial
pressure.
• If concentration c, is in mol/L or mol/dm3, and p is in bar then p = cRT (R = 0.0831
bar-L/mol-K)
• At constant temperature, the pressure of the gas is proportional to its concentration i.e.,
p ∝ [gas]
• For a general reaction
aA + bB cC + dD

Kp =
( p )( p ) C   D  ( RT )(
c
C
=
d
D
c d c+d )

( p )( p )  A  B ( RT )(
a
A
b
B
a b a +b )

C   D RT (c+d )−( a+b)

c d

b ( )
=
 A  B
a

 C   D
c d

b (
RT ) = K c ( RT )
n n
=
 A  B
a

92
 where ∆n = (number of moles of gaseous products) – (number of moles of gaseous
reactants) in the balanced chemical equation.
• It is necessary that while calculating the value of Kp, pressure should be expressed in
bar because standard state for pressure is 1 bar.
• 1 pascal, Pa=1 Nm–2, and 1 bar = 105 Pa.

➢ Heterogeneous Equilibria
• Equilibrium in a system having more than one phase is called heterogeneous
equilibrium.
• Examples
o The equilibrium between water vapour and liquid water in a closed container –
H 2O ( l ) H 2O ( g )
o Equilibrium between a solid and its saturated solution –
Ca ( OH )2 ( s ) + ( aq ) Ca2+ ( aq ) +2OH – ( aq )
• The molar concentration of a pure solid or liquid is constant (i.e., independent of the
amount present).
• It must be remembered that for the existence of heterogeneous equilibrium pure solids
or liquids must also be present (however small the amount may be) at equilibrium, but
their concentrations or partial pressures do not appear in the expression of the
equilibrium constant. For example – for the reaction
Ni ( s ) + 4CO ( g ) Ni ( CO )4 ( g ) , both Ni and CO must be present initially for
attainment of equilibrium, but Ni doesn’t appear in equilibrium constant expression.
 Ni ( CO )4 
Kc = 
CO 
➢ Summary of Features of Equilibrium constant
• Expression for equilibrium constant is applicable only when concentrations of the
reactants and products have attained constant value at equilibrium state.
• The value of equilibrium constant is independent of initial concentrations of the
reactants and products.

93
 • Equilibrium constant is temperature dependent having one unique value for a particular
reaction represented by a balanced equation at a given temperature.
• The equilibrium constant for the reverse reaction is equal to the inverse of the
equilibrium constant for the forward reaction.
• 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

1. Predict the extent of a reaction based on its magnitude –
• An equilibrium constant does not give any information about the rate at which the
equilibrium is reached.
• A high value of K is suggestive of a high concentration of products and vice-versa.
• If Kc > 103, products predominate over reactants, i.e., if Kc is very large, the reaction
proceeds nearly to completion. Examples of such reactions –
o 2H 2 + O2 ⎯⎯⎯
500 K
→ 2H 2O
o H 2 + Cl2 ⎯⎯⎯
300 K
→ 2HCl
o H 2 + Br2 ⎯⎯⎯
300 K
→ 2HBr
• If Kc < 10–3, reactants predominate over products, i.e., if Kc is very small, the
reaction proceeds rarely. Examples of such reactions –
o The decomposition of H2O into H2 and O2 at 500 K.
o N2 ( g ) + O2 ( g ) 2 NO ( g )  At 298 K 
• If Kc is in the range of 10–3 to 103, appreciable concentrations of both reactants and
products are present. Examples –
o H2 ( g ) + I2 ( g ) 2HI ( g )  At 700 K 
o N2O4 ( g ) 2 NO2 ( g )  At 298 K 

2. Predict the direction of the reaction

For a general reaction: aA + bB cC + dD
C   D 
c d

Qc =
 A  B
a b

94
 Where Q is the reaction quotient (Qc with molar concentrations and QP with partial
pressures) is defined in the same way as the equilibrium constant Kc except that the
concentrations in Qc are not necessarily equilibrium values.

● If Qc < Kc, net reaction goes from left to right

● If Qc > Kc, net reaction goes from right to left.
● If Qc = Kc, no net reaction occurs.

3. Calculate 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 steps shall be followed:
o Step 1. Write the balanced equation for the reaction.
o Step 2. Under the balanced equation, make a table that lists for each substance
involved in the reaction:
(a) the initial concentration
(b) the change in concentration on going to equilibrium, and
(c) the equilibrium concentration
o Step 3. Substitute the equilibrium concentrations into the equilibrium equation
for the reaction and solve for x.
o Step 4. Calculate the equilibrium concentrations from the calculated value of x.
o 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 = G + RT ln Q
−G
• At equilibrium - ∆G = 0 and Q = Kc, G = −RT lnK or K = e RT

• If G  0  K  1  a spontaneous reaction or the reaction which proceeds in

the forward direction to such an extent that the products are present predominantly.
• If G  0  K  1  a non-spontaneous reaction or a reaction which proceeds
in the forward direction to such a small degree that only a very minute quantity of
product is formed.

95
➢ Factors Affecting Equilibria
• One of the principal goals of chemical synthesis is to maximise the conversion of the
reactants to products while minimizing the expenditure of energy. This implies
maximum yield of products at mild temperature and pressure conditions.
• Annual world production of ammonia is about hundred million tonnes, primarily for
use as fertilizers.
• To decide what course the reaction adopts and make a qualitative prediction about the
effect of a change in conditions on equilibrium we use Le Chatelier’s principle.
• Le Chatelier’s principle: It 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.
• Le Chatelier’s principle is applicable to all physical and chemical equilibria.

A. Effect of Concentration Change

● The concentration stress of an added reactant/product is relieved by net reaction in
the direction that consumes the added substance.
● The concentration stress of a removed reactant/product is relieved by net reaction in
the direction that replenishes the removed substance.
● In the large-scale production of CaO (used as important building material) from
CaCO3, constant removal of CO2 from the kiln drives the reaction to completion.
2+
● For the reaction - Fe
3+
( aq )+ SCN − ( aq )  Fe ( SCN )  ( aq )
Yellow Colourless deep red

o Oxalic acid (H2C2O4), reacts with Fe3+ ions to form the stable complex ion
[Fe(C2O4)3]3–, thus decreasing the concentration of free Fe3+(aq). Intensity of red
colour decreases.
o Addition of aq. HgCl2 also decreases red colour because Hg2+ reacts with SCN–
ions to form stable complex ion [Hg(SCN)4]2–. Equilibrium shifts right to left.
o Addition of potassium thiocyanate increases the colour intensity of the solution
as it shift the equilibrium to right.

B. Effect of Pressure Change

● 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.
● With increase in pressure the equilibrium shifts in a direction in which the number
of moles of the gas or pressure decreases (we know pressure is proportional to moles
of the gas) and vice versa.

C. Effect of Inert Gas Addition

● At constant volume: the equilibrium remains undisturbed.
● At constant pressure: the equilibrium will shift towards the direction in which there
is increase in number of moles of gases.

96
D. Effect of Temperature Change
• When a change in temperature occurs, the value of equilibrium constant, Kc is
changed.
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.
• Exothermic reactions are favoured by low temperature whereas endothermic
reactions are favoured by high temperature.
• In the reaction - 2 NO2 N2O4 ; H = –57.2 kJ mol –1
o At low temperatures, the forward reaction of formation of N2O4 is preferred, as
reaction is exothermic, and thus, intensity of brown colour due to NO2
decreases.
o High temperature favours the reverse reaction of formation of NO2 and thus, the
brown colour intensifies.
• In the endothermic reaction -
3+
Co ( H 2O )6  ( aq )+ 4Cl − ( aq ) CoCl4  ( aq )+ 6H 2O (l )
2−

pink colourless blue

o At room temperature, the equilibrium mixture is blue due to [CoCl4]2–. When

cooled in a freezing mixture, the colour of the mixture turns pink due to
[Co(H2O)6]3+.

E. Effect of a Catalyst
• A catalyst increases the rate of the chemical reaction by making available a new
low energy pathway for the conversion of reactants to products.
• It increases the rate of forward and reverse reactions that pass through the same
transition state and does not affect equilibrium.
• Catalyst lowers the activation energy for the forward and reverse reactions by
exactly the same amount.
• 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.
• German chemist, Fritz Haber discovered that iron can catalyse the reaction of
formation of ammonia from nitrogen and hydrogen.
• Optimum conditions of temperature and pressure for the synthesis of NH3 using
catalyst are around 500°C and 200 atm.
• In manufacture of sulphuric acid by contact process, platinum or divanadium penta-
oxide (V2O5) is used as catalyst to increase the rate of the reaction.

97
 IONIC EQUILIBRIUM

• Equilibrium involving ions in aqueous solution is called ionic equilibrium.

• Michael Faraday classified the substances into two categories based on their ability to
conduct electricity.
o One category of substances conducts electricity in their aqueous solutions and are
called electrolytes.
o The other do not and are thus, referred to as non-electrolytes.
• Faraday further classified electrolytes into strong and weak electrolytes.
o Strong electrolytes on dissolution in water are ionized almost completely, while the
weak electrolytes are only partially dissociated.
• In weak electrolytes, equilibrium is established between ions and the unionized
molecules.

➢ Acids, Bases and Salts

• Hydrochloric acid present in the gastric juice is secreted by the lining of our stomach
in a significant amount of 1.2-1.5 L/day and is essential for digestive processes.
• Acetic acid is known to be the main constituent of vinegar.
• Lemon and orange juices contain citric and ascorbic acid.
• Tartaric acid is found in tamarind paste.
• The word “acid” has been derived from a latin word “acidus” meaning sour.
• A common example of a base is washing soda used for washing purposes.
• When acids and bases are mixed in the right proportion, they react with each other to
give salts.
• Sodium chloride (common salt) is an important component of our diet and is formed
by reaction between hydrochloric acid and sodium hydroxide.
• Sodium chloride exists in solid state as a cluster of positively charged sodium ions and
negatively charged chloride ions which are held together due to electrostatic
interactions between oppositely charged species.
• The electrostatic forces between two charges are inversely proportional to dielectric
constant of the medium. Water, a universal solvent, possesses a very high dielectric
constant of 80. Thus, when sodium chloride is dissolved in water, the electrostatic
interactions are reduced by a factor of 80 and this facilitates the ions to move freely in
the solution. Also, they are well separated due to hydration with water molecules.
• The extent to which ionization occurs depends upon the strength of the bond and the
extent of solvation of ions produced.
• Dissociation refers to the process of separation of ions in water already existing as such
in the solid state of the solute, as in sodium chloride. On the other hand, ionization
corresponds to a process in which a neutral molecule splits into charged ions in the
solution.

98
➢ Arrhenius Concept of Acids and Bases
● Acids: substances that dissociates in water to give hydrogen ions H+

● Bases: substances that dissociates in water to give hydroxyl ions OH–

MOH ( aq ) → M + ( aq ) + OH − ( aq )
● Arrhenius concept of acid and base, however, suffers from the limitation of being
applicable only to aqueous solutions and, does not account for the basicity of substances
like, ammonia which do not possess a hydroxyl group.
● 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 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.

➢ The Brönsted-Lowry Acids and Bases (by Johannes Brönsted and Thomas M. Lowry)
● Acids: substances that are capable of donating a hydrogen ion H+.
● Bases: substances capable of accepting a hydrogen ion, H+.

● The acid-base pair that differs only by one proton is called a conjugate acid-base pair.
● If Brönsted acid is a strong acid then its conjugate base is a weak base and vice-versa.
● 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.

99
➢ Lewis Acids and Bases (by G.N. Lewis)
● Acids: species which accepts electron pair. Eg. BF3, AlCl3 , Co3+ , Mg2+, etc.
● Bases: species which donates an electron pair. Eg. H2O, NH3 , OH– etc.
● As far as bases are concerned, there is not much difference between Brönsted-Lowry
and Lewis concepts, as the base provides a lone pair in both the cases.
● In Lewis concept many acids do not have proton.

➢ Ionization of Acids And Bases

● According to Arrhenius concept they are strong acids and bases as they are able to
completely dissociate and produce H3O+ and OH– ions respectively in the medium.
● In terms of Brönsted-Lowry concept of acids and bases, a strong acid means a good
proton donor and a strong base implies a good proton acceptor.
● The equilibrium moves in the direction of formation of weaker acid and weaker base
because the stronger acid donates a proton to the stronger base.
● Strong acids have very weak conjugate bases. Similarly, a very strong base would give
a very weak conjugate acid.
o Strong acids like perchloric acid (HClO4), hydrochloric acid (HCl), hydrobromic
acid (HBr), hydroiodic acid (HI), nitric acid (HNO3) and sulphuric acid (H2SO4)
will give conjugate base ions ClO4–, Cl–, Br–, I–, NO3– and HSO4, which are much
weaker bases than H2O.
o Examples of weak acids are nitrous acid (HNO2), hydrofluoric acid (HF) and acetic
acid (CH3COOH). It should be noted that the weak acids have very strong conjugate
bases. For example, NH2–, O2– and H– are very good proton acceptors and thus,
much stronger bases than H2O.
• Certain water-soluble organic compounds like phenolphthalein and bromothymol blue
behave as weak acids and exhibit different colours in their acid (HIn) and conjugate
base (In–) forms.
HIn ( aq ) + H 2O ( l ) H 3O + ( aq ) + In − ( aq )
Such compounds are useful as indicators in acid-base titrations and finding out H+ ion
concentration.

➢ The Ionization Constant of Water and its Ionic Product

• In pure water, one H2O molecule donates proton and acts as an acid and another water
molecules accepts a proton and acts as a base at the same time. The following
equilibrium exists:
H 2O ( l ) + H 2O ( l ) H 3O + ( aq ) + OH − ( aq )
 H 3O +  OH − 
Dissociation constant:
 H 2O 
• Ionic product of water, Kw =  H +  OH – 
• The concentration of H+ has been found out experimentally as 1.0 × 10–7 M at 298 K.
• The value of Kw at 298 K = 10–14 M2.

100
 • The density of pure water is 1000 g / L and its molar mass is 18.0 g /mol. From this the
ratio of dissociated water to that of undissociated water can be given as
10−7
= 1.8  10−9
55.5
• Acidic solution: [H3O+] > [OH–]
Neutral solution: [H3O+] = [OH–]
Basic solution: [H3O+] < [OH–]

➢ The pH Scale
 H + 
• pH = − log10 ( aH + ) = − log10
mol L–1
• In dilute solutions (< 0.01 M), activity of hydrogen ion (H+) is equal in magnitude to
molarity represented by [H+].
 H + 
• Activity has no units and is defined as: ( aH + ) =
mol L–1
• At 25 °C –
o The pH of pure water is 7.
o Acidic solution has pH < 7
o Basic solution has pH > 7
o Neutral solution has pH = 7
• pKw = pH + pOH = 14
• Although Kw may change with temperature the variations in pH with temperature are
so small that we often ignore it.
• Change in pH by just one unit also means change in [H+] by a factor of 10.
• 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 pH paper is available with four strips
on it. The different strips have different colours at the same pH. The pH in the range of
1-14 can be determined with an accuracy of ~0.5 using pH paper.

• For greater accuracy pH meters are used. pH meter is a device that measures the pH-
dependent electrical potential of the test solution within 0.001 precision.

101
➢ Ionization Constants of Weak Acids:
Consider a weak acid HX that is partially ionized in the aqueous solution.
HX ( aq ) + H 2O ( l ) H 3O + ( aq ) + X − ( aq )
 H 3O +   X −  C 2 2 C 2
• Ka = = =
 HX  C (1 −  ) (1 −  )
Ka = dissociation or ionization constant of acid HX
c = initial concentration of the undissociated acid, HX at time, t = 0.
α = extent up to which HX is ionized into ions.
• At a given temperature T, Ka is a measure of the strength of the acid HX i.e., larger the
value of Ka, the stronger is the acid.

• Ka is a dimensionless quantity with the understanding that the standard state

concentration of all species is 1 M.
• pKa = − log ( Ka )

102
➢ Ionization of Weak Bases
The ionization of base MOH can be represented by equation:
MOH(aq) M+ (aq) + OH− (aq)
 M +  OH −  C 2 2 C 2
• Kb = = =
 MOH  C (1 −  ) (1 −  )
Kb = base ionization constant.
c = initial concentration of base
α = degree of ionization of base i.e. the extent to which the base ionizes.

• Many organic compounds like amines are weak bases. For example, methylamine,
codeine, quinine and nicotine all behave as very weak bases due to their very small Kb.
• pKb = – log (Kb)

➢ Relation between Ka and Kb

• Ka and Kb represent the strength of an acid and a base, respectively. In case of a
conjugate acid-base pair, they are related in a simple manner so that if one is known,
the other can be deduced.
Kw = Ka × Kb
pKa + pKb = pKw = 14 (at 298 K)

➢ Di- and Polybasic Acids and Di- and Polyacidic Bases

• Some of the acids like oxalic acid, sulphuric acid and phosphoric acids have more than
one ionizable proton per molecule of the acid. Such acids are known as polybasic or
polyprotic acids.
• The ionization reactions for example for a dibasic acid H2 X are represented by the
equations:

 H +   HX −   H +   X 2− 
K a1 = and K a2 =
H2 X   HX − 

103
 Here, Ka1 and Ka2 are called the first and second ionization constants respectively of
the acid H2X.
• Higher order ionization constants (Ka2, Ka3) are smaller than the lower order ionization
constant (Ka1) of a polyprotic acid. The reason for this is that it is more difficult to
remove a positively charged proton from a negative ion due to electrostatic forces.

➢ Factors Affecting Acid Strength

● The extent of dissociation of an acid depends on the strength and polarity of the H-A
bond.
● When strength of H-A bond decreases, that is, the energy required to break the bond
decreases, HA becomes a stronger acid.
● When the H-A bond becomes more polar, cleavage of the bond becomes easier thereby
increasing the acidity.
● In the same group of the periodic table, H-A bond strength is a more important factor
in determining acidity than its polar nature.

Similarly, H2S is stronger acid than H2O.

● When we discuss elements in the same row of the periodic table, H-A bond polarity
becomes the deciding factor for determining the acid strength.

➢ Common Ion Effect in the Ionization of Acids and Bases

• It can be defined as a shift in equilibrium on adding a substance that provides more of
an ionic species already present in the dissociation equilibrium.

➢ Hydrolysis of Salts and the pH of their Solutions

• Process of interaction between water and cations/anions or both of salts is called
hydrolysis. The pH of the solution gets affected by this interaction.
• The cations (e.g., Na+, K+, Ca2+, Ba2+, etc.) of strong bases and anions (e.g., Cl –, Br–,
NO3–, ClO4– etc.) of strong acids simply get hydrated but do not hydrolyse, and

104
 therefore the solutions of salts formed from strong acids and bases are neutral i.e., their
pH is 7.
• Hydrolysis of the salts of weak acid and strong base (ex. CH3COO–Na+), anion
undergoes hydrolysis in water to give weak acid and OH– ions. This results in increase
of OH– ion concentration in solution making it alkaline. The pH of such a solution is
more than 7.
• Hydrolysis of the salts of strong acid and weak base (ex. NH4+Cl–), cation undergoes
hydrolysis in water to give weak base and H+ ions. This results in increase of H+ ion
concentration in solution making it acidic. The pH of such a solution is less than 7.
• Hydrolysis of the salts of weak acid and weak base (ex. CH3COO–NH4+), both cation
and anion undergoes hydrolysis in water. Degree of hydrolysis is independent of
concentration of solution, and pH of such solutions is determined by their pK values:
1
pH = 7 + ( pKa − pKb )
2

➢ BUFFER SOLUTIONS
• Blood or urine have definite pH and any deviation in their pH indicates malfunctioning
of the body.
• The solutions which resist change in pH on dilution or with the addition of small
amounts of acid or alkali are called Buffer Solutions.
• A mixture of acetic acid and sodium acetate acts as buffer solution around pH 4.75 and
a mixture of ammonium chloride and ammonium hydroxide acts as a buffer around pH
9.25.

➢ SOLUBILITY EQUILIBRIA OF SPARINGLY SOLUBLE SALTS

• Calcium chloride is so soluble that it is hygroscopic in nature and even absorb water
vapour from atmosphere.
• Lithium fluoride has so little solubility that it is termed as insoluble.
• The solubility depends on several factors important amongst which are - the lattice
enthalpy of the salt and the solvation enthalpy of the ions in a solution.
o For a salt to dissolve in a solvent the strong forces of attraction between its ions
(lattice enthalpy) must be overcome by the ion-solvent interactions.
o The solvation enthalpy of ions is referred to in terms of solvation which is always
negative i.e., energy is released in the process of solvation.
o The amount of solvation enthalpy depends on the nature of the solvent. In case of a
non-polar (covalent) solvent, solvation enthalpy is small and hence, not sufficient
to overcome lattice enthalpy of the salt. Consequently, the salt does not dissolve in
non-polar solvent.
o for a salt to be able to dissolve in a particular solvent its solvation enthalpy must be
greater than its lattice enthalpy so that the latter may be overcome by former.
• We classify salts based on their solubility in the following three categories –

105
➢ Solubility Product Constant
A solid salt of the general formula M p+ q–
x X y with molar solubility S in equilibrium with its

saturated solution may be represented by the equation:

M x X y (s) xM p+ ( aq ) + yX q− ( aq )
( where x  p +
= y  q− )
x y ( x+ y )
Here, K sp =  M p +   X q −  = x x . y y .S
• Ksp = Solubility product constant or solubility product
• S = Molar solubility of the salt
• If the concentration in Ksp expression is not at equilibrium, it is called Qsp.

➢ Common Ion Effect on Solubility of Ionic Salts

• If we increase the concentration of any one of the ions, it should combine with the ion
of its opposite charge and some of the salt will be precipitated till once again Ksp = Qsp.
• If the concentration of one of the ions is decreased, more salt will dissolve to increase
the concentration of both the ions till once again Ksp = Qsp.
• If we take a saturated solution of sodium chloride and pass HCl gas through it, then
sodium chloride is precipitated due to increased concentration (activity) of chloride ion
available from the dissociation of HCl. Sodium chloride thus obtained is of very high
purity and we can get rid of impurities like sodium and magnesium sulphates.
• 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. Thus, we can precipitate silver ion as silver chloride, ferric ion as its
hydroxide (or hydrated ferric oxide) and barium ion as its sulphate for quantitative
estimations.
• The solubility of salts of weak acids like phosphates increases at lower pH. This is
because at lower pH the concentration of the anion decreases due to its protonation.
This in turn increase the solubility of the salt so that Ksp = Qsp.

106
 Redox Reactions

● Where there is oxidation, there is always reduction.

● 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 nonmetals, manufacturing of chemical compounds like caustic soda,
operation of dry and wet batteries and corrosion of metals fall within the purview of
redox processes.
● Environmental issues like Hydrogen Economy (use of liquid hydrogen as fuel) and
development of ‘Ozone Hole’ have started figuring under the redox phenomenon.

➢ CLASSICAL IDEA OF REDOX REACTIONS – OXIDATION AND REDUCTION

REACTIONS
● Originally, the term oxidation was used to describe the addition of oxygen to an element
or a compound.
● The following reactions represent oxidation processes according to the limited
definition of oxidation:
○ 2Mg(s) + O2(g) → 2MgO(s)
○ S(s) + O2(g) → SO2(g)
○ CH4 (g) + 2O2 (g) → CO2(g) + 2H2O(l)
● Removal of hydrogen can also be cited as an oxidation reaction.
○ 2H2S(g) + O2(g) → 2S(s) + 2H2O(l)
● Removal of electropositive elements can also be cited as oxidation.
○ 2K4[Fe(CN)6](aq) + H2O2(aq) → 2K3[Fe(CN)6](aq) + 2KOH(aq)
○ Removal of K from K4[Fe(CN)6] if considered its oxidation.
● The term reduction has been broadened these days to include removal of
oxygen/electronegative elements from a substance or addition of hydrogen/
electropositive elements to a substance.
○ 2HgO(s) → 2Hg(l) + O2(g)
(removal of oxygen from mercuric oxide)
○ 2FeCl3(aq) + H2(g) → FeCl2(aq) + 2HCl(aq)
(removal of electronegative element, chlorine from ferric chloride)
○ CH2 = CH2(g) + H2(g) → H3C – CH3(g)
(addition of hydrogen)
○ 2HgCl2(aq) + SnCl2(aq) → Hg2Cl2(s) + SnCl4(aq)
(addition of mercury to mercuric chloride)
● Oxidation and reduction always occur simultaneously (as will be apparent by re-
examining all the equations given above), hence, the word “redox” was coined for this
class of chemical reactions.

➢ REDOX REACTIONS IN TERMS OF ELECTRON TRANSFER REACTIONS

● Half reactions that involve loss of electrons are called oxidation reactions.
● The half reactions that involve gain of electrons are called reduction reactions.
● Oxidation: Loss of electron(s) by any species.
● Reduction: Gain of electron(s) by any species.
● Oxidising agent: Acceptor of electron(s).

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 ● Reducing agent: Donor of electron(s).

➢ Competitive Electron Transfer Reactions

● Place a strip of metallic zinc in an aqueous solution of copper nitrate, for about one
hour. You may notice that the strip becomes coated with reddish metallic copper and
the blue colour of the solution disappears.
○ Formation of Zn2+ ions among the products can easily be judged when the blue
colour of the solution due to Cu2+ has disappeared.
○ If hydrogen sulphide gas is passed through the colourless solution containing Zn2+
ions, the appearance of white zinc sulphide, ZnS, can be seen in making the solution
alkaline with ammonia.
○ The reaction between metallic zinc and the aqueous solution of copper nitrate is:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
● However on placing a strip of metallic copper in a zinc sulphate solution, no visible
reaction is noticed.
○ Attempts to detect the presence of Cu2+ ions by passing H2S gas through the
solution to produce the black colour of cupric sulphide, CuS, does not succeed.
○ Cupric sulphide has such a low solubility that this is an extremely sensitive
test; yet the amount of Cu2+ formed cannot be detected.
● We thus conclude that the state of equilibrium for the reaction Zn(s) + Cu2+(aq) →
Zn2+(aq) + Cu(s) greatly favours the products over the reactants.
● Similarly, on placing copper metal and silver nitrate solution in water, The solution
develops blue colour due to the formation of Cu2+ ions on account of the reaction:
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)
➔ Cu(s) is oxidised to Cu2+(aq) and Ag+(aq) is reduced to Ag(s). Equilibrium greatly
favours the products Cu2+(aq) and Ag(s).
● When metallic cobalt placed in nickel sulphate solution -
Co(s) + Ni2+(aq) → Ni(s) + Co2+(aq)
➔ At equilibrium, chemical tests reveal that both Ni2+(aq) and Co2+(aq) are present at
moderate concentrations. In this case, neither the reactants [Co(s) and Ni2+(aq)] nor the
products [Co2+(aq) and Ni (s)] are greatly favoured.
● By comparison we have come to know that zinc releases electrons to copper and copper
releases electrons to silver and, therefore, the electron releasing tendency of the metals
is in the order: Zn > Cu > Ag.
● We can develop a table in which metals and their ions are listed on the basis of their
tendency to release electrons called activity series or electrochemical series.

➢ OXIDATION NUMBER
● In a good number of reactions involving covalent compounds the charge transfer is only
partial and is perhaps better described as an electron shift rather than a complete
loss/gain of electrons.
● In order to keep track of electron shifts in chemical reactions involving formation of
covalent compounds, a more practical method of using oxidation number has been
developed.
○ In this method, it is always assumed that there is a complete transfer of electrons
from a less electronegative atom to a more electronegative atom.

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● Oxidation number denotes the oxidation state of an element in a compound ascertained
according to a set of rules formulated on the basis that an electron pair in a covalent
bond belongs entirely to a more electronegative element.
● If two or more than two atoms of an element are present in the molecule/ion such as
Na2S2O3/Cr2O72–, the oxidation number of the atom of that element will then be the
average of the oxidation number of all the atoms of that element.
● The rules for the calculation of oxidation number:
○ 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.
○ For ions composed of only one atom, the oxidation number is equal to the charge
on the ion.
■ In their compounds all alkali metals have oxidation number of +1
■ all alkaline earth metals have an oxidation number of +2
■ Aluminium is regarded to have an oxidation number of +3 in all its compounds
○ The oxidation number of oxygen in most compounds is –2. However, we come
across two kinds of exceptions here.
■ While in peroxides (e.g., H2O2, Na2O2), each oxygen atom is assigned an
oxidation number of –1, in superoxides (e.g., KO2, RbO2) each oxygen atom is
assigned an oxidation number of –(½).
■ When oxygen is bonded to fluorine. In such compounds e.g., oxygen difluoride
(OF2) and dioxygen difluoride (O2F2), the oxygen is assigned an oxidation
number of +2 and +1, respectively.
○ The oxidation number of hydrogen is +1, except when it is bonded to metals in
binary compounds (that is compounds containing two elements). For example, in
LiH, NaH, and CaH2, its oxidation number is –1.
○ In all its compounds, fluorine has an oxidation number of –1.
■ Other halogens (Cl, Br, and I) also have an oxidation number of –1, when they
occur as halide ions in their compounds
■ Chlorine, bromine and iodine when combined with oxygen, for example in
oxoacids and oxoanions, have positive oxidation numbers.
○ 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.
● Metallic elements have positive oxidation numbers and nonmetallic elements have
positive or negative oxidation numbers.
● The atoms of transition elements usually display several positive oxidation states.
● The highest oxidation number of a representative element is the group number for the
first two groups and the group number minus 10 (following the long form of periodic
table) for the other groups.
● The highest value of oxidation number exhibited by an atom of an element generally
increases across the period in the periodic table.
○ In the third period, the highest value of the oxidation number changes from 1 to
7.
● The oxidation number denotes the oxidation state of an element in a compound.

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 ● The oxidation number/state of a metal in a compound is sometimes presented according
to the notation given by German chemist, Alfred Stock. It is popularly known as Stock
notation.
○ The oxidation number is expressed by putting a Roman numeral representing the
oxidation number in parenthesis after the symbol of the metal in the molecular
formula. Examples -
■ aurous chloride - Au(I)Cl
■ auric chloride - Au(III)Cl3
■ stannous chloride - Sn(II)Cl2
■ stannic chloride - Sn(IV)Cl4
● This change in oxidation number implies change in oxidation state, which helps to
identify whether the species is present in oxidised form or reduced form.
○ 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 also called oxidants.
○ Reducing agent: A reagent which lowers the oxidation number of an element in a
given substance. These reagents are also called reductants.
○ Redox reactions: Reactions which involve change in oxidation number of the
interacting species.

➢ Types of Redox Reactions

● Combination reactions:
○ 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 reaction.
○ All combustion reactions, which make use of elemental oxygen, as well as other
reactions involving elements other than dioxygen, are redox reactions.
○ Examples -
■ C(s) + O2(g) → CO2(g)
■ 3Mg(s) + N2(g) → Mg3N2(s)
■ CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
● Decomposition reactions:
○ 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 -
■ 2H2O(l) → 2H2 (g) + O2(g)
■ 2NaH(s) → 2Na (s) + H2(g)
■ 2KClO3(s) → 2KCl(s) + 3O2(g)
○ All decomposition reactions are not redox reactions. For example –
CaCO3(s) → CaO(s) + CO2(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.

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○ It may be denoted as: X + YZ → XZ + Y
○ Metal displacement: A metal in a compound can be displaced by another metal in
the uncombined state. Examples -
■ CuSO4(aq) + Zn (s) → Cu(s) + ZnSO4(aq)
■ V2O5 (s) + 5Ca (s) → 2V(s) + 5CaO(s)
■ TiCl4 (l) + 2Mg (s) → Ti(s) + 2MgCl2(s)
■ Cr2O3(s) + 2Al (s) → Al2O3(s) + 2Cr(s)
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.
○ 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 reductants, will displace hydrogen from cold water.
● 2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
● Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)
■ Less active metals such as magnesium and iron react with steam to produce
dihydrogen gas.
● Mg(s) + 2H2O(l) → Mg(OH)2(s) + H2(g)
● 2Fe(s) + 3H2O(l) → Fe2O3(s) + 3H2(g)
■ Many metals, including those which do not react with cold water, are capable
of displacing hydrogen from acids. Dihydrogen from acids may even be
produced by such metals which do not react with steam. Cadmium and tin are
examples of such metals.
■ Examples of displacement of hydrogen from acids -
● Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
● Mg (s) + 2HCl (aq) → MgCl2(aq) + H2(g)
● Fe(s) + 2HCl(aq) → FeCl2(aq) + H2(g)
■ The reactivity of metals is reflected in the rate of hydrogen gas evolution.
■ Very less active metals, which may occur in the native state such as silver (Ag),
and gold (Au) do not react even with hydrochloric acid.
○ Like metals, activity series also exist for the halogens.
■ The power of these elements as oxidising agents decreases as we move down
from fluorine to iodine in group 17 of the periodic table.
■ Fluorine is so reactive that it can replace chloride, bromide and iodide ions in
solution.In fact, fluorine is so reactive that it attacks water and displaces the
oxygen of water.
2H2O (l) + 2F2(g) → 4HF(aq) + O2(g)
■ Chlorine can displace bromide and iodide ions in an aqueous solution as shown
below:
Cl2(g) + 2Br–(aq) → 2Cl– (aq) + Br2(l)
Cl2(g) + 2I–(aq) → 2Cl– (aq) + I2(s)
■ As Br2 and I2 are coloured and dissolve in CCl4, can easily be identified from
the colour of the solution. The above reactions form the basis of identifying Br–
and I– in the laboratory through the test popularly known as ‘Layer Test’.

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 ■ There is no way to convert F– ions to F2 by chemical means. The only way to
achieve F2 from F– is to oxidise electrolytically.

● 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.
○ Examples -
■ Decomposition of hydrogen peroxide
2H2O2(aq) → 2H2O(l) + O2(g)
■ Phosphorous, sulphur and chlorine undergo disproportionation in the alkaline
medium –
P4(s) + 3OH–(aq)+ 3H2O(l) → PH3(g) + 3H2PO2–
S8(s) + 12OH–(aq) → 4S2–(aq) + 2S2O32– (aq) + 6H2O(l)
■ The formation of household bleaching agents –
Cl2(g) + 2OH–(aq) → ClO–(aq) + Cl–(aq) + H2O(l)
The hypochlorite ion (ClO–) formed in the reaction oxidises the colour-bearing
stains of the substances to colourless compounds

➢ The Paradox of Fractional Oxidation Number

● Fractional oxidation state is the average oxidation state of the element under
examination.
● The structural parameters reveal that the element for whom fractional oxidation state is
realised is present in different oxidation states.
● Examples -
○ Carbon suboxide, C3O2 [where oxidation number of carbon is (4/3)]

○ Tribromo Octaoxide, Br3O8 [where oxidation number of bromine is (16/3)]

○ tetrathionate ion, S4O62– (where oxidation number of sulphur is 2.5)

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 ○ Fe3O4, Mn3O4, Pb3O4 are some of the other examples of the compounds, which are
mixed oxides, where we come across fractional oxidation states of the metal atom.
○ The oxidation states may be in fraction as in O2+ and O2– where it is +½ and –½
respectively.

➢ Balancing of Redox Reactions

(a) Oxidation Number Method
● Step 1: Write the correct formula for each reactant and product.
● Step 2: Identify atoms which undergo change in oxidation number in the reaction
by assigning the oxidation number to all elements in the reaction
● Step 3: Calculate the increase or decrease in the oxidation number per atom and for
the entire molecule/ion in which it occurs. If these are not equal then multiply by a
suitable number so that these become equal.
● Step 4: Ascertain the involvement of ions if the reaction is taking place in water,
add H+ or OH– ions to the expression on the appropriate side so that the total ionic
charges of reactants and products are equal. If the reaction is carried out in an acidic
solution, use H+ ions in the equation; if in the basic solution, use OH– ions.
● Step 5: Make the numbers of hydrogen atoms in the expression on the two sides
equal by adding water (H2O) molecules to the reactants or products. Now, also
check the number of oxygen atoms. If there are the same number of oxygen atoms
in the reactants and products, the equation then represents the balanced redox
reaction.
(b) Half Reaction Method
● Step 1: Produce unbalanced equation for the reaction in ionic form
● Step 2: Separate the equation into half-reactions
● Step 3: Balance the atoms other than O and H in each half reaction individually.
● Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms and
H+ to balance H atoms.
● Step 5: Add electrons to one side of the half reaction to balance the charges. If need
be, make the number of electrons equal in the two half reactions by multiplying one
or both half reactions by appropriate numbers.
● 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.
● Step 7: Verify that the equation contains the same type and number of atoms and
the same charges on both sides of the equation. This last check reveals that the
equation is fully balanced with respect to the number of atoms and the charges.
● Step 7: (optional) For the reaction in a basic medium, first balance the atoms as is
done in acidic medium. Then for each H+ ion, add an equal number of OH– ions to
both sides of the equation. Where H+ and OH– appear on the same side of the
equation, combine these to give H2O.

➢ 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. For example -
○ Type 1: where the reagent itself is intensely coloured, e.g., permanganate ion,
MnO4–. Here MnO4– acts as the self indicator. The visible end point in this case is

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 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).
○ Type 2: 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 oxidises the indicator substance diphenylamine just
after the equivalence point to produce an intense blue colour, thus signalling the
end point.
○ Type 3: Its use is restricted to those reagents which are able to oxidise I– ions, for
example - 2Cu2+(aq) + 4I–(aq) → Cu2I2(s) + I2(aq)
➔ Iodine itself gives an intense blue colour with starch and has a very specific
reaction with thiosulfate ions (S2O32–), 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

● In the 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.

➢ REDOX REACTIONS AND ELECTRODE PROCESSES

● A redox couple is defined as having together the oxidised and reduced forms of a
substance taking part in an oxidation or reduction half reaction.
○ This is represented by separating the oxidised form from the reduced form by a
vertical line or a slash representing an interface (e.g. solid/solution).
○ Oxidised form is put before the reduced form. Ex. Zn2+/Zn and Cu2+/Cu.
● 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.
○ This provides an electric contact between the two solutions without allowing them
to mix with each other.
● When two different redox couples in different beakers are connected externally through
a metallic wire and a salt bridge, current flows through the wire and reactions take place
in both the beakers. An example is Daniel cell-

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 ➔ The transfer of electrons now does not take place directly from Zn to Cu2+ but
through the metallic wire connecting the two rods.
➔ Electrons produced at the anode due to oxidation of Zn travel through the external
circuit to the cathode where these reduce the copper ions.
➔ The circuit is completed inside the cell by the migration of ions through the salt
bridge..
➔ The electricity from solution in one beaker to solution in the other beaker flows
by the migration of ions through the salt bridge.
➔ The direction of current is opposite to the direction of electron flow.
● 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 298 K, then the potential of each electrode is said
to be the Standard Electrode Potential.
● By convention, the standard electrode potential (E°) of a 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 E° means that the redox couple is a stronger reducing agent than the
H+/H2 couple.
○ A positive E° means that the redox couple is a weaker reducing agent than the
H+/H2 couple.

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 Hydrogen

➢ Position of hydrogen in the periodic table

● Placed separately in the periodic table (1st period, group not defined)
● Like alkali metals, hydrogen forms oxides, halides and sulphides
● Unlike alkali metals, it has a very high ionization enthalpy and does not possess metallic
characteristics under normal conditions
● In terms of ionization enthalpy, hydrogen resembles more with halogens,
● Like halogens, it forms a diatomic molecule, combines with elements to form hydrides
and a large number of covalent compounds

➢ Dihydrogen - H2
● Most abundant element in the universe & principal element in the solar atmosphere
● Due to its light nature, it is much less abundant (0.15% by mass) in the atmosphere
● In the combined form it constitutes 15.4% of the earth's crust and the oceans.

➢ Isotopes of Hydrogen
● Hydrogen has three isotopes: Protium, 1H1,1H2 or D (Deuterium) and 1H3 or T
(Tritium)
● The predominant form is protium. Terrestrial hydrogen contains 0.0156% of deuterium
mostly in the form of HD
● The tritium concentration is about one atom per 1018 atoms of protium as it is
radioactive
● They have almost the same chemical properties. The only difference is in their rates of
reactions, mainly due to their different enthalpy of bond dissociation
● In physical properties these isotopes differ considerably due to their large mass
differences.

➢ PREPARATION OF DIHYDROGEN, H2
Laboratory Preparation of Dihydrogen
a) Usually prepared by the reaction of granulated zinc with dilute hydrochloric acid.

b) Can also be prepared by the reaction of zinc with aqueous alkali.

➢ Commercial Production of Dihydrogen

a) Electrolysis of acidified water using platinum electrodes

b) High purity (>99.95%) di hydrogen is obtained by electrolysing warm aqueous barium

hydroxide solution between nickel electrodes.
c) Obtained as a byproduct in the manufacture of sodium hydroxide and chlorine by the
electrolysis of brine solution. Reactions that take place are:

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 d) Reaction of steam on hydrocarbons at high temperatures in the presence of catalyst

● The mixture of CO and H2 is called water gas

● As this mixture of CO and H2 is used for the synthesis of methanol and a number of
hydrocarbons, it is also called synthesis gas or 'syngas'
● 'Syngas' is produced from sewage, saw-dust, scrap wood, newspapers etc. The process
of producing 'syngas' from coal is called 'coal gasification'.

● The production of dihydrogen can be increased by reacting carbon monoxide of syngas

mixtures with steam in the presence of iron chromate as catalyst.

This is called water-gas shift reaction. Carbon dioxide is removed by scrubbing with
sodium arsenite solution.

➢ PROPERTIES OF DIHYDROGEN
● Physical Properties
❖ Colourless, odourless, tasteless, combustible gas, lighter than air and insoluble in
water.
● Chemical Properties
❖ The H–H bond dissociation enthalpy is the highest for a single bond between two
atoms
❖ It is because of this factor that the dissociation of dihydrogen into its atoms is only
~0.081% around 2000K which increases to 95.5% at 5000K
❖ It is relatively inert at room temperature.
❖ Atomic H is produced at a high temperature in an electric arc or under ultraviolet
radiations

➢ Dihydrogen reactions:
a) Reaction with halogens:

Gives hydrogen halides

While the reaction with fluorine occurs even in the dark, with iodine it requires a
catalyst
b) Reaction with dioxygen:
Forms water. The reaction is highly exothermic.

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 c) Reaction with dinitrogen:

Forms ammonia
This is the method for the manufacture of ammonia by the Haber process.
d) Reactions with metals:
Combines at a high temperature to yield the corresponding hydrides

e) Reactions with metal ions and metal oxides:

Reduces some metal ions in aqueous solution and oxides of metals (less active than
iron) into corresponding metals.

f) Reactions with organic compounds:

i. Hydrogenation of vegetable oils using nickel as catalyst gives edible fats
(margarine and vanaspati ghee)
ii. Hydroformylation of olefins yields aldehydes which further undergo reduction to
give alcohols.

➢ Uses
● In synthesis of ammonia which is used to make nitric acid and nitrogenous fertilizers.
● In preparation of hydrogen chloride, a highly useful chemical.
● In metallurgical processes, it is used to reduce heavy metal oxides to metals.
● Atomic hydrogen and oxy-hydrogen torches find use for cutting and welding purposes.
Atomic hydrogen atoms (produced by dissociation of dihydrogen with the help of an
electric arc) are allowed to recombine on the surface to be welded to generate the
temperature of 4000 K.
● Used as a rocket fuel in space research.
● Used in fuel cells for generating electrical energy. It does not produce any pollution and
releases greater energy per unit mass of fuel in comparison to gasoline and other fuels.

➢ 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., MgH) or emhn (e.g., B2H6)
The hydrides are classified into three categories :
(i) Ionic or saline or salt like hydrides
(ii) Covalent or molecular hydrides

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 (iii) Metallic or non-stoichiometric hydrides

➢ Ionic or saline or salt like hydrides

● Stoichiometric compounds of dihydrogen formed with most of the s-block elements
which are highly electropositive in character
● Significant covalent character is found in the lighter metal hydrides such as lih, beh2
and mgh2. In fact beh2 and mgh2 are polymeric in structure.
● Crystalline, non-volatile and non conductive in solid state
● Their melts conduct electricity and on electrolysis liberate dihydrogen gas at anode

● Saline hydrides react violently with water producing dihydrogen gas.

● Lithium hydride is rather unreactive at moderate temperatures with oxygen and

chlorine. It is, therefore, used in the synthesis of other useful hydrides

➢ Covalent or Molecular Hydride

● Hydrogen compounds of nonmetals have also been considered as hydrides.
● Being covalent, they are volatile compounds.
Molecular hydrides are further classified according to the relative numbers of electrons
a) Electron-deficient hydride has too few electrons for writing its conventional
Lewis structure. Ex - B2H6
b) Electron-precise compounds have the required number of electrons to write their
conventional Lewis structures. All elements of group 14 form such compounds
c) Electron-rich hydrides have excess electrons which are present as lone
pairs.They will behave as Lewis bases i.e., electron donors

➢ Metallic or Non-stoichiometric (or Interstitial ) Hydrides

● Are formed by d-block and f-block elements except 7,8,9 group and Cr from 6th group.
● Conduct heat and electricity though not as efficiently as their parent metals
● Earlier it was thought that in these hydrides, hydrogen occupies interstices in the metal
lattice producing distortion without any change in its type. Consequently, they were
termed as interstitial hydrides
● Recent studies have shown that except for hydrides of Ni, Pd, Ce and Ac, other hydrides
of this class have a lattice different from that of the parent metal.
● Some of the metals (e.g., Pd, Pt) can accommodate a very large volume of hydrogen
and, therefore, can be used as its storage media. This property has high potential for
hydrogen storage and as a source of energy

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➢ Water
Physical Properties of Water
● Colourless and tasteless liquid
● The unusual properties of water in the condensed phase (liquid and solid states) are due
to the presence of extensive hydrogen bonding between water molecules
● This leads to high freezing point, high boiling point, high heat of vaporisation and high
heat of fusion in comparison to H2S and H2Se
● It has a higher specific heat, thermal conductivity, surface tension, dipole moment and
dielectric constant, etc
● The high heat of vaporisation and heat capacity are responsible for moderation of the
climate and body temperature of living beings
➢ Structure of Water
● In the gas phase water is a bent molecule with a bond angle of 104.5°, and H-O–H bond
length of 95.7 pm
● At atmospheric pressure ice crystallises in the hexagonal form, but at very low
temperatures it condenses to a cubic form.
➢ Structure of Ice
● Ice has a highly ordered three dimensional hydrogen bonded structure
● X-rays show 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
➢ Chemical Properties of Water
a) Amphoteric Nature
● Has the ability to act as an acid as well as a base
● In the Brönsted sense it acts as an acid with NH3 and a base with H2S.

The auto protolysis (self ionization) of water takes place as follow -

b) Redox Reactions Involving Water

● Can be easily reduced to dihydrogen by highly electropositive metals

Thus, This is a great source of dihydrogen.

Water is oxidised to O2 during photosynthesis.

With fluorine also it oxidised to O2.

120
 c) Hydrolysis Reaction:
● Due to high dielectric constant, it has a very strong hydrating tendency. It dissolves
many ionic compounds. However, certain covalent and some ionic compounds are
hydrolysed in water

d) Hydrates Formation:
From aqueous solutions many salts can be crystallised as hydrated salts. Such an
association of water is of different types viz.,

➢ Hard and Soft Water

● Presence of calcium and magnesium salts in the form of hydrogen carbonate, chloride
and sulphate in water makes water ‘hard’
● Water free from soluble salts of calcium and magnesium is called Soft water.
● Hard water forms scum/precipitate with soap. Soap containing sodium stearate
(c17h35coona) reacts with hard water to precipitate out Ca/Mg stearate.

Hardness of water is of two types:

(i) temporary hardness (ii) permanent hardness.

➢ Temporary Hardness
Presence of magnesium and calcium hydrogen carbonates is the reason of temporary
hardness. These are the methods of removal -
A) Boiling:
During boiling, the soluble Mg(HCO3)2 is converted into insoluble Mg(OH)2 and
Ca(HCO3)2 is changed to insoluble caco3. It is because of high solubility product of
Mg(OH)2 as compared to that of mgco3, that Mg(OH)2 is precipitated. These precipitates
can be removed by filtration.

B) Clark’s method:
Calculated amount of lime is added to hard water. It precipitates out calcium carbonate
and magnesium hydroxide which can be filtered off

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➢ Permanent Hardness
● Due to the presence of soluble salts of magnesium and calcium in the form of chlorides
and sulphates in water
● Can not be removed by boiling.

➢ Methods to remove -
a) Treatment with washing soda (sodium carbonate):
Washing soda reacts with soluble calcium and magnesium chlorides and sulphates in
hard water to form insoluble carbonates.

b) Calgon’s method:
Sodium hexametaphosphate (Na6P6O18), commercially called ‘calgon’, when added to
hard water, the following reactions take place.

c) Ion-exchange method / zeolite/permutit process

Hydrated sodium aluminium silicate is zeolite/permutit. Sodium aluminium silicate
(naalsio4) can be written as naz. It is added in hard water, exchange reaction happens

Permutit/zeolite is said to be exhausted when all the sodium in it is used up. It is

regenerated for further use by treating with an aqueous sodium chloride solution.

d) Synthetic resins method:

Nowadays hard water is softened by using synthetic cation exchangers. This method
is more efficient than zeolite process. Cation exchange resins contain large organic
molecule with - SO3H group and are water insoluble. Ion exchange resin (RSO3H) is
changed to rna by treating it with nacl. The resin exchanges Na+ ions with Ca2+ and
Mg2+ ions present in hard water to make the water soft. Here R is resin anion.

The resin can be regenerated by adding aqueous nacl solution. Pure demineralised
(de-ionized) water free from all soluble mineral salts is obtained by passing water
successively through a cation exchange (in the H+ form) and an anion exchange (in
the OH– form) resins:

In this cation exchange process, H+ exchanges for Na+, Ca2+, Mg2+ and other cations
present in water. This process results in proton release and thus makes the water acidic. In
the anion exchange process:

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 OH– exchanges for anions like Cl–, HCO3–, SO42– etc. Present in water. OH– ions, thus,
liberated neutralise the H+ ions set free in the cation exchange.

The exhausted cation and anion exchange resin beds are regenerated by treatment with
dilute acid and alkali solutions.

➢ HYDROGEN PEROXIDE (H2O2)

An important chemical used in pollution control treatment of domestic and industrial
effluents.

➢ Preparation Methods
a) By acidifying barium peroxide and removing excess water by evaporation under
reduced pressure gives hydrogen peroxide.

b) Peroxodisulphate, obtained by electrolytic oxidation of acidified sulphate solutions at

high current density, on hydrolysis yields hydrogen peroxide.

This method is now used for the laboratory preparation of D2O2.

c) Industrially it is prepared by the auto oxidation of 2-alkyl anthraquinone.

In this case 1% H2O2 is formed. It is extracted with water and concentrated to ~30% (by
mass) by distillation under reduced pressure
● Can be further concentrated to ~85% by careful distillation under low pressure. The
remaining water can be frozen out to obtain pure H2O2

➢ Physical Properties
● In pure state H2O2 is an almost colourless (very pale blue) liquid.
● Miscible with water in all proportions and forms a hydrate H2O2.H2O (mp 221K).
● A 30% solution of H2O2 is marketed as ‘100 volume’ hydrogen peroxide. It means that
one millilitre of 30% H2O2 solution will give 100 ml of oxygen at STP. Commercially
marketed sample is 10 V, which means that the sample contains 3% H2O2.

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➢ Structure Hydrogen peroxide -
A non-planar structure. The molecular dimensions in the gas phase and solid phase are
shown

➢ Chemical Properties:
Acts as an oxidising as well as reducing agent in both acidic and alkaline media.
(i) Oxidising action in acidic medium

(ii) Reducing action in acidic medium –

(iii) Oxidising action in basic medium

(iv) Reducing action in basic medium

➢ Storage
● H2O2 decomposes slowly on exposure to light.

● In the presence of metal surfaces or traces of alkali (present in glass containers), the
above reaction is catalysed. It is, therefore, 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:
● Its wide scale use has led to tremendous increase in the industrial production of H2O2.
Some of the uses are listed below:
(i) Used as a hair bleach and, mild disinfectant, antiseptic. It is sold in the market as
perhydrol.

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 (ii) Used to manufacture chemicals like sodium perborate and per -carbonate, which
are used in high quality detergents.
(iii) Used in the synthesis of hydroquinone, tartaric acid and certain food products and
pharmaceuticals (cephalosporin) etc.
(iv) Used in the industries as a bleaching agent for textiles, paper pulp, leather, oils,
fats, etc.
(v) Used in Environmental Chemistry. For example, in pollution control treatment of
domestic and industrial effluents, oxidation of cyanides, restoration of aerobic
conditions to sewage
➢ HEAVY WATER, D2O
Extensively used as a moderator in nuclear reactors.
● In exchange reactions for the study of reaction mechanisms.
● Can be prepared by hard electrolysis of water or as a by-product in some fertilizer
industries
● It is used for the preparation of other deuterium compounds, for example:

➢ DIHYDROGEN AS A FUEL
● Releases large quantities of heat on combustion as compared to other fuels
● The data on energy released by combustion of different fuels are compared in table 9.5.
● Pollutants in combustion of dihydrogen will be less than petrol. The only pollutants will
be the oxides of dinitrogen (due to the presence of dinitrogen as impurity with
dihydrogen). This, of course, can be minimised by injecting a small amount of water
into the cylinder to lower the temperature so that the reaction between dinitrogen and
dioxygen may not take place.
● A cylinder of compressed dihydrogen weighs about 30 times as much as a tank of petrol
containing the same amount of energy. Mass of tank is a big issue.
● Dihydrogen gas is converted into liquid state by cooling to 20K. This would require
expensive insulated tanks. Tanks of metal alloy like nani5, Ti–tih2, Mg–MgH2 etc.
● The basic principle of hydrogen economy is the transportation and storage of energy in
the form of liquid or gaseous dihydrogen. Initially 5% dihydrogen has been mixed in
CNG for use in four-wheeler vehicles. It is being increased to reach the optimum level.
● 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

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 The s-Block Elements

➢ General properties:
● Last electron enters outermost s-orbital
● Has two groups (1 & 2) as s-orbital can accommodate only 2 electrons.

Group-1 elements
➢ General points:
● Also called as alkali metals because they form hydroxides on reaction with water,
which are highly alkaline in nature.
● General valence shell electronic configuration: ns1.
● Readily looses electron to form monovalent ions and are most electropositive metals
because the outermost s-electron is loosely held
● Elements and their electronic configuration:

● Abundance in lithosphere:
❖ Abundant: Na, K
❖ Less abundant: Li, Rb, Cs
● Fr is radioactive and has a half life of 21 minutes.
➢ Physical properties:

Property Order Points

Size Li < Na < K < Rb < Cs 1. Have larger sizes than other elements
in their corresponding period
2. Size of M+ < M
3. From Na to K there is a greater
increase in the size compared to
others.

At. weight Li < Na < K < Rb < Cs

Density Li < K < Na < Rb < Cs 1. Low densities due to large size

126
 2. Density (mass/volume) of K < Na
because the increase in size is greater
than that of increase in mass.

BP & MP Li > Na > K > Rb > Cs 1. Low MP & BP due to weak metallic
bonding (only one electron
participates in Metallic bonding)

IE Li > Na > K > Rb > Cs

HE Li+ > Na+ > K+ > Rb+ 1. Li+ has a maximum degree of
(Hydratio > Cs+. hydration. Eg: LiCl. 2H2O
n energy)

Std Li > Rb > Cs > K > Na 1. Increases down the group, except for
oxidation Li
potential 2. Std. potential measures the overall
and change in sublimation enthalpy,
reducing ionisation enthalpy and hydration
nature enthalpy.
3. Highest reducing power is shown by
Li due to high hydration enthalpy
and least is shown by Na

● Flame test:
❖ Imparts characteristic color to an oxidising flame.
❖ Colour is imparted due to excitation and deexcitation of the electron in the ns
orbital. Colours imparted by each metal is shown in the table below:
Note that ‘λ’ corresponds to the highest intensity wavelength emitted during flame
test

❖ Cs, K are used as electrodes in photochemical cells because simply by irradiating

them with light they can loose electron.
➢ Chemical properties:
● Reactivity towards air:
❖ Tarnish in dry air due to formation of oxides.

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 ❖ Li can form only oxide. Na can form oxide as well as peroxide. K, Rb, Cs form
oxides, peroxide and superoxides. In all the cases the metals are in +1 oxidation
state.
4 Li +O2 →2Li2O (oxide)
2Na +O2 →Na2O2 (peroxide)
M+ O2 →MO2 (superoxide) (M = K, Rb, Cs)
❖ Li also forms LiN3 (lithium nitride) by reacting directly with nitrogen
❖ Alkali metals are kept in kerosene due to their high reactivity towards air and
water.
● Reactivity towards water:
❖ React to form hydroxides and H2 gas.
❖ Order of reactivity: Li < Na < K < Rb < Cs
❖ Li is less reactive, Na reacts vigorously and other metals react explosively with
water.
❖ Even though E0 (Li/Li+) > E0 (Na/ Na+), the reactivity of lithium is lower than
that of sodium. This can be attributed to the small size and very high hydration
energy of Li.
❖ They react with proton donors such as alcohols, alkynes and gaseous ammonia.
● Reactivity towards dihydrogen
❖ Form hydrides which are ionic solids having high melting points.
❖ 2M + H2 → 2M+H-
● Reactivity towards halogens
❖ Forms ionic halides of type M+X- except lithium halides which are covalent in
nature due to high polarising power of Li+ ion and high polarisability of large
anion X- (Using Fazan’s rules).
❖ Lithium iodide is the most covalent halide in nature compared to other lithium
halides (Using Fazan’s rules)
● Solutions in liquid ammonia
❖ Dissolve in ammonia forming a conducting deep blue coloured solution.
M+ (x + y) NH3 → [M (NH3)x ]+ + [e(NH3 )y ]−
❖ Colour is due to an ammoniated electron which absorbs energy from visible light
region.
❖ Solution on standing liberates hydrogen gas slowly.
M+(ammoniated) + e- + NH3 (l) → MNH2 (ammoniated) + ½ H2(g)
❖ Solution is paramagnetic in nature. If concentrated then the blue colour changes to
bronze and becomes diamagnetic.

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➢ General characteristics of the compounds of alkali metals
● Oxides and hydroxides
❖ General formula: Oxides - M2O, peroxides - M2O2, superoxides- MO2
❖ Stability of the peroxide or superoxide increases, as the size of the metal ion
increases, due to the stabilisation of large anions by larger cations through lattice
energy.
❖ Pure oxides, peroxides, superoxides can be formed under appropriate conditions.
❖ Pure oxides, peroxides are colourless and pure superoxides are yellow or orange
in colour because of their paramagnetic nature
❖ Oxides on hydrolysis form hydroxides.

❖ All hydroxides are white crystalline solids and dissolve in water easily by
liberating huge hydration energy.
● Halides
❖ General formula: MX
❖ Properties: High MP, colourless, crystalline solids.
❖ Preparation: M2O/ MOH/ M2CO3 with HX (hydrohalic acid)
❖ MP, BP: fluoride > chloride > bromide > iodide
❖ Solubility:
▪ All halides are soluble in water
▪ Lithium halides are also soluble in ethanol, acetone and ethyl acetate; LiCl is
soluble in pyridine also.
▪ LiF: low soluble in water due to high lattice enthalpy.
▪ CsI: low soluble in water due to low hydration enthalpy
❖ ΔfH0 values:
▪ Highly negative. Become less negative from fluorides to iodides
▪ Fluorides: Less negative down the group
▪ Chlorides/Bromides/Iodides: More negative down the group
● Salts of oxoacids
❖ Oxoacid: Acidic proton on OH group along with an oxo group attached to the
same atom. Eg: H2CO3, H2SO4.
❖ Alkali metals form salts with oxoacids
❖ General properties: Soluble in water and thermally stable
❖ Carbonates and bicarbonates:
❖ Thermal stability: Increases down the group as the electropositive nature
increases.Li2CO3 is not stable to heat due to small size Li and decomposes to form
Li2O and H2O. Its hydrogen carbonate does not exist as solid.

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➢ Anomalous behaviour of Lithium
● Due to small size and high polarising power, high covalent character in its
compounds, it shows differences from other elements of the group.
● Difference between Li and other group-1 elements:
❖ MP,BP: higher than others and is harder
❖ Least reactive but has high reducing power
❖ On reaction with air forms Li2O and Li3N
❖ LiCl is deliquescent i.e forms hydrides LiCl. 2H2O. Other chlorides don’t form
hydrides
❖ Lithium hydrogen carbonate is not in solid form while others form solid hydrogen
carbonates.
❖ Doesn’t form ethynide on reaction with ethyne
❖ Differ in the decomposition of the nitrates from others

❖ Oxides and fluorides are less soluble in water compared to others.

● Similarity with Magnesium (Diagonal relationship):
❖ Similarity is due to similar sizes
❖ Both are harder and lighter than other elements in the group and form nitrides on
reaction with nitrogen.
❖ Their oxides and hydroxides are less soluble and hydroxides decompose on
heating
❖ Carbonates decompose on heating and liberate CO2.Their hydrogen carbonates
are not solids.
❖ Their chlorides are deliquescent (LiCl.2H2O, MgCl2. 8H2O) and are soluble in
ethanol.
➢ Important compounds of group-1:
● Sodium carbonate (washing soda):
❖ Formula: Na2CO3.10 H2O
❖ Preparation: Solvay’s process

Due to low solubility of NaHCO3, it is precipitated.

NH3 can be recycled using the following reaction:

NOTE: Solvay’s process cannot be used for K2CO3 due to high solubility of
KHCO3.

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 ❖ Properties:
▪ White crystalline solid, decahydrate, readily soluble in water forming alkaline
solution.
▪ On heating it follows the below reactions:

❖ Uses:
▪ Water softening, laundering and cleaning.
▪ In the manufacture of glass, soap, borax and caustic soda.
▪ In paper, paints and textile industries.
▪ Important laboratory reagent both in qualitative and quantitative analysis
● Sodium chloride:
❖ Formula: NaCl
❖ Preparation:
▪ Crude NaCl is prepared by crystallization of brine solution (sea water).
Impurities include sodium sulphate,calcium sulphate, calcium chloride and
magnesium chloride.
▪ Table salt is deliquescent due to presence of CaCl2 and MgCl2
❖ Purification:
▪ By dissolving crude salt in a small amount of water followed by filtration to
remove insoluble impurities. The water is then passed through HCl to
precipitate out the NaCl with MgCl2 and CaCl2 remaining dissolved in water.
❖ Properties:
▪ MP: 1081K
▪ Solubility in water: 36g/100ml of water at 273K. Also note that solubility
doesn’t increase appreciably with increase in temperature.
❖ Uses:
▪ Table salt and preparation of Na2O2, NaOH, Na2CO3

● Sodium hydroxide (Caustic soda):

❖ Formula: NaOH
❖ Preparation: Electrolysis of NaCl (In castner kellner cell)
▪ Cathode: Mercury, Anode: Carbon, Brine solution
▪ On electrolysis, sodium amalgam is produced at cathode and this is treated
with water to form NaOH

❖ Properties:

131
 ▪ White, translucent solid, MP: 591K, gives a strong alkaline solution with
water.
▪ When exposed to air, reacts with CO2 to form Na2CO3
❖ Uses:
▪ Lab reagent and preparation of pure fats and oils
▪ Manufacture of soap, paper, artificial silk
▪ Petrol refining, Purification of bauxite.
▪ In the textile industries for mercerising cotton fabrics
● Sodium Hydrogen carbonate (Baking soda):
❖ Formula: NaHCO3
❖ Preparation: By saturating the solution of sodium carbonate with CO2 or by
solvay’s process.
▪ Na2CO3 + H2O + CO2 ---> NaHCO3
❖ Properties:
▪ White crystalline and less soluble comparatively ( It is precipitated out
during solvay’s process due to its low solubility)
▪ Decomposes on heating to generate bubbles of CO2 (makes cakes fluffy
and thus called baking soda).
❖ Uses:
▪ In baking, antiseptic for skin infections and in fire extinguishers.
➢ Uses:
● ‘Li’
❖ Li, Pb alloy -‘white metal’ bearings for motor engines
❖ Li, Al alloy - Aircrafts
❖ Li, Mg alloy - Armour plates
❖ In thermonuclear reactions, electrochemical cells,
● ‘Na’
❖ In biological systems
❖ Na,Pb alloy - To make PbEt4, PbMe4 which are used as anti-knock additives to
petrol, but nowadays vehicles use lead-free petrol.
❖ Liquid sodium is used as a coolant in fast breeder nuclear reactors
● ‘K’
❖ In biological systems
❖ Potassium chloride - fertilizer
❖ Potassium hydroxide - manufacture of soft soap, absorbent of CO2
● ‘Cs’:
❖ In photoelectric cells

132
➢ Biological importance of sodium and potassium:
● Concentration of Na+ and K+

Ion Intracellular.conc Extracellular.conc Points

K+ High (105 mmol/L Low (5 mmol/L in 1. Found primarily inside the cell.
in blood plasma) RBC) 2. Activate many enzymes inside
cell, participate in the oxidation
of glucose to produce ATP and,
in transmission of nerve signals

Na+ Low (10 mmol/L High (143 mmol/L 1. Found primarily outside the cell
in RBC) in blood plasma) in blood plasma and interstitial
fluid which surrounds cells
2. Transmission of nerve signals,
regulation of water flow across
the membrane and in transport
of sugars into cell etc

The concentration gradient of K+ and Na+ across the cell is maintained by the
mechanism of sodium-potassium pump across the cell membrane. It consumes more than
one-third of the ATP used by a resting animal.

Group-2 elements
➢ General points:
● Group-2 elements except beryllium are also called alkaline earth metals because their
hydroxides and oxides are highly alkaline and their oxides are found abundantly in the
earth’s crust.
● Beryllium slightly differs from others and shows similarities with aluminium
(Diagonal relationship)
● General valence shell electronic configuration: ns2
● Compounds of them are predominantly ionic
● Elements and their electronic configuration:

133
 ● Abundance:
❖ Beryllium is rare and radium is the rarest
❖ Ca, Mg rank 5th and 6th abundance in the earth crust
❖ Sr, Ba have low abundances
➢ Physical properties:

Property Order Points

Size Be< Mg < Ca < Sr < Ba 1. Increases down the group (both
metallic and ionic radii)

At. weight Be< Mg < Ca < Sr < Ba

Density Ca < Mg < Be < Sr < Ba 1. Density decreases from Be till

Ca and them increases from Sr
to Ba

BP & MP Irregular 1. Higher than alkali metals

2. Irregular trends
3. High MP: Be , Low MP: Mg
4. High BP: Be , Low BP: Mg

IE1 Be > Mg > Ca > Sr > Ba 1. IE1 (group-1) < IE1 (group-2)

IE2 Be > Mg > Ca > Sr > Ba 1. IE2 (group-1) > IE2 (group-1)

HE Be2+> Mg2+ > Ca2+ > Sr2+ 1. Decreases down the group
(Hydration > Ba2+ 2. HE is greater for group-2 than
energy) group-1 elements, thus highly
hydrated
Eg: MgCl2 and CaCl2 exist as
MgCl2.6H2O and CaCl2· 6H2O
while NaCl and KCl do not form
such hydrates

Std oxidation Be< Mg < Ca < Sr < Ba 1. Increases down the group
potential and 2. Std. potential measures the
reducing overall change in sublimation
nature enthalpy, ionisation enthalpy and
hydration enthalpy.
3. The reducing power is less than
their corresponding Alkali
metals.

134
 4. Be2+ has large hydration
enthalpy and high enthalpy of
atomisation.
5. Thus electropositive nature
increases down the group

● High thermal and electrical conductivities indicating they are metals

● Flame test:
❖ Be, Mg doesnt show flame test becoz the energy is not sufficient to excite the
electrons.
Ca Brick red

Sr Crimson red

Ba Apple green
❖ Flame test for Ca, Sr and Ba is helpful in their detection in qualitative analysis
and estimation by flame photometry
➢ Chemical properties:
● Reactivity towards air:
❖ Be, Mg are rendered passive to oxygen and water due to formation of oxide film
on the surface.
❖ Be powder can easily form BeO and Be3N2 on reaction with air. Similar
behaviour is shown by Mg.
❖ Unlike group-1, all the elements form oxides and nitrides on reaction with O2 and
N2.
❖ On reaction with water forms hydroxides and the virgourosity increases down the
group.
● Reactivity towards halogens:
❖ React with halogens at elevated temperatures to form halides
❖ BeF2, BeCl2 are produced differently.
▪ BeF2 is prepared by thermal decomposition of (NH4)2BeF4.
▪ BeCl2 is formed from its oxide
BeO + C + Cl2 -----> BeCl2 + CO
● Reactivity towards hydrogen:
❖ All metals except Be form hydrides on heating with hydrogen.
❖ BeH2 is formed using LiAlH4

● Reactivity towards acids:

❖ Liberate hydrogen on treatment with acids

135
 ● Solution with ammonia:
❖ Form a deep blue ammoniated solution.

❖ Ammoniates [M(NH3)6]2+ can be recovered from the solution.

➢ General characteristics of the compounds of alkaline earth metals
● Oxides and hydroxides
❖ Alkaline earth metals burn in oxygen to form monoxide (MO) have rocksalt
structure except for BeO.
❖ Enthalpy of formation of oxides are quite high and also they are stable to heat.
❖ All oxides - Ionic and basic except BeO - covalent and amphoteric.
❖ All oxides react with water to form sparingly soluble hydroxides.
❖ Solubility, thermal stability, basicity of hydroxides:
▪ Increases down the group from Mg(OH)2 to Ba(OH)2.
▪ Less stable and lesser basic compared to alkali metals
▪ Be(OH)2 is amphoteric and reacts with both acid and base.

● Halides
❖ Halides are ionic except beryllium halides which are covalent and soluble in
organic solvents.
❖ Structure of BeCl2
▪ Solid state: Chain structure

▪ Vapour phase: Dimer structure (Chloro bridged dimer) and forms liner
monomer at high temperatures (Approx 1200K).
❖ Tendency to form hydrates decreases down the group.
Eg: MgCl2·8H2O, CaCl2·6H2O, SrCl2·6H2O and BaCl2·2H2O
❖ On heating Ca, Sr, Ba halides get dehydrated whereas Be and Mg will suffer
hydrolysis.
❖ Fluorides are less soluble than chlorides due to their high lattice energies.
● Salts of oxoacids
❖ Carbonates
▪ Insoluble in water and can be precipitated easily by addition of sodium or
ammonium carbonate to the solution of metal carbonate solution (due to
common ion effect)
▪ Solubility decreases down the group
▪ Unstable to heat and decompose to form oxide and CO2 on heating.

136
 ▪ Thermal stability increases down the group. BeCO3 is unstable and can be
kept only in the atmosphere of CO2.
❖ Suplates
▪ Properties: White solids
▪ Solubility decreases from CaSO4 to BaSO4. BeSO4 and MgSO4 are readily
soluble (Due to high hydration enthalpy which overcomes lattice enthalpy) .
▪ Stable to heat.
❖ Nitrates
▪ Preparation: Carbonates + dil. Nitric acid.
▪ Tendency to form hydrates decreases down the group due to decrease in
hydration enthalpy.
▪ Eg: Mg(NO3)2 crystallises with 6H2O, whereas Ba(NO3)2 crystallises as the
anhydrous salt.
▪ Decompose on heating similar to LiNO3.

➢ Anomalous behaviour of Beryllium

● Different from the rest of its group elements and shows diagonal relationship with
Aluminium.
● ‘Be’ compounds are highly covalent and get easily hydrolysed due to small size and
high IE.
● Max coordination number of ‘Be’ is 4 while others show 6 due to availability of d-
orbitals.
● Oxides and hydroxides of Be are amphoteric unlike others which are basic.
● Similarities with Aluminium (Diagonal relationship)
❖ Both have approx same ionic sizes and thus shows similarities with ‘Al’
❖ Both are rendered passive to acids due to formation of oxide film on the surface
❖ Both the hydroxides dissolve in excess alkali forming beryllate ion ([Be(OH)4]2–)
and aluminate ion ([Al(OH)4]–).
❖ Both of their chlorides form Cl- bridged structure in vapour phase. Both chlorides
are soluble in organic solvents, strong lewis acids and are used as friedel crafts
catalysts.
❖ Both have strong tendency to form complexes BeF42-, AlF63-
➢ Important compounds of group-2:
● Calcium oxide (Quick lime)
❖ Formula: CaO
❖ Preparation:
▪ Heating of limestone (CaCO3) in a rotary kiln at 1070-1270 K.
▪ CaCO3 → CaO + CO2
▪ CO2 is removed immediately to enable the reaction to the completion
❖ Properties:

137
 ▪ White amorphous solid, MP: 2870K
▪ Absorbs moisture and CO2 from atmosphere

▪
▪ Basic oxide and combines with acidic oxides at high temperature.

▪
▪ Slaking the lime: Adding a limited amount of water to the lump of lime.
▪ Soda lime: Slaking lime with soda to form soda lime.
❖ Uses:
▪ Manufacturing of cement, sodium carbonate from caustic soda, dye stuffs.
▪ In purification of sugar.
● Calcium hydroxide (Slaked lime)
❖ Formula: Ca(OH)2
❖ Preparation: Adding quicklime (CaO) to water.
❖ Properties:
▪ White amorphous powder and sparingly soluble in water
▪ Milk of lime: Suspension of slaked lime in water. Milk of lime reacts with
chlorine to form hypochlorite, a constituent of bleaching powder.

▪
▪ Lime water: Aqueous solution of calcium hydroxide. When CO2 is passed
through lime water it turns milky due to the formation of CaCO3. With excess
CO2, the precipitate dissolves and forms calcium hydrogen carbonate.
▪
▪
❖ Uses:
▪ Preparation of mortar (building material)
▪ White wash (as it is disinfectant in nature)
▪ Making of glass, in the tanning industry, preparation of bleaching powder and
purification of sugar.
● Calcium carbonate
❖ Formula: CaCO3.
❖ Occurrence: In the form of limestone, marble, chalk etc
❖ Preparation: 2 ways

Note: Avoid excess of CO2 as it leads to the formation of calcium hydrogen carbonate
❖ Properties:
▪ White fluffy powder

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 ▪ Insoluble in water.
▪ Other reactions:

❖ Uses:
▪ Manufacture of quicklime , in building material as marble.
▪ Along with MgCO3 is used as flux in extraction of Iron and few other metals.
▪ Manufacture of high quality paper.
▪ Antacid, mild abrasive in toothpaste, in chewing gums and filler in cosmetics.
● Calcium sulphate (Plaster of paris)
❖ Formula: CaSO4. ½ H2O
❖ Preparation: Heating gypsum

Note: Above 393K no water will be left forming CaSO4 and is called dead burnt
plaster.
❖ Properties:
▪ Property of setting with water. It forms plastic mass which hardens to solid in
5 to 15 min when mixed with adequate water.
❖ Uses:
▪ In the building industry and plasters for bone fracture or sprain.
▪ In dentistry for ornamental work.
▪ Casts for statues and busts
● Cement
❖ Important building material. Also called portland cement as it resembles natural
limestone quarried in the Isle of Portland.
❖ Preparation:
▪ Raw materials are limestone and clay. Mixing material rich in line, CaO with
clay containing silica along with oxides of Al, Mg, Fe.
▪ Clay and limestone are strongly heated, fused and thus react and form
‘cement clinker’. This clinker is mixed with 2-3% by weight of gypsum
(CaSO4·2H2O) to form cement.
❖ Composition of portland cement:
▪ CaO: 50- 60%, SiO2: 20-25%, Al2O3: 5-10%, MgO: 2- 3%, Fe2O3: 1-2% and
SO3: 1-2%.
▪ Important ingredients: dicalcium silicate (Ca2SiO4) 26%, tricalcium silicate
(Ca3SiO5) 51% and tricalcium aluminate (Ca3Al2O6) 11%.
❖ For a good quality cement:
▪ The ratio of silica to alumina should be between 2.5 and 4

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 ▪The ratio of lime to the total of the oxides of silicon, aluminium and iron
should be as close as possible to 2.
❖ Setting of cement:
▪ With water form a hard mass due to hydration of molecules and their
rearrangement.
▪ Gypsum is added to slow down the process of setting so that it gets
sufficiently hardened.
❖ Uses:
▪ Most important next to iron and steel
▪ Used in concrete and reinforced concrete, in construction of buildings, bridges
and dams, in plastering etc
➢ Uses:
● ‘Be’ :
❖ Manufacture of alloys.
❖ Cu-Be alloy - High strength springs.
❖ Metallic Be - Windows of x ray tubes
● ‘Mg’:
❖ Mg forms alloys with Al, Zn, Mn, Sn
❖ Mg-Al alloys - Aircraft construction due to their lightweight properties.
❖ Mg powder and ribbon in flash powders, bulb, incendiary bombs and signals.
❖ Milk of magnesia (suspension of Mg(OH)2 in water) - Antacid
❖ MgCO3 - in toothpaste
● ‘Ca’
❖ Extraction of metal oxides which are difficult to reduce with ‘C’
❖ Ca (also Ba) used to remove air from vacuum tubes as they react with air to form
oxides and nitrides.
● ‘Ra’
❖ In radiotherapy
➢ Biological importance of Ca, Mg:
● Daily requirement: 25g Mg, 1200g Ca
● Magnesium:
❖ Chlorophyll contains Mg.
❖ All enzymes that utilize ATP require Mg as cofactor
● Calcium:
❖ 99% of calcium in body is present in bones and teeth
❖ Important role in neuromuscular function and interneuronal transmission, cell
membrane integrity and blood coagulation.
❖ Calcium concentration in plasma is regulated by calcitonin and parathyroid
hormone.
Bone is regularly remodelled in the body i.e it is solubilised and redeposited everyday to
an extent of 400mg in man per day. All the Calcium passes through the plasma.

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 The p-Block Elements

Group 13 and 14
➢ P-block: General introduction
• What makes the heavier p-block elements chemistry interesting: the influence of d and
f electrons in the inner core.
• Last electron → outermost p orbital.
• Total groups in P-block- six groups, numbered from 13 to 18.
• Valence shell electronic configuration- ns2 np1-6 (except for He).
• Maximum oxidation state- the total number of valence electrons (i.e., the sum of the s-
and p-electrons).
• The important oxidation states exhibited by p-block elements are shown in Table below.

• Occurrence of oxidation states two unit less than the group oxidation- ‘inert pair effect’.
• Non-metals and metalloids exist only in- p-block.
• Non-metallic character- decreases down the group- best illustrated by the nature of
oxides they form.
• Non-metal oxides- acidic or neutral || metal oxides- basic.
• Heaviest element in each p-block group is the most metallic in nature.
• Boron (second period elements of p-groups)-max covalency is 4 eg..BF4-
• Third period elements (3s23pn) utilize the vacant 3d orbitals to expand their covalence
above four. For example, aluminium gives [AlF6]3– ion.

➢ Group 13- Boron family:

• Boron- non-metal, Aluminium- metal but shows many chemical similarities to boron.
• Gallium, Indium, Thallium and nihonium- metallic in character.
• Boron (fairly rare element, poorly abundant) occurs as orthoboric acid, (H3BO3), borax,
Na2B4O7·10H2O, and kernite, Na2B4O7·4H2O.
• Two isotopic forms of boron- 10B (19%) and 11B (81%).

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• Aluminium- third most abundant element in the earth’s crust
• Important minerals of Aluminium- Bauxite, Al2O3. 2H2O and cryolite, Na3AlF6
• Half life of its most stable isotope of Nihonium (synthetically prepared radioactive
element)- 20 seconds.
• Outer electronic configuration of B family- ns2np1.
• Refer to the following table for various physical properties of group 13 elements.

• Atomic radii order- B < Ga < Al < In < Tl.

• Boron- non-metal. Extremely hard and black coloured solid.
• Gallium- unusual low melting point (303K).
• B forms covalent bonds- Due to the small size of boron, the sum of its first three
ionization enthalpies is very high. This prevents it to form +3 ions and forces it to form
only covalent compounds.
• Relative stability of +1 oxidation state progressively- Al<Ga<In<Tl
• Boron in BF3 has only six electrons- electron deficient molecule- Lewis acid. BCl3
easily accepts a lone pair of electrons from ammonia to form BCl3NH3.

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• The tendency to behave as Lewis acid decreases with the increase in the size down the
group.
• AlCl3 achieves stability by forming a dimer

• Group 13 trichlorides on hydrolysis in water form tetrahedral M(OH)4− species where

M is sp3 hybridised.
• AlCl3 in acidified aqueous solution forms octahedral [Al(H2O)6]3+ ion. In this complex,
3d orbitals of Al are involved and the hybridisation state of Al is sp3d2.
• Boron is unreactive in crystalline form.
• Amorphous boron and aluminium metal on heating in air form B2O3 and Al2O3
respectively.
• B2O3 is acidic and reacts with basic (metallic) oxides forming metal borates.
• Al2O3 and Ga2O3- amphoteric. In 2O3 and Tl2O3- basic.

• With dinitrogen at high temperature they form nitrides.

• Boron does not react with acids and alkalies even at moderate temperature.
• Aluminium shows amphoteric character. Aluminium dissolves in dilute HCl and
liberates dihydrogen.

• Al forms a protective oxide layer on the surface when reacted with conc. nitric acid
• Dihydrogen gas is released when Al reacts with alkali.

• Group 13 elements react with halogens to form trihalides (except TlI3).

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➢ Borax:
White crystalline solid Na2B4O7.10H2O. contains the tetranuclear units [B4O5(OH)4]2−
Correct formula; therefore, is Na2[B4O5 (OH)4].8H2O.
• Borax dissolves in water to give an alkaline solution.

• Borax bead (glass like material) is obtained on heating borax.

• Borax bead test is performed to identify metaborates of many transition metals that have
characteristic colours.
• Co(BO2)2 bead is blue in color.
• Orthoboric acid:
• A weak monobasic acid.
• A protonic acid but acts as a Lewis acid
• H3BO3 is a white crystalline sparingly soluble in water but highly soluble in hot water
prepared by acidifying an aqueous solution of borax.

• It has layer structure in which planar BO3 units are joined by hydrogen bonds

• On heating, orthoboric acid above 370K forms metaboric acid, HBO2 which on further
heating yields boric oxide, B2O3.

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 • Diborane B2H6: colourless, highly toxic gas with a b.p. of 180 K. catches fire in air.

• Prepared by treating BF3 with LiAlH4

• laboratory method to prepare diborane:

• Industry method to prepare diborane:

• Boranes are readily hydrolysed by water

• Reaction of diborane with Lewis bases(L) to give borane adducts, BH3L.

• Reaction of diborane with ammonia to give borazine, B3N3H6 known as “inorganic

benzene”

➢ Structure of B2H6:

Each B atom- sp3 hybridised.

The terminal B-H bonds are normal 2-centre-2-electron bonds but the two bridge bonds are 3-
centre-2-electron bonds (banana bonds).
• Boron forms a series of hydridoborates of several metals:

➢ USES OF BORON AND ALUMINIUM AND THEIR COMPOUNDS:

• Boron fibres are used in making bullet-proof vest and light composite material for
aircraft.
• Metal borides (10B isotope) are used in nuclear industry as protective shields and
control rods.
• Industrial application of borax and boric acid- manufacture of heat resistant glasses
(e.g., Pyrex), glass-wool and fibreglass.
• Borax: used as a flux for soldering metals, and as constituent of medicinal soaps.

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 • Orthoboric acid- aqueous solution is generally used as a mild antiseptic.
• Electrical conductivity of aluminium is twice that of copper.
• Aluminium and its alloys: pipe, tubes, rods, wires, plates or foils, construction,
aeroplane and transportation industry.
➢ Group 14: Carbon family
• Members: C, Si, Ge, Sn, Pb, Fl
• Carbon- most versatile element- available as coal, graphite and diamond. In combined
state- metal carbonates, hydrocarbons and carbon dioxide gas (0.03%) in air.
• Carbon isotopes: 12C, 13C, and 14C.
• Silicon in nature- in the form of silica and silicates used in ceramics, glass and cement.
• Germanium exists only in traces. Tin occurs mainly as cassiterite, SnO2 and lead as
galena, PbS. Flerovium is a synthetically prepared radioactive element.
• Ultrapure form of germanium and silicon- used to make transistors and semiconductor
devices.
• valence shell electronic configuration- ns2np2.
• Refer to the following table for various physical properties of group 14 elements

• All members of group14 are solids

• Carbon and silicon- non-metals
• Ge- metalloid.
• Tin and lead -soft metals with low melting points.
• The common oxidation states- +4 and +2.
• Group 14 (except carbon) halides undergo hydrolysis and have a tendency to form
complexes by accepting electron pairs from donor species. For example, the species

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 like SiF62–, [GeCl6]2–, [Sn(OH)6]2– exist where the hybridisation of the central atom is
sp3d2.
• Oxides: monoxide (MO) and dioxide (MO2)
• Oxides in higher oxidation states of elements are generally more acidic than those in
lower oxidation states.
• CO2, SiO2 and GeO2 are acidic, whereas SnO2 and PbO2 are amphoteric in nature.
• CO is neutral, GeO is distinctly acidic whereas SnO and PbO are amphoteric.
• Tin decomposes steam to form dioxide and dihydrogen gas.

• These elements form covalent halides of formula MX2 and MX4 (where X = F, Cl, Br,
I).
• SnF4 and PbF4, which are ionic in nature. PbI4 does not exist.
• Ge to Pb are able to make halides of formula MX2.
• SiCl4 undergoes hydrolysis leading to the formation of Si(OH)4

➢ IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF CARBON

• Carbon forms p𝝅– p𝝅 multiple bonds with itself (allotropic forms) and with other atoms
of small size and high electronegativity.
• Carbon atoms have the tendency to link with one another through covalent bonds to
form chains and rings. This property is called catenation.
• The order of catenation is C > > Si >Ge ≈Sn.
• Allotropic forms of C: many (Diamond, graphite, and fullerenes).

➢ Diamond:
• crystalline lattice
• Hybridisation of each C: sp3
• C–C bond length is 154 pm
• Diamond is the hardest substance on the earth.
• Uses: as an abrasive for sharpening hard tools, in
making dyes and in the manufacture of tungsten
filaments for electric light bulbs.

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➢ Graphite:
• layered structure
• Layers are held by van der Waals forces and distance
between two layers is 340 pm.
• Each layer is composed of planar hexagonal rings of
carbon atoms. C—C bond length within the layer is
141.5 pm.
• Hybridisation of each C: sp2. Fourth electron forms a
bond.
• The electrons are delocalised over the whole sheet and
hence conducts electricity.
• very soft and slippery
• Uses: as a dry lubricant
• Fullerenes: cage like molecules
• Made by heating graphite in an electric arc in the
presence of inert gases such as helium or argon.
• Fullerenes are the only pure form of carbon because they have smooth structure without
having ‘dangling’ bonds.

➢ Buckminsterfullerene: C60
• Contains twenty six- membered rings and twelve five-
membered rings
• A six membered ring is fused with six or five membered
rings but a five membered ring can only fuse with six
membered rings.
• Hybridisation of each C: sp2.
• The fourth electron delocalise in molecular orbitals,
which in turn give aromatic character to molecule.
• This spherical fullerenes are also called bucky balls in
short. C60 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 138.3 pm respectively.
• Graphite is thermodynamically most stable allotrope of carbon
• ΔfH° of graphite is taken as zero. ΔfH° values of diamond and fullerene, C60 are 1.90
and 38.1 kJ mol–1, respectively. Other (impure) forms of elemental carbon like carbon
black, coke, and charcoal.
• Uses of Carbon: embedded in plastic material form high strength, lightweight
composites- tennis rackets, fishing rods, aircrafts
• graphite is used for electrodes in batteries
• activated charcoal is used in adsorbing poisonous gases
• Coke is used as a fuel and largely as a reducing agent in metallurgy. Diamond is used
in jewellery.

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➢ SOME IMPORTANT COMPOUNDS OF CARBON AND SILICON
• Carbon Monoxide (CO): colourless,odourless and almost water insoluble gas.
• Produced by direct oxidation of C in limited supply of oxygen.

• For small scale production: dehydration of formic acid with conc H2SO4 at 373 K

• Commercial production: by the passage of steam over hot coke.

• The mixture of CO and H2 gas is known as water or synthesis gas.

• Producer gas is produced if coke is heated in air.

• CO is a powerful reducing agent.

• CO has one sigma and two 𝝅-bonds.

• Because of the presence of a lone pair on carbon, CO molecule acts as a donor.
• CO forms a complex with haemoglobin, which is about 300 times more stable than the
oxygen-haemoglobin complex.
• Carbon Dioxide (CO2): a colourless and odourless gas
• Prepared by complete combustion of carbon and carbon containing fuels in excess of
air.

➢ Laboratory method:

• On commercial scale, it is obtained by heating limestone.

• CO2 react with water to form carbonic acid, H2CO3 (a weak dibasic acid)

• H2CO3/HCO3– buffer system helps to maintain pH of blood between 7.26 to 7.42.

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➢ Photosynthesis:

• CO2 cause greenhouse effect

• Solid CO2 is called dry ice
• C-O bond length is 115 pm on CO2 due to resonance

• Silicon Dioxide, SiO2: a covalent, three-

dimensional network solid.
• Each silicon atom is covalently bonded
to four oxygen atoms.
• Each oxygen atom is covalently bonded
to another silicon atoms
• eight membered rings are formed with
alternate silicon and oxygen atoms

• SiO2 can be attacked by HF and NaOH

• Quartz is extensively used as a piezoelectric material Kieselghur, an amorphous form

of silica is used in filtration plants

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 • Silicones: organosilicon polymers having R2SiO as a repeating unit
• Starting material of silicones: RnSiCl(4–n) R is alkyl or aryl group.
• Hydrolysis of dimethyldichlorosilane, (CH3)2SiCl2 followed by condensation
polymerisation yields straight chain polymers.
• The chain length of the polymer can be controlled by adding (CH3)3SiCl

- Uses: Used as sealant, greases,

electrical insulators and for
waterproofing of fabrics.

- Being biocompatible they are also

used in surgical and cosmetic plants.

• Silicates: examples are feldspar, zeolites, mica

and asbestos
• The basic structural unit of silicates is SiO44–
• Silicate units links together to form chain, ring,
sheet or three-dimensional structures
• Man made silicates: glass and cement.
• Zeolites: aluminosilicate
• Cations present in zeolites: Na+, K+ or Ca2+
• Zeolites as a catalyst: e.g., ZSM-5 used to
convert alcohols directly into gasoline.
• Hydrated zeolites are used as ion exchangers in softening of “hard” water.

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 Organic Chemistry – Some Basic Principles and Technique
● Berzilius, a Swedish chemist proposed that a ‘vital force’ was responsible for the formation
of organic compounds.
● 1828 F. Wohler synthesized an organic compound, urea from an inorganic compound,
ammonium cyanate.

● Acetic acid synthesize by Kolbe (1845) and methane synthesize by Berthelot (1856)
⮚ The Shapes of Carbon Compounds
● Hybrid orbitals with more s character will be closer to the nucleus and have more
electronegativity and form shorter and stronger bonds.
● sp hybrid orbital with 50% s character is more electronegative, have more bond energy,
than sp2 or sp3 hybridised orbitals.
⮚ Some Characteristic Features of π Bonds
● In a π (pi) bond formation, parallel orientation of the two p orbitals on adjacent atoms
is necessary for a proper sideways overlap.
● Thus, in the H2C=CH2 molecule all the atoms must be in the same plane.
● π bonds provide the most reactive centres in the molecules containing multiple bonds.
⮚ Structural Representations of organic compounds
❖ Complete structural formulas
● A single dash represents a single bond, double dash is used for double bond and a
triple dash represents triple bond.
● Lone-pairs of electrons on heteroatoms (e.g.,oxygen, nitrogen, sulphur, halogens
etc.) may or may not be shown

❖ Condensed structural formula:

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.

CH3CH2CH2CH2CH2CH2CH2CH3 can be further condensed to CH3(CH2)6CH3

❖ Bond-line structural
● 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),

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 while the line junctions denote carbon atoms bonded to the appropriate number of
hydrogens required to satisfy the valency of the carbon atoms.

❖ Three-Dimensional Representation of Organic Molecule

● Solid and dashed wedge formula

❖ Classification of Organic Compounds

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 I. Acyclic or open chain compounds
These compounds are also called aliphatic compounds and consist of straight or
branched chain compounds.

II. Alicyclic or closed chain or ring compound

● Alicyclic (aliphatic cyclic) compounds contain carbon atoms joined in the
form of a ring (homocyclic).
● Heterocyclic: Atoms other than carbon (O, N, S) are present in the ring.

❖ Aromatic compounds
Aromatic compounds are special types of compounds

Heterocyclic aromatic compounds

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 ❖ Functional Group
● Atom or group of atoms joined in a specific manner which is responsible for the
characteristic chemical properties of the organic compounds are called functional
groups.
● For example hydroxyl group (–OH), aldehyde group (–CHO) etc.
❖ Homologous Series
● The successive members differ from each other in molecular formula by a –CH2–
unit.
● Represented by general molecular formula.
● Ex. alkanes, alkenes, alkynes, haloalkanes, alkanols, alkanals, alkanoic acids, etc.
⮚ Nomenclature of Organic Compounds:
IUPAC (International Union of Pure and Applied Chemistry
● Names which are traditional are considered as trivial or common names.
● Ex Citric acid is named so because it is found in citrus fruits and the acid found in red
ant is named formic acid.
● Buckminsterfullerene is a common name given to the newly discovered C60 cluster.
Common or Trivial Names of Some Organic Compound

❖ The IUPAC System of Nomenclature: A systematic name of an organic compound

is generally derived by identifying the parent hydrocarbon and the functional group(s)
attached to it.

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⮚ IUPAC Nomenclature of Alkanes
● Straight chain hydrocarbons: The names of such compounds are based on their chain
structure, and end with suffix ‘- ane -’ and carry a prefix indicating the number of
carbon atoms present in the chain (except from CH4 to C4H10, where the prefixes are
derived from trivial names.
● Paraffin (Latin: little affinity) was the earlier name given to alkanes
IUPAC Names of Some Unbranched Saturated Hydrocarbons

● Branched chain hydrocarbons:

The small carbon chains (branches) are called alkyl groups which are named by
substituting ‘ yl ’ for ‘ane ’ in the corresponding alkane.
Thus, CH4 becomes -CH3 and is called methyl group.

Abbreviations are used for some alkyl groups. For example, methyl is abbreviated as
Me, ethyl as Et, propyl as Pr and butyl as Bu
Common branched groups have specific trivial names

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❖ The rules for naming
1. First of all, the longest carbon chain in the molecule is identified.

2. The numbering is done in such a way that the branched carbon atoms get the
lowest possible numbers.

3. If different alkyl groups are present, they are listed in alphabetical order.
4. For identical substituents, prefixes such as di (for 2), tri (3), tetra (4), penta (5),
hexa (6) etc. are used & these prefixes are not considered for alphabetical order.

5. If the two substituents are found in equivalent positions, the lower number is
given to the one coming first in the alphabetical listing.

6. In branched alkyl groups the carbon atom of the branch that attaches to the root
alkane is numbered 1.

● While writing the trivial names of substituents in alphabetical order, the prefixes
iso- and neo- are considered to be the part of the fundamental name of alkyl
group.
● The prefixes sec- and tert- are not considered to be part of the fundamental name.
❖ In multi-substituted compounds, the following rules may also be remembered:
● If there happens to be two chains of equal size, then that chain is to be selected
which contains more number of side chains.
● After selection of the chain, numbering is to be done from the end closer to the
substituent.

157
❖ Cyclic Compounds:
Named by prefixing ‘cyclo’ to the corresponding straight chain alkane.

❖ Nomenclature of Organic Compounds having Functional Group(s)

● The longest chain of carbon atoms containing the functional group is Numbered in
such a way that the functional group is attached at the carbon atom possessing the
lowest possible number in the chain.
● In polyfunctional compounds, one of the functional groups is chosen as the
principal functional group and the compound is then named on that basis.
● The remaining functional groups are named as substitutes using the appropriate
prefixes.
● The choice of principal functional group is made on the basis of preference order.

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● Decreasing priority order for some functional groups is:
-COOH, –SO3H, -COOR (R=alkyl group), COCl,-CONH2, -CN, -HC=O,
>C=O, -OH, -NH2 , >C=C<,-C≡C- .
● The –R, C6H5-, halogens (F, Cl, Br, I), –NO2, alkoxy (–OR) etc. are always prefix
substituents.
Ex . HOCH2(CH2)3CH2COCH3 will be named as 7-hydroxyheptan-2-one
BrCH2CH=CH2 is named as 3-bromoprop-1-ene and not 1-bromoprop-2-en
● If more than one functional group of the same type is present, their number is
indicated by adding di, tri, etc before the class suffix.
● The ending – ane of the parent alkane is dropped in the case of compounds having
more than one double or triple bond; for example, CH2=CH-CH=CH2 is named as
buta–1,3–diene.
● Some Functional Groups and Classes of Organic Compounds

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❖ Nomenclature of Substituted Benzene Compounds
● The substituent is placed as a prefix to the word benzene.

● If a benzene ring is disubstituted, the position of substituents is defined by

numbering the carbon atoms of the ring such that the substituents are located at the
lowest numbers possible.

● In the trivial system of nomenclature the terms ortho (o), meta (m) and para (p)
are used as prefixes to indicate the relative positions 1,2- ;1,3- and 1,4- respectively.
● In some cases, the common name of benzene derivatives is taken as the base
compound.
● Substituent of the base compound is assigned number 1 and then the direction of
numbering is chosen such that the next substituent gets the lowest number. The
substituents appear in the name in alphabetical order.

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 ● When a benzene ring is attached to an alkane with a functional group, it is
considered as substituent, instead of a parent. and as phenyl (C6H5-, also
abbreviated as Ph).
❖ Isomerism
The phenomenon of existence of two or more compounds possessing the same
molecular formula but different properties is known as isomerism. Such compounds
are called isomers.

● Structural Isomerism: Compounds having the same molecular formula but

different structures (manners in which atoms are linked) are classified as structural
isomers.
I. Chain isomerism: Same molecular formula but different carbon skeletons.
For example, C5H12 represents three compounds

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 II. Position isomerism: Differ in the position of substituent atom or functional group
on the carbon skeleton. For example, C3H8O represents two alcohols:

III. Functional group isomerism: same molecular formula but different functional
groups. For example, C3H6O represents an aldehyde and a ketone

IV. Metamerism: It arises due to different alkyl chains on either side of the functional
group in the molecule.
For example, C4H10O represents methoxypropane (CH3OC3H7) and ethoxyethane
(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 stereoisomerism and can
be classified as geometrical and optical isomerism.
⮚ Fundamental Concepts In Organic Reaction Mechanism:
The general reaction is depicted as follows

● Substrate is that reactant which supplies carbon to the new bond and the other reactant
is called reagent. If both the reactants supply carbon to the new bond then choice is
arbitrary and in that case the molecule on which attention is focused is called substrate.
● A sequential account of each step, describing details of electron movement, energetics
during bond cleavage and bond formation, and the rates of transformation of reactants
into products (kinetics) is referred to as reaction mechanism.
❖ Fission of a Covalent Bond

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 A covalent bond can get cleaved either by:
I. Heterolytic cleavage: The bond breaks in such a fashion that the shared pair of
electrons remains with one of the fragments.
⮚ Carbocation:

● A species having a carbon atom possessing a sextet of electrons and a positive charge
is called a carbocation (earlier called carbonium ion).
● Carbocation is classified as primary, secondary or tertiary.
● Carbocations are highly unstable and reactive species.
● Alkyl groups directly attached to the positively charged carbon stabilise the
carbocations due to inductive and hyperconjugation effects, & order of stability is:
+ + + +
C H 3  CH 3 C H 2  ( CH 3 )2 C H  ( CH 3 )3 C
● Carbocations have a trigonal planar shape with sp2 hybridised.

⮚ Carbanion:

● Negative charge on a carbon atom is called carbanion.

● The organic reactions which proceed through heterolytic bond cleavage are called ionic
or heteropolar or just polar.
● Carbanions are also unstable and reactive species.
II. Homolytic cleavage: One of the electrons of the shared pair in a covalent bond
goes with each of the bonded atoms.
● Neutral species (atom or group) which contains an unpaired electron are called free
radicals.

● Alkyl radicals are classified as primary, secondary, or tertiary. & stability order

● Organic reactions, which proceed by homolytic fission are called free radical or
homopolar or nonpolar reactions

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⮚ Nucleophiles and Electrophiles:
● A reagent that brings an electron pair is called a nucleophile (Nu:) i.e., nucleus seeking
and the reaction is then called nucleophilic.
Ex. Negatively charged ions HO–, NC– and carbanions (R3C:–).
Neutral molecules etc.,
● A reagent that takes away an electron pair is called electrophile (E+) i.e., electron
seeking and the reaction is called electrophilic.
Ex carbocations (+CH3) and carbonyl group (>C=O) or alkyl halides (R3C-X, where X
is a halogen atom).
⮚ Electron Movement in Organic Reactions:
To show the change in position of a pair of electrons, a curved arrow starts from the point
from where an electron pair is shifted and it ends at a location to which the pair of electrons
may move.
Presentation of shifting of electron pair is given below:

Movement of single electron is indicated by a single barbed ‘fish hooks

⮚ Electron Displacement Effects in Covalent Bonds

❖ Inductive Effect
● The electron density is more towards the more electronegative atom of the bond
and it results in a polar C – Cl bond.
● Carbon-1 gains some positive charge (δ+) and the chlorine gains some negative
charge (δ–).

● Such polarisation of σ-bond caused by the polarisation of adjacent σ-bond is

referred to as the inductive effect.
● This effect decreases rapidly as the number of intervening bonds increases and
becomes vanishingly small after three bonds.
● Substituents can be classified as electron-withdrawing (-I) or electron donating
groups(+I) relative to hydrogen.
Electron-withdrawing groups: Halogens, nitro (-NO2), cyano (-CN), carboxy (-
COOH), ester (-COOR), aryloxy (-OAr, e.g. – OC6H5), etc.

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 Electron donating groups: Alkyl groups like methyl (–CH3) and ethyl (–CH2–
CH3).
⮚ Resonance Structure

● Actual structure of benzene cannot be adequately represented by any of these structures,

rather it is a hybrid of the two structures (I and II) called resonance structures
● The resonance structures (canonical structures or contributing structures) are
hypothetical and individually do not represent any real molecule.
● They contribute to the actual structure in proportion to their stability.
● The energy of the actual structure of the molecule (the resonance hybrid) is lower than
that of any of the canonical structures.
● The difference in energy between the actual structure and the lowest energy resonance
structure is called the resonance energy.
● The more the number of contributing structures, the more is the resonance energy.
❖ Rules for writing resonance structures:
● The resonance structures have
(i) The same positions of nuclei.
(ii) The same number of unpaired electrons.
● Among the resonance structures, more stable is one which has
I. more number of covalent bonds.
II. All the atoms with octet of electrons (except hydrogen which has a
duplet).
III. Less separation of opposite charges.
IV. A negative charge if any on more electronegative atoms and a positive
charge if any on more electropositive atoms.
V. More dispersal of charge.
⮚ Resonance Effect.
● The resonance effect is defined as ‘the polarity produced in the molecule by the
interaction of two π-bonds or between a π-bond and lone pair of electrons present on
an adjacent atom’.
● The presence of alternate single and double bonds in an open chain or cyclic system is
termed as a conjugated system. and the π-electrons are delocalized and the system
develops polarity
● The examples are 1,3- butadiene, aniline and nitrobenzene etc.
I. Positive Resonance Effect (+R effect)
When the transfer of electrons is away from an atom or substituent group attached
to the conjugated system.

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 +R effect substituent groups: – halogen, –OH, –OR, –OCOR, –NH2, –NHR, –
NR2, –NHCOR.
II. Negative Resonance Effect (-R effect)
When the transfer of electrons is towards the atom or substituent group attached to
the conjugated system

-R effect substituent groups: – COOH, –CHO, >C=O, – CN, –NO2

⮚ Electromeric Effect (E effect)
● It is a temporary effect.
● The organic compounds having a multiple bond (a double or triple bond) show this
effect in the presence of an attacking reagent only.
● Defined as the complete transfer of a shared pair of π-electrons to one of the atoms
joined by a multiple bond on the demand of an attacking reagent.
I. Positive Electromeric Effect (+E effect) : π−electrons of the multiple bond are
transferred to that atom to which the reagent gets attached.

II. Negative Electromeric Effect (–E effect) : π - electrons of the multiple bond are
transferred to that atom to which the attacking reagent does not get attached.

Note: When inductive and electromeric effects operate in opposite directions, the
electromeric effect predominates.
⮚ Hyperconjugation
● Delocalization of σ 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.
● Hyperconjugation is a permanent effect, also regarded as no bond resonance.
● Electrons of the C-H bonds of the methyl group can align in the plane of empty p orbital
of positively charged carbon atom and get delocalized into the empty p orbital as
depicted in below figure

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 ● This type of overlap stabilises the carbocation because electron density from the
adjacent σ bond helps in dispersing the positive charge.
● Greater the number of alkyl groups attached to a positively charged carbon atom, the
greater is the hyperconjugation interaction and stabilisation of the cation.
● Relative stability order of carbocations:

● Hyperconjugation is also possible in alkenes and alkylarenes

⮚ Types of Organic Reactions and Mechanisms

Organic reactions can be classified into the following categories:
(i) Substitution reactions
(ii) Addition reactions
(iii) Elimination reactions

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 (iv) Rearrangement reactions
⮚ Methods of Purification of Organic Compounds
The common techniques used for purification are as follows :
(i) Sublimation (ii) Crystallisation (iii) Distillation
(iv) Differential extraction (v) Chromatography
I. Sublimation:
Used to separate sublimable compounds from non-sublimable impurities
II. Crystallisation
● Crystallisation is one of the most commonly used techniques for the purification of
solid organic compounds.
● It is based on the difference in the solubilities of the compound and the impurities in a
suitable solvent.
● The impure compound is dissolved in solvent and heated at higher temp. on cooling the
hot and conc. solution pure compounds crystallizes out.
● 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.
III. Distillation
Simple Distillation
● Used to separate
(i) Volatile liquids from nonvolatile impurities.
(ii) The liquids have sufficient difference in their boiling points.
● Ex Chloroform (b.p 334 K) and aniline (b.p. 457)
● On boiling, the vapours of the 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 components form later and the liquid can be collected
separately.

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⮚ Fractional Distillation:
● Used when the difference in boiling points of two liquids is not much.
● A fractionating column provides many surfaces for heat exchange, some of the
condensing liquid in the fractionating column obtains heat from the ascending vapours
and revaporises.
● The vapours thus become richer in low boiling components & ascend to the top of the
column.
● On reaching the top, the vapours become pure in a low boiling component and pass
through the condenser and the pure liquid is collected in a receiver.
● After a series of successive distillations, the remaining liquid in the distillation flask
gets enriched in a high boiling component.
● Each successive condensation and vaporisation unit in the fractionating column is
called a theoretical plate.
● It is used to separate different fractions of crude oil in petroleum industry

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⮚ Distillation under reduced pressure
● Used to purify liquids having very high boiling points and those, which decompose at
or below their boiling points.
● Liquids are made to boil at a temperature lower than their normal boiling points by
reducing the pressure on their surface with help of water pump or vacuum pump
● Ex. Glycerol can be separated from spent-lye in soap industry

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⮚ Steam Distillation
● Used to separate substances which are steam volatile and are immiscible with water.
● The mixture of steam and the volatile organic compound is condensed and collected.
● The compound is later separated from water using a separating funnel.
● Aniline is separated by this technique from aniline – water mixture.

III. Differential Extraction

● Used to separate organic compounds present in an aqueous medium, by shaking it with
an organic solvent in which it is more soluble than in water.

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● 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 a separatory funnel.
● The organic solvent is later removed by distillation or by evaporation to get back the
compound.
● If the organic compound is less soluble in the organic solvent, then, technique of
continuous extraction is employed in which the same solvent is repeatedly used.

IV. Chromatography
● 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 mobile phase.

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● Based on the principle involved, chromatography is classified into different categories.
(a) Adsorption chromatography, and (b) Partition chromatography.
(a) Adsorption Chromatography:
● Based on the fact that different compounds are adsorbed on an adsorbent to different
degrees.
● Commonly used adsorbents are silica gel and alumina.
● Two main types of chromatographic techniques
(i) Column chromatography, and (ii) Thin layer chromatography
I. Column Chromatography:
● It involves separation of a mixture over a column of adsorbent (stationary phase) packed
in a glass tube.
● The mixture is placed on the top of the adsorbent column
● An appropriate eluant which is a liquid or a mixture of liquids is allowed to flow down
the column slowly.
● The most readily adsorbed substances are retained near the top and others come down
to various distances in the column.
II. Thin Layer Chromatography:
● It involves separation of substances of a mixture over a thin layer (about 0.2mm thick)
of an adsorbent coated on a glass tube.
● The plate is known as thin layer chromatography plate or Chroma plate.
● The solution of the mixture to be separated is applied as a small spot about 2 cm above
one end of the TLC plate.
● As the 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. R f value
Distance moved by the substance from base line (x)
Rf =
Distance moved by the solvent from base line (y)
● The spots of colourless compounds, which are invisible to the eye, can be detected by
putting the plate under ultraviolet light.
● Another detection technique is to place the plate in a covered jar containing a few
crystals of iodine. Spots of compounds, which adsorb iodine, will show up as brown
spots.
● Sometimes an appropriate reagent may also be sprayed on the plate. For example,
amino acids may be detected by spraying the plate with ninhydrin solution

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(b) Partition Chromatography: based on continuous differential partitioning of
components of a mixture between stationary and mobile phases.

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 ● Paper chromatography is a type of partition chromatography.
● In paper chromatography, a special quality paper known as chromatography
paper is used. which 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 & 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 a 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
❖ Detection of Carbon and Hydrogen:
● Presence of carbon and hydrogen is 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.

● Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted
from the fused mass by boiling it with distilled water. This extract is known as
sodium fusion extract.
(A) Test for Nitrogen
● The sodium fusion extract is boiled with iron (II) sulphate and then acidified with
concentrated sulphuric acid. The formation of Prussian blue colour confirms the
presence of nitrogen.
● On heating with concentrated sulphuric acid some iron (II) ions are oxidised to iron
(III) ions.

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 (B) Test for Sulphur
(a) The sodium fusion extract is acidified with acetic acid and lead acetate is added to
it. A black precipitate of lead sulphide indicates the presence of sulphur.
S2– + Pb2+ → PbS (Black)
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a
violet colour further indicates the presence of sulphur

If 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.
NaSCN + 2Na → NaCN + Na2S
(C) Test for Halogens:
● The sodium fusion extract is acidified with nitric acid and then treated with silver
nitrate.
● White precipitate, soluble in ammonium hydroxide shows the presence of chlorine.
● Yellowish precipitate, sparingly soluble in ammonium hydroxide shows the
presence of bromine.
● 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. These ions would otherwise interfere with
silver nitrate test for halogens
(D) Test for Phosphorus
● The compound is heated with an oxidising agent (sodium peroxide). The
phosphorus present in the compound is oxidised to phosphate.
● The solution is boiled with nitric acid and then treated with ammonium molybdate.
A yellow colouration or precipitate indicates the presence of phosphorus.

⮚ Quantitative Analysis

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The percentage composition of elements present in an organic compound is determined by
the methods.
❖ Carbon and Hydrogen
● A known mass of an organic compound is burnt in the presence of excess oxygen
and copper (II) oxide.
CxHy + (x + y/4) O2 → x CO2 + (y/2) H2O
● 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 a concentrated solution of
potassium hydroxide.

● 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’s method
(ii) Kjeldahl's Method.
(i) Dumas’s method:
CxHyNz + (2x + y/2) CuO → x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu

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 let the mass of organic compound = m g
Volume of nitrogen collected = V1 mL
Room temperature = T1 K
p V  273
Volume of nitrogen at STP = 1 1
760  T1
( Let it be V mL )
Where p1 and V1 are the pressure and volume of nitrogen.
The value of p1 is obtained by the relation; p1= Atmospheric pressure – Aqueous
tension
22400 mL N2 at STP weighs 28 g.

(ii) Kjeldahl’s method

Let the mass of organic compound taken = m g

Volume of H2SO4 of molarity, M,taken = V mL
Volume of NaOH of molarity, M, used for titration of excess of H2SO4 = V1 mL
V1mL of NaOH of molarity M= V1 /2 mL of H2SO4 of molarity M
Volume of H2SO4 of molarity M unused= (V - V1/2) mL (V - V1/2) mL of H2SO4 of
molarity M = 2(V - V1/2) mL of NH3 solution of molarity M.

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 1000 mL of 1 M NH3 solution contains 17g NH3 or 1 g of N

Note: Kjeldahl method is not applicable to compounds containing nitrogen in nitro

and azo groups and nitrogen present in the ring (e.g. pyridine) as nitrogen of these
compounds does not change to ammonium sulphate under these conditions.
⮚ 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.
● The halogen present forms the corresponding silver halide (AgX).
● Let the mass of organic compound taken = m g
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of X

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⮚ Sulphur
● 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 barium chloride solution in water.
● 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

⮚ Phosphorus
● A known mass of an organic compound is heated with fuming nitric acid where
phosphorus oxidised to phosphoric acid.
● It is precipitated as ammonium phosphomolybdate, (NH4)3PO4.12MoO3, by adding
ammonia and ammonium molybdate, or maybe precipitated as MgNH4PO4 by
adding magnesia mixture which on ignition yields Mg2P2O7.
● Let the mass of organic compound taken= m g
mass of ammonium phosphomolybdate (Mg2P2O7) = m1g
Molar mass of (NH4)3PO4.12MoO3 = 1877 g

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 where, 222 u is the molar mass of Mg2P2O7
⮚ Oxygen:
● The percentage of oxygen in an organic compound is usually found by the
difference between the total percentage composition (100) and the sum of the
percentages of all other elements.
● Oxygen can also be estimated directly as follows

● On making the amount of CO produced in equation (A) equal to the amount of CO

used in equation (B), we find that each mole of oxygen liberated from the compound
will produce two moles of carbon dioxide; Thus 88 g carbon dioxide is obtained if
32 g oxygen is liberated.
Let the mass of organic compound taken be m g
Mass of carbon dioxide produced be m1 g
 m1 g carbon dioxide is obtained from
32  m1
gO2
88
32  m1  100
 Percentage of oxygen = %
88  m

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 Hydrocarbons
Compounds of carbon and hydrogen
⮚ Classification
● Classified as (i) saturated (ii) unsaturated (iii) aromatic hydrocarbons.
● Saturated hydrocarbons contain carbon-carbon single bonds
● Unsaturated hydrocarbons contain carbon-carbon multiple bonds – double bonds, triple
bonds or both.
● Aromatic hydrocarbons are a special type of cyclic compounds
⮚ Alkanes
● Alkanes are saturated open chain hydrocarbons & general formula is CnH2n+2
● Alkanes are inert under normal conditions as they do not react with acids, bases and
other reagents. they were earlier known as paraffins (latin : parum, little; affinis,
affinity)
● First member of alkane is Methane (CH4) & it is gas found in coal mines and marshy
places & have a tetrahedral structure

● In alkanes, tetrahedra are joined together in which C-C and C-H bond lengths are
154 pm and 112 pm
⮚ Nomenclature and Isomerism
● First three alkanes – methane, ethane and propane have only one structure but higher
alkanes can have more than one structure.
● Structures for C4H10
● Structures for C5H12

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● Difference in properties due to difference in the structures of compound with the same
molecular formula, they are known as structural isomers.
● Structural isomers which differ in chain of carbon atoms are known as chain isomers
● C6H14 has five isomers, C7H16 has nine and C10H22 has 75 isomers
● Carbon atom is classified as:
Primary (1°): Carbon atom attached to no other carbon atom
Secondary (2°): Carbon atom attached to two carbon atoms
Tertiary (3°): Carbon atom attached to three carbon atoms
Quaternary (4°): Carbon atom attached to four carbon atoms

● Writing structure from the given IUPAC name

Ex. 3-ethyl-2, 2–dimethylpentane in the following steps
i) Draw the chain of five carbon atoms: C – C – C – C – C
ii) Give number to carbon atoms: C1– C2– C3– C4– C5

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 iii) Attach ethyl group at carbon 3 and two methyl groups at carbon 2

iv) Satisfy the valence of each carbon atom by putting requisite number of hydrogen
atoms

⮚ Preparation.
1. From unsaturated hydrocarbons
● Hydrogenation: Addition of H2 gas to alkenes and alkynes

2. From alkyl halides : (i) Reduction of alkyl halide (except fluorides)

(ii) Wurtz reaction: on treatment with sodium metal in dry ethereal (free from
moisture) solution give higher alkanes. (Containing even number of carbon atoms)

3. From carboxylic acids

i) Decarboxylation: The process of elimination of carbon dioxide from a carboxylic
acid
This method gives alkanes containing one carbon atom less than the carboxylic acid.

ii) Kolbe’s electrolytic method:

● On electrolysis we get alkane containing an even number of carbon atoms at the
anode.
● Methane cannot be prepared by this method.

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 ● The reaction is supposed to follow the following path:

⮚ Properties
❖ Physical properties
● Alkanes are colourless & odourless, almost non-polar molecules, soluble in non-
polar solvent.
● They possess weak van der Waals forces which increase with increase of the
molecular size or the surface area of the molecule. That’s why C1 to C4 are gases,
C5 to C17 are liquids and C18 & higher members are solids at 298 K.
● Boiling point increases with increase in molecular mass
● Boiling point decreases with increase in number of branched chains, as the
molecule attains the shape of a sphere which has lower surface area.

❖ Chemical properties
1. Substitution reactions

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 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.
Halogenation: One or more hydrogen atoms of alkanes can be replaced by
halogens. Halogenation takes place either at higher temperature (573-773 K) or in
the presence of diffused sunlight or ultraviolet light

● Rate of reaction of alkanes with halogens is F2 > Cl2 > Br2 > I2
● Rate of alkanes is: 3° > 2° > 1°.
● Fluorination is too violent to be controlled and Iodination is very slow and a
reversible reaction. It can be carried out in the presence of oxidizing agents like
HIO3 or HNO3.

❖ Halogenation Mechanism: free radical chain mechanism

I. Initiation: initiated by homolysis of chlorine molecules in the presence of light or
heat.

II. Propagation:

Many other propagation steps are possible which gives more highly halogenated
products

III. Termination: The reaction stops after some time due to consumption of reactants
and or due to the side reactions:
The possible chain terminating steps are:

2. Combustion:

❖ The general combustion equation for any alkane is

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● During incomplete combustion with insufficient amount of air or dioxygen, carbon
black is formed which is used in the manufacture of ink, printer ink, black pigments
and as filters.

3. Controlled oxidation: On heating with a regulated supply of dioxygen or air at

high pressure and in the presence of suitable catalysts give a variety of oxidation
products.

IV. Ordinarily alkanes resist oxidation but alkanes having tertiary H atom can be
oxidized to corresponding alcohols by potassium permanganate.

4. Isomerization

5. Aromatization: n-Alkanes having six or more carbon atoms get dehydrogenated

and cyclised to benzene and its homologues. This reaction is known as
aromatization or reforming.

6. Reaction with steam; this method is used for industrial preparation of dihydrogen
gas.

7. Pyrolysis: Decomposition of higher alkanes into smaller fragments by the

application of heat is called pyrolysis or cracking.

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 ● Pyrolysis is a free radical reaction.
● Pyrolysis of dodecane, a constituent of kerosene oil.

⮚ Conformations:
● 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.
● Rotation around a C-C single bond is hindered by a small energy barrier of 1-20 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:
● Rotation results in an 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.
● 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 as possible is known as the staggered conformation. Any other intermediate
conformation is called a skew conformation.
● 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
▪ The molecule is viewed along the molecular axis.
▪ Central C – C bond represented by a longer straight line.
▪ The front carbon is shown at the lower end & rear carbon is shown at the upper
end.
▪ Each carbon has three lines inclined at an angle of 120° to each other.

188
 2. Newman projections
▪ The molecule is viewed at the C–C bond head on.
▪ The carbon atom nearer to the eye is represented by a point.Three hydrogen
atoms attached to the front carbon atom are shown by three lines drawn at an
angle of 120° to each other.
▪ The rear carbon atom (the carbon atom away from the eye) is represented by a
circle and the three hydrogen atoms are shown attached to it by the shorter lines
drawn at an angle of 120° to each other.
⮚ Relative stability of conformations:
● Staggered forms have minimum repulsive forces, minimum energy and maximum
stability & eclipsed forms have minimum repulsive forces, more energy and thus have
lesser stability.
● Magnitude of torsional strain depends upon the angle of rotation about the C–C bond.
This angle is also called dihedral angle or torsional angle.
● In ethane, the staggered form has the least torsional strain and the eclipsed form, the
maximum torsional strain
● The energy difference between the two extreme forms is of the order of 12.5 kJ mol–1
● 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 & also
known as olefins (oil forming).
● General formula is CnH2n
❖ Structure of Double Bond
● Alkenes consists of one strong sigma (σ) bond (bond enthalpy about 397 kJ mol–1)
due to head-on overlapping of sp2 hybridised orbitals and one weak pi (π) bond
(bond enthalpy about 284 kJ).
● Alkenes are easily attacked by reagents or compounds which are in search of
electrons due to weak pi bonds. Such reagents are called electrophilic reagents

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❖ Nomenclature:
● Numbering of the chain is done from the end which is nearer to the double bond.
● The suffix ‘ene’ replaces ‘ane’ of alkanes.
● First member of the alkene series is (:CH2) known as methene but has a very short
life.
● First stable member of alkene series is C2H4 known as ethylene (common) or
ethene (IUPAC)

❖ Isomerism
● Alkenes show both structural isomerism and geometrical isomerism.
Structural isomerism
● Alkenes higher than propene have different structures
Structure of C4H8:

● Structures I and III, and II and III are the examples of chain isomerism whereas
structures I and II are position isomers.

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❖ Geometrical isomerism:
● Restricted rotation of atoms or groups around the doubly bonded carbon atoms
gives rise to different geometries of such compounds. The stereoisomers of this
type are called geometrical isomers.
● The isomer in which two identical atoms or groups lie on the same side of the
double bond is called cis-isomer & if lie on the opposite sides of the double bond
is called trans isomer.
● These isomers differ in their properties like melting point, boiling point, dipole
moment, solubility etc.
● Geometrical or cis-trans isomers of but-2-ene are represented below

● Cis form of alkene is found to be more polar than the trans.

● Trans isomer has higher melting point than the cis form.
● Geometrical or cis-trans isomerism is also shown by alkenes of the types XYC =
CXZ and XYC = CZW
❖ Preparation
1. From alkynes:
● Partial reduction of alkynes by Partially deactivated palladised charcoal is known
as Lindlar’s catalyst, gives cis alkene.
● Reduction with sodium in liquid ammonia forms trans alkenes.

2. From alkyl halides:

● Alkyl halides (R-X) on heating with alcoholic potash eliminate one molecule of
halogen acid to form alkenes. This reaction is known as dehydrohalogenation i.e.,
removal of halogen acid.
● This is example of β-elimination reaction, since hydrogen atom is eliminated from
the β carbon atom

191
 ● Rate of reaction for halogens is: Iodine > Bromine > Chlorine
● Rate of reaction alkyl groups is: tert > secondary > primary
3. From vicinal dihalides (dehalogenation)
● Dihalides in which two halogen atoms are attached to two adjacent carbon atoms
are known as vicinal dihalides.

4. From alcohols by acidic dehydration:

● Water molecule is eliminated from the alcohol molecule in the presence of an acid,
this reaction is known as acidic dehydration of alcohols ( β-elimination reaction).

⮚ Properties
● Physical properties
❖ The first three members are gases, the next fourteen are liquids & 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 non-polar
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.
⮚ Chemical properties
● Addition of dihydrogen: Alkenes add up one molecule of dihydrogen gas in the
presence of finely divided nickel, palladium or platinum to form alkanes.
● Addition of halogens:
❖ Halogens like bromine or chlorine add up to alkene to form vicinal dihalides.
Iodine does not show addition reaction under normal conditions.
❖ 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.
❖ It is an electrophilic addition reaction involving cyclic halonium ion formation.

192
3. Addition of hydrogen halides: It is an electrophilic addition reaction.
● Hydrogen halides (HCl, HBr, HI) add up to alkenes to form alkyl halides.
● Order of reactivity of the hydrogen halides is HI > HBr > HCl.
❖ Addition reaction of HBr to symmetrical alkenes

● Addition reaction of HBr to unsymmetrical alkenes (Markovnikov Rule)

Markovnikov rule: The negative part of the addendum (adding molecule) gets
attached to that carbon atom which possesses a lesser number of hydrogen atoms.
According to rule, product I i.e., 2-bromopropane is major
Mechanism: Hydrogen bromide provides an electrophile, H+, which attacks the
double bond to form carbocation as shown below:

I. The secondary carbocation (b) is more stable than the primary carbocation (a),
therefore, the former predominates because it is formed at a faster rate.
II. The carbocation (b) is attacked by Br– ionto form the product as follows:

● Anti Markovnikov addition or peroxide effect or Kharash effect

● In the presence of peroxide, addition of HBr to unsymmetrical alkenes like propene
takes place contrary to the Markovnikov rule. This reaction is known as peroxide
or Kharash effect or addition reaction anti to Markovnikov rule.

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⮚ Mechanism: Peroxide effect proceeds via free radical chain mechanism as given below:

● Peroxide effect happens only with HBr but not with HCl and Hl, because the H–Cl
bond being stronger than H–Br bond, is not cleaved by the free radical, whereas the H–
I bond is weaker and iodine free radicals combine to form iodine molecules instead of
adding to the double bond.
4. Addition of sulphuric acid: Cold concentrated sulphuric acid adds to alkenes in
accordance with Markovnikov rule to form alkyl hydrogen sulphate by the electrophilic
addition reaction

5. Addition of water: Follow the Markovnikov rule.

6. Oxidation:
(a) Alkenes on reaction with cold, dilute, aqueous solution of potassium permanganate
(Baeyer’s reagent) produce vicinal glycols.
● Decolourisation of KMnO4 solution is used as a test for unsaturation.

194
 (b) Acidic potassium permanganate or acidic potassium dichromate oxidises alkenes to
ketones and/or acids depending upon the nature of the alkene and the experimental
conditions.

7. Ozonolysis:
This reaction is highly useful in detecting the position of the double bond in alkenes or
other unsaturated compounds.

8. Polymerisation:
Polythene is obtained by the combination of a 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 polymer are made are called monomers

⮚ Alkynes
● Containing at least one triple bond between two carbon atoms. General formula is
CnH2n–2.
● First stable alkyne is ethyne which is popularly known as acetylene.
● Acetylene is used for arc welding purposes in the form of oxyacetylene flame
obtained by mixing acetylene with oxygen gas.
❖ Nomenclature and Isomerism
● In IUPAC system,replacing ‘ ane ’ by the suffix ‘ yne ’

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 ● Two possible structures for butyne – (i) but-1-yne and (ii) but-2-yne. This are
position isomers
● Possible Structure for alkyne C5H8

● Structures I and II are position isomers and structures I and III or II and III are chain
isomers.
❖ Structure of Triple Bond
● 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)
● The C ≡ C bond length is shorter (120 pm) than those of C = C
(133 pm) and C–C (154 pm)

❖ Preparation
1. From calcium carbide:

2. From vicinal dihalides:

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❖ Properties
Physical properties:
● All alkynes are colourless. Ethyene has a characteristic odour. Other members are
odourless.
● Alkynes are weakly polar in nature. They are lighter than water and immiscible
with water but soluble in organic solvents like ethers, carbon tetrachloride and
benzene.
● Their melting point, boiling point and density increase with increase in molar mass.
Chemical properties:
A. Acidic character of alkyne:
▪ Due to the maximum percentage of s character (50%), the sp hybridised orbitals
have highest electronegativity; hence, these attract the shared electron pair of the
C-H bond & hydrogen atoms can be liberated as protons.
▪ Hence hydrogen atoms of ethyne attached to triply bonded carbon atoms are
acidic in nature.

▪ Trend in their acidic behaviour

B. Addition reactions:
▪ Formation of the addition product takes place according to the following steps.

▪ The addition product formed depends upon the stability of vinylic cation.
▪ Addition in unsymmetrical alkynes takes place according to Markovnikov rule.
i. Addition of dihydrogen:

ii. Addition of halogens:

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 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)

iv. Addition of water:

● Like alkanes and alkenes, alkynes are also immiscible and do not react with
water.
● However, one molecule of water adds to alkynes on warming with mercuric
sulphate and dilute sulphuric acid at 333 K to form carbonyl compounds

v. Polymerization
(a) Linear polymerisation:
● linear polymerisation of ethyne produce polyacetylene or polyethyne
containing repeating units of (CH = CH – CH = CH) and can be represented
as —(CH = CH – CH = CH)n—
● Under special conditions, this polymer conducts electricity. Thin film of
polyacetylene can be used as electrodes in batteries.
(b) Cyclic polymerisation:
● This is the best route for entering from aliphatic to aromatic compounds.

⮚ 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’.

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 ● Aromatic compounds containing benzene ring are known as benzenoids and those not
containing a benzene ring are known as non-benzenoids

⮚ Nomenclature and Isomerism

Three different position isomers 1, 2 or 1, 6 are known as the ortho (o –), the 1, 3 or 1, 5
as meta ( m –) and the 1, 4 as para ( p –) disubstituted compounds.

Structure of Benzene:
● Kekulé in 1865 proposed a structure for benzene & suggested the concept of oscillating
nature of double bonds in benzene as given below.

● All the six carbon atoms are sp2 hybridized & contain one unhybridized p orbital
perpendicular to the plane of the ring to form a π bond by lateral overlap
● There are two equal possibilities of forming three π bonds by overlap of p orbitals of
C1 –C2, C3– C4, C5 – C6 or C2– C3, C4– C5,C6 – C1 respectively

⮚ Resonance and stability of benzene

Aromaticity: Benzene was considered as the parent ‘aromatic’ compound.
Characteristics for a compound to be aromatic.
i. Planarity

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 ii. Complete delocalisation of the π electrons in the ring
iii. Presence of (4n + 2) π electrons in the ring where n is an integer (n = 0, 1, 2,…). This
is often referred to as Huckel Rule.

⮚ Preparation of Benzene:
Benzene is commercially isolated from coal tar.
I. Cyclic polymerisation of ethyne:

II. Decarboxylation of aromatic acids:

III. Reduction of phenol:

⮚ Properties
Physical properties

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 ● These are non- polar molecules & have characteristic aroma. Ex naphthalene balls are
used in toilets and for preservation of clothes because of the unique smell of the
compound and the moth repellent property.
● These are immiscible with water but are readily miscible with organic solvents.
● They burn with sooty flame.
⮚ Chemical properties
● Electrophilic substitution reactions:
I. Nitration:

II. Halogenation:

on treatment with excess of chlorine it formed hexachlorobenzene (C6Cl6)

III. Sulphonation:

IV. Friedel-Crafts alkylation reaction:

V. Friedel-Crafts acylation reaction:

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⮚ Mechanism of electrophilic substitution reactions
(a) Generation of electrophile E⊕
Anhydrous AlCl3, being a Lewis acid helps in generation of the electrophile Cl⊕,
R⊕,RC⊕O by combining with the attacking reagent.

In nitration, electrophile,NO2+ is produced by gaining proton (from sulphuric acid)

sulphuric acid serves as an acid and nitric acid as a base.

(b) Formation of Carbocation(arenium ion): Attack of electrophile results in the

formation of σ -complex or arenium ion in which one of the carbon is sp3 hybridised.

The Sigma complex loses its aromaticity because delocalisation of electrons stops at
sp3 carbon.
(c) Removal of proton: To restore the aromatic character, σ -complex releases proton from
sp3 hybridised carbon on attack by [AlCl4]– (in case of halogenation, alkylation and
acylation) and [HSO4]– (in case of nitration).

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 ● Addition reactions

● Combustion: When heated in air, benzene burns with sooty flame producing CO2 and
H2O.

General combustion reaction for any hydrocarbon may be given by

⮚ Directive influence of a functional group in monosubstituted benzene

● Ortho and para directing groups:
● Phenol is resonance hybrid of following structures:

● electron density is more on o– and p– positions. Hence, the substitution takes place
mainly at these positions.
● –I effect of –OH group also operates due to which the electron density is slightly
reduced, but the overall electron density increases due to resonance.
● –OH, –NH2, –NHR, –NHCOCH3, –OCH3,–CH3, –C2H5, etc group activates the
benzene ring for the attack by an electrophile.
● In 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.
⮚ Meta directing group:

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 ● The groups direct the incoming group to meta position.
● Meta directing groups are –NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H, etc.
● Nitro group reduces the electron density in the benzene ring due to its strong –I effect.

● The overall electron density on the benzene ring decreases making further substitution
difficult, therefore these groups are also called ‘deactivating groups’.
● The electron density on o – and p – position is comparatively less than that at meta
position. Hence electrophile attacks on comparatively electron rich meta position
resulting in meta substitution.
⮚ Carcinogenicity and Toxicity
● Benzene and polynuclear hydrocarbons containing more than two benzene rings fused
together are toxic and said to possess cancer producing (carcinogenic) properties.
● These are formed on incomplete combustion of organic materials like tobacco, coal and
petroleum.
● They enter into the human body and undergo various biochemical reactions and finally
damage DNA and cause cancer. Some of the carcinogenic hydrocarbons are given
below (see box).

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 Environmental Chemistry

• Elements of environment: Atmosphere, Lithosphere, Hydrosphere (Non-Living

components), Biosphere
• Environmental pollution: Air, land and water pollution
• A substance responsible for pollution, is called as pollutant
➢ Atmosphere
• Height of atmosphere: 500 km
• Approx. mass of atmosphere: 4.5-5x1015 tons
• Composition of dry air at sea level:
❖ Major components: Nitrogen, oxygen, water vapour
❖ Minor components: Argon, Carbon dioxide
❖ Trace components: Neon, Helium, methane etc.
• Major regions of the atmosphere:
Region Height (km) Temperature (0C) Main constituents
Troposphere 0-11 15 to -56 O2, N2, CO2, H2O
Stratosphere 11-50 -56 to -2 O3
Mesosphere 50-90 -2 to -92 O2+, NO+
Thermosphere 90-500 -92 to 1200 O2+, O+, NO+
➢ Types of pollutants
• Primary and secondary pollutants:
❖ Primary pollutants: Those which after their formation enter the environment and
remain as such. Ex.: NO, NO2, SO2
❖ Secondary pollutants: The harmful material which are formed by chemical reaction
between primary pollutants in the atm. Ex.: Hydrocarbon + Oxide of nitrogen
compound
• Bio degradable and Non bio degradable pollutants:
❖ Bio degradable pollutants: Materials (eg. cow dungs) which are easily decomposed
but in excess in environment, they do not undergo degradation completely and thus
become pollutant.
❖ Non bio degradable pollutants:- Materials (eg. Hg, Al, DDT) which do not undergo
degradation (or degrade very slowly) but even in very small amount in the
environment is very harmful. They may react with other compounds present in the
environment and produce more toxic compound.
➢ Tropospheric gaseous air pollutants
Oxides of carbon:
Carbon Monoxide
• Colorless, odourless, tasteless, non-irritating gas, sparingly soluble in water
• Fatal above 100 ppm (silent killer)
• Major sources: incomplete combustion of fossil fuels, cigarette smoke, coal gas (5-
10%), water gas (30-40%), forest fire, volcanic eruptions, marine algae, marine
siphmophone

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➢ Poisoning:
• Hb + 4O2 ⇌ HbO8 oxy-haemoglobin (formed when oxygen combines with blood)
• HbO8 + CO ⇌ HbCO+4O2 carboxy-haemoglobin (when O in oxy-haemoglobin is
replaced with CO)
• Oxygen carrying capacity of blood is decreased, leading to anoxia (oxygen starvation).
• Effects of anoxia: headache, dizziness, cardiac and pulmonary complications, improper
growth of foetus in pregnant women.
• HbCO is 300 times more stable than HbO8.
• Poisoning cured by exposing the victim to oxygen under 2-2.5 atm.
HbCO + 4O2 HbO8 + CO
➢ Carbon dioxide
• Colorless, odourless, 1.5 times heavier than air, non-poisonous (death in high CO2
atmosphere caused by lack of oxygen leading to suffocation), does not support life.
• small amount of CO2 is not harmful so not considered a pollutant.
• High amount of CO2 causes global warming (it is a green house gas) and hence is a
pollutant in large amount.
• Major sources: burning of fossil fuels, cultivation of soil, industrial manufacturing
processes, decay of dead organisms, forest fire, volcanic eruptions, etc.
• Plants absorb CO2 through photosynthesis and converts it into carbohydrates.
• Algae in oceans also absorb CO2
• Effect of CO2: Global warming (green house effect), maintaining pH of rain water at
5.6
➢ Oxides of sulphur.
Sulphur dioxide
• Colorless, suffocating smell (like that of burning sulphur), irritates the respiratory
system and damages lungs
• Major sources: Burning fossil fuels, volcanic eruptions, H2S released in atmosphere is
oxidised to SO2, roasting of sulphide ores.
• Effects of SO2:
• Poisonous to both plant and animal
• Small amount causes bronchitis, asthama, emphysema, irritation to the eyes,
• Discoloration of leaves on prolonged exposure (hampers formation of chlorophyll)
• Discoloration of fabrics, leather, paper etc.
• Reactions for acid rain
1 h
SO2 + O2 ⎯⎯ → SO3
2
h
SO2 + O3 ⎯⎯ → SO3 + O2
SO3 + H2O → H2 SO4

➢ Oxides of nitrogen
• Nitrogen combines with oxygen to form N2O (nitrous oxide), NO (nitric oxide), NO2
(nitrogen dioxide), N2O3 (dinitrogen trioxide), N2O4 (dinitrogen tetraoxide), N2O5
(dinitrogen pentoxide)
• Major sources:

206
 electrical

❖ N2 + O2 ⎯⎯⎯⎯ → NO . Theses reactions take place during thunderstorms and

disch arg e

2NO + O2 → NO2
lightening
❖ Combustion of fuel at high temperature, N2O is produced by action of aerobic and
anaerobic bacteria on nitrogenous fertilizers, bacterial decay of organic matter,
NO2 is released as by-product during manufacture of TNT.
• Effects :
❖ NO, NO2 destroy O3 layer.
❖ NO2 causes extensive leaf-dropping in plants, higher concentration retards rate of
photosynthesis
❖ Inhalation of NO2 for about 2 hours causes damage to lungs, liver and kidney
❖ They react with hydrocarbons and sunlight to form photochemical smog
➢ Hydrocarbons
• Produced due to incomplete combustion of fuel
• Carcinogenic in nature
• Harm plants by causing ageing, shading of leaves, flowers and twigs
➢ Particulates in Atmospheric Pollution
• Particulates are the tiny solid or liquid particles suspended in air. These particles are
usually individually invisible to the naked eye. Collectively, however, small particles
often form a haze that restricts visibility.
• Particulates in the atmosphere may be viable or non-viable.
• Viable particulates: minute living organisms that are dispersed in atmosphere (bacteria,
fungi, moulds, algae etc). Human beings are allergic to some of the fungi found in air.
Fungi can also cause plant diseases.
• Non-viable particulates (particle size (0.001-100µm): formed either by the breakdown
of larger materials or by the condensation of minute particles and droplets.
• Four types of non-viable particulates in the atmosphere: mists, smoke, fumes and dust.
❖ Mists: particles of spray liquids (herbicides and insecticides) and the condensation
of vapours in air.
❖ Smoke: very small soot(carbon) particles produced by burning and combustion of
organic matter. Oil smoke, tobacco smoke and carbon smoke are typical
examples.
❖ Fumes are condensed vapours: fumes of metals, metallurgical fumes and alkali
fumes.
❖ Dust: Particles produced during crushing, grinding and attribution of solid
materials, ground limestone, sand tailings from floatation, pulverised coal,
cement, fly ash and silica dust.
• Effects:
❖ Affects foetus by damaging the DNA.
❖ Visibility decreases as the atmospheric particulate concentrations increase.
❖ Mercury causes headache, nervousness, fatigue, breakdown of CNS (central
nervous system)
❖ Lead damages liver, kidneys, intestines, CNS. Prolonged exposure leads to
accumulation in tissues causing anaemia

207
 ❖ Cadmium pollution from extraction of Zn and Cu causes lung irritation, vomiting
and hypertension
❖ Major role in formation of photochemical smog
❖ coarser particles of size greater than 5 microns are likely to lodge in the nasal
passages
❖ smaller ones are more likely to penetrate the lungs - the rate of penetration being
inversely proportional to the size of particles. A number of these fine particulates
are carcinogens.
❖ Inhalation of small particles irritates the lungs and prolonged exposure causes
'scarring' or 'fibrosis' of the lung lining known as 'Pneumoconiosis'.
❖ Suspended particulate matter in the atmosphere effectively reduces the number of
light rays reaching the surface of the earth and thus lowers the temperature of the
earth. By blocking the sunlight, they contribute to a drop in the earth's temperature
and by providing condensation nuclei; they contribute to increased fog and rain in
cities.
➢ Green House Effect:
• Warming of earth due to remission of sun's energy absorbed by the earth. The remission
of earth's energy is absorbed by CO2 molecules and H2O vapour present near the earth's
surface and then its radiation back to the earth, is called as green house effect. So the
temp. of the earth is increased is called as global warming.
• Height of O3 layer: 15-60 km from the surface (thickest layer of O3 at 23 km)
• Height of CO2 layer: 15 km from the surface
• Major green house gases and their sources:
Gas Sources
Carbon dioxide (CO2) 1. Fossil fuel combustion (coal, oil,
natural gas)
2. Deforestation and land use changes
Methane (CH4) 1. Enteric fermentation in cattle and
insects
2. Biomass burning and garbage land fills.
3. Leakage of gases from coal mines and
natural gas.
4. Rice paddies
5. Swamps and tundra
Chloro fluoro carbon 1. plastic foams
2. Refrigeration and air-conditioning
3. Aerosols (spray propellants) CFC’
4. Industrial solvents
Nitrous oxide (N2O) 1. Fertilizer use
2. Fossil fuel combustion
3. Biomass burning
4. Changing land use

208
➢ Acid Rain:
• The rain containing H2SO4, HNO3 (and small amount of HCl) which are formed from
the oxide of S and N2 present in the air is called as acid rain. The pH of acid rain is 4-
5. (pH of pure rain 5.6 due to dissolved CO2 present as H2CO3)
• Formation of acid rain:
electrical
N2 + O2 ⎯⎯⎯⎯
discharg e
→ NO
a. 2NO + O2 → NO2 HNO3 comes down with rain to earth.
NO2 + H2O → HNO3 + NO
1
SO2 + O2 ⎯⎯ U.V
→ SO3
b. 2
SO3 + H2O → H2 SO4
c. Presence of H2S and Cl2 in atmosphere
• Composition: H2SO4 = 60–70%, HNO3 = 30–40%, HCl = Very small amount.
• Aerosol particles of oxides or ammonium salts in rain drops result in wet deposition.
SO2 is absorbed directly on solid/liquid surfaces and is thus deposited by dry deposition
• Harmful effect of acid-rain:
❖ It affects human nervous, respiratory and digestive system
❖ It damages building and statues which contain marble, lime stone, state, mortar
etc.
CaCO3 + H2SO4 → CaSO4 + H2O + CO2
❖ It damages iron and steel structure.
❖ It corrodes water pipe, so heavy metal (like Fe,Pb, Cu) get mixed with water
which have toxic effect.
❖ The acid rain increases the acidity of the lake which is harmful to fishes.
❖ It damages the trees, plants and retards the growth of the plant.
❖ It increases the acidity of soil
➢ Smogs (Smoke + fog)
Classical smog:
• Occurs in cool humid climate and present in the lower atmosphere
• Formed due to condensation of H2SO4 and HNO3 on particulate matter from fuel
combustion
• Decreases visibility, causes diseases like bronchitis, asthama, irritation to eyes, nose
and throat
• When smog formed is from smoke of burning coal it is called reducing smog
Photochemical smog:
• Occurs in warm, dry and sunny climate, in those cities which have very large
populations and high vehicular density.
• Results from the action of sunlight on the nitrogen oxides and hydrocarbons produced
by automobiles and factories along with smoke, dust and fog.
• Photochemical smog is an oxidising smog having a high concentration of oxidising
agents whereas classical smog is chemically reducing smog with high concentrations
of SO2.
• Formation of photochemical smog

209
 • chemicals such as formaldehyde, acrolein and peroxyacetyl nitrate (PAN) that cause
the eyes to water and burn and are harmful to the respiratory system.
• The brownish haze of photochemical smog is largely attributed to the brown colour or
NO2.
• Effects of Photochemical Smog:
❖ Pungent smelling, smog-produced by ozone is known to be toxic, causes
coughing, wheezing, bronchial constriction
❖ Peroxyacetyl nitrates (PAN) and aldehydes found in smog are eye irritants, has
the highest toxicity to plants, attacking younger leaves and causing 'bronzing' and
'glazing' of their surfaces
❖ Rubber has a high affinity for ozone and is cracked and aged by it, corrodes
metals, building materials and painted surfaces
❖ Smog also affects to cause damage to vegetation and reduction in plant growth
and crop productivity.
• Control of Photochemical Smog:
❖ Installation of efficient catalytic converters in the automobiles
❖ Photochemical smog can also be suppressed by certain compounds, which act as
free radical traps. When these compounds are sprayed in the atmosphere, they
generate free radicals which readily combine with free radical precursors of
photochemical smog.
❖ Using reformed gasoline which contains about 10% fuel oxygenates (methyl tert.
Butyl ether) which makes the fuel burn more efficiently.
❖ Plants like Juniparus, Quercus, Pyrus, Vitis and Pinus metabolise nitrogen oxide
➢ Stratospheric Pollution
Formation of ozone layer
In the stratosphere (11-50 km), the O2 is partially converted into O3. Now at an altitude of
25-30 km, we have a layer in which the conc. of O3 is 10 ppm. It absorbs all radiation
having wavelength less than 0.4 micron
h
step (I) : O2 ⎯⎯ → O• + O•
h
step (II) : O2 + O• ⎯⎯ → O3 . Heat is also given out from this reaction which warm up
stratosphere.
O3 ⎯⎯ UV
→ O2 + O• In this way the O3 cycle is completed in this region.

210
➢ Depletion of ozone layer
NO and CFC are responsible for depletion of O3 layer.
a) NO (Nitric oxide) : NO + O3 → NO2 + O2
NO2 +O → NO + O2
Thus, no NO is consumed but O3 gets depleted.
b) Chlorofluoro carbons (CFC) or freons:
h
CF2Cl2 ⎯⎯ → CF2Cl• + Cl•
h
CFCl3 ⎯⎯ → CFCl2• + Cl•
The reactive chlorine atoms then destroy the ozone layer through the following sequence
of reaction. Which are repeated because chlorine atom are regenerated in the second
reaction.
Cl• + O3 → ClO• + O2
Reaction.
ClO• + O• → Cl• + O2
one molecule of CFC can destroy more than 100,00 O3 molecules in the stratosphere.
Ozone concentration is measured in Dobson units, each corresponding to 2.69x1016 ozone
molecules per cm2

➢ Effect of depletion of O3 layer

• damage the cornea and lens of the eyes.
• affect the plant proteins so reduce the generation of chlorophyll.
• Upset the heat balance of the earth.
• Degradation of immune system
• Various forms of skin cancer
• Affects growth of phytoplankton
Replace usual CFCs with HCFC-123 (CHCl2CF3) and HFC-134 (CH2FCF3)

➢ Ozone hole
In summer
ClO•(g) + NO2(g) → ClONO2(g) & Cl•(g) + CH4 (g) → CH3•(g) + HCl(g)
In winter, on polar stratospheric clouds
ClONO2(g) + H2O(g) → HOCl(g) + HNO3(g) & ClONO2(g) + HCl(g) → Cl2(g) + HNO3(g)
In spring
HOCl(g) ⎯⎯
UV
→OH•(g) + Cl•(g) & Cl2(g) ⎯⎯
UV
→Cl•(g) The chlorine radical formed initiates
the chain reaction for O3 depletion.
➢ Water Pollution
Pollutant Source
Microorganisms Domestic sewage
Organic wastes Domestic sewage, animal waste,
decaying animals and plants and
discharge from food processing factories
Plant nutrients Chemical fertilizers
Toxic heavy metals Discharge from Factories
Sediments Erosion of soil

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 Pesticides Farming
Radioactive substances Mining of radioactive minerals
Heat Cooling water used by industries
In addition, industrial wastes also contaminate water.
• Heavy Metals: Cadmium and mercury can cause kidneys, liver brain and central
nervous system. These metals are cumulative poisons, the body does not excrete them
and their concentration builds up.
• Detergents and Fertilizers: The addition of phosphorus to water, in the form of the
phosphate anion PO43–, encourages the formation of algae, which reduces the
dissolved oxygen concentration of water. The process, known as eutrophication,
impedes the development of higher life forms, such as fish.
• Acid-polluted water (pH < 3): This is deadly to most forms of aquatic life. Acid mine
water principally contain suhphuric acid produced by the oxidation of iron pyrites
(FeS2).
• Polychlorinated biphenyls (PCBs): Having high stabilities, PCBs are used as fluids in
transformer, capacitors. PCBs are resistant to oxidation and their release into the
environment causes skin disorders in humans (carcinogens).
International standards for drinking water must be obeyed if water is to be used for
drinking purposes. These are :
• Fluoride:
❖ Soluble fluoride is added to drinking water up to a conc. of 1 ppm to protect
against tooth delay.F- ion makes the enamel harder by converting hydroxyapatite
[3Ca3(PO4)2.Ca(OH)2] into much harder [3Ca3(PO4)2.CaF2]
❖ Conc. above 2 ppm causes brown mottling of teeth.
❖ High concentrations of fluoride are harmful to bone and teeth at levels over 10
ppm.
• Lead:
❖ The limit for the concentration of lead ions in drinking water is 50 ppb.
❖ If water is acidic and lead pipes are used, then the water is liable to get
contaminated with lead.
• pH:
❖ The pH of drinking water should be between 5.5 and 9.5. A decrease in the pH of
the water increases the solubility of metal ions.
• Sulphate:
❖ excessive sulphate (> 500 ppm) is thought to have a laxative effect.
• Nitrate:
❖ Excess nitrate in drinking water can lead to methemoglobinemia (blue-baby
syndrome), stomach cancer. A maximum limit of 50 ppm for the nitrate ion in
drinking water has been set.
• Other Metals:
Metal Max. concentration (ppm)
Zn 5
Fe 0.2
Mn 0.05
Cu 3
Cd 0.005
Al 0.2

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➢ Importance of dissolved Oxygen in water :
• The fish growth is inhibited if the dissolve concentration of oxygen in water is below
6 ppm.
• The lower the concentration of dissolved oxygen, the more polluted is the water
sample.
• The dissolved oxygen in water is consumed rapidly by microorganisms to oxidise
organic matter of sewage, bio-oxidation of nitrogenous material, chemical or
biochemical oxidation of chemical reducing agents

➢ Biochemical Oxygen Demand (BOD)

• Biochemical oxygen demand (BOD) is a measure of the dissolved oxygen that would
be needed by the microorganisms to oxidise organic and inorganic pollutants.
• BOD, therefore, is a measure of the contamination caused by the totality of those
compounds which can be oxidised in the presence of microorganisms.
• 'clean water' would have a BOD value of less than 5 ppm whereas highly polluted
river water could have a BOD value of 17 ppm or more.

➢ Chemical Oxygen Demand (COD) :

• In COD (Chemical Oxygen Demand) determination, the water sample is treated with
a known quantity of an oxidising agent, usually potassium dichromate K2Cr2O7 in
acidic medium.
• The remaining K2Cr2O7 is determined by back titration with a suitable reducing agent
like Mohr's salt.
• From the concentration of K2Cr2O7 consumed, the amount of oxygen used in the
oxidation may be calculated using the following chemical equation
K2Cr2O7(aq) + 4H2SO4(aq) → K2SO4(aq) + Cr2(SO4)3(aq) + 4H2O(l) + 3O(aq)
• The results are expressed in terms of amount of oxygen, in ppm, that would be
required to oxidise the contaminants.

➢ Land Pollution
Most of the land pollution is caused by pesticides and other chemicals which are added to
the soil grow better crops. Solid wastes are another cause of land pollution.
Pesticides : Pesticides are substances that are used to kill or block the reproductive
processes of unwanted organisms.
Insecticides : Control of insects by insecticides helps to cure disease (for example malaria
and yellow fever) and protect crops. The best known organochlorine compound is DDT
(dichlorodiphenyltrichloroethane) Organochlorines are stable in the environment, toxic to
insects in small amounts, but much less so to humans; and because they are organic
compounds, not very soluble in water. These insecticides by accumulating in the
environment affect many non-target organisms, not just the target pests.
Herbicides: Herbicides are used to kill weeds. Sodium chlorate, NaClO3 and sodium
arsenite Na3AsO3 were commonly used as weed killers in the first half of the last century,
but inorganic arsenic compounds in particular are toxic to mammals. Organic herbicides
are, therefore, now used. They are much more toxic to certain types of plants than to others.

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 Fungicides: Fungicides are used to check the growth of fungi. Organic compounds of
mercury have been used as fungicides. These compounds break down in solid and thus has
had disastrous consequences
➢ Strategy for control of environmental pollution
The management of waste: The production and improper disposal of waste are causes
for a great deal of environmental pollution.
Recycling: When materials are recycled, there are several benefits, apart from saving on
the cost of raw materials, waste disposal costs are reduced.
Sewage treatment: The main stages in the treatment of sewage are as follows:
• The removal of large solids that get into the system of filtering the waste water
through screens.
• Settlement in tanks to allow the removal of solids that settle out (called sludge). This
process also allows removal of grease which floats to the surface and can be skimmed
off.
• The degradation of the organic content of waste water by microbial oxidation.
• Application of various physical and chemical processes for improving the quality of
waste water. The processes include chemical removal of phosphate, coagulation,
filtration and disinfection using chlorine.
The safe disposal of the sludge produced during water treatment is a problem. The
sludge is dried and then many be incinerated, digested or dumped.
Incineration: Incineration converts organic materials to CO2 and H2O. It may serve to
destroy household waste, chemical waste and biological waste (e.g. from hospitals). A high
temperature is required usually in excess of 1000°C, and a plentiful supply of oxygen.
Exhaust gases must be filtered. The process greatly reduced the volume of waste (around
90%) -an inorganic ash is left behind, which is disposed of as landfill. The chief
disadvantage of incineration is that it leads to air pollution.
Digestion: Anaerobic digestion occurs when microganisms degrade wastes in the absence
of oxygen. It may be used to treat sewage sludge, but the process can also be used to degrade
a variety of toxic organic wastes. Carbon dioxide and methane, which may be used as a
fuel, are the products.
Dumping: Ocean dumping of sewage sludge has been widely practiced in the seas around
the worked. Urban areas produce sludge with high toxic metal content, so the amount of
such sludge dumped in this way must be carefully controlled.

➢ Green Chemistry
An ideal chemical reaction should have a number of attributes: safety, simplicity,
selectivity, high yield, energy efficiency, use of renewable or recyclable materials,
minimizing by-product formation.
Concept of green chemistry introduced by Paul Anastas in 1994
% atom economy = Formula mass of product/ sum of formula mass of all the reactants.

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