Base in Chemistry

SURFACE CHEMISTRY
It is the branch of chemistry that deals with the study of nature of surfaces and the different processes taking
place at the surface. The important surface phenomena are adsorption, corrosion, electrode process, heterogeneous
catalysis, dissolution etc.
ADSORPTION
It is the process of concentration or accumulation of a substance on the surface of another substance. The
substance which is adsorbed is called adsorbate and the substance whose surface on which adsorption takes place is
called adsorbent. The commonly used adsorbents are charcoal, silica gel, alumina gel, clay, colloids, metals in finely
divided state etc.
Adsorption is a surface phenomenon. Some examples of adsorption are:
1. Powdered charcoal adsorbs gases like H2, O2, CO, Cl2, NH3, SO2 etc.
2. Silica gel adsorbs moisture
3. Animal charcoal adsorbs colouring material from sugar solutions
Desorption: The process of removal of an adsorbed substance from the surface of adsorbent is called desorption.
i.e. it is the reverse of adsorption.
Distinction between adsorption and absorption
In adsorption, the substance is concentrated only at the surface while in absorption, the substance is uniformly
distributed throughout the bulk of the solid. So adsorption is a surface phenomenon while absorption is a bulk
phenomenon.
Sorption: If adsorption and absorption occur simultaneously, the process is called sorption.
Mechanism of Adsorption
The surface particles of the adsorbent are not in the same environment as the particles inside the bulk (inner part).
Inside the adsorbent, all the forces are mutually balanced. But at the surface, there is always some unbalanced or
residual forces. These forces of the adsorbent are responsible for adsorption.
Heat of adsorption (Enthalpy of Adsorption)
Adsorption is an exothermic process. i.e. some heat is always evolved during adsorption. The amount of heat evolved
when 1 mole of an adsorbate is adsorbed on the surface of an adsorbent is called heat of adsorption.
Thermodynamic aspects of adsorption
Adsorption is an exothermic process. When a gas is adsorbed, the degree of freedom (randomness) of its
molecules decreases and hence the entropy decreases. i.e., ΔS becomes negative. Adsorption is thus accompanied by
decrease in enthalpy as well as decrease in entropy of the system. For a process to be spontaneous, ΔG must be
negative. On the basis of equation, ΔG = ΔH – TΔS, ΔG can be negative if ΔH >TΔS. As the adsorption proceeds, ΔH
becomes less and less negative ultimately ΔH becomes equal to TΔS and ΔG becomes zero. At this state equilibrium is
attained.
Types of adsorption
Depending on the force of attraction between adsorbent and adsorbate, adsorption is of two types – physical
adsorption or physisorption and chemical adsorption or chemisorption.
If the force of attraction between adsorbent and adsorbate is weak van der Waals force, it is called physical
adsorption or physisorption. For physisorption, the heat of adsorption is low and it is not specific since the van der
Waals forces are universal. That is any substance can form van der Waals force with any surface.
In chemisorptions, the force of attraction between adsorbent and adsorbate is chemical bond. It is also called
activated adsorption since it involves some activation energy. For chemisorption, the enthalpy of adsorption is high and
it takes place at high temperature. It is highly specific in nature and it will occur only if there is some possibility of
chemical bonding between adsorbent and adsorbate.
A physisorption at low temperature may pass into chemisorption at high temperature. For e.g. Hydrogen gas is
first adsorbed on nickel by van der Waals force. But at high temperature, the molecules of H2 dissociate to form H atoms
and they are adsorbed on the surface of Ni by chemical bond.
Both physisorption and chemisorption increases with increase in surface area of the adsorbent. Surface area can
be increased by powdering the adsorbent.
Surface Chemistry-Anil-HSSLiVE Page 1

Distinction between physisorption and chemisorption
Properties Physisorption Chemisorption

1 Force of attraction Weak van der Waals force Strong chemical bond
2 Specificity Not specific in nature Highly specific
3 Reversibility Reversible Irreversible
4 Extend of adsorption Easily liquefiable gases (e.g. CO2, HCl, NH3 Gases which can react with the adsorbent
and nature of gas etc) are easily adsorbed than permanent show chemisorption
gases (e.g. H2, N2, O2 etc)
5 Heat of adsorption Low (20-40 kJ/mol) High (80-240kJ/mol)
6 Temperature Low temperature is favourable. It High temperature is favourable. It increases
decreases with increase in temperature with increase in temperature
7 Activation energy No appreciable activation energy is High activation energy is required
needed
8 Nature of layer Multimolecular layer of adsorption occurs Only unimolecular layer of adsorption occurs
Adsorption Isotherms
The variation in the amount of gas adsorbed by the adsorbent with pressure at constant temperature can be
expressed by means of a graph called adsorption isotherm.
Freundlich adsorption isotherm:
Freundlich gave an empirical relationship between the quantity of gas adsorbed by unit mass of solid adsorbent and
pressure, at a particular temperature. The relationship can be expressed by the following equation:
x/m = k.P1/n (where n > 1)
where x is the mass of the gas adsorbed, m is the mass of the adsorbent, k and n are constants which depend on
the nature of the adsorbent and the gas at a particular temperature.
The above relationship can be represented in the form of a graph as follows:
From the graph it is clear that x/m (extend of adsorption) increases with
pressure upto a certain pressure called saturation pressure (Ps) and
after that it becomes constant.
If we take logarithm of the above equation, we get x/m
log x/m = logk + 1/n logP
This equation is of the form y = mx+c, equation for a straight line. So if we
plot log x/m against log P, we get a straight line, which verifies Freundlich isotherm.
The value of 1/n in Freundlich isotherm ranges from 0 to 1
When 1/n = 0, x/m = a constant. i.e. the adsorption is independent of pressure. P Ps
When 1/n = 1, x/m = k.p, the adsorption varies linearly with pressure.
Freundlich adsorption isotherm failed to explain adsorption at very high pressures.
Adsorption from solution
Certain solid adsorbents can adsorb solute particles from solution. This is known as adsorption from solution. E.g.:
1. When a solution of acetic acid in water is shaken with charcoal, a part of the acid is adsorbed by the charcoal
and the concentration of the acid decreases in the solution.
2. Animal charcoal adsorbs colouring materials from sugar solution. So it is used for the purification of sugar.
The important characteristics of adsorption from solution are:
(i) The extent of adsorption decreases with an increase in temperature.
(ii) The extent of adsorption increases with an increase of surface area of the adsorbent.
(iii) The extent of adsorption depends on the concentration of the solute and the nature of the adsorbent and the
adsorbate.

Freundlich adsorption isotherm is applicable to adsorption from solution also. Here instead of pressure,
concentration of the solution is used.
i.e., x/m = kC1/n (where C is the equilibrium concentration).
On taking logarithm of the above equation, we have
log x/m = logk + 1/n logC
On plotting log x/m against log C, a straight line is obtained which verifies Freundlich isotherm.
Applications of adsorption
The important applications of adsorption are:
1. Production of high vacuum: For the complete evacuation of a vessel, activated charcoal is used.
2. Gas masks: The poisonous gases in coal mines can be removed by using gas masks containing activated charcoal.
3. Control of humidity: Silica and aluminium gels are used as adsorbents for removing moisture and controlling
humidity.
4. Animal charcoal is used for the purification of cane sugar solution.
5. Adsorption finds application in heterogeneous catalysis.
6. A mixture of noble gases can be separated by adsorption on coconut charcoal at different temperatures.
7. In curing diseases: A number of drugs are used to kill germs by getting adsorbed on them.
8. In froth floatation process for the purification of sulphide ores in metallurgy.
9. Adsorption indicators like eosin, fluorescein etc. are used in volumetric analysis.
10. Chromatographic analysis for the separation of a mixture is based on adsorption.
CATALYSIS
A catalyst is a substance that changes the rate of a chemical reaction without undergoing any permanent
chemical change by itself. The process of changing the rate of a chemical reaction by a catalyst is known as Catalysis.
Eg: MnO2 (Manganese dioxide) acts as a catalyst in the decomposition of KClO3 (Potassium chlorate)
2KClO3 → 2KCl + 3 O2
Promoters and poisons
Promoters are substances that enhance the activity of a catalyst while poisons decrease the activity of a catalyst.
For example, in Haber’s process for the manufacture of ammonia, molybdenum (Mo) acts as a promoter for the catalyst
iron.
N2 +3H2 Fe/Mo 2NH3
Types of Catalysis
Positive and Negative Catalyst
A catalyst that increases the rate of a chemical reaction is called Positive catalyst and that decreases the rate of
a chemical reaction is called negative catalyst (inhibitors).
E.g. In the Haber’s process for the manufacture of ammonia, Fe acts as a positive catalyst
N2 +3H2 Fe/Mo 2NH3
For decreasing the rate of dissociation of H2O2, Phosphoric acid is used as a negative catalyst.
Homogenous and Heterogeneous Catalysis
Homogeneous Catalysis
A catalytic process in which the reactants and the catalyst are in the same phase (i.e., liquid or gas), is said to be
homogeneous catalysis.
e.g.: (i) In the lead chamber process for the manufacture of Sulphuric acid, oxidation of sulphur dioxide into
sulphur trioxide is done in the presence of Nitric Oxide as catalyst
2SO2 (g) + O2 (g) NO (g) 2SO3 (g)
Here the reactants (sulphur dioxide and oxygen) and the catalyst (nitric oxide) are all in the same phase.
(ii)Acid catalysed hydrolysis of methyl acetate
CH3COOCH3(l) + H2O(l) HCI(l) CH3COOH(aq) + CH3OH(aq)
(iii) Hydrolysis of sugar is catalysed by H+ ions furnished by sulphuric acid.
C12H22O11(l) + H2O(l) H2SO4 C6H12O6(aq) + C6H12O6(aq)

Heterogeneous catalysis
The catalytic process in which the reactants and the catalyst are in different phases is known as heterogeneous
catalysis.
Some of the examples of heterogeneous catalysis are:
(i) In contact process for the manufacture of H2SO4, Oxidation of sulphur dioxide into sulphur trioxide is done in
presence of V2O5.
2SO2(g) + O2(g) V2O5(s) 2SO3(g)
Here the reactants are in gaseous state while the catalyst is in the solid state.
(ii) In Haber’s process for the manufacture of ammonia finely divided iron is used as catalyst.
N2(g) +3H2 (g) Fe(s) 2NH3
Here the reactants are in gaseous state while the catalyst is in the solid state.
(iii) Oxidation of ammonia into nitric oxide in the presence of platinum gauze in Ostwald’s process.
Here also the reactants are in gaseous state while the catalyst is in the solid state.
(iv) Hydrogenation of vegetable oils in the presence of finely divided nickel as catalyst.
Adsorption Theory of Heterogeneous Catalysis
This theory explains the mechanism of heterogeneous catalysis. According to this theory the catalytic activity
takes place on the surface of the catalyst. The mechanism involves five steps:
(i) Diffusion of reactants to the surface of the catalyst.
(ii) Adsorption of reactant molecules on the surface of the catalyst.
(iii) Occurrence of chemical reaction on the catalyst’s surface through formation of an intermediate.
(iv) Desorption of reaction products from the catalyst surface.
(v) Diffusion of reaction products away from the catalyst’s surface.
This theory explains why the catalyst remains unchanged in mass and chemical composition at the end of the reaction
and is effective even in small quantities. But it does not explain the action of
catalytic promoters and catalytic poisons.
Important features of solid catalysts
1. Activity
The activity is the ability of a catalyst to increase the rate of a chemical reaction. It depends upon the strength of
chemisorption.
e.g.: H2 combines with O2 to form H2O in presence of Platinum (Pt) catalyst
H2 + O 2 Pt H2O
In absence of Pt, the reaction does not take place.
2. Selectivity
It is the ability of a catalyst to direct a chemical reaction to a particular product.
e.g.: CO reacts with H2 to form different products based on the nature of the catalyst.
Shape-Selective Catalysis by Zeolites

The catalytic reaction that depends upon the pore structure of the catalyst and the size of the reactant and
product molecules is called shape-selective catalysis.
Zeolites are good shape-selective catalysts because of their honey comb-like structures. They are microporous
aluminosilicates with three dimensional networks of silicates in which some silicon atoms are replaced by aluminium
atoms. They contain Al–O–Si framework. The reactions taking place in zeolites depend upon the size and shape of
reactant and product molecules as well as upon the pores and cavities of the zeolites. They are found in nature as well
as prepared artificially.

Zeolites are used as catalysts in petrochemical industries for cracking of hydrocarbons and isomerisation. An
important zeolite catalyst used in the petroleum industry is ZSM-5. It converts alcohols directly into gasoline (petrol) by
dehydrating them to give a mixture of hydrocarbons.
Enzyme Catalysis
Enzymes are complex nitrogenous organic compounds which are produced by living plants and animals. They
are actually protein molecules of high molecular mass. They are very effective catalysts and catalyse numerous reactions
taking place in plants and animals. So enzymes are also called biochemical catalysts and the phenomenon is known as
biochemical catalysis.
e.g.: (i) Inversion of cane sugar: The enzyme invertase converts cane sugar into glucose and fructose.
C12H22O11(aq) + H2O(l) invertase C6H12O6(aq) + C6H12O6(aq)
Cane sugar Glucose Fructose
(ii) Conversion of glucose into ethyl alcohol: The enzyme zymase converts glucose into ethyl alcohol and carbon dioxide.
C6H12O6(aq) zymase 2C2H5OH(aq) + 2CO2(g)
Glucose Ethanol
(iii) Conversion of starch into maltose: The enzyme diastase converts starch into maltose.
2(C6H10O5)n(aq) + nH2O(l) Diastase n C12H22O11(aq)
Starch Maltose
(iv) Conversion of maltose into glucose: The enzyme maltase converts maltose into glucose.
C12H22O11(aq) + H2O(l) Maltase 2C6H12O6(aq)
Maltose Glucose
(v) Decomposition of urea into ammonia and carbon dioxide: The enzyme urease catalyses this decomposition.
NH2CONH2(aq) + H2O(l) Urease 2 NH3(g) + CO2(g)
Urea
Characteristics of enzyme catalysis
The important characteristics of enzyme catalysis are:
1. Enzyme catalysis is highly specific in nature. I.e., Each enzyme is specific for a given reaction or an enzyme that
catalyses a particular reaction does not catalyse another reaction.
2. Enzyme activity is highly efficient. i.e., one molecule of an enzyme may transform one million molecules of the
reactant per minute.
3. The rate of an enzyme reaction becomes maximum at a definite temperature, called the optimum temperature.
The optimum temperature range for enzymatic activity is 298-310K.
4. The rate of an enzyme-catalysed reaction is maximum at a particular pH called optimum pH, which is between
pH values 5-7.
5. The enzymatic activity is increased in the presence of certain substances, known as co-enzymes.
6. Enzymes activity is inhibited or poisoned by the presence of certain substances.
Mechanism of enzyme catalysis
There are a number of cavities present on the surface of colloidal particles of enzymes. These cavities have
characteristic shape and possess active groups such as -NH2, -COOH, -SH, -OH, etc. These are the active centers on the
surface of enzyme particles. The molecules of the reactant (substrate) fit into these cavities just like a key fits into a lock.
So an activated complex is formed, which then decomposes to yield the products. This theory is known as lock and key
theory. Thus, the enzyme-catalysed reactions may be considered to proceed in two steps.
Step 1: The enzyme combines with the substrate to form an activated complex.
E + S → ES*
Step 2: Decomposition of the activated complex to form product.
ES* → E + P
The schematic representation of the mechanism of enzyme catalysis is as follows:

THE COLLOIDAL STATE
Colloid is an intermediate state between true solution and suspension. In a true solution, the size of the particles
is < 1nm. The particles do not settle down under the influence of gravity or by any method and they cannot be filtered
by a filter paper. A true solution is homogeneous and transparent.
In a suspension the size of the particles is > 1000nm. The particles settle down under the influence of gravity. They can
be filtered by an ordinary filter paper. It is heterogeneous and opaque.
In colloids, the particle size is in between 1 nm and 1000nm. The particles do not settle down
under the influence of gravity. They cannot be filtered by ordinary filter paper, but can be filtered by ultra
filters. They are heterogeneous and translucent.
Colloids are heterogeneous systems containing two phases – dispersed phase and dispersion medium. The
substance which is dispersed (distributed) is called dispersed phase and the medium in which the particles are dispersed
is called dispersion medium.
e.g.: In starch solution, starch is the dispersed phase and water is the dispersion medium.
Classification colloids
1. Based on the physical state of dispersed phase and the dispersion medium
Depending upon physical state of the dispersed phase and the dispersion medium, there are eight types of
colloidal systems. A gas mixed with another gas forms a homogeneous mixture and hence is not a colloidal system. The
different types colloidal dispersion are:
Dispersed Phase Dispersion medium Type of colloid Examples
Solid Solid Solid Sol Some coloured glasses and gem stones
Solid Liquid Sol Paints, Cell fluids
Solid Gas Aerosol of solid Smoke, dust
Liquid Solid Gel Cheese, butter, jellies
Liquid Liquid Emulsion Milk, hair cream, cod liver oil
Liquid Gas Aerosol of liquid Fog, mist, cloud, insecticide sprays
Gas Solid Solid foam Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather
2. Based on the dispersion medium, colloids are classified as follows:
Dispersion medium Name of colloid
Air Aerosol
Water Hydrosol
Alcohol Alco sol
Benzene benzosol
3. Based on the attraction between the dispersed phase and the dispersion medium, colloids are of two types:
lyophilic (solvent loving) and lyophobic (solvent hating). If the force of attraction between dispersed phase and
dispersion medium is strong, it is called lyophilic sol
e.g. gum, gelatin, starch, rubber etc in suitable dispersion medium.
If the force of attraction between dispersed phase and dispersion medium is weak, it is called lyophobic sol.
e.g. Arsenic sulphide (As2S3) sol, sulpher sol and metal sols like gold sol, silver sol etc.
Differences between lyophilic and lyophobic sols

Properties Lyophilic sol Lyophobic sol
Force of Strong Weak
attraction
Preparation Can be easily prepared by mixing the dispersed phase Some special methods are used for the
with the dispersion medium preparation
Reversibility Reversible (i.e. they can be easily separated and irreversible
remixed)
Stability Self stabilized Less stable and requires some stabilizing agent
Coagulation large amount of electrolyte is required for coagulation Only small amount of electrolyte is required.
4. Based on the nature of particles:

Based on this, colloids are of three types – Multimolecular colloids, Macro molecular colloids and Associated
colloids.
1. Multimolecular colloids: They contain an aggregate of atoms or molecules having dimension < 1nm. These
particles are bind together by weak van der Waal’s force of attraction and form particles of colloidal dimension.
e.g. Arsenic sulphide (As2S3) sol, sulpher sol and metal sols like gold sol, silver sol etc.
2. Macromolecular colloids: Macromolecules (Polymers) in suitable solvents form solutions in which the size of the
particle is in the colloidal range. Such systems are called macromolecular colloids. These colloids are quite stable and
resemble true solutions in many properties.
Example: solutions of starch, cellulose, proteins, enzymes, polythene, nylon, polystyrene, synthetic rubber, etc. in
suitable dispersion medium.
3. Associated colloids: These are substances which behave as normal strong electrolytes
at low concentrations, but as colloids at higher concentrations. The colloidal behavior is because of the formation of
aggregates. They are also called micelles.
The formation of micelles takes place only above a particular temperature called Kraft temperature (Tk) and
above a particular concentration called critical micelle concentration (CMC).
Surface active agents such as soaps and synthetic detergents are examples for micelles. These colloids have both
lyophobic and lyophilic parts.
Mechanism of micelle formation
An example for micelle is soap solution. Soap is sodium or potassium salt of a higher fatty acid and may be
represented as RCOO–Na+. When dissolved in water, it dissociates into RCOO– and Na+ ions. The RCOO– ions consist of
two parts — a long hydrocarbon chain R (also called non-polar ‘tail’) which is hydrophobic (water repelling), and a polar
group COO– (also called polar-ionic ‘head’), which is hydrophilic (water loving).
The RCOO– ions are present on the surface with their COO– groups in water and the hydrocarbon chains (R) at
the surface. But at critical micelle concentration, the anions are pulled into the bulk of the solution and aggregate to
form a spherical shape. Thus a micelle is formed.

Cleansing action of soaps
The cleansing action of soap is due to micelle formation. The soap molecules form micelle around the oil droplet
in such a way that hydrophobic part is in the oil droplet and hydrophilic part projects out. Since the polar groups
(hydrophilic end) can interact with water, the oil droplets are pulled in water and removed from the dirty surface. Thus
soap helps in emulsification and washing away of oils and fats.
Preparation of colloids
Some of the methods used for the preparation of colloids are:
a) Chemical methods:
Colloidal solutions can be prepared by chemical reactions like oxidation, reduction, double decomposition, hydrolysis
etc.
1. Oxidation: Sulphur sol can be prepared by passing H2S gas through an aqueous solution of sulphur dioxide.
SO2 + 2H2S Oxidation 3S(sol) + 2H2O
2. Reduction: Sols of metals like silver, gold and platinum are obtained by the reduction of their salts with reducing
agents like formaldehyde, stannous chloride etc.
2AuCl3 + 3HCHO + 3H2O Reduction 2Au(sol) + 3HCOOH + 6HCl
3. Hydrolysis: Ferric hydroxide sol is obtained when concentrated solution of ferric chloride is added drop-wise to
hot water.
FeCl3 + 3H2O Hydrolysis Fe(OH)3 (sol) + 3HCl
4. Double decomposition: A colloidal solution of arsenic sulphide is formed by passing H2S through a dilute solution
of arsenious oxide in water.
As2O3 + 3H2S Double decomposition As2S3(sol) + 3H2O
b) Electrical disintegration (Bredig’s arc method):
This method is used for the preparation of metal sols like Ag, Au, Pt etc. The metal whose sol is to be prepared is
taken in the form of two rods and it is kept in suitable dispersion medium containing small amount of electrolyte. The
whole arrangement is kept in an ice bath. When high voltage is passed through the metal, the intense heat produced
vapourises the metal, which then condensed to form particles of colloidal dimension.
c) Peptization:
The process of conversion of a freshly prepared precipitate into a colloidal sol by shaking it with suitable
dispersion medium in the presence of small amount of electrolyte is called peptization. The electrolyte added is called
peptizing agent.

During peptization, the precipitate adsorbs one of the ions of the electrolyte on its surface and forms a positive or
negative charge on it. Thus the particles of the precipitate break up into smaller particles of the colloidal size.
Purification of colloids
The colloidal solution prepared contains excess amount of electrolyte and some other soluble impurities. Even
though small amount of electrolyte is required for the stability of colloid, large amount may cause precipitation. The
process of reducing the concentration of electrolyte and other impurities is known as purification of colloids. Some
methods used for purification are:
1. Dialysis: It is the process of removing dissolved substances from a colloidal solution by means of diffusion
through a semi-permeable membrane. Here the sol particles are taken in a parchment or cellophane bag and it is
suspended in a running stream of water. The impurities are diffused through the membrane and the sol particles are left
behind. These particles are then suspended in suitable dispersion medium so as to get a colloidal dispersion.
The speed of dialysis can be increased by using hot water instead of cold water. Then the process is known as hot
water dialysis.
The speed of dialysis can also be increased by dipping two electrodes and passing electricity. Then the process is
known as electrodialysis.
2. Ultrafiltration: It is the process of separating the colloidal particles from the impurities by using a special type of
filter paper called ultrafilters or ultra filter paper. It is prepared by dipping ordinary filter paper in collodion solution (a
4% solution of nitrocellulose in a mixture of alcohol and ether).
When colloidal particles are filtered using ultrafilters, the sol particles are retained on the filter paper while the
impurities and the electrolyte are passed through it. When these sol particles are suspended in suitable dispersion
medium, we get a colloidal solution.
Properties of colloids
1. Colligative properties:
In colloids, the number of particles are very small compared to that of true solution. So the values of colligative
properties such as relative lowering of vapour pressure, elevation of boiling point, depression of freezing point and
osmotic pressure are small compared to that of true solution.
2. Tyndall effect:
When a light beam is passed through a colloidal solution, we can see the path of the light beam. This phenomenon is
known as Tyndall effect. It is due to the scattering of light beam by the colloidal particles. The visible path is called
tyndall cone.
Tyndall effect is observed only when the following conditions are satisfied:
(i) The diameter of the dispersed particles is much larger than the wavelength of the light used.
(ii) The refractive indices of the dispersed phase and the dispersion medium differ greatly in magnitude.
True solutions do not show tyndall effect since the size of particles are very small so that they cannot scatter the
light beam. Thus tyndall effect is used to distinguish a colloidal solution from a true solution.
Ultramicroscope used to see the colloidal particles works on the principle of tyndall effect.
3. Brownian movement
In colloids, the particles of dispersion medium are in a state of continuous zig-zag motion. This motion was first
observed by Robert Brown and it is known as Brownian movement. It is independent of the nature of the colloidal
particles but depends on the size of the particles and viscosity of the solution. Smaller the size and lesser the viscosity of
the medium, faster is the motion.
Brownian movement is due to the unbalanced bombardment of particles of the dispersed phase by the particles of
dispersion medium. It is responsible for the stability of colloids.
4. Charge on colloidal particles:
Colloidal particles always carry an electric charge. For a given colloidal solution, the nature of the charge is the same
on all the particles.
Positively charged sol Negatively charged sol
Hydrated metallic oxides like Fe2O3.xH2O, Al2O3.xH2O, CrO3.xH2O etc. Metal sols (e.g. Cu sol, Ag sol, Au sol)
Basic dyes (e.g. methylene blue) Metallic sulphides (e.g. As2S3, CdS etc)

Haemoglobin in blood Acid dyes (e.g. eosin, congo red etc.)
Metal oxides (TiO2) Sols of starch, gum, gelatin, clay, charcoal etc.
The charge on the sol particles is mainly due to preferential adsorption of ions from solution. When 2 or more
ions are present in the dispersion medium, preferential adsorption of the ion common to the colloidal particle takes
place.
e.g. when AgNO3 is added to KI, AgI is precipitated, which adsorbs iodide ions from the dispersion medium and
thus get a negative charge.
AgNO3 + KI → AgI + KNO3
But when KI is added to AgNO3, the precipitated AgI adsorbs Ag+ ions from the solution and thus get a positive
charge.
Due to the positive or negative charge in the sol particles, they attract the counter ions (opposite ions) from the
medium. Thus a double layer of opposite charges is formed. This is known as Helmholtz electrical double layer. The
layer in which the ions are directly adsorbed to the sol particles is termed as fixed layer. The second layer is mobile and
is termed as diffused layer.
Due to the opposite charges on the fixed and diffused layers, there arises a potential difference between these
layers. This potential difference between the fixed layer and the diffused layer of opposite charges is called the
electrokinetic potential or zeta potential.
The presence of similar charges on colloidal particles leads to repulsion between the particles and prevent them
from coagulation when they come closer. So the charge on the sol particles is mainly responsible for the stability of
colloidal solution.
5. Electrophoresis:
Since colloidal particles carry charge, they move under the influence of an electric field. This movement of colloidal
particles is called electrophoresis. The positively charged sol particles move towards cathode (cataphoresis) and the
negatively charged particles move towards the anode (anaphoresis).
If the movement of the sol particles is prevented by some suitable method, the particles of dispersion medium
itself move under the presence of electric field. This migration is termed as electro-osmosis.
6. Coagulation (precipitation or flocculation)
The process of settling of colloidal particles is called coagulation or precipitation of the sol. This can be done by
different ways:
i) By electrophoresis
ii) By mixing two oppositely charged sols
iii) By continuous dialysis
iv) By boiling
v) By the addition of electrolyte
When an electrolyte is added to the sol, the ions carrying opposite charge to that of the sol neutralize the charge
and causes precipitation. The ion of the electrolyte which causes the precipitation is called the coagulating ion or the
flocculating ion. A negatively charged ion causes the precipitation of positively charged sol and vice versa.
Generally, the greater the valency of the coagulating ion, the greater will be the coagulating power. This is known
as Hardy – Schulze rule.
Thus for the coagulation of a negative sol like As2S3, the flocculating power of the +ve ions is of the order:
Al3+ > Ba2+ > Na+
Similarly for a +ve sol like ferric hydroxide, the flocculating power of the counter ion is of the order:
[Fe(CN)6]4- > PO43- > SO42- > Cl-
Coagulating value: The minimum concentration of an electrolyte in millimoles per litre required for the coagulation of a
sol within 2 hours is called coagulating value. The smaller the coagulating value, the higher will be the coagulation
power.
Protection of colloids
Lyophilic sols are self stabilized, while lyophobic sols require some stabilizing agents. For this purpose, some
lyophilic sols are added to lyophobic sols. These lyophilic sols are called protective colloids.
When a lyophilic sol is added to a lyophobic sol, the lyophilic particles form a layer around lyophobic particles
and thus protect them from electrolytes.
EMULSIONS
These are colloidal solutions in which a liquid is dispersed in another liquid. Generally one of the two liquids is
water. There are two types of emulsions: 1. Oil in water (O/W) type and 2. Water in oil (W/O) type
In oil in water type emulsion, oil is the dispersed phase and water is the dispersion medium.
E.g. milk. In milk, the liquid fat is dispensed in water
In water in oil type emulsion, water is the dispersed phase and oil is the dispersion medium.
E.g. butter and cream
An emulsion obtained by mixing oil with water or water with oil is not stable. In order to prepare a stable
emulsion, a third substance called emulsifying agent is added. The emulsifying agent forms an inter facial film between
dispersed phase and the dispersion medium.
The common emulsifying agents for O/W emulsions are proteins, gums, natural and synthetic soaps, etc., and
for W/O, heavy metal salts of fatty acids, long chain alcohols, lampblack, etc.
The two types of emulsions can be distinguished by dilution with dispersion medium.
The droplets in emulsions carry negative charge and they can be precipitated by electrolytes. They also show Brownian
movement and Tyndall effect.
Applications of Colloids
1. Formation of Delta:
Deltas are formed at the river mouth. This is because river water is a negatively charged colloid of sand particles.
When this water enters into sea, the positive ions present in sea water coagulate the colloidal solution of sand and
so the particles settle down. This will result in the formation of delta.
2. Electrical precipitation of smoke (Cottrell precipitation):
Smoke is a colloidal solution of carbon, arsenic compounds, dust particles etc. in air. The smoke before coming
out of the chimney is passed through a chamber (Cottrell precipitator) containing plates having a charge opposite to
that of smoke particles. Thus neutralization of charges occurs and the particles settle down and pure air flows out of
the chimney.
3. Purification of drinking water:
The water obtained from natural sources often contains suspended impurities. In order to coagulate these
impurities, alum is added to water. The positive ions present in alum neutralize the suspended impurities and hence
get purified.
4. Medicines:
Most of the medicines are colloidal in nature. This is because they have large surface area and are therefore
easily assimilated. For example, argyrol is a silver sol used as an eye lotion. Colloidal antimony is used in curing
kalaazar. Colloidal gold is used for intramuscular injection.
5. Tanning:
Animal hides are colloidal in nature. When a hide, which has positively charged particles, is soaked in tannin
(which contains negatively charged colloidal particles) mutual coagulation takes place. This results in the hardening
of leather. This process is termed as tanning.
6. Photographic plates and films:
Photographic plates or films are prepared by coating an emulsion of the light sensitive silver bromide in gelatin
over glass plates or celluloid films.
7. Rubber industry:
Rubber latex is a colloidal solution of rubber particles which are negatively charged. Rubber is obtained by
coagulation of the latex.
8. Food articles:
Milk, butter, halwa, ice creams, fruit juices, etc., are all colloids in nature.
9. Blood:

Blood is a colloidal solution of an albuminoid substance. When alum and ferric chloride (FeCl3) solution are
added to blood, then coagulation of particles take place which results in clotting of blood.
10. Industrial products:
Paints, inks, synthetic plastics, rubber, graphite lubricants, cement, etc., are all colloidal in nature.
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14. ENVIRONMENTAL CHEMISTRY
Environmental chemistry deals with the study of the origin, transport, reactions, effects and fates of chemical
species in the environment.
What is mean by environmental pollution?
It is the effect of undesirable changes in our surroundings that have harmful effects on plants, animals and
human beings.
What is a pollutant?
A substance which causes pollution is known as pollutant. It may be a solid, liquid or gaseous substance
present in greater concentration than the normal level.
Which are the different types of pollutants?
Pollutants are of two types – degradable and non-degradable. Degradable pollutants are rapidly broken down
by natural processes. E.g. vegetable wastes.
Non-degradable pollutants are not dissociated by natural processes or by micro-organisms and remain in the
environment for a long time. E.g. DDT, plastic materials, heavy metals, many chemicals, nuclear wastes etc.
What is mean by Tropospheric pollution?
The presence of undesirable solid or gaseous particles in the lower layer of atmosphere (Troposphere) is called
tropospheric pollution.
“Sulphur dioxide is poisonous to both animals and plants”. Justify the statement.
Low concentration of sulphur dioxide causes respiratory diseases like asthma, bronchitis etc and irritation to
the eyes. High concentration of SO2 leads to stiffness of flower buds. Also it produces acid rain.
How does Nitrogen dioxide form in the atmosphere?
During lightning, atmospheric nitrogen combines with oxygen to form nitric oxide (NO), which further
combines with oxygen to form nitrogen dioxide (NO2). Also due to the combustion of fossil fuels in automobile engine,
NO2 is released to the atmosphere.
What are the harmful effects of NO2?
The adverse effects (bad effects) of NO2 are:
a) Its higher concentration damages the leaves of plants and retards the rate of photosynthesis.
b) It is a lung irritant and cause severe respiratory disease in children. It is toxic to living tissues also.
c) It is also harmful to various textile fibres and metals.
d) Excess NO2 in atmosphere results in acid rain and photochemical smog.
Carbon monoxide is one of the most serious air pollutants. How does it affect human being?
Carbon monoxide binds to haemoglobin of our blood to form carboxyhaemoglobin, which is more stable than
the oxygen-haemoglobin complex. So it reduces the oxygen carrying capacity of blood. This oxygen deficiency results
into headache, weak eyesight, nervousness and cardiovascular disorder.
What is mean by the green house effect?
When the concentration of carbon dioxide in the atmosphere is above the normal level (0.03%), it absorbs
more infra-red radiation from the solar energy and hence the temperature of the earth’s atmosphere increases. This is
known as Green house effect. It results in global warming.
What is mean by green house gases? OR,
What are the major gases which contribute towards global warming?
The gases responsible for green house effect are called green house gases. They are CO2, methane, water -
vapour, chlorofluorocarbons (CFC’s), nitrous oxide and ozone.
What are the adverse effects of global warming and green house effect?
Due to global warming, the average global temperature will increase. This will lead to the melting of polar ice
caps and flooding of low lying areas all over the earth. Increase in the global temperature results in the infectious
diseases like dengue, malaria, yellow fever, sleeping sickness etc.
What can we do to reduce global warming?
Global warming can be reduced by the following methods:
a) Reduce the burning of fossil fuels by minimizing the use of automobiles.
b) Plant trees and encourage afforestation.
c) Avoid burning of dry leaves, wood etc.
XI Chemistry Study Notes by Anil Kumar K.L- HSSLiVE.IN
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d) Aware the public about the bad effects of global warming.
What is mean by acid rain? What are the major compounds responsible for acid rain?
When the pH of the rain water drops below 5.6, it is called acid rain. Oxides of nitrogen and sulphur (e.g. SO2
and NO2) are mainly responsible for acid rain.
What are the harmful effects of acid rain?

a) Acid rain is harmful for agriculture, trees and plants.
b) It causes respiratory ailments and skin cancer in human beings and animals.
c) It affects plants and animal life in aquatic ecosystem.
d) It corrodes water pipes resulting in the dissolution of heavy metals into the drinking water.
e) Acid rain damages buildings and other structures made of stone or metal (e.g. The Taj Mahal).
What are the different measures to reduce acid rain?
Acid rain can be reduced by the following methods:
a) Reduce the use of automobiles.
b) Encourage the use of natural gas instead of coal.
c) Catalytic converters must be used in motor vehicles to reduce the emission of CO and oxides of Nitrogen to
the atmosphere.
d) Acidity of the soil can be reduced by adding powdered limestone.
e) Aware the public about acid rain.
Define particulate pollutants?
Particulates pollutants are the minute solid particles or liquid droplets in air. These are present in vehicle emissions,
smoke particles from fires, dust particles and ash from industries.
What is mean by viable and non-viable particulate pollutants? Give examples.
The viable particulates are minute living organisms that are dispersed in the atmosphere. E.g., bacteria, fungi,
moulds, algae etc. The non-viable particulates are non-living like smoke, fumes, mist, dust etc.
What is mean by ‘smog’? Which are the different types of smog? Explain.
Smog means smoke and fog. There are two types of smog – classical smog and photochemical smog. Classical
smog occurs in cool humid climate. It is a mixture of smoke, fog and sulphur dioxide. Chemically it is a reducing
mixture and so it is also called as reducing smog.
Photochemical smog occurs in warm, dry and sunny climate. The main components of the photochemical
smog are nitrogen oxides, unburnt hydrocarbons, formaldehyde etc. Photochemical smog has high concentration of
oxidising agents and so it is also called oxidising smog.
How is photochemical smog formed?
When fossil fuels burnt, hydrocarbons and nitric oxide are released into the atmosphere. The nitric oxide (NO)
so formed is first converted to NO2, which further breaks up to form nitric oxide and free nitrogen atom in presence of
sunlight.
NO2(g) sun light NO(g) + O(g)
The atomic oxygen rapidly combines with atmospheric oxygen to form ozone.
O(g) + O2(g) O3(g)
Both NO2 and O3 are strong oxidising agents and reacts with unburnt hydrocarbons to produce compounds like
formaldehyde, acrolein and peroxyacetyl nitrate (PAN). These are the main components of photochemical smog.
What are the adverse effects of photochemical smog?
a) Photochemical smog causes serious health problems like headache, chest pain, dryness of the throat, cough
and difficulty in breathing.
b) It leads to cracking of rubber and extensive damage to plant life.
c) It also causes corrosion of metals, stones, building materials, rubber and painted surfaces.
How can we control photochemical smog?
We can control photochemical smog by the following methods:
a) Use catalytic converters in automobiles, which prevent the release of nitrogen oxide and hydrocarbons to the
atmosphere.
b) Certain plants like Pinus, can metabolise nitrogen oxide. So their plantation helps to reduce these oxides.
HSSLiVE.IN
Explain the formation of ozone in stratosphere. Write necessary equations.
Ozone is formed in the upper stratosphere by the interaction of uv radiation on dioxygen.
O2(g) sun light O(g) + O(g)
O(g) + O2(g) O3(g)
Explain with chemical equation, the destruction of ozone by chloroflurocarbons causing ozone hole.
The main reason for ozone layer depletion is the release of chloroflurocarbons (CFC’s) to the atmosphere. In
stratosphere, CFC’s get broken down by UV radiations, releasing chlorine free radical.
CF2Cl2(g) uv Cl●(g) + ●CF2Cl(g)
The chlorine radical then react with ozone to form chlorine monoxide radicals and molecular oxygen.
Cl●(g) + O3(g) ClO●(g) + O2(g)
Reaction of chlorine monoxide radical with atomic oxygen produces more chlorine radicals.
ClO●(g) + O(g) Cl●(g) + O2(g)
The chlorine radicals are continuously regenerated and cause the breakdown of ozone.
What are the harmful effects of ozone depletion?
Due to the depletion of ozone layer, more UV radiation reaches into troposphere and leads to the following harmful
effects:
i) It leads to ageing of skin, cataract, sunburn, skin cancer, killing of many phytoplanktons, damage to fish
productivity etc.
ii) It leads to the harmful mutation of cells.
iii) It also increases evaporation of surface water through the stomata of the leaves and decreases the moisture
content of the soil.
iv) Increase in UV radiations damage paints and fibres, causing them to fade faster.
What is Biological Oxygen Demand (BOD)?
The amount of oxygen required by bacteria to break down the organic matter present in a certain volume of a
sample of water, is called Biochemical Oxygen Demand (BOD). The amount of BOD in the water is a measure of the
amount of organic material in the water. Clean water would have BOD value of less than 5 ppm whereas highly
polluted water could have a BOD value of 17 ppm or more.
How do organic pollutants affect aquatic life?
As the amount of organic matter in water increases, more oxygen is required to decompose them by bacteria.
So the amount of dissolved oxygen in water decreases. This causes oxygen dependent aquatic life to die.
What is mean by eutrophication?
Nutrient enriched water bodies support a dense plant population, but kills animal life by reducing the amount
of free oxygen. This results in the loss of biodiversity and is known as Eutrophication.
There are international standards regarding drinking water. Write any four among them.
The International Standards for drinking water are given below:
1. Fluoride: For drinking purposes, water should contain fluoride upto 1 ppm (parts per million).
2. Lead: The upper limit concentration of lead in drinking water is about 50 ppb (parts per billion).
3. Sulphate: Less than 500 ppm
4. Nitrate: The maximum limit of nitrate in drinking water is 50 ppm.
What are the following abbreviations stands for? PCB, PAN, BOD, CFC, DDT.
PCB – Polychlorinated biphenyls (Pollution control Board)
PAN – peroxyacetyl nitrate
BOD – Biological Oxygen Demand
CFC – Chlorofluorocarbon
DDT – Dichlorodiphenyltrichloroethane
Give some examples for pesticides and herbicides?
Pesticides – DDT, aldrin, Dieldrin etc.
Herbicides – sodium chlorate (NaClO3), sodium arsinite (Na3AsO3) etc.
What is Green Chemistry?
Green chemistry (also called sustainable chemistry) is an area of chemistry focused on the design of products
and processes that minimize the use and generation of dangerous substances.
HSSLiVE.IN
Give some applications of Green Chemistry in day-to-day life.
(i) Dry Cleaning of Clothes: Liquefied carbondioxide, with a suitable detergent is used for dry cleaning clothes.
(ii) Bleaching of Paper: Hydrogen peroxide (H2O2) with suitable catalyst is used for bleaching paper.
(iii) Synthesis of Chemicals: Ethanal (CH3CHO) is now commercially prepared by one step oxidation of ethene in the
presence of ionic catalyst in aqueous medium.
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2. SOLUTIONS
Solutions are homogeneous mixtures containing two or more components. Generally, the component
that is present in larger quantity is called solvent. Solvent determines the physical state of the solution. One
or more components present in the solution other than solvent are called solutes. [Or, the substance which is
dissolved is called solute and the substance in which solute is dissolved is called solvent].
Solutions containing only two components are called binary solutions. Here each component may be
solid, liquid or in gaseous state. Based on this, solutions are of the following types:
Types of Solution Solute Solvent Examples

Gas Gas Mixture of O2 and CO2
Gaseous solutions Liquid Gas Chloroform mixed with nitrogen gas, water-vapour in air
Solid Gas Camphor in nitrogen gas, naphthalene in air
Gas Liquid Oxygen dissolved in water, soda water
Liquid solutions Liquid Liquid Alcohol dissolved in water, dilute acids and alkalies
Solid Liquid Salt in water, glucose in water
Gas Solid Hydrogen in Pd, Pt, Ni etc
Solid solutions Liquid Solid Amalgam of mercury with sodium
Solid Solid Gold ornaments, alloys of metals
Concentration of Solutions
Composition of a solution can be expressed in terms of concentration. Concentration is defined as the
number of moles of solute present per litre of the solution. The concentration of a solution can be expressed
by several ways.
(i) Mass percentage (w/w): The mass percentage of a component in a solution is defined as the mass of
the component present in 100 parts by mass of the solution.
i.e. Mass % of a component = Mass of the component in the solution × 100
Total mass of the solution
For e.g. 10% aqueous solution of glucose by mass means that 10 g of glucose is dissolved in 90 g of water
resulting in a 100 g solution.
Concentration described by mass percentage is commonly used in industrial chemical applications.
(ii) Volume percentage (v/v): The volume percentage is defined as the volume of a component present
in 100 parts by volume of the solution.
i.e. Volume % of a component = Volume of the component ×100
Total volume of solution
For example, 10% ethanol solution in water means that 10 mL of ethanol is dissolved in 90 mL of water such
that the total volume of the solution is 100 mL.
Concentration of solutions containing liquids is commonly expressed in this unit.
(iii) Mass by volume percentage (w/v): It is the mass of solute dissolved in 100 mL of the solution
It is commonly used in medicine and pharmacy.
Mass/volume % of a component = Mass of the component in the solution × 100
Total volume of the solution
(iv) Parts per million (ppm): When a solute is present in trace quantities (i.e. very small amounts), its
concentration is expressed in parts per million (ppm). It is defined as the number of parts of a
particular component in million parts of the solution.
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i.e. Parts per million (ppm) = Number of parts of the component × 106
Total number of parts of all the components of the solution
Concentration in parts per million can be expressed as mass to mass, volume to volume and mass to volume.
The concentration of pollutants in water or atmosphere is expressed in terms of μg mL–1 or ppm.
(v) Mole fraction (x): It is defined as the ratio of the number of moles of a particular component to the
total number of moles of solution.
Mole fraction of a component = Number of moles of the component
Total number of moles of all the components
For example, in a binary solution, if the number of moles of A and B are nA and nB respectively,
then the mole fraction of A ( xA) = nA/(nA + nB)
and that of the component B (xB) = nB/(nA + nB)
xA + xB = 1
i.e. in a given solution sum of the mole fractions of all the components is unity. If there are i components,
then
x1 + x2 + x3 + .................. + xi = 1
Mole fraction is useful in describing the calculations involving gas mixtures.
(vi) Molarity (M): It is defined as the number of moles of solute dissolved per litre of solution.
i.e. Molarity (M) = Number of moles of solute (n)
Volume of solution in litre (V)
Or, Molarity (M) = Mass of solute
Molar mass of solute x Volume of solution in L
Or, Molarity (M) = Mass of solute (WB) x 1000
Molar mass of solute (MB) x Volume of solution in mL (V)
For example, 0.25 M solution of NaOH means that 0.25 mol of NaOH is dissolved in one litre of solution.
(vii) Molality (m): It is defined as the number of moles of the solute present per kilogram (kg) of the solvent.
i.e. Molality (m) = Number of moles of solute(n)
Mass of solvent in kg (WA)
Or, Molality (m) = Mass of solute (WB)
Molar mass of solute (MB) x Volume of solution in L (V)
Or, Molality (m) = Mass of solute (WB) x 1000
Molar mass of solute (MB) x Volume of solution in mL (V)
For example, 1 molal (m) solution of KCl means that 1 mol (74.5 g) of KCl is dissolved in 1 kg of water.
(vii) Normality (N): It is defined as the no. of gram equivalents of solute present per litre of the solution.
i.e., Normality (N) = Number of gram equivalents of solute
Volume of solution in litre
Or, Normality (N) = Mass of solute
Equivalent mass of solute x Volume of solution in L
Or, Normality (N) = Mass of solute x 1000
Equivalent mass of solute x Volume of solution in mL
Among the different methods for expressing the concentration of solution, mass %, ppm, mole
fraction and molality are independent of temperature; whereas molarity, normality and volume % are
depend on temperature. This is because volume depends on temperature and the mass does not.
SOLUBILITY
Solubility of a substance is its maximum amount that can be dissolved in a specified amount of
solvent. It depends upon the nature of solute and solvent, temperature and pressure.
Solubility of a Solid in a Liquid
It is observed that polar solutes dissolve in polar solvents and non polar solutes in non polar solvents.
In general, a solute dissolves in a solvent if the intermolecular interactions are similar in the two or the
general principle related to solubility is that “like dissolves like”.
Saturated and Unsaturated solutions
A solution in which no more solute can be dissolved at the same temperature and pressure is called a
saturated solution. Here there is a dynamic equilibrium between the dissolved solute and the undissolved
solute. A solution in which more solute can be dissolved at the same temperature is called an unsaturated
solution.
Effect of temperature
The solubility of a solid in a liquid mainly depends on temperature. Since the dissolution of a solid in a
liquid is an equilibrium process, it should follow Le Chateliers Principle. In general, if in a nearly saturated
solution, the dissolution process is endothermic (Δsol H > 0), the solubility should increase with rise in
temperature and if it is exothermic (Δsol H > 0) the solubility should decrease with temperature.
Effect of pressure
Since solids and liquids are highly incompressible, pressure does not have any significant effect on
solubility of solids in liquids.
Solubility of a Gas in a Liquid
Solubility of gases in liquids is greatly affected by pressure and temperature. The solubility of a gas
increases with increase of pressure.
A quantitative relation between pressure and solubility of a gas in a liquid was first given by Henry,
which is known as Henry’s law. “The law states that at a constant temperature, the solubility of a gas in a
liquid is directly proportional to the pressure of the gas”.
Or, “the partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of the gas
(x) in the solution” and is expressed as:
p = KH x
Here KH is the Henry’s law constant. The value of KH depends on the nature of the gas and
temperature. As the value of KH increases, the solubility of the gas in the liquid decreases.
A graph of partial pressure (p) of the gas against mole fraction (x) of the gas in solution is a straight
line as follows. The slope of the graph gives the value of KH.
Vapour pressure (p)
Mole fraction (x)

As the temperature increases solubility of a gas in a liquid decreases. It is due to this reason that
aquatic species are more comfortable in cold waters rather than in warm waters.
Applications of Henry’s law

1. To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high
pressure.
2. Scuba divers carry oxygen cylinders to breath under deep sea. At high pressure under water, the
solubility of atmospheric gases in blood increases. When the divers come towards surface, the
pressure gradually decreases. This releases the dissolved gases and leads to the formation of bubbles
of nitrogen in the blood. This blocks capillaries and creates a medical condition known as bends. To
avoid bends the cylinders used by scuba divers are filled with air diluted with helium (11.7% helium,
56.2% nitrogen and 32.1% oxygen).
3. At high altitudes the partial pressure of oxygen is less than that at the ground level. This leads to low
concentrations of oxygen in the blood and tissues of people living at high altitudes or climbers. Low
blood oxygen causes climbers to become weak and unable to think clearly. This condition is known as
anoxia.
Effect of Temperature
Solubility of gases in liquids decreases with rise in temperature. When dissolved, the gas molecules
are present in liquid phase and the process of dissolution can be considered similar to condensation and heat
is evolved during this process. The dissolution process involves a dynamic equilibrium and thus follows
Le-Chatelier’s Principle. As dissolution is an exothermic process, the solubility should decrease with increase
of temperature.
Vapour Pressure of Liquid Solutions
In liquid solutions, the solvent is always a liquid. The solute can be a gas, a liquid or a solid. Generally,
the liquid solvent is volatile. The solute may or may not be volatile. Based on the volatility of solute, the
vapour pressure of the solution is greater or less than that of the solvent.
Vapour Pressure of Liquid-Liquid Solutions – Raoult’s Law
A quantitative relationship between the vapour pressure and mole fraction of solute in a solution was
first given by a French chemist F.M Raoult and it is known as Raoult’s Law. It states that for a solution of
volatile liquids, the partial vapour pressure of each component in the solution is directly proportional to its
mole fraction.
Consider a binary solution of two volatile liquids 1 and 2. Let p1 and p2 be the partial vapour pressures
of the two components 1 and 2 respectively and ptotal be the total vapour pressure. Let x1 and x2 be the mole
fractions of the two components 1 and 2 respectively.
Then according to Raoult’s law,
for component 1, p1 ∝ x1
or, p1 = p10x1
and for component 2, p2 ∝ x2
or, p2 = p20x2
Where p10 and p20are the vapour pressures of the pure components 1 & 2 respectively.
According to Dalton’s law of partial pressures, the total pressure (p total) will be the sum of the partial
pressures of the components of the solution.
So, ptotal = p1 + p2
Substituting the values of p1 and p2, we get
ptotal = x1 p10 + x2 p20
= (1 – x2) p10 + x2 p20
Or, ptotal = p10 + (p20 – p10) x2
Plots of p1 or p2 against the mole fractions x1 and x2 give straight lines (I and II). Similarly the plot of
ptotal versus x2 (line III) is also linear.

The composition of vapour phase in equilibrium with the solution is determined from the partial
pressures of the components. If y1 and y2 are the mole fractions of the components 1 and 2 respectively in
the vapour phase then, using Dalton’s law of partial pressures:
p1 = y1 ptotal and p2 = y2 ptotal
In general, pi = yi ptotal
Raoult’s Law as a special case of Henry’s Law
According to Raoult’s law, the vapour pressure of a volatile component in a solution is given by
pi = xi pi0. According to Henry’s law, solubility of a gas in a liquid is given by p = KH x.
If we compare the equations for Raoult’s law and Henry’s law, we can see that the partial pressure of
the volatile component or gas is directly proportional to its mole fraction in solution. Only the proportionality
constant KH differs from p10. Thus, Raoult’s law becomes a special case of Henry’s law in which KH becomes
equal to p10.
Vapour Pressure of Solutions of Solids in Liquids
The vapour pressure of a liquid is the pressure exerted by the vapour in equilibrium with its own
liquid. If a non-volatile solute is added to a pure solvent, the vapour pressure of the resulting solution is
always lower than that of the pure solvent. This is because in a pure solvent, there are only solvent
molecules, which can vapourise. But when a non-volatile solute is added to the solvent, a fraction of the
surface is occupied by solute molecules. So the number of solute molecules passing to the vapour phase
decreases and hence the vapour pressure also decreases. The decrease in the vapour pressure of solvent
depends on the quantity of non-volatile solute present in the solution and not on its nature.
For such a solution the Raoult’s law can be stated as, for any solution, the partial vapour pressure of each
volatile component in the solution is directly proportional to its mole fraction.
Consider a binary solution containing a solvent 1 and solute 2. Since the solute is non-volatile, only the
solvent molecules are present in vapour phase and contribute to vapour pressure.
Let p1 be the vapour pressure of the solvent, x1 be its mole fraction, p10 be its vapour pressure in the
pure state. Then according to
Raoult’s law, p1 ∝ x1
or, p1 = p10x1
A graph between the vapour pressure and the mole fraction of the solvent is linear as follows:

Ideal and non-ideal solutions
Liquid – liquid solutions can be classified into ideal and non-ideal solutions on the basis of Raoult’s law.
1. Ideal solutions:
These are solutions which obey Raoult’s law over the entire range of concentration. For such
solutions, the enthalpy of mixing (∆H mix) of the pure components is zero and also volume of mixing (∆V mix) is
zero. i.e. for an ideal solution,
P1 = P10x1, P2 = P20x2, ∆H mix = 0 and ∆V mix = 0
Ideal behaviour can be explained by considering two components A and B. In pure components, the
inter molecular attractive interactions will be of types A-A and B-B. In solution, in addition to these two
interactions, A-B type of interaction will also be present. If the A-A and B-B interactions are nearly equal to
the A-B interaction, the solution behaves ideally. i.e. solute-solute interactions and solvent-solvent
interactions are nearly equal to solute-solvent interaction.
A perfectly ideal solution is rare. But some solutions are nearly ideal in behaviour.
E.g. solutions of n-hexane and n-heptane, bromoethane and chloroethane, benzene and toluene etc.
2. Non-ideal solutions:
These are solutions which do not obey Raoult’s law over the entire range of concentration. The vapour
pressure of such a solution is either higher or lower than that predicted by Raoult’s law. If it is higher, the
solution exhibits positive deviation and if it is lower, it exhibits negative deviation from Raoult’s law. The plots
of vapour pressure against mole fractions for such solutions are as follows:
In the case of positive deviation from Raoult’s law, A-B interactions are weaker than A-A and B-B
interactions. i.e., in this case solute-solvent interactions are weaker than solute-solute and solvent-solvent

interactions. So more molecules are escaped to vapour phase and hence the vapour pressure of the solution
increases.
E.g. solutions of ethanol and acetone, acetone and CS2, acetone and CCl4 etc.
In case of negative deviation from Raoult’s law, the A-B interactions are stronger than A-A and B-B
interactions. i.e. solute-solvent interactions are stronger than solute-solute interaction and solvent-solvent
interaction. So number of molecules escaped to vapour phase decreases and hence the vapour pressure of
the solution decreases.
E.g. solution of phenol and aniline, chloroform and acetone etc.
Azeotropes
They are binary mixtures having the same composition in liquid and vapour phase and boil at a
constant temperature. For such solutions, it is not possible to separate the components by fractional
distillation. There are two types of azeotropes: minimum boiling azeotrope and maximum boiling azeotrope.
The solutions which show a large positive deviation from Raoult’s law form minimum boiling
azeotrope at a particular composition. E.g. 95% ethanol solution by volume.
The solutions which show large negative deviation from Raoult’s law form maximum boiling azeotrope
at a particular composition. E.g. a mixture of 68% Nitric acid and 32% water by mass forms a maximum
boiling azeotrope at 393.5 K.
COLLIGATIVE PROPERTIES AND DETERMINATION OF MOLARMASS
The properties which depend only on the number of solute particles and not on their nature are called
Colligative properties. The important colligative properties are: Relative lowering of Vapour pressure,
Elevation of Boiling point, Depression of Freezing point and Osmotic Pressure.
1. Relative lowering of Vapour Pressure

When a non-volatile solute is added to a pure solvent, the vapour pressure (V.P) of the resulting
solution is lower than that of the pure solvent. The difference between the vapour pressure of pure solvent
and that of the solution is called lowering of vapour pressure (∆P).
Consider a binary solution containing a non-volatile solute 2 dissolved in a solvent 1. Let P10 be the
vapour pressure of pure solvent 1 and P1 be the vapour pressure of solution. Then according to Raoult’s law,
P1 = P10.x1
The lowering of vapour pressure of the solvent (∆P) = P10 – P1
= P10 – P10x1
Or, ∆P = P10(1-x1)
But x1 + x2 = 1. Therefore 1-x1 = x2
So ∆P = P10.x2
Or, ∆P = x2, the mole fraction of the solute.
P10
Where ∆P/P10 is called relative lowering of vapour pressure. It is defined as the ratio of the lowering of
vapour pressure to the vapour pressure pure solvent.
But x2 = n2
n1 + n2
Where n1 and n2 are the number of moles of solvent and solute respectively.
For dilute solutions, n2 << n1 and hence n2 in the denominator can be neglected.
So, x2 = n2/n1
Therefore, ∆P = n2
P10 n1

Or, ∆P = w2/M2
P10 w1/M1
Or, ∆P = w2 x M1
P10 w1 x M2
Where w1 and w2 are the masses and M1 and M2 are the molar masses of solvent and solute
respectively.
2. Elevation of Boiling Point (∆Tb)
Boiling point of a liquid is the temperature at which its vapour pressure becomes equal to the
atmospheric pressure.
When a non-volatile solute is added to a pure solvent, the boiling point of the resulting solution is always
greater than that of the pure solvent. The difference between the boiling point of solution (∆Tb) and that of
the pure solvent (Tb0) is called elevation of boiling point (Tb).
i.e. ∆Tb = Boiling point of solution – Boiling point of pure solvent
Or, ∆Tb = Tb – Tb0
If we plot a graph between the vapour pressure and temperature, we get the following graphs for the
pure solvent and the solution.
For dilute solutions, the elevation of boiling point is directly proportional to molality (m).
i.e. ∆Tb α m
or, ∆Tb = Kb.m
Where Kb is a constant called Boiling Point Elevation Constant or Molal Elevation Constant or Ebullioscopic
Constant. It is defined as the elevation of boiling point for 1 molal solution.
The unit of Kb is K kg/mol. For water, Kb = 0.52K kg/mol.
But molality m = w2 x 1000
M2 x w1
Therefore, ∆Tb = Kb. w2 x 1000
M2.w1
Or, ∆Tb = 1000Kb.w2
w1.M2
Where w1 = mass of solvent, w2 = mass of solute, M2 = molar mass of solute. By using this equation, we can
calculate the molar mass of unknown solute.
3. Depression of Freezing point (∆Tf)
Freezing point is the temperature at which the solid phase and liquid phase of a substance has the
same vapour pressure.

According to Raoult’s law, when a non-volatile solute is added to a pure solvent, its vapour pressure
decreases. Now it would become equal to that of solid solvent at lower temperature. Thus the freezing point
of the solvent decreases. The difference between the freezing point (f.p) of pure solvent (Tf0)and that of the
solution (Tf) is called depression of freezing point (∆Tf).
i.e. ∆Tf = Tf0 - Tf
The vapour pressure – temperature graph representing the freezing point of pure solvent and solution
is as follows:
For dilute solutions, it is found that the depression of freezing point (∆Tf) is directly proportional to
molality (m) of the solution.
Thus ∆Tf α m
Or, ∆Tf = Kf.m
Where Kf is a constant called Freezing Point Depression Constant or Molal Depression Constant or
Cryoscopic Constant. It is defined as the depression of freezing point for 1 molal solution. The unit of Kf is K
kg/mol. For water, Kf = 1.86 K kg/mol.
We know that molality m = w2 x 1000
M2 x w1
Therefore, ∆Tf = Kf. w2 x 1000
M2.w1
Or, ∆Tf = 1000Kf.w2
w1.M2
4. Osmosis and Osmotic Pressure
Osmosis is the process of flow of solvent molecules from pure solvent to solution through a semi-
permeable membrane. Or, it is the flow of solvent molecules from lower concentration side to a higher
concentration side through a semi-permeable membrane (SPM).
A membrane that allows the passage of solvent molecules only is called a semi-permeable
membrane. E.g. egg membrane, all animal and plant membrane. Cellulose acetate is an example for
artificial SPM.
Osmotic pressure is defined as the excess pressure that must be applied on solution side to stop
osmosis. Or, it is the pressure that just stops the flow of solvent molecules. It is denoted by π. It is a
colligative property, since it depends on the number of solute molecules and not on their nature.
For dilute solutions, osmotic pressure is proportional to the molarity (C) and temperature (T).
i.e. π = CRT
Here R is the universal gas constant. (R= 0.0821 Latm/K/mol or R = 0.083Lbar/K/mol).
But C = n2/V, the concentration of the solution.
Therefore, π = n2.RT
V
Or, πV = n2RT
Or, πV = w2RT
M2
Where V is the volume of the solution, w2 is the mass of solute and M2 is the molar mass of solute.
Thus by knowing all other values, we can calculate the molar mass of the unknown solute by the equation:
M2 = w2RT
πV
Advantages of osmotic pressure measurement over other colligative property measurement
1. Osmotic pressure measurement can be done at room temperature.
2. Here molarity of the solution is used instead of molality, which can be determined easily.
3. The magnitude of osmotic pressure is large even for very dilute solutions.
4. This method can be used for the determination of molar masses of Biomolecules (which are generally not
stable at higher temperatures) and for polymers (which have poor solubility).
Examples for osmosis:
a) Raw mango placed in concentrated salt solution loses water and shrink.
b) Wilted flowers revive when placed in fresh water
c) Blood cells collapse when suspended in saline water.
d) The preservation of meat by salting and fruits by adding sugar protect against bacterial action. Through
the process of osmosis, a bacterium on salted meat or candid fruit loses water, shrinks and dies.
Isotonic, hypertonic and hypotonic solutions
Two solutions having same osmotic pressure at a given temperature are called isotonic solutions.
When such solutions are separated by a semi-permeable membrane, no osmosis occurs.
For e.g. our blood cells are isotonic with 0.9% (mass/volume) sodium chloride solution, called normal
saline solution. So it is safe to inject intravenously.
A solution having higher osmotic pressure than another is called hypertonic solution. While a solution
having lower osmotic pressure than another is called hypotonic solution.
If we place our blood cells in a solution containing more than 0.9% (mass/volume) sodium chloride
solution, water will flow out of the cells and they would shrink. On the other hand, if they are placed in a
solution containing less than 0.9% (mass/volume) NaCl, water will flow into the cells and they would swell.
Reverse osmosis and water purification
The direction of osmosis can be reversed if a pressure larger than the osmotic pressure is applied to
the solution side. Now the pure solvent flows out of the solution through the semi permeable membrane.
This phenomenon is called reverse osmosis and is used in desalination of sea water.
When pressure more than osmotic pressure is applied, pure water is squeezed out of the sea water
through the membrane. Commonly used SPM is cellulose acetate. A schematic representation of reverse
osmosis is as follows:

ABNORMAL MOLARMASS
The molar mass obtained by colligative property measurement is incorrect, if there is association or
dissociation of particles. Such molar masses are called abnormal molar masses.
For e.g. acetic acid dimerises in benzene due to hydrogen bonding. So the number of molecules in
solution decreases and hence the colligative property decreases and molecular mass increases.
In order to correct the abnormal molar masses, van’t Hoff introduced a factor called van’t Hoff factor
(i). It is defined as:
i = Normal Molar mass
Abnormal molar mass
Or, i = Observed colligative property
Calculated colligative property
Or, i = Total number of moles of particles after association/dissociation
Number of moles of particles before association/dissociation
In the case of association, the value of i < 1 and in dissociation, the value of i > 1.
Thus for NaCl, i =2, for K2SO4, i = 3, for CaCl2, i = 3 and for acetic acid in benzene, i = ½
Inclusion of van’t Hoff factor modifies the equations for colligative properties as follows:
1. Relative lowering of vapour pressure, ∆P =i x w2 x M1
P10 w1 x M2
2. Elevation of Boiling point (∆Tb) = i.Kb.m
3. Depression of freezing point (∆Tf) = i.Kf.m
4. Osmotic Pressure (π) = i.CRT

CHEMISTY IN EVERYDAY LIFE
SHORT NOTES
Chemotherapy: Treatment of diseases using Antiseptic Disinfectant

chemicals is called chemotherapy.  They don’t harm  Harmful to the living
THERAPEUTIC ACTION OF DIFFERENT CLASSES OF the living tissues. tissues
DRUGS  Prevent or kill  Destroy harmful
harmful organisms microorganisms
 They are applied  They are used to
 Antacids: The medicines used to reduce to wounds cleaning disinfect
acidity in our body are called Antacids.  Eg:Iodine,Boric floor & cleaning of
Eg: Sodiumbicarbonate, Mixture of Aluminum acid equipments
& Magnesium hydroxide  Eg: Phenol
 Anihistamines (Anti allergic): The drugs which
are used to destroy Histamine in our body Ant fertility Drugs: medicine used which are used
called Anihistamines. against anti fertility.
Eg: Dimetapp, Seldane Eg: Novestrol
 Neurologically Active drugs
a) Tranquilizers: Chemicals which are used CHEMICALS IN FOOD
for the treatment of mental diseases
called tranquilizers. 1) Artificial Sweetening agents: Chemicals which
Eg: Baburtic acid, Phenelzine are used to give sweetness to food.
b) Analgesics: Medicines which are used for Eg: Sacarine
relieving pain is called Analgesics. 2) Food preservatives: Chemical substance
1) Non-Narcotics: Remove the cause of which are used to preserve food.
pain. Eg: Comon Salt. Vinegar etc.
Eg: Aspirin, analagin
2) Narcotic: Remove the cause of pain CLEANING AGENTS
by including sleep to the person.
Eg: Morphine, Heroine Soap Detergent
c) Antipyretics: the medicine used for  Soaps are sodium  They are sodium
salt of long chain salt of long chain
reducing the temperature in high fever
of fatty acid alkyl sulphates.
are called Antipyretics  They can’t used in  Used in acidic
Eg: Aspirin (Acetyl salicylic acid), acidic solution. solution
Paracetmol (4-acetamido phenol)  They can’t be  Used in hard
d) Antibiotics: Chemical substance which used in hard water
produced by microorganism are called water  Not
Antibiotics. It prevents or kills the growth  Biodegradable biodegradable
 Don’t cause any
of microorganisms.
pollution
Eg: Pencilin
1) Narrow Spectrum: Antibiotics which Biodegradable Non- Biodegradable
are effective against few  Detergent having  Detergent
microorganisms. straight hydro Contain branched
Eg: Pencilin carbon chain. hydrocarbon
2) Broad Spectrum: Antiseptics which Eg: Sodium lauryl chain.
are effective against wide range of sulphate Eg: Sodium 4-
(1,3,5,7 tetra
microorganisms.
methyloctyl)
Eg: Tetracyclin, Streptomycin
Prepared by Krishna Sampreeth|WOVHSS MUTTIL

16. CHEMISTRY IN EVERYDAY LIFE
1. What are drugs?
Drugs are chemicals of low molecular masses which interact with macromolecular targets and
produce a biological response.
2. What is mean by chemotherapy?
Use of chemicals for therapeutic effect is called chemotherapy
3. Explain the classification of drugs?
Drugs are classified on the basis of the following criteria:
i) Based on pharmacological effect
ii) Based on drug action
iii) Based on molecular structure
iv) Based on molecular target
4. What are antacids? Give example.
Over production of acid in the stomach causes irritation and pain. The chemicals used to reduce the
acdidity in stomach are called antacids. E.g. NaHCO3, metal hydroxides etc.
5. What are anti-histamines?
An important reason for the hyperacidity in stomach is a chemical substance called histamine. It
stimulates the secretion of pepsin and hydrochloric acid. It is also responsible for the nasal congestion
associated with common cold and allergic response to pollen. The drugs which reduce the action of
histamine are called anti-histamines.
E.g. brompheniramine (Dimetapp), terfenadine (seldane), cimetidine, ranitidine etc.
6. ………………. Is a potent vasodilator? Ans: Histamine
7. Distinguish between tranquilizers and analgesics?
Tranquilizers and analgesics are neurologically active drugs.
Tranquilizers are a class of chemical compounds used for the treatment of stress, and mild or even
severe mental diseases. These relieve anxiety, stress, irritability or excitement by inducing a sense of well-
being. They are essential component of sleeping pills.
E.g. Iproniazid, phenelzine (nardil), chlordiazepoxide, meprobamate, Equanil, derivatives of
barbituric acid like veronal, amytal, nembutal, luminal and seconal.
Analgesics reduce or abolish pain without causing impairment of consciousness, mental confusion
etc. These are classified into two:
(i) Non-narcotic (non-addictive) analgesics:
These groups of drugs are antipyretics and analgesics. They give immediate relief from pain and
fever and prevent platelet coagulation. They abolish (remove) the cause of pain.
E.g. aspirin, paracetamol, novalgin etc.
(ii) Narcotic analgesics:
These are sleep inducing analgesics. They help to relieve the feeling of pain, but they do not
remove the cause of pain. E.g. morphine, heroin, codeine etc.
8. Name two antidepressant drugs.
Ans: Iproniazid, phenelzine
9. Which is the chemical substance discovered by Paul Ehlrich for the treatment of syphilis?
Ans: Salvarsan
10. What are antibiotics? Give e.g.
Antibiotics are substances produced wholly or partially by chemical synthesis, which in low
concentrations inhibit the growth or destroys micro organisms by intervening in their metabolic processes.
Chemistry in Everyday Life[Anil Kumar K.L] Page 1
The first antibiotic ‘pencillin’ was developed by Alexander Fleming from the fungus Pencillium
notatum. Other examples are Ofloxacin, Erythromycin, Aminoglycosides, Tetracycline, Chloramphenicol,
Vancomycin, Ampicillin, Amoxycillin etc.
11. Give the difference between bactericidal and bacteriostatic antibiotics?
Ans: Bactericidal is a type of antibiotic that kills bacteria whereas bacteriostatic is a type of antibiotics that
inhibit the growth and reproduction of bacteria. Pencillin, Aminoglycosides, Ofloxacin etc. are bactericidal
while, Erythromycin, Tetracycline, Chloramphenicol etc are bacteriostatic antibiotics.
12. What is mean by spectrum of action of antibiotics? Explain the classification of antibiotics based on this?
Ans: The range of bacteria or other microorganisms that are affected by a certain antibiotic is expressed as
its spectrum of action.
Antibiotics which kill or inhibit a wide range of Gram-positive and Gram-negative bacteria are called broad
spectrum antibiotics. E.g. Ampicillin, Amoxycillin, Chloramphenicol, Vancomycin, Ofloxacin etc.
Antibiotics which are effective mainly against Gram-positive or Gram-negative bacteria are narrow
spectrum antibiotics. E.g. Penicillin G
Antibiotics which are effective against a single organism or disease are called limited spectrum antibiotics.
13. Distinguish between antiseptics and disinfectants?
Antiseptics and disinfectants are the chemicals which kill or prevent the growth of microorganisms.
Antiseptics can be applied to the living tissues such as wounds, cuts, ulcers and diseased skin surfaces.
Examples are furacine, soframicine, tincture of iodine, bithional, dettol etc.
Disinfectants are applied to inanimate objects such as floors, drainage system, instruments, etc.
Some substance can act both as an antiseptic and disinfectant at different concentrations. For example
0.2% solution of phenol is an antiseptic, while its one percent solution is disinfectant. Cl2, SO2 etc. in very
low concentration are disinfectant.
14. Distinguish between antibiotics and antiseptics?
Both, antibiotics and antiseptics, are chemical substances that prevent the growth and development
of the micro-organisms. The differences are:
• Antibiotics are effective only against bacteria while antiseptic acts against a wide range of micro-
organisms.
• Antibiotics kill and stop the growth of bacteria while antiseptic prevents the growth and
development of the micro-organism without necessarily killing them.
• Antibiotics are used internally as well as externally, but antiseptics are mainly used externally.
15. What are artificial sweetening agents?
They are substitute for sugar in foods and soft drinks. They are non-nutritive in nature.
E.g. Saccharin (it is about 550 times sweeter than cane sugar), aspartame, alitame, sucralose etc.
16. What are cleansing agents?
Detergents are called cleansing agents. These are of two types – soaps and synthetic detergents.
Soaps are sodium or potassium salt of long chain fatty acids. They are produced by heating fat with
aqueous NaOH. The process is known as saponification.
17. Soaps do not work in hard water. Why?

Hard water contains Ca2+ and Mg2+ ions. These ions form insoluble calcium and magnesium salts
with soap. So hard water does not easily form lather with soap. Synthetic detergents can form lather with
soap.
18. Explain the different types of synthetic detergents with example?
Synthetic detergents are classified into three types: (i) Anionic detergents (ii) Cationic detergents
and (iii) Non-ionic detergents

i) Anionic Detergents:
Anionic detergents are sodium salts of sulphonated long chain alcohols or hydrocarbons.
In anionic detergents, the anionic part of the molecule is involved in the cleansing action. They are used in
toothpastes.
E.g. Sodium salts of alkylbenzenesulphonates.
ii) Cationic Detergents:
Cationic detergents are quaternary ammonium salts of amines with acetates, chlorides or bromides
as anions. Cationic part possesses a long hydrocarbon chain and a positive charge on nitrogen atom. Hence
these are called cationic detergents. They have germicidal properties.
E.g. Cetyltrimethylammoniumbromide and it is used in hair conditioners.
iii) Non-ionic Detergents:
They do not contain any ion in their constitution. Liquid dishwashing detergents are non-ionic type.
E.g. detergent formed when stearic acid reacts with polyethyleneglycol.
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THE SOLID STATE
Solids are substances having definite shape and definite volume. In solids, the particles are closely
packed and the force of attraction between the particles is strong. So solids are rigid and incompressible.
Their constituent particles (atoms, molecules or ions) have fixed positions and can only vibrate about their
mean positions.
Classification of solids
On the basis of orderly arrangement of particles, solids can be classified into two – Crystalline solids
and Amorphous solids
1. Crystalline solids
In these solids, the constituent particles have a well ordered arrangement throughout the solid, i.e.,
they have a long range order. They consist of a large number of small crystals. They have a definite
geometrical shape, melting point and heat of fusion.
E.g.: Quartz, Diamond, Graphite, fullerene, NaCl, CuSO4.5H2O, ice, naphthalene, SiC etc.
2. Amorphous solids
In these solids, the ordered arrangement of constituent particles is only at some portions of the solid,
i.e., they have only a short range order. The structure of these solids is similar to that of liquids. They have
no definite geometrical shape, melting point and heat of fusion.
E.g.: Plastic, Glass (quartz glass), Rubber, amorphous silica, coal, charcoal, coke, PVC etc.
Like liquids amorphous solids have a tendency to flow, though very slowly. Therefore, sometimes
these are also called pseudo solids or super cooled liquids.
Glass panes fixed to windows or doors of old buildings are slightly thicker at the bottom than at the
top. This is because the glass flows down very slowly and makes the bottom portion slightly thicker.
Amorphous solids on heating become crystalline at some temperature. Some glass objects from
ancient civilizations are found to become milky in appearance due to some crystallization.
Anisotropic and isotropic substances
Solids in which the physical properties like electrical conductance, refractive index etc are different
when measured in different directions are said to be anisotropic in nature. This is due to the different
arrangement of particles in different directions. Crystalline solids are anisotropic.
Solids in which the physical properties are same along any direction are said to be isotropic in nature.
This is due to the irregular arrangement of particles along different directions. Amorphous solids are
isotropic.
Differences between Crystalline solids and Amorphous solids
Properties Crystalline solids Amorphous solids

Orderly Long range order Only short range order
arrangement of
particles
Geometrical shape Definite characteristic geometrical No definite Geometrical shape
shape
Melting point Definite m.p No definite m.p
Heat of fusion Definite Not definite
Mode of cleavage Give regular cleavage on cutting Give irregular cleavage on cutting
Nature True solids Pseudo solids
Isotropy/anisotropy Anisotropic in nature Isotropic in nature
The Solid State[Anil Kumar K.L-HSSLiVE] Page 1

Classification of Based on the nature of particles and binding force
On the basis of nature of particles and binding force between the particles, crystalline solids are
classified into four types- molecular solids, ionic solids, metallic solids and covalent solids.
1. Molecular Solids: Here the constituent particles are molecules. These are further sub-divided into
three:
i. Non-polar molecular solids: Here the constituent particles are either atoms like Ar, He etc. or non-polar
molecules like H2,Cl2, I2 etc and the binding force between the particles is London dispersion forces or
weak van der Waal’s forces. These are soft solids and are non-conductors of electricity. They have low
melting points and are usually liquid or gaseous state at room temperature and pressure.
ii. Polar molecular solids: Here the constituent particles are polar molecules like HCl, CO2, SO2 etc. and the
binding force between the particles is relatively stronger dipole-dipole interactions. These are soft and
non-conductors of electricity. Their melting points are higher than those of non-polar molecular
solids. Most of them are gases or liquids at room temperature and pressure.
iii. Hydrogen bonded molecular solids: Here the constituent particles are molecules which contain atoms
like H and F, O or N. The binding force between the particles is strong hydrogen bond. They are non-
conductors of electricity and are volatile solids or soft solids at room temperature and pressure. E.g.:
H2O, NH3 etc.
2. Ionic Solids: Here the constituent particles are ions and the binding force between the particles is
strong electrostatic force of attraction (ionic bond). They are hard and brittle and have high m.p & b.p.
They are electrical insulators in the solid state, since the ions are not free to move about. But in the molten
or solution state, the ions become free to move about and they conduct electricity. E.g.: NaCl, KCl, CaCl2
etc.
3. Metallic Solids: They contain a large number of metal ions which are surrounded by a sea of
electrons. The particles are held together by strong electrostatic force of attraction (metallic bond). Due to
the presence of a large number of free electrons, they are good conductors of heat and electricity,
malleable and ductile and show metallic lustre. E.g. All metals
4. Covalent or Network Solids: Here the constituent particles are atoms and the binding force between
the particles is strong covalent bond. They are very strong and brittle, have extremely high melting point
and are electrical insulators. E.g. Diamond, Silicon Carbide (SiC, commonly known as Carborundum),
Quartz, Graphite etc.
Graphite has exceptional properties i.e., it is soft and good conductor of electricity. In graphite
carbon atoms are arranged in different layers and each atom is covalently bonded to three adjacent
carbon atoms. The fourth electron is free to move about between different layers. So Graphite is a good
conductor of electricity. The different layers are held together by weak van der Waal’s force of attractions.
So each layer can slide over the other and hence it is soft and used as a good lubricant.
Crystal lattice
The regular three dimensional arrangements of constituent particles of a crystal in space is called
crystal lattice or space lattice.
The important characteristics of a crystal lattice are:
(a) Each point in a lattice is called lattice point or lattice site.
(b) Each point in a crystal lattice represents one constituent particle which may be an atom, a molecule
(group of atoms) or an ion.
(c) Lattice points are joined by straight lines to bring out the geometry of the lattice.
There are only 14 possible three dimensional lattices. These are called Bravais Lattices.

Unit cell
A unit cell is the smallest repeating unit of a crystal lattice which, when repeated in three dimension
we get a whole crystal. Or, it is the building block of a crystal. A unit cell is characterised by its edge lengths
(a, b and c) and angle between the edges – α (between b and c), β (between a and c) and γ (between a and
b). Thus a unit cell is characterised by 6 parameters – a, b, c, α, β and γ.
Unit cells can be broadly divided into two - primitive and centred unit cells.
1. Primitive Unit Cells:
Here the constituent particles are present only at the corners of the unit cell.
2. Centred Unit Cells:
Here the constituent particles are present at the corners and other positions of the unit cell. These
are of three types:
i. Body-centred unit cells: Here the constituent particles are present at the body centre and at
the corners of the unit cell.
ii. Face-centred unit cells: Here the constituent particles are present at the centre of each
faces and at the corners of the unit cell.
iii. End-centred unit cells: Here the constituent particles are present at the centre of any two
opposite faces and at the corners of the unit cell.
Seven types of crystal systems and their possible variations
Crystal Systems Possible Edge lengths Axial angles Examples
variations
Cubic Primitive, a=b=c α = β = γ = 900 NaCl, Zinc
body-centred, blende (ZnS), Cu
face-centred
Tetragonal Primitive, a =b ≠ c α = β = γ = 900 White tin, TiO2,
body-centred SnO2, CaSO4
0
Orthorhombic Primitive, a≠b≠c α = β = γ = 90 Rhombic
body-centred, sulphur, KNO3,
face-centred, BaSO4
end-centred
Monoclinic Primitive, end- a≠b≠c α = γ = 900, β Monoclinic
centred ≠ 900 sulphur,
Na2SO4.10H2O
Hexagonal Primitive a=b≠c α = β = 900, γ Graphite, ZnO,
=1200 CdS
Rhombohedral or Primitive a=b=c α = β= γ ≠ 900 Calcite(CaCO3),
trigonal HgS (Cinnabar)
Triclinic Primitive a≠b≠c α ≠ β ≠ γ ≠ 900 K2Cr2O7, H3BO3,
CuSO4.5H2O
Calculation of Number of atoms in a unit cell (z)

1. Primitive cubic (Simple Cubic) unit cell:
Here atoms are present only at the corners of the cube. Each corner atom is shared by 8 unit cells.
Therefore, contribution to one unit cell = 1/8
Since each unit cell has 8 atoms at the corners, the total number of atoms in one unit cell = 8×1/8 = 1
So for a primitive (simple cubic) unit cell, z = 1

2. Body-centred cubic (bcc) unit cell:
Here the particles are present at the corners of the cube and also one atom at the body centre.
The number of atoms at the corner = 8×1/8 = 1
The atom present at the centre of the body is not shared by other atoms.
So the number of atoms at the body-centre = 1
Therefore, total number of atoms in the unit cell = 1+1=2
So, for a bcc, z = 2
3. Face-centred cubic (fcc) unit cell:
Here the atoms are present at the corners and also at the centre of each faces. Each corner atom is
shared by 8 unit cells and each face centre atom is shared by 2 unit cells.
Number of corner atoms = 8×1/8 = 1
Number of face-centre atoms = 6×1/2 = 3
Therefore, total number of atoms = 1+3 = 4
So, for an fcc, z = 4
Close packing in solids
In solids the particles are closely packed. In close packed structures the particles are considered as
hard spheres. Solids are three dimensional and the 3 dimensional structure can be obtained by the following
three steps:
1. Close packing in One Dimensions
Here the spheres are arranged in a row touching each other. In this arrangement each sphere is in
contact with 2 adjacent spheres. Therefore, co-ordination number of each sphere is 2.
2. Close packing in Two Dimensions
Here the spheres are arranged in two directions – length-wise and breadth-wise. This can be done in two
different ways.
i. Square close packing: Here the spheres of second row are placed exactly above those of the first
row. In this arrangement, each sphere is in contact with four adjacent spheres. So the co-ordination
number of each sphere is 4. When we join the centres of these spheres, we get a square. So this
close packing is called square close packing in two dimensions.
ii. Hexagonal close packing: Here the spheres of the second row are placed in the depressions of the
first row, the spheres of the third row are placed in the depressions of the second row and so on.
In this arrangement, each sphere is in contact with six adjacent spheres. So the co-ordination
number of each sphere is 6. When we join the centres of these spheres, we get a hexagon. So this
close packing is called hexagonal close packing in two dimensions.
Square close packing Hexagonal close packing

Hexagonal close packing is more efficient than square close packing in two dimensions. This is
because in Hexagonal close packing maximum space is occupied by spheres.
3. Close packing in Three Dimensions
Here the particles are arranged in layers. This can be possible in two ways.
i. Three dimensional close packing from two dimensional square close-packed layers:
Here the spheres of the second layer are placed exactly above those of the first layer. In this
arrangement spheres of both the layers are perfectly aligned horizontally as well as vertically. The
spheres of the third layer are placed exactly above those of the second layer and so on. If the
arrangement of the spheres in the first layer is denoted as ‘A’, all the layers are of ‘A’ type. So this
arrangement forms AAA….. type pattern. The lattice thus generated is the simple cubic lattice and its unit
cell is the primitive cubic unit cell.
ii. Three dimensional close packing from two dimensional hexagonal close-packed layers:
Here the first layer is arranged as hexagonal manner. The second layer is placed above the
depressions of the first layer. On placing the second layer there arises two types of voids (vacant spaces)
above the second layer – tetrahedral voids and octahedral voids. Thus when we place the third layer
over the second there are two possibilities:
Covering tetrahedral voids: Here the spheres of the third layer are placed above the
tetrahedral voids of the second layer. In this arrangement, the spheres of the third layer are vertically
above those of the first layer, i.e. the first layer and the third layer are identical. If we call the first layer
as ‘A’ and the second layer as ‘B’, then the third layer will be ‘A’, the fourth layer will be ‘B’ and so on.
This will form the pattern ABAB…… This type of close packing is called Hexagonal close packing (hcp) in
three dimensions. This type of arrangement is found in metals like Mg, Zn etc.
Covering octahedral voids: Here the spheres of the third layer are placed above the
octahedral voids of the second layer. In this arrangement, the third layer is different from the first or
the second layer. But the spheres of the fourth layer are vertically above those of the first layer, i.e. the
first layer and the fourth layer are identical. If we call the first layer as ‘A’, the second layer as ‘B’, and
the third layer as ‘C’, then the fourth layer will be ‘A’, the fifth layer will be ‘B’ and so on. This will form
the pattern ABCABC…… This type of close packing is called Cubic close packing (ccp) or face-centred
cubic(fcc) packing in three dimensions. This type of arrangement is found in metals like Cu, Ag etc.
In both hcp and ccp 74% of the available space is occupied by spheres. So both are equally efficient.
Co-ordination Number
In a close packed arrangement the number of nearest neighbours with which a given sphere is in
contact is called the co-ordination number of that sphere. In both hcp and ccp each sphere is in contact with
12 adjacent spheres. Thus the co-ordination number in both hcp and ccp is 12.

Interstitial voids
The vacant space in close packed arrangement is called voids. These are of two types- tetrahedral
voids and octahedral voids.
Tetrahedral void: A void surrounded by four spheres in tetrahedral position is called tetrahedral void. In a
close packed arrangement the number of tetrahedral voids is double the number of spheres, i.e. there are
two tetrahedral voids per sphere.
Octahedral voids: A void surrounded by six spheres in octahedral position is called octahedral void. In a
close packed arrangement the number of octahedral voids is equal to the number of spheres, i.e. there is
only one octahedral void per sphere.
If there are N close packed spheres,
The number of tetrahedral voids = 2N and
The number of octahedral voids = N
Packing Efficiency
The percentage of the total space occupied by spheres (particles) is called packing efficiency.
Volume occupied by all the spheres in the unit cell × 100
Packing Efficiency = %
Total volume of the unit cell
Calculation of Packing Efficiency G B

1) In hcp and ccp structures
Consider a cube with edge length ‘a’ and face diagonal ‘b’
In ∆ABC, AC2 = AB2+BC2 H A
i.e. b2 = a2+a2
or, b2 = 2a2
or,b= √2a b
If ‘r’ is the radius of the sphere, then b = 4r
.
. . 4r = √2a
C
F
Or, a = 4r/√2 = 2√2r
We know that, volume of a sphere = (4/3)πr3
In ccp (fcc) or hcp, there four spheres per unit cell
E D
. 3
. . Volume of four spheres = 4×(4/3)πr
Volume of the cube = a3
= (2√2r) 3

Volume occupied by four spheres in the unit cell × 100
4×(4/3)πr3 ×100
= %
(2√2r) 3
(16/3) πr3 ×100

= % = 74%
3
16√2r
2) In Body-centred cubic (bcc) structures:
Consider a cube with edge length ‘a’, face diagonal ‘b’ and body diagonal ‘c’
From the figure it is clear that the atom at the centre is in contact
with the other two atoms diagonally placed. G B
In ∆EFD,
FD2 = EF2 + ED2
i.e. b2 = a2 + a2 = 2a2 A
H
or, b = √2a
In ∆AFD,
AF2 = AD2 + FD2 c
2 2 2
i.e. c =a +b
= a2 + 2a2 = 3a2 F
Or, c = √3a C
But, c = 4r (where r is the radius of the particle) b
.
. . 4r = √3a
a
Or, a = 4r/√3 (also r = √3a/4)
In a bcc, the no. of atoms present per unit cell = 2 E
a D
Volume of 2 spheres = 2 × (4/3)πr3
Volume of the cube = a3 = (4r/√3)3
Volume occupied by two spheres in the unit cell × 100 %

.
. . Packing Efficiency = Total volume of the unit cell
3
2×(4/3)πr ×100 % a
= (4r/√3) 3
(8/3) πr3 ×100
= 64/(3√3)r3
3) In simple cubic structures:
Consider a cube with edge length ‘a’ and the radius of
the particle ‘r’. Here the edge length is related to the radius of
the particle as a = 2r
The volume of the cubic unit cell = a = (2r) =8r

A simple cubic unit cell contains only one particle.
Volume of one sphere = (4/3) πr3
Volume occupied by the spheres in the unit cell × 100
(4/3) πr3 ×100

= %
3
8r
= π/6 × 100 % = 52.4%
Calculation of Density of the unit cell (Solid)

Consider a cubic unit cell with edge length ‘a’. Then volume of the unit cell = a3.
Let ‘M’ be the atomic mass of the element in the unit cell (i.e. mass of Avogadro number (NA) of atoms).
Then mass of one atom = M/ NA.
Let the number of particles present per unit cell = z
Then mass of the unit cell = z x M/ NA
Density of the unit cell = Mass of the unit cell
Volume of the unit cell
i.e. density (d) = z x M/ NA Or, d = z.M
3
a NA.a3
Imperfections in solids (Crystal Defects)
The deviation from the regular orderly arrangement of particles of a solid is termed as imperfections
or crystal defects. The crystal defects are broadly classified into two – point defects and line defects.
The imperfection around a point (an atom) in a crystalline substance, it is termed as point defect.
The imperfection along a row is termed as line defect.
Point defects
Point defects can be classified into three types: Stoichiometric defects, Non-stoichiometric defects
and Impurity defects.
1. Stoichiometric defects:
These are point defects which do not disturb the stoichiometry of the solid. They are also called
intrinsic or thermodynamic defects, because these defects can also develop when a substance is heated.
These are of two types – vacancy defects and interstitial defects.
a. Vacancy defect: When some of the lattice sites are vacant, the crystal is said to have vacancy
defect. This defect decreases the density of the solid.
b. Interstitial defect: When some constituent particles occupy an interstitial site, the crystal is
said to have interstitial defect. This defect increases the density of the solid.
The above two types of defects are shown by non-ionic solids.
Ionic solids show two types of stoichiometric defects – Schottky defect and Frenkel defect.
i. Schottky defect: It is basically a vacancy defect. It arises due to the missing of equal number of
anions and cations from the lattice site. It is shown by ionic crystals in which the anionic and cationic sizes
are almost equal. NaCl, KCl, CsCl, AgBr etc. show Schottky defect. Due to this defect the density of the solid
decreases.

ii. Frenkel defect: It is a stoichiometric defect arising due to the misplacing of an ion (generally a
cation) from the lattice site to the interstitial site. It is also called dislocation defect. This type of defect is
shown by ionic solids in which there is a large difference in the size of the ions. E.g. ZnS, AgCl, AgBr, AgI etc.
This defect does not change the density of the solid.
Schottky Defect Frenkel Defect

b) Non-Stoichiometric defects: These are point defects which change the stoichiometry of a solid. These
defects are of two types:
i) Metal excess defect and ii) Metal deficiency defect
i) Metal excess Defect:
Here the number of cations is greater than the number of anions. This arises in two ways:
• Metal excess defect due to anionic vacancies: Here some of the anions are missing from the lattice
site. The electrical neutrality is maintained by occupying electrons in the anionic sites. These electrons are
called f-centres because they give colour to the crystal.
This defect is shown by alkali metal halides. For example when NaCl is heated in an atmosphere of
sodium vapour, some sodium atoms are deposited at the surface of the crystal. The Cl- ions diffuse to the
surface of the crystal and combines with Na atom to form NaCl.
Na + Cl- NaCl + e-
The electron so formed diffuse into the crystal and occupies the anion vacancy. These electrons
absorb light energy and get excited. As a result the crystal becomes yellow in colour. Similarly, excess of Li
makes LiCl crystals pink and excess of K makes KCl crystals violet.
• Metal excess defect due to extra cations at interstitial sites: Here some cations occupy the interstitial
sites. The electrical neutrality is maintained by occupying some electrons in adjacent interstitial sites.
E.g. When ZnO crystals are heated, the white coloured crystals becomes yellow. This is because on heating,
the crystal loses oxygen as follows:
ZnO Zn2+ + ½ O2 + 2e-
The Zn ions now move to the interstitial sites and the electrons to neighbouring interstitial sites.
Metal excess Defect Metal excess Defect

due to anion vacancy due to extra cation

ii) Metal deficiency Defect:
Here the number of cations is smaller than the number of anions. This is mainly arises due to cation
vacancies. This type of defect is commonly shown by transition metal compounds. E.g. FeO
c) Impurity Defects: It is the defect arising due to the presence of foreign particles in a crystal. For
example if molten NaCl containing a little amount of SrCl2 is crystallised, some of the sites of Na+ ions are
occupied by Sr2+. Each Sr2+ replaces two Na+ ions. It occupies the site of one ion and the other site remains
vacant. The cationic vacancies thus produced are equal to the number of Sr2+ ions. Another similar example
is a solid solution of CdCl2 and AgCl.
Properties of solids
1) Electrical properties: Based on the electrical conductivity, solids are classified into three types:
i. Conductors: They are solids which allow the passage of electricity through them. Their conductivity
ranges from 104 to 107 ohm-1m-1. Metals have conductivities in the order of 107 ohm-1m-1.
ii. Semi-conductors: They are solids which allow the passage of electricity only partially. Their conductivity
ranges from 104 to 10-6 ohm-1m-1.
iii. Insulators: They are solids which do not allow the passage of electricity through them. Their conductivity
ranges from 10-10 to 10-20 ohm-1m-1.
Conduction of Electricity in metals - Band Model
Metals conduct electricity in solid as well as in molten state. The conductivity of metals depends
upon the number of valence electrons. The atomic orbitals of metals combine to form molecular orbitals,
which are so closely spaced that they form a band. If this band is partially filled or it overlaps with a higher
energy unoccupied conduction band, the electrons can flow easily under an applied electric field and the
metal shows conductivity.
If the gap between filled valence band and the unoccupied conduction band is large the electrons
cannot jump to it and such substances act as insulators.

Small Forbidden
energy gap energy gap
(large)
Partially Overlapped
filled band bands
Metals Semiconductor
s Insulators
Conduction of Electricity in semi-conductors
In the case of semiconductors, the gap between the valence band and the conduction band is small.
So some electron may jump from valence band to conduction band and show some conductivity. Their
conductivity increases with rise in temperature, since more electrons can jump to the conduction band. Such
semiconductors are also called intrinsic semiconductors. E.g.: Si, Ge etc.
The conductivity of intrinsic semiconductors is very low. Their conductivity can be increased by
adding an appropriate impurity. The process is called doping. Addition of impurities creates electronic
defects in them. Such semiconductors are called extrinsic semiconductors. Doping can be done by the
addition of either electron rich impurity or electron deficit impurity.
a) Doping by electron rich impurity:
When a group 14 (which contains 4 electrons in the valence shell) element like Si or Ge is doped with
a group 15 element (which contains 5 electrons in the valence shell) like P or As, four electrons are used for
the formation of covalent bonds and the fifth electron becomes free. The
presence of this delocalised electron increases the conductivity and hence silicon doped with electron rich
impurities is called n-type semiconductor.
b) Doping by electron deficient impurity:
When a group 14 (which contains 4 electrons in the valence shell) element like Si or Ge is doped with
a group 13 element (which contains 3 electrons in the valence shell) like B, Al, or Ga, the three electrons are
used for the formation of covalent bonds and the fourth valence electron is missing. This creates an electron
hole or electron vacancy. An electron from a neighbouring atom can come and fill the electron hole. So the
position of the hole is moved in the direction opposite to that of the electron has moved. Under the
influence of electric field, electrons would move towards the positively charged plate through electronic
holes. It would appear as if electron holes are positively charged. This type of semiconductors are called p-
type semiconductors..
A large variety of solids which have lattices similar to Ge or Si have been prepared by the
combination of groups 13&15 or 12&16. E.g. for 13and15 group compounds are InSb, AlP & GaAs. They are
used as semiconductors. E.g. for 12 and 16 group compounds are ZnS, CdS, CdSe & HgTe.
2) Magnetic properties
Every solid has some magnetic properties associated with it due to the presence of electrons. Each
electron in an atom behaves like a tiny magnet. Electron being a charged particle and due to spin and orbital
motions, has a permanent spin and orbital magnetic moment. The magnitude of this magnetic moment is

very small and is a measured in the unit called Bohr Magneton (μB). (1 μB = 9.27×10-24 Am2 (ampere-
metresquare)).
Based on the magnetic properties, solids can be classified into five types.
1. Diamagnetic Substances: These are weakly repelled by an external magnetic field. Diamagnetism
arises due to the presence of only paired electrons. Pairing of electrons cancels their magnetic
moments and so they have no net magnetic moment. E.g.: H2O, NaCl, Benzene (C6H6)
2. Paramagnetic Substances: They are weakly attracted by an external magnetic field. Paramagnetism
is due to the presence of one or more unpaired electrons. They have a net magnetic moment. They
lose their magnetism in the absence of external magnetic field. So they are temporary magnets.
Eg: O2, Cu2+, Fe3+, Cr3+ etc.
3. Ferromagnetic Substances: They are very strongly attracted by a magnetic field and can be
permanently magnetised. In solid state, the metal ions of ferromagnetic substances are grouped
together into small regions called domains. In the absence of an external magnetic field, these
domains are randomly oriented. When the substance is placed in a magnetic field, all the domains
get oriented in the direction of the magnetic field and a strong magnetic effect is produced. This
ordering of domains do not change even when the externalmagnetic
field is removed and so they become permanent magnets.
Eg: Fe, Co, Ni, Gd (Gadolinium), CrO2 etc.
4. Anti-ferromagnetic Substances: Here the domains are oppositively
oriented and cancel each other. So they have no net magnetic moment.
Eg: MnO
5. Ferrimagnetic Substances: Here the domains are arranged in opposite
directions but in unequal numbers. So they have a net magnetic moment.
Eg: Fe3O4 (magnetite) and ferrites like MgFe2O4, ZnFe2O4 etc
@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@

3. ELECTROCHEMISTRY
It is a branch of chemistry that deals with the relationship between chemical energy and electrical
energy and their inter conversions.
ELECTROCHEMICAL CELLS
These are devices that convert chemical energy of some redox reactions to electrical energy. They
are also called Galvanic cells or Voltaic cells. An example for Galvanic cell is Daniel cell.
It is constructed by dipping a Zn rod in ZnSO4 solution and a Cu rod in CuSO4 solution. The two
solutions are connected externally by a metallic wire through a voltmeter and a switch and internally by a
salt bridge.
A salt bridge is a U-tube containing an inert electrolyte like NaNO3

or KNO3 in a gelly like substance. The functions of a salt bridge are:
1. To complete the electrical circute
2. To maintain the electrical neutrality in the two half cells.
The reaction taking place in a Daniel cell is
Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s)
This reaction is a combination of two half reactions:
(i) Cu2+ + 2 e- → Cu(s) (reduc-on half reac-on)
(ii) Zn(s) → Zn2+ + 2 e- (oxidation half reaction)
These reactions occur in two different portions of the Daniel cell. The reduction half reaction occurs
on the copper electrode while the oxidation half reaction occurs on the zinc electrode. These two portions
of the cell are also called half-cells or redox couples. The copper electrode may be called the reduction half
cell and the zinc electrode, the oxidation half-cell.
Electrode Potential
The tendency of a metal to lose or gain electron when it is in contact with its own solution is called
electrode potential. When the concentrations of all the species involved in a half-cell is unity then the
electrode potential is known as standard electrode potential. According to IUPAC convention, standard
reduction potential is taken as the standard electrode potential.
In a galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative
potential. The other half-cell in which reduction takes place is called cathode and it has a positive potential.
In a cell, the electrons flow from negative electrode to positive electrode and the current flows in
opposite direction.
The potential difference between the two electrodes of a galvanic cell is called the cell potential and
is measured in volts. The cell potential is the difference between the electrode potentials (reduction
potentials) of the cathode and anode.
The cell electromotive force (emf) of the cell is the potential difference between the two electrodes,
when no current is flow through the cell.
By convention, while representing a galvanic cell, the anode is written on the left side and the
cathode on the right side. Metal and electrolyte solution are separated by putting a vertical line and a salt
bridge is denoted by putting a double vertical line.
For Daniel cell, the cell representation is Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)
Under this convention the emf of the cell is positive and is given by the potential of the half-cell on the right
hand side minus the potential of the half-cell on the left hand side
i.e. Ecell = Eright – Eleft Or, Ecell = ER – EL .
GHSS ASHTAMUDI Electrochemistry Page 1
Measurement of Electrode Potential
The potential of individual half-cell cannot be measured. We can measure only the difference between the
two half-cell potentials that gives the emf of the cell. For this purpose a half-cell called Standard Hydrogen
Electrode (SHE) or Normal Hydrogen Electrode (NHE) is used.
It consists of a platinum electrode coated with platinum black.
The electrode is dipped in an acidic solution of one molar concentration
and pure hydrogen gas at 1 bar pressure and 298K is bubbled through it.
It is represented as Pt(s)/H2(g)/H+ (aq).
By convention, the electrode potential of SHE is taken as zero.
To determine the electrode potential of an electrode, it is connected

In series with the standard hydrogen electrode and the emf of the resulting
cell is determined by the equation,
Ecell = ER – EL
Since the electrode potential of SHE is zero, the value of Ecell is equal to the electrode potential of the given
electrode.
If the standard electrode potential of an electrode is greater than zero (i.e. +ve), then its reduced
form is more stable compared to hydrogen gas. Similarly, if the standard electrode potential is negative
then hydrogen gas is more stable than the reduced form of the species.
Electrochemical series
It is a series in which various electrodes are arranged in the decreasing order of their reduction
potential. In this table, fluorine is at the top indicating that fluorine gas (F2) has the maximum tendency to
get reduced to fluoride ions (F–). Therefore fluorine gas is the strongest oxidising agent and fluoride ion is
the weakest reducing agent.
Lithium has the lowest electrode potential indicating that lithium ion is the weakest oxidising agent while
lithium metal is the most powerful reducing agent in an aqueous solution.
Nernst Equation
Nernst proposed an equation to relate the electrode potential of an electrode (or, emf of a cell) with
the electrolytic concentration.
He showed that for the electrode reaction:
Mn+(aq) + ne- –→ M(s)
the electrode potential can be given by:
E(M n+/M) = E0(M n+/M) + RT ln [M n+]
nF [M]
Since the concentration of any solid is taken as unity, the above equation becomes:
E(M n+/M) = E0(M n+/M) + RT ln [M n+]

nF
Or, E(M n+/M) = E0(M n+/M) + 2.303RT log [M n+]
nF
or, Eel. = E el. + 2.303RT log [M n+]
0
nF
Where E is the standard electrode potential, R is the gas constant (8.314 JK–1 mol–1), F is Faraday
0
constant (96500 C mol–1), T is temperature in Kelvin and [M n+] is the concentration of the species, M n+.
In Daniel cell, the electrode reactions are:
Cu2+ + 2 e- → Cu(s) (cathode)
Zn(s) → Zn2+ + 2 e- (anode)

The electrode potentials are given as
For Cathode:
E(Cu2+/Cu) = E0(Cu2+/Cu) + RT ln [Cu2+]
2F
For anode: E(Zn2+/Zn) = E0(Zn2+/Zn) + RT ln [Zn2+]

2F
The cell potential, Ecell = E(Cu2+/Cu) - E(Zn2+/Zn)
= {E0(Cu2+/Cu) + RT ln [Cu2+]} – {E0(Zn2+/Zn) + RT ln [Zn2+]}
2F 2F
= [E0(Cu2+/Cu) – E0(Zn2+/Zn) ] + RT ln [Cu2+]
2F [Zn2+]
0 2+
Or, Ecell = E cell + RT ln [Cu ]
2F [Zn2+]
On changing the base of logarithm, we get
Ecell = E0cell + 2.303RT log [Cu2+]
2F [Zn2+]
On substituting the values of R (8.314 JK–1 mol–1), F (96500 C mol–1) at 298K, the above equation becomes,
Ecell = E0cell + 0.0591 log [Cu2+]
2 [Zn2+]
For a general electrochemical reaction of the type:
a A + bB ⎯⎯ ne-⎯→ cC + dD
Nernst equation can be written as:
Ecell = E0cell + 0.0591 log [A]a[B]b
n [C]c[D]d
Equilibrium Constant from Nernst Equation
For a Daniel cell, the emf of the cell at 298K is given by:
Ecell = E0cell + 0.0591 log [Cu2+]
2 [Zn2+]
When the cell reaction attains equilibrium, Ecell = 0
So, 0 = E0cell + 0.0591 log [Cu2+]
2 [Zn2+]
Or, E0cell = - 0.0591 log [Cu2+]
2 [Zn2+]
= 0.0591 log [Zn2+]
2 [Cu2+]
But at equilibrium, [Zn2+] = Kc
[Cu2+]
So the above equation becomes,
E0cell = 0.0591 log Kc
2
0
In General, E cell = 2.303RT log Kc
nF
or, E0cell = 0.0591 log Kc at 298 K
n

Electrochemical Cell and Gibbs Energy of the Reaction
Electrical work done in one second is equal to electrical potential multiplied by total charge passed.
Also the reversible work done by a galvanic cell is equal to decrease in its Gibbs energy. Therefore, if the
emf of the cell is E and nF is the amount of charge passed,
then the Gibbs energy of the reaction, ΔG = – nFEcell
If the concentration of all the reacting species is unity, then Ecell = E0cell .
So, ΔG0 = –nFE0 cell
Thus, from the measurement of E0cell, we can calculate the standard Gibbs energy of the reaction.
Conductance of Electrolytic Solutions
Resistance (R): The electrical resistance is the hindrance to the flow of electrons. Its unit is ohm (Ω). The
resistance of a conductor is directly proportional to the length of the conductor (Ɩ) and inversely
proportional to the area of cross-section (A) of the conductor.
i.e. R α Ɩ /A
or, R = a constant x Ɩ/A
or, R = ρ x Ɩ/A, where ρ (rho) is a constant called resistivity.
Its unit is ohm-metre (Ω m) or ohm-centimetre (Ω cm).
1 Ω m = 100 Ω cm, 1 Ω cm = 10-2 Ω m
Resistivity is defined as the resistance offered by a conductor having unit length and unit area of cross-
section.
Conductance (G): It is the inverse of resistance.
i.e. G = 1/R.
Its unit is ohm-1 or mho or Siemens (S)
Or, G = 1 x A
ρ Ɩ
Or, G = ƙ x A/Ɩ
Where, ƙ is called conductivity. It is defined as the conductance of a conductor having unit length and unit
area of cross-section.
Its unit is ohm-1 m-1 or mho m-1 or S m-1 .
1 S cm-1 = 100 S m-1
1 S m-1 = 10-2 S cm-1
There are of two types of Conductance - electronic or metallic conductance and electrolytic or ionic
conductance.
Electrical conductance through metals is called metallic or electronic conductance and it is due to
the movement of electrons. It depends on the nature and structure of the metal, the no. of valence
electrons per atoms and temperature. For electronic conductance, when temperature increases,
conduction decreases.
The conductance of electricity by ions present in solutions is called electrolytic or ionic conductance.
It depends on i) the nature of electrolyte ii) size of the ion produced and their solvation iii) the nature of the
solvent and its viscosity iv) concentration of the electrolyte and v) temperature (As temperature increases
electrolytic conduction also increases).
Note: Substances which allow the passage of electricity in molten state or in solution state are called
electrolytes. On the passage of electricity, they undergo chemical decomposition.
Measurement of the conductivity of ionic solutions
We know that, conductivity G = ƙ x A/ Ɩ
So conductivity, ƙ = G x Ɩ/A
The quantity Ɩ/A is called cell constant (G*). It depends on the distance between the electrodes and their
area of cross-section. Its unit is m-1.

i.e. conductivity = conductance x cell constant
So in order to determine the conductivity of an electrolytic solution, first determine the resistance by using
a Wheatstone bridge. It consists of two resistances R3 and R4, a variable resistance R1 and the conductivity
cell having the unknown resistance R2. It is connected to an AC source (an oscillator, O) and a suitable
detector (a headphone or other electronic device, P). Direct current (DC) cannot be used since it causes the
decomposition of the solution.
The bridge is balanced, when no current passes through the detector.
Under this condition,

R1 = R3
R2 R4
Therefore, the unknown resistance, R2 = R1R4
R3
By knowing the resistance, we get the value of conductance and conductivity.
Conductivity cell
It consists of two platinum electrodes coated with platinum black. The electrodes are separated by a
distance Ɩ and their area of cross-section is A.
The cell constant of a conductivity cell is usually determined by measuring the resistance of the cell
containing a solution whose conductivity is already known (e.g. KCl solution).
Molar conductivity (λm)
It is the conductivity of 1 mole of an electrolytic solution kept between two electrodes with unit area of
cross section and at a distance of unit length. It is related to conductivity of the solution by the equation,
λm= ƙ/C (where C is the concentration of the solution)
Or, λm = 1000 ƙ/M (where M is the molarity)
The unit of molar conductivity is Ω-1cm2 mol-1 or S cm2 mol-1.
1S m2 mol-1 = 104 S cm2 mol-1
1S cm2 mol-1 = 10– 4 S m2 mol-1

Variation of conductivity and Molar conductivity with concentration (dilution)
Both conductivity and molar conductivity change with the concentration of the electrolyte. We
know that when a solution is diluted, its concentration decreases. For both strong and weak electrolytes,
conductivity always decreases with dilution. This is because conductivity is the conductance of unit volume
of electrolytic solution. As dilution increases, the number of ions per unit volume decreases and hence the
conductivity decreases.
For both strong and weak electrolytes, the molar conductivity increase with dilution (or decrease
with increase in concentration), but due to different reasons.
For strong electrolytes, as dilution increases, the force of attraction between the ions decreases and
hence the ionic mobility increases. So, molar conductivity increases. When dilution reaches maximum or
concentration approaches zero, the molar conductivity becomes maximum and it is called the limiting
molar conductivity (λ0m).
For strong electrolytes, the relation between λm and concentration can be given as:
λm = λ0m - A√c
Where ‘c’ is the concentration and A is a constant depends on temperature, the nature of the electrolyte
and the nature of the solvent. All electrolytes of a particular type have the same value for ‘A’.
For weak electrolytes, as dilution increases, the degree of dissociation increases. So the number of
ions and hence the molar conductivity increases.
The variation of λm for strong and weak electrolytes is shown in the following graphs:
λ0m
Strong electrolyte
λm
Weak electrolyte
√c
For strong electrolytes, the value of λ0m can be determined by the extrapolation of the graph. But
for weak electrolytes, it is not possible since the graph is not a straight line. So their λ0m values are
calculated by applying Kohlrausch’s law of independent migration of ions.
Kohlrausch’s law of independent migration of ions

The law states that the limiting molar conductivity of an electrolyte can be represented as the sum of the
individual contributions of the anion and the cation of the electrolyte.
Thus if an electrolyte on dissociation gives n(+) cations and n(-) anions, its limiting molar conductivity is given
as:
λ0m = n(+)λ0(+) + n(-)λ0(-)
For NaCl, λ0m(NaCl) = λ0(Na+) + λ0(Cl-)
For CaCl2, λ0m(CaCl2) = λ0(Ca2+) + 2 x λ0(Cl-)
Applications of Kohlrausch’s law

1) Determination of λ0m of weak electrolytes
By knowing the λ0m values of strong electrolytes, we can calculate λ0m of weak electrolytes. For e.g.
we can determine the λ0m of acetic acid (CH3COOH) by knowing the λ0m of CH3COONa, NaCl and HCl as
follows:
λ0m (CH3COONa) = λ0CH3COO- + λ0Na+ …………. (1)
λ0m (HCl) = λ0H+ + λ0 Cl- …………….. (2)
λ0m (NaCl) = λ0Na+ + λ0Cl- ………….. (3)
(1) + (2) - (3) gives:
λ m (CH3COONa) + λ0m (HCl) - λ0m (NaCl) = λ0CH3COO- + λ0Na+ + λ0H+ + λ0Cl- - λ0Na+ - λ0Cl-
0
= λ0CH3COOH
2) Determination of degree of dissociation of weak electrolytes
By knowing the molar conductivity at a particular concentration (λcm) and limiting molar conductivity
(λ0m), we can calculate the degree of dissociation (α) as,
α = λCm
λ0m
By using α, we can calculate the dissociation constant of acid as:
Ka = c α2
1-α
Electrolytic Cells and Electrolysis
In an electrolytic cell, the electrical energy is converted to chemical energy. The dissociation of an
electrolyte by the passage of electricity is called electrolysis.
For e.g. when CuSO4 solution is electrolysed by Cu electrodes, Cu is deposited at the cathode and Cu2+ ions
are liberated from the anode.
Quantitative Aspects of electrolysis – Faraday’s laws
1) Faraday’s first law
It states that the amount of substance deposited or liberated at the electrodes (m) is directly
proportional to the quantity of electricity (Q) flowing through the electrolyte.
Mathematically, mαQ
Or, m = zQ
Where z is a constant called electrochemical equivalent (ECE). Z = equivalent weight/96500
But quantity of electricity is the product of current in ampere (I) and time in second (t).
i.e. Q = It
Therefore, m= zIt
1 Faraday is the charge of 1 mole of electron or it is the amount of electricity required to deposit one gram
equivalent of any substance. Its value is 96500 C/mol.
For the deposition of 1 mole of Na, the amount of charge required = 1 F (Since Na+ + e- → Na)
For Ca, Q = 2F (since Ca2+ + 2e- → Ca)
2) Faraday’s second law
It states that when same quantity of electricity is passed through solutions of different substances,
the amount of substance deposited or liberated is directly proportional to their chemical equivalence.
For e.g. when same quantity of electricity is passed through solutions of two electrolytes A and B, then
Mass of A deposited = Equivalent mass of A

Mass of B deposited Equivalent mass of B

Products of electrolysis
The products of electrolysis depend on the following factors:
i) The nature of the electrolyte: The electrolyte may be in molten state or in aqueous solution state. For
e.g. if molten NaCl is electrolysed, Na is deposited at the cathode and chlorine is liberated at the
anode.
NaCl → Na+ + Cl-
At cathode: Na+ + e- → Na
At anode: Cl- → ½ Cl2 + e-
If NaCl solution is electrolysed, we get H2 gas at the cathode and Cl2 gas at the anode.
NaCl solution contains 4 ions – Na+, Cl-, H+ and OH-
Cathode reaction: H+ + e- → ½ H2
Anode reaction: Cl- → ½ Cl2 + e-
NaOH is formed in the solution.
ii) The type of electrodes used: If the electrode is inert (e.g. Pt, gold, graphite etc.), it does not participate
in the electrode reaction. While if the electrode is reactive, it also participate in the electrode reaction.
iii) The different oxidising and reducing species present in the electrolytic cell and their standard electrode
potentials. Some of the electrochemical processes are very slow and they do not take place at lower
voltages. So some extra potential (called overpotential) has to be applied, which makes such process
more difficult to occur.
For e.g. during the electrolysis of NaCl solution, the possible reactions at anode are:
Cl– (aq) → ½ Cl2 (g) + e–; E0cell = 1.36 V
2H2O (l )→ O2 (g) + 4H+(aq) + 4e–; E0cell = 1.23 V
At anode, the reaction with lower value of E0cell is preferred and so water should get oxidised in
preference to Cl– (aq). However, on account of overpotential of oxygen, the first reaction is preferred and
hence Cl2 is formed at anode.
Batteries
A battery is basically a galvanic cell in which the chemical energy of a redox reaction is converted to
electrical energy. They are of mainly 2 types – primary batteries and secondary batteries.
a) Primary cells:
These are cells which cannot be recharged or reused. Here the reaction occurs only once and after use
over a period of time, they become dead E.g. Dry cell, mercury button cell etc.
1. Dry Cell
It is a compact form of Leclanche cell. It consists of a zinc container as anode and a carbon (graphite)
rod surrounded by powdered manganese dioxide (MnO2) and carbon as cathode. The space between the
electrodes is filled by a moist paste of ammonium chloride (NH4Cl) and zinc chloride (ZnCl2). The electrode
reactions are:
Anode: Zn(s) → Zn2+ + 2e–
Cathode: MnO2+ NH4++ e–→ MnO(OH) + NH3
Ammonia produced in this reaction forms a complex with Zn2+ and thus corrodes the cell. The cell has a
potential of nearly 1.5 V.

2. Mercury cell
Here the anode is zinc – mercury amalgam and cathode is a paste of HgO and carbon. The electrolyte is a
paste of KOH and ZnO. The electrode reactions are:
Anode reaction: Zn(Hg) + 2OH– → ZnO(s) + H2O + 2e–
Cathode reaction: HgO + H2O + 2e– → Hg(l ) + 2OH–
The overall reaction is : Zn(Hg) + HgO(s) → ZnO(s) + Hg(l )
The cell has a constant potential of 1.35 V, since the overall reaction does not involve any ion in solution.
b) Secondary cells
A secondary cell can be recharged and reused again and again. Here the cell reaction can be reversed
by passing current through it in the opposite direction. The most important secondary cell is lead storage
cell, which is used in automobiles and invertors.
It consists of lead as anode and a grid of lead packed with lead dioxide (PbO2) as the cathode. The
electrolyte is 38% H2SO4 solution.
The cell reactions are:
Anode: Pb(s) + SO42- (aq) → PbSO4(s) + 2e-
Cathode: PbO2(s) + SO42-(aq) + 4H+(aq) + 2e- → PbSO4 (s) + 2H2O (l )
The overall cell reaction is: Pb(s)+PbO2(s)+2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
On charging the battery, the reaction is reversed and PbSO4(s) on anode and cathode is converted into Pb
and PbO2, respectively.
Another example for a secondary cell is nickel – cadmium cell. Here the overall cell reaction is
Cd (s)+2Ni(OH)3 (s) → CdO (s) +2Ni(OH)2 (s) +H2O(l )
Fuel cells
These are galvanic cells which convert the energy of combustion of fuels like hydrogen, methane,
methanol, etc. directly into electrical energy.
One example for fuel cell is Hydrogen – Oxygen fuel cell, which is used in the Apollo space
programme. Here hydrogen and oxygen are bubbled through porous carbon electrodes into concentrated
aqueous sodium hydroxide solution. To increase the rate of electrode reactions, catalysts like finely divided
platinum or palladium metal are filled into the electrodes.
The electrode reactions are:

Cathode: O2(g) + 2H2O(l ) + 4e–→4OH–(aq)
Anode: 2H2 (g) + 4OH–(aq) → 4H2O(l) + 4e–
Overall reaction is: 2H2(g) + O2(g) ⎯→ 2 H2O(l )
Advantages of Fuel cells
1. The cell works continuously as long as the reactants are supplied.
2. It has higher efficiency as compared to other conventional cells.
3. It is eco-friendly (i.e. pollution free) since water is the only product formed.
4. Water obtained from H2 – O2 fuel cell can be used for drinking.

Corrosion
It is the process of formation of oxide or other compounds of a metal on its surface by the action of
air, water-vapour, CO2 etc. Some common examples are: The rusting of iron, tarnishing of silver, formation
of green coating on copper and bronze (verdigris) etc.
Most familiar example for corrosion is rusting of iron. It occurs in presence of water and air. It is a redox
reaction. At a particular spot of the metal, oxidation takes place and that spot behaves as anode. Here Fe is
oxidized to Fe2+.
2 Fe (s)→2 Fe2+ + 4 e–
Electrons released at anodic spot move through the metal and go to another spot on the metal and reduce
oxygen in presence of H+ . This spot behaves as cathode. The reaction taking place at this spot is:
O2(g) + 4 H+(aq) + 4 e– ⎯→ 2 H2O (l )
The overall reaction is: 2Fe(s)+O2(g) + 4H+(aq) → 2Fe2 +(aq)+ 2 H2O (l )
The ferrous ions (Fe2+) are further oxidised to ferric ions (Fe3+) and finally to hydrated ferric oxide
(Fe2O3. x H2O), which is called rust.
Methods to prevent corrosion
1. By coating the metal surface with paint, varnish etc.
2. By coating the metal surface with another electropositive metal like zinc, magnesium etc. The
coating of metal with zinc is called galvanisation and the resulting iron is called galvanized iron.
3. By coating with anti-rust solution.
4. An electrochemical method is to provide a sacrificial electrode of another metal (like Mg, Zn, etc.)
which corrodes itself but saves the object (sacrificial protection).
^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^

4. CHEMICAL KINETICS
The branch of Chemistry that deals with the rate of chemical reaction, factors affecting the rate and the
mechanism of a reaction is called Chemical Kinetics.
Rate of a chemical reaction
The rate of a chemical reaction is the change in concentration of any one of the reactant or product in unit
time. Or, it is the rate of decrease in concentration of any one of the reactant or the rate of increase in
concentration of any one of the product.
For a chemical reaction, if ∆x is the change in concentration of a reactant or a product in a time ∆t, the rate
of reaction (r) = ∆x/∆t.
For a hypothetical reaction R → P, the rate of reac%on can be expressed by decrease in concentra%on of
reactants or by increase in concentration of products.
i.e., Rate of reaction = Rate of disappearance of R
r = Decrease in concentration of R
Time taken
Or, r = –∆[R]
∆t [Since, Δ[R] is a negative quantity (as concentration of reactants is
decreasing), it is multiplied with –1 to make the rate of the reaction a positive quantity].
Or, Rate of reaction = Rate of appearance (formation) of P

= Increase in concentration of P
Time taken
i.e., r = ∆[P]
∆t
The above rate expressions are also called Average rate.
Units of Rate of reaction
If concentration is expressed in moles/L and time is in second, the unit of rate of reaction is mol/L/s. In
general the dimension of rate of reaction is Concentration/Time. For gaseous reactions, the concentration is
replaced by partial pressure and so the unit of rate of reaction is atm/s.
Instantaneous Rate of a reaction
The rate of a reaction at a particular instant of time is called Instantaneous Rate of a reaction. Or, it is the
rate of a reaction when the time interval approaches zero.
i.e., Instantaneous Rate of a reaction = Limit ∆x = dx
∆t → 0 ∆t dt
For the reaction, R→ P, the Instantaneous Rate is given by, rinst = – d[R] = d[P]
dt dt
For the reaction, 2N2O5 → 4NO2 + O2, rinst = – ½ d[N2O5] = ¼ d[NO2] = d[O2]
dt dt dt
For the reaction, H2 + I2 → 2HI, rinst = – d[H2] = – d[I2] = ½ d[HI]
dt dt dt
And rav. = – ∆[H2] = – ∆[I2]= ½ ∆[HI]
∆t ∆t ∆t
Determination of Instantaneous Rate of a reaction
Instantaneous Rate of a reaction can be determined graphically. First conduct the chemical reaction and
find out the concentration of reactants or product at a regular interval of time. Then plot a graph between
concentration along y-axis and time along x-axis.
In order to determine the Instantaneous Rate at a particular time, mark the point on the graph at that time
and draw a tangent at the point. The slope of this tangent gives the instantaneous rate at that time.
Chemical Kinetics-Anil-HSSLiVE Page 1

For a general reaction aA + bB → cC + dD, the rate is given by
rinst = -1 d[A] = -1 d[B] = 1 d[C] = 1 d[D]
a dt b dt c dt d dt
Factors affecting rate of a reaction

The important factors which affect the rate of a chemical reaction are:
1. Nature of the reactants
2. Concentration of the reactants
3. Temperature
4. Pressure (for gaseous reaction only)
5. Effect of catalyst
6. Influence of radiation
Dependence of Rate of reaction on concentration
It is found experimentally that Rate of reaction is directly proportional to the concentration of reactants.
Thus for a general reaction, aA + bB → cC + dD,
Rate α [A]x[B]y
Or, r = k [A]x[B]y (where x and y may or may not be equal to a and b)
This expression is known as rate law or rate equation. Thus rate law is a “mathematical equation relating
the rate of a chemical reaction and concentration of reactants, in which each concentration term is raised to a
power which may or may not be equal to the stoichiometric coefficients in the balanced chemical equation.”
In the above equation ‘k’ is a constant called rate constant or velocity constant or specific reaction rate of
the reaction. It is defined as the rate of the reaction when the concentration of each of the reactants is unity.
Order of reaction
Order is the sum of the powers of the concentration terms of the reactants in the rate law. It is an
experimental quantity. It can have the values 0,1,2,3,…… or a fraction. It is applicable to both elementary and
complex reactions.
For a general reaction, aA + bB → cC + dD; r = k[A]x[B]y, Order of the reaction = x + y
If the order of a reaction is zero, it is called zero order reaction, if it is one, it is called first order reaction, if it is two,
it is called second order reaction and so on.
Molecularity of a reaction
It is the total number of reacting species collides simultaneously in a chemical reaction. It is a theoretical
quantity. It cannot be zero or fractional. It can have values 1,2,3 etc. it is applicable only to elementary reactions.

If the molecularity of a reaction is 1, it is called unimolecular reaction.
e.g. Decomposition of ammonium nitrite
NH4NO2 → N2 + 2H2O
If the molecularity of a reaction is 2, it is called bimolecular reaction.
e.g. Decomposition of Hydrogen Iodide
2HI → H2 +I2
Differences between Order and Molecularity of a reaction
Order Molecularity
1. It is the sum of the powers of the concentration terms in the It is the total number of reactant species collide
rate law expression simultaneously in a chemical reaction
2. It is an experimental quantity It is a theoretical quantity
3. It can be zero or fractional It cannot be zero or fractional
4. It is applicable to both elementary and complex reactions It is applicable only to elementary reactions
Elementary and complex reactions
A reaction that takes place in a single step is called elementary reaction. While a reaction that occurs in
more than one step is called a complex reaction. In a complex reaction one of the steps is slower than the other
steps and this step is called the Rate determining step. The overall rate of the reaction is controlled by this slowest
step. The sequence of steps by which a chemical reaction occurs is called the mechanism of the reaction.
Consider the decomposition of hydrogen peroxide which is catalysed by iodide ion in alkaline medium.
2H2O2 I- 2H2O + O2
Alkaline Medium
The rate equation for this reaction is found to be r = – d[H2O2]
dt
This reaction is first order with respect to both H2O2 and I–. This reaction takes place in two steps
(1) H2O2 + I– H2O + IO–
–
(2) H2O2 + IO H2O + I– + O2
Here the first step is slower than the second. So it is the rate determining step (rds).
Unit of Rate constant
Different ordered reactions have different units for k.
For an nth order reaction nA products, rate = k[A]n
Therefore, k = rate
[Concentration]n
mol/L/sec
1-n
Unit of k = ( mol/L) n = (mol/L) s-1
The units of rate constant for different ordered reactions are:
Reaction Order Unit of rate constant

Zero order reaction 0 Mol L-1s-1
First order reaction 1 s-1
Second order reaction 2 Mol-1L s-1
Integrated Rate law Equations
These are equations relating the rate of a reaction and concentration of reactants. Different ordered
reactions have different integrated rate law equations.
1. Integrated Rate law Equation for a Zero Order Reaction
Zero order reactions are reactions in which the rate of reaction is independent of concentration of the
reactants. Consider a zero order
R P
The rate expression for the above reaction is r= – d[R]
dt ………………. (1)
Rate law for the above reaction is r= k[R]0 = k ………………… (2)
From equations (1) & (2), we can write – d[R] = k
dt
The above equation is known as differential rate equation for a zero order reaction.
Or, d[R] = – k.dt

On integrating the above equation we get,
[R] = –kt +C …………………. (3)
Where C is the constant of integration. To evaluate the value of C,, consider the initial conditions. i.e., when t=0, [R] =
[R]0
Substitute these values in eqn. (3)
[R]0 = – k x0 + C
Or, C = – [R]0
Substituting in equation (3), we get
[R] = – kt – [R]0 …………. (4)
Or, [R]0 - [R] = kt
Or, k= [R]0 - [R]
t …………………. (5)
This equation is of the form of a straight line, y = mx + c. So if we plot [R] against t, we get a straight line with slope =
–k and intercept equal to [R]0.
Example for zero order reaction is tthe decomposition of gaseous ammonia on a hot platinum surface at high
pressure.
N2 + H 2 2 NH3
In this reaction, platinum metal acts as a catalyst. At high pressure, the metal surface gets saturated with gas
molecules. So, a further change in reaction conditions does not change the rate of thehe reaction. So it becomes a zero
order reaction.
Another e.g. is the
he thermal decomposition of HI on gold surface
surface.
2. Integrated Rate law Equation for a First order reaction
Here the rate of the reaction is proportional to the
the concentration of the reactant
reactant.
Consider a first order reaction, R P
The rate expression for the above reaction is r= – d[R]
dt ………………. (1)
Rate law for the above reaction is r = k[R] ………………… (2)
From equations (1) & (2), we can write – d[R] = k[R]

dt …………………… (3)
The above equation is known as differential rate equation for a 1st order reaction.
reaction
Or, – d[R] = k.dt

[R]
On integrating the above equation we get,
– ln[R] =kt +C …………………. (3)
Where ‘C’ is the constant of integration. To evaluate the value of C, consider the initial conditions.
i.e., when t=0, [R] = [R]0
Substitute these values in eqn. (3)
– ln[R]0 = k x0 +C
Or, C = – ln[R]0
Substituting in equation (3), we get
– ln[R] = kt – ln[R]0 …………. (4)
Or, ln[R]0 – ln[R] = kt
Or, ln[R]0/[R] = kt …………….. (5)
K = 1 ln [R]0
t [R] …………………. (6)
On changing the base we get
k= 2.303 log [R]0
t [R] ………………… (7)
This equation is known as integrated rate equation for a first order reaction.
From eqn. (4), -ln[R] = kt - ln[R]0
On changing the sign we get ln[R] = -kt + ln[R]0
This equation is of the form y = mx + c, equation for a straight line. So if we plot a graph between ln[R]
against time, t we get straight line graph as follows:
From the eqn. (5) ln[R]0/[R] = kt
Or, 2.303 log[R]0/[R] = kt
Or, log[R]0/[R] = kt/ 2.303

So if we plot a graph between log[R]0/[R] against ‘t’, we get a straight line graph as shown above.
Examples for 1st order reactions are:
1. Hydrogenation of ethene: C2H4(g) + H2(g) → C2H6(g); r = k[C2H4]
2. All natural and artificial radioactive decay
Half life of a reaction (t1/2)

The half-life of a reaction is the time taken for concentration of a reactant is reduced to one half of its initial
concentration. Or, it is the time taken for half of a reaction to complete. It is represented as t1/2.
1. Half life of a zero order reaction
For a zero order reaction, the integrated rate law is: k = [R]0 – [R]
t
When t = t1/2, [R] = ½ [R]0
On substituting these values in the above equation,
k = [R]0 – ½ [R]0
t1/2
or, t1/2 = [R]0
2k
i.e. half life of a zero order reaction is directly proportional to the initial concentration of the reactants and inversely
proportional to the rate constant.
2. Half life of a first order reaction
For a first order reaction, k = 2.303 log[R]0
t [R]
When t = t1/2, [R] = [R]0/2
Substitute these values in the above equation
k = 2.303 log[R]0
t1/2 [R]0/2
Or, t1/2 = 2.303 log2 = 2.303 x 0.3010
k k
Or, t1/2 = 0.693
k
Thus for a first order reaction, half-life period is constant. i.e., it is independent of initial concentration of the
reacting species.
Pseudo first order reaction
These are reactions which appear to follow higher order but actually follow first order kinetics. In these
reactions the concentration of one of the reactants is large excess and so its change in concentration does not
affect the rate of the reaction.
e.g. 1. Hydrolysis of ester (ethyl acetate)
CH3COOC2H5 + H2O H+ CH3COOH + C2H5OH; r = k [CH3COOC2H5]
Here the concentration of water does not change during the reaction.
2. Inversion of cane sugar
C12H22O11 + H2O H+ C6H12O6 + C6H12O6; r = k [C12H22O11]
Cane sugar Glucose Fructose
Rate of reaction and Temperature
Most of the chemical reactions are accelerated by increase in temperature. It has been found that for a
chemical reaction, when the temperature is increased by 10°, the rate of the reaction and the rate constant is nearly
doubled. The ratio of the rate constants of a reaction at two temperatures differing by 100 is called temperature
coefficient.
i.e., Temperature coefficient = Rate constant of the reaction at (T + 10)K
Rate constant of the reaction at T K
The temperature dependence of the rate of a chemical reaction can be accurately explained by Arrhenius
equation. The equation is:
- Ea /RT
k=Ae ……………………………….. (1)

Where A is a constant called the Arrhenius parameter or the frequency factor or the pre-exponential factor. It is
constant for a particular reaction. R is the universal gas constant and Ea is activation energy measured in
joules/mole (J mol –1).
According to Arrhenius, a chemical reaction occurs by the collision of reactant molecules. All the molecular
collisions are not effective. For effective collision, the colliding molecules should have a minimum kinetic energy
called activation energy. When such molecules collide, an unstable intermediate called activated complex is
formed, which decomposes to form products.
For e.g. the reaction between H2 and I2 to form HI takes place in the following steps.
H2 + I2 → 2HI
If we plot a graph between potential energy and the progress of reaction, we get the following graph.
Reaction coordinate represents the profile of energy change when reactants change into products.
In a chemical reaction, all the molecules in the reacting species do not have the same kinetic energy. Ludwig
Boltzmann and James Clark Maxwell calculated the distribution of kinetic energy among molecules. They plotted a
graph between the fraction of molecules with a given kinetic energy against kinetic energy. This plot is known as
Maxwell- Boltzmann distribution curve of molecular energies.
Maxwell-Boltzmann Distribution curve Distribution curves at 2 different temperatures
The peak of the curve corresponds to the most probable kinetic energy. It is the kinetic energy possessed
by maximum fraction of molecules.
When the temperature is raised, the maximum of the curve moves to the higher energy value and the curve
spreads to the right. That is the fraction of molecules with activation energy increases (almost doubled).

At normal temperature the fraction of molecules having energy equal to or greater than activation energy is
very low. As the temperature increases, the fraction of molecules having energy equal to or greater than
activation energy increases and hence the rate of reaction also increases.
In the Arrhenius equation the factor e -Ea /RT corresponds to the fraction of molecules that have kinetic
energy greater than Ea.
Taking logarithm on both sides of equation (1), we get
ln k = – Ea + ln A
RT
This equation is of the form y = mx + c, equation for a straight line. So if we plot a graph between ln k against 1/T,
we get a straight line with slope = – Ea/R and the y-intercept ln A
If k1 is the rate constant at temperature T1 and k2 is the rate constant at temperature T2, then
………………. (2) and
……………… (3)
Equation (2) – (3) gives,

ln k2 – ln k1 = Ea – Ea
RT1 RT2

From this equation we can calculate the value of activation energy (Ea), by knowing all other values.
Effect of Catalyst
A catalyst is a substance which alters the rate of a reaction without itself undergoing any permanent
chemical change. The action of the catalyst can be explained by intermediate complex theory. According to this
theory, a catalyst participates in a chemical reaction by forming an intermediate complex. This is unstable and
decomposes to yield products and the catalyst.
A catalyst increases the rate of a chemical reaction by providing an alternate pathway or reaction
mechanism by reducing the activation energy between reactants and products.
The important characteristics of a catalyst are:
1. A small amount of the catalyst can catalyse a large amount of reactants.
2. A catalyst does not alter Gibbs energy, ΔG of a reaction. It catalyses the spontaneous reactions but does not
catalyse non-spontaneous reactions.
3. A catalyst does not change the equilibrium constant of a reaction, but it helps to attain the equilibrium
faster by increasing the rate of both forward as well as the backward reactions.
Collision Theory
This theory was developed by Max Trautz and William Lewis. It is based on kinetic theory of gases. According
to this theory, the reactant molecules are assumed to be hard spheres and reaction is occurred when molecules
collide with each other. The number of collisions per second per unit volume of the reaction mixture is known as
collision frequency (Z).
Another factor which affects the rate of chemical reactions is activation energy. For a bimolecular
elementary reaction
A + B → Products
Rate of reaction can be expressed as
Rate (r) = ZAB e –Ea/RT
Ea /RT
Where ZAB represents the collision frequency of reactants, A and B and e – represents the fraction of
molecules with energies equal to or greater than Ea. Comparing with Arrhenius equation, we can see that A is
related to collision frequency.
A third factor which affects the rate of a chemical reaction is the proper orientation. To account for this, a
factor P called the probability or steric factor is introduced. So the above equation becomes:
–Ea/RT
Rate (r) = PZAB e

Thus, in collision theory activation energy and proper orientation of the molecules together determine the
criteria for an effective collision and hence the rate of a chemical reaction.
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SURFACE CHEMISTRY

Surface Chemistry-Anil-HSSLiVE Page 1

Properties Physisorption Chemisorption

Surface Chemistry-Anil-HSSLiVE Page 2

Surface Chemistry-Anil-HSSLiVE Page 3

Shape-Selective Catalysis by Zeolites

Surface Chemistry-Anil-HSSLiVE Page 4

Surface Chemistry-Anil-HSSLiVE Page 5

Surface Chemistry-Anil-HSSLiVE Page 6

4. Based on the nature of particles:

Surface Chemistry-Anil-HSSLiVE Page 7

Surface Chemistry-Anil-HSSLiVE Page 8

Surface Chemistry-Anil-HSSLiVE Page 9

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Surface Chemistry-Anil-HSSLiVE Page 12

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XI Chemistry Study Notes by Anil Kumar K.L- HSSLiVE.IN

Types of Solution Solute Solvent Examples

Mole fraction (x)

SOLUTIONS-Anil Kumar K.L -HSSLiVE Page 3

SOLUTIONS-Anil Kumar K.L -HSSLiVE Page 4

SOLUTIONS-Anil Kumar K.L -HSSLiVE Page 5

SOLUTIONS-Anil Kumar K.L -HSSLiVE Page 6

1. Relative lowering of Vapour Pressure

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SOLUTIONS-Anil Kumar K.L -HSSLiVE Page 8

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Chemotherapy: Treatment of diseases using Antiseptic Disinfectant

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Chemistry in Everyday Life[Anil Kumar K.L] Page 3

Properties Crystalline solids Amorphous solids

The Solid State[Anil Kumar K.L-HSSLiVE] Page 1

The Solid State[Anil Kumar K.L-HSSLiVE] Page 2

Calculation of Number of atoms in a unit cell (z)

The Solid State[Anil Kumar K.L-HSSLiVE] Page 3

Square close packing Hexagonal close packing

The Solid State[Anil Kumar K.L-HSSLiVE] Page 5

Calculation of Packing Efficiency G B

The Solid State[Anil Kumar K.L-HSSLiVE] Page 6

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The Solid State[Anil Kumar K.L-HSSLiVE] Page 7

(4/3) πr3 ×100

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Calculation of Density of the unit cell (Solid)

The Solid State[Anil Kumar K.L-HSSLiVE] Page 8

Schottky Defect Frenkel Defect

Metal excess Defect Metal excess Defect

The Solid State[Anil Kumar K.L-HSSLiVE] Page 9

The Solid State[Anil Kumar K.L-HSSLiVE] Page 10

The Solid State[Anil Kumar K.L-HSSLiVE] Page 11

The Solid State[Anil Kumar K.L-HSSLiVE] Page 12

A salt bridge is a U-tube containing an inert electrolyte like NaNO3

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GHSS ASHTAMUDI Electrochemistry Page 3