1.

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 the following ways:
(i) Mass percentage (w/w): It is defined as the mass of the component present in 100g 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): It is defined as the volume of a component present in 100 mL 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.
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. *μg is
microgram]
(v) Mole fraction (χ): It is defined as the ratio of the number of moles of a particular component to the
total number of moles of the solution.
Mole fraction of a component = Number of moles of the component
Total number of moles of the solution
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 (χA) = nA
(nA + nB)
and that of the component B (χB) = nB
(nA + nB)
χA + χB = 1
i.e. in a given solution sum of the mole fractions of all the components is unity. If there are i components,
then
χ1 + χ2 + χ3 + ................... + χi = 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)
For example, 1 M (molar) NaOH solution means that 1 mol (40g) 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
Mass of solvent in kg
For example, 1 molal (m) solution of KCl means that 1 mol (74.5 g) of KCl is dissolved in 1 kg of water.
Among the different methods for expressing the concentration of solution, mass percentage, ppm (in
terms of mass), mole fraction and molality are independent of temperature; whereas molarity, mass by
volume percentage and volume percentage 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
at a particular temperature. It depends upon the nature of solute, nature of the 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 dissolve 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
When a solid solute is added to the solvent, some solute dissolves and its concentration increases in
solution. This process is known as dissolution. Some solute particles in solution collide with the solid solute
particles and get separated out of solution. This process is known as crystallisation. After sometime, the rate
of dissolution and crystallization becomes equal and a dynamic equilibrium is reached. At this stage the
concentration of solute in the solution remain constant and such a solution is called saturated solution.
A solution in which no more solute can be dissolved at the same temperature and pressure is called a
saturated solution. For such a solution, the concentration of the solution is equal to its solubility.
A solution in which more solute can be dissolved at the same temperature is called an unsaturated solution.
Effect of temperature on the solubility of a solid in a liquid
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 on the solubility of a solid in a liquid
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
(χ) in the solution” and is expressed as:
p = KH χ
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 (χ) 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 (χ)

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. A medical condition known as bends in scuba divers. To avoid bends the cylinders used by scuba divers
are filled with air diluted with helium (The composition of the air in the cylinders used by scuba divers
is 32.1% oxygen, 56.2% nitrogen and 11.7% helium).
3. A medical condition known as anoxia in people living at high altitudes and in mountaineers or
climbers.
Effect of Temperature on the solubility of a gas in a liquid
Solubility of gases in liquids decreases with rise in temperature. When dissolved, the gas molecules
are present in liquid phase. So the process of dissolution can be considered similar to condensation, which is
exothermic. Hence solubility decreases with increase of temperature.

Vapour Pressure of a liquid

In a liquid, the molecules with higher energy are escaped to vapour phase. This process is called
evaporation. As the density of the vapour increases, the molecules collide with each other and so their
energy decreases and returns to the liquid state. This process is called condensation.
 After some time, the rate of evaporation becomes equal to rate of condensation and the two
processes attain equilibrium. At this condition, the pressure exerted by the vapour is called vapour pressure.
So vapour pressure is defined as the pressure exerted by the vapour in equilibrium with its own liquid. It
depends on the nature of the liquid and the temperature. As the temperature increases, the vapour pressure
also increases.
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 p 1 and p2 be the partial vapour pressures
of the two components 1 and 2 respectively and ptotal be the total vapour pressure. Let χ1 and χ2 be the mole
fractions of the two components 1 and 2 respectively.
Then according to Raoult’s law,
for component 1, p1 𝖺 χ1
or, p1 = p10χ1
and for component 2, p2 𝖺 χ2
or, p2 = p20χ2
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 = χ1 p10 + χ2 p20
= (1 – χ2) p10 + χ2 p20
Or, ptotal = p1 0 + (p20 – p10) χ2
Plots of p1 or p2 against the mole fractions χ1 and χ2 give straight lines (I and II). Similarly the plot of
ptotal versus χ2 (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
P1 = χ1 p10. According to Henry’s law, solubility of a gas in a liquid is given by p = KH χ.
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.
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 vapour pressure of a component in the solution is equal to the vapour pressure of the pure
component multiplied by its mole fraction in the solution.
i.e. p1 = p10 χ1 and p2 = p20 χ2
For such solutions, no heat change occurs during the mixing of the pure components [i.e. ∆mixH = 0].
Also, the volume of the solution is equal to the sum of the volumes of the components. Or, there is no change
in the volume of the solution during mixing the components *i.e. ∆mixV = 0]
Thus for an ideal solution, p1 = p10 χ1 , p2 = p20 χ2 , ∆mixH = 0 and ∆mixV = 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 shows positive deviation from Raoult’s law and if it is lower, it shows negative deviation from
Raoult’s law.
(i) Solutions which show positive deviation from Raoult’s law:
For such solutions, p1 > p10 χ1 , p2 > p20 χ2 , ∆mixH > 0 and ∆mixV > 0
Here 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.
(ii) Solutions which show negative deviation from Raoult’s law:
For such solutions, p1 < p10 χ1 , p2 < p20 χ2 , ∆mixH < 0 and ∆mixV < 0
Here 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.
The plots of vapour pressure curves for ideal solution, solutions which show positive deviation and
negative deviation from Raoult’s law are as follows:
 Solutions showing Positive Solutions showing Negative
Ideal Solutions
deviation from Raoult’s law deviation from Raoult’s law

Azeotropes [Constant Boiling Mixtures]

These 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% aqueous ethanol solution by volume at 78.20C [351.35 K].
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.
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 in solution.
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, χ1 be its mole fraction, p10 be its vapour pressure in the
pure state. Then according to
Raoult’s law, p1 𝖺 χ1
or, p1 = p10χ1
A graph between the vapour pressure and the mole fraction of the solvent is linear as follows:
 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 [V.P of solution = V.P of the
solvent in the solution, since the solute is non-volatile].
Then according to Raoult’s law,
p1 = p10.χ1
The lowering of vapour pressure of the solvent (∆p) = p10 – p1
= p 1 0 – p 10 χ 1
Or, ∆p = p10 (1-χ1)
But χ1 + χ2 = 1. Therefore 1-χ1 = χ2
So ∆p = p10.χ2
Or, ∆p = χ2 , the mole fraction of the solute.
p 10
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
0
p1 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)
When a liquid is heated, its vapour pressure increases. At a particular temperature, the vapour pressure
becomes equal to the external pressure (atmospheric pressure). This temperature is called boiling point of
the liquid. So boiling point 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 (∆T b) 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 (i.e. it is the increase in boiling
point of a solution containing 1 mol of a solute in 1 kg of the solvent).
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. So the freezing point (f.p) of the solution is less than that of the pure solvent. The difference
between the freezing point (f.p) of pure solvent (T f0) and that of the solution (T f) 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 (∆T f) 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
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 an unknown solute.
4. Osmosis and Osmotic Pressure
Osmosis is the process of flow of solvent molecules from pure solvent to the 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 only solvent molecules is called a semi-permeable
membrane. E.g. egg membrane, parchment, pig’s bladder, all animal and plant membrane. Cellulose
acetate is an example for artificial semi-permeable membrane.
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 α CT
Or, π = CRT
Here R is the universal gas constant (R= 0.0821 Latm/K/mol or R = 0.083 Lbar/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
normalsaline 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
tothe solution side. Now the pure solvent flows out of the solution through the semi permeable
membrane. This phenomenon is called reverse osmosis. It 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 semi-permeable membrane is cellulose acetate. A schematic
representation of reverse osmosis is as follows:

Reverse osmosis is also used in the purification of water.

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
insolution 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/dissociationNumber 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
 2. ELECTROCHEMISTRY
It is a branch of chemistry that deals with the relationship between chemical energy
andelectrical energy and their inter conversions.
ELECTROCHEMICAL CELLS
These are devices that convert chemical energy of some redox reactions to electrical energy. They
arealso 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
saltbridge.
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) (reduction half reaction)
(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 ofthe cell are also called half-cells or redox couples. The copper electrode may be called the
reduction half celland 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
theopposite 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
cathodeon 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. [The concentration of the electrolyte is shown in simple
brackette]. 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
theright hand side minus the potential of the half-cell on the left hand side.
i.e. Ecell = Eright – Eleft
Or, Ecell = ER – EL
 Measurement of Electrode Potential
The potential of an 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 foil coated with platinum black (finely divided Pt).
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 through a volt meter. Here SHE
isalways connected on LHS 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
formis 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
getreduced 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:
It is an equation relating electrode potential or emf of a cell with electrolytic concentration.
(i) Nernst equation relating Electrode potential and Electrolytic concentration:
n+
Consider the electrode reaction: M(aq) + ne- –→ M(s)
Nernst equation for the electrode potential can be given
n+ 0 n+
by:E|M)(M |M) = E (M + RT ln [M n+]
nF [M]
Since the concentration of any solid is taken as unity, the above equation
becomes:
| M) E(M n+|M) = E0(M n+ + 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

or, Eel. = E0el. – 2.303RT log 1

nF [M n+]
Where E el. is the standard electrode potential, R is the universal gas constant (R = 8.314 JK–1 mol–
0
1
), F is Faraday constant (96500 C/mol), T is temperature in Kelvin and [M n+] is the concentration of the ion
Mn+.On substituting the values of R and F at 298K, the equation becomes:
Eel = E0el + 0.0591 log [Mn+]
n
 (ii) Nernst equation relating emf of a cell and electrolytic concentration:
A Daniel cell can be represented as: Zn(s) | Zn2+(aq) || Cu2+(aq) |
Cu(s)The electrode reactions are:
Cu2+ + 2 e- → Cu(s) (cathode reaction)
Zn(s) → Zn2+ + 2 e- (anode
reaction)The electrode potentials are:
for cathode:
2+ 0 2+ 2+
E(Cu /Cu) = E (Cu /Cu) + RT ln [Cu ]
2F
for anode: E(Zn /Zn) = E (Zn /Zn) + RT ln [Zn2+]
2+ 0 2+

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+]
Or, Ecell = [E0(Cu 2+/Cu) – E0(Zn2+/Zn) ] – RT ln [Zn2+]
2F [Cu2+]
Or, Ecell = E cell – RT ln [Zn ] (Since E (Cu /Cu) – E0(Zn2+/Zn) = E0cell)
0 2+ 0 2+

2F [Cu2+]
On changing the base of logarithm, we get
Ecell = E0cell – 2.303RT log [Zn2+]
2F [Cu2+]
On substituting the values of R (8.314 JK mol ), F (96500 C mol–1) at 298K, the above equation becomes,
–1 –1

Ecell = E0cell – 0.0591 log [Zn2+]

2 [Cu2+]
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 [C]c[D]d
n [A]a[B]b
(where n is the no. of electrons involved in the cell reaction)
Equilibrium Constant from Nernst Equation
For a Daniel cell, the emf of the cell at 298K is given by:
Ecell = E0cell – 0.0591 log [Zn2+]
2 [Cu2+]
When the cell reaction attains equilibrium, Ecell =
0So, 0 = E0cell – 0.0591 log [Zn2+]
2 [Cu2+]
Or, E0cell = 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
 On substituting the values of R (8.314 JK–1 mol–1), F (96500 C mol–1) at 298K, the above equation becomes,
E0cell = 0.0591 log Kc
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
emfof the cell is Ecell 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 = –nFE0cell
Thus, from the measurement of E0cell, we can calculate the standard Gibbs energy of the
reaction.By knowing ΔG0, we can calculate equilibrium constant by the equation: ΔG0 = – RT ln
Kc.
Or, ΔG0 = – 2.303RT log Kc
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. It is defined as the resistance offered by
aconductor having unit length and unit area of cross-section.
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
Conductance (G): It is the reciprocal 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 = fi x A/Ɩ
Where, ƙ is called conductivity. It is defined as the conductance of a conductor having unit length and
unitarea 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
ionicconductance.
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.
Itdepends 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 = fi x A/ Ɩ
So conductivity, fi = G x Ɩ/A
The quantity Ɩ/A is called cell constant (G*). It depends on the distance between the electrodes and their
areaof 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
aWheatstone 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 (aheadphone 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 (finely powdered platinum). The
electrodes are separated by a distance Ɩ and their area of cross-section is A.

Two types of conductivity cells

The solution confined between the electrodes can be considered as a column of length l and area of cross
section A. The cell constant of a conductivity cell is usually determined by measuring the resistance of the
cellcontaining a solution whose conductivity is already known (e.g. KCl solution).
 Molar conductivity (Λm – lambda m):
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.
OR,
Molar conductivity of a solution at a given concentration is the conductance of ‘V’ volume of a solution
containing one mole of electrolyte kept between two electrodes with area of cross section A and distance of
unit length.
It is related to conductivity of the solution by the equation,
Λm = fi (where C is the concentration of the solution)
C
Or, Λm = 1000 fi
M (where M is the molarity of the solution)
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 increases with dilution (or
decreaseswith 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 (Λm0 ).
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 depending on temperature, the nature of the
electrolyteand 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:

Weak Electrolyte
Λm

Λ0m Strong Electrolyte

√c

For strong electrolytes, the value of Λ0m can be determined by the extending the graph to y-axis. But
for weak electrolytes, it is not possible, since the graph is not a straight line. So their Λ0m values are
calculatedby 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
representedas 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(-)λ 0(-)
For an electrolyte like AxBy the dissociation can be denoted as: AxBy xAy+ + yBx-
Λ0m(AxBy) = x.λ0(Ay+) + y.λ 0(Bx-)
0 0 0
For NaCl, Λ m (NaCl) = λ (Na+) + λ (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 Λm0 of weak electrolytes. For
0 0
e.g.we can determine the m Λ of acetic acid3(CH COOH) by knowing the m Λ of CH
3 COONa, 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:
Λ0m (CH3COONa) + Λ0 m(HCl) – Λ0m (NaCl) = λ0CH3COO–+ λ0Na+ + λ0H+ + λ0Cl– – λ0Na+ – λ0Cl–
= Λ0m(CH3COOH)
2) Determination of degree of dissociation of weak electrolytes
By knowing the molar conductivity at a particular concentration (Λcm) and limiting molar conductivity
0
(Λm ), we can calculate the degree of dissociation (α) as,
α = Λcm
Λ 0m
By using α, we can calculate the dissociation constant of weak acid (Ka) as:
Ka = cα2
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 [Equivalent
weight of an ion = Atomic mass/valency.
 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
gramequivalent of any substance. Its value is 96487 C/mol or, 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 participates 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.
When dilute H2SO4 is electrolysed, O2 gas is liberated from the anode.
2H2O(l) O2 (g) + 4H+ (aq) + 4e–
while if we use conc. H2SO4, peroxodisulphate ion is formed at the anode.
2SO42– (aq) S2O82– (aq) + 2e–
In both cases H2 gas is liberated from the cathode.
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 Zn 2+ and thus corrodes the cell. The cell has
apotential 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. E.g.: Lead storage cell, Ni- Cd cell (Nicad cell).
Lead storage cell:
It is used in automobiles and invertors. It consists of lead as anode and a grid of lead packed with
leaddioxide (PbO2) as the cathode. The electrolyte is 38% H2SO4 solution.
The cell reactions are:
Anode: Pb(s) + SO42- (aq) → PbSO4(s) + 2e-
2-
Cathode: PbO2(s) + SO 4 (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
Pband 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 dividedplatinum 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,
formationof green coating on copper and bronze (verdigris) etc.
Most familiar example for corrosion is rusting of iron.
Chemistry of rusting of iron:
Rusting of iron is a redox reaction, which occurs in presence of air and water. At a particular spot
ofthe metal iron, 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
+ +
reduceoxygen in presence of H [H is formed by dissolving atmospheric CO2 in moisture]. This spot
behaves as cathode. The reaction taking place at the cathodic 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 used 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 used is connecting the iron object with a sacrificial electrode of
another metal (like Mg, Zn, etc.), which corrodes itself but saves theobject (sacrificial
protection).
^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
 3.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
reactants or products in unit time. Or, it is the rate of decrease in concentration of any one of the
reactants or the rate of increase in concentration of any one of the products.
For a chemical reaction, if ∆x is the change in concentration of reactant or product in time interval ∆t,
the rate of reaction (r) = ∆x/∆t.
For a hypothetical reaction R → P, the rate of reaction can be expressed by decrease in concentration
of reactant or by increase in concentration of product.
i.e. Rate of reaction (r) = Rate of disappearance of R
r = Decrease in concentration of R
Time taken
Or, r = – ∆[R]
∆t [Since, concentration of reactant decreases with time, ∆[R] is negative.
But rate of reaction cannot be negative. So in order to make it positive, it is multiplied with –1].
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 of reaction.
For a gaseous reaction, at constant temperature, concentration is directly proportional to the partial
pressure. Hence the rate of reaction can also be expressed as the rate of change in partial pressure of the
reactant or product.
Units of rate of reaction
If concentration is expressed in mol/L and time is in second, the unit of rate of reaction is
mol/L/s [mol L-1 s-1]. In general the dimension of rate of reaction is concentration/time. For gaseous
reaction, 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. for the smallest time interval).
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 = – 1 d[N2O5] = 1 d[NO2] = d[O2]
2 dt 4 dt dt
– – +
For the reaction, 5 Br (aq) + BrO3 (aq) + 6 H (aq) 3 Br2 (aq) + 3 H2O (l)
rinst = – 1 d[Br–] = – d[BrO3–] = –1 d[H+] = 1 d[Br2] = 1 d[H2O]
5 dt dt 6 dt 3 dt 3 dt
For a general reaction aA + bB → cC + dD, the instantaneous 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
 Determination of Instantaneous rate of a reaction
Instantaneous rate of a reaction can be determined graphically. For this first conduct the chemical
reaction and find out the concentration of any one of the reactants or products 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.
Concentration

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. Catalyst
6. Radiation or light
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 the stoichiometric coefficients 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. It is defined as the rate of the
reaction when the concentration of each of the reactants is unity.
Order of reaction (n)
Order of a reaction 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
Here „x‟ is the order with respect to the reactant A, „y‟ is the order with respect to B and (x + y) is the overall
order of the reaction.
If the order of a reaction is zero, it is called zero order reaction.
E.g.: Decomposition of ammonia at the surface of platinum at high pressure.
If the order of a reaction is one, it is called first order reaction.
E.g. Decomposition of hydrogen peroxide.
If the order of a reaction is two, it is called second order reaction and so on.
E.g. for fractional order reactions are:
Decomposition of acetaldehyde: CH3-CHO CH4 + CO; r = k[CH3-CHO]3/2
Chlorination of chloroform: CHCl3 + Cl2 CCl4 + HCl; r = k[CHCl3][Cl2]1/2
Molecularity of a reaction
It is the total NUMBEr of reacting species collides sIMULTAneoUSly in a chemical reaction.
It is a theoretical QUANtity. It can have valUES 1,2,3 etc. It cannot be ZEro or fractional. 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 It is the total number of reactant species
terms in the rate law collide simultaneously in a
expression 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 It is applicable only to elementary
complex reactions 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 steps is called a complex reaction. In a complex reaction one of the steps is slower than
the other steps. The overall rate of the reaction is controlled by this step and this step is called the rate
determining step (rds). 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] = k[H2O2][I–]
dt
This reaction is first order with respect to both H2O2 and I–. The reaction takes place in two steps and its
mechanism can be written as:
(1) H2O2 + I– slow/rds H2O + IO–
(2) H2O2 + IO– fast 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 n A products, rate = k[A]n
Therefore, k = rate
[Concentration]n
Unit of k = mol/L/sec = (mol/L)1-ns-1 = mol1-n Ln-1 s-1
( mol/L) n
The units of rate constant for different ordered reactions are:
Reaction Order (n) 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 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 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] ................. (1)
dt
Rate law for the above reaction is r= k[R] = k ................... (2) [Since [R]0 = 1]
0

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 „C‟ in equation (3), we get
[R] = – kt + [R]0 .................... (4)
Or, kt = [R]0 – [R]
Or, k= [R]0 – [R] .......................(5)
t
This equation is of the form y = mx + c, equation for a straight line, 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 the decomposition of gaseous ammonia on a hot platinum
surface at high pressure.
2 NH3(g) Pt/high p N2(g) + 3 H2(g) ; r = k[NH3]0
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 pressure does not change the rate of the reaction. Hence it
becomes a zero order reaction.
Another e.g. is the thermal decomposition of HI on gold surface.
2HI(g) Au/high p H2(g) + I2(g); r= k[HI]0

2. Integrated Rate Equation for a First order reaction

For a first order reaction, the rate of the reaction is proportional to the first power of
the concentration of the reactant.
Consider a first order reaction, R P
The rate expression for the above reaction is r= – d[R] ................. (1)
dt
Rate law for the above reaction is r = k[R] .................... (2)

From equations (1) & (2), we can write – d[R] = k[R]

dt
This equation is known as differential rate equation for a 1st order 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 x 0 +C
Or, C = – ln[R]0
Substituting the value of „C‟ in equation (3), we get
– ln[R] = kt – ln[R]0 .................... (4)
Or, ln[R]0 – ln[R] = kt
Or, ln[R]0 = kt................ (5)
[R]
Or, k = 1 ln [R]0
t [R] ................... (6)
On changing the base of logarithm, 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
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 = kt

[R]
Or, 2.303 log [R]0 = kt
[R]
Or, log [R]0 = k.t
[R] 2.303
So if we plot a graph between log[R]0/[R] against „t‟, we get a straight line graph as shown below:

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.
3. Decomposition of N2O5 and N2O
N2O5 2NO2 + ½ O2; r = k [N2O5]
Half life of a reaction (t1/2)
The half-life of a reaction is the time taken for the concentration of a reactant
is reduced to one half of its initial concentration. 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 independent of initial concentration of the
reactants. Or, it is a constant.
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 + H2 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:
k = A e - Ea /RT
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, T is the
absolute temperature and Ea is activation energy measured in joules/mole (J mol –1). [The above
equation was first proposed by J H van‟t Hoff, but its physical justification and interpretation was given by
Arrhenius.]
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 progress of reaction.

In a 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, this fraction 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.
The logarithmic form of Arrhenius equation is:
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 graph as follows:
The slope of the graph = – Ea and the y-intercept ln A.
R

Calculation of Activation energy by knowing the rate constants at two different temperatures

Consider a reaction R P. If k1 is the rate constant of the reaction at temperature T1 and k2 is the rate
constant at temperature T2, then

………………. (1) and

……………… (2)
Equation (2) – (1) gives,

ln k2 – ln k1 = – Ea + ln A – – Ea- + ln A
RT2 RT2
Or, ln k2 = – Ea + Ea
k1 RT2 RT1

On changing the base of logarithm, we get:

2.303 log
Or,

From this equation we can calculate the value of activation energy (E a), by knowing all other values.

Effect of Catalyst
A catalyst is a substance that increases 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 combines with reactant to form an unstable intermediate complex,
which decomposes to form products and the catalyst.
A catalyst increases the rate of a chemical reaction by providing an alternate path with
low activation energy between reactants and products.
[A substance that decreases the rate of a reaction is called inhibitor].
 The energy profile diagram for a reaction with catalyst and without catalyst is shown below:

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 change the Gibbs energy of a reaction (ΔrG). 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
Where ZAB represents the collision frequency of reactants, A and B and e – Ea /RT 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. The proper
orientation of reactant molecules lead to bond formation. While, improper orientation makes them
bounce back and no products are formed. To account for this, probability or steric factor (P) is introduced.
So the above equation becomes:
Rate (r) = PZAB e –Ea/RT
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.
 The d and f Block Elements
Elements from 3rd group to 12th group in the Modern Periodic table are called d-block elements. In
these elements their last electron enters in the penultimate d- sub shell. They are placed in between s-block
and p-block elements. They show a regular transition from the highly electropositive metals of s-
block elements to the less electropositive p-block elements. So they are called transition
elements.
Transition elements can be defined as elements which contain partially filled d orbitals in
their atomic state or in any of their oxidation state. The elements Zn, Cd and Hg contain only
completely filled d-orbitals. So they are not regarded as transition elements. Or, they are called pseudo
transition elements.
There are four series of transition elements.
1) 3d series [from Scandium (Sc, z = 21) to zinc (Zn, z = 30)]
2) 4d series [from Yttrium(Y, z = 39) to cadmium, (Cd, z = 48)]
3) 5d series [from Lanthanum, (La, z =57), Hafnium, (Hf, z = 72) to Mercury, (Hg, z=80)]
4) 6d series [from Actinium, (Ac, z=89), Rutherfordium, (Rf, z=104) to copernicium, (Cp, z=112)]
Electronic Configuration
General outer electronic configuration of d-block elements is (n-1) d1-10 ns1-2. There is only a small
difference in energy between (n-1)d orbital and ns orbital. So in some cases ns electrons are also transferred
to (n-1)d level.
The electronic configurations of Cr and Cu in the 3d series show some exceptions.
5 1
24Cr – [Ar] 3d 4s
10 1
29Cu – [Ar] 3d 4s
This is due to the extra stability of half-filled (d5) and completely-filled electronic configurations (d10). The
electronic configurations of Zn, Cd and Hg are represented by the general formula (n-1)d10 ns2.
The orbitals in these elements are completely filled in the ground state as well as in their common oxidation
states. So they are not regarded as transition elements.

Electronic configuration of first row transition series elements:

Atomic number Element Symbol Electronic configuration
21 Scandium Sc [Ar] 3d1 4s2
22 Titanium Ti [Ar] 3d2 4s2
23 Vanadium V [Ar] 3d3 4s2
24 Chromium Cr [Ar] 3d4 4s2
25 Manganese Mn [Ar] 3d5 4s1
26 Iron Fe [Ar] 3d6 4s2
27 Cobalt Co [Ar] 3d7 4s2
28 Nickel Ni [Ar] 3d8 4s2
29 Copper Cu [Ar] 3d10 4s1
30 Zinc Zn [Ar] 3d10 4s2
 General characteristics of transition elements
1. Atomic and ionic radii
In a transition series, the atomic and ionic radii first decrease, then become constant and increases
towards the end of the series. This is because in transition elements, the new electron enters in a
penultimate d-orbital. Initially since there is a few numbers of d electrons, the shielding effect is very poor. As
the atomic number increases, the nuclear charge also increases, so the atomic radius decreases. Towards the
middle of the series, the increase in nuclear charge is balanced by the shielding effect and so the atomic
radius becomes constant. Towards the end of the series, as the e- - e- repulsion increases the atomic radius
also increases
The atomic and ionic radii of 2nd and 3rd row transition metals are quite similar. This is due to the
Lanthanide contraction. In between the 2nd and 3rd row transition elements, 4f electrons are present. The 4f
electrons have very poor shielding effect and as a result the atomic and ionic radii of Lanthanides decrease
from left to right (Lanthanide contraction).
2. Melting and boiling points
Transition elements are generally very hard and have
high melting and boiling points. This is due to the participation
of (n-1)d electrons (penultimate d electrons) in addition to the
ns electrons (valence s electrons) in metallic bonding.
In a transition series, the melting and boiling points 1st
increases up to the middle and then decreases. This can be
explained in terms of metallic bond strength and heat of
atomization which depend on the number of unpaired
electrons. As the number of unpaired electrons increases, the
metallic bond strength increases and hence the heat of
atomization. In a transition series, the number of unpaired
electrons increases up to the middle and then decreases.
Hence the melting point also increases first and then decreases.
Manganese (Mn) and Technetium (Tc) have low melting point even though they have d5
configuration. This is because of their low heat of atomization. The m.ps of second and third row
transition series are higher than that of the first row due to their higher enthalpies of atomization.
3. Ionisation enthalpy
The ionisation enthalpy of transition elements generally increases from left to right. This is due to increase
in the nuclear charge from left to right. But the increase is not regular. This can be explained as follows.
After the removal of one electron, the relative energies of 4s and 3d orbitals get changed. Hence
the remaining electron in the 4s level is transferred to 3d level. So the unipositive ions have d n configuration
with no 4s electrons. During this re-organisation of electrons, some energy is released and it is known as
exchange energy. So the net energy required to remove the 1st electrons is equal to the sum of ionisation
enthalpy and exchange energy.
The first ionisation enthalpies of Cr and Cu are low. This is because the removal of one electron
does not change their d configuration. Similarly first ionisation enthalpy of Zn is high because after the
removal of one electron there is no change in the d configuration. Zn
+ - 10 2 10 1
→ Zn + e 3d 4s 3d 4s
 The 2nd I.E of Cr and Cu are very high. This is because the removal of one more e- from these
metals disrupted their stable configuration (d5 or d10)
The 2nd ionisation enthalpies of Mn and Zn are low, this is because after the removal of one more
electron, they attain the stable half filled or completely filled electronic configuration.
4. Oxidation State
Transition metals show variable oxidation states. This is because in these elements d and s
electrons have comparable energies. So in chemical reaction along with s-electrons, d-electrons also
participate.
In a given transition series, the maximum oxidation state increases up to the middle and then
decreases. This is due to the half-filled or fully filled electronic configuration (noble gas configuration). The
common oxidation state of 1st row transition elements is +2. The maximum oxidation state increases from top
to bottom in a group. In lower oxidation state, the transition element mainly forms ionic compounds.
Scandium generally shows +3 oxidation state because after the removal of 3 electrons, it gets a stable noble
gas configuration (d0). The oxidation state of Zinc is +2, because of the completely filled configuration of Zn2+.
5. Electrode Potential
The electrode potential values of first row transition series elements generally increases from left to right
with some exceptions. The E0(Cu2+|Cu) is positive (+0.34V), while the E0 values of all the other first row
transition elements are –ve. This is because the electrode potential depends on heat of atomization,
ionization enthalpies and hydration enthalpy. For copper, the high energy to transform solid Cu to aqueous
Cu2+ is not balanced by its hydration enthalpy. So, copper does not easily react with acid and liberate H2. Only
oxidizing acids [e.g. HNO3 and hot conc. H2SO4] react with Cu and the acid get reduced.
Along the series the E0 values become less –ve due to the increase in the sum of 1st and 2nd ionisation
enthalpies. The E0 values of Mn2+ and Zn2+ are more –ve, this is because of the half-filled configuration of
Mn2+ (d5) and completely filled configuration of Zn2+ (d10). E0(M3+|M2+) value of scandium (Sc) is very low and
that for zinc (Zn) is very high. This is because of their stable electronic configuration.
E0 (Mn3+|Mn2+) is high because of the stable half-filled configuration of Mn2+. Similarly E0(Fe2+|Fe3+) is low, this
is because after the removal of one electron from Fe2+, it gets a stable electronic configuration.
Fe2+ → Fe3+ + e-
3d6 3d5
Q. Cu2+ is more stable than Cu+ in aqueous solution. Why?
This is due to the greater –ve hydration enthalpy of Cu2+(aq) than Cu+(aq). In the case of Cu2+, the
hydration enthalpy is compensated by second ionisation enthalpy.
6. Magnetic Properties
Transition metals show mainly two types of magnetic properties - paramagnetism and diamagnetism.
Some transition metals also show ferromagnetism which is an extreme case of paramagnetism.
Paramagnetism arises from the presence of unpaired electrons. Each unpaired e- is associated with
a spin magnetic moment and an orbital magnetic moment. For the compounds of 1 st row transition elements,
the contribution of orbital magnetic moment is effectively cancelled and so only spin magnetic moment is
considered. It is determined by the no. of unpaired e-s and is calculated by the spin only formula:µs = √n(n+2)
where n is the no. of unpaired electrons and µs is the spin only magnetic moment in the unit of
Bohr Magneton (B.M).
The magnetic moment increases with increase in no. of unpaired e-s. Thus the observed magnetic
moment gives an idea about the no. of unpaired e-s present in the atom or ion.

7. Formation of coloured ions or compounds

Most of the Transition metals ions or compounds are coloured. This is because of the presence
of partially filled d orbitals. When an electron from a lower energy d orbital is exited to higher d level, it
absorbs energy and this is equal to the energy of certain colours in visible region. So the colour observed is
the complementary colour of the light absorbed.
In aqueous solution most of the transition metal ions are coloured since water molecules act as
the ligands.
Among Ti2+ and Ti4+, Ti2+ is coloured while Ti4+ is colourless. This is because Ti4+ has no partially filled d
orbitals.
Ti2+ - [Ar] 3d2 Ti4+ - [Ar] 3d0
Similarly among Cu+ and Cu2+, Cu2+ is coloured while Cu+ is colourless. This is due to the lack (absence)
of partially filled d orbitals in Cu+.
8. Formation of Complexes
Transition metals form a large no. of complexes. This is due to:
1. Comparatively smaller size
2. High ionic charge
3. Presence of partially filled d orbitals
4. Ability to show variable oxidation state
Eg: K4[Fe(CN)6], K3[Fe(CN)6], [Ni(CO)4] etc.
9. Catalytic Property
Transition metals act as catalysts in a large no. of chemical reactions. This is due to their large
surface area and their ability to show variable oxidation state.
10. Interstitial Compound Formation
These are formed when smaller atoms like H, N, C, B etc. are trapped inside the crystal lattice of the
metal. They are usually non-stoichiometric and neither typically ionic nor covalent.
E.g.: Fe3H, Mn4N, TiC, VH0.56, TiH1.7 etc.
Some the properties of these compounds are:
1) They have high melting point.
2) They are very hard.
3) They retain metallic conductivity.
4) They are chemically inert.
11.Alloy Formation
Alloys are homogeneous solid solutions of elements in which at least one element is a metal. They are
formed by atoms with metallic radii within about 15% of each other. Because of similar radii and other
characteristics of transition metals, they readily form alloys. The alloys formed are hard and have high
melting point. E.g.: Bronze (Cu and Sn), Brass (Cu and Zn), Stainless steel (Fe, C, Ni, Mn and Cr) etc. Some
Important Compounds of Transition Elements
1. Potassium dichromate ( K2Cr2O7)
Potassium dichromate is generally prepared from chromite ore (FeCr2O4). The preparation involves
three steps.
1. Conversion of chromite ore to SODIUm chromate
 Chromite ore is first fused with sodium carbonate in presence of air to form sodium chromate.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
2. Acidification of sodiUM chromate to sodIUm dichromate
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to orange
sodium dichromate.
2Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O
3. Conversion of sodiUM dichromate to potassIUm dichromate
The solution of sodium dichromate is treated with potassium chloride so that orange crystals
of potassium dichromate crystallise out.
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
Properties: The chromate and dichromate are inter convertible in aqueous solution depending upon p H of the
solution. Chromate on acidification gives dichromate and the dichromate on treating with alkali gives
chromate.
2 CrO42– + 2H+ → Cr2O72– + H2O
Cr2O72– + 2OH- → 2 CrO42– + H2O
The oxidation state of chromium in chromate and dichromate
is +6.
Structure
The chromate ion is tetrahedral while, the dichromate
ion consists of two tetrahedra sharing one corner with Cr–O–
Cr bond angle of 126°.
Sodium and potassium dichromates are strong oxidising agents. Sodium dichromate is most
commonly used as oxidizing agent, due to its greater solubility in water. Potassium dichromate is used as a
primary standard in volumetric analysis.
Oxidising Property
K2Cr2O7 is a good oxidising agent in acidic medium. Its oxidising action can be represented as follows: Cr 2O72– +
14H+ + 6e– → 2Cr3+ + 7H2O
Thus, acidified potassium dichromate will oxidise
1) Iodides to iodine
6 I – → 3I2 + 6 e-
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
6I – + Cr2O72– + 14H+ → 3I2 + 2Cr3+ + 7H2O
2) Sulphides to sulphur
3S2- → 3 S + 6e-
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
3S2- + Cr2O72– + 14H+ → 3S + 2Cr3+ + 7H2O
3) Tin(II) to tin(IV)
3 Sn2+ → 3Sn4+ + 6 e-
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
3Sn2+ + Cr2O72– + 14H+ → 3 Sn4+ + 2Cr3+ + 7H2O
4) Iron(II) to iron(III) OR, Ferrous ion to ferric ion
6 Fe2+ → 6Fe3+ + 6 e-
 Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
Cr2O72– + 14 H+ + 6 Fe2+ → 2 Cr3+ + 6 Fe3+ + 7 H2O
USES: It is used as a primary standard in volumetric analysis, as an oxidising agent in many reactions, in
leather industry etc.
2. Potassium permanganate ( KMnO4)
Potassium permanganate is commercially prepared from MnO2 (Pyrolusite). The preparation
involves two steps:
i) Conversion of MnO2 to potassium manganate (K2MnO4) by fusing with KOH in presence of air
(or an oxidizing agent like KNO3).
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
ii) Potassium manganate is oxidised to potassium permanganate either by electrolysis or by
acidification.

Or, 3MnO4 2- + 4H+ → 2MnO4 - + MnO2 + 2H2O

Properties:
Potassium permanganate forms dark purple crystals which are iso-structural with those of potassium
perchlorate (KClO4).
When heated it decomposes and liberate O2.
2KMnO4 → K2MnO4 + MnO2 + O2
Structure: The manganate and permanganate ions are
tetrahedral. The green manganate is paramagnetic with one
unpaired electron but the permanganate is diamagnetic.
Note: In permanganate ion, Mn is in +7 oxidation state with no
d-electrons. So the colour of permanganate is due to ligand to
metal charge transfer. i.e. an electron is transferred from
oxygen atom to the vacant d-orbital of Mn.

Oxidising Property of KMnO4

KMnO4 is a good oxidizing agent in acidic, basic and neutral media. The oxidizing action in acidic
medium is due to the reaction:
MnO4- + 8H++ 5e-→ Mn2+ + 4H2O
Acidified permanganate solution oxidises:
 1)Oxalates to carbon
dioxide 5 x (C2O42-→2
CO2 + 2e–)
2 x (MnO - + 8H4++ 5e-→ Mn2+ + 4H O) 2

5 C2O4 +2 2-
16H → 10 CO2 +2 Mn2+ + 8H2O
MnO4- + +

2) Iron(II) to iron(III)
5 Fe2+ → 5 Fe3+ + 5e–
MnO - + 8H4++ 5e-→ Mn2+ + 4H O 2
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 4H2O
3) Nitrites to nitrates
5NO2– + 5H2O → 5NO3- + 10H+ + l0e–
2 x (MnO - + 8H4++ 5e-→ Mn2+ + 4H O) 2
5NO2– +2 MnO4- + 6H+ → 5NO3- + 2 Mn2+ + 3H2O
4) Iodides to free iodine.
10 I → 5I2 + 10e–
–

2 x (MnO - + 8H4++ 5e-→ Mn2+ + 4H O) 2

10 I + 2 MnO + 16H → 5 I2 + 2 Mn2+ + 8 H2O

- - +

5) Sulphite to sulphate
2 x (MnO - + 8H4++ 5e-→ Mn2+ + 4H O) 2
5 x (SO32- + H2O → SO42- + 2 H+ + 2e-)
5SO32- +2 MnO - + 6H4+ → 5SO42- + 2 Mn2+ + 3H2O
In alkaline or neutral medium, permanganate ion is reduced to MnO2 MnO
- -
4 → MnO
+ 2H O + 3e 2 + 4OH- 2

In alkaline medium it oxidises

1) Iodide to iodate
(MnO4- + 2H2O + 3e-→ MnO2 + 4OH-) x
2 I- + 6OH- →3 IO - + 23 H O + 6 e–
2 MnO4 - + H2O + I - → 2 MnO2 + 2 OH-+ IO3 -
2) Thiosulphate to sulphate
(MnO4- + 2H2O + 3e-→ MnO2 + 4OH-) x 8
(S2O32- + 10OH- → 2SO42- + 5 H2O + 8e-) x
3
8MnO4 - + H2 O +3 S2 O32- → 8MnO2 + 2OH-+ 6SO42-
Note: For acidification of permanganate, hydrochloric acid (HCl) is not used, since it is oxidised to
chlorine. Uses: It is used as an oxidising agent in acidic, basic and neutral medium. It is used as a primary
standard in volumetric analysis. It is used for the bleaching of wool, cotton, silk and other textile fibres
and also for the decolourisation of oils.
THE INNER TRANSITION ELEMENTS ( f-BLOCK)
The elements in which the last electron enters in the anti-penultimate f-subshell are called f-block
elements. They include lanthanides of the 6th period and actinides of the 7th period. They are also called
inner transition elements. Since lanthanum (57La) closely resembles lanthanides, it is also included along
with them. Similarly, actinium (89Ac) is included along with actinoids because of its close resemblance with
 them.The Lanthanoids or lanthanides
The 14 elements after lanthanum of the 6th period are called lanthanides or lanthanoids or
lanthanones or rare earths. They include elements from 58Ce to 71Lu. They are generally represented as
Ln. Atomic and ionic radii - Lanthanide Contraction
In lanthanides, the atomic and ionic radii decrease regularly from lanthanum to lutetium. This regular
decrease in the atomic and ionic radii along lanthanide series (though very slightly) is called
lanthanide contraction.
Reason: In lanthanides, as the atomic number increases, the nuclear charge increases one by one and the
electrons are added to the anti-penultimate f subshell. Due to its diffused shape, f orbitals have poor
shielding effect. So the nucleus can attract the outer most electrons strongly and as a result the radii
decreases.
Consequences of Lanthanide contraction:
1) Due to Lanthanide Contraction the 2nd and 3rd row transition series elements have similar
radii.
E.g. Zr – 160pm and Hf -159pm
2) Lanthanides have similar physical properties and they occur together in nature. So
their isolation is difficult.
3) The basic character of their hydroxides decreases from lanthanum to lutetium. i.e,
La(OH)3 is more basic than Lu(OH)3.
Oxidation number
In lanthanoids, the most common oxidation state is +3. However, +2 and +4 ions in solution or in
solid compounds are also obtained. This irregularity arises mainly from the extra stability of empty, half-
filled or filled f subshells. Cerium shows the oxidation state +4 due to its noble gas configuration.
Praseodymium (Pr), neodymium (Nd), terbium (Tb) and dysprosium (Dy) also exhibit +4 state but only in
oxides, MO2.
Europium (Eu) and ytterbium (Yb) shows +2 oxidation state because of the stable f 7 or f14
configuration. Samarium (Sm) shows +2 oxidation state also.
General properties of Lanthanoides
All the lanthanoids are silvery white soft metals and tarnish rapidly in air. Their hardness
increases with increasing atomic number. They have typical metallic structure and are good conductors
of heat and electricity.
Most of the lanthanoid ions are coloured both in the solid state and in aqueous solutions. Colour of
these ions is due to the presence of f electrons. But La3+ or Lu3+ ion are colourless. The lanthanoid ions
other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+ and Lu3+) are all paramagnetic. The
paramagnetism rises to maximum in neodymium.
Chemical properties
Some of the chemical reactions of lanthanides are: Ln +
O2 ∆ Ln2O3
Ln + S ∆
Ln2S3 Ln +
N2 ∆ LnN
 Ln + C 2773K LnC2
Ln + H2O Ln(OH)3 + H2
Ln + X2 LnX3
Ln + HCl LnCl3 + H2
Uses of Lanthanides
The main use of the lanthanoids is for the production of alloy steels. An important alloy is
mischmetall which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. It is
mainly used in Magnesium based alloy to produce bullets, shell and lighter flint.
Mixed oxides of lanthanoids are used as catalysts in petroleum cracking. Some lanthanide oxides
are used as phosphors in television screens and similar fluorescing surfaces.
The Actinoids or Actinones
The 14 elements after actinium in the 7th period of modern periodic table are called actinides or
actinoids or actinones. They include elements from 90Th to 103Lr. Most of them are artificially prepared
and are short lived. They are radioactive. The elements after Uranium are artificially prepared and so
they are called trans-uranium elements or trans-uranic elements.
Atomic and ionic radii
In actinoid series the atomic and ionic radii decrease regularly from left to right. This is known as
Actinoid contraction.
Oxidation state
Common oxidation state of actinoids is +3. The elements in the first half of the series show
higher oxidation states. The maximum oxidation state increases from +4 in thorium (Th) to +5, +6 and +7
respectively in protactinium (Pa), uranium (U) and neptunium (Np) but decreases in succeeding
elements. The actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4
state.
Comparison between lanthanoids and acinoids
1. Most of the actinoids are artificially prepared and are radioactive.
2. The first ionisation enthalpy of early actinoids is lower than those of lanthanoids.
3. Actinoid contraction is greater from elements to elements than lanthanoid contraction. This is due
to greater shielding effect of 5f electrons.
USES OF d AND f BLOCK ELEMENTS
I. d and f block elements and their compounds are used as catalysts in many chemical reactions.
II. In the Wacker process, the oxidation of ethyne to ethanal is catalysed by PdCl2.
III. Iron and steels are the most important construction materials.
IV. Alloys of d and f block elements are used in various fields.
V. Copper (Cu), Silver (Ag), Gold (Au) and some alloys are used for making coins.
VI. TiO is used in pigment industry.
VII. Zn, Ni, cadmium (Cd), MnO2 etc are used in making batteries.
VIII. Compounds of Ag are used in photography.
IX. Nickel complexes are useful in the polymerisation of alkynes and other organic compounds such
as benzene.
X. An alloy of lanthanoids known as mischmetall is used in Magnesium based alloy to produce
bullets, shell and lighter flint.
XI.Uranium is used as fuel in nuclear reactors.
 5. CO-ORDINATION COMPOUNDS
Double salt and Complex salt
A salt that keeps its identity only in solid state is called a double salt. In solution they dissociate
into component ions. E.g.: Mohr‟s salt [FeSO4.(NH4)2SO4.6H2O], Carnalite [KCl.MgCl2.6H2O], Potash
alum [K2SO4.Al2(SO4)3.24H2O].
The salt that keeps its identity both in solid state and in solution state is called a complex salt.
E.g.: Potassium ferrocyanide {K4[Fe(CN)6]}, Cuprammonium sulphate [Cu(NH3)4]SO4, K2[PtCl4], [Ni(CO)4] etc.
Some definitions
1. Co-ordination entity: The central metal atom or ion along with ligands form a co-ordination entity.
For example, [CoCl3(NH3)3] is a co-ordination entity in which the cobalt ion is surrounded by three ammonia
molecules and three chloride ions. Other examples are [Ni(CO)4], [PtCl2(NH3)2], [Fe(CN)6]4–, [Co(NH3)6]3+.
2. Central atom/ion: In a co-ordination entity, the atom/ion to which a fixed number of ions/neutral
molecules are attached is called the central atom or ion. For example, the central atom/ion in the
2+ 3– 2+ 3+ 3+
co- ordination entities: [NiCl2(H2O)4], [CoCl(NH3)5] and [Fe(CN)6] are Ni , Co and Fe
respectively.
These central atoms/ions are also referred to as Lewis acids, since they accept electron pairs from ligands.
3. Ligands: The negative ions or neutral molecules which are bonded to the central atom/ion in the
coordination entity are called ligands. For a species to act as ligand, it can donate atleast one pair of
electron to the central atom.
Examples for ligands are Cl-, Br-, F-, I-, OH-, CN-, NC-, CNO-, NCO-, SO42-, NO3-, CNS-, H2O, NH3, CO etc.
The atom of the ligand which is directly bonded to the central atom or ion is called co-ordinating atom
or donor atom. For example in the ligan NH3, Nitrogen is the co-ordinating atom (donor atom).
Types of ligands
Based on the number of donor atoms of the ligand that binds to a metal ion or atom, the ligands are
classified as follows:
a) Monodentate or unidentate ligand: A ligand that binds to the central atom/ion through a single
donor atom, is said to be unidentate ligand. E.g.: Cl-, Br-, I-, OH-, H2O, NH3, CN-, NC-, SCN- etc.
b) Bidentate (Didentate) ligands: A ligand that binds to the central atom through two donor atoms is
called a bidentate ligand. E.g.: Ethane-1,2-diamine or ethylenediamine (H2NCH2CH2NH2) notated as ‗en‘
2–
and oxalate ion (C2O4 ).
c) Polydentate ligand: A ligand that binds to the central atom through more than two donor atoms is
called polydentate ligand.
E.g.: Triethylamine ammonia [N(CH2-CH2-NH2)3], Ethylenediamine tetraacetate ion (EDTA4–) etc.
Ethylenediamine tetraacetate ion (EDTA4–) is an important hexadentate ligand. It can bind to the central
atom through two nitrogen and four oxygen atoms.

Ethylenediamine tetraacetate ion

4–
(EDTA ) Ligands are also classified as:
i) Ambidentate ligands: They are unidentate ligands which contain more than one donor atoms and can
co-ordinate to the central atom through two different atoms. E.g.: NO2 ,– CN ,– SCN ,– CNO etc.
–

NO2– ion can co-ordinate either through nitrogen or through oxygen atom to the central metal atom/ion. If
the donor atom is N, it is written as NO2- and is called nitrito (N) and if it is O, it is written as ONO- and is
called nitrito(O). Similarly, SCN– ion can co-ordinate either through sulphur atom (←SCN – thiocyanato) or
through nitrogen atom (←NCS – isothiocyanato).
 ii) Chelating Ligands: Di- or polydentate ligands can bind to the central atom through two or more
donor atoms and form ring complexes. Such complexes are called chelates and such types of ligands are
said to be chelating ligands. Complexes containing chelating ligands are more stable than those containing
unidentate ligands. For e.g. the complex [Co(en)3]3+ is a chelate and ethane-1,2-diamine (en) is a chelating
ligand.
4. Denticity: The number of donor atoms of a particular ligand that are directly bonded to the central atom
is called denticity. For unidentate ligands, the denticity is 1, for didentate ligands it is 2 and so on.
5. Co-ordination number: The co-ordination number (C.N) of a metal ion in a complex is the total
number of ligand donor atoms to which the metal is directly bonded. It is determined only by the
number of sigma bonds formed by the ligand with the central atom/ion.
For example, in the complex ion [PtCl6]2– the co-ordination number of Pt is 6 and in [Ni(NH3)4]2+, the
co-ordination number of Ni is 4. Similarly, in the complex ions, [Fe(C2O4)3]3– and [Co(en)3]3+, the co-
ordination number of both Fe and Co, is 6 because C2O42– and en (ethane-1,2-diamine) are bidentate
ligands. Generally, the co-ordination number of most of the complexes is 2, 4 or 6.
6. Co-ordination sphere: The central atom/ion and the ligands attached to it are enclosed in square
bracket and is collectively termed as the co-ordination sphere. The ionisable groups are written
outside the bracket and are called simple ions or counter ions. For example, in the complex K4[Fe(CN)6],
the coordination sphere is [Fe(CN)6]4– and the counter ion is K+.
7. Co-ordination polyhedron: The spatial arrangement of the ligands around the central atom/ion defines a
co-ordination polyhedron about the central atom. The most common co-ordination polyhedra are
octahedral, square planar and tetrahedral. For example, [Co(NH3)6]3+ is octahedral, [Ni(CO)4] is tetrahedral
and [PtCl4]2– is square planar.
8. Oxidation number of central atom: The oxidation number of the central atom in a complex is defined as
the residual charge on it, if all the ligands are removed along with their electron pairs that are shared with
the central atom. The oxidation number is represented by a Roman numeral in simple brackets. For
example, oxidation number of copper in [Cu(CN)4]3– is +1 and it is written as Cu(I).
9. Homoleptic and Heteroleptic complexes: Complexes which contain only one type of ligand are called
homoleptic complexes. E.g.: [Co(NH3)6]3+, [Fe(CN)6]4- etc.
Complexes which contain more than one type of ligands are called heteroleptic complexes.
e.g., [Co(NH3)4Cl2]+, [Cu(NH3)2Cl2] etc.
IUPAC Nomenclature of Co-ordination Compounds
The following rules are used while naming co-ordination compounds:
(i) The cation is named first in both positively and negatively charged co-ordination entities.
(ii) The ligands are named in alphabetical order before the name of the central atom/ion.
(iii) Names of the anionic ligands end in –o, those of neutral and cationic ligands are the same except „aqua‟
for H2O, „ammine‟ for NH3, „carbonyl‟ for CO and „nitrosyl‟ for NO.
(iv) Prefixes mono, di, tri, etc., are used to indicate the number of individual ligands in the co-ordination
entity. When the names of the ligands include a numerical prefix, then the terms bis (for 2 such ligands), tris
(for 3), tetrakis (for 4) are used. Here the name of the ligand is placed in simple bracket.
(v) Oxidation state of the metal is indicated by Roman numeral in simple bracket.
(vi) If the complex ion is a cation, the central atom is named same as the element. If the complex ion is an
anion, the name of the metal ends with the suffix –ate. For example ferrate for iron, cobaltate for cobalt,
zincate for Zn etc.
(vii) The neutral complexes are named similar to cationic complexes.
Name the following:
Complex IUPAC Name
K3[Fe(CN)6] Potassium hexacyanidoferrate(III)
K2[Zn(OH)4] Potassium tetrahydroxidozincate(II)
 Na2[PdCl4] Sodium tetrachloridopalladate(II)
[Ni(CO)4] Tetracarbonylnickel(0)
K3[Fe(C2O4)3] Potassium trioxalatoferrate(III)
[Co(NH3)6]Cl3 Hexaamminecobalt(III) chloride
[Co(NH3)5Cl]Cl2 Pentaamminechloridocobalt(III) chloride
[Pt(NH3)2Cl(NH2CH3)]Cl Diamminechloridomethanamineplatinum(II) chloride
[Co(NH3)5(CO3)]Cl Pentaamminecarbonatocobalt(III) chloride
[Pt(NH3)2Cl(NO2)] Diamminechloridonitrito-N-platinum(II)
[CoCl2(en)2]Cl Dichloridobis(ethane-1,2-diamine)cobalt(III) chloride
Hg[Co(SCN)4] Mercury tetrathiocyanatocobaltate(III)

Formulas of Mononuclear Co-ordination Entities

The following rules are used while writing the formulas:
(i) The central atom is listed first.
(ii) The ligands are then listed in alphabetical order. In the case of abbreviated ligand, the first letter of the
abbreviation is used for alphabetical order.
(iii) The formula for the entire coordination entity is enclosed in square brackets. When ligands are
polyatomic, their formulas are enclosed in bracket.
(iv) There should be no space between the ligands and the metal within a coordination sphere.
(v) For complex ions, the charge is indicated outside the square brackets as a right superscript with the
number before the sign.
(vi) The charge of the cation(s) is balanced by the charge of the anion(s).

Write the formulas for the following complexes:

Name of the complex Formula
Tetraammineaquachloridocobalt(III) chloride [Co(NH3)4(H2O)Cl]Cl2
Potassium tetrahydroxidozincate(II) K2[Zn(OH)4]
Dichloridobis(ethane-1,2-diamine)cobalt(III) [CoCl2(en)2]+
Potassium trioxalatoaluminate(III) K3[Al(C2O4)3]
Potassium tetracyanidonickelate(II) K2[Ni(CN)4]
Dichloridobis(ethane–1,2–diamine)platinum(IV) nitrate [PtCl2(en)2](NO3)2
Iron(III) hexacyanidoferrate(II) Fe4[Fe(CN)6]3
Amminebromidochloridonitrito-N-platinate(II) [Pt(NH3)(Br)(Cl)(NO2)]–

Isomerism in Co-ordination Compounds

Compounds that have the same molecular formula but different structural formula or spatial
arrangement of atoms are called isomers and the phenomenon is called isomerism. Isomers differ in
physical or chemical properties. The isomerism shown by co-ordination compounds are broadly divided into
two – structural isomerism and stereo isomerism.
I) Structural Isomerism
These are isomers which differ in the structural arrangement of ligands around the central atom. They
are of four types:
1) Ionisation Isomerism: It arises due to the inter change of ions between the inside and outside of the
co-ordination sphere. They give different types of ions in aqueous solution. In order to show this
isomerism, the ion outside the co-ordination sphere can also act as ligand.
E.g.: [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4, [Pt(NH3)3Cl]Br and [Pt(NH3)3Br]Cl
2) Solvate isomerism: It arises due to the difference in the no. of solvent molecule which are directly
bonded to the metal ion as ligand. It is similar to ionisation isomerism. If water is the solvent, this
isomerism is also known as „hydrate isomerism‟.
An example is [Cr(H2O)6]Cl3 (violet) and its solvate isomer [Cr(H2O)5Cl]Cl2.H2O (grey-green).
3) Linkage isomerism: It arises in a co-ordination compound containing ambidentate ligand, which can
bind to the central atom through more than one donor atoms. For example complexes containing
thiocyanate ligand, SCN–, may bind either through nitrogen to give M–NCS or through sulphur to give M–
SCN. Another e.g. is [Co(NH3)5(ONO)]Cl2, in which the nitrite ligand is bound through oxygen (–ONO), and
[Co(NH3)5(NO2)]Cl2 in which the nitrite ligand is bound through nitrogen (–NO2).
4) Co-ordination Isomerism: If both anionic and cationic parts of a complex are in complex form, the
isomerism arises due to the interchange of ligands between cationic and anionic entities. This type of
isomerism is called co-ordination isomerism. An example is [Co(NH3)6][Cr(CN)6], in which the NH3 ligands
are bound to Co3+ and the CN– ligands to Cr3+ and [Cr(NH3)6][Co(CN)6], the NH3 ligands are bound to Cr3+
and the CN– ligands to Co3+.

II) Stereoisomerism
These are isomers which differ only in the spatial arrangement of ligands around the central atom. They
have same atom to atom bond. These are of two types:
(i) Geometrical isomerism (ii) Optical isomerism
i) Geometrical Isomerism: This type of isomerism is shown by complexes. It arises due to the
different possible geometric arrangements of the ligands around the central atom. Isomer in which the
same ligands are on the same side of the central metal atom is called cis isomer and the isomer in which
the same ligands are on the opposite side is called trans isomer.
This isomerism is mainly found in heteroleptic complexes with co-ordination numbers 4 (square
planar complexes) and 6 (octahedral complexes). Square planar complexes with formula [MX 2L2] (X
and L are unidentate ligands) can show this isomerism. E.g.: [Pt(NH3)2Cl2]

Square planar complexes of the type MABXL (where A, B, X, L are unidentate ligands) show three
geometrical isomers-two cis and one trans.
Octahedral complexes with formula [MX2L4] can also show this type of isomerism. Here the
two ligands X may be oriented cis or trans to each other.
e.g.: [Co(NH3)4Cl2]+

This type of isomerism also arises when bidentate ligands (L – L) are present in complexes with
formula [MX2(L – L)2] e.g.: [Co (en)2Cl2]+
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cis-Dichloridobis(ethane-1,2-diamine)cobalt(III) trans-Dichloridobis(ethane-1,2-diamine)cobalt(III)
Fac-mer isomerism: It is a type of geometrical isomerism occurs in octahedral co-ordination entities of the
type [Ma3b3]. If similar ligands occupy three adjacent positions of an octahedral face, it is called facial
(fac) isomer. When the positions are around the meridian of the octahedron, it is called meridional
(mer) isomer. Eg. [Co(NH3)3(NO2)3].

Tetrahedral complexes do not show geometrical isomerism because in a tetrahedron all the positions are
equivalent. So the relative positions of the ligands attached to the central metal atom are the same with
respect to each other.
ii) Optical Isomerism
Optical isomers are mirror images that cannot be superimposed on one another. These are also
called enantiomers. The molecules or ions that cannot be superimposed are called chiral.
There are two forms of optical isomers - dextro (d) and laevo (l) depending on the direction they
rotate the plane of polarised light in a polarimeter. The isomer which rotates the plane polarized light
towards right are called dextro (d) isomer and that rotates to left are called laevo(l) isomer.
Optical isomerism is common in octahedral complexes involving bidentate ligands.
In a co-ordination entity of the type [PtCl2(en)2]+, only the cis-isomer shows optical activity. The
trans- isomer has a plane of symmetry and is optically inactive.

Another e.g. is [Co(en)3]3+

 Theories of Co-ordination Compounds
1. Werner’s Co-ordination Theory
The first theory related to co-ordination compounds was proposed by Alfred Werner. He studied
the aminocomplexes of Co, Pt etc. and proposed the following postulates:
1) Every metal has two types of valencies – primary (10) valency and secondary (20) valency. Primary
valency is ionisable, while secondary valency is non-ionisable.
2) Primary valency is denoted by doted lines, while secondary valency is denoted by thick lines.
3) Primary valency gives the oxidation state of the metal, while secondary valency gives the co-
ordination number of the metal.
4) Primary valency is always satisfied by –ve ions, while secondary valency may be satisfied by –ve ions
or neutral molecules.
5) Every metal has a fixed number of secondary valencies. In order to satisfy this requirement, some –
ve ions may perform dual character – i.e., they act as primary and secondary valencies
simultaneously.
6) The primary valencies are non-directional, while the secondary valencies are directional. i.e. they are
directed to some fixed positions in space.
7) Since secondary valencies are directional, co-ordination compounds have a definite geometry and
they show isomerism.
Demerits: Werner could not explain why only certain elements form co-ordination compounds. Also he
could not explain the directional nature of bonds in co-ordination compounds and their magnetic and
optical properties.
In order to explain the above properties, many theories such as Valence Bond Theory (VBT),
Crystal Field Theory (CFT), Ligand Field Theory (LFT) and Molecular Orbital Theory (MOT) are proposed.
2. The Valence Bond Theory (VBT)
This theory was put forward by Linus Pauling. The important postulates of this theory are:
1) In co-ordination compounds, the central metal atom/ion provides some vacant orbitals in order to
accommodate the electrons donated by the ligands. The number of vacant orbitals formed is equal
to the co-ordination number of the metal atom.
2) The vacant orbitals of the metal undergo hybridisation to form a set of new orbitals called hybrid
orbitals. The type of hybridisation gives the shape of the compound.
3) Tetrahedral, square planar and octahedral complexes are formed as a result of sp3, dsp2 and d2sp3
(sp3d2) hybridisation respectively.
4) Each ligand should contain at least one pair of electron.
5) The vacant hybrid orbitals of the metal overlap with the filled orbitals of the ligands to form ligand
– metal co-ordinate bond.
6) If a complex contains unpaired electron, it is paramagnetic and if it contains only paired electron, it
is diamagnetic.
Applications of VBT
It is usually possible to predict the geometry of a complex from the knowledge of its magnetic
behaviour on the basis of the valence bond theory.
E.g.: 1) [Co(NH3)6]3+
Here the central atom Cobalt is in +3 oxidation state.
27Co – [Ar]3d7 4s2
 Co3+ – [Ar]3d6 4s04p0

In this complex, the co-ordination number of Co is 6 and hence the no. of vacant orbitals required = 6.
In presence of the ligand NH3, the electrons in 3d level get paired. Now the two 3d orbitals, one 4s orbital
and three 4p orbitals undergo d2sp3 hybridization to form 6 new orbitals. Since the hybridisation is d 2sp3, the
shape of the molecule is octahedral.

Six pairs of electrons, one from each NH3, occupy these six hybrid orbitals.

Due to the absence of unpaired electron, the complex is diamagnetic.

In the formation of this complex, since the inner d orbitals (3d) are used for hybridization, the
complex is called an inner orbital or low spin or spin paired complex.
2) [CoF6]3-
Here the central atom cobalt is in +3 oxidation state.
27Co – [Ar]3d7 4s2
Co3+ - [Ar]3d6 4s04p0

In this complex the co-ordination number of Co is 6 and hence the no. of vacant orbitals required = 6.
In presence of the ligand F –, the electrons in 3d level do not get paired. So, one 4s orbital, three 4p orbitals
and two 4d orbitals undergo sp3d2 hybridization to form 6 new orbitals. Since the hybridisation is sp3d2, the
shape of the complex is octahedral.

These hybrid orbitals overlap with the filled orbitals of the ligand to form ligand– metal co-ordinate bond.

Due to the presence of 5 unpaired electrons, it is highly paramagnetic.

Since the outer d-orbitals (4d ) are used for hybridisation (sp3d2), this complex is called outer orbital or high
spin or spin free complex.
3) [Ni(CN)4]2-
Here the central atom Ni is in +2 oxidation state.
28Ni – [Ar]3d84s2
Ni 2+ - [Ar]3d8 4s04p0
 In this complex the co-ordination number of Ni is 4 and hence the no. of vacant orbitals required = 4.
Even though it contains 4 orbitals, in presence of the ligand CN -, the electrons in 3d level get paired.
Now the one 3d orbital, one 4s orbital and two 4p orbitals undergo dsp 2 hybridization to form 4
new orbitals.

Four pairs of electrons, one from each CN- ions, occupy these four hybrid orbitals.

Thus, the complex has square planar geometry and is diamagnetic, because of the absence of unpaired
electron.
4) [NiCl4]2- : Here the central atom Ni is in +2 oxidation state.
28Ni – [Ar]3d84s2
Ni 2+ - [Ar]3d8 4s04p0

In this complex the co-ordination number of Ni is 4 and hence the no. of vacant orbitals required = 4.
In presence of the ligand Cl-, the electrons in 3d level do not get paired.
Now the one 4s orbitals and three 4p orbitals undergo sp3 hybridization to form 4 new orbitals.

These four hybrid orbitals are occupied by the four electron pairs from each Cl- ligands.

Thus, the complex has tetrahedral geometry and is paramagnetic because of the presence of unpaired
electron.

Magnetic Properties of Co-ordination Compounds

By knowing the magnetic moment, we can predict the geometry of complexes. For e.g. [Mn(CN)6]3–
has magnetic moment of two unpaired electrons while [MnCl6] 3– has a paramagnetic moment of four
unpaired electrons. [Fe(CN) 6] 3– has magnetic moment of a single unpaired electron while [FeF6] 3– has a
paramagnetic moment of five unpaired electrons. [CoF6]3– is paramagnetic with four unpaired electrons
while [Co(C2O4) 3] 3– is diamagnetic. This can be explained by valence bond theory in terms of formation of
inner orbital and outer orbital co-ordination entities. [Mn(CN) 6] 3–, [Fe(CN) 6] 3– and [Co(C2O4) 3] 3– are
inner orbital complexes involving d2sp3 hybridisation. Also [Mn(CN) 6] 3– and [Fe(CN) 6] 3– are paramagnetic
while [Co(C2O4) 3] 3– is diamagnetic. On the other hand, [MnCl6] 3–, [FeF6] 3– and [CoF6] 3– are outer
orbital complexes involving sp3d2 hybridisation and are paramagnetic corresponding to four, five and four
unpaired electrons.
 Limitations of Valence Bond Theory
Even though the VB theory explains the formation, structure and magnetic behaviour of co-
ordination compounds, it has the following limitations:
(i) It involves a large number of assumptions.
(ii) It does not give quantitative interpretation of magnetic data of complexes.
(iii) It does not explain the colour exhibited by co-ordination compounds.
(iv) It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of co-
ordination compounds.
(v) It does not make exact predictions regarding the tetrahedral and square planar structures of 4-co-
ordinated complexes.
(vi) It does not distinguish between weak and strong ligands.

3. Crystal Field Theory

The crystal field theory (CFT) is an electrostatic model which considers the metal-ligand bond as
purely ionic. Here the ligands are treated as point charges in case of anions or as dipoles in case of
neutral molecules. The five d orbitals in an isolated gaseous metal atom/ion have same energy, i.e., they
are degenerate. This degeneracy is maintained if a spherically symmetrical field of negative charges
surrounds the metal atom/ion. But when this negative field is due to ligands in a complex, the
degeneracy of the d orbitals is lost. It results in splitting of the d orbitals. This splitting of d-orbitals is
termed as Crystal field splitting and it depends on the nature of the field.
(a) Crystal field splitting in octahedral co-ordination entities (Octahedral splitting)
In an octahedral co-ordination entity, there are six ligands surrounding the metal atom/ion and they
are along the axis of the octahedron. So the repulsion between the electrons in metal d orbitals and the
electrons (or negative charges) of the ligands is greater for thexd- 2y 2 and dz 2 orbitals, which are pointing
towards the axes, than the dxy, dyz and dxz orbitals, which are directed between the axes. So the energy of
22
xthe
-y d and
z d 2 orbitals (called
g e orbitals) will be raised and that of the
xy d yz
, d and xz
d orbitals (called t2g
orbitals) will be lowered. Thus, the degeneracy of the d orbitals has been removed. This splitting of the
degenerate levels due to the presence of ligands in a definite geometry is termed as crystal field splitting
and the energy separation is denoted by Δo (the subscript o is for octahedral). Thus, the energy of the
two eg
orbitals will increase by 3/5 Δo and that of the three t2g orbitals will decrease by 2/5 Δo.

Strong field ligands produce large splitting whereas weak field ligands produce small splitting of d
orbitals.
Filling of electrons
For d1, d2 and d3 coordination entities, the d electrons occupy the t2g orbitals singly in accordance with
the Hund‟s rule. For d4 ions, two possible patterns of electron distribution arise:
(i) the fourth electron could either enter the t2g level and pair with an existing electron, or
(ii) it could enter into the eg level.
 Here the electron distribution depends on the relative magnitude of the crystal field splitting (Δo)
and the pairing energy (P). If Δo < P, the fourth electron enters one of the eg orbitals giving the
configuration
3 1
t2ge g. Ligands for which Δo < P are known as weak field ligands and form high spin complexes.
If Δo > P, the fourth electron occupy a t2g orbital with configuration t2g4eg0. Ligands for which Δo < P
are known as strong field ligands and form low spin complexes.
b) Crystal field splitting in Tetrahedral co-ordination entities (Tetrahedral splitting)
A tetrahedron can be considered as a cube in which only alternate corners are occupied by ligands
and the metal ion is at the centre of the cube. The dx2-y2 and dz2 orbitals (called e orbitals) point towards
the centre of each faces of the cube and the dxy, dyz and dxz orbitals (called t2 orbitals) point towards the
edge centre of the cube. Since the ligands are approaching through the corners, there is no direct
interaction between the ligands and the d-orbitals. However, the „t2‟ orbitals lie closer to the ligands than
the „e‟ orbitals. As a result the energy of the „t2‟ orbitals increases and that of „e‟ orbitals decreases. So the
d orbitals split into two – triply degenerate „t2’ orbitals with higher energy and doubly degenerate „e’

orbitals with lower energy.

The splitting in tetrahedral field is less than that in octahedral field. It is found that Δt = 4/9 Δo.
This is because in tetrahedral field, there are only four ligands (but in octahedral field, the number of
ligands is six) and there is no direct interaction between the ligands and the d-orbitals.
Spectrochemical series
It is a series in which the ligands are arranged in the increasing order of their field strength. The
series is: I-< Br- < SCN-< Cl- < S2- < F- < OH- < C O 2- < H2O < NCS– < edta4- < NH3 < en < CN– < CO.
It is an experimentally determined series based on the absorption of light by complexes with different
ligands.
Colour in Coordination Compounds
Most of the complexes of transition metals are coloured. This can be explained in terms of the crystal
field theory. In presence of the ligands, the crystal field splitting occurs. So the electrons from lower d level
(t2g level) can excite to higher d level (eg level). For this some energy is required, which is absorbed from the
white light. The colour of the complex is complementary to that which is absorbed. Thus according to
crystal field theory the coloUR of the coordination compoUNDs is DUE to d-d transition of the electron.
For example, the complex [Ti(H2O)6]3+ is violet in colour. This is an octahedral complex where the
single electron (Ti3+ is a 3d1 system) in the metal d orbital is in the t2g level in the ground state of the
complex. The next higher state available for the electron is the empty eg level. If light corresponding to the
energy of yellow-green region is absorbed by the complex, it would excite the electron from t2g level to the
eg level.
Consequently, the complex appears violet in colour.
In the absence of ligand, crystal field splitting does not occur and hence the substance is colourless.
For example, when [Ti(H2O)6]3+ is heated it becomes colourless. Similarly, anhydrous CuSO4 is white, but
CuSO4.5H2O is blue in colour.
The colour of a complex depends on the strength of ligand and the nature of the field.
 Limitations of Crystal Field Theory
1. From the assumptions, that the ligands are point charges, it follows that anionic ligands should exert
the greatest splitting effect. But the anionic ligands actually are found at the low end of the
spectrochemical series.
2. It does not take into account the covalent character of bonding between the ligand and the central
atom.
Stability of Coordination Compounds
The stability of a complex in solution refers to the degree of association between the metal ion and
ligands in the state of equilibrium. The magnitude of the (stability or formation) equilibrium constant for the
association, quantitatively expresses the stability.
For a reaction of the type:
M + 4L → ML4, β = [ML4]/[M][L]4
As the value of the stability constant increases, the stability of the complex also increases.
The above reaction can be considered to take place in 4 steps:
M + L → ML, K1 = [ML]/[M][L]
ML + L → ML2, K2 = [ML2]/[ML][L]
ML2 + L → ML3, K3 = [ML3]/[ML2][L]
ML3 + L → ML4, K4 = [ML4]/[ML3][L]
Where K1, K2,K3 and K4 are referred to as stepwise stability constants.
The overall stability constant, β = K1 × K2 × K3 × K4
The stability of a complex depends on the following factors:
1. The nature of the metal ion: Greater the charge to radius of the metal ion, greater will be the stability
of the complex.
2. Nature of the ligand: The greater the basic strength of the ligand, the greater will be the stability of
the complex.
3. Presence of chelating ligands: increases the stability of the complex.
Bonding in Metal Carbonyls
Transition metals form a large number of homoleptic carbonyls. Eg. [Ni(CO)4], [Fe(CO)5],
[Cr(CO)6], [Co2(CO)8], [Mn2(CO)10] etc. These carbonyls have simple, well defined structures.

The metal-carbon bonds in metal carbonyls possess both  and  character. The M–C  bond is
formed by the donation of lone pair of electrons on the carbonyl carbon into a vacant orbital of the metal.
 The M–C  bond is formed by the donation of a pair of electrons from a filled d orbital of metal into the
vacant anti-bonding * orbital of carbon monoxide. Thus the metal to ligand bonding creates a synergic
effect which strengthens the bond between CO and the metal.

Application of Co-ordination Complexes

1. In Qualitative & Quantitative Analysis: Co-ordination compounds find use in many qualitative and
quantitative chemical analyses. For e.g. Ni2+ is detected and estimated by the formation of a complex with
Dimethyl Glyoxime (DMG). The brown ring test for the detection of nitrate ion is due to the formation of
the brown complex [Fe(H2O)5NO]2+. The Ca2+ and Mg2+ ions are estimated by the formation of stable
complexes with EDTA.
2. In water treatment: The Hardness of water is estimated by simple titration with Na2EDTA (sodium salt of
EDTA). The Ca2+ and Mg2+ ions form stable complexes with EDTA. The hardness of water can be removed by
the formation of a complex with calgon (Sodium polymetaphosphate)
3. In Metallurgy: Metals like silver and gold are extracted by the formation of complexes with CN- ligands.
Gold forms the complex [Au(CN)2]- and silver forms [Ag(CN)2]- which are separated with Zn.
Similarly, co-ordination compounds also find application in the refining of some metals. For example,
impure nickel is converted to [Ni(CO)4], which is decomposed to yield pure nickel
4. Biological Applications: Co-ordination compounds are of great importance in biological systems.
Chlorophyll is a co-ordination compound of magnesium, Haemoglobin, is a co-ordination compound of
iron and Vitamin B12 (cyanocobalamine) is a co-ordination compound of cobalt.
5. In Catalysis: Co-ordination compounds are used as catalysts for many industrial processes. For e.g.
Tris(triphenylphosphine)rhodiumchloride, [(Ph3P)3RhCl] (Wilkinson catalyst), is used for the
hydrogenation of alkenes.
6. In electroplating: Articles can be electroplated with silver and gold by using the solutions of the
complexes, [Ag(CN)2]- and [Au(CN)2] - respectively as electrolytes.
7. In Photography: In black and white photography, the developed film is fixed by washing with hypo
solution which dissolves the undissociated AgBr to form a complex ion, [Ag(S2O3)2]3–.
8. In medicine: Cis-platin is used for the treatment of cancer. Excess of copper and iron in animal or plant
body are removed by the chelating ligands D–penicillamine and desferrioxime B through the formation of
co-ordination compounds. EDTA is used for the treatment of lead poisoning.

*****
 6. HALOALKANES AND HALOARENES
These are compounds containing halogen atoms attached to an alkyl or aryl group. The general
representation of haloalkanes is R-X and that of haloarenes is Ar-X [where X = F, Cl, Br, I].
Classification
I) On the basis of number of halogen atoms:
Based on this, haloalkanes and haloarenes are classified as mono, di or polyhalogen compounds.
Monohalogen compounds contain only one halogen atom, dihalocompounds contain 2 halogen atoms and
polyhalogen compounds contain more than 2 halogen atoms.
II) Compounds containing sp3 C-X bond: They include
a) Alkyl halides or haloalkanes (R-X): Here the halogen atom is directly bonded to an sp 3
hybridized C atom of an alkyl group. They are further classified as primary, secondary or
tertiary according to the nature of carbon to which halogen atom is attached. Their general
formula may be:
Primary haloalkane: R-CH2-X
Secondary haloalkane: R2CH-X
Tertiary haloalkane: R3C-X
b) Allylic halides: Here the halogen atom is bonded to an sp3 hybridized carbon atom next to a C
= C bond. E.g.: CH2=CH-CH2X
c) Benzylic halides: These are compounds in which the halogen atom is bonded to an sp3
hybridized carbon atom next to an aromatic ring. E.g.: C6H5-CH2-X
III) Compounds having sp2 C-X bond: They include
a) Vinylic halides: Here the halogen atom is directly bonded to an sp2 hybridized carbon atom of
a C=C bond. E.g.: CH2=CH-X
b) Aryl halides: Here the halogen atom is directly bonded to an sp2 hybridized carbon atom of an
aromatic ring. E.g. : C6H5-X
Nomenclature
Common name of alkyl halides is obtained by adding –yl halide to the word root (i.e. word root + yl
halide) and the IUPAC name is obtained by adding the prefix ‘halo’ to the name of the parent alkane (i.e. halo
+ alkane). Some examples are:

Compound Common Name IUPAC Name

CH3-Cl Methyl chloride Chloromethane
CH3-CH2-Br Ethyl bromide Bromoethane
CH3-CH2-CH2-Cl n-Propyl chloride 1-Chloropropane
CH3-CHCl-CH3 Isopropyl chloride 2-Chloropropane
CH3-CH2-CH2-CH2-Br N-Butyl bromide 1-Bromopropane
(CH3)3C-Cl tert-butyl 2-Chloro-2-methyl
chloride propane
C6H5-Cl Chlorobenzene Chlorobenzene
C6H5-CH2-I Benzyl iodide Iodophenylmethane
Methods of preparation
I) From alcohols:
a) By the action of concentrated halogen acids on alcohols in presence of anhydrous ZnCl2 as catalyst.
R-OH + HX an. ZnCl2 R-X + H2O
 Reactions of primary and secondary alcohols with HI require the presence of anhydrous ZnCl2, while
tertiary alcohols do not require the catalyst.
b) Alkyl chlorides are obtained by the action of PCl3, PCl5 or SOCl2 with alcohols.
3R-OH + PCl3 3 R-Cl + H3PO3
R-OH + PCl5 R-Cl + POCl3 + HCl
R-OH + SOCl2 R-Cl + SO2 + HCl
Among these methods, the reaction with thionyl chloride (SOCl2) is preferred, since the
byproducts are gases and are easily escaped from the reaction medium.
For the preparation of alkyl bromides and iodides, alcohols are treated with bromine or iodine
in presence of red phosphorus, since PBr3 and PI3 are unstable.
R-OH X2/Red P R-X (where X2 = Br2 or I2)
II) From Hydrocarbons
a) Free radical halogenation:
Alkanes react with chlorine or bromine in presence of sunlight; we get a mixture of mono, di and
polyhaloalkanes. For e.g. when methane is chlorinated in presence of sunlight (uv light), we get a mixture
of 4 products namely monochloromethane (methyl chloride, CH3-Cl), dichloromethane (methylene
chloride, CH2Cl2), trichloromethane (chloroform, CHCl3) and tetrachloromethane (carbon tetrachloride,
CCl4).
CH4 + Cl2 uv light or heat CH3Cl + CH2Cl2 + CHCl3 + CCl4
b) Electrophilic substitution:
Benzene or its derivatives when heated with Cl2 or Br2 in presence of iron or Lewis acids like
anhydrous FeCl3 (ferric chloride) or AlCl3, we get aryl chlorides or bromides.

The ortho and meta isomers can be easily separated due to their large difference in melting point.
For the preparation of aryl iodides, arenes are treated with I2 in presence of an oxidising agent like
HNO3 or HIO4 (periodic acid) to oxidise the HI formed during the reaction.
c) Sandmeyer’s reaction:
Aromatic primary amines when treated with mineral acids like HCl and sodium nitrite (NaNO2) at cold
condition (0 – 50C), an aromatic diazonium salt is formed. This reaction is called Diazotisation.
 When a diazonium salt is treated with HX in presence of cuprous halide (Cu2X2), we get a halobenzene.
This reaction is called Sandmeyer‘s reaction.

Note: If the cuprous halide is replaced by copper powder, the reaction is called Gattermann’s reaction.
For the preparation of iodobenzene, the diazonium salt is treated with potassium iodide (KI).

d) From alkene:
i) Addition of hydrogen halide (HX): Alkenes add HX (HCl, HBr or HI) to form alkyl halides. In the case of
unsymmetrical alkenes, the addition takes place according to Markownikoff’s rule. *The rule states
that “when an unsymmetrical reagent is added to an unsymmetrical alkene, the negative part of the
addendum (adding molecule) gets attached to the carbon containing lesser number of hydrogen
atoms”+.
e.g. CH3-CH=CH2 + HBr CH3-CH2-CH2Br + CH3-CHBr-CH3
(minor) (major)
ii) Addition of halogen: Alkenes add halogen to form vicinal dihalides (2 halogen atoms on adjacent C
atoms). For e.g. addition of bromine in CCl4 to an alkene results in the formation of vicinal dibromides
and also in the discharge of the reddish brown colour of Br2 in CCl4. So this is used as a test for
unsaturation.
e.g. CH2=CH2 + Br2 CCl4 CH2Br – CH2Br
(1,2-dibromoethane)
III) Halogen Exchange Reactions
a) Finkelstein reaction: Alkyl chlorides or bromides when treated with NaI in dry acetone,
alkyl iodides are formed. This reaction is known as Finkelstein reaction.
R-X + NaI R-I + NaX (where X = Cl, Br)
b) Swarts reaction: This method is used for the preparation of alkyl fluorides. Here alkyl
chloride or bromide is treated with a metallic fluoride like AgF, Hg2F2, CoF2 or SbF3, to
get alkyl fluoride.
R-X + AgF R-F + AgX (where X = Cl or Br)
R-X + CoF2 R-F + CoX2
Physical Properties Melting
and boiling points:
In haloalkanes, the C-X bond is polar due to the greater electronegativity of halogen atom. Due to
greater polarity and higher molar mass, the inter molecular forces of attraction (dipole-dipole and van der
Waals forces) are strong and so they have higher melting and boiling points than hydrocarbons of comparable
molar mass.
For the same alkyl group, the boiling points of alkyl halides decrease in the order: RI> RBr> RCl> RF. This
is because with the increase in size and mass of halogen atom, the magnitude of van der Waal forces
increases.
 The boiling points of isomeric haloalkanes decrease with increase in branching. This is because as
branching increases, the surface area of the molecule decreases. So the van der forces decreases and
hence the b.p.
Among isomeric dihalobenzenes, the para-isomers are high melting as compared to their ortho
and meta-isomers. It is due to symmetry of para-isomers that fits in crystal lattice better as compared
to ortho- and meta-isomers.
Solubility
The haloalkanes are only very slightly soluble in water. This is because they cannot form hydrogen
bonds with water (except alkyl fluorides).
CHEMICAL REACTIONS OF HALOALKANES
i) Nucleophilic Substitution Reactions:
These are reactions in which a weak nucleophile is replaced by a strong nucleophile [Nucleophiles are
electron rich species attacks at electron deficient centre]. In general these reactions can be represented by:

The important Nucleophilic substitution reactions of haloalkanes are:

1. Reaction with aqueous alkali: Haloalkanes react with aq. NaOH or KOH to form alcohols.
R-X + KOH(aq) R-OH + KX
e.g.: CH3-CH2-Br + KOH(aq) CH3-CH2-OH + KBr
2. Reaction with water: Haloalkanes react with water to form alcohols.
R-X + H2O R-OH + HX
3. Reaction with Sodium alkoxide (R-ONa) [Williamson’s ether synthesis]: Haloalkanes react with
sodium alkoxide to give ethers (R-O-R).
R-X + R-ONa R-O-R + KX
e.g.: CH3-Br + CH3-CH2-ONa CH3-O-CH2-CH3 + NaBr
4. Reaction with Sodium iodide (NaI) [Finkelstein Reaction]: Alkyl halides (Chlorides or Bromides) react
with sodium alkoxide to form alkyl iodides.
R-X + NaI R-I + NaX [X = Cl or Br]
5. Reaction with ammonia [Hoffmann’s reaction]: Alkyl halides react with alcoholic ammonia to give a
mixture of 10, 20 and 30 amines and quaternary ammonium salt.
R-X + NH3 R-NH2 + R2NH + R3N + R4N+X-
If ammonia is in excess, only primary amine is formed.
6. Reaction with KCN: Alkyl halides react with alcoholic KCN to give alkane nitriles or alkyl cyanides (R-
CN).
R-X + KCN R-CN+ KX
7. Reaction with Silver cyanide (AgCN): Alkyl halides react with AgCN to give alkyl isocyanides or carbyl
amines (R-NC).
R-X + AgCN R-NC + AgX
CN- is an ambident nucleophile. i.e. here both C and N contain lone pair of electrons and can
bind to the carbon atom of the alkyl group either through C or through N. Another e.g. is NO 2-
Reaction with KCN gives alkyl cyanides. This is because KCN is mainly ionic and gives CN- ions in
solution. So both C and N are free to donate electron pairs. But C – C bond is stronger than C – N
bond. So cyanides are formed as the major product. But AgCN is mainly covalent and only N is free to
donate an electron pair. So isocyanides are the main product.

8. Reaction with Potassium nitrite (KNO2): Alkyl halides react with KNO2 to give alkane nitrite (R-ONO).
R-X + KNO2 R-ONO + KX
 9. Reaction with Silver nitrite (AgNO2) : Alkyl halides react with AgNO2 to give nitroalkane (R-NO2)
R-X + AgNO2 R-NO2 + AgX
10. Reaction with Silver salt of carboxylic acid (Hunsdiecker reaction) : Alkyl halides react with Silver salt
of carboxylic acid (R-COOAg) to give esters (R-COOR).
R-X + R-COOAg R-COOR + AgX
11. Reduction: Alkyl halides when reduced with lithium aluminium hydride (LiAlH4) to give alkane.
R-X + [H) LiAlH4 R-H + HX
Mechanism of Nucleophilic Substitution Reactions
There are two types of mechanisms: Substitution Nucleophilic bimolecular (SN2) and Substitution
Nucleophilic unimolecular (SN1)
1. Substitution Nucleophilic Bimolecular (SN2) Mechanism:
Here the incoming nucleophile interacts with alkyl halide causing the carbon-halogen bond to break
while forming a new carbon-OH bond. These two processes take place simultaneously in a single step and no
intermediate is formed. As the reaction proceeds, the bond between the nucleophile and the carbon atom
starts forming and the bond between carbon atom and leaving group (the halogen atom) weakens. In the
case of optically active alkyl halides, during this process, the configuration of carbon atom inverts and hence
this process is called as inversion of configuration. In the transition state, the carbon atom is simultaneously
bonded to five atoms and therefore is unstable.
An example is the reaction between CH3Cl and hydroxide ion to yield methanol and chloride ion. This
reaction follows a second order kinetics, i.e., the rate depends upon the concentration of both the reactants.
Mechanism of this reaction is:

Since this mechanism requires the approach of the nucleophile to the carbon bearing the leaving group, the
presence of bulky substituents on or near the carbon atom decreases the rate of this reaction. Thus the order
of reactivity of alkyl halides towards SN2 reaction is: Primary halide > Secondary halide > Tertiary halide.
2. Substitution nucleophilic unimolecular (SN1):
SN1 reactions are generally carried out in polar protic solvents (like water, alcohol, acetic acid, etc.). Here
the reaction occurs in two steps. In the first step, the C—X bond undergoes slow cleavage to produce a
carbocation and a halide ion. In the second step, the carbocation is attacked by the nucleophile to form the
product. Here first step is the slowest and reversible. So it is the rate determining step. Since this step
contains only one reactant, it follows first order kinetics.
E.g.: The reaction between tert-butyl bromide and hydroxide ion to give tert-butyl alcohol.

This reaction occurs in two steps. In step I, the polarised C—Br bond undergoes slow cleavage to produce a
carbocation and a bromide ion. The carbocation thus formed is then attacked by nucleophile in step II to form
the product.
 Thus in SN1 reaction, there is an intermediate called carbocation. The greater the stability of the
carbocation, the greater will be the rate of the reaction. In case of alkyl halides, 30 alkyl halides undergo SN1
reaction very fast because of the high stability of 30 carbocations. So the order of reactivity of alkyl halides
towards SN1 reaction is: 30 > 20 > 10.
Allylic and benzylic halides show high reactivity towards the SN1 reaction. This is because of the higher
stability of the carbocation formed. The allyl and benzyl halides are stabilized through resonance as follows:

Allyl carbocation

Benzyl Carbocation
For both the mechanisms, the reactivity of halides follows the order: R–I> R–Br>R–Cl>>R–F.
Differences between SN1 and SN2 reactions

SN1 Reaction SN2 Reaction

Proceeds in 2 steps
An intermediate (carbocation) is formed
Order of the reaction is 1
For optically active compounds, the reaction
proceeds through retention of configuration.
The order of reactivity of alkyl halide is 30 > 20 > 10
Proceeds in a single step
No intermediate is formed
Order is 2
For optically active compounds, the reaction
proceeds through inversion of configuration.
The order of reactivity of alkyl halide is 10 > 20 > 30

Stereochemical Aspects of nucleophilic substitution Reactions

Plane Polarised light
It is a light beam in which the particles vibrate in only one direction. It is produced by passing ordinary
light beam through a Nicol prism. When such a light beam is passed through solutions of certain compounds,
they rotate the plane of polarisation. Such compounds are called optically active compounds. The angle by
which the plane polarised light is rotated is called optical rotation, which is measured by an instrument called
polarimeter. If a compound rotates the plane polarised light towards right (i.e. clock-wise direction), it is called
dextro rotatory or d-form or + form and if it rotates the plane polarised light towards left (i.e. anticlock- wise
direction), it is called laevo rotatory or l-form or – form. The d and l form of a compound are called optical
isomers and the phenomenon is called optical isomerism.
Molecular asymmetry and Optical isomerism
Optical isomerism is due to molecular asymmetry. If all the 4 valencies of a carbon atom are satisfied by 4
different groups, it is called asymmetric carbon or chiral carbon or stereo centre. The resulting molecule is
called asymmetric molecule. Such molecules are non-super imposable to their mirror images and are called
chiral molecules and this property is known as chirality. The molecules which are super imposable to their
mirror images are called achiral molecules.
A chiral carbon is denoted by an asteric (*) mark.
*
e.g.: 2-Chlorobutane [CH3 – CHCl – CH2 – CH3]
Here the 2nd C is chiral, since all the four valencies of this C are satisfied by 4 different groups.
*
Other examples: 2-butanol [CH3 – CHOH –CH2 – CH3]
*
2-bromopropanoic acid [CH3 – CHBr – COOH]
*
Lactic acid [CH3 – CHOH – COOH]
Enantiomers
The stereo isomers related to each other as non-super imposable mirror images are called
enantiomers. They have identical physical properties. They differ only in the direction of rotation of
the plane polarised light. If one of the enantiomers is dextro rotatory, the other will be laevo rotatory.
Racemic mixture
An equimolar mixture of d and l form of a compound has zero optical rotation and such a mixture
is called racemic mixture or racemic modification. It is denoted by dl or (+). Here the rotation due to
one isomer is cancelled by the rotation due to the other isomer. The process of conversion of an
enantiomer in to a racemic mixture is called racemisation.
Retention and Inversion of configuration
If during a chemical reaction, there is no change in the spatial arrangement of bonds to an
asymmetric centre, we can say that the reaction proceeds through retention of configuration. (Or,
preservation of the integrity of configuration of a compound is termed as retention).

In general, if during a chemical reaction, no bond to the stereo centre is broken, the product will have the
same configuration as that of the reactant. Such reactions always proceed through retention of configuration.
E.g. Reaction of 2-Methyl-1-butanol with HCl.

If during a chemical reaction, the incoming group is attached to a position opposite to that of the
leaving group, the configuration of the resulting product is inverted and we can say that the reaction
proceeds through inversion of configuration.
a a
c Y- Y
X b
b c
Nucleophilic Substitution and Optical Activity
In the case of optically active alkyl halides, the product formed as a result of SN2 mechanism has the
inverted configuration. This is because here the nucleophile attacks on the side opposite to that of the
halogen atom.
 (-) 2-Bromooctane (+) octan-2-ol

In the case of optically active alkyl halides, SN1 reactions follow through racemisation. Here the
intermediate carbocation formed is sp2 hybridised and hence it is planar. So the attack of nucleophile can
take place from either side resulting in a mixture of products with opposite configuration.
e.g. Hydrolysis of optically active 2-bromobutane results in the formation of (+) 2-butanol, a racemic mixture.

CH3 – CHBr – CH2 – CH3 OH– CH3 – CHOH – CH2 – CH3 + Br–
Step – I

Step – II

(-) 2-Butanol Planar carbocation (+) 2-butanol

ii) Elimination Reactions
Alkyl halides having β-hydrogen atom when treated with alcoholic solution of KOH, they undergo
elimination of one hydrogen halide molecule (dehydrohalogenation) to form alkenes. Since β-hydrogen
atom is eliminated, the reaction is also called β-elimination.
e.g. : CH3-CH2-Br + KOH (alc) CH2 = CH2 + KBr + H2O
[Carbon on which halogen atom is directly attached is called α-carbon and the carbon atom adjacent to this carbon is
called β-carbon.]
If there is possibility of formation of more than one alkene during dehydrohalogenation reaction, the
major product is selected by Zaitsev (Saytzeff) rule. The rule states that ―in dehydrohalogenation
reactions, if there is possibility of formation of more than one alkene the preferred product is that
alkene which contains greater number of alkyl groups attached to the doubly bonded carbon atoms.‖
So if 2-bromobutane is treated with alcoholic KOH, 2-butene is formed as the major product.
CH3-CH2-CHBr-CH3 + KOH (alc) CH3-CH2-CH=CH2 + CH3-CH=CH-CH3
2-Bromobutane 1-butene (minor) 2-butene (major)
iii) Reaction with metals
a) Alkyl halides react with Mg metal in ether medium to form alkyl magnesium halide (an
organometallic compound) commonly called Grignard reagent.
R-X + Mg ether RMgX [Grignard reagent]
CH3-CH2-Br + Mg ether CH3-CH2MgBr
Grignard reagent is an example for organometallic compound. These are compounds in which carbon atom of an
organic compound is directly bonded to metal atom. Other examples are tetraethyl lead, trimethyl aluminium
etc.
In the Grignard reagent, the carbon-magnesium bond is covalent but highly polar and the magnesium
halogen bond is ionic.
 Grignard reagents are highly reactive and react with any source of proton (water, alcohols,
amines etc) to give hydrocarbons (alkanes). It is therefore necessary to avoid even traces of moisture
from a Grignard reagent.
R-MgX + H2O R-H +MgX(OH)
R-MgX + R-OH R-H +MgX(OR)
R-MgX + NH3 R-H +MgX(NH2)
b) Wurtz reaction: Alkyl halides react with sodium in dry ether to give alkanes with double
the number of carbon atoms. This reaction is known as Wurtz reaction.
R-X +2 Na +X-R R-R + 2NaX
CH3-Br + 2Na + Br-CH3 CH3-CH3 + 2NaBr
Reactions of Haloarenes
1. Nucleophilic Substitution Reaction:
Aryl halides are less reactive towards Nucleophilic substitution reactions due to the following
reasons:
i) Due to resonance effect: In haloarenes, the electron pairs on halogen atom are in conjugation
with π-electrons of the ring and the following resonating structures are possible.

Due to resonance, the C—X bond acquires a partial double bond character. Since it is difficult to
break a double bond, the replacement of halogen atom by other atoms is not easy. So haloarenes
are less reactive towards nucleophilic substitution reactions.
ii) Due to the difference in hybridisation of carbon atom in C—X bond: In haloalkane, the
halogen atom is attached to an sp3 hybridised carbon while in haloarene, it is attached to an sp 2
hybridised carbon. Due to the greater s-character of sp2 hybridised carbon, it is more electronegative
and can hold the electron pair of C—X bond more tightly than sp3-hybridised carbon in haloalkane. So
the C – X bond in haloarene is shorter than that in haloalkane. Since it is difficult to break a shorter
bond than a longer bond, haloarenes are less reactive than haloalkanes towards Nucleophilic
substitution reaction.
iii) Due to the instability of phenyl cation: In haloarenes, the phenyl cation formed as a result of
self-ionisation will not be stabilized by resonance and therefore, S N1 mechanism does not occur.
iv) Due to the repulsion between nucleophile and electron rich benzene ring: Because of the
possible repulsion, it is less likely for the electron rich nucleophile to approach electron rich arenes.
Replacement by hydroxyl group (Conversion to phenol)
Chlorobenzene when heated with aqueous sodium hydroxide solution at a temperature of
623K and a pressure of 300 atmospheres followed by acidification, we get phenol.
The presence of an electron withdrawing group (-NO2) at ortho- and para-positions increases the reactivity of
haloarenes.

The effect is more when -NO2 group is present at ortho and para- positions. However, no effect
on reactivity is observed by the presence of electron withdrawing group at meta-position.
2. Electrophilic substitution reactions:
Haloalkanes are resonance stabilized as follows:

In the resonating structures, the electron density is greater on ortho-para positions. So the electrophile
enters at these positions and hence halo group is an ortho-para directing group. Also because of its electron
withdrawing Inductive effect, the halogen atom has a tendency to withdraw electrons from the benzene ring.
So it is a deactivating group. Hence the electrophilic substitution reactions in haloarenes occur slowly and
require more vigorous conditions.
i) Halogenation: Haloalkanes react with halogen (Chlorine or bromine) in presence of anhydrous
ferric chloride to form o-dichlorobenzene and p-dichlorobenzene.
ii) Nitration: On nitration using Conc. HNO3 and Conc. H2SO4, chlorobenzene gives p-
nitrochlorobenzene as the major product.

iii) Sulphonation: On sulphonation using Conc. H2SO4, chlorobenzene gives p-

chlorobenzenesulphonic acid as the major product

iv) Friedel – Crafts Alkylation: Chlorobenzene when treated with methyl chloride (CH3-Cl) in presence
of anhydrous AlCl3, we get p-chlorotoluene as the major product.

v) Friedel – Crafts Acylation: Chlorobenzene when treated with acetyl chloride (CH3-CO-Cl) in
presence of anhydrous AlCl3, we get p-chloroacetophenone as the major product.

3. Reaction with metals:

a) Wurtz-Fittig reaction: When a mixture of alkyl halide and aryl halide is treated with
sodium in dry ether, an alkyl arene is formed and this reaction is called Wurtz-Fittig reaction.

For e.g. when Chlorobenzene is treated with methyl chloride in presence of metallic sodium in
ether medium, we get toluene.
C6H5-Cl + 2Na + CH3-Cl ether C6H5-CH3 + 2NaCl
Chlorobenzene Toluene
 b) Fittig reaction: Aryl halides when treated with sodium in dry ether, we get diaryls
(diphenyls). This reaction is called Fittig reaction.

Diphenyl
Polyhalogen compounds
Carbon compounds containing more than one halogen atom are usually referred to as polyhalogen
compounds. Some polyhalogen compounds are:
1. Dichloromethane (Methylene chloride, CH2Cl2): It is widely used as a solvent, as a paint remover, as a
propellant in aerosols, and as a process solvent in the manufacture of drugs. It is also used as a metal
cleaning and finishing solvent.
2. Trichloromethane (Chloroform, CHCl3): It is used as a solvent for fats, alkaloids, iodine and other
substances. The major use of chloroform is in the production of the freon refrigerant R-22.
Chloroform is slowly oxidised by air in the presence of light to an extremely poisonous gas,
carbonyl chloride (COCl2), also known as phosgene.
2CHCl3 + O2 light 2COCl2 + HCl
It is therefore stored in closed dark coloured bottles filled up to the neck in order to avoid air.
3. Tetrachloromethane (Carbon tetrachloride, CCl4): It is used in the manufacture of refrigerants and
propellants for aerosol cans. It is also used as feedstock in the synthesis of chlorofluorocarbons and
other chemicals, pharmaceutical manufacturing, and general solvent use.
4. Freons: The chlorofluorocarbon compounds of methane and ethane are collectively known as
freons. They are extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable
gases. Freon 12 (CCl2F2) is one of the most common freons in industrial use. It is manufactured from
tetrachloromethane by Swarts reaction. These are usually produced for aerosol propellants,
refrigeration and air conditioning purposes.
5. p,p’-Dichlorodiphenyltrichloroethane(DDT): DDT was the first chlorinated organic insecticide. The
effectiveness of DDT as an insecticide was first invented by Paul Muller. The structure of DDT is:
 7. ALCOHOLS, PHENOLS AND ETHERS

These are compounds containing C – O single bond. The functional group present in Alcohols and
phenols is –OH (hydroxyl) group and that present in ethers is –O – group (oxy group). In alcohols, the –OH
group is bonded to an alkyl group. So the general formula of alcohols is R-OH. But in phenols, the –OH group
is bonded to an aryl group. So the general formula of phenols is Ar-OH.
Classification of Alcohols
1. Depending on the number of –OH groups: Based on this alcohols are classified as monohydric
(contain only one –OH group), dihydric (contain two –OH groups), trihydric (contain three –OH groups) and
polyhydric (contain more than two –OH groups). Examples for monohydric alcohols are methanol (CH3-OH),
ethanol (CH3-CH2-OH) etc. Example for dihydric alcohol is ethylene glycol (HO-CH2-CH2-OH) and for trihydric
alcohol is glycerol (HOCH2-CHOH-CH2OH).
Monohydric alcohols may be further classified according to the hybridisation of the carbon atom to which
the hydroxyl group is attached.
i) Compounds containing sp3 C-OH bond: Here the –OH group is attached to an sp3 hybridised
carbon atom of an alkyl group. They are further classified as follows: Primary, secondary and
tertiary alcohols.
Allylic alcohols: In these alcohols, the —OH group is attached to an sp3 hybridised carbon next to
the carbon-carbon double bond. E.g. CH2=CH-CH2-OH (Allyl alcohol)
Benzylic alcohols: In these alcohols, the —OH group is attached to an sp3 hybridised carbon atom
next to an aromatic ring.
Allylic and benzylic alcohols may be primary, secondary or tertiary.
ii) Compounds containing sp2 C −OH bond: These alcohols contain —OH group bonded to a carbon-
carbon double. These may be vinyl alcohols or phenols.
Vinyl alcohols: CH2=CH-OH
Phenols:

Nomenclature of Alcohols
Common Name: By suffixing alcohol to the name of alkyl group (i.e. word root + yl alcohol)
IUPAC Name: By substituting ‘e’ of alkane with the suffix ‘ol’. (i.e. alkanol)
Some examples:
Compound Common Name IUPAC name
CH3-OH Methyl alcohol Methanol
CH3-CH2-OH Ethyl alcohol Ethanol
CH3-CH2-CH2-OH n-Propyl alcohol 1-Propanol
CH3-CHOH-CH3 Isopropyl alcohol 2-Propanol
CH3-CH2-CH2-CH2-OH n-Butyl alcohol 1-Butanol
CH3-CHOH-CH2-CH3 sec-butyl alcohol 2-Butanol
(CH3)2CH-CH2-OH Isobutyl alcohol 2-Methylpropan-1-ol
(CH3)3C-OH tert-butyl alcohol 2-Methylpropan-2-ol
(CH3)3C-CH2-OH Neopentyl alcohol 2,2-Dimethylpropan-1-ol
 Nomenclature of Phenols

Preparation of Alcohols
1. From alkenes:
i) By acid catalysed hydration: Alkenes react with water in the presence of acid as catalyst to form
alcohols. In the case of unsymmetrical alkenes, the addition reaction takes place in accordance with
Markovnikov’s rule.

ii) By hydroboration–oxidation reaction: Alkenes add diborane to give trialkyl boranes as addition
product. This on oxidation by hydrogen peroxide in the presence of aqueous sodium hydroxide to
form alcohols. This reaction is known as hydroboration -oxidation reaction.
The net reaction is the addition of a water molecule to the alkene in a way opposite to the
Markovnikov’s rule.

2. From carbonyl compounds

i) Reduction: Carbonyl compounds (aldehydes and ketones) when reduced using lithium aluminium
hydride (LiAlH4 or sodium borohydride (NaBH4) or on catalytic hydrogenation (using finely divided
metal such as nickel, platinum or palladium), we get alcohols.
Aldehydes give primary alcohols and ketones give secondary alcohols.
 R-CHO + [H] LiAlH4 R-CH2OH
R2CO + [H] LiAlH4 R2CH-OH
Commercially, acids are reduced to alcohols by converting them to the esters followed by their
reduction using hydrogen in the presence of catalyst (catalytic hydrogenation).

ii) From Grignard reagents: Aldehydes and ketones add Grignard reagent followed by hydrolysis, we
get alcohols.

Formaldehyde (methanal) gives primary alcohols, aldehydes other than formaldehyde gives
secondary alcohols and ketones give tertiary alcohols.
H-CHO + RMgX R-CH2-OMgX H2O R-CH2-OH + MgX(OH)
Formaldehyde adduct 10 alcohol
R-CHO + RMgX R2CHOMgX H2O R2CHOH + MgX(OH)
Aldehyde adduct 20 alcohol
R2CO + RMgX R3COMgX H2O R3C-OH + MgX(OH)
Ketone adduct 30 alcohol
Preparation of Phenols
1. From haloarenes: When chlorobenzene is fused with NaOH at 623K temperature and 320
atmospheric pressure, sodium phenoxide is formed which on acidification, we get phenol.

Chlorobenzene Sodium phenoxide Phenol

2. From benzene sulphonic acid: Benzene on sulphonation with oleum, benzene sulphonic acid is
formed which on treating with NaOH followed by acidification, we get phenol.

3. From diazonium salts: When an aromatic primary amine (e.g. aniline) is treated with nitrous
acid (prepared by mixing NaNO2 & HCl) at 273-278K, a diazonium salt is formed, which on
warming with water or treating with dilute acids, we get phenol.

4. From cumene: Cumene is isopropylbenzene (2-phenyl propane). It is oxidised in presence of air,

we get cumene hydroperoxide, which on treating with dilute acid, phenol and acetone are
formed. This method is used for the manufacture of phenol.
 Physical Properties of Alcohols and Phenols
1. Boiling Points: Boiling points of alcohols and phenols are higher than hydrocarbons, ethers,
haloalkanes and haloarenes of comparable molecular masses. This is because the –OH group in
alcohols and phenols is involved in intermolecular hydrogen bonding.
H R H R H R H R H R H

R – O…..H – O…..H – O….. H – O…..H – O….. H – O…..H – O….. H – O…..H – O….. H – O…..H – O…..

H – O…………..H – O……………H – O…………..H – O………… H – O……………H – O… ........... H – O……

The boiling points of alcohols and phenols increase with increase in the number of carbon atoms. This is
because as the number of carbon atoms increases, the van der Waals forces of attraction increases and
hence the boiling point. In alcohols, the boiling points decrease with increase of branching in carbon
chain (because of decrease in van der Waals forces with decrease in surface area).
2. Solubility: Alcohols and phenols are soluble in water. But the solubility of alcohols is higher than that
of phenols. Solubility of alcohols and phenols in water is due to their ability to form hydrogen bonds with
water molecules (inter molecular hydrogen bonding). The solubility decreases with increase in size of
alkyl/aryl groups.
Chemical Reactions of Alcohols and Phenols
A) Reactions involving cleavage of O–H bond
1. Acidity of alcohols and phenols:
i) Reaction with metals: Alcohols and phenols react with active metals such as sodium, potassium
and aluminium to yield corresponding alkoxides/phenoxides and hydrogen.
R-OH + Na → R-ONa + ½ H2
(sod. Alkoxide)
C6H5-OH + Na → C6H5-ONa + ½ H2
(sod. Phenoxide)
Phenols also react with aqueous sodium hydroxide to form sodium phenoxides.
C6H5-OH + NaOH → C6H5-ONa + H2O
The above reactions show that alcohols and phenols are acidic in nature.
ii) Acidity of alcohols: The acidic character of alcohols is due to the polar nature of O–H bond. An
electron-releasing group (e.g. alkyl groups like –CH3, –C2H5 etc.) increases the electron density on oxygen and
hence decrease the polarity of O-H bond. This decreases the acid strength. So the acid strength of alcohols
decreases in the order:
Primary alcohols > Secondary alcohols > Tertiary alcohols
But alcohols are weaker acids than water.
 iii) Acidity of phenols: In phenols, the –OH group is directly bonded to an sp2 hybridized carbon atom
of the benzene ring. Due to the greater electronegativity of sp2 hybridized carbon (due to greater s-character),
the benzene ring acts as an electron withdrawing group. So the lone pair electrons present in oxygen atom of
–OH group enters in the benzene ring and the following resonating structures are obtained:

(I) (II) (III) (IV) (V)

In the resonating structures (II), (III) and (IV), there is a positive charge on the electronegative
oxygen atom and hence it attracts the bond pair of electrons in O-H bond. So it is easy to remove the
hydrogen atom as H+ ion and thus phenol is acidic in nature.
Phenol is more acidic than alcohol. This is due to the following reasons:
1. In alcohol, the O-H group is directly bonded to an sp hybridized carbon atom, but in phenol, it is
3

bonded to an sp2 hybridized carbon. Due to the greater s-character and electronegativity of sp2
hybridized carbon, the ease of O-H bond cleavage is greater on phenol and hence it is more
acidic than alcohol.
2. The ionization of alcohol and phenol is as follows:

The alkoxide ion (R-O-) formed by the ionization of alcohol is not resonance stabilized. So the negative
charge is localized on oxygen atom. But the phenoxide ion (C6H5-O-) formed by the ionization of phenol is
resonance stabilized as follows.

Due to resonance, the negative charge is delocalized and hence phenoxide ion is more stable which favours
the ionization of phenol. Also phenoxide ion is more stable than phenol, because in phenol, there is a +ve
charge on electronegative oxygen atom. So it is less stable and readily lose H+ ion.
The presence of electron withdrawing groups (like nitro group) at ortho and para positions
increases the acidic strength of phenol. It is due to the effective delocalisation of negative charge in
phenoxide ion. On the other hand, electron releasing groups (like alkyl groups) at these positions
decreases the acidic strength of phenol. So cresols are less acidic than phenol.
2. Esterification:
Alcohols and phenols react with carboxylic acids, acid chlorides and acid anhydrides to form
esters. The reaction with carboxylic acid and acid anhydride are carried out in the presence of conc. H 2SO4.
The reaction with acid chloride is carried out in the presence of a base (pyridine) so as to neutralise HCl
formed during the reaction.
R-OH + R’-COOH R-OCOR’ + H2O
(ester)
C6H5-OH + R’-COOH C6H5-OCOR’ + H2O
R-OH + (R’CO)2O R-OCOR’ + R’COOH
(acid anhydride)
C6H5-OH + (R’CO)2O C6H5-OCOR’ + R’COOH

R-OH + R’-COCl pyridine R-OCOR’ + HCl [Schotten-Baumann reaction]

(acid chloride)
C6H5-OH + R’-COCl pyridine C6H5-OCOR’ + HCl
The introduction of acetyl (CH3CO) group in alcohols or phenols is known as acetylation.
Acetylation of salicylic acid produces aspirin, which is used as an analgesic.

B) Reactions involving cleavage of carbon – oxygen (C–O) bond in alcohols

1. Reaction with hydrogen halides: Alcohols react with hydrogen halides in presence of anhydrous zinc
chloride (ZnCl2) to form alkyl halides.
ROH + HX an. ZnCl2 R–X + H2O
The reactivity of primary, secondary and tertiary alcohols with HCl is different and hence this reaction is used
for the distinction of the three types of alcohols by a test called Lucas Test.
The difference in reactivity of three classes of alcohols with HCl distinguishes them from one another (Lucas
test).
LUCAS TEST:
Lucas reagent is amixture of Conc. HCl and anhydrous ZnCl2. Alcohols are soluble in Lucas reagent
while their halides are immiscible and produce turbidity in solution.
Tertiary alcohols react with Lucas reagent and form immediate turbidity; secondary alcohols
form turbidity within 5 minutes, while primary alcohols do not produce turbidity at room temperature.
They give turbidity only on heating.
2. Reaction with phosphorus trihalides (PX3): Alcohols react with phosphorus trihalides to give alkyl
halides.
3R-OH + PX3 3 R-X + H3PO3 (X= Cl or Br)
3. Dehydration: Alcohols undergo dehydration (removal of a molecule of water) on treating with a
protic acid like concentrated H2SO4 or H3PO4, or catalysts such as anhydrous zinc chloride or alumina to form
alkenes.

The relative ease of dehydration of alcohols follows the order: Tertiary > Secondary > Primary.
 For example ethanol undergoes dehydration by heating it with concentrated H2SO4 at 443 K, we
get ethene.

Secondary and tertiary alcohols are dehydrated under milder conditions.

4. Oxidation:
Alcohols on oxidation give carbonyl compounds (aldehydes and ketones) or carboxylic acids
depending on the nature of oxidising agent used. Primary alcohols when oxidized using mild oxidising agent
like anhydrous CrO3, we get aldehydes. But with strong oxidising agents like acidified potassium
permanganate or potassium dichromate, carboxylic acids are formed.
R-CH2OH [O] R-CHO [O] R-COOH
RCH2OH CrO3 RCHO
Primary alcohols are oxidised to aldehydes in good yield by pyridinium chlorochromate (PCC) [a
complex of chromium trioxide with pyridine and HCl].
CH3 −CH = CH−CH2OH ⎯⎯PCC⎯→ CH3 – CH = CH−CHO
[crotyl alcohol] [crotanaldehyde]
Secondary alcohols are oxidised to ketones by chromic anhydride (CrO3).
R2CHOH CrO3 R2CO
With strong oxidising agents, secondary alcohols give carboxylic acids with lesser number of carbon atoms.
R2CHOH [O] R2CO [O] R-COOH
Tertiary alcohols do not readily undergo oxidation reaction. But in presence of strong oxidising
agents (KMnO4) and at high temperature, they first give ketones with lesser number of carbon atoms which
on further oxidation give carboxylic acids with still lesser number of carbon atoms.
R3C-OH [O] R2CO [O] R-COOH
5. Reaction with hot copper catalyst
Primary alcoholic vapours when passed through hot Cu catalyst at 573K, undergo dehydrogenation to
form aldehydes, while secondary alcohols undergo dehydrogenation to give ketones.
R-CH2OH hot Cu/573K R-CHO
R2CHOH hot Cu/573K R2CO
Tertiary alcohols react with hot Cu catalyst at 573 K, undergo dehydration to give alkenes.

REACTIONS OF PHENOLS
1. Electrophilic Substitution reaction:
In phenol, the –OH group attached to the benzene ring donate electron pairs and hence it activates
it towards electrophilic substitution. Also, in the resonating structures of phenol, the electron density is
greater on ortho and para positions. So the electrophile enters at these positions.
The common electrophilic aromatic substitution reactions taking place in phenol are:
a) Nitration: Phenol reacts with conc. Nitric acid to give an yellow precipitate of 2,4,6-
trinitrophenol commonly called picric acid.

Picric acid can also be prepared by treating phenol first with concentrated sulphuric acid followed by
treating with concentrated nitric acid.
For the preparation of ortho and para nitrophenols, phenol is treated with dil. HNO3 at low
temperature (298K).

The ortho and para isomers can be separated by steam distillation. o-Nitrophenol is steam
volatile due to intramolecular hydrogen bonding while p-nitrophenol is less volatile due to intermolecular
hydrogen bonding which causes the association of molecules.
b) Halogenation: When phenol is brominated using Br2 in CHCl3 or CS2 at low temperature, we get a
mixture of ortho and para bromophenols. The reaction takes place in the absence of Lewis acid
catalyst (like FeBr3). It is due to the highly activating effect of –OH group attached to the benzene ring.

When phenol is treated with bromine water, we get a white precipitate of 2,4,6-tribromophenol.

2. Kolbe’s Reaction: Phenol when treated with sodium hydroxide, we get sodium phenoxide which
on treating with carbon dioxide followed by acidification, we get orthohydroxybenzoic acid
commonly called Salycilic acid. This reaction is called Kolbe’s reaction.
 3. Reimer-Tiemann reaction: Phenol when treated with chloroform in the presence of sodium
hydroxide, followed by acidification, we get salycylaldehyde (o-hydroxybenzaldehyde). Thiis
reaction is known as Reimer - Tiemann reaction.

4. Reaction with zinc dust: Phenol when heated with Zn dust, we get benzene.

5. Oxidation: When phenol is oxidised with chromic acid we get a conjugated diketone known as
benzoquinone.

In the presence of air, phenols are slowly oxidised to dark coloured mixtures containing quinones.

Some Commercially Important Alcohols

1. Methanol (CH3OH):
Methanol is also known as ‗wood spirit‘ since it can be produced by the destructive distillation of wood.
It is manufactured by the catalytic hydrogenation of carbon monoxide at about 573-673 K
temperature and 200-300 atm pressure and in the presence of ZnO – Cr2O3 catalyst.

It is highly poisonous in nature. It is used as a solvent in paints, varnishes and for making formaldehyde.
2. Ethanol (CH3CH2OH):
Ethanol is commonly known as spirit or grain alcohol. It is obtained commercially by the fermentation
of sugar. The sugar in molasses, sugarcane or fruits like grapes is converted to glucose and fructose, in
the presence of an enzyme, invertase. Glucose and fructose undergo fermentation in the presence of
another enzyme, zymase to give ethanol and carbondioxide. Both the enzymes invertase and zymase are
produced by yeast.
C12H22O11 + H2O Invertase C6H12O6 + C6H12O6
Sucrose Glucose Fructose
C6H12O6 Zymase 2C2H5OH + 2 CO2
Ethanol
Fermentation takes place in anaerobic conditions i.e. in absence of air. If air gets into fermentation
mixture, the oxygen of air oxidises ethanol to ethanoic acid (acetic acid), which destroys the taste of alcohol.
 The ethanol solution obtained by fermentation contains only 8-10% ethanol and it is called wash. It can
be concentrated upto 95.6% by fractional distillation. 95.6% alcohol is called Rectified spirit. It is
concentrated to 100% by distilling with small amount of benzene. Ethanol free from water and other
impurities (100% pure ethanol) is known as absolute alcohol.
Ethanol is a colourless liquid. It is used as a solvent in paint industry and in the preparation of a number of
carbon compounds.
The commercial alcohol is made unfit for drinking by mixing in it some copper sulphate (to give it a
colour) and pyridine (a foul smelling liquid). It is known as denaturation of alcohol and the resulting
alcohol is known as denatured spirit. If methanol is used for denaturation, it is called methylated spirit.
Ethanol can also be manufactured by hydration of ethene.
CH2=CH2 + H2O H+ CH3-CH2-OH
ETHERS
Nomencla
ture
Common names of ethers are derived from the names of alkyl/aryl groups written as separate
words in alphabetical order and adding the word ‘ether’ at the end. If both the alkyl groups are the same,
the prefix ‘di’ is added before the alkyl group.
In IUPAC system of nomenclature, ethers are named as ‘Alkoxyalkane’. The larger alkyl (R) group is
chosen as the parent
hydrocarbon. Some examples
are:
Compound Common Name IUPAC Name
CH3OCH3 Dimethyl ether Methoxymethane
C2H5OC2H5 Diethyl ether Ethoxyethane
CH3OCH2CH2CH3 Methyl n-propyl ether 1-Methoxypropane
C6H5OCH3 Methylphenyl ether Methoxybenzene
(Anisole) (Anisole)
C6H5OCH2CH3 Ethylphenyl ether Ethoxybenzene
(Phenetole)
C6H5O(CH2)6 – CH3 Heptylphenyl ether 1-Phenoxyheptane

If the two alkyl groups on both sides of the –O- group are identical, it is called symmetric ether and if they are
different, it is called asymmetric ether.

Preparation of ethers
1. By dehydration of alcohols:
Alcohols undergo dehydration in the presence of protic acids like H2SO4 or H3PO4 to give ethers based on
the reaction conditions.
For example, ethanol when dehydrated with conc. H2SO4 at 413 K, we get diethyl ether but at 443 K, we
get ethene.

This method is suitable for the preparation of ethers having primary alkyl groups only. In the case of 20 and 30
alcohols, alkenes are formed as the major product.
 2. Williamson’s ether synthesis:
Alkyl halide reacts with sodium alkoxide to form ether. This reaction is called Williamson‘s ether
synthesis.
R-X + R’-ONa → R-O-R’ + NaX
For preparing ethers containing secondary and tertiary alkyl groups, the alkyl halide used should
be primary and the alkoxide should be secondary or tertiary.

If the alkoxide used is primary, dehydrohalogenation occurs and the product formed is an
alkene. This is because of the strong basic character of 10 alkoxide.

The reaction follows SN2 mechanism.

For the preparation of aromatic ethers, one of the reactants should be sodium phenoxide.

Physical Properties
Ethers have lower boiling point than alcohols. This is because in alcohols, there is inter molecular
hydrogen bonding, which is absent in ethers. Lower ethers are miscible with water due to the formation of
hydrogen bonding with water.
Chemical reactions
1. Reaction with HX:
Ethers on reaction with Hydrogen halide, the C-O bond cleavage occurs and alkyl halides are formed.
R-O-R + HX → R-OH + R-X
R-OH + HX → R-X + H2O
In the case of ethers containing two different alkyl groups (primary and secondary), the lower alkyl
group forms the alkyl halide (10 alkyl halide).
CH3-O-CH2-CH3 + HI CH3-I + CH3-CH2-OH
The order of reactivity of hydrogen halides is as follows: HI > HBr > HCl.
Mechanism:
Step 1: The ether molecule is protonated to form an oxonium ion.

Step 2: The Iodide ion attacks the least substituted carbon of the oxonium ion and displaces an alcohol
molecule by SN2 mechanism.

When one of the alkyl group is tertiary, the halide formed is a tertiary halide.
This is because in step 2 of the reaction, the departure of leaving group (HO–CH3) creates a more stable
carbocation [(CH3)3C+], and the reaction follows SN1 mechanism.

In the reaction of alkyl aryl ethers with HX, one of the products formed is always phenol. Here
the O-R bond is weaker than the O–C6H5 bond because the carbon of phenyl group is sp2 hybridised and there
is a partial double bond character.

2. Electrophilic substitution Reactions: The alkoxy group (-OR) is ortho, para directing and activates the
benzene ring. So the product formed is a mixture of ortho and para isomers.
a) Halogenation: Anisole on bromination with bromine in ethanoic acid to give a mixture of o-
bromoanisole and p-bromoanisole

b) Nitration: Anisole reacts with a mixture of conc. sulphuric acid and conc. nitric acid to give a mixture
of ortho and para nitroanisole.

c) Friedel-Crafts reactions:
i) Alkylation: Anisole undergoes Friedel-Crafts alkylation reaction in presence of anhydrous
aluminium chloride (a Lewis acid) as catalyst, we get a mixture of ortho and para alkylated
anisole.
ii) Acylation:

*****
 8.ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

Thesearecompoundscontaining carbon-oxygendoublebond[>C=O,called carbonylgroup].In aldehydes,

the carbonyl group is bonded to a carbon and hydrogen while in ketones, it is bonded to two carbon atoms. The
carbonyl compounds in which carbonyl group is bonded to oxygen are known as carboxylic acids, and their
derivatives (e.g. esters, anhydrides) while in compounds where carbon is attached to nitrogen and to halogens are
called amides and acyl halides respectively. The general formulas of these compounds are as follows:

Aldehydes and Ketones

Nomenclature:
The common names of most aldehydes are derived from the common names of the corresponding carboxylic
acids by replacing the ending –ic acid with aldehyde. The position of the substituent in the carbon chain is indicated
by Greek letters α, β, γ, δ, etc.
The common names of ketones are derived by naming two alkyl or aryl groups bonded to the carbonyl group
and by suffixing ketone. The positions of the substituents are indicated by Greek letters, α α′, β β′ and so on.
The IUPAC names of open chain aliphatic aldehydes and ketones are derived from the names of the
corresponding alkanes by replacing the ending –e with ‘–al’ and ‘–one’ respectively. In case of aldehydes the longest
carbon chain is numbered starting from the carbon of the aldehyde group while in case of ketones the numbering
begins from the end nearer to the carbonyl group.
Some examples are:
Compound Common name IUPAC name
ALDEHYD
ES
HCHO Formaldehyde Methanal
CH3CHO Acetaldehyde Ethanal
(CH3)2CHCHO Isobutyraldehyde 2-Methylpropanal
CH3CH(OCH3)CHO α- 2-Methoxypropanal
Methoxypropionaldehyde
CH3CH2CH2CH2CHO Valeraldehyde Pentanal
CH2=CHCHO Acrolein Prop-2-enal

Phthalaldehyde Benzene-1,2-dicarbaldehyde

3-Bromobenzenecarbaldehyde Or
m-Bromobenzaldehyde
3-Bromobenzaldehyde
 KETONES
CH3-CO-CH3 Acetone Propanone
CH3-CO-CH2-CH3 Ethyl methyl ketone Butanone
CH3-CO-CH2-CH2-CH3 Methyl n-propyl ketone Pentan-2-one
CH3-CH2-CO-CH2-CH3 Diethyl ketone Pentan-3-one
(CH3)2CH-CO-CH(CH3)2 Diisopropyl ketone 2,4-Dimethylpentan-3-one
(CH3)2C=CH-CO-CH3 Mesityl oxide 4-Methylpent-3-en-2-one

α-Methylcyclohexanone 2-Methylcyclohexanone

Preparation of Aldehydes and Ketones

1. By oxidation of alcohols: Primaryalcoholson oxidation with mild oxidising agents like CrO3 to give
aldehydes while secondary alcohols give ketones.
R-CH2OH [O] R-CHO
R2CHOH [O] R2CO
2. By dehydrogenation of alcohols: Alcohols when heated with Cu or Silver catalyst at 573K, we get
carbonyl compounds. Primary alcohols give aldehydes, while secondary alcohols give ketones.
R-CH2OH Cu/573 K R-CHO
R2CHOH Cu/573 K R2CO
3. By ozonolysis of alkenes: Alkenes add ozone followed by hydrolysis with zinc dust and water, we get
aldehydes or ketones.

4. By hydration of alkynes: Alkynes add water in the presence of H2SO4 and HgSO4 to give
carbonyl compounds. Ethyne (acetylene) gives acetaldehyde and all other alkynes give ketones.
CH ≡ CH + H2O H2SO4/HgSO4 CH3-CHO
Ethyne Acetaldehyde
CH3-C ≡ CH + H2O H2SO4/HgSO4 CH3-CO-CH3
Propyne Acetone
Preparation of Aldehydes
1. From acyl chloride or, acid chloride [RosenmUND’S ReDUCTion]:
Acid chlorides react with hydrogen in presence of palladium (Pd) supported on barium sulphate
(BaSO4), we get aldehydes. This reaction is called Rosenmund‘s reduction.
R-COCl + H2 Pd/BaSO4 R-CHO + HCl

Benzoyl chloride Benzaldehyde

 2. From nitriles and esters:
Nitriles when reduced with stannous chloride in the presence of hydrochloric acid, we get imines,
which on hydrolysis give corresponding aldehyde. This reaction is called Stephen reaction.
RCN + SnCl2 + HCl R-CH=NH H3O+ R-CHO
Nitriles can also be selectively reduced by diisobUTYLalUminIUm hydride (DIBAL-H) to imines followed
by hydrolysis to aldehydes. DIBAL-H does not affect other reducable groups like double bonds.
R-CN 1. AlH(i-Bu)2 R-CHO
2. H2O
CH3-CH=CH-CH2-CN 1. DIBAL-H CH3-CH=CH-CH2-CHO
2. H2O
Esters are also reduced to aldehydes with DIBAL-H. CH3-
CH2-COOCH3 1. DIBAL-H CH3-CH2-CHO
2. H2O
Preparation of Aromatic aldehydes:
1. By oxidation of methylbenzene:
Methyl benzenes when oxidised by using mild oxidising agents like chromyl chloride (CrO2Cl2) or chromic oxide
(CrO3) in acetic anhydride, we get benzaldehyde.
Chromyl chloride oxidises methyl group to a chromium complex, which on hydrolysis gives
corresponding benzaldehyde. This reaction is called Etard reaction.

On treating with chromic oxide in acetic anhydride, methyl benzene is converted to benzylidene diacetate
which on acidification gives benzaldehyde.

2. By side chain chlorination followed by hydrolysis [Manufacture of Benzaldehyde]

Side chain chlorination of toluene gives benzal chloride, which on hydrolysis gives benzaldehyde.
This method is used for the manufacture of benzaldehyde.

3. By Gatterman – Koch reaction:

When benzene is treated with carbon monoxide and hydrogen chloride in the presence of anhydrous
aluminium chloride or cuprous chloride, we get benzaldehyde. This reaction is known as Gatterman-Koch
reaction.
 Preparation of Ketones
1. From acyl chlorides: Acid chlorides react with dialkylcadmium, we get ketones. Dialkyl cadmium is
prepared by the reaction of cadmium chloride with Grignard reagent.
2 R-MgX + CdCl2 R2Cd + 2Mg(X)Cl
2 R’-COCl + R2Cd 2 R’-CO-R + CdCl2
2. From nitriles: Nitriles add Grignard reagent followed by hydrolysis gives ketones.

3. From benzene or substituted benzenes [Friedel – Crafts acylation reaction]

When benzene or substituted benzene is treated with acid chloride (R-COCl) in the presence of anhydrous aluminium
chloride, we get a ketone. This reaction is known as Friedel-Crafts acylation reaction.

Physical Properties of Aldehydes and Ketones

1. Boiling Point:
The boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of comparable molecular
masses. It is due to dipole-dipole interactions which results in weak molecular association. But their boiling points
are lower than those of alcohols of similar molecular masses due to absence of intermolecular hydrogen
bonding.
2. Solubility:
The lower members of aldehydes and ketones are miscible with water in all proportions, because they form
hydrogen bond with water. But the solubility decreases rapidly on increasing the length of alkyl chain.
3. Physical state:
Methanal is a gas at room temperature, ethanal and acetone are volatile liquids and other aldehydes and ketones are
liquid or solid at room temperature.
Structure of the Carbonyl group
The carbonyl carbon atom is sp2-hybridised and forms three sigma (ς) bonds. The fourth valence electronof
carbonformsaπ-bondwith oxygen.In addition,theoxygen atomalsohastwo nonbonding
electron pairs. Thus,the carbonyl carbon and thethree atoms attached to it lie inthe sameplane and the π- electron
cloud is above and below this plane. The bond angles are approximately 1200.
The carbon-oxygen double bond is polarised due to higher electronegativity of oxygen. Hence, the carbonyl
carbon is an electrophilic (Lewis acid), and carbonyl oxygen, a nucleophilic (Lewis base) centre. The high polarity of the

carbonyl group is explained on the basis of resonance as follows:

Chemical Reactions of Aldehydes and Ketones
Since aldehydes and ketones contain a carbonyl group, they undergo similar chemical reactions. The important
reactions of aldehydes and ketones are:
 1. Nucleophilic addition reactions:
A nucleophile attacks the electrophilic carbon atom of the polar carbonyl group from a direction approximately
perpendicular to the plane of sp2 hybridised orbitalsof carbonyl carbon. As a result, the hybridisation of carbon changes
from sp2 to sp3 and a tetrahedral alkoxide intermediate is produced. This intermediate captures a proton from the
reaction medium to give the product.

Tetrahedral Intermediate Addition Product

Aldehydes are generally more reactive than ketones in nucleophilic addition reactions
due to steric and electronic reasons. Sterically, the presence of two bulky alkyl groups in ketones
hinders the approach of nucleophile to carbonyl carbon than in aldehydes. Electronically, ketones are
less reactive because of the electron releasing nature of the two alkyl groups reduces the
electrophilicity of the carbonyl carbon.
Some important nucleophilic addition reactions of aldehydes and ketones are:
a) Addition of hydrogen cyanide (HCN): Aldehydes and ketones react with hydrogen cyanide (HCN) in
presence of a base to give cyanohydrins.

Intermediate Cyanohydrin
Aldehydes give aldehyde cyanohydrins and ketones give ketone cyanohydrins. The cyanohydrins are useful
synthetic intermediates since it can be converted to carboxylic acids, amines, amides etc.
b) Addition of sodium hydrogensulphite: Aldehydes and ketones add sodium hydrogensulphite to
form the addition products (bisulphite adduct).

The bisulphate adduct are water soluble and can be converted back to the original aldehyde or ketone by
treating it with dilute mineral acid or alkali. Therefore, this reaction is used for the separation and
purification of aldehydes and ketones.
c) Addition of Grignard reagents: Carbonyl compounds add Grignard reagent followed by hydrolysis,
alcohols are formed. Formaldehyde gives primary alcohols, other aldehydes give secondary alcohols and
ketones give tertiary alcohols.
d) Addition of alcohols: Aldehydes react with monohydric alcohol in the presence of dry HCl to give
alkoxyalcohol intermediate (known as hemiacetals), which further react with one molecule of alcohol to give
a gem-dialkoxy compound known as acetal.

Ketones react with ethylene glycol in presence of dry HCl to form cyclic products known as ethylene glycol
ketals.
Acetals and ketals are hydrolysed with aqueous mineral acids to give corresponding aldehydes and ketones
respectively.

e) Addition of ammonia and its derivatives: Nucleophiles like ammonia and its derivatives H2N-Z
are added to the carbonyl group of aldehydes and ketones. The reaction is reversible and catalysed by acid.

i) Addition of ammonia: Aldehydes and ketones add ammonia followed byelimination of a water
molecule to give imines.
R-CHO + NH3 → R-CH(OH)NH2 → R-CH=NH + H2O
(imines)
R2CO + NH3 → R2C(OH)NH2 → R2C=NH + H2O
ii) Addition of Amine: Carbonyl compounds add amines to give substituted imines (Schiff’s bases).
R-CHO + R’-NH2 → R-CH(OH)NHR’ → R-CH=NR’ + H2O R2CO +
R’-NH2 → R2C(OH)NHR’ → R2C=NR’ + H2O
iii) Addition of hydroxyl amine (NH2-OH): Carbonyl compoundscondensedwithhydroxylamine
to give oximes.
R-CHO + NH2OH → R-CH=N-OH + H2O
(aldoxime)
R2CO + NH2OH → R2C=N-OH + H2O
iv) Addition of hydrazine (NH2-NH2): Carbonyl compounds condensed with hydrazine to give
hydrazone.
R-CHO + NH2-NH2 → R-CH=N-NH2 + H2O
(hydrazone)
R2CO + NH2-NH2 → R2C=N-NH2 + H2O
v) Addition of phenyl hydrazine (NH2-NH-C6H5): Carbonyl compounds condensed with
phenyl hydrazine to give phenyl hydrazone.
R-CHO + NH2-NH-C6H5 → R-CH=N-NH-C6H5 + H2O
(phenyl hydrazone)
 R2CO + NH2-NH-C6H5 → R2C=N-NH-C6H5 + H2O
vi) Addition of 2,4-dinitrophenyl hydrazine (2,4-DNP): Carbonyl compounds condensed with
2,4- dinitrophenyl hydrazine to give 2,4-dinitrophenyl hydrazone.

+ H2O
2,4-dinitrophenyl hydrazine 2,4-dinitrophenyl hydrazone
2,4-dinitrophenylhydrazineisalso knownasBorsches reagent.2,4-DNP-derivatives areyellow, orange or
red solids and hence this reaction is used for the characterisation of aldehydes and ketones.
vii) Addition of Semicarbazide (NH2-NH-CO-NH2): Carbonyl compounds condensed
with semicarbazide to yield samicarbazone.
R-CHO + NH2-NH-CO-NH2 → R-CH=N-NH-CO-NH2 + H2O
(semicarbazone)
R2CO + NH2-NH-CO-NH2 → R2C=N-NH-CO-NH2 + H2O
2. Reduction:
i) Reduction to alcohols: When reduced using sodium borohydride (NaBH4) or lithium aluminium
hydride (LiAlH4) or H2 in presence of Ni, Pd or Pt catalyst (Catalytic hydrogenation), aldehydes give
primary alcohols, while ketones give secondary alcohols.
R-CHO [H] R-CH2OH
R2CO [H] R2CHOH
ii) Reduction to Hydrocarbons:
Clemmensen reDUCTion: Aldehydes and ketones can be reduced to alkanes on treatment with zinc
amalgam and concentrated hydrochloric acid. During this reaction, the carbonyl group is reduced
to CH2 (methylene) group.

CH3-CHO + [H] Zn/Hg CH3-CH3

Acetaldehyde Ethane
CH3-CO-CH3 +[H] Zn/Hg CH3-CH2-CH3
Acetone Propane
Wolff-Kishner reduction: Carbonyl group can also be reduced to methylene group, by treating
with hydrazine followed by heating with sodium or potassium hydroxide in high boiling solvent
such as ethylene glycol.

CH3-CHO 1) NH2-NH2 2) KOH/Ethylene glycol/∆ CH3-CH3

CH3-CO-CH3 1) NH2-NH2 2) KOH/Ethylene glycol/∆ CH3-CH2-CH3
3. Oxidation:
Aldehydesareeasilyoxidised tocarboxylicacidsontreatment withcommon oxidising agents like nitric acid,
potassium permanganate, potassium dichromate etc. Mild oxidising agents like CrO3, Tollens’ reagent and
Fehlings’ reagent can also oxidise aldehydes.
R-CHO [O] R-COOH
CH3-CHO [O] CH3-COOH
Ketones when oxidised using strong oxidising agents and at high temperatures, we get a mixture of
carboxylic acids having lesser number of carbon atoms. During this reaction carbon-carbon bond cleavage occurs.
 E.g. CH3-CH2-CO-CH2-CH2-CH3 [O] 2 CH3-CH2-COOH + CH3-COOH + CH3-CH2-CH2-COOH
Hexan-3-one Propanoic acid Ethanoic acid Butanoic acid
4. Haloform Reaction:
Aldehydes or ketones having CH3-CO- group or CH3-CHOH- group, when treated with sodium
hypohalite or halogen in presence of NaOH, we get a haloform (CHX3). This reaction is called
haloform reaction. During this reaction, the methyl group is converted to haloform. This reaction does not
affect a carbon-carbon double bond, if present in the molecule.
R-CO-CH3 NaOX R-COONa + CHX3 (where X = Cl, Br or I)

The reaction with sodium hypoiodite gives an yellow precipitate of iodoform and this reaction is
used for the detection of CH3-CO- group or CH3-CHOH- group in a compound (Iodoform Test).
E.g.: 2-pentanone and 3-pentanone can be distinguished by iodoform reaction. 2-pentanone gives this reaction.
5. Aldol condensation Reaction:
Aldehydes and ketones having at least one α-hydrogen atom when treated with dilute alkali, we
get β-hydroxy aldehydes (aldol) or β-hydroxy ketones (ketol) respectively. This is known as Aldol
reaction. The product formed contains both aldehydic (ketonic) and alcoholic group. So the name aldol or ketol is
used.
The aldol or ketol on heated undergo dehydration to give α,β-unsaturated aldehyde or ketone.
This reaction is called Aldol condensation.
2CH3-CHO dil. NaOH CH3-CH(OH)-CH2-CHO CH3-CH=CH-CHO
Ethanal 3-Hydroxybutanal (aldol) But-2-enal (Crotanaldehyde)

6. Cross aldol condensation: When aldol condensation is carried out between two different
aldehydes or ketones, it is called cross aldol condensation. If both of them contain α-hydrogen
atoms, we get a mixture of four products.
CH3-CHO + CH2-CH2-CHO NaOH/∆ CH3-CH=CH-CHO + CH3-CH2-CH=C(CH3)-CHO + CH3-CH=C(CH3)-CHO
Ethanal Propanal But-2-enal 2-methylpent-2-enal 2-methylbut-2-enal
+ CH3-CH2-CH=CH-CHO
Pent-2-enal
 7. Cannizzaro Reaction:
Aldehydes having no α-hydrogen atom (e.g. HCHO, C6H5-CHO, CCl3-CHO etc), when treated with
conc. alkali (NaOH or KOH) undergo self oxidation and reduction (disproportionation) to form one
molecule of the alcohol and one molecule of carboxylic acid salt. This reaction is called Cannizzaro
reaction.
2 HCHO conc. KOH CH3-OH + H-COOK
Formaldehyde methanol potassium formate
2 C6H5-CHO conc. KOH C6H5-CH2OH + C6H5-COOK
Benzaldehyde benzyl alcohol potassium benzoate
8. Electrophilic Substitution Reactions:
Aldehydic and ketonic groups are meta directing and deactivating. So on electrophilic substitution reactions,
they givemeta-derivatives.
e.g. Nitration:

Tests to distinguish Aldehydes and Ketones

1. Tollens’ test:
Tollen‘s reagent is freshly prepared ammoniacal Silver nitrate. On warming Tollens‘
reagent, aldehydes give a bright silver mirror. During this reaction, the aldehyde is oxidised to
corresponding carboxylate ion and silver nitrate is reduced to silver metal.
R-CHO + 2[Ag(NH3)2]+ + 3OH– R-COO– + 2 Ag + 2 H2O + 4 NH3
2. Fehling’s test:
Fehling reagent is a mixture of two solutions, Fehling solution A and Fehling solution B.
Fehling solution A is aqUEOUS copper SUlphate and Fehling solution B is alkaline SODIUm potassiUm
tartarate (Rochelle salt). On heating with Fehling‘s reagent, aldehyde gives a reddish brown
precipitate of cuprous oxide (Cu2O). Aromatic aldehydes do not give this test.
R-CHO + 2Cu2+ + 5OH – R-COO– + Cu2O + 3H2O
(Cuprous oxide)
The above tests are not answered by ketones.

Carboxylic Acids
Carbon compounds containing a carboxyl functional group (–COOH) are called carboxylic acids. The carboxyl group
consists of a carbonyl group attached to a hydroxyl group, hence its name carboxyl. Aliphatic carboxylic acids containing
12 to 18 C atoms are called fatty acids. They occur in natural fats as esters of glycerol.
Nomenclature
The common names of carboxylic acids end with the suffix –ic acid and have been derived from Latin or
Greek names of their natural sources. For example, formic acid (HCOOH) was first obtained from red ants (Latin:
formica means ant), acetic acid (CH3COOH) from vinegar (Latin: acetum, means vinegar), butyric acid
(CH3CH2CH2COOH) from rancid butter (Latin: butyrum means butter).
In the IUPAC system, aliphatic carboxylic acids are named by replacing the ending –e in the name of the
corresponding alkane with – oic acid. In numbering the carbon chain, the carboxylic carbon is numbered one. For
naming compounds containing more than one carboxyl group, the ending –e of the alkane is retained. The
number of carboxyl groups is indicated by adding the prefixes di, tri, etc. to the term oic.
 Some examples are:
Compound Common name IUPAC name
HCOOH Formic acid Methanoic acid
CH3COOH Acetic acid Ethanoic acid
CH3CH2COOH Propionic acid Propanoic acid
CH3CH2CH2COOH Butyric acid Butanoic acid
(CH3)2CHCOOH Isobutyric acid 2-Methylpropanoic
acid
CH3CH2CH2CH2COOH Valeric acid Pentanoic acid
CH3CH2CH2CH2CH2COOH Caproic acid Hexanoic acid
HOOC-COOH Oxalic acid Ethanedioic acid
HOOC -CH2-COOH Malonic acid Propanedioic acid
HOOC -(CH2)2-COOH Succinic acid Butanedioic acid
HOOC -(CH2)3-COOH Glutaric acid Pentanedioic acid
HOOC -(CH2)4-COOH Adipic acid Hexanedioic acid
HOOC -CH2-CH(COOH)-CH2-COOH Propane-1, 2, 3-
tricarboxylic acid
Benzenecarboxylic acid
Benzoic acid
(Benzoic acid)
Phenylacetic
2-Phenylethanoic acid
acid

Benzene-1, 2-
Phthalic acid
dicarboxylic acid
Methods of Preparation of Carboxylic acids
1. From primary alcohols and aldehydes:
Primary alcohols are readily oxidised to carboxylic acids with common oxidising agents such as potassium
permanganate (KMnO4) in neutral, acidic or alkaline media or by potassium dichromate (K2Cr2O7) and chromium
trioxide (CrO3) in acidic media.
R-CH2OH alkaline KMnO4/H3O+ R-COOH CH3-
CH2-OH CrO3/H2SO4 CH3-COOH
Aldehydes on oxidation with mild oxidising agents like CrO3 or Tollen’s reagent to give carboxylic
acids.
R-CHO [O] R-COOH
CH3-CHO [O] CH3-COOH
2. From alkylbenzenes:
Aromatic carboxylic acids can be prepared by vigorous oxidation of alkyl benzenes with chromic acid or acidic
or alkaline potassium permanganate. Primary and secondary alkyl groups are oxidised in this manner while tertiary
group is not affected.
E.g.: Toluene when oxidized using alkaline KMnO4 followed by acidification we get benzoic acid.

Toluene Potassium Benzoate Benzoic acid

Here the entire side chain is oxidised to the carboxyl group irrespective of length of the side chain.
 1-phenylpropane Potassium benzoate Benzoic acid
3. From nitriles and amides:
Hydrolysis of nitriles in presence of acid or alkali as catalyst first give amides, which on further give carboxylic
acids. Mild reaction conditions are used to stop the reaction at the amide stage.

Benzamide Benzoic acid

4. From Grignard reagents:
Grignard reagents react with carbon dioxide (dry ice) in dry ether to form salts of carboxylic
acids which on acidification give corresponding carboxylic acids.

Grignard reagents and nitriles can be prepared from alkyl halides. So the above two reactions are used for
converting alkyl halides into corresponding carboxylic acids having one carbon atom more than that present in
alkyl halides.
5. From acyl halides and anhydrides:
Acid chlorides and anhydrides when hydrolysed with water give carboxylic acids. The rate of hydrolysis
increases in alkaline medium.

6. From esters:
Acidic hydrolysis of esters gives directly carboxylic acids while basic hydrolysis gives salt of carboxylic acids which
on acidification give corresponding carboxylic acids.
CH3-CH2-COOCH3 CH3-CH2-COONa + CH3OH

CH3-CH2-COOH + NaOH
 Physical Properties
1. Physical state: Aliphatic carboxylic acids upto nine carbon atoms are colourless liquids at room
temperature with unpleasant odours. The higher acids are wax like solids and are practically odourless due to
their low volatility.
2. Boiling point: Carboxylic acids are higher boiling liquids than aldehydes, ketones and alcohols of
comparable molecular masses. This is due to more extensive association of carboxylic acid molecules through
intermolecular hydrogen bonding. Most carboxylic acids exist as dimer in the vapour phase or in the aprotic
solvents.
3. Solubility:Simple aliphatic carboxylicacids havingupto four carbon atoms are miscible in waterdue to the
formation of hydrogen bonds with water. The solubility decreases with increasing number of carbon atoms.
The simplest aromatic carboxylic acid, benzoic acid, is nearly insoluble in cold water. Carboxylic acids are also
soluble in less polar organic solvents like benzene, ether, alcohol, chloroform, etc.
Chemical Reactions
(A) Reactions Involving Cleavage of O–H Bond:
1. Acidity:
Reactions with metals and alkalies: Like alcohols and phenols, carboxylic acids react with
electropositive metals and liberate hydrogen gas.
2 R-COOH + 2 Na 2 R-COONa + H2
R-COOH + NaOH R-COONa + H2O
Carboxylic acids react with sodium carbonates and bicarbonates and give brisk effervescence of
carbon dioxide. This reaction is not given by alcohols and phenols. So this reaction is used to distinguish
carboxylic acids from alcohols and phenols.
R-COOH + NaHCO3 R-COONa + H2O +CO2
Carboxylic acids dissociate in water to give resonance stabilized carboxylate anions and hydronium ion.
R-COOH + H2O R-COO –+ H3O+
Due to the formation of hydronium ion in water, carboxylic acids are acidic in nature.
The acidity of a substance is expressed in terms of pKa value, which is the negative logarithm of Ka.
i.e. pKa = - logKa
Greater the value of Ka, smaller will be pKa and stronger will be the acid.
Comparison of acidic character
Carboxylic acids are weaker than mineral acids, but they are stronger acids than other organic compounds like
alcohols and many simple phenols. The higher acidity of carboxylic acids as compared to phenols can be explained
as follows:
The carboxylate ion formed from the ionization of carboxylic acid is stabilised by two equivalent
resonance structures in which the negative charge is at the more electronegative oxygen atom. But the
phenoxide ion formed from the ionization of phenol has non-equivalent resonance structures in which
the negative charge is at the less electronegative carbon atom.

Also the negative charge is delocalised over two electronegative oxygen atoms in carboxylate ion,
whereas it is less effectively delocalised over one oxygen atom and less electronegative carbon atoms in
phenoxide ion. Therefore carboxylate ion is more stable than phenoxide ion and hence carboxylic acids
easily donate H+ ion and form carboxylate ion. So it is more acidic.
Effect of substituents on the acidity of carboxylic acids:
Electron withdrawing groups increase the acidity of carboxylic acids by stabilising the carboxylate ion
through delocalisation of the negative charge by inductive and resonance effects. But electron donating groups
decrease the acidity by destabilising the carboxylate ion.

The effect of the following groups in increasing acidity order is Ph < I <
Br < Cl < F < CN < NO2 < CF3
Direct attachment of groups such as phenyl or vinyl to the carboxylic acid, increases the acidity
of corresponding carboxylic acid. This is because of greater electronegativity of sp2 hybridised carbon to which
carboxyl carbon isattached. The presence of electron withdrawing group on the phenylof aromatic carboxylic acid
increases their acidity while electron donating groups decrease their acidity.
A) Reactions Involving Cleavage of C–OH Bond
1. Formation of anhydride: Carboxylic acids on heating with mineral acids like H2SO4 or with P2O5
undergo dehydration to give acid anhydrides.
R-COOH + HOOC-R P2O5/∆ (R-CO)2O + H2O
+
CH3-COOH + HOOC-CH3 H /∆ (CH3-CO)2O + H2O
Acetic acid Acetic anhydride
2. Esterification:Carboxylic acids when heated with alcohols or phenols in the presence of a
mineral acid like concentrated H2SO4 or HCl gas, we get esters. This reaction is reversible and
is known as esterification.

CH3-COOH + CH3-OH CH3-COO-CH3 + H2O

Acetic acid methanol methyl acetate
3. Reactions with PCl3, PCl5 and SOCl2: Carboxylic acids on treating with PCl3, PCl5 or SOCl2, we get acid
chlorides.
Reaction with thionyl chloride (SOCl2) is preferred because the byproducts are gases and are easily escaped from the
reaction mixture so that we get pure acid chloride.
R-COOH + PCl3 R-COCl + H3PO3
R-COOH + PCl5 R-COCl + POCl3+ HCl R-
COOH + SOCl2 R-COCl + SO2 + HCl
4. Reaction with ammonia: Carboxylic acids react with ammonia to give ammonium salts which on
further heating at high temperature give amides.

Benzoic acid Ammonium benzoate Benzamide

Strong
 B) Reactions Involving –COOH Group
1. Reduction: Carboxylic acids when reduced with lithium aluminium hydride or with diborane,
primary alcohols are formed. Diborane does not reduce functional groups like ester, nitro, halo, etc.
Sodium borohydride does not reduce the carboxyl group.
R-COOH i) LiAlH4/ether or B2H6 ii) H3O+ R-CH2OH

CH3-COOH i) LiAlH4/ether or B2H6 ii) H3O+ CH3-CH2OH

2. Decarboxylation:
i) When sodium salts of carboxylic acid are heated with sodalime (a mixture of NaOH and
CaO), they undergo decarboxylation (elimination of CO2) to form alkanes.
R-COONa + NaOH CaO/∆ R-H +
Na2CO3 CH3-COONa + NaOH CaO/∆ CH4
+ Na2CO3
ii) Kolbe’s electrolysis: When an aqueous solution of sodium or potassium salt of carboxylic
acid is electrolysed, we get alkanes having twice the number of carbon atoms that present
in the alkyl group of the acid. This reaction is known as Kolbe electrolysis.
2 R-COOK + 2H2O electrolysis R-R + 2KOH + H2 + 2CO2
2 CH3-COOK + 2 H2O electrolysis CH3-CH3 + 2KOH + H2 + 2CO2
C) Substitution Reactions in the Hydrocarbon Part:
1. Halogenation [HVZ Reaction]
Carboxylic acids having an α-hydrogen atom, when treated with halogen (chlorine or
bromine) in the presence of red phosphorus, we get α-halocarboxylic acids. This reaction is known
as Hell-Volhard- Zelinsky(HVZ) reaction.

α-halocarboxylic acid
CH3-CH2-COOH i) Cl2/ Red P ii) H2O CH3-CHCl-COOH + HCl
` Propanoic acid 2-chloropropanoic acid
This reaction is synthetically important since the halogen atom can be replaced by other groups.
2. Electrophilic substitution reactions:
The –COOH group is a deactivating group and meta-directing. So on electrophilic substitution reactions, we get
meta derivatives.
E.g. 1. Nitration

2. Bromination

But carboxylic acids do not undergo Friedel-Crafts reactions because the carboxyl group is
deactivating and the catalyst aluminium chloride (Lewis acid) gets bonded to the carboxyl group to
form salts.

9. AMINES
Amines are the derivatives of ammonia. Like ammonia, the nitrogen atom in amines is also sp 3
hybridised with an unpaired electron in one of the sp3 hybridised orbitals. So the shape of amines is also
pyramidal.
Amines are classified into three types – primary (10), secondary (20) and tertiary (30) amines. If one
hydrogen atom of ammonia is replaced by R (alkyl) or aryl (Ar) group, we get 10 amine. Their general formula
is R-NH2. If two hydrogen atoms of ammonia are replaced by two alkyl (R) or aryl (Ar) groups, we get 20amine.
Their general formula is R2NH. If three hydrogen atoms of ammonia are replaced by R or Ar groups we get
30amine. Their general formula is R3NH.
If all the alkyl or aryl groups are the same, that amine is called simple amine and if they are different,
it is called mixed amine.
Nomenclature: In common system, amines are named by prefixing alkyl group to amine, i.e. alkyl amine. In
secondary and tertiary amines, when the alkyl groups are same, the prefix di or tri is used before the name of
the alkyl group. In IUPAC system, amines are named by replacing of ‘e’ of alkane by the word amine, i.e.
alkanamine. In the case of secondary and tertiary amines, the alkyl group containing the maximum number of
carbon atom is taken as the parent chain and the other alkyl groups are taken as substituents. While naming
aryl amines according to IUPAC system, the suffix ‘e’ of arene is replaced by ‘amine’, i.e. arenamine. E.g.
benzenamine.

Amine Common name IUPAC name

CH-NH2 Methyl amine Methanamine
CH3-CH2-NH2 Ethylamine Ethanamine
CH3–CH2–CH2–NH2 n-Propylamine Propan-1-amine
(CH3)2CH-NH2 Isopropylamine Propan-2-amine
CH3-NH-CH2-CH3 Ethylmethylamine N-Methylethanamine
(CH3)3N Trimethylamine N,N-Dimethylmethanamine
CH3-CH2-CH2-CH2-N(C2H5)2 n-Butyldiethylamine N,N-Diethylbutan-1-amine
CH2=CH-CH2-NH2 Allylamine Prop-2-en-1-amine
H2N–CH2 –CH2 –NH2 Ethylene diamine Ethane-1,2-diamine
H2N-(CH2)6-NH2 Hexamethylenediamine Hexane-1,6-diamine
C6H5-NH2 Aniline Aniline or Benzenamine
(C6H5)2NH Diphenyl amine N-phenylbenzenanamine

o-Toluidine 2-Aminotoluene

4-Bromobenzenamine
p-Bromoaniline
Or, 4-Bromoaniline
N,N-Dimethylaniline N,N-Dimethylbenzenamine
Preparation of Amines
1. Reduction of nitro compounds:
Nitro compounds when reduced by passing hydrogen gas in the presence of finely divided nickel,
palladium or platinum or by reduction with metals in acidic medium, we get amines.
R-NO2 + H2 Pd/ethanol R-NH2
Nitrobenzene when reduced using H2 in presence of Ni, Pd or Pt Or, by using iron or tin and HCl,
we get aniline.

Reduction with iron and hydrochloric acid is preferred because FeCl2 formed gets hydrolysed to release
hydrochloric acid during the reaction. Thus, only a small amount of hydrochloric acid is required to initiate
the reaction.
2. Ammonolysis of alkyl halides:
Alkyl halides when treated with alcoholic solution of ammonia at 373 K, undergo nucleophilic
substitution reaction to give a mixture of primary, secondary and tertiary amines and quaternary
ammonium salt (R4N+X –). This process of cleavage of C-X bond by ammonia is called ammonolysis
(Hofmann’s Ammonolysis).
R-X + NH3 (alc.) R-NH2 + R2NH + R3N + R4N+X –
If large excess of ammonia is used, primary amine is formed as the major product. The order of reactivity
of alkyl halides with amines is RI > RBr >RCl.
3. Reduction of Nitriles:
Nitriles on reduction with lithium aluminium hydride (LiAlH4) or catalytic hydrogenation to give
primary amines. This reaction is used for ascending in amine series, i.e., for preparation of amines
containing one carbon atom more than the starting amine.
R-CN i) LiAlH4 R-CH2-NH2
ii) H2O
4. Reduction of amides:
Acid amides on reduction with lithium aluminium hydride give amines.
R-CO-NH2 i) LiAlH4 R-CH2-NH2
ii) H2O
CH3-CO-NH2 LiAlH4/H2O CH3-CH2-NH2
Ethanamide (acetamide) Ethanamine

5. Gabriel phthalimide synthesis:

This method is used for the preparation of aliphatic primary amines only. Phthalimide when treated
with ethanolic solution of potassium hydroxide to form potassium salt of phthalimide which on
heating with alkyl halide followed by alkaline hydrolysis produces the corresponding primary amine.
 Phthalimide potassium salt of phthalimide N-alkyl phthalimide

Aromatic primary amines cannot be prepared by this method because aryl halides do not undergo
nucleophilic substitution with the anion formed by phthalimide.
6. Hoffmann bromamide degradation reaction:
When an amide is treated with bromine and ethanolic solution of NaOH, we get a 10 amine. This
reaction is called Hoffmann bromamide degradation reaction. It is used for the conversion of an
amide to a primary amine with one carbon atom less than that present in the amide.
R-CO-NH2 + Br2 + 4 NaOH R-NH2 + Na2CO3 + 2 NaBr + 2 H2O
CH3-CO-NH2 + Br2 + 4 NaOH CH3-NH2 + Na2CO3 + 2 NaBr + 2 H2O
Ethanamide (acetamide) Methanamine

Physical Properties: Lower amines have fishy smell.

1. Solubility: Lower aliphatic amines are soluble in water because they can form hydrogen bonds with
water molecules. However, solubility decreases with increase in molar mass of amines due to increase in size
of the hydrophobic alkyl part. Higher amines are insoluble in water. Amines are soluble in organic solvents
like alcohol, ether and benzene.
2. Boiling point: Primary and secondary amines are associated through intermolecular hydrogen
bonding. This intermolecular association is more in primary amines than in secondary amines. Tertiary
amines do not have intermolecular association due to the absence of hydrogen atom. Therefore, the order of
boiling points of isomeric amines is as follows: Primary > Secondary > Tertiary
Chemical Reactions
1. Basic character of amines: Amines react with acids to form salts. This reaction shows that they are basic
in nature.
R-NH2 + HX R-NH3+X–
C6H5-NH2 + HCl C6H5NH3+Cl –
Aniline Anilinium chloride
In amine, there is an unshared pair of electrons on nitrogen atom and hence it can donate this
electron pair. So it acts as a Lewis base. Basic character of amines can be expressed in terms of Kb and pKb.
(pKb = - log Kb)
Greater the value of Kb, smaller will be the pKb value and stronger will be the base.
Aliphatic amines are stronger bases than ammonia. This is due to the +I effect of alkyl groups
leading to greater electron density on the nitrogen atom. But aromatic amines are weaker bases than
ammonia. This is due to the electron withdrawing nature of the aryl group.
 Besides inductive effect, there are some other effects like solvation effect, steric hindrance etc. affect
the basic strength of amines.
Structure-basicity relationship of amines
Basicity of amines is related to their structure. Basic character of an amine depends upon the ease of
formation of the cation by accepting a proton from the acid. As the stability of the cation increases, the
basicity also increases.
a) Comparison of basicity of alkyl amines (alkanamines) and ammonia
Due to the electron releasing nature of alkyl group (R) in alkyl amines, it (the alkyl group) pushes
electrons towards nitrogen and thus makes the unshared electron pair more available for sharing with the
proton of the acid. Also the substituted ammonium ion formed from the amine gets stabilized charge by the
+I effect of the alkyl group. Hence, alkyl amines are stronger bases than ammonia.
The basic nature of aliphatic amines should increase with increase in the number of alkyl groups. But
this trend is followed only in gas phase. The order of basicity of amines in the gaseous phase is:
Tertiary amine > Secondary amine > Primary amine > NH3.
In the aqueous solution, in addition to inductive effect, there are some other effects like solvation
effect and steric hindrance determine the basicity. The greater the size of the ion, lesser will be the solvation
and the less stabilised is the ion. So the basicity also decreses. Thus, the order of basicity of aliphatic amines
should be: primary > secondary > tertiary, which is opposite to the inductive effect based order.
When the alkyl group is small, there is no steric hindrance to H-bonding. In case the alkyl group is
bigger than CH3 group, there will be steric hindrance to H-bonding. Therefore, the size of the alkyl group also
determines the order of basic strength. Thus inductive effect, solvation effect and steric hindrance of
the alkyl group decide the basic strength of alkyl amines in the aqueous state.
The order of basic strength in case of methyl substituted amines and ethyl substituted amines
in aqueous solution is as follows:
(C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
20 30 10
(CH3)2NH > CH3NH2 > (CH3)3N > NH3
20 10 30
b) Comparison of basicity aryl amines and ammonia
Aryl amines are less basic than ammonia. This is because in aryl amines, the -NH2 group is attached
directly to the benzene ring. So the lone pair electrons present in the nitrogen atom enter into the
benzene ring and the following resonating structures are formed.

So the electron pairs are less available for protonation and hence aryl amines are less basic.
Also the anilinium ion formed by accepting a proton can have only two resonating structures as follows:
 So it is less stable and hence aniline does not easily accept proton. So it is less basic.
In the case of substituted aniline, the electron releasing groups like –OCH3, –CH3 increase basic
strength while electron withdrawing groups like –NO2, –SO3, –COOH, –X etc. decrease the basic
strength.
2. Alkylation:
Amines react with alkyl halides undergo nucleophilic substitution reaction to form a mixture of secondary
and tertiary amines and quaternary ammonium salt. (Hofmann’s Ammonolysis)
R-X + R-NH2 (alc.) R2NH + R3N + R4N+X –
3. Acylation: Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and esters
in presence of base like pyridine to form substituted amides. This reaction is known as acylation.
CH3-NH2 + CH3-CO-Cl base CH3-NH-CO-CH3 + HCl
Methanamine N-methylethanamide (N-methyl acetamide)
(C2H5)2NH + CH3-CO-Cl base (C2H5)2N-CO-CH3 + HCl
N-Ethylethanamine N,N-Diethylethanamide
C6H5-NH2 + CH3-CO-O-CO-CH3 C6H5-NH-CO-CH3 + CH3-COOH
Aniline ethanoic anhydride N-Phenylethanamide (Acetanilide)
Amines react with benzoyl chloride (C6H5COCl) to form N-alkyl benzamide. This reaction is known as
benzoylation.
CH3-NH2 + C6H5-CO-Cl CH3-NH-CO-C6H5 + HCl
Methanamine Benzoyl chloride N-Methylbenzamide
4. Carbylamine reaction (isocyanide test): Test for primary amines.
Aliphatic and aromatic primary amines on heating with chloroform and alcoholic potassium hydroxide
form foul smelling isocyanides or carbylamines. This reaction is known as carbylamines reaction or
isocyanide test and is used as a test for primary amines. Secondary and tertiary amines do not
give this reaction.
R-NH2 + CHCl3 + 3 KOH heat R-NC + 3 KCl + 3 H2O
CH3-NH2 + CHCl3 + 3 KOH heat CH3-NC + 3 KCl + 3 H2O
Methanamine methyl carbylamine
C6H5-NH2 + CHCl3 + 3 KOH heat C6H5-NC + 3 KCl + 3 H2O
Aniline phenyl carbylamine
5. Reaction with nitrous acid:
Aliphatic 10 amines react with nitrous acid (prepared by mixing sodium nitrite and HCl) to form
alcohols with the liberation of nitrogen gas. From the amount of nitrogen evolved, we can estimate
amino acids and proteins.
R-NH2 + HNO2 NaNO2 + HCl [R-N2+Cl-] H2O R-OH + N2 + HCl
Aromatic primary amines react with nitrous acid at 0 to 50C (273-278 K) to form aromatic
diazonium salts [Diazotisation].
C6H5-NH2 NaNO2 + HCl C6H5N2+Cl- + NaCl + 2H2O
Aniline Benzenediazoniumchloride
6. Reaction with benzene sulphonyl chloride [Hinsberg’s Test]:
Benzenesulphonyl chloride (C6H5SO2Cl) is known as Hinsberg‘s reagent. It is used to distinguish
primary, secondary and tertiary amines and also for the separation of a mixture of amines.
 a) Primary amines react with benzenesulphonyl chloride to form a precipitate of N-alkyl
benzenesulphonamide, which is soluble in alkail.

Benzene sulphonyl chloride ethanamine N-ethylbenzenesulphonamide

b) Secondary amines react with benzene sulphonyl chloride to give a precipitate of N,N-
dialkylbenzene sulphonamide, which is insoluble in alkali.

Benzene sulphonyl chloride N-ethylethanamine N,N-diethylbenzenesulphonamide

c) Tertiary amines do not react with benzenesulphonyl chloride.
Nowadays, Benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride.
7. Electrophilic substitution Reactions:
–NH2 group is ortho and para directing and a powerful activating group. So the reactions are very
vigorous.
a) Bromination: Aniline reacts with bromine water at room temperature to give a white precipitate of 2,4,6-
tribromoaniline.

In order to prepare o-bromoaniline and p-bromoaniline, first reduce the activating power of –
NH2 group by protecting it through acetylation with acetyl chloride or acetic anhydride. Then the
resulting acetanilide is brominated by Br2 in acetic acid followed by hydrolysis, we get p-bromoaniline as
the major product.

Aniline Acetanilide p-Bromoacetanilide p-Bromoaniline

b) Nitration
Direct nitration of aniline with conc. HNO3 and conc. H2SO4 gives a mixture of ortho, meta and para
nitroanilines and some tarry (tar-like) products.
 A large amount of meta-isomer is formed, eventhough -NH2 is ortho-para directing. This is because
in strongly acidic medium, aniline is protonated to form the anilinium ion which is meta directing.

H+

Aniline Anilinium ion

For the preparation of p-nitroaniline, the –NH2 group is first deactivated by acetylation. The
acetanilide thus formed is nitrated followed by hydrolysed.

c) Sulphonation:
Aniline reacts with concentrated sulphuric acid to form anilinium hydrogensulphate which on heating
with sulphuric acid at 453-473K produces p-aminobenzene sulphonic acid, commonly known as sulphanilic
acid, as the major product. Sulphanilic acid contains both acidic and basic groups and so it forms
internal salts called zwitter ions.

Aniline does not undergo Friedel-Crafts reaction (alkylation and acylation) since it form salt with
anhydrous aluminium chloride, which is used as catalyst in the reaction.

AROMATIC DIAZONIUM SALTS

They have the general formula ArN2+ X– where Ar is an aryl group and X– may be Cl–, Br–, HSO4− , BF4− ,
etc. The N2+ group is called diazonium group. They are named by suffixing diazonium to the name of the
parent hydrocarbon followed by the name of anion such as chloride, hydrogensulphate, flouroborate etc.
Some examples are:
1. C6H5N2+Cl – Benzenediazoniumchloride
+ –
2. C6H5N2 HSO4 Benzenediazoniumhydrogensulphate
3. C6H5N2+BF4 – Benzenediazoniumfluoroborate
Preparation – Diazotisation: Aromatic diazonium salts are prepared by treating an aromatic primary amine
with Nitrous acid (which is prepared by mixing NaNO2 and HCl) at 273 – 278K (0-50C). The conversion of
primary aromatic amines into diazonium salts is known as diazotisation.
E.g. benzenediazonium chloride is prepared by the reaction of aniline with nitrous acid at 273-278K.
C6H5NH2 + NaNO2 + 2HCl 273 – 278 K C6H5N2+Cl – + NaCl + 2H2O
Aromatic diazonium salts are stable only at low temperatures. So it is produced in situ (in site).
 Chemical reactions
The reactions of diazonium salts can be broadly divided into two categories – Reactions involving
displacement of nitrogen and reactions involving retention of diazo group.
A) Reactions involving displacement of nitrogen
1. Replacement by halide or cyanide ion: When a diazonium salt is treated with hydrogen halide in
presence of cuprous halide, we get halobenzene. This reaction is called Sandmeyer’s reaction. For the
preparation of cyanobenzene, benzenediazonium salt is treated with KCN in presence of cuprous
cyanide.
C6H5N2+Cl- + HX CuX C6H5-X + N2 + HCl [where X = Cl or Br]
+ -
C6H5N2 Cl + KCN CuCN C6H5-CN + N2 + HCl
If cuprous halide is replaced by copper powder, the reaction is called Gattemann’s reaction.
C6H5N2+Cl- + HX Cu C6H5-X + N2 + CuCl
2. Replacement by iodide ion: When the diazonium salt solution is treated with potassium iodide,
iodobenzene is formed.
C6H5N2+Cl- + KI C6H5-I + N2 + KCl
3. Replacement by fluoride ion: When benzenediazonium chloride is treated with fluoroboric acid (HBF4),
benzene diazonium fluoroborate is formed which on heating decomposes to give flourobenzene. This
reaction is called Balz-Schiemann reaction.
C6H5N2+Cl- + HBF4 C6H5- N2+BF4– ∆ C6H5-F + BF3 +N2
4. Replacement by H: When benzenediazonium chloride is treated with reducing agents like
hypophosphorous acid (phosphinic acid) or ethanol, we get benzene.
C6H5N2+Cl- + H3PO2 + H2O C6H6 + N2 + H3PO3 + HCl
C6H5N2+Cl– + CH3CH2OH C6H6 + N2 + CH3-CHO + HCl
5. Replacement by hydroxyl group: When benzenediazoniumchloride is warmed with water, we get phenol.
C6H5N2+Cl- + H2O C6H5-OH + N2 + HCl
6. Replacement by –NO2 group: When benzenediazonium fluoroborate is heated with aqueous sodium
nitrite solution in the presence of copper, the diazonium group is replaced by –NO2 group.

B) Reactions involving retention of diazo group

Coupling reactions: When benzene diazonium chloride is treated with phenol or aniline, the para
position of is coupled with the diazonium salt to form p-hydroxyazobenzene or p-
aminoazobenzene. This type of reaction is known as coupling reaction. This is an example of
electrophilic substitution reaction.

Benzenediazonium chloride Phenol p-hydroxyazobenzene

Benzenediazonium chloride Aniline p-aminoazobenzene

 10.BIOMOLECULES
The molecules present in living system like carbohydrates, proteins, nucleic acids, lipids, vitamins etc.
which are essential for the growth and maintenance of our body are called Biomolecules.
Carbohydrates
These are the hydrates of carbon and most of them have a general formula Cx(H2O)y. They can be
defined as optically active polyhydroxy aldehydes or ketones or the compounds which produce such
units on hydrolysis. Some of the carbohydrates are crystalline, water soluble and sweet in taste. They are
called sugars. Carbohydrates which are not crystalline, water insoluble and have no sweet taste are called
non-sugars. Carbohydrates are also called ‘Saccharides’.
Classification of carbohydrates
I) Based on their behaviour on hydrolysis:
Based on this, carbohydrates are classified into three types:
1) Monosaccharides: These are carbohydrates which cannot be hydrolysed into simpler units of
polyhydroxyaldehydes or ketones. E.g. glucose, fructose, ribose, galactose etc.
2) Oligosaccharides: These are carbohydrates which give two to ten monosaccharide units on
hydrolysis. They are further classified as disaccharides, trisaccharides, tetrasaccharides etc. E.g.
Sucrose, maltose, lactose.
Sucrose on hydrolysis gives one molecule each of glucose and fructose, maltose gives two molecules of
glucose while lactose gives one molecule each of glucose and galactose.
3) Polysaccharides: These are carbohydrates which give a large number of monosaccharide units on
hydrolysis. E.g. starch, cellulose, glycogen etc.
II) Based on their reducing character:
Based on this, carbohydrates are of two types – reducing sugar and non-reducing sugar.
Carbohydrates which contain free aldehydic or ketonic groups are called reducing sugars, while
those which do not contain free aldehydic or ketonic group are called non-reducing sugars. All
monosaccharides are reducing sugars. Disaccharides like maltose and lactose are reducing while sucrose
is non-reducing.
III) Based on the functional group and no. of carbon atoms: A monosaccharide containing an aldehyde
group is known as aldose, while a monosaccharide containing a ketonic group is known as ketose.
Monosaccharides containing 3 carbon atoms are called triose, 4 carbon atoms are called tetrose etc.

MONOSACCHARIDES
Glucose (C6H12O6)
Glucose is an aldohexose and is also known as dextrose. It is the monomer of starch, cellulose. It is
probably the most abundant organic compound on earth.
Methods of preparation
1. From sucrose (Cane sugar): If sucrose is boiled with dilute HCl or H2SO4 in alcoholic solution, glucose
and fructose are obtained in equal amounts.

2. From starch: Commercially glucose is obtained by hydrolysis of starch by boiling it with dilute
H2SO4 at 393 K under pressure.
 Structure of glucose
1. Molecular formula of glucose is C6H12O6.
2. On continuous heating with HI, glucose forms n-hexane. This indicates that all the six carbon
atoms in glucose are in a straight chain.
3. Glucose reacts with hydroxylamine to form an oxime and adds a molecule of hydrogen cyanide to
give cyanohydrin. These reactions confirm the presence of a carbonyl group (>C = O) in glucose.
4. On oxidation using mild oxidising agents like bromine water, Glucose gives gluconic acid (six
carbon carboxylic acid). This indicates that the carbonyl group present is an aldehydic group.
5. Acetylation of glucose with acetic anhydride gives glucose pentaacetate which confirms the
presence of five –OH groups. Since it exists as a stable compound, five –OH groups should be
attached to different carbon atoms.
6. On oxidation with nitric acid, glucose gives saccharic acid (a dicarboxylic acid). This indicates the
presence of a primary alcoholic (–OH) group in glucose.
Based on the above informations, Fischer proposed an open chain structure for glucose as follows:

D- Glucose (Open chain structure)

But this open chain structure cannot explain the following observations:
1. Glucose does give 2,4-Dinitrophenyl hydrazine test (2,4-DNP test or Borsche’s test), Schiff’s test and
does not give addition product with NaHSO3.
2. The pentaacetate of glucose does not react with hydroxylamine indicating the absence of free —CHO
group.
3. The existence of two different anomeric forms of glucose (α and β form).
In order to explain the above, it was proposed that one of the –OH groups may add to the –CHO
group and form a cyclic hemi-acetal structure. The –OH at C5 is involved in ring formation. (1,5 – oxide

ring).
Thus the two cyclic forms exist in equilibrium with the open chain structure. The two cyclic hemi-
acetal forms of glucose differ only in the configuration at first carbon (anomeric carbon). So they are called
anomers. These are stereo isomers which differ only in the configURATion at the first carbon.
The Pyranose structure of Glucose (Haworth Structure)
The six membered cyclic structure of glucose is called Pyranose structure. The anomeric forms of
glucose can be represented as follows:
Fructose (C6H12O6)
Fructose is a ketohexose. It has also the molecular formula C6H12O6. On the basis of its reactions,
it was found to contain a ketonic group at 2nd carbon and six carbons in straight chain. It is laevorotatory
and can be written as D-(–)-fructose. Its open chain structure is:

Ring Structure of fructose

Fructose also exists in two cyclic forms which are obtained by the addition of —OH at C5 to
the Carbonyl group. The ring, thus formed is a five membered ring (2,5-oxide ring structure).

α-D-(-)-Fructose β-D-(-)-Fructose
Haworth structure (Furanose structure) of Fructose
The cyclic structure of fructose is analogous to the heterocyclic compound furan and is called furanose
structure.

Assigning D, L Notation
D, L notation is assigned based on the structure of Glyceraldehyde. Glyceraldehyde contains one
asymmetric carbon atom and exists in two enantiomeric forms as shown below:

(+)-Glyceraldehyde with the –OH group on right side is assigned as D-Glyceraldehyde and (-)-
Glyceraldehyde with the –OH group on left side is assigned as L-Glyceraldehyde.
For assigning the configuration of a monosaccharide, first write the compound in such a way that the
most oxidisable carbon (like –CHO group) is at the top. Then compare the configuration of the lowest
asymmetric carbon atom of the compound with glyceraldehyde. If the —OH group is on the right side, the
compound is assigned as D-configuration and if it is on the left side, the compound is assigned as L-
configuration.
 DISACCHARIDES:
These are carbohydrates which on hydrolysis give two monosaccharide units. Important
disaccharides are Sucrose, Maltose and Lactose.
1. Sucrose (C12H22O11) [Cane sugar or Grape sugar]:
It is formed by the combination of 2 monosaccharides α-D-glucose and β-D-fructose. So sucrose (Cane
sugar) on hydrolysis gives an equimolar mixture of D-(+)-glucose and D-(-)-fructose.
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose D(+)Glucose (+52.5 ) D(-)Fructose (-92.40)
0

Sucrose is dextro rotatory but after hydrolysis it gives dextro rotatory glucose and laevo
rotatory fructose. Since the laevo rotation of fructose (-92.40) is more than dextro rotation of glucose
(+52.50), the mixture is laevo rotatory. So the process is called inversion of cane SUgar and the product
formed is called invert SUgar.
In sucrose, the two monosaccharides [D-(+)-glucose and D-(-)-fructose] are held together by a glycosidic
linkage between C1 of α-D-glucose and C2 of β-D-fructose. Since the reducing groups of glucose and
fructose are involved in glycosidic bond formation, sucrose is a non reducing sugar.
Glycosidic linkage: The C-O-C linkage formed between monosaccharide units during the formation of a
disaccharide or polysaccharide is called Glycosidic linkage.
2. Maltose (C12H22O11) [Malt sugar]:
It is formed by the combination of two α-D-glucose units in which C1 of one glucose is linked to C4 of
another glucose unit. The free aldehyde group can be produced at C1 of second glucose in solution
and so it is a reducing sugar.
3. Lactose (C12H22O11) [Milk Sugar]:
It is formed by the combination of β-D-galactose and β-D-glucose. The glycosidic linkage is between
C1 of galactose and C4 of glucose. Free aldehyde group can be produced at C1 of glucose unit in
solution and hence it is a reducing sugar.

POLYSACCHARIDES:
These are carbohydrates which on hydrolysis give a large number of monosaccharide units. They
are natural polymers.
Important polysaccharides are Starch, Cellulose and Glycogen.
1. Starch, (C6H10O5)n :
It is the main storage polysaccharide of plants. It is a polymer of α-glucose and consists of two
components — Amylose and Amylopectin.
Amylose is water soluble component which constitutes about 15-20% of starch. Chemically
amylose is a linear polymer of α-D-(+)-glucose units with C1 – C4 glycosidic linkage.
Amylopectin is insoluble in water and constitutes about 80-85% of starch. It is a branched chain
polymer of α-D-glucose units in which chain is formed by C1 – C4 glycosidic linkage and branch is
formed by C1 – C6 glycosidic linkage.

2. Cellulose, (C6H10O5)n :
It is the main constituent of cell wall of plants. Cellulose is a straight chain polysaccharide of β-
D-glucose units which are joined by C1 – C4 glycosidic linkage.

3. Glycogen: The carbohydrates are stored in animal body as glycogen. It is also known as animal starch
because its structure is similar to amylopectin. It is present in liver, muscles and brain. It is also found
in yeast and fungi.
 No. Sugar Reducing Monosaccharides Glycosidic linkage
character
1. Sucrose Non-reducing One units each of α-D- C1 of α-glucose and C2 of β-fructose (C1 –
sugar glucose and β-D-fructose C2)
2. Maltose Reducing 2 units of α-D-glucose C1 of one α-glucose and C4 of another α-
sugar glucose (C1 – C4)
3. Lactose Reducing One units each of β-D- C1 of galactose and C4 of glucose
sugar galactose and β-D-
glucose
4. Cellulose Non-reducing β-D-glucose C1 of one glucose and C4 of another
glucose
5. Starch Non-reducing α-D-glucose It contains two components – amylose and
amylopectin. Amylose is a linear polymer
of α-D-glucose (C1-C4) and amylopectin is a
branched chain polymer of α-D-glucose
(C1-C4 & C1-C6)
Uses of carbohydrates
Carbohydrates are used as storage molecules as starch in plants and glycogen in animals. Cell wall of
bacteria and plants is made up of cellulose. Carbohydrates are used as raw materials for many important
industries like textiles, paper, lacquers and breweries. Carbohydrate in the form of wood is used for
making furniture etc.
Amino acids
These are compounds containing amino group (–NH2) and carboxyl (–COOH) group. Depending
upon the relative position of amino group with respect to carboxyl group, the amino acids can be classified as
α, β, γ, δ and so on. The simplest amino acid is glycine (H2N-CH2-COOH). Except glycine, all other
naturally occurring α-amino acids are optically active, since the α-carbon atom is asymmetric.
Amino acids are generally represented by a three letter symbol. (e.g. ‘Gly’ for glycine, ‘Ala’ for alanine
etc). Amino acids are classified as acidic, basic or neutral depending upon the relative number of amino and
carboxyl groups in their molecule. Amino acids having equal number of amino and carboxyl groups is neutral;
those containing more number of amino groups are basic and those containing more number of carboxyl
groups are acidic.
For e.g. glycine, alanine, valine etc. are neutral, arginine, lysine etc. are basic and glutamic acid, aspartic
acid etc. are acidic.
Essential and Non-essential Amino acids: Our body requires 20 amino acids. Among these some are
synthesized in the body and the remaining should be obtained through our diet.
The amino acids which can be synthesised in the body are known as non-essential amino acids.
E.g.: Glycine, Alanine, Glutamic acid, Aspartic acid, Glutamine, Serine, Cysteine and Proline.
The amino acids which cannot be synthesised in the body and must be obtained through diet, are known
as essential amino acids.
E.g.: Valine, Leucine, Isoleucine, Arginine, Lysine, Threonine, Methionine, Phenylalanine, Tryptophan and
Histidine.
In aqueous solution, the carboxyl group can lose a proton and amino group can accept a proton, giving
rise to a dipolar ion known as zwitter ion. This is neutral but contains both positive and negative charges. In
zwitter ionic form, amino acids show amphoteric behaviour as they react both with acids and bases.
 Most naturally occurring amino acids have L-configuration. L-Aminoacids are represented by
writing the –NH2 group on left hand side.
Peptides and polypeptides
A peptide is formed by the combination of α-amino acid molecules. Chemically peptide linkage is an
amide formed between –COOH group and -NH2 group. When two molecules of amino acids combine, the
amino group of one molecule reacts with –COOH group of another molecule by losing one water molecule
to form a -CO-NH- linkage, commonly called peptide linkage.
The peptide formed between two amino acid molecules is called a dipeptide.
H2N-CH2-COOH + H2N-CH2-COOH → H2N-CH2-CO-NH-CH2-COOH
Glycine Glycine Glycylglycine (Gly-Gly)
The peptide formed by the combination of 3 amino acid molecules is called a tripeptide. When the
number of amino acid molecules is more than 10, the product is called a polypeptide. A polypeptide with
more than 100 amino acid residues and molecular mass greater than 10,000u is called a protein.
[Polypeptides having less than 100 amino acid units are also called protein, if they have a well-defined
structure. E.g. Insulin (It contains only 51 aminoacids)].
Proteins
Proteins are the polymers of α-amino acids. The word protein is derived from Greek word, “proteios”
which means prime importance.
Classification of proteins
Based on the molecular shape, proteins are classified into 2 types:
a) FibroUs proteins: They have fibre – like structure. Here the linear polypeptide chains are held
together by H-bond and disulphide bond. They are generally insoluble in water.
E.g. Keratin (present in hair, wool, silk etc.) and myosin (present in muscles).
b) GlobULAR proteins: Here the chains of polypeptides coil around to give a spherical shape. These
are usually soluble in water. Insulin and albumins are the common examples of globular proteins.
Structure of proteins
Structure of proteins can be studied at four different levels. They are primary, secondary, tertiary
and quaternary structure.
1. Primary structure: It gives the sequence of amino acid molecules in a polypeptide chain of protein.
Any change in the primary structure creates a different protein.
2. Secondary structure: The secondary structure of protein refers to the shape in which a long
polypeptide chain can exist. There are two different types of secondary structures- α-helix and
β-pleated sheet structure. These structures arise due to the regular folding of the backbone of the
polypeptide chain due to hydrogen bonding between >CO and –NH– groups of the peptide bond.
3. Tertiary structure: The tertiary structure represents overall folding of the polypeptide chains.
i.e., further folding of the secondary structure. It gives rise to two major molecular shapes -
fibrous and globular.
4. Quaternary structure: Some of the proteins contain two or more polypeptide chains called sub-units.
The spatial arrangement of these sub-units is known as quaternary structure.

Denaturation of Proteins
 When a protein is subjected to physical change (like change in temperature) or chemical change
(like change in pH), it loses the biological activities. This process is called denatURATion of protein.
During denaturation, secondary and tertiary structures are destroyed, while primary structure remains
unaffected.
E.g. coagulation of egg white on boiling, curdling of milk etc.
Enzymes
Enzymes are biological catalysts, which catalyse the different reactions taking place in living
body. Almost all the enzymes are globular proteins. Enzymes are very specific in nature. A small amount of
enzyme is required to catalyse a large amount of reactants.
E.g. for enzyme catalysis: The enzyme maltase catalyses the hydrolysis of maltose to glucose.
Vitamins
These are organic compounds required in the diet in small amounts to perform specific biological
functions for normal maintenance of optimum growth. Vitamins are designated by alphabets A, B, C, D, etc.
Some of them are further named as sub-groups e.g. B1, B2, B6, B12, etc.
Classification of Vitamins
Vitamins are classified into two groups depending upon their solubility in water or fat.
i) Fat soluble vitamins: e.g. Vitamins A, D, E, & K. They are stored in liver and adipose (fat storing)
tissues.
ii) Water soluble vitamins: e.g. Vitamins B & C. These vitamins are readily excreted through urine
and cannot be stored (except vitamin B12) in our body.
Some vitamins and their deficiency diseases
Vitamin Deficiency Disease
Vitamin A Night blindness (Xerophthalmia)
Vitamin B1 Beri-beri
Vitamin B2 Cheilosis
Vitamin B6 Convulsions
Vitamin B12 Pernicious anaemia
Vitamin C Scurvy
Vitamin D Rickets and osteomalacia
Vitamin E Increased fragility of RBCs and muscular
weakness
Vitamin K Hemophilia (Increased blood clotting time)

Nucleic acids
Nucleic acids are long chain polymers of nucleotides and are responsible for transmission of
heredity. These are mainly of two types – deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). Since
nucleic acids are long chain polymers of nucleotides, they are also called polynucleotides.
Nucleic acid contains a pentose sugar, phosphoric acid and a nitrogen base. In DNA, the pentose
sugar is β–D-2-deoxy ribose, while in RNA it is β–D-ribose.
DNA contains 4 bases – Adenine (A), Guanine (G), Cytosine (C) and Thymine (T). [A, G, C &T]
RNA contains Adenine (A), Guanine (G), Cytosine (C) and Uracil (U). [A, G, C & U]
The pentose sugar combines with the base to form nucleoside, which combines with the phosphoric acid
group to form nucleotide. The nucleotide units combine to form nucleic acid.
Structure of Nucleic Acids
Nucleic acids have two types of structures – primary structure and secondary structure.
Primary structure gives the sequence of nucleotides in a nucleic acid chain. The secondary structure of DNA
was given by James Watson and Francis Crick. They gave a double strand helix structure for DNA. The two
strands in the helix are complementary to each other. They are held together by hydrogen bonds between
the bases. Adenine forms 2 hydrogen bonds with thymine while cytosine forms 3 hydrogen bonds with
GUanine.
RNA molecules are of three types and they perform different functions. They are named as messenger
RNA (m-RNA), ribosomal RNA (r-RNA) and transfer RNA (t-RNA).

Differences between DNA and RNA

DNA
DNA is double stranded
The pentose sugar is deoxy ribose
The nitrogen bases are Adenine,
Guanine, Cytosine and Thymine.
RNA
RNA is single stranded
The pentose sugar is ribose
The nitrogen bases are Adenine,
Guanine, Cytosine and Uracil.

Biological functions of nucleic acids

The important functions of Nucleic acids are:
1. DNA is responsible for the transmission of hereditary characters from one generation to
other.
2. Another important function of nucleic acids is protein synthesis.
Hormones
Hormones are molecules that act as intercellular messengers. In terms of chemical nature, they are
classified as steroids (e.g., estrogens and androgens), poly peptides (E.g. insulin and endorphins) and amino
acid derivatives (e.g epinephrine and norepinephrine).
Functions of Hormones
They help to maintain the balance of biological activities in the body.
For example the hormones insulin and glucagon together regulate the glucose level in the blood.
Epinephrine and norepinephrine mediate responses to external stimuli.
Thyroxine produced in the thyroid gland is an iodinated derivative of amino acid tyrosine. Abnormally
low level of thyroxine leads to hypothyroidism. Increased level of thyroxine causes hyperthyroidism. Low
level of iodine in the diet may lead to hypothyroidism and enlargement of the thyroid gland.
Testosterone is the major male sex hormone and estradiol is the main female sex hormone.

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