ST JOSEPH’S INDIAN COMPOSITE PU COLLEGE

CHEMISTRY REMEDIAL NOTES

IMPORTANT QUESTIONS COMPULSORILY TO BE STUDIED BY REMEDIAL STUDENTS
1. *Calculate the packing efficiency in simple cube
2. *Calculate the packing efficiency in ccp/FCC
3. *Calculate the packing efficiency in BCC
4. *Derive the first order rate equation
5. *Derive the zero order rate equation
6. *Derive the equation for half life of a zero order reaction
7. *Derive the equation for half life of a first order reaction
8. *With a neat labeled diagram of standard hydrogen electrode (SHE), explain the working of
SHE, write the cell representation and half cell reaction
9. *Define fuel cell. Draw the schematic representation of H2 – O2 fuel cell. Write the anodic and
cathodic reactions.
10. Define a) tyndall effect b) Brownian movement, c) electrophoresis d) coagulation
e) Hardy-Schulze rule
11. Explain the lock and key mechanism of enzyme catalysis
12. *Extraction of copper from copper matte with equations
13. *Extraction of aluminium from bauxite by Hall Heroult process – diagram, importance of
cryolite & flourospar, anodic and cathodic equations.
14. *Leaching of bauxite ore with equations
15. *Purification of Ni by Mond’s process and Zr/Ti by Van –Arkel process
16. *Preparation of ammonia by Habers process – flow chart, catalyst promoters and reaction
conditions.
17. *Preparation of nitric acid by Ostwalds process- balanced equations with explaination and
conditions
18. *Preparation of sulphuric acid by Contact process- balanced equations with explaination and
conditions
19. *Preparation of K2Cr2O7 from chromite ore – explaination and balanced equations
20. *Preparation of KMnO4 from MnO2 (pyrolusite) – explaination and balanced equations.
21. *Explain using VBT the hybridization, geometry and magnetic property in the following
complexes
a) [CoF6]3- b) [Co(NH3)]3+ c) [NiCl4]2- d) [Ni(CN)4]2-
22. *Explain SN1 mechanism for the conversion of tertiary butyl bromide to tertiary butyl alcohol
23. *Explain SN2 mechanism for the conversion of methylchloride to methyl alcohol
24. *Explain with mechanism the dehydration of ethanol to ethane
25. *Write the mechanism for the addition of HCN to an aldehyde or ketone with an example
26. Commonly asked named reactions :-
- Sandmeyers reaction, Swarts reaction, Finkelsteins reaction
- Fittig, Wurtz-Fittig, Wurtz reaction
- Reimer-Tiemann reaction
- Kolbe’s reaction
- Cumenes process
- Grignard reagent reactions
- Rosenmund’s reduction
- Stephen’s reaction
- Etards reaction
- Clemmenson’s reduction
- Wolff- Kishner reduction
- Aldol condensation
- Cannizaro’s reaction
- Hell-Volhard-Zelinsky reaction (HVZ)
- Conversion of carboxylic acid to an amide
- Gabriel phthalimide reaction
- Hoffmann bromamide degradation
- Carbylamines reaction
- Diazotization and coupling reactions.
 SOLIDS
Number of particles in simple cubic unit cell or primitive unit cell
Each cubic unit cell has 8 atoms on its corners, and each corner is shared by 8 unit cells
Therefore the total number of atoms in one unit cell = 8 corner x 1/8 per corner atom = 1 atom.
Number of particle in a BCC unit cell
A BCC unit cell contain 8 atoms on all its corners and one atom at the centre of the unit cell
Thus in a body-centered cubic (bcc) unit cell:
- 8 corner x 1/8 per corner atom = 1 atom.
- 1 body centre atom = 1 × 1 = 1 atom
∴ Total number of atoms per BCC unit cell = 2 atoms
Number of particle in a FCC unit cell
A FCC unit cell contains 8 atoms on all its corners and also at the centre of each face
Thus in a face centered cubic (FCC) unit cell:
- 8 corners x 1/8 per corner atom = 1 atom.
- 6 faces x ½ per face atom = 3 atoms
∴ Total number of atoms per FCC unit cell = 1+3 = 4 atoms
Formula of a Compound is based on the number of octahedral voids and tetrahedral voids:
The numbers of these two types of voids depend upon the number of close packed spheres.
Let the number of close packed spheres be N, then
The number of octahedral voids generated = N
The number of tetrahedral voids generated = 2N
Packing efficiency
a) Packing efficiency in simple cube

In a simple cubic lattice the atoms are located only on the corners of the cube.
The particles touch each other along the edge.
Thus, the edge length or side of the cube ‘a’, and the radius of each particle, ‘r’ are related as
a = 2r
The volume of the cubic unit cell = a3 = (2r)3 = 8r3
Since a simple cubic unit cell contains only 1 atom
The volume of the space occupied by one atom = 4/3r3
∴ Packing efficiency = Volume of one atom x 100%
Volume of cubic unit cell
= 4/3r3 x 100 = 52.36% = 52.4 %
8r3
b) Packing efficiency in body centered cubic (BCC) lattice

In a BCC lattice the atom at the centre will be in touch with the other two atoms
diagonally arranged.
In ∆ EFD,
b2 = a2 + a2 = 2a2
b = √2a
in ∆ AFD
c2 = a2 + b2 = a2 + 2a2 = 3a2
c = √3a
 The length of the body diagonal c is equal to 4r, where r is the radius of the sphere (atom), as all the
three spheres along the diagonal touch each other.
Therefore, √3a = 4r or a = 4r /√3
BCC unit cell contains 2 atoms per unit cell therefore their total volume = 2 x 4/3r3
Volume of the unit cell = a3 = (4 r /√3)3
∴ Packing efficiency = Volume occupied by 2 spheres in the unit cell x 100%
Total Volume of unit cell
= 2 x 4/3r3 x 100 = 68 %
(4 r /√3 )3
c) Packing efficiency in face centered cubic (FCC) unit cell

In a ccp / FCC lattice the atoms on the corners are in touch with the atoms in
the centre of the face along the face diagonal.
In ∆ABC
AC2 = b2 = BC2 + AB2
= a2+a2 = 2a2 or
b =√2a
If r is the radius of the sphere,
We find b = 4r = √2a or
a = 4r /√2 = 2√2 r

Each unit cell in ccp/FCC structure, has effectively 4 spheres.

Total volume of four spheres = 4 x 4/3r3
Volume of the cube = a3 = (2√2 r)3

∴ Packing efficiency = Volume occupied by 4 spheres in the unit cell x 100%

Total Volume of unit cell
3
= 4 x 4/3r x 100 = 74 %
(2√2 r)3
Density of unit cell:
density of the unit cell = mass of unit cell
volume of unit cell
d = z x m or d = z x M
a3 NA x a3 (problems based on density are very important)
Defects in solids:
i. Frenkel defect (dislocation defect):-
- defect is shown by ionic solids.
- The smaller ion (usually cation) is dislocated from its normal site to an interstitial site
- It creates a vacancy defect at its original site and an interstitial defect at its new location.
- It does not change the density of the solid.
- Defect is shown by ZnS, AgCl, AgBr and AgI
ii. Schottky defect:-
- Type of vacancy defect shown by ionic solids in which the cation and anion are of similar sizes
- Equal number cations and anions will be missing from the lattice points to maintain electrical neutrality.
- The density of the solid decreases.
- Eg:- NaCl, KCl, CsCl and AgBr
iii. Metal excess defect Due to anionic vacancies
- Shown by alkali halides like NaCl and KCl
- This happens when anion diffuse to the surface of the substance and react with the metal to form metal
ions.
- The electrons released by the metals occupy the anionic sites.
- The anionic sites occupied by unpaired electrons are called F-centres.
Paramagnetism:
- Weakly attracted by a magnetic field and are magnetised in a magnetic field in the same direction.
- Paramagnetism is due to presence of one or more unpaired electrons which are attracted by the
magnetic field. Eg:- O2, Cu2+, Fe3+, Cr3+
Diamagnetism:
- Diamagnetic substances are weakly attracted by a magnetic field and shown by those substances in
which there are no unpaired electrons
- Eg:- H2O, NaCl and C6H6
Ferromagnetism:
- attracted very strongly by a magnetic field
- When the substance is placed in a magnetic field all the domains get oriented in the direction of the
magnetic field and a strong magnetic effect is produced.
- Ferromagnetic substance remains a magnet even after the magnetic field is removed.
- Eg:- iron, cobalt, nickel, gadolinium and CrO2
Antiferromagnetism: they have domain structure similar to ferromagnetic substance, but their domains are
oppositely oriented and cancel out each other's magnetic moment eg:- MnO
Ferrimagnetism:
- Observed when the magnetic moments of the domains in the substance are aligned in parallel and anti-
parallel directions in unequal numbers.
- are weakly attracted by magnetic field as compared to ferromagnetic substances.
- Eg:- Fe3O4 (magnetite) and ferrites like MgFe2O4 and ZnFe2O4
SOLUTIONS
Henry’s law:- “The solubility of a gas in liquid is directly proportional to the partial pressure of the gas
present above the solution”
Or “The partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of the gas (x) in
the solution. p = kH x, where kH is the Henry’s law constant”
Applications of Henry’s Law:
- In manufacture of soft drinks and soda water, CO2 is passed at high pressure to increase its solubility.
- To minimise the painful effects of bends (formation of nitrogen bubbles in the blood due to change in
pressure) accompanying the decompression of deep sea divers, O2 diluted with less soluble He gas is
used as breathing gas.
- At high altitudes, the partial pressure of O2 is less than that at the ground level. This leads to low
concentrations of O2 in the blood of climbers which causes “anoxia” ( due to lack of oxygen climbers
become weak and cannot think properly).
Raoult’s Law,
“For a solution of two volatile liquids, partial vapour pressure of each component of the solution is directly
proportional to its mole fraction present in the solution”.
ie., P total = p10 x1 + p20 x2

Ideal solution Non-ideal solution

- Obeys Raoult’s law - Does not obey Raoult’s Law
- Vmixing = 0 - Vmixing ≠ 0
- Hmixing = 0 - Hmixing ≠ 0
- Eg: n-hexane + n-heptane - Eg: phenol + aniline
- Azeotropes:
These are binary mixtures having same composition in the liquid and vapour phase and boils at a constant
temperature. The components of an azeotrope cannot be separated by fractional distillation.
There are two types of azeotropes: minimum boiling and maximum boiling azeotrope
- Minimum boiling azeotrope: these solutions show large positive deviation from Raoult’s law. Eg:
95% ethanol-water mixture.
- Maximum boiling azeotrope: these solutions show large negative deviation from Raoult’s law. Eg:
68% nitric acid in water.
- Osmotic pressure: The pressure that just stops the flow of solvent to the solution through a semi
permeable membrane is called osmotic pressure.
- Isotonic solutions: Two solutions having same osmotic pressure at a given temperature
- 0.9% w/v sodium chloride solution called the normal saline solution
- The direction of osmosis can be reversed if a pressure larger than the osmotic pressure is applied to the
solution side. i.e. pure solvent will flow out of the solution. This phenomenon is called Reverse
Osmosis.
- Abnormal molar masses: If the non-volatile solute added undergo dissociation or association in the
solution there will abnormality in the colligative property observed when compared to the expected
value.
- To account for the extent of dissociation and association vant Hoff’s factor ‘i’ is introduced which is
defined as

- If the vant Hoff’s factor i ˂ 1(unity) then the solute undergoes association
- If the vant Hoff’s factor i > 1 (unity) then the solute undergoes dissociation

Problems based on the following formulae

- Mass % of a component = Mass of the component in the solution x 100
Total mass of the solution
- Volume % of a component = Volume of the component x 100
Total volume of solution
- Mole fraction = no. of moles of the component
Total no. of moles of all the components in the solution
- For a binary solution, if the number of moles of A and B are nA and nB respectively, the mole fraction of
A (xA ) and mole fraction of B(xB) will be
xA = nA / nA + nB and xB = nB / nA + nB
- xA + xB = 1

- Molarity (M) = mass of solute (in gram) x 1000g

mol. wt. of solute x volume of solution (in mL)

- Molality (m) = mass of solute in gram x 1000g

mol. wt. of solute x mass of solvent (in g)

- Relative lowering of vapour pressure

- Elevation in boiling point

- Depression in freezing point

- Osmotic pressure

ELECTROCHEMISTRY
Standard hydrogen electrode (SHE):

represented by Pt(s)/ H2(g)/ H+(aq)

half-cell reaction and E0SHE = 0.0V

- The standard hydrogen electrode consists of a platinum electrode coated with platinum black. The
electrode is dipped in an acidic solution (1M concentration) and pure hydrogen gas is bubbled through
it at 1 bar pressure.
Kohlrausch’s Law of Independent Migration of ions:
- “Limiting molar conductivity of an electrolyte can be represented as the sum of the individual
contributions of the anion and cation of the electrolyte.”
- m = ν+ λ0+ + ν– λ0–
Faraday’s First Law: “The amount of chemical reaction which occurs at any electrode during electrolysis
by a current is proportional to the quantity of electricity passed through the electrolyte (solution or melt).”

Faraday’s Second Law: “The amounts of different substances liberated by the same quantity of electricity
passing through the electrolytic solution are proportional to their chemical equivalent weights (Atomic Mass
of Metal ÷ Number of electrons required to reduce the cation).”
Fuel cell: Galvanic cells designed to convert the energy of combustion of fuels like hydrogen, methane,
methanol etc. directly into electrical energy are called FUEL CELLS
H2 – O2 fuel cell - It uses the reaction of hydrogen with oxygen giving water.

- Hydrogen and oxygen are bubbled through porous carbon electrodes into conc. Aq.NaOH
- Catalysts like finely divided Pt or Pd

Problems based on the following formulae

M1(s) / M1n+(aq) // M2n+ (aq) / M2(s)
E0cell = E0right – E0left or E0cell = E0cathode – E0anode

- Nernst equation for a galvanic cell:

- Ecell = E0cell - 2.303RT log [oxidized species]
nF [reduced species]
ie., for the galvanic cell, M1(s) / M1n+(aq) // M2n+ (aq) / M2(s)
- Ecell = E0cell - 2.303RT log [M1n+]
nF [M2n+]
At T = 298 K, R = 8.314 JK–1 mol–1 and F = 96487 Cmol–1
Ecell = E0cell - 0.0591 log [oxidized species]
n [reduced species]
0
E cell = 0.0591 log Kc
n
∆G0 = – nFE0cell or ∆G0 = – 2.303 RT log Kc

m = molar conductivity and  = conductivitty

 CHEMICAL KINETICS
First order reaction: the rate of the reaction is proportional to the first power of the concentration of the
reactant R.
Consider a general reaction
R P
Rate = - d[R]/ dt = k[R]1
d[R]/ [R] = -kdt
Integrating the above equation we get
ln [R] = -kt + I ---------------- (1)
Evaluate I
When t = 0, [R] = [R]0 where [R]0 = initial concentration of the reactant, equation (1) can be written
as
ln[R]0 = -k x 0 + I
ln[R]0 = I
Substitute the value of I in equation 1, we get
ln [R] = -kt + ln[R]0
Rearranging this equation we get
k = 1 ln [R]0
t [R]
k = 2.303 log [R]0
t [R]
Zero order rate equation: Zero order reaction means that the rate of the reaction is proportional to zero
power of the concentration of reactants
Consider a general reaction
R P
Rate = - d[R]/ dt = k[R]0
d[R] = -kdt
Integrating the above equation we get
[R] = -kt + I
Evaluate I
When t = 0, [R] = [R]0 where [R]0 = initial concentration of the reactant, equation 1 can be written as
[R]0 = -k x 0 + I
[R]0 = I
Substitute the value of I in equation 1, we get
[R] = -kt + [R]0
Rearranging this equation we get
k = [R]0 - [R]
t
Half-life of a Zero order reaction:
k = [R]0 - [R] t
at t = t1/2 , [R] = ½ [R]0 the rate constant at t1/2 becomes k = [R]0 - ½ [R]0 t1/2
t1/2 = [R]0 2k
- the t1/2 of a zero order reaction is directly proportional to the initial concentration of the reactants
[R]0
Half-life of a First order reaction:
k = 2.303 log [R]0
t [R]
at t = t1/2 , [R] = ½ [R]0 the rate constant at t1/2 becomes
k = 2.303 log [R]0
t ½ [R]0
t1/2 = 2.303 log 2
t
t1/2 = 0.693 / k
- The t1/2 of a first order reaction is independent of the initial concentration of the reactants [R]0
Pseudo first order reactions: These are chemical reaction of higher order but will obey the rate law of a
first order reaction when the concentration of all the reactants except one is taken in large excess. Some of
the common examples are:
- Hydrolysis of ethyl acetate
- Hydrolysis of sucrose
The temperature dependence of the rate of a chemical reaction is mathematically given by Arrhenius
equation. k = A e -Ea /RT where A is the Arrhenius factor or the frequency factor. It is a constant
specific to a particular reaction R is gas constant and Ea is activation energy measured in J mol–1.

- Problems based on
Effect of temperature on the rate of a reaction:

Effect of catalyst on the rate of a reaction

The number of collisions per second per unit volume of the reaction mixture is known as collision
frequency (Z).
- criteria for effective collisions –
(a) The collisions in which molecules collide with sufficient kinetic energy (called threshold
energy*) and
(b) Proper orientation, so as to facilitate breaking of bonds between reacting species and formation
of new bonds
SURFACE CHEMISTRY
- The accumulation of molecular species at the surface rather than in the bulk of a solid or liquid is termed
adsorption.
- Adsorption is an exothermic process ie., ∆H of adsorption is always negative
- During adsorption the entropy of the gas decreases ie., ∆S is negative
physisorption chemisorption
- Caused by van der waal’s forces - Caused by chemical bond formation
- Not specific in nature - Highly specific
- It is reversible - It is irreversible
- Enthalpy of adsorption is low - Enthalpy of adsorption is high
- Rate of adsorption decreases with increase in - Rate of adsorption increases with increase in
temperature temperature
- No activation energy required - High activation energy required
- Results in multimolecular layer adsorption - Results in only unimolecular layer adsorption
Freundlich adsorption isotherm:

or
Catalysis: Substances, which accelerate the rate of a chemical reaction and themselves remain chemically
and quantitatively unchanged after the reaction, are known as catalysts, and the phenomenon is known as
catalysis. There are two types of catalysis - homogenous and heterogenous catalysis.
Homogeneous catalysis - When the reactants, products and the catalyst are in the same phase (i.e., liquid or
gas), the process is said to be homogeneous catalysis.
Eg:
Heterogenous catalysis - The catalytic process in which the reactants and the catalyst are in different phases
is known as heterogeneous catalysis
Eg: ,

- Ability of a catalyst is the extend to which the rate of the reaction is altered
- Selectivity of a catalyst is the ability of a catalyst to direct a reaction to a particular product.
- Shape selective catalysis - The catalytic reaction that depends upon the pore structure of the catalyst and
the size of the reactant and product molecules. Eg: ZSM-5 helps in converting alcohol directly into
gasoline (petrol)

Characteristics of Enzyme catalysis:

- Highly specific, highly active at optimum temperature and pH
- Its activity increases in the presence of activators and coenzymes.

Mechanism of enzyme catalysis – lock and key model

Step 1 – binding of enzyme to substrate to form enzyme-substrate complex

E+S ES*

Step 2 – decomposition of enzyme-substrate complex to form product

ES* E +P
COLLOIDS:
A colloid is a heterogeneous system in which one substance is dispersed (dispersed phase) as very fine
particles in another substance called dispersion medium.
CLASSIFICATION OF COLLOIDS:
1. Based on the Physical state of dispersed phase and dispersion medium

2. Based on Nature of Interaction between Dispersed Phase and Dispersion Medium : clsassified as
lyophilic and lyophobic colloids.
Lyophilic colloids Lyophobic colloids
- There is affinity between the dispersed phase and - No affinity between the dispersed phase and
dispersion medium dispersed medium
- Obtained by simple mixing of particles with the - Can be prepared only by specific methods
medium
- These are reversible sols - These are irreversible sols
- They are stable and do not coagulate easily - Needs stabilizing agent for preservation and can
be coagulated easily
3. Based on Type of Particles of the Dispersed Phase: classified as Multimolecular, Macromolecular and
Associated Colloids
- Multimolecular colloids: On dissolution, a large number of atoms or smaller molecules of a substance
aggregate together to form species having size in the colloidal range (1–1000 nm). These species formed
are called multimolecular colloids
- Macromolecular colloids: Macromolecules in suitable solvents form solutions in which the size of the
macromolecules may be in the colloidal range. Such systems are called macromolecular colloids.
- Associated colloids (Micelles): There are some substances which at higher concentrations exhibit
colloidal behaviour due to the formation of aggregates. The aggregated particles thus formed are called
micelles. These are also known as associated colloids
- The formation of micelles takes place only above a particular temperature called Kraft temperature
(Tk) and above a particular concentration called critical micelle concentration (CMC)
Preparation of colloids: Bredig’s electric arc method: in this method, electric arc is struck between
electrodes of the metal immersed in the dispersion medium. The intense heat produced vapourises the metal,
which then condenses to form particles of colloidal size.
- Peptization: Peptization may be defined as the process of converting a precipitate into colloidal sol by
shaking it with dispersion medium in the presence of a small amount of electrolyte.
- The electrolyte used for this purpose is called peptizing agent.
Purification of colloids: The process used for reducing the amount of impurities to a requisite minimum is
known as purification of colloidal solution.
Dialysis: It is a process of removing a dissolved substance from a colloidal solution by means of diffusion
through a suitable membrane. If this process is done under the influence of electric current then it is called
electrodialysis
Ultrafiltration: Ultrafiltration is the process of separating the colloidal particles from the solvent and
soluble solutes present in the colloidal solution by specially prepared filters, which are permeable to all
substances except the colloidal particles. The pores of filter paper can be reduced in size by impregnating
with collodion solution to stop the flow of colloidal particles.
Properties of colloidal solution:
- Tyndall effect: the scattering of light by the colloidal particles
- Brownian movement: the zig-zag movement fo colloidal particles.
- Electrophoresis: the movement of charged colloidal particles to the respective electrodes under the
influence of applied electrical potential.
- Coagulation: the process of settling the colloidal particles by boiling, by persistent dialysis or by ddition
of electrolyte
- Hardy-Schulze rule: “Greater the valency of the flocculating ion, greater is its power to coagulate.”

GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

1. Concentration of ore: The removal of impurities (gangue) from the ores is known as ore concentration.
Gravity separation or hydraulic washing
- The separation is based on the difference in the specific gravities of the gangue particles and the ore
particles
- The powdered ore is agitated with water or washed with a running stream of water. The heavy ore
particles settle down while the lighter particles of sand, clay, etc., are washed away
Magnetic separation
- A magnetic separator consisting a belt moving on two rollers is used. One of which is a strong magnet.
- The powdered ore is dropped on the belt from one end (non-magnetic) and at the other end (magnetic),
the magnetic particles are attracted and fall nearer the roller while non-magnetic particles fall away from
the roller
Oil or Froth flotation process: This method is used for the concentration of sulphide ores
- The powdered ore is added to water containing pine oil (frothing agent). A vigorous stream of air is now
passed through, which thoroughly agitates the mixture and disposes the oil into colloid sized particles.
- As a result of this, the sulphide particles of the ore stick to the oil droplets and rise to the surface in the
form of froth supported by air bubbles.
- Water wets the gangue particles which sink to the bottom.
- If two sulphide ores like PbS &ZnS are present depreesent like NaCN to be used which will allow PbS
to come with froth but prevents ZnS
Leaching of alumina from bauxite: there are three steps
- The powdered ore is digested with 45% caustic soda at 473-523K and 35-36 bar pressure
- Alumina goes into the solution forming soluble sodium aluminate
Al2O3.2H2O(s) + 2NaOH(aq) + H2O 2Na[Al(OH)4]
- The solution is filtered to remove insoluble impurities. Filterate is neutralised with CO2 to form hydrated
alumina(seeded with prepared samples of aluminium hydroxide)
2Na[Al(OH)4](s) + CO2(g) Al2O3.xH2O(s)+2NaHCO3
- Hydrated alumina is strongly heated to remove the water of hydration
Al2O3.xH2O(s) Al2O3 +x H2O
Roasting: heating of the ore below its melting point in presence of excess of air
2PbS + 3O2 →2PbO + 2SO2
2Cu2S + 3O2 →2Cu2O + 2SO2
Calcination: heating of the ore below its melting point in absence or limited supply of air

Extraction of iron: smelting done in blast furnace

There are 4 zones in the blast furnace
1. combustion zone- 2000K

2. reduction zone- 1000K

3. slag zone- 1200K

4. fusion zone: molten iron is obtained with 4% carbon called pig iron
Extraction of copper from copper matte (Cu2S + FeS)
Copper matte is taken into silica lined convertor along with some silica and hot air is blown to convert the
remaining FeS, FeO, Cu2S and Cu2O to metallic copper. Solidified copper thus obtained has blistered
appearance due to evolution of SO2 so its called blister copper

Extraction of zinc:
Reduction of zinc oxide is done using coke by heating. For heating, the oxide is made into brickettes with
coke and clay.
ZnO + C Zn + CO
Extraction of aluminium from bauxite by Hall-Heroult process:
• Electrolysis of pure alumina(Al2O3)dissolved in molten cryolite(Na3AlF6)containing small amount of
flourospar (CaF6). Alumina is a bad conductor therefore cryolite is used to improve conductivity.
Flourospar is used to bring down the fusion temperature of alumina to 1140K.
• Electrolysis cell consists of an iron tank lined with carbon which acts as cathode. A series of graphite
rods act as anode.

Extraction of gold/ silver by oxidation-reduction method (hydrometallurgy)

• Au/Ag is leached out with cyanide. Metal dissolves and forms cyanides leaving out impurities.
(oxidation). Metal ions are ppted by adding more reactive metals like zinc dust ( reduction)
Refining of metal:
Zone refining: Elements such as Si, Ge, Ga, etc., Which are used as semi-conductors are refined by this
method. Highly pure metals are obtained. The method is based on the difference in solubility of impurities in
molten and solid state of the metal.
A movable heater is fitted around a rod of the impure metal. The heater is slowly moved across the rod. The
metal melts at the point of heating and as the heater moves on from one end of the rod to the other end, the
pure metal crystallises while the impurities pass on the adjacent melted zone.

Vapour phase refining: the metal is converted into its volatile compound which is collected and
decomposed to give pure metal.
Mond Process for Refining Nickel: nickel is heated in a stream of carbon monoxide forming a volatile
complex named as nickel tetracarbonyl. This complex is decomposed at higher temperature to obtain pure
metal.

van Arkel method for refining Zirconium or Titanium:

The crude metal is heated in an evacuated vessel with iodine. The metal iodide being more covalent,
volatilizes.

The metal iodide is decomposed on a tungsten filament, electrically heated to about 1800K. The pure metal
deposits on the filament

p-BLOCK ELEMENTS
Important preparations:
Habers process: The optimum conditions for the production of ammonia are
➢ pressure of 200 × 105 Pa (about 200 atm),
➢ temperature of ~ 700 K and
➢ Use of a catalyst such as iron oxide with small amounts of K2O and Al2O3 to increase the rate of
attainment of equilibrium.

Flow chart of Habers process

Ostwald’s process: preparation of nitric acid
- Catalytic oxidation of NH3 by atmospheric oxygen to form nitric oxide.

- Nitric oxide combines with oxygen giving NO2

- Nitrogen dioxide is dissolved in water to give HNO3

Contact process: preparation of sulphuric acid

- Burning of sulphur or sulphide ores in air to generate SO2

- Conversion of SO2 to SO3 by the reaction with oxygen in the presence of a catalyst (V2O5)

- Absorption of SO3 in H2SO4 to give Oleum (H2S2O7).

- Dilution of oleum with water gives H2SO4 of the desired concentration. The sulphuric acid obtained by
Contact process is 96-98% pure.
Ozone preparation: When a slow dry stream of oxygen is passed through a silent electrical discharge,
conversion of oxygen to ozone (10%) occurs. The product is known as ozonised oxygen.
3O2 2O3
Chlorine preparation:
- By heating manganese dioxide with concentrated hydrochloric acid.

- Deacon’s process: By oxidation of hydrogen chloride gas by atmospheric oxygen in the presence of
CuCl2 (catalyst) at 723 K

Reasons for Anomalous properties of certain elements:

- Nitrogen – It has a small size. It does not have d – orbitals, It has high electronegativity & It has high
ionization enthalpy
- Oxygen – due to its small size, high electronegativity & absence of d-orbitals
- Fluorine – due to Small size, Highest electronegativity, Low F-F bond dissociation enthalpy due to its
small size and possible repulsion between the lone pairs of electrons as they are very close in F2
molecule &Non availability of d-orbitals
Give reason: interhalogen compounds are more reactive than halogens except fluorine.
- This is because the X-X’ bond in interhalogens is weaker than X-X bond.
Important reactions (COMMONLY ASKED)
CH4 + 2O2 CO2 + 2H2O
2Fe3+ + SO2 + 2H2O 2Fe2+ + SO42- + 4H+
C12H22O11 conc.H2SO4 12C + 11 H2O
H2SO4 + SO3 H2S2O7
2NaOH + Cl2 NaCl + NaOCl + H2O
(cold & dil)
6NaOH +3Cl2 5 NaCl + NaClO3 + 3H2O
(hot & conc.)
Cl2 + 3F2 (excess) 3ClF3
Na2SO3 + 2HCl NaCl + H2O + SO2
PbS + 4O3 PbSO4 + 4O2
Cu + 2 H2SO4 CuSO4 + SO2 + 2H2O
Cl2 + SO2 H2SO4 + 2HCl
8 NH3 (excess) + 3Cl2 NH4Cl + N2
heat
2 KClO3 2KCl + 3O2
SO2 + Cl2 + 2H2O H2SO4
P4 + NaOH + 3H2O PH3 + 3 NaH2PO2

Noble gases (one mark):

- Mention the commercial source of helium
Natural gas
- Which noble gas is the most abundant in atmospheric dry air?
Argon
- How is Xe+PtF6- prepared?(Bartlett reaction) – first noble gas compound preparation
It is prepared by mixing Xe and PtF6 , Xe + PtF6 Xe+PtF6-
- Noble gases have very low boiling point. Why?
Because the atoms of noble gases are held by weak interatomic interaction called dispersion forces
- XeF6 + 3H2O XeO3 + HF
- Why group 18 elements are called noble gases?
Because they are chemically inert and form very few compounds
- Name the noble gas with the lowest boiling point.
Helium
- Which noble gas is used for clinical purposes?
Helium

d- AND f- BLOCK ELEMENTS

Important preparations:
Preparation of potassium dichromate
Step 1: Preparation of sodium chromate
- The chromite ore is fused with sodium carbonate in the presence of oxygen to give sodium chromate.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
Step 2: Conversion of sodium chromate into sodium dichromate
- Sodium chromate is then acidified with conc. sulphuric acid to give sodium dichromate.
2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
Step 3: Conversion of sodium dichromate to potassium dichromate:
- Sodium dichromate is treated with KCl to give potassium dichromate.
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
Preparation of potassium permanganate from pyrolusite (MnO2):
- MnO2 is fused with an alkali metal hydroxide and an oxidising agent like KNO3.
- This produces the dark green K2MnO4 (potassium manganate) which disproportionate in a neutral or
acidic solution to give permanganate.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O
Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic
oxidation of manganate (Vl).

Calculation of magnetic moment: magnetic moment is calculated by using the spin only formula which is
given as
µ = √ n (n +2)
where n = number of unpaired electrons
µ = magnetic moment
BM = units of magnetic moment ( Bohr magneton)
Give reasons:
- Transition metals and their compounds acts as good catalysts : Due to their ability to adopt multiple
oxidation states, their ability to form complexes and Presence of vacant d orbitals
- Cu+ is diamagnetic and Cu2+ is paramagnetic: Cu+ has d10 configuration and no unpaired electrons but
Cu2+ has d9 configuration with unpaired elctrons which makes it paramagnetic.
- Transitions exhibit higher enthalpies of atomization: As they have large number of unpaired
electrons, they have stronger interatomic attractions or metallic bond.
- Cr2+ is a stronger reducing agent than Fe2+ : E0 of Cr3+/ Cr2+ is negative whereas E0 of Fe3+/Fe2+ is
positive
- Actinides show more number of oxidation states than lanthanides: Because of the comparable
energies of 5f, 6d and 7s orbitals
- The atomic radii of Zr and Hf are very close to each other:
Due to lanthanoid contraction
- The spin only magnetic moment of Sc3+ is zero (Z= 1)
Sc3+ = 3d0, it has no unpaired electrons, thus n = 0
- Ti4+/ Sc3+ salts are colourless while Cr3+ salts are coloured
Ti4+/ Sc3+ have no unpaired electrons while Cr3+ has 3 unpaired electrons that can undergo d-d transition.
- Transition elements exhibit variable oxidation: Due to the participation of ns and (n-1)d electrons
bonding as the energies of both subshells are the same.
- Fe3+ is more stable than Fe2+: Fe3+ has half-filled d-orbitals.
- Most of the transition metals have high boiling and melting points
This is because the electrons of (n-1)d orbitals and ns electrons are involved in metallic bonding.
- 2nd ionization enthalpy of Cu is exceptionally high
Because the Cu+ ion has d10 configuration
- Name the common oxidation state of actinoids
+3
- Name the metal of the 1st row transition series that has maximum number of unpaired electrons in
the ground state - Chromium
- Name the element which has zero spin only magnetic moment in its +2 oxidation state
Zinc
- Name the transition element which exhibits maximum number of oxidation states
Manganese
 COORDINATION COMPOUNDS
Werner’s postulates:
- In coordination compounds metals show two types of linkages (valences)-primary and secondary.
- The primary valences are normally ionisable and are satisfied by negative ions.
- The secondary valences are non ionisable. These are satisfied by neutral molecules or negative ions. The
secondary valence is equal to the coordination number and is fixed for a metal.
- The ions/groups bound by the secondary linkages to the metal have characteristic spatial arrangements
corresponding to different coordination numbers
Structures of some complexes based on Valence bond theory
Structure of [Co(NH3)6]3+
- the cobalt ion is in +3 oxidation state and has the electronic configuration 3d6

- NH3 is a strong field ligand hence its approach towards the central metal ion results in the pairing of 3d
electrons and leads to d2sp3 hybridisation

- Six NH3 ligands donate six pairs of electrons to the hybrid orbitals forming octahedral geometry

- The complex has diamagnetic behavior due to the absence of unpaired electrons.
Structure of [CoF6]3–
- the cobalt ion is in +3 oxidation state and has the electronic configuration 3d6

- F- being a weak field ligand doesn’t lead to the pairing of electrons in d orbitals.
- In this complex the hybridization occurs between 4s, 4p and outer 4d orbitals leading to sp3d2
hybridization.

- Six F- ligands contribute electrons to the sp3d2 orbital to form octahedral geometry.

- The complex is paramagnetic due to the presence of unpaired electrons.

Structure of [NiCl4]2-
- nickel is in +2 oxidation state and the ion has the electronic configuration 3d8

- Since Cl- is a weak field ligand hence pairing of d electrons do not take place. The 4s and 4p orbitals
hybridise to form sp3 hybridization
- Each Cl- donates a pair of electrons to the sp3 hybrid orbitals and form a tetrahedral structure

- The complex is paramagnetic due to the presence of unpaired electrons.

Structure of [Ni(CN)4]2–
- nickel is in +2 oxidation state and the ion has the electronic configuration 3d8

- CN- is a strong field ligand and hence pairing of d electrons will take place. It uses its 3d, 4s and 4p
orbitals to get dsp2 hybridization

- Each orbital gets a pair of electrons from the CN- ligands and forms a square planar geometry.

- The complex is diamagnetic in nature due to the absence of unpaired electron

Crystal field splitting: The splitting of the degenerate levels due to the presence of ligands in a definite
geometry is termed as crystal field splitting.
Crystal field splitting in octahedral complexes:
- In octahedral complex, the metal is surrounded by six ligands and there will be repulsion between the
metal d-orbitals and electrons of the ligands.
- Such repulsion is more when the metal is directed towards the ligands.
- Thus the dx2-y2 and dz2 orbitals experience more repulsion as they are directed towards the ligands and
will be raised in energy than dxy, dyz and dzx orbitals. Thus the degeneracy of the metal d-orbitals is
lost and the splitting of degenerate levels occur into higher eg level (dx2-y2 and dz2) and lower t2g level
(dxy, dyz and dzx) with an octahedral splitting energy of ∆o

Crystal field splitting in octahedral complexes.

- The octahedral crystal field splitting energy ∆o, depends upon the field produced by the ligand and
charge on the metal ion
- Some ligands are able to produce strong fields in which case, the splitting will be large whereas others
produce weak fields and consequently result in small splitting of d orbitals.
- I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O < NCS– < edta4– < NH3 < en < CN– < CO
- ligands can be arranged in a series in the order of increasing field strength termed as spectrochemical
series
Colour of coordination compounds:
- The colour of the coordination compounds is due to d-d transition of the electron between the higher eg
level and the lower t2g level.
Bonding in Metal Carbonyls – synergic bonding

Possess both σ and π character

- The M–C σ 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 π bond is formed by the donation of a pair of electrons from a filled d orbital of metal into the
vacant antibonding π* orbital of carbon monoxide.
- The metal to ligand bonding creates a synergic effect which strengthens the bond between CO and the
metal
Important definitions:
- Coordination entity - A coordination entity constitutes a central metal atom or ion bonded to a fixed
number of ions or molecules. For example, [CoCl3(NH3)3] is a coordination entity
- Ligands - The ions or molecules bound to the central atom/ion in the coordination entity are called
ligands
- Unidentate ligand - ligand is bound to a metal ion through a single donor atom eg:- Cl–, H2O or NH3
- Didentate - ligand can bind through two donor atoms eg:H2NCH2CH2NH2 (ethane-1,2-diamine) or
C2O42– (oxalate)
- Polydentate - when several donor atoms are present in a single ligand eg:- Ethylenediaminetetraacetate
ion (EDTA4–
- Ambidentate ligand - Ligand which has two different donor atoms and either of the two ligates in the
complex eg: NO2– and SCN– ions
- Coordination number - The coordination number (CN) of a metal ion in a complex can be defined as
the number of ligand donor atoms to which the metal is directly bonded.
- Coordination polyhedron
The spatial arrangement of the ligand atoms which are directly attached to the central atom/ion defines a
coordination polyhedron about the central atom.
- Complexes in which a metal is bound to only one kind of donor groups, e.g., [Co(NH3)6]3+, are known as
homoleptic
- Complexes in which a metal is bound to more than one kind of donor groups, e.g., [Co(NH3)4Cl2]+, are
known as heteroleptic
- Linkage Isomerism - arises in a coordination compound containing ambidentate ligand.
Eg: [Co(NH3)5(NO2)]Cl2 & [Co(NH3)5(ONO)]Cl2
- Ionisation Isomerism - This form of isomerism arises when the counter ion in a complex salt is itself a
potential ligand and can displace a ligand which can then become the counter ion.
Eg: [Co(NH3)5(SO4)]Br and [Co(NH3)5Br]SO4.
- Solvate Isomerism - Solvate isomers differ by whether or not a solvent molecule is directly bonded to
the metal ion or merely present as free solvent molecules in the crystal lattice
Eg: aqua complex [Cr(H2O)6]Cl3 (violet) and its solvate isomer [Cr(H2O)5Cl]Cl2.H2O (grey-green)
- Geometrical isomerism: arises in heteroleptic complexes due to different possible geometric
arrangements of the ligands

- Geometrical isomerism in complexes with coordination no. 6

- Eg:[Co(NH3)3(NO2)3
- If three donor atoms of the same ligands occupy adjacent positions at the corners of an octahedral
face, we have the facial (fac) isomer.
- When the positions are around the meridian of the octahedron, we get the meridional (mer) isomer

- Optical isomerism: Optical isomers are mirror images that cannot be superimposed on one another.

eg: optical isomers of [Co(en)3]3+

- Coordination isomerism: arises from the interchange of ligands between cationic and anionic entities of
different metal ions present in a complex
Eg:- [Co(NH3)6][Cr(CN)6], in which the NH3 ligands are bound to Co3+ and the CN– ligands to Cr3+.
In its coordination isomer [Cr(NH3)6][Co(CN)6], the NH3 ligands are bound to Cr3+ and the CN– ligands
to Co3+