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## Chapter: The Solid State

 Classification of solids:
 Crystalline and Amorphous solids:
S.No. Crystalline Solids Amorphous solids

## 1 Regular internal irregular internal

arrangement of arrangement of particles
particles

## 3 Regarded as true solids Regarded as super cooled

liquids or pseudo solids

##  Based on binding forces:

Crystal Classification Unit Binding Properties Examples
Particles Forces
Atomic Atoms London Soft, very Noble
dispersion low melting, gases
forces poor thermal
and electrical
conductors
Molecular Polar or Vander Fairly soft, Dry ice
non – Waal’s low to (solid,
polar forces moderately methane
molecules (London high melting
dispersion, points, poor
dipole – thermal and
dipole electrical
forces conductors
hydrogen
bonds)
Ionic Positive Ionic bonds Hard and NaCl, ZnS
and brittle, high
negative melting
ions points, high

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heats of
fusion, poor
thermal and
electrical
conductors
Covalent Atoms Covalent Very hard, Diamond,
that are bonds very high quartz,
connected melting silicon
in covalent points, poor
bond thermal and
network electrical
conductors
Metallic Solids Cations in Metallic Soft to very All
electron bonds hard, low to metallic
cloud very high elements,
melting for
points, example,
excellent Cu, Fe, Zn
thermal and
electrical
conductors,
malleable
and ductile
 Bragg Equation:
nλ = 2dsinθ,
Where,
d= distance between the planes
n = order of refraction
θ= angel of refraction
λ = wavelength
 Crystal Systems:
 Total number of crystal systems: 7
 Total number of Bravais Lattices: 14
Crystal Systems Bravais Intercepts Crystal angle Example
Lattices
Cubic Primitive, a=b=c a=b=g= Pb,Hg,Ag,Au
Face 90o Diamond,
Centered, NaCl, ZnS
Body

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Centered
Orthorhombic Primitive, a≠b≠c a=b=g= KNO2, K2SO4
Face 90o
Centered,
Body
Centered,
End Centered
Tetragonal Primitive, a=b≠c a=b=g= TiO2,SnO2
Body 90o
Centered
Monoclinic Primitive, End a≠b≠c a = g = 90o, CaSO4,2H2O
Centered b≠ 90o
Triclinic Primitive a≠b≠c a≠b≠g≠900 K2Cr2O7,
CaSO45H2O
Hexagonal Primitive a=b≠c a = b = 900, g Mg, SiO2,
= 120o Zn, Cd
Rhombohedra Primitive a=b=c a = g = 90o, As, Sb, Bi,
b≠ 90o CaCO3

##  Number of atoms in unit cells.

 Primitive cubic unit cell:
 Number of atoms at corners = 8×1/8 =1
 Number of atoms in faces = 0
 Number of atoms at body-centre: =0
 Total number of atoms = 1
 Body-centred cubic unit cell:
 Number of atoms at corners = 8×1/8 =1
 Number of atoms in faces = 0
 Number of atoms at body-centre: =1
 Total number of atoms = 2
 Face-centred cubic or cubic-close packed unit cell:
 Number of atoms at corners = 8×1/8 =1
 Number of atoms in faces = 6×1/2 = 3
 Number of atoms at body-centre: = 0
 Total number of atoms = 4

 Packing Efficiency
 Packing Efficiency = (Volume occupied by all the atoms present in unit cell / Total
volume of unit cell) ×100

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## Close structure Number of atoms Relation between Packing Efficiency

per unit cell ‘z’. edge length ‘a’ and
hcp and ccp or fcc 4 r = a/(2√2) 74%

##  Density of crystal lattice:

r = (Number of atoms per unit cell × Mass number)/(Volume of unit cell × NA)

##  Octahedral and Tetrahedral Voids:

Number of octahedral voids = Number of effective atoms present in unit cell
Number of tetrahedral voids = 2×Number of effective atoms present in unit cell
So, Number of tetrahedral voids = 2× Number of octahedral voids.
 Coordination numbers and radius ratio:
Coordination Geometry Radius ratio (x) Example
numbers
2 Linear x < 0.155 BeF2

## 3 0.155 ≤ x < 0.225 AlCl3

Planar Triangle
4 0.225 ≤ x < 0.414 ZnS
Tetrahedron
4 0.414 ≤ x < 0.732 PtCl42-
Square planar
6 0.414 ≤ x < 0.732 NaCl
Octahedron
8 Body centered 0.732 ≤ x < 0.999 CsCl
cubic

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##  Classification of Ionic Structures:

Structures Descriptions Examples

Rock Salt Anion(Cl-) forms fcc units and cation(Na+) NaCl, KCl, LiCl, RbCl
Structure occupy octahedral voids. Z=4 Coordination
number =6
Zinc Blende Anion (S2-) forms fcc units and cation (Zn2+) ZnS, BeO
Structure occupy alternate tetrahedral voids Z=4
Coordination number =4
Fluorite Cation (Ca2+) forms fcc units and anions (F-) CaF2, UO2, and ThO2
Structures occupy tetrahedral voids Z= 4 Coordination
number of anion = 4 Coordination number of
cation = 8
Anti- Fluorite Na2O, K2O and Rb2O.
Structures Oxide ions are face centred and metal ions
occupy all the tetrahedral voids.
Caesium Halide Halide ions are primitive cubic while the All Halides of Caesium.
Structure metal ion occupies the centre of the unit cell.
Z=2
Coordination number of = 8
Pervoskite One of the cation is bivalent and the other is CaTiO3, BaTiO3
Structure tetravalent. The bivalent ions are present in
primitive cubic lattice with oxide ions on the
centers of all the six square faces. The
tetravalent cation is in the center of the unit
cell occupying octahedral void.
Spinel and Spinel: M2+M23+O4, where M2+ is present in MgAl2O4 , ZnAl2O4,
Inverse Spinel one-eighth of tetrahedral voids in a FCC Fe3O4,FeCr2O4etc.
Structure lattice of oxide ions and M3+ ions are present
in half of the octahedral voids. M2+ is usually
Mg, Fe, Co, Ni, Zn and Mn; M3+ is generally Al,
Fe, Mn, Cr and Rh.

 Defects in crystal:
 Stoichiometric Defects
 Schottky Defect
 Some of the lattice points in a crystal are unoccupied.
 Appears in ionic compounds in which anions and cations are of nearly
same size.
 Decreases the density of lattice

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##  Examples: NaCl and KCl

 Frenkel Defects
 Ion dislocate from its position and occupies an interstitial position
between the lattice points
 Appears in crystals in which the negative ions are much larger than the
positive ion.
 Does not affect density of the crystal.
 Examples: AgBr, ZnS

 Non-Stoichiometric Defects
 Metal Excess defect: Metal excess defect occurs due to
 Anionic vacancies or
 Presence of extra cation.
 F-Centres: hole produced due to absence of anion which is occupied by
an electron.
 Metal deficiency defect: Metal deficiency defect occurs
 Due to variable valency of metals
 When one of the positive ions is missing from its lattice site and the extra
negative charge is balanced by some nearby metal ion acquiring two

Chapter: Solutions
 Basics:
 Solutions: Solutions are the homogeneous mixtures of two or more than two
components.
 Binary solution: A solution having two components is called a binary solution.
 Components of a binary solution:
 It includes solute and solvent.
 When the solvent is in solid state, solution is called solid solution.
 When the solvent is in liquid state, solution is called liquid solution.
 When the solvent is in gaseous state, solution is called gaseous solution.
 Concentration: It is the amount of solute in given amount of solution.
 Mass by volume percentage (w/v): Mass of the solute dissolved in 100 mL of
solution.
 Molality (m): The number of moles of solute present in 1kg of solvent.
Number of moles of solute
𝑀𝑜𝑙𝑎𝑙𝑖𝑡𝑦 =
Mass of solvent in kilograms
 Molarity (M): The number of moles of solute present in 1L of solution.
Number of moles of solute
Molarity = Volume of solution in litres

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##  Normality: The number of gram equivalent of solute dissolved per litre of

solution.
Number of gram equivalent of solute
𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 =
Volume of solution in litres

##  Solubility: It is the maximum amount that can be dissolved in a specified amount of

solvent at a specified temperature.

 Saturated solution:
 It is a solution in which no more solute can be dissolved at the same temperature
and pressure.
 In a nearly saturated solution if dissolution process is an endothermic process,
solubility increases with increase in temperature.
 In a nearly saturated solution if dissolution process is an exothermic process,
solubility decreases with increase in temperature.

 Henry’s Law: It states “at a constant temperature the solubility of gas in a liquid is
directly proportional to the pressure of gas”. In other words, “the partial pressure of gas
in vapour phase is proportional to the mole fraction of the gas in the solution”.
P = KH x
When a non-volatile solute is dissolved in a volatile solvent, the vapour pressure of solution
is less than that of pure solvent.
 Vapour Pressure:
 The pressure exerted by vapours over the liquid surface at equilibrium is
called vapour pressure of the liquid.
 If solute is non-volatile solid or liquid the vapour pressure of solution is equal to
partial vapour pressure of solvent in the solution.
 If the solute is volatile solid or liquid, then vapour pressure will be equal to the sum
of partial vapour pressure of solute and that of solvent.
 Raoult’s Law:
“The partial vapour pressure of any component in the solution is directly proportional to its
mole fraction”.

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## For a binary solution of two components A and B,

P A = XA
P B = XB
Where,
P0A = vapour pressure of component A in pure state.
PA = vapour pressure of component A in the solution.
P0B = vapour pressure of component B in pure state.
PB = vapour pressure of component B in the solution
 Limitations of Raoult’s Law
 Raoult’s law is applicable only to very dilute solutions.
 It is applicable to solutions containing non-volatile solute only.
 It is not applicable to solutes which dissociate or associate in a particular
solution
 Raoult’s Law in Combination with Dalton’s Law of Partial Pressure:
PT = XA P0A + XB P0B = P0B + (P0A -P0B) XA
Where
PT = Total Vapour Pressure of the Solution.
 Comparison of Raoult’ law and Henry’s law:
 It is observed that the partial pressure of volatile component or gas is directly
proportional to its mole fraction in solution.
 In case of Henry’s Law, the proportionality constant is KH and it is different
from p1o which is partial pressure of pure component.
 Raoult’s Law becomes a special case of Henry’s Law when KH becomes equal to
p10 in Henry’s law.
 Ideal and Non-Ideal Solutions:
 Ideal Solution:
 These solutions obey Raoult’s law at all compositions of solute in solvent at all
temperature.
 Two liquids A and B form and ideal solution when A –A and B–B molecular
attractions will be same and hence A–B molecular attraction will be almost
same as A–A and B–B molecular attraction.
 For Ideal Solutions:
 dHmixing = 0, i.e. no heat should be absorbed or evolved during mixing
 dVmixing = 0, i.e. no expansion or contraction on mixing
 Examples, Ethyl chloride and ethyl bromide, n–hexane and n–heptane,
CCl4 and SiCl4

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 Non-Ideal Solution:
 These solutions deviate from ideal behavior and do not obey Raoult’s law over
entire range of composition.
 For non-ideal solutions,
 dHmixing ≠ 0
 dHmixing ≠ 0
Here we may have two cases
 Non-ideal solution showing positive deviation
 The vapour pressure of a solution is higher than that predicted by Raoult’s Law.
 The intermolecular attractive forces between solute-solvent molecules are
weaker than those between solute-solute and solvent-solvent molecules i.e.,
A-B<A-AandB- B interactions.
 P A > XA & P B > X B
 2. dHmix > 0
 3. dVmix > 0
 Example: Cyclohexane and Ethanol

##  Non-ideal solution showing negative deviation

 The vapour pressure of a solution is lower than that predicted by Raoult’s Law.
 The intermolecular attractive forces between solute-solvent molecules are
stronger than those between solute-solute and solvent-solvent molecules i.e.
A-B > A-A and B- B interactions.
 P A > XA & P B > X B
 2. dHmix < 0
 3. dVmix < 0

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 Azeotropes:
 These are binary mixtures having same composition in liquid and vapour phase and
boil at constant temperature.
 Liquids forming azeotrope cannot be separated by fractional distillation.
 Types of azeotropes:
 Minimum boiling azeotrope: The solutions which show a large positive deviation
from Raoult’s law form minimum boiling azeotrope at a specific composition.
 Maximum boiling azeotrope: The solutions that show large negative deviation
from Raoult’s law form maximum boiling azeotrope at a specific composition.
 Colligative Properties
The properties of dilute solutions which depend only on number particles of solute present in
the solution and not on their identity are called colligative properties (denoting depending
upon collection).

##  Lowering of Vapour Pressure by a Non-Volatile Solute

 The relative lowering of vapour pressure of a solution containing a non-volatile
solute is equal to the mole fraction of the solute present in the solution.

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##  Elevation of Boiling Point by a Non-Volatile Solute:

 Since the addition of a non-volatile solute lowers the vapour pressure of the
solvent, the vapour pressure of a solution is always lower than that of the pure
solvent, and hence it must be heated to a higher temperature to make its vapour
pressure equal to atmospheric pressure.

##  Osmosis and Osmotic Pressure:

 Osmosis: The phenomenon of the passage of pure solvent from a region of lower
concentration (of the solution) to a region of its higher concentration through a
semi-permeable membrane.
 Osmotic Pressure: Excess pressure which must be applied to a solution in order to
prevent flow of solvent into the solution through the semi-permeable
membrane.
V = nRT

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##  Isotonic Solutions: A pair of solutions having same osmotic pressure is called

isotonic solutions.
 Hypertonic solution: If a solution has more osmotic pressure than other solution it
is called hypertonic solution.
 Hypotonic solution: If a solution has less osmotic pressure than other solution it is
called hypotonic solution

##  Abnormal Molecular Weight and Van't Hoff Factor:

 Van't Hoff Factor: Van't Hoff, in order to account for all abnormal cases introduced
a factor i known as the Van't Hoff factor, such that

##  Degree of Association: The fraction of the total number of molecules which

combine to form bigger molecule

## Let a be the degree of association, then,

The number of unassociated moles = 1-
The number of associated moles = /n
Total number of effective moles = 1- + /n

Obviously, i < 1
 Degree of Dissociation: The fraction of the total number of molecules which
dissociates in the solution, that is, breaks into simpler molecules or ions.

KCl ↔ K+ + Cl-
1-

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## Thus, the total number of moles after dissociation = 1- + + = 1+

Hence, i = (1+ )/1
i = 1+ = 1+ (2–1)
In general, i = 1+ (n–1) ,
Where, n = number of particles (ions) formed after dissociation
From the above formula, it is clear that i > 1

Chapter: Electrochemistry
 Electrolytic Conductance:

R = ρ× l /A

Where,

R = Resistance

κ = 1/ ρ

##  Equivalent Conductance (Λ):

Conducting power of all the ions produced by one g-equivalent i.e. one equivalent of
an electrolyte in a given solution

Λ = 1000 κ /C

equivalent/L.

Units: W–1cm2

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##  Molar Conductance (Λm):

Conductance of solution due to all the ions produced by one mole of the dissolved
electrolyte in a given solution.

Λm = κ/c

Λm = κ×1000/M

##  Relation between Λ and Λm

Λm = n Λ

Where n = n-factor of the electrolyte = total charge carried by either ion = M/E

##  Specific conductance: Decrease with dilution due to decrease in number of ions

per c.c. of the solution.
 Molar and Equivalent Conductance: Increases with increase in dilution.
 Weak electrolyte: Increase is due to increase in extent of ionization.
 Strong electrolyte: Increase is due to increase in mobility of ions because of
decreased inter-ionic attraction.

 Debye-Hückel-Onsager Equation

Where,

## A & B = Debye-Hückel constants.

C = Molar concentration

At 298 K,

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##  Kohlransch’s Law of Independent Migration of Ions:

 At infinite dilution, when dissociation is complete, each ion makes a definite
contribution towards equivalent conductance of the electrolyte irrespective of the
nature of the ion with which it is associated and the value of equivalent conductance
at infinite dilution for any electrolyte is the sum of contribution of its constituent
ions", i.e., anions and cations.

where,

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##  Faraday’s Laws of Electrolysis:

 First Law: The mass of a substance deposited or liberated at any electrode is directly
proportional to the amount of charge passed.

w = zQ

## Where z = electrochemical equivalent i.e. the mass of the substance in grams

deposited or liberated by passing one coulomb of charge.

##  Second Law: Mass of a substance deposited or liberated at any electrode on passing

a certain amount of charge is directly proportional to its chemical equivalent weight.

## That is w a E where w is the mass of the substance in grams while E is its

chemical equivalent weight in gms per equivalent=

 The charge possessed by 1 mole of electrons = 1.6 10–19 6.023 x 1023 ≈ 96500 C

## This charge is called as 1 Faraday.

If we pass one Faraday of charge, it means that we are passing one mole of electron and by
passing 1 Faraday of charge 1gm equivalent weight of the substance will be deposited or
liberated.

## By combining the first and second law, we get

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 Electrochemical Cells:

## Electrolytic Cell Galvanic cell

Electrical energy is converted into chemical Chemical energy is converted into electrical
energy. energy.
Anode positive electrode. Cathode Anode negative electrode. Cathode
negative electrode positive electrode.
Ions are discharged on both the electrodes. Ions are discharged only on the cathode

## If the electrodes are inert, concentration of Concentration of the anodic half-cell

the electrolyte decreases when the electric increases while that of cathodic half-cell
current is circulated decreases when the two electrodes are
joined by a wire
Both the electrodes can be fitted in the The electrodes are fitted in different
same compartment compartment

##  Standard electrode potential: The potential difference developed between metal

electrode and the solution of its ions of unit molarity (1M) at 25°C (298 K)
 IUPAC Cell Representation:

Example:

## M1A + m2B .... n1X + n2Y + .... .......(i)

Occurring in the cell, the Gibbs free energy change is given by the equation

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where

'a' represents the activities of reactants and products under a given set of conditions and

ΔGo refers to free energy change for the reaction when the various reactants and products
are present at standard conditions.

The free energy change of a cell reaction is related to the electrical work that can be
obtained from the cell, i.e.,

##  Some other important relations:

o Keq = enE/FRT
o ΔH = nF [T(dE/dT)-E]
o ΔS = nF(dE/dT)P

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##  Some Important Half Cells:

 Hydrogen Electrode:
 The electrode reaction: H2 -> 2H+ + 2e–
 Electrode representation: Pt | H2 (1 atm) | H+ (1M).
 Ferrous – Ferric Electrode:
 Electrode reaction: Fe3+ + e– -> Fe2+
 Electrode representation: Pt | Fe2+ (C1), Fe3+ (C2).

##  Quin – Hydrone Electrode:

 Electrode reaction:

##  Electrode representation: Pt.|QH2, Q, H+ (C)

 Calomel electrode:
 Electrode reaction: ½ Hg2Cl2 +e- ↔ Hg +Cl-
 Electrode is representation: Cl- (1M) | Hg2Cl2, Hg

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##  Oxidation is defined as the loss of electrons by a chemical species (atom, ion or

molecule).
 Reduction is the gain of electrons by a chemical species (atom, ion or molecule).
 An oxidising agent that chemical species which takes electrons thus it is an electron
acceptor.

1. A reducing agent is the chemical species that gives electrons and thus acts as an
electron donor.

2. When Fe2+(aq) ions are being oxidised, they are acting as reducing agents, and when
Fe3+(aq) ions are being reduced they are acting as oxidising agents. In general;

o Neither reduction nor oxidation occur alone. Both of them occur simultaneously.
Since both these reactions must occur at the same time they are often termed as
"redox reactions". The oxidation or reduction portion of a redox reaction, including

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## the electrons gained or lost can be determined by means of a Half-Reaction

 Oxidation Number

##  The oxidation number for an element in a covalent compound is by taking the

oxidation number to be equal to the charge that the element would carry, if all the
bonds in the compound were regarded as ionic instead of covalent.
 The sum of the oxidation numbers of all the atoms in an uncharged compound is
zero.
 In case of an ion, the algebraic sum of the oxidation numbers of all the atoms is
equal to the charge on the ion.
 Oxidation number of any element in its elementary state is zero.
 Fluorine is the most electronegative element. Its oxidation number is always -1.
 Oxygen after fluorine is the second most electronegative element.
 It shows an oxidation state of -2 in almost all the compounds excepts peroxides and
superoxides,
 In all compounds, except ionic metallic hydrides, the oxidation number of hydrogen
is +1.
 In any compounds has more than two elements, the oxidation number of any one of
them may have to be obtained by first assigning reasonable oxidation numbers to
the other elements.

## Oxidising agent Effective Change Decrease in

Oxidation Number
KMnO4 in acid solution MnO4 - → Mn2+ 5

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## manganese (IV) oxide MnO2 → Mn2+ 2

chlorine Cl → Cl- 1

## Reducing agent Effective Change Increase in Oxidation

Number
iron (II) salts (acid) Fe2+ → Fe3+ 1

## Chapter: Chemical Kinetics

 Chemical kinetics: It is the branch of chemistry that deals with the study of reaction
rates and their mechanisms.

 Rate of Reaction:
 Rate of change of extent of reaction is the rate of reaction.
 Rate of reaction is positive for product and negative for reactant.
 For reaction aA →bB
Rate =1/b(Δ[B]/ Δ t) = -1/a (Δ [A]/ Δt)

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##  It goes on decreasing as the reaction progress due to decrease in the

concentration(s) of the reactant(s).

##  Unit of rate of reaction: mol L-1 s-1

 The rate measured over a long-time interval is called average rate and the rate
measured for an infinitesimally small-time interval is called instantaneous rate.
 In a chemical change, reactants and products are involved. As the chemical reaction
proceeds, the concentration of the reactants decreases, i.e., products is produced.
 The rate of reaction (average rate) is defined as the change of concentration of any
one of its reactants (or products) per unit time.
 For reaction: A + B →C + D

𝑑[𝐴]
Rate of disappearance of 𝐴 = − 𝑑𝑡
Where;
d[A] is small change in concentration of ‘A’ and dt is small interval of
time.
𝑑[𝐵]
Similarly, rate of disappearance of 𝐵 = − 𝑑𝑡 ,
𝑑[𝐶]
Rate of appearance of 𝐶 = ,
𝑑𝑡

𝑑[𝐷]
Rate of appearance of 𝐷 = 𝑑𝑡 .
 Rate law or rate equation:
 It is the expression which relates the rate of reaction with concentration of the
reactants.
 The constant of proportionality ‘k’ is known as rate constant.
 Rate constant: When the concentration of reactants is unity, then the rate of
reaction is known as rate constant. It is also called specific reaction rate.

 Order of Reaction

##  For reaction aA + bB + ….. → cC+ ….

 R ∝[A]m[B]n or R = k[A]m[B]n….

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##  Where m and n may or may not be equal to a & b.

 m is order of reaction with respect to A and n is the order of reaction with
respect to B.
 m + n +… is the overall order of the reaction.
 Elementary Reaction:
 It is the reaction which completes in a single step.

 A reaction may involve more than one elementary reactions or steps also.

 Overall rate of reaction depends on the slowest elementary step and thus it is
known as rate determining step.
 Molecularity of Reaction:
 Number of molecules taking part in an elementary step is known as its molecularity.
 Order of an elementary reaction is always equal to its molecularity.
 Elementary reactions with molecularity greater than three are not known because
collisions in which more than three particles come together simultaneously are rare.

## PCl5 → PCl3 + Cl2 Unimolecular

2HI → H2 + I2 Bimolecular

## 2SO2 + O2 → 2SO3 Trimolecular

NO + O3 → NO2 + O2 Bimolecular

##  Differential and Integrated Rate Laws:

 Zero Order Reactions:

## For Reaction: A → Product

𝑑[𝐴]
= 𝑘[𝐴]0
𝑑𝑡
On integrating from limits [A]0 to [A]t
[A]0-[A]t = k0t

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Where,
[A]0 = Initial concentration of A
[A]t = Concentration of A at time t.
k0 = Rate constant for zero order reaction.
Half Life:
t1/2 = [A]0/2k
Unit of rate constant = mol dm-3s-1

##  First Order Reactions:

A → Product
𝑑[𝐴]
= 𝑘[𝐴]1
𝑑𝑡
On integrating from limits [A]0 to [A]t
[𝐴] = [𝐴0 ]𝑒 −𝑘𝑡
Half Life:
t1/2 = 0.693/k
Half-life is independent of the initial concentration of the reactant for a first order
reaction.
Units of k1 = s-1

##  Pseudo First Order Reactions:

 These are the reactions in which more than one species is involved in the rate
determining step but still the order of reaction is one.
 This may happen because one of the reactants have almost constant
concentration.
 The kinetics of the reaction and half-life will be same as first order reaction.
nth (n>1) order reactions:
𝑑[𝐴]
= −𝑘[𝐴]𝑛
𝑑𝑡

1 1
= + 𝑘𝑡
[𝐴]𝑛−1 [𝐴]𝑜𝑛−1

Half Life:
2𝑛−1 −1
t1/2 = 𝑘[𝐴]𝑜𝑛−1

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##  Parallel Reactions: The reactions in which a substance reacts or decomposes in more

than one way are called parallel or side reactions.

## k1 = fractional yield of B × kav

k2 = fractional yield of C × kav
If k1 > k2 then
A → B main and
A → C is side reaction
Let after a definite interval x mol/litre of B and y mol/litre of C are formed.

i.e

This means that irrespective of how much time is elapsed, the ratio of
concentration of B to that of C from the start (assuming no B and C in the
beginning) is a constant equal to k1/k2.

 Sequential Reactions:
 This reaction is defined as that reaction which proceeds from reactants to final
products through one or more intermediate

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##  stages. The overall reaction is a result of several successive or consecutive

steps.
A → B → C and so on

…....(i)

…......(ii)

….......(iii)
Integrating equation (i), we get

 Arrhenius Equation:
k = A exp(-Ea/RT)
Where, k = Rate constant
A = pre-exponential factor
Ea = Activation energy

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 Temperature Coefficient
 The temperature coefficient of a chemical reaction is defined as the ratio of
the specific reaction rates of a reaction at two temperatures differing by 10oC.
μ = Temperature coefficient= k(r+10)/kt
 Let temperature coefficient of a reaction be ' μ ' when temperature is raised
from T1to T2; then the ratio of rate constants or rate may be calculated as

##  Collision Theory of Reaction Rate

 A chemical reaction takes place due to collision among reactant molecules.
 The number of collisions taking place per second per unit volume of the
reaction mixture is known as collision frequency (Z).
 The value of collision frequency is very high, of the order of 1025 to 1028 in case
of binary collisions.
 Every collision does not bring a chemical change.
 The collisions that actually produce the products are effective collisions.
 The effective collisions which bring chemical change are few in comparison to
the form a product are ineffective elastic collisions, i.e., molecules just collide
and disperse in different directions with different velocities.
 For a collision to be effective, the following two barriers are to be cleared.

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 Energy Barrier
 Orientation Barrier

 For radioactive decay A ->B
 -(dNA/dt) =λ NA
 Where, λ = decay constant of reaction
 NA = number of nuclei of the radioactive substance at the time when rate is
calculated.
 Arrhenius equation is not valid for radioactive decay.
 Integrated Rate Law: Nt = Noe-lt
 Half Life: t1/2= 0.693/λ
 Average life time: Life time of a single isolated nucleus, tav= 1/λ
 Activity: Rate of decay
A = dNA/dt, Also, At = Aoe- λ t
Specific Activity: activity per unit mass of the sample.

## Chapter: Surface Chemistry

 The accumulation of molecular species at the surface rather than in the bulk of a

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## solid or liquid is termed as adsorption.

 It is a surface phenomenon.
 The concentration of adsorbate increases only at the surface of the adsorbent.
 Adsorbate: It is the substance which is being adsorbed on the surface of another
substance.
 Adsorbent: It is the substance present in bulk, on the surface of which adsorption is
taking place.
 Desorption: It is the process of removing an adsorbed substance from a surface on
 Absorption:
 It is the phenomenon in which a substance is uniformly distributed throughout the
bulk of the solid.
 It is a bulk phenomenon.
 The concentration is uniform throughout the bulk of solid.
 Sorption: When adsorption and absorption take place simultaneously, it is called
sorption.
 Enthalpy or heat of adsorption:
 Since, adsorption occurs with release in energy, i.e., it is exothermic in nature.
 The enthalpy change for the adsorption of one mole of an adsorbate on the surface
 If the adsorbate is held on a surface of adsorbent by weak van der Waals’ forces,
 It is non-specific.
 It is reversible.
 The amount of gas depends upon nature of gas, i.e., easily liquefiable gases like
NH3, CO2, gas adsorbed to greater extent than H2 and He. Higher the critical
temperature of gas, more will be the extent of adsorption.
 The extent of adsorption increases with increase in surface area, e.g. porous and
finely divided metals are good adsorbents.
 There are weak van der Waals’ forces of attraction between adsorbate and
 It has low enthalpy of adsorption (20 - 40 kJ mol-1).
 Low temperature is favorable.
 No appreciable activation energy is needed.
 It forms multimolecular layers.

##  Chemical adsorption or chemisorption:

 If the forces holding the adsorbate are as strong as in chemical bonds, the
 It is highly specific.
 It is irreversible.

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 The amount of gas adsorbed is not related to critical temperature of the gas.
 It also increases with increase in surface area.
 There is strong force of attraction similar to chemical bond.
 It has enthalpy heat of adsorption (180 - 240 kJ mol-1).
 High temperature is favorable.
 High activation energy is sometimes needed.
 It forms unimolecular layers.
 Factors affecting adsorption of gases on solids:
 Physical adsorption is non-specific in nature and therefore every gas gets
adsorbed on the surface of any solid to a lesser or greater extent.
 However, easily liquefiable gases like NH3, HCl, CO2, etc. which have higher
critical temperatures are absorbed to greater extent whereas H2, O2, N2 etc. are
 The chemical adsorption being highly specific, therefore, a gas gets adsorbed on
specific solid only if it enters into chemical combination with it.
 Activated carbon, metal oxides like aluminum oxide, silica gel and clay are
 They have their specific adsorption properties depending upon pores.
 Specific area of the adsorbent:
 The greater the specific area, more will be the extent of adsorption.
 That is why porous or finely divided forms of adsorbents adsorb larger quantities
 The pores should be large enough to allow the gas molecules to enter.
 Pressure of the gas: Physical adsorption increases with increase in pressure.

 The variation in the amount of gas adsorbed by the adsorbent with pressure at constant
temperature can be expressed by means of a curve is termed as adsorption isotherm.
x
 Freundlich Adsorption isotherm: The relationship between m and pressure of the gas at
constant temperature is called adsorption isotherm and is given by
1
x
= kpn (n>1)
m
Where x- mass of the gas adsorbed on mass m of the adsorbent and the gas at a particular
temperature k and n depends upon the nature of gas.
x
 The solid m first increases with increase in pressure at low pressure but becomes
independent of pressure at high pressure.

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## Taking logarithm on both sides, we get,

𝑥 1
log 𝑚 = log k + 𝑛 log 𝑝

x
 If we plot a graph between log m and log P, we get a straight line.

1
 The slope of line is n and intercept will be equal to log k
 Catalyst: These are substances which alter the rate of a chemical reaction and they
remain chemically and quantitatively unchanged after the reaction and the
phenomenon is known as catalysis.
 Promoters: These are the substances which increase the activity of catalyst. Example -
Mo is promoter whereas Fe is catalyst in Haber's Process.
Fe(s)/Mo(s)
N2 + 3H2(g) 2NH3(g)
 Catalytic poisons (Inhibitors): These are the substances which decrease the activity of
catalyst. Example - Arsenic acts as catalytic poison in the manufacture of sulphuric acid
by 'contact process.'
 Types of catalysis:
 Homogeneous catalysis: When the catalyst and the reactants are in the same phase,
this kind of catalytic process is known as homogeneous catalysis.
 Heterogeneous catalysis: When the catalyst and the reactants are in different phases,
the catalytic process is said to be heterogeneous catalysis.
 Activity of a catalyst: It is the ability of a catalyst to increase the rate of a chemical
reaction.
 Selectivity of catalyst: It is the ability of catalyst to direct a reaction to yield a particular
product (excluding others).
For example: CO and H2 react to form different products in presence of different
catalysts as follows:
 CO(g) + 3H2(g) Ni CH4 (g) +H2O(g)
 CO(g) + 2H2(g) Cu/ZnO-Cr O
2 3 CH3OH(g)
 CO(g) + H2(g) Cu HCHO(g)
 Shape - selective catalysis: It is the catalysis which depends upon the pore structure of
the catalyst and molecular size of reactant and product molecules. Example - Zeolites
are shape - selective catalysts due to their honey- comb structure.

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 Enzymes: These are complex nitrogenous organic compounds which are produced by
living plants and animals. They are actually protein molecules of high molecular mass.
They are biochemical catalysts.
 Steps of enzyme catalysis:
 Binding of enzyme to substrate to form an activated complex.
 Decomposition of the activated complex to form product.
 Characteristics of enzyme catalysis:
 They are highly efficient. One molecule of an enzyme can transform 106 molecules
of reactants per minute.
 They are highly specific in nature. Example - Urease catalysis hydrolysis of urea only.
 They are active at optimum temperature (298 - 310 K).
 The rate of enzyme catalyzed reaction becomes maximum at a definite temperature
called the optimum temperature.
 They are highly active at a specific pH called optimum pH.
 Enzymatic activity can be increased in presence of coenzymes which can be called as
promoters.
 Activators are generally metal ions Na+, Co2+ and Cu2+ etc. They weakly bind to
enzyme and increase its activity.
 Influence of inhibitors (poison): Enzymes can also be inhibited or poisoned by the
presence of certain substances.
 True solution:
 It is homogeneous.
 The diameter of the particles is less than 1 nm.
 It passes through filter paper.
 Its particles cannot be seen under a microscope.

 Colloids:
 It appears to be homogeneous but is actually heterogeneous.
 The diameter of the particles is 1 nm to 1000 nm.
 It passes through ordinary filter paper but not through ultra-filters.
 Its particles can be seen by a powerful microscope due to scattering of light.
 Suspension:
 It is heterogeneous.
 It does not pass through filter paper.
 Its particles can be seen even with naked eye.
 Dispersed phase: It is the substance which is dispersed as very fine particles.
 Dispersion medium: It is the substance present in larger quantity.
 Classification of colloids on the basis of the physical state of dispersed phase and
dispersion medium:
Name of Colloid Dispersed phase Dispersed medium
Solid sol Solid Solid
Sol Solid Liquid

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## Aerosol Solid Gas

Gel Liquid Solid
Emulsion Liquid Liquid
Aerosol Liquid Gas
Solid sol Gas Solid
Foam Gas Liquid

##  Classification of colloids on the basis of nature of interaction between dispersed phase

and dispersion medium, the colloids are classified into two types namely,
 Lyophobic sols
 Lyophilic sols
 Lyophobic sols:
 These colloids are liquid hating.
 In these colloids the particles of dispersed phase have no affinity for the dispersion
medium.
 They are not stable.
 They can be prepared by mixing substances directly.
 They need stabilizing agents for their preservation.
 They are irreversible sols.
 Lyophilic sols:
 These colloids are liquid loving.
 In these colloids, the particles of dispersed phase have great affinity for the
dispersion medium.
 They are stable.
 They cannot be prepared by mixing substances directly. They are prepared only by
special methods.
 They do not need stabilizing agents for their preservation.
 They are reversible sols.
 Classification of colloids on the basis of types of particles of the dispersed phase:
 Multimolecular colloids: The colloids in which the colloidal particles consist of
aggregates of atoms or small molecules. The diameter of the colloidal particle
formed is less than 1 nm.
 Macromolecular colloids: These are the colloids in which the dispersed particles are
themselves large molecules (usually polymers). Since these molecules have
dimensions comparable to those of colloids particles, their dispersions are called
macromolecular colloids, e.g., proteins, starch and cellulose form macromolecular
colloids.
 Associated colloids (Micelles): Those colloids which behave as normal, strong
electrolytes at low concentrations, but show colloidal properties at higher
concentrations due to the formation of aggregated particles of colloidal dimensions.
Such substances are also referred to as associated colloids.
 Kraft Temperature (Tk): Micelles are formed only above a certain temperature called
Kraft temperature.
 Critical Micelle Concentration (CMC): Micelles are formed only above a particular

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## concentration called critical micelle concentration.

 Soaps: These are are sodium or potassium salts of higher fatty acids e.g., sodium
stearate CH3(CH2)16COO-Na+
 Methods of preparation of colloids:
 Chemical methods:
 Colloids can be prepared by chemical reactions leading to the formation of
molecules.
 These molecules aggregate leading to formation of sols.

##  Electrical disintegration or Bredig’s Arc method:

 In this method, electric arc is struck between electrodes of the metal
immersed in the dispersion medium.
 The intense heat produced vaporizes the metal which then condenses to form
particles of colloidal size.
 Peptization:
 It is 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:
 Dialysis: It is a process of removing a dissolved substance from a colloidal solution by
means of diffusion through a suitable membrane.
 Electro dialysis. The process of dialysis is quite slow. It can be made faster by
applying an electric field if the dissolved substance in the impure colloidal solution is
only an electrolyte.
 Ultrafiltration: It 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.
 Ultracentrifugation: In this process, the colloidal solution is taken in a tube which is
placed in ultracentrifuge. On rotating the tube at very high speed, the colloidal
particles settle down at the bottom of the tube and the impurities remain in
solution. The settled particles are mixed with dispersion medium to regenerate the
sol.
 Properties of colloids:
 Colour: The colour of colloidal solution depends upon the wavelength of light
scattered by the colloidal particles which in turn depends upon the nature and size
of particles. The colour also depends upon the manner in which light is received by
the observer.
 Brownian movement: Colloidal particles move in zig - zag path. This type of motion
is due to colliding molecules of dispersion medium constantly with colloidal particles.
 Colligative properties: The values of colligative properties (osmotic pressure,
lowering in vapour pressure, depression in freezing point and elevation in boiling
point) are of small order as compared to values shown by true solutions at the same
concentrations.
 Tyndall effect: The scattering of a beam of light by colloidal particles is called Tyndall
effect. The bright cone of light is called the Tyndall cone.

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 Charge on colloidal particles: Colloidal particles always carry an electric charge. The
nature of this charge is the same on all the particles in a given colloidal solution and
may be either positive or negative.
 Positively charged colloidal particles:
 These include hydrated metallic oxides such as Fe 2O3. x H2O, Cr2O3. x H2O,
 AI2O3. x H2O
 Basic dye stuff like malachite green, methylene blue sols.
 Example - Haemoglobin (blood).
 Negatively charged colloidal particles:
 Metallic sulphides like As2S3, Sb2S3 sols.
 Acid dye stuff like eosin, methyl orange, Congo red sols.
Examples - Starch sol, gum, gelatin, clay, charcoal, egg albumin, etc.
 Helmholtz electrical double layer: When the colloidal particles acquire negative or
positive charge by selective adsorption of one of the ions, it attracts counter ions
from the medium forming a second layer. The combination of these two layers of
opposite charges around colloidal particles is called Helmholtz electrical double
layer.
 Zeta potential: The potential difference between the fixed layer and the diffused
layer of opposite charges is called electrokinetic potential or zeta potential.
 Electrophoresis: The movement of colloidal particles under an applied electric
potential is called electrophoresis.
 Coagulation or precipitation: The process of settling of colloidal particles as
precipitate is called coagulation.
 Hardy - Schulze rules:
 Oppositely charged ions are effective for coagulation.
 The coagulating power of electrolyte increases with increase in charge on the ions
used for coagulation. Examples - Al3+ > Ba2+ > Na+ for negatively charged colloids. Fe
(CN)e]4- > PO 4 3 - > SO 4 2 - > Cl- for positively charged colloids.
 Types of emulsions:
 Water dispersed in oil: When water is the dispersed phase and oil is the dispersion
medium. E.g. butter
 Oil dispersed in water: When oil is the dispersed phase and water is the dispersion
medium. E.g. milk
 Emulsification: It is the process of stabilizing an emulsion by means of an emulsifier.
 Emulsifying agent: These are the substances which are added to stabilize the emulsions.
Examples - soaps, gum
 Demulsification: It is the process of breaking an emulsion into its constituent liquids by
freezing, boiling, centrifugation or some chemical methods.

##  Types of Ores: Ores may be divided into four groups

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 Native Ores:

 These ores contain the metal in free state eg. Silver gold etc.
 These are usually formed in the company of rock or alluvial impurities like
clay, sand etc.
 Oxidised Ores:

##  These ores consist of oxides or oxysalts (eg. carbonates, phosphate) and

silicate of metal.
 Important oxide ore includes, Fe2O3, Al2O3.2H2O etc. and important cabonate
ores are limestone (CaCO3), Calamine (ZnCO3) etc.
 Sulphurised Ores:

 These ores consist of sulfides of metals like iron, lead, mercury etc.
 Examples are iron pyrites (FeS2). galena (PbS), Cinnabar (HgS)
 Halide ores:

 Metallic halides are very few in nature. Chlorides are most common examples
include horn silver (AgCl) carnallite KCl. MgCl2.6H2O and fluorspar (CaF2) etc.

 Metallurgy:
 It is the process of extracting a metal from its ores.
 The following operations are carried out for obtaining the metal in the pure form.
 Crushing of the ore
 Dressing or concentration of the ore.
 Reduction of metal.
 Purification or refining of the metal
 Concentration
 Physical Methods
 Gravity separation:

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##  The powdered ores is agitated with water or washed with a running

stream of water.
 The heavy ore particles of sand, clay etc. are washed away.
 Froth Floatation Process:
 The finely divided ore is introduced into water containing small quantity
of oil (e.g. Pine Oil).
 The mixture is agitated violently with air a froth is formed which carries
away along with it the metallic particles on account of the surface tension
forces.
 The froth is transferred to another bath where gangue-free ore settles
down.

##  Electro Magnetic Separator:

 A magnetic separator consists of a belt moving over two rollers, one of
which is magnetic.
 The powdered ore is dropped on the belt at the other end.
 Magnetic portion of the ore is attracted by the magnetic roller and falls
near to the roller while the non-magnetic impurity falls farther off

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 Chemical Methods
 Calcination:
 Carbonate or hydrated oxide ores are subjected to the action of heat
in order of expels water from hydrated oxide and carbon dioxide from
a carbonate.
 Examples:
ZnCO3 --> ZnO + CO2
CaCO3 --> CaO + CO2
Al2O3×2H2O --> Al2O3 + 2H2O
2Fe2O3×3H2O --> 2Fe2O3 + 3H2O
 Roasting:
 Sulphide ores either are subjected to the action of heat and air at
temperatures below their melting points in order to bring about
chemical changes in them.
 Examples:
2PbS + 3O2 --> 2PbO + 2SO2
PbS + 2O2 --> PbSO4
2ZnS + 3O2 --> 2ZnO + 2SO2
ZnS + 2O2 --> ZnSO4
CuS + 2O2 --> CuSO4

 Leaching:
 It involves the treatment of the ore with a suitable reagent as to
make it soluble while impurities remain insoluble.
 The ore is recovered from the solution by suitable chemical method.
Al2O3 + 2NaOH -->2 NaAlO2 + H2O

 Smelting:

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##  Reduction of a metal from its ore by a process involving melting Several

reducing agents such as sodium, magnesium and aluminium are used for
reduction.
 The calcined or roasted ore is mixed with carbon (coal or coke) and
heated in a reverberatory or a blast furnace.
 Carbon and carbon monoxide produced by incomplete combustion of
carbon reduce the oxide to the metal.

● Flux:
 The ores even after concentration contain some earthy matter called gangue
which is heated combine with this earthy matter to form an easily fusible
material.
 Such a substance is known as flux and the fusible material formed during
reduction process is called slag.

● Refining
 The metals obtained by the application of above reduction methods from the
concentration ores are usually impure.
 The impure metal is thus subjected to some purifying process known as
refining in order to remove undesired impurities.
 Various process for this are:
 Liquation process
 Distillation process
 Cupellation
 Poling
 Electrolytic refining
 Bessemerisation

## ● Thermodynamic Principles of Metallurgy:

ΔG =ΔH-TS or ΔG0 =-RT ln K

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## ● An element A can reduce element B if ΔG value for oxidation of A to AO is lower than

the ΔG value for oxidation of B to BO.
ΔG(A→AO) < ΔG(B→BO)
● Extraction of Aluminium:
 Important Ores of Aluminium:
 Bauxite : Al2O3×2H2O

 Cryolite: Na3AlF6
 Feldspar: K2OAl2O3×6SiO2 or KAlSi3O8
 Mica: K2O×3Al2O3×6SiO2×2H2O
 Corundum: Al2O3
 Alumstone: K2SO4×Al2(SO4)3×4Al(OH)3

● Purification of Bauxite

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## ● Electrolysis of fused pure alumina (Hall & Herwlt Method)

 The addition of cryolite and fluorspar makes alumina a good conductor of electricity and
lowers its Fusion temperature from 2323 to 1140 K. the reactiontaking place during
electrolysis.

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● Refining of Aluminium:
 The graphite rods dipped in pure aluminium and Cu–Al alloy rod at the
bottom in the impure aluminium work as conductors.
 On electrolysis, aluminium is deposited at cathode from the middle layer and
equivalent amount of aluminium is taken up by the middle layer from the
bottom layer (impure aluminium).
 Therefore, aluminium is transferred from bottom to the top layer through
middle layer while the impurities are left behind. A
 luminium thus obtained is 99.98% pure.
● Hydrometallurgy (solvent extraction)
 Solvent extraction is the latest separation technique and has become popular
because of its elegance, simplicity and speed.
 The method is based on preferential solubility principles.
 Solvent or liquid-liquid extraction is based on the principle that a solute can
distribute itself in a certain ratio between two immiscible solvents, one of
which is usually water and the other an organic solvent such as benzene,
carbon tetrachloride or chloroform.
 In certain cases, the solute can be more or less completely transferred into
the organic phase.
● Extraction of Iron:
 Important Ores of Iron
 Hematite Fe2O3 (red oxide of iron)
 Limonite Fe2O3×3H2O (hydrated oxide of iron)
 Magnetite Fe3O4 (magnetic oxide of iron)

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## ● Extraction of Cast Iron:

● Extraction of Copper:
 Ores of Copper:
 Copper glance (chalcocite) : Cu2S
 Copper pyrites (Chalopyrites): CuFeS2
 Malachite : Cu(OH)2 .CuCO3
 Cuprite: Cu2O
● Azurite : Cu(OH)2.2CuCO3

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## Chapter: The p-Block Elements

● p-Block elements:
 Elements belonging to groups 13 to 18 of the periodic table are called p-block
elements.
 General electronic configuration of p-block elements: The p block elements are
characterized by the ns2 np1-6 valence shell electronic configuration.
● Representative elements: Elements belonging to the s and p-blocks in the periodic
table are called the representative elements or main group elements.
● Inert pair effect: The tendency of ns2 electron pair to participate in bond formation
decreases with the increase in atomic size. Within a group the higher oxidation state

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becomes less stable with respect to the lower oxidation state as the atomic number
increases.
● This trend is called ‘inert pair effect’.
● In other words, the energy required to unpair the electrons is more than energy
released in the formation of two additional bonds.
● Nitrogen family:
 The elements of group 15 – nitrogen (N), phosphorus (P), arsenic (As), antimony
(Sb) and bismuth (Bi) .
 Their general electronic configuration is ns2 np3.
● Oxygen family:
 Group 16 of periodic table consists of five elements – oxygen (O), sulphur (S),
selenium (Se), tellurium (Te) and polonium (Po).
 Their general electronic configuration is ns2 np4.
● The halogen family:
 Group 17 elements, fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and
astatine (At), belong to halogen family.
 Their general electronic configuration is ns2 np5.
● Group 18 elements:
 Helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn) are
Group 18 elements.
 They are also called noble gases.
 Their general electronic configuration is ns2 np6 except helium which has
electronic configuration 1s2.
 They are called noble gases because they show very low chemical reactivity.
 Group 15 Elements
 Covalent and ionic radii increase down the group.
 There is appreciable increase in covalent radii from N to P.
 There is small increase from As to Bi due to presence of completely filled d or
f orbitals in heavy elements.
 Ionisation energy:
 It goes on decreasing down the group due to increase in atomic size.
 Group 15 elements have higher ionisation energy than group 14 elements
due to smaller size of group 15 elements.
 Group 15 elements have higher ionization energy than group 16 elements
because they have stable electronic configuration i.e., half-filled p-orbitals.
 Allotropy: All elements of Group 15 except nitrogen show allotropy.

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 Catenation:
 Nitrogen shows catenation to some extent due to triple bond but phosphorus
shows catenation to maximum extent.
 The tendency to show catenation decreases down the group.
 Oxidation states:
 The common oxidation states are +3, +5, –3.
 The tendency to show –3 oxidation state decreases down the group due to
decrease in electronegativity which is due to increase in atomic size.
 The stability of +5 oxidation state decreases whereas stability of +3 oxidation
state increases due to inert pair effect.
 Nitrogen shows oxidation states from –3 to +5. Nitrogen and phosphorus
with oxidation states from +1 to +4 undergo oxidation as well as reduction in
acidic medium.
 This process is called disproportionation.
 Reactivity towards metals: All elements react with metals to form binary
compounds in –3 oxidation state.
 Anomalous behaviour of nitrogen: The behaviour of nitrogen differs from rest of
the elements.
 Reason:
● It has a small size.
● It does not have d – orbitals
● It has high electronegativity
● It has high ionization enthalpy
 Dinitrogen:
 Preparation:

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 Ammonia:
 Ammonia molecule is trigonal pyramidal with nitrogen atom at the
apex.
 It has 3 bond pairs and 1 lone pair. N is sp3 hybridised.
 Preparation:
 Haber’s process:

##  Nitric Acid: Ostwald Process

 Phosphorus:
 It shows the property of catenation to maximum extent due to
most stable P – P bond.
 It has many allotropes, the important ones are :
 White phosphorus
 Red phosphorus
White phosphorus Red phosphorus Black phosphorus

## Discrete tetrahedral P4 Polymeric structure Exists in two forms - α

molecules consisting of chains of P4 black P and β black P

## Translucent waxy solid Has an iron grey luster Has an opaque

monoclinic or
rhombohedral crystals

## Soluble in CS2 but Insoluble in water as -

insoluble in water well as CS2

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 Preparation

 Phosphine: Preparation

 Phosphine is highly poisonous, colourless gas and has a smell of rotten fish.
PCl3 PCl5

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## Pyramidal shape, sp3 hybridisation TBP geometry, sp3 d hybridisation

 Group 16 Elements
 Oxidation states:
 They show -2, +2, +4, +6 oxidation states.
 Oxygen does not show +6 oxidation state due to absence of d – orbitals.
 Po does not show +6 oxidation states due to inert pair effect.
 The stability of -2 oxidation state decreases down the group due to increase
in atomic size and decrease in electronegativity.
 Oxygen shows -2 oxidation state in general except in OF2 and O2F2
 The stability of +6 oxidation state decreases and +4 oxidation state increases
due to inert pair effect.
 Ionisation enthalpy:
 Ionisation enthalpy of elements of group 16 is lower than group 15 due to
half-filled p-orbitals in group 15 which are more stable.
 However, ionization enthalpy decreases down the group.
 Electron gain enthalpy:
 Oxygen has less negative electron gain enthalpy than S because of small size
of O.
 From S to Po electron gain enthalpy becomes less negative to Po because of
increase in atomic size.
 Melting and boiling point:
 It increases with increase in atomic number.
 Oxygen has much lower melting and boiling points than sulphur because
oxygen is diatomic (O2) and sulphur is octatomic (S8).
 Reactivity with hydrogen:
 All group 16 elements form hydrides.
 Bent shape

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##  Acidic nature: H2O < H2S < H2Se < H2Te

 This is because the H-E bond length increases down the group.
 Therefore, the bond dissociation enthalpy decreases down the group.
 Thermal stability: H2O < H2S < H2Se < H2Te < H2Po
 This is because the H-E bond length increases down the group. T
 Therefore, the bond dissociation enthalpy decreases down the group.
 Reducing character: H2O < H2S < H2Se < H2Te < H2Po
 This is because the H-E bond length increases down the group.
 Therefore, the bond dissociation enthalpy decreases down the group.
 Reactivity with oxygen: EO2 and EO3
 Reducing character of di-oxides decreases down the group because oxygen
has a strong positive field which attracts the hydroxyl group and removal of
H+ becomes easy.
 Acidity also decreases down the group. SO2 is a gas whereas SeO2 is solid.
 This is because SeO2 has a chain polymeric structure whereas SO2 forms
discrete units.
 Reactivity with halogens: EX2 , EX4 and EX6
 The stability of halides decreases in the order F- > Cl- > Br- > I- .
 This is because E-X bond length increases with increase in size.
 Among hexa halides, fluorides are the most stable because of steric reasons.
 Dihalides are sp3 hybridised, are tetrahedral in shape.
 Hexafluorides are only stable halides which are gaseous and have sp 3d2
hybridisation and octahedral structure.
 H2O is a liquid while H2S is a gas.
 This is because strong hydrogen bonding is present in water.
 This is due to small size and high electronegativity of O.

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 Oxygen:
 Preparation:

 Oxides: The compounds of oxygen and other elements are called oxides.
 Types of oxides:
 Acidic oxides: Non- metallic oxides are usually acidic in nature.

 Basic oxides:
 Metallic oxides are mostly basic in nature. Basic oxides dissolve in water
forming bases e.g.,

 Amphoteric oxides: They show characteristics of both acidic as well as basic
oxides.

##  Neutral oxides: These oxides are neither acidic nor basic.

 Example: Co, NO and N2O
 Ozone:
 Preparation: It is prepared by passing silent electric discharge through pure
and dry oxygen 10 – 15 % oxygen is converted to ozone.

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Structure of Ozone: Ozone has angular structure. Both O = O bonds are of
equal bond length due to resonance.
 Sulphur:
 Sulphur exhibits allotropy:
 Yellow Rhombic (α - sulphur)
 Monoclinic (β- sulphur)
 Sulphuric acid:
 Preparation: By contact process

##  It is dibasic acid or diprotic acid.

 It is a strong dehydrating agent.
 It is a moderately strong oxidizing agent.

 Group 17 Elements
 Atomic and ionic radii: Halogens have the smallest atomic radii in their respective
periods because of maximum effective nuclear charge.
 Ionisation enthalpy: They have very high ionization enthalpy because of small
size as compared to other groups.
 Electron gain enthalpy:
 Halogens have maximum negative electron gain enthalpy because these
elements have only one electron less than stable noble gas configuration.
 Electron gain enthalpy becomes less negative down the group because atomic
size increases down the group.
 Electronegativity: These elements are highly electronegative and
electronegativity decreases down the group. They have high effective nuclear
charge.
 Bond dissociation enthalpy follows the order Cl2 > Br2 > F2 > I2
 This is because as the size increases bond length increases.

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 Bond dissociation enthalpy of Cl2 is more than F2 because there are large
electronic repulsions of lone pairs present in F2.
 Colour: All halogens are coloured because of absorption of radiations in visible
region which results in the excitation of outer electrons to higher energy levels.
 Oxidising power: All halogens are strong oxidising agents because they have a
strong tendency to accept electrons.
 Order of oxidizing power is F2 > Cl2 > Br2 > I2
 Reactivity with H2:
 Acidic strength: HF < HCl < HBr < HI
 Stability: HF > HCl > HBr > HI
 This is because of decrease in bond dissociation enthalpy.
 Boiling point: HCl < HBr < HI < HF
 HF has strong intermolecular H bonding
 As the size increases van der Waals forces increases and hence boiling point
increases.
 % Ionic character: HF > HCl > HBr > HI
 Dipole moment: HF > HCl > HBr > HI
 Electronegativity decreases down the group.
 Reducing power: HF < HCl < HBr < HI
 Reactivity with metals: Halogens react with metals to form halides.
 Ionic character: MF > MCl > MBr > MI
 Halides in higher oxidation state will be more covalent than the one in the lower
oxidation state