MINIMUM LEVEL OF LEARNING (MLL)

CHEMISTRY (XII) - 2022-2023

PREPARED BY
ABDUL HAYEE

CHAPTER -01 Solution

A solution is a homogeneous mixture of two or more chemically non-reacting substances.

Solutions are the homogeneous mixtures of two or more than two components. A solution
having two components is called a binary solution. It includes solute and solvent.

A solution may be classified as solid, liquid or a gaseous solution.

Types of Solutions:

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): It is the number of moles of solute present in 1kg of solvent.

Molarity (M): It is the number of moles of solute present in 1L of solution.

Normality: It is the number of gram equivalent of solute dissolved per litre of solution.

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.

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In a nearly saturated solution if dissolution process is an exothermic process, solubility
decreases with increase in temperature.

Solubility is defined as the amount of solute in a saturated solution per 100g of a solvent. The

solubility of a gas in a liquid depends upon:

(a) the nature of the gas and the nature of the liquid,

(b) the temperature of the system, and

(c) the pressure of the gas.

The effect of pressure on the solubility of a gas in a liquid is governed by Henry’s Law
Law: It

states that the solubility of a gas in a liquid at a given temperature in directly proportional to
the partial pressure of the gas

p = KH x

Where p is the partial pressure of the gas; and x is the mole fraction of the gas in the solution
and KH is Henry’s Law constant.

The vapour pressure of a liquid is the pressure exerted by its vapour when it is in dynamic

equilibrium with its liquid, in a closed container.

Raoult’s Law,, the vapour pressure of a solution containing a non

non-volatile
volatile solute is directly

proportional to the mole fraction of the solvent (XA). The proportionality constant being the

vapour pressure of the pure solvent,

The binary liquid in liquid solutions can be classified into two types; ideal and non-ideal
non

solutions.

Ideal solution: An ideal solution is a solution where the intermolecular interactions between

solute-solute (A-A) and solvent-solvent

solvent (B
(B-B)
B) are similar to the interaction between
solutesolvent

(A-B).
B). An ideal solution fulfills the following criteria:

all the concentration and temperature ranges. This states that the

partial vapour pressure of each component is proportional to the mole fraction of the

component in a solution at a given temperature.

temp

means that no heat is absorbed or

released.

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equal to the sum of the volume of components.

The ideal solution is possible with components of the same size and polarity. There is no

association, dissociation or reaction taking place between components. A perfect ideal solution
is rare but some solutions are near to the ideal solution. Examples are Benzene and toluene,
hexane and heptane, Bromoethane and Chloroethane, Chlorobenzene and bromobenzene, etc.

Non-ideal Solution:

ranges it is known as a non-ideal

ideal solution. A non-ideal
non ideal solution may show positive or

negative deviation from Raoult‗s

‗s law.

(a) Non-ideal
ideal solution showing positive deviation

Here the total vapour pressure is higher than that calculated from Raoult
Raoult‗s
‗s equation. The

interaction between solute-solvent

solvent (A
(A-B)
B) is weaker than those of pure components (A-A
(A or B-
B).

The ΔHmix and ΔVmix are positive. E.g., ethanol and acetone, carbon disulphide and acetone,
acetone and benzene, etc.

(b) Non-ideal
ideal solution showing negative deviation

Here
re the total vapour pressure is lower than that calculated from Raoults equation. The

interaction between solute-solvent

solvent (A
(A-B)
B) is stronger than those of pure components (A-A
(A or
BB).

The ΔHmix and ΔVmix are negative. E.g., phenol and aniline, chloroform aand
nd acetone, etc.

Colligative properties of solutions are those properties which depend only upon the number
of solute particles in the solution and not on their nature.
Such properties are:
(a) Relative lowering in vapour pressure,
(b) Elevation of boiling point,
(c) Depression of freezing point and
(d) Osmotic pressure.
(a) Relative lowering in vapour pressure: According to Raoult‗s Law, the relative lowering
of vapour pressure of a solution is equal to the mole fraction of the solute.

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(b) Elevation of boiling point: Boiling point of a liquid is the temperature at which its vapour
pressure becomes equal to the atmospheric pressure. The boing point of the pure solvent is T b0
while that of the solution is Tb. Since, Tb is greater than Tb0, there is an elevation or increase in
boiling temperature of the solution as compared to that of solvent. The elevation in boiling
point, ΔTb may be expressed as: ΔTb = Tb - Tb0

The elevation in boiling point is found to be proportional to the molality of the solution.

ΔTb α m

ΔTb = Kb m,
where ΔTb is the elevation in boiling point, m is the molality and Kb is the Molal elevation
constant

ΔTb = Kb m = (Kb x wB x 1000)/MB x wA

MB = (Kb x wB x 1000)/ΔTb x wA

(c) Depression of freezing point: Freezing point is the temperature at which the solid and the

liquid states of the substance have the same vapour pressure. Freezing point temperature of
pure solvent is Tf0 and freezing point temperature of the solution is Tf. The Tf is less than Tf0.
This shows that the freezing temperature of the solution is less than that of pure solvent and
the depression in freezing temperature (ΔTf )is given as: ΔTf = Tf0 – Tf

The depression in freezing point (ΔTf) is proportional to the molality of the solution.

ΔTf α m

ΔTf = Kf m

Where Kf is molal depression constant (freezing point depression constant).

ΔTf = Kf m = (Kf x wB x 1000)/MB x wA

MB = (Kf x wB x 1000)/ΔTf x wA

Osmosis: The spontaneous flow of solvent molecules from a dilute solution into a
concentrated solution when the two are separated by a perfect semi permeable membrane.

(d) Osmotic pressure (π) is the pressure which must be applied to the solution side (more

concentrated solution) to just prevent the passage of pure solvent into it through a semi
permeable membrane. According to Van‗t Hoff equation,

π = CRT= (nB/V) RT = (wB/MBV) RT

MB = (wB/ π V) RT

where n is the osmotic pressure of the solution,

C is the concentration of solution, nB is the number of moles of solute, MB is the molar mass
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of the solute, V is the volume of the solution in liters, R is the gas constant, and T is the
temperature on the Kelvin scale.

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Reverse Osmosis: The direction of osmosis can be reversed if a pressure larger than the
osmotic pressure is applied to the solution side. That is, now the pure solvent flows out of the
solution through the semi permeable membrane. This phenomenon is called reverse osmosis

Isotonic solutions are those solutions which have the same osmotic pressure. Also, they have

same molar concentration.

For isotonic solutions, π1 = π2 Also, C1 = C2

Hypertonic solutions if a solution has more osmotic pressure than some other solutions.

Hypotonic solutions if a solution has less osmotic pressure than some other solutions.

Abnormal molecular mass: A molar mass that is either lower or higher than the expected or

normal value is called as abnormal molar mass.

Van't Hoff factor: In 1880 Van‗t Hoff introduced a factor i, known as the Van‗t Hoff factor,
to account for the extent of dissociation or association. This factor i is defined as:
i = Normal molar mass / Abnormal molar mass
= Observed colligative property / Calculated colligative property
i = Total number of moles of particles after association/dissociation
Number of moles of particles before association/dissociation
Here abnormal molar mass is the experimentally determined molar mass and calculated
colligative properties are obtained by assuming that the non-volatile solute is neither
associated nor dissociated.
In case of association, value of i is less than unity while for dissociation it is greater than unity.
For example, the value of i for aqueous KCl solution is close to 2, while the value for ethanoic
acid in benzene is nearly 0.5.
Inclusion of Van‗t Hoff factor modifies the equations for colligative properties as follows:
Elevation of Boiling point, ΔTb = i Kb m
Depression of Freezing point, ΔTf = i Kf m
Osmotic pressure of solution, ᴨ = i nB R T / V

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 Chapter -2- Electrochemistry
Importance of Electrochemistry
● Production of metals like Na, Mg. Ca and Al.
● Electroplating.
● Purification of metals.
● Batteries and cells used in various instruments.
Metallic Conductors or Electronic Conductors
Substances which allow the electric current to pass through them by the movement of electrons
are called metallic conductors, e.g.. metals.

Electrolytic Conductors or Electrolytes

Substances which allow the passage of electricity through their fused state or aqueous solution
and undergo chemical decomposition are called electrolytic conductors, e.g., aqueous solution
of acids. Bases and salts.

Strong electrolytes: The electrolytes that completely dissociate or ionise into ions are called
strong electrolytes. e.g., HCl, NaOH, K2SO4
Weak Electrolytes: The electrolytes that dissociate partially (ex < 1) are called weak
electrolytes, e.g., CH3COOH, H2CO3, NH4OH, H2S, etc.
Electro Chemical Cell or Galvanic cell
An electrochemical cell that converts the chemical energy of spontaneous redox reactions
into electrical energy is known as a galvanic cell or a voltaic cell. Galvanic cell Voltaic cell is
an electrochemical cell that makes use of chemical reactions to generate electrical energy.
Zn(s) + Cu2+(aq) ------------� Zn2+(aq) + Cu(s)
Cell representation: Zn(s)/ Zn2+(aq)// Cu2+(aq) / Cu(s)

Electrode Potential
When an electrode is in contact with the solution of its ions in a half-cell, it has a tendency to
lose or gain electrons which is known as electrode potential. It is expressed in volts. It is an
intensive property, i.e., independent of the amount of species in the reaction.

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Reduction potential: The tendency to gain electrons in the above case is known as reduction
potential. According to IUPAC convention, the reduction potential alone be called as the
electrode potential unless it is specifically mentioned.
Standard electrode potential: The potential difference developed between metal electrode
and solution of ions of unit molarity (1M) at 1 atm pressure and 25°C (298 K) is called
standard electrode potential. It is denoted by E°.

Reference Electrode
The electrode of known potential is called reference electrode. It may be primary reference
electrode like hydrogen electrode or secondary reference electrode like calomel
electrode.Standard hydrogen electrode (SHE) Standard hydrogen electrode (SHE). also known
as normal hydrogen electrode (NHE), consists of platinum wire, carrying platinum foil coated
with finely divided platinum black. The wire is sealed into a glass tube. placed in beaker
containing 1 M HCl. The hydrogen gas at 1 atm pressure is bubbled through the solution at
298K. Half-cell is Pt/H2 (1 atm) /H+ (1 M)

Standard EMF of the Cell

The potential difference between the two electrodes of a galvanic cell is called the all potential
and is measured in volts. The cell potential is the difference between the electrode potentials
(reduction potentials) of the cathode and anode. It is called the standard electromotive force
(emf) of the cell when no current is drawn through the cells.(E 0 Cell )

Nernst Equation

Nernst gave a relationship between electrode potentials and the concentration of electrolyte
solutions

For a general electrode reaction, Mn+ (aq) + ne¯ ——-> M(s)

The electrochemical cell reaction is:

Zn(s) + Cu2+ (aq) ——> Zn2+ (aq) + Cu (s)

The electrode potential for the two electrodes can be calculated by using Nernst equation:

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Equilibrium constant from Nernst Equation

Zn(s) + Cu2+ (aq) ⇔ Zn2+ (aq) + Cu (s)

Electrochemical Cell and Gibbs energy of the Reaction

ΔrGø = wmax = -nFEøcell

Significance
The above equation helps us to predict the feasibility of the cell reaction. For a cell reaction to
be spontaneous, ΔrG must be negative. This means that E must be positive for a spontaneous
cell reaction.

Conductance (G)
It is the ease of flow of electric current through the conductor. It is reciprocal of resistance (R).
G = (1/R), units ohm-1 mhos or Ω-1
The electronic conductance depends on:
1. the nature and structure of the metal
2. the number of valence electrons per atom
3. temperature (it decreases with the increase of temperature)

Specific Conductivity (K)

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Conductivity (k)
It is the reciprocal of resistivity.

The conductivity of electrolytic (ionic) solutions depends on:

● the nature of the electrolyte added
● size of the ions produced and their solvation
● the nature of the solvent and its viscosity
● the concentration of the electrolyte
● temperature (it increases with the increase of temperature).
Factoring Affecting Electrolyte Conductance
● Nature of electrolyte or interionic attractions: Lesser the solute-solute interactions,
greater will be the freedom of movement of ions and higher will be the conductance.
● Solvation of Ions: Larger the magnitude of solute-solvent interactions, greater is the
extent of solvation and lower will be the electrical conductance.
● The nature of the solvent and its viscosity: Larger the solvent-solvent interactions,
larger will be viscosity and more will be the resistance offered by the solvent to flow of
ions and hence lesser will be the electrical conductance.
● Temperature: As the temperature of the electrolytic solution rises solute-solvent,
solvent-solvent interactions decreases, this results in the increase of electrolytic
conductance.

Molar conductivity (ʌm)

It may be defined as the conducting power of all the ions produced by dissolving one mole of
an electrolyte placed between two large electrodes at one centimetre apart.
Mathematically,

Variation of Conductivity and Molar Conductivity with Dilution

Conductivity decreases with the decrease in concentration, this is because the number of ions
per unit volume that carry the current in the solution decreases on dilution.
Molar conductivity (ʌm = k x V) increases with the decrease in concentration. This is because
the total volume V of the solution containing one mole of electrolyte also increases.
It has been found that the decrease in on dilution of a solution is more than compensated by
increases in its volume.
Graphic representation of the variation of ʌm vs c1/2

Kohlraush's law
The limiting molar conductance Λ0m is the basis for kohlraush law. At infinite dilution, the
limiting molar conductivity of an electrolyte is equal to the sum of the limiting molar
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conductivities of its constituent ions. i.e., the molar conductivity is due to the independent
migration of cations in one direction and anions in the opposite direction.
For a uni – univalent electrolyte such as NaCl, the Kohlraush's law is expressed as
(Λ0m)NaCl = ( λ0 )Na+
m + ( λ0 )Cl-
m
Applications of Kohlrausch's Law
1. Calculation of molar conductance at infinite dilution of a weak electrolyte.
It is impossible to determine the molar conductance at infinite dilution for weak electrolytes
experimentally. However, the same can be calculated using Kohlraush‘s Law.
2. Calculation of degree of dissociation of weak electrolytes
The degree of dissociation of weak electrolyte can be calculated from the molar conductivity at
a given concentration and the molar conductivity at infinite dilution using the following
expression

Calculation of dissociation constant using Λm values. According to Ostwald dilution Law,

Products of Electrolysis
Faraday‘s – First Law of Electrolysis
It is one of the primary laws of electrolysis. It states, during electrolysis, the amount of
chemical reaction which occurs at any electrode under the influence of electrical energy is
proportional to the quantity of electricity passed through the electrolyte.

Faraday‘s – Second Law of Electrolysis

Faraday‘s second law of electrolysis states that if the same amount of electricity is passed
through different electrolytes, the masses of ions deposited at the electrodes are directly
proportional to their chemical equivalents.
Combination of Two Faraday's Law
W=EIt/F
By the passage of 1 mole of electrons (1F=96500 C), the equivalent weight of a substance is
deposited or liberated.
This is a combined Faraday's Law of Electrolysis.

Electrolysis of molten lead bromide using platinum electrodes

In the molten state, PbBr2 exists as
PbBr2 ⇔ Pb2+ + 2 Br‾
At anode
2 Br¯ ——-> Br2(g)+ 2e¯
At cathode
Pb2+ +2 e¯ ———-> Pb
The overall reaction is
PbBr2 ———> Pb + Br2(g)
Electrolysis of aqueous sodium chloride
In water, sodium chloride ionises as
NaCl ⇔ Na+ (aq) + Cl¯ (aq)
Water also dissociates into ions, though to very slight degree as
H2O (l) ⇔ H+(aq) + OH‾(aq)
During electrolysis, it has been observed that

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Thus, the aqueous solution of sodium chloride contains Na +, H+, OH¯ and Cl‾ ions. When
electric current is passed through the solution, Cl2 gas is evolved at the anode and hydrogen is
evolved at the cathode. The resulting solution contains Na+ and OH¯ ions.
Na+ (aq) + e¯ ———-> Na(s) Eø = -2.71 V
H+ (aq) + e¯ ———> ½ H2 (g) Eø = 0.00 V
The reaction with higher value of Eø is preferred and therefore, the reaction at the cathode
during is :
H+ (aq) + e¯ ———> ½ H2 (g)
But H+ (aq) ions are produced by the dissociation of water as:
H2O (l) + e¯ ——–> H+ (aq) + OH¯ (aq)
Therefore, the net reaction at the cathode may be written as:
H2O (l) + e¯ ——–> ½ H2 (g) + OH¯ (aq)
At the anode, the following reactions are possible :
Cl¯ (aq) ——–> ½ Cl2(g) + e¯ Eø = + 1.36 V
2 H2O (l) ——–> O2 (g) + 4 H+ (aq) + 4 e¯ Eø = +1.23 V
In concentrated solution of NaCl, oxidation of chloride ions is preferred than water at anode
and therefore Cl2 gas is liberated.
Cl‾(aq) ——–> ½ Cl2(g) + e¯
The net reactions:
NaCl (aq) + H2O (l) ———>Na+ (aq) + OH¯ (aq) + ½ H2 (g) + ½ Cl2(g)
Thus, during the electrolysis of aqueous sodium chloride, H 2, gas is liberated at the cathode
and Cl2 , gas is liberated at the anode and the solution contains sodium hydroxide.
Electrolysis of aqueous copper sulphate solution
Copper sulphate and water ionise as:
CuSO4 (aq) ⇔ Cu2+(aq) + SO 24 ¯
H2O (l) ⇔ H+(aq) + OH¯ (aq)
During electrolysis, copper is deposited at the cathode while oxygen is liberated at the anode.
At anode (oxidation)
2 H2O (l) ——-> 4 H+ + O2 +4 e¯
At cathode (reduction)
Cu2+ (aq) +2e‾ ———> Cu(s) x 2
The overall reaction is :
2Cu2+ (aq) + 2 H2O (l) ———> Cu(s) + 4 H+ + O2 (g)
2Cu2+ (aq) + 2SO 2 + 2 H O (l) ——-> 2Cu(s) + 4 H+ + O (g) + 2SO 2
4 ¯ 2 2 4¯
Electrolysis Of Sulphuric acid
During the electrolysis of sulphuric acid, hydrogen is liberated at cathode:
At cathode
H+ + e¯ ——-> ½ H2
The following two reactions occur at anode:
2 H2O2 (l) ———–> O22(g) + 4 e¯ Eø = ø1.23 V (FOR DILUTE SOLUTION)
2 SO (aq) ——> S O ¯ (aq) + 2 e¯ E = 1.96 V (FOR CONCENTRATED SOLUTION)
4 ¯ 28

Commercial Cells or Batteries

Batteries
There are two basic kinds of batteries: disposable, or primary, batteries, in which the electrode
reactions are effectively irreversible and which cannot be recharged; and rechargeable, or
secondary, batteries, which form an insoluble product that adheres to the electrodes. These
batteries can be recharged by applying an electrical potential in the reverse direction. The
recharging process temporarily converts a rechargeable battery from a galvanic cell to an
electrolytic cell.
Primary Cell
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Secondary Cell

NI-Cd Cell Lead Storage Cell

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Fuel Cells
A fuel cell is a galvanic cell that requires a constant external supply of reactants because the
products of the reaction are continuously removed. Unlike a battery, it does not store chemical
or electrical energy; a fuel cell allows electrical energy to be extracted directly from a chemical
reaction. In principle, this should be a more efficient process than, for example, burning the
fuel to drive an internal combustion engine that turns a generator, which is typically less than
40% efficient, and in fact, the efficiency of a fuel cell is generally between 40% and 60%. In
practice, their use has been restricted to applications in which mass may be a significant cost
factor, such as US manned space vehicles. This cell is environment friendly.
H2-O2 Fuel Cell

Topics for Bright students

Concentration cell is an electrolytic cell that is comprised of two half-cells with the same
electrodes, but differing in concentrations. A concentration cell acts to dilute the more
concentrated solution and concentrate the more dilute solution, creating a voltage as the cell
reaches an equilibrium. This is achieved by transferring the electrons from the cell with the
lower concentration to the cell with the higher concentration.

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Q) Calculate cell potential for a concentration cell with two silver electrodes with
concentrations 0.2 M and 3.0 M.
A) Ag(s)|Ag+(0.2 M)||Ag+(3.0 M)|Ag(s)
E=E∘−0.059/2 (log 0.02/3.0) Eo = 0 for concentration cells
E = 0.0644 V
Uses of Concentration Cells
A pH meter is a specific type of concentration cell that uses the basic setup of a concentration
cell to determine the pH, or the acidity/basicity, of a specific solution. It is comprised of two
electrodes and a voltmeter. One of the electrodes, the glass one has two components: a metal
(commonly silver chloride) wire and a separate semi-porous glass part filled with a potassium
chloride solution with a pH of 7 surrounding the AgCl. The other electrode is called the
reference electrode, which contains a potassium chloride solution surrounding a potassium
chloride wire. The purpose of this second electrode is to act as a comparison for the solution
being tested. When the glass electrode comes into contact with a solution of different pH, an
electric potential is created due to the reaction of the hydrogen ions with the metal ions. This
potential is then measured by the voltmeter, which is connected to the electrode. The higher
the voltage, the more hydrogen ions the solution contains, which means the solution is more
acidic.

Li ion Battery

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 CHAPTER 3: CHEMICAL KINETICS

1.)Classification of chemical reactions on the basis of their rate:

A) Fast reaction B.) Reaction with moderate speed D.) slow reaction

2.) Rate of reaction:

•Definition: It is the amount of chemical change of reactants or products occurs in unit time.
• Types of rate of reaction :
A.) Average of reaction: Average rate of a reaction is the change in concentration of the
species taking part in a reaction divided by the time taken for the change.
rav = - Δ[R] /Δ[t] = Δ[P] / Δ[t]
PB.)Instantaneous rate of reaction:
Instantaneous rate of a reaction is the average rate at the smallest interval of
time. r(inst) = - d[R] /d[t] = d[P] / d[t]
Unit of rate of reaction: Mol.L-1.S-1 or M.S- 1
3. Rate equation:

Experimentally obtained relation between rate of a reaction and concentration of reactants of

the reaction is called rate equation.
A + B ----- > Products
Rate(r)=K[A].[B]

4) Order of a reaction:
It is the sum of exponents to which the contraction term have been raised in the rate
equation. nA + mB ------C +D
Rate = K [A]n.[B]m
The order of the reaction is (m+n).

5) Molecularity of a reaction :
The number of molecules taking part in an elementary step of a chemical reaction is called
molecularity of the reaction. E.g-
2A + 3B -----> 2C + D
Molecularity:( 2+3)=5

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6) Integrated rate equation for zero order reaction:
R ----> P
Initially [R]° 0
After time 't' [R] x
Integrated rate equation: [R]°-[R]= Kt

7.) Integrated rate equation for first Order reaction:

R -----> P
Initially CR° 0
After time ‗t‘ CR x

Integrated rate equation:

Kt=Ln[ CR°÷ CR ] [ :. CR°-CR= x]

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 CHAPTER-4 The d-and f-Block Elements

The d-block elements in the Periodic Table contains the elements of the groups 3 to group 12 in which the last
electron enters into the d·orbital.

There are mainly three series of the elements,

First transition series (Sc to Zn)

Second transition series (Y to Cd)

and Third transition series (La to Hg omitting Ce to Lu).

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Transition Elements
Elements having partially filled d-orbitals in ground state or in excited state are known as transition elements.
These elements are placed in between s-block and p-block elements in Periodic Table

General Electronic Configuration of Transition Elements

Transition elements have the electronic configuration (n – 1) d1 – 10 ns0 –2,

Zn, Cd, Hg, the last members of first three series have general electronic configuration
(n – 1) d10ns2. These elements do not show properties of transition elements because their d - orbital is
completely filled.

Electronic Configuration of Transition Elements( optional Study)

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General Physical Properties of Transition Elements

i) Atomic and ionic size: The atoms or ions of the transition series from left to right exhibit regular decrease in
radius with increasing atomic number, because the new electron enters into the d – orbital and nuclear charge
increases by unity but added electron have no effect.
But this decrease in size occurs up to the middle of the series Sc to Cr) after that the size remains almost const.
This is due to the decrease in number of unpaired electrons after middle Mn)
## As the number of unpaired d- electrons increases from Sc to Cr, the screening effect increases and size
decreases.
## After that pairing of electrons start which causes the electron - electron repulsion results increase in size.
These two opposing force increasing nuclear charge and electron - electron repulsion counter balance each other
and size remains almost const.
### In last element i.e. Zn, Hg, Cd of the series, a small increase in size is observed due to electron-electron
repulsion is greater than increasing nuclear charge.

*** (Atomic and ionic radii of elements increase from first transition series to second transition series but the
radii of the third transition series are similar as those of the corresponding member of the second series. It can
be explained on the basis of lanthanide contraction [poor shielding of 4f electrons].

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Due to lanthanide contraction Zr and Hf have almost similar radii.

ii) Ionisation enthalpies : In a series as we move from left to right, ionization enthalpy increases due to
increase in nuclear charge but not in regular way.
The first ionisation enthalpy of d - block elements are higher than s - block elements but are lesser than p -
block elements

iii) Oxidation states : Transition metals show variable oxidation state due to involvement of ( n - 1) d and ns
electrons in compounds formation. Because the energies of (n - 1) d and ns electrons are almost same
The transition elements in their lower oxidation states (+2 and +3) usually form ionic compounds. In higher
oxidation state compounds are normally covalent.

iv) Enthalpy of atomisation : Transition elements exhibit higher enthalpies of atomization. Because of the
presence of a large number of unpaired electrons in their atoms, they have stronger interionic attractions and
hence, stronger metallic bond.

v) Density : All these metals have high density because the electrons enter into the penultimate shell ( n - 1)d
which screened the increased nuclear charge and the outer most ns electrons are strongly attracted by the
nucleus.

vi) Melting point and Boiling point: If we move from left to right in a series the Melting point and Boiling
point increases as the number of unpaired electrons increases. This is happened in the mid way of the series
after that decreases as the number of unpaired electrons decreases.

## Mn and Tc ( technetium) has maximum number of unpaired electrons however it has lower Melting point
and Boiling point because half filled (n - 1)d5 and completely filled ns2 orbitals make Mn and Tc stable which
reduce the delocalization of electrons resulting weaker metallic bonding.

Generally transition elements have high melting and boiling point due to stronger metallic bond

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vii) Formation of coloured ions and compounds: Transitions elements are generally formed coloured
compounds due to the presence of unpaired d electrons (incomplete d - orbital) and d- d transition

Zn, Hg, Cd, Cu+, Sc3+ etc are not coloured because they have vacant d electrons [ Sc 3+ (d0) ]or fully filled d -
electrons [Zn, Hg, Cd , Cu+ ( d10]

viii) Magnetic properties: Generally the transition elements and their compounds are paramagnetic in
nature due to the presence of unpaired d- electrons.
Larger the number of unpaired electrons greater is the paramagnetic character and greater magnetic
moment.
Magnetic moment, µ = √n(n+2) B.M
n = number of unpaired electrons.

ix) Tendenct to form Complexes: The transition elements are generally form large number of
coordination compounds (complex) due to
i) Small size
ii) High nuclear charge
iii) Availability of vacant d- orbitals to accept lone pair of electrons.

x) Catalytic properties: Many transition elements, Fe, Cd, Ni, Pt, etc and their compounds V 2O5, Cr2O3
etc act as a good catalyst because-
i) The transition elements form reaction intermediate which give reaction path of lower activation energy
and increase the rate of reactions. These intermediate is formed due to presence of vacant d- orbital.
ii) In some cases the transition elements provide large surface area.
xi) Formation of Interstitial Compounds: Transition elements form interstitial compounds because of
vacant d - orbital. These elements and their compounds can easily trapped small size non- metallic atoms
like H, B, C, N etc in vacant space of metallic lattice.

Preparation of Potassium dichromate, K2Cr2O7

K2Cr2O7 is prepared from chromite ore, FeCr2O4 Fuse

i) FeCr2O4 + NaOH + O2 Na2CrO4 + Fe2O3 + H2O

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 Sodium chromate
ii) Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Sodium dichromate
iii) Na2Cr2O7 + KCl K2Cr2O7 + NaCl
Potassium dichromate

Preparation of Potassium Permanganate, KMnO4

KMnO4 is prepared from pyrolusite, MnO2 ore

Fuse
MnO2 + KOH + O2 K2MnO4 + H2O
Potassium maganate (green)

K2MnO4 + Cl2 KMnO4 + KCl

Potassium Permanganate (Purple)

Some important reactions for fill in the blanks (on product sides:)

MnO4 — + H2O MnO2 + OH—

MnO4 — + H+ Mn 2+ + H2O
I— + MnO4 — + H+ Mn 2+ + H 2O + I 2
MnO4 — + NO2 — + H+ Mn 2+ + NO3 — + H2O
**(Balancing is essential but without balancing eqns, it is considered)

2—
DRAW THE STRUCTURE OF i) CrO4 ii) Cr2O7 2—

iii) MnO4 — iv) MnO4 2—

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.
f – Block Elements

The mantle of Thorium Lantern (Not existing nowadays) Nuclear Reactor

The elements in which last electron enters into f - orbital are called f - block elements. In the periodic
table at the bottom there are two series of elements known as lanthanide (Ce to Lu) and actinide (Th to
Lr) series of elements.

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Properties of the lanthanides:

(a) General electronic configuration is [Xe] 4f1-14 5d0-1 6s2.

(b) The metals are silvery-white in colour. They are malleable, ductile, have low tensile strength and are good
conductors of heat and electricity.
(c) They have relatively high density and possess high melting points.
(d) The lanthanides exhibit a principal oxidation state of + 3. However, some elements also exhibit + 2
(Eu2+) and + 4 (Ce4+) oxidation states.
(e) Many of the lanthanide ions are coloured due to the electronic transition between different 4 f-levels.
(f) The majority of the lanthanide ions exhibit paramagnetism due to the presence of unpaired electrons. The
lanthanide ions that do not exhibit paramagnetism are those with either no 4f-electrons, e. g., La3+ and Ce4+ or
with a completed 4f-level, e.g., Yb2+ and Lu3+.
(g) The lanthanides readily tarnish in air and bum to give trioxides (except cesium, which forms CeO 2).
(h) The oxides and hydroxides of the lanthanides are basic in character.
(i) The lanthanide compounds are generally ionic.

This gradual decrease in atomic size with increasing atomic number across the first f- transition element series
is called lanthanide contraction.

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Properties of actinides:
(a) General electronic configuration is [Rn] 5f0-14 6ds0-1 7s2.
(b) The elements are all silvery-white metals.
(c) The melting points of the actinides are moderately high.
(d) The ionic size of the actinides decreases gradually along the series.
(e) The actinides have the ability to exhibit several oxidation states. However, +4 oxidation state is preferred in
actinides.
(f) Some actinide elements can exist in + 6 oxidation state, e.g., uranium, neptunium and plutonium.
(g) Many actinide elements are radioactive. The elements beyond uranium are man-made.
(h) The actinides have a much greater tendency to form complexes than lanthanides.

Difference between Lanthanoids and Actinoids

Lathanoids
1. Mainly + 3 oxidation state
2. Binding energy is higher
3. complex formation tendency is less
4. Except Pm all are non radioactive
5. Most of their ions are colourless
6. Lanthanide compounds are less basic
Actinoids
1. Show +3, +4, +5, +6, and +7 oxidation state
2. Binding energy is lower
3. complex formation tendency is greater
4. All are radioactive
5. Most of their ions are coloured
6. Actinide compounds are more basic

Lanthanide contraction

The steady decrease in atomic and ionic size of lanthanide elements with increasing atomic number is
called lanthanide contraction.

Consequences of lanthanide contraction:

1. Resemblance of second and third transition series

2. Similarity among lanthanides
3. Basic difference (the basic strength of hydroxides with increase in atomic number,
e.g. La(OH)3 is most basic than Lu(OH)3 ]

Uses of Lanthanides:

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Pure metals have no specific use. There compounds are used.
Mish metal is the alloy or mixture of lanthanide elements
1. Mish metal is used in cigarettes and gas lighters.
(2) It is used in flame throwing tanks.
(3) It is used in tracer bullets and shells.

Similarities between Lanthanide and Actinide

Lanthanide Actinide

1. The metals are silvery-white in colour The elements are all silvery-white metals

2. Last electron enter into f - orbital ( inner -

penultimate shell) 2. Last electron enter into f - orbital

3. Lanthanide contraction is caused due to f- 3. Actinide contraction is caused due to f-

electrons
electrons

4. Mainly exhibit +3 oxidation state 4. Mainly exhibit +3 oxidation state

MLL for weaker section of students (Study Materials)

There are mainly three series of the elements,

First transition series (Sc to Zn)

Second transition series (Y to Cd)

and Third transition series (La to Hg omitting Ce to Lu).

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Transition Elements
Elements having partially filled d-orbital in ground state or in excited state are known as transition elements.

General Electronic Configuration of Transition Elements

Transition elements have the electronic configuration (n – 1) d1 – 10 ns0 –2,

Zn, Cd, Hg, the last members of first three series have general electronic configuration
(n – 1) d10ns2. These elements do not show properties of transition elements because their d - orbital is
completely filled.
i) Atomic and ionic size: The atoms or ions of the transition series from left to right exhibit regular
decrease in radius with increasing atomic number, because the new electron enters into the d – orbital and
nuclear charge increases by unity but added electron have no effect.
But this decrease in size occurs up to the middle of the series Sc to Cr) after that the size remains almost
const. This is due to the decrease in number of unpaired electrons after middle Mn)
## As the number of unpaired d- electrons increases from Sc to Cr, the screening effect increases and size
decreases.
## After that pairing of electrons start which causes the electron - electron repulsion results increase in size.
These two opposing force increasing nuclear charge and electron - electron repulsion counter balance each
other and size remains almost const.
### In last element i.e. Zn, Hg, Cd of the series, a small increase in size is observed due to electron-electron
repulsion is greater than increasing nuclear charge.

*** (Atomic and ionic radii of elements increase from first transition series to second transition series but
the radii of the third transition series are similar as those of the corresponding member of the second series.
It can be explained on the basis of lanthanide contraction [poor shielding of 4f electrons].

Due to lanthanide contraction Zr and Hf have almost similar radii.

ii) Ionisation enthalpies : In a series as we move from left to right, ionization enthalpy increases due to
increase in nuclear charge but not in regular way.
The first ionisation enthalpy of d - block elements are higher than s - block elements but are lesser than p -
block elements

iii) Oxidation states : Transition metals show variable oxidation state due to involvement of ( n - 1) d and
ns electrons in compounds formation. Because the energies of (n - 1) d and ns electrons are almost same

iv) Enthalpy of atomisation : Transition elements exhibit higher enthalpies of atomization. Because of the
presence of a large number of unpaired electrons in their atoms, they have stronger interionic attractions and
hence, stronger metallic bond.

v) Density : All these metals have high density because the electrons enter into the penultimate shell ( n -
1)d which screened the increased nuclear charge and the outer most ns electrons are strongly attracted by the
nucleus.

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vi) Melting point and Boiling point: If we move from left to right in a series the Melting point and
Boiling point increases as the number of unpaired electrons increases. This is happened in the mid way of
the series after that decreases as the number of unpaired electrons decreases.

## Mn and Tc ( technetium) has maximum number of unpaired electrons however it has lower Melting
point and Boiling point because half filled (n - 1)d5 and completely filled ns2 orbitals make Mn and Tc stable
which reduce the delocalization of electrons resulting weaker metallic bonding.

Generally transition elements have high melting and boiling point due to stronger metallic bond

vii) Formation of coloured ions and compounds: Transitions elements are generally formed coloured
compounds due to the presence of unpaired d electrons (incomplete d - orbital) and d- d transition

Zn, Hg, Cd, Cu+, Sc3+ etc are not coloured because they have vacant d electrons [ Sc 3+ (d0) ]or fully filled d
-electrons [Zn, Hg, Cd , Cu+ ( d10]

viii) Magnetic properties: Generally the transition elements and their compounds are paramagnetic
in nature due to the presence of unpaired d- electrons.
Larger the number of unpaired electrons greater is the paramagnetic character and greater magnetic
moment.
Magnetic moment, µ = √n(n+2) B.M

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n = number of unpaired electrons.

ix) Tendenct to form Complexes: The transition elements are generally form large number of
coordination compounds (complex) due to

i) Small size
ii) High nuclear charge
iii) Availability of vacant d- orbital to accept lone pair of electrons.

x) Catalytic properties: Many transition elements, Fe, Cd, Ni, Pt, etc and their compounds V 2O5,
Cr2O3 etc act as a good catalyst because-
i) The transition elements form reaction intermediate which give reaction path of lower activation energy
and increase the rate of reactions. These intermediate is formed due to presence of vacant d- orbital.
ii) In some cases the transition elements provide large surface area.
xi) Formation of Interstitial Compounds: Transition elements form interstitial compounds because of
vacant d - orbital. These elements and their compounds can easily trapped small size non- metallic
atoms like H, B, C, N etc in vacant space of metallic lattice.

Preparation of Potassium dichromate, K2Cr2O7

K2Cr2O7 is prepared from chromite ore, FeCr2O4

Fuse
i) FeCr2O4 + NaOH + O2 Na2CrO4 + Fe2O3 + H2O
Sodium chromate
ii) Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Sodium dichromate
iii) Na2Cr2O7 + KCl K2Cr2O7 + NaCl
Potassium dichromate

Preparation of Potassium Permanganate, KMnO4

KMnO4 is prepared from pyrolusite, MnO2 ore

Fuse
MnO2 + KOH + O2 K2MnO4 + H2O
Potassium maganate (green)

K2MnO4 + Cl2 KMnO4 + KCl

Potassium Permanganate (Purple)

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The elements in which last electron enters into f - orbital are called f - block elements.

Difference between Lanthanoids and Actinoids

Lanthanoids
1. Mainly + 3 oxidation state
2. Binding energy is higher
3. complex formation tendency is less
4. Except Pm all are non radioactive
5. Most of their ions are colourless
6. Lanthanide compounds are less basic
Actinoids
1. Show +3, +4, +5, +6, and +7 oxidation state
2. Binding energy is lower
3. complex formation tendency is greater
4. All are radioactive
5. Most of their ions are coloured
6. Actinide compounds are more basic

Lanthanide contraction

The steady decrease in atomic and ionic size of lanthanide elements with increasing atomic number is
called lanthanide contraction.

Consequences of lanthanide contraction:

1. Resemblance of second and third transition series

2. Similarity among lanthanides
3. Basic difference (the basic strength of hydroxides with increase in atomic number,
e.g. La(OH)3 is most basic than Lu(OH)3 ]

Uses of Lanthanides:

Pure metals have no specific use. There compounds are used.

Mish metal is the alloy or mixture of lanthanide elements
1. Mish metal is used in cigarettes and gas lighters.
(2) It is used in flame throwing tanks.
(3) It is used in tracer bullets and shells.

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Similarities between Lanthanide and Actinide

Lanthanides
1. Mainly exhibit +3 oxidation state
2. Last electron enter into f - orbital ( inner -
penultimate shell)
3. Lanthanide contraction is caused due to f-
electrons
4. The metals are silvery-white in colour
Actinides
1. Mainly exhibit +3 oxidation state
2. Last electron enter into f - orbital
3. Actinide contraction is caused due to f-
electrons
4. The elements are all silvery-white metals

2—
DRAW THE STRUCTURE OF i) CrO4 ii) Cr2O7 2—

iii) MnO4 — iv) MnO4 2—

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CBSE Questions for MLL (1 mark)

1. Which of the d-block elements may not be regarded as the transition elements?
[ Zn, Cd & Hg]
2. Why does transition element show variable oxidation state?
3. Name the element in first transition series to show only +3 oxidation state. [Sc]
4. Name the element in first transition series which does not show variable oxidation state. [Zn]
5. Give reason:
i) Transition metals and many of their compounds show paramagnetic behaviour.[ see study
material]
ii) The enthalpies of atomisation of the transition metals are high. .[ see study material]
iii) The transition metals generally form coloured compounds. .[ see study material]
iv) Transition metals and their many compounds act as good catalyst. .[ see study material]
v) Transition elements form alloy.[ see study material]
vi) Why are Cu+ and Cd +2 salts white? [Fulfilled d- orbital, d 10]
ix) Why Mn have abnormally lower melting point though it has maximum number
of unpaired electrons ? [because half filled (n - 1)d5 and completely filled ns2 orbitals make
Mn and Tc stable which reduce the delocalization of electrons]
x) Transition elements form interstitial compounds
6. What is lanthanide contraction? What are the consequences of
lanthanide contraction? [See above study materials]
7. What are alloys? Name an important alloy which contains some of
the lanthanide metals. Mention its uses. [Mixture of two or more elements, Mish metal, U alloy,
used in cigarettes and gas lighters]
8. Write the two points of similarities between Lanthanides and Actinides[See above study
materials]

9. Compare the chemistry of actinoids with that of the Lanthanoids with special reference to:
(i) electronic configuration (iii) oxidation state
(ii) atomic and ionic sizes and (iv) chemical reactivity.

Reference actinoids Lanthanoids

electronic [Rn] 5f0-14 6ds0-1 7s2. [Xe] 4f1-14 5d0-1 6s2. e- enter
configuration e- enter into 5f orbital into inner penultimate 4f orbital

oxidation state Show +3, +4, +5, +6, and +7 Mainly + 3 oxidation state
oxidation state
atomic and ionic sizes Size decreases due to actinide Size decreases due to
contraction lanthanide contraction

chemical reactivity Highly reactive more than Highly reactive

lanthanides

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 MOST IMPORTANT REPEATED CBSE BOARD QUESTIONS
10. Answer the following:

iii ) Explain why Cu + ion is not stable in aquous solution? [Due to high negative Hydration
Energy]
iv) With 3d4 configuration, Cr 2+ act as reducing agent but Mn 3+ act as oxidising agent.
[ Cr2+ (d4) − 1e− Cr3+ (d3), most stable in aquous solution act as reducing agent
3+ 4
Mn (d ) + 1e− Mn2+ (d5), most stable in aquous solution act as oxidising agent
]

v) The actinides exhibit variable oxidation state more than lanthanides. Give reason.
[due to involvement of 5f, 6d & 7s electrons in chemical reaction as there is very small energy gap
between5f, 6d & 7s orbital]
vi) Out of Mn 3+ and Cr 3+, which is more paramagnetic and why? (at. No. Mn = 25, Cr = 24 ) [Mn 3+
is more paramagnetic because no. of unpaired electrons is more (d4) than Cr 3+ (d3) ]
11. The elements of 3d transition series are given :
Sc Ti V Cr Mn Fe Co Ni Cu Zn

Answer the following

i) Write the element which shows maximum number of oxidation state. [Mn]
ii) Which element has the highest melting point? [Cr]
iii) Which element shows only +3 oxidation state ? [Sc]
iv) Which element is a strong oxidising agent in +3 oxidation state and why?
[Mn, Mn 3+(d4) + 1e− Mn2+ (d5), most stable in aquous solution act as oxidising
agent ]

12. Give reason; (1, 2 &3 marks)

i) Among the lanthanides Ce 3+ can be easily oxidised to Ce 4+ ( at. no Ce =58)
[Ce 3+ ( d1) very unstable so gain 1 e− to gain stability to become Ce 4+ ( d0) ]
ii) Zr and Hf exhibit similar properties? [See above study materials]
iii) Actinides contraction is stronger from element to element than lanthanides
contraction. [due to very poor shielding effect of 5f electrons in actinides than 4f electrons
in lanthanides]
+
iv) Cu ion is not known in aquous solution. [See above]
viii) There are hardly any increases in atomic size with increasing atomic numbers
in a series of transition metals. [The increase nuclear charge is partly cancelled byincreases
shielding effect of penultimate d orbital electrons]
13. Describe the preparation of potassium dichromate from iron chromite ore. [See study materials]
14. Describe the preparation of potassium permanganate [See above study materials]

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Questions for Brighter Section of Students ( HOTs)
1. How would you account for the following:
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) ( Mn 3 + ) is
Strongly oxidising.
[ Cr (d4) − 1e−
2+
Cr3+ (d3), most stable in aquous solution act as reducing agent
Mn 3+(d4) + 1e− Mn2+ (d5), most stable in aquous solution act as oxidising agent

(ii) Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is
easily oxidised. [Cobalt (II) in the presence of complexing reagents it is easily oxidised to
Co(III) which has a greater tendency to form complex than Cobalt (II)
(iii) The d1 configuration is very unstable in ions. [because after losing 1 more e- it become stable
(d0)
(ii) Metal - metal bonding is more frequent for the 4d (second series) and 5d (third
series) than for 3d series of transition metals.[ due to their greater enthalpies of
atomisation]
vi) Cr 2+ is a stronger reducing agent than Fe 2+.
Cr 2+ is 3d4 electrons, to gain stability it lose 1 electron to become 3d 3 stable configuration in
aquous solution, hence it is a reducing agent but Fe 2+ do not lose electrons easily because its
electrode potential value is more positive.]
2. Complete the reactions:
i) Fe 2+ + Cr2O7 2- + H +
ii) FeCr2O4 + NaOH + O2
iii) MnO4 — + NO2 — + H+
iv) Cr2O7 2- + I- + H+
v) Cr2O7 2- + OH -
vi) CrO4 2 - + OH -
[ Hint: i. Fe 3+ + Cr 3+ + H2O
ii. Na2CrO4 + Fe2O3 + H2O
iii. Mn 2+ + NO3 — + H2O
iv. Cr 3+ + I2 + H 2O
v. CrO4 2 - + H 2O
vi. Cr2O7 2- + H 2O ]
3. What is the effect of increasing pH on a solution of potassium dichromate?
[ Hint; The dichromate ion exists in equilibrium with chromate CrO4 2− ion
at pH 4. However, by changing the pH, they can be interconvert.
Acid
2−
CrO4 Cr2O7 2−
Yellow Base orange
Potassium dichromate exit in acid medium have lower PH but potassium chromate exit in basic medium
having higher PH ]
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 CHAPTER: COORDINATION COMPOUNDS

A coordination compound contains a central When two salts in stoichiometric ratio are
metal atom or ion surrounded by number of crystallised together from their saturated solution
oppositely charged ions or neutral molecules. These they are called double salts
ions or molecules are bonded to the metal atom or
ion by a coordinate bond.

1) Difference between coordination compound and double salt:

Coordination compound - Example: K4[Fe(CN)6]

They do not dissociate into simple ions when dissolved in water.

Double salt - Example: FeSO4. (NH4)2SO4.6H2O(Mohr‘s salt)

They dissociate into simple ions when dissolved in water.

2) Werner's coordination theory: -

Werner was able to explain the nature of bonding in complexes. The postulates of Werner's theory are:

a) Metal shows two different kinds of valencies: primary valency and secondary valency

Primary valence- This valence Is normally ionisable. These valencies are satisfied by negatively charged
ions.Example: in CrCl3, the primary valency is three. It is equal to oxidation state of central metal ion.

Secondary valence - This valence is non-ionisable. It is commonly satisfied by neutral and negatively charged,
sometimes by positively charged ligands.

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 The secondary valency equals the number of ligand atoms
Primary valence -
coordinated to the metal. It is also called
Itisequaltopositivechargeoncentralmetal atom
coordinationnumberof themetal.

b.Theions/groupsboundbysecondarylinkagestothemetalhavecharacteristicspatialarrangements
correspondingtodifferent coordinationnumbers.

C.N 4 – dsp2 (square planar) OR sp3 (tetrahedral)

C.N 6 – sp3d2/d2sp3 (octahedral)

c.Themostcommongeometricalshapesincoordinationcompoundsareoctahedral,squareplanarand tetrahedral.

Isomers : Two or more compounds which have same chemical formula but different arrangement of atoms are
called isomers,Types of isomerism:

a. Structural isomerism

i) Linkage isomerism

ii) lonisation isomerism

iii) Solvate isomerism or hydrate isomerism

iv.Coordination isomerism

b. Stereoisomerism
I. Geometrical isomerism
ii. Opticalisomerism
a) Structural isomerism: This type of isomerism arises due to the difference in structures of coordination

compounds. Structural isomerism, or constitutional isomerism, is a form of isomerism in which molecules with
the same molecular formula have atorns bonded together in different orders.
i) 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.

Example: [Co(NH3)5Br]SO4 and [Co(NH3)5 SO4]Br

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ii) Solvateisomerism:It isisomerisminwhichsolventisinvolvedasligand.Ifsolventiswateritiscalledhydrate
isomerism.
e.g. [Cr(H2O)3Cl3] and [CrCl2(H2O)4Cl2.2H2O
iii) Linkage isomerism: Linkage isomerism arises in a coordination compound containing an ambidentate
ligand.In this type of isomerism,aIigandcanform linkage withthe metal atom/ionthroughdifferent atoms.

Example: [Co(NH3)5ONO]Cl2 and [Co(NH3)5NO2]CI2

iv) Coordination isomerism: This type of isomerism arises from the interchange of ligands between

cationic and anionicentities of different metal ionspresentinacomplex.

Example: [Co(NH3)6][Cr(C2O4)3] and [Cr(NH3)6][Co(C2O4)3]
b) Stereoisomerism:This type of isomerism arises because of different spatial arrangement.

i) Geometrical isomerism: It arises in heteroleptic complexes due to different possible geometrical

arrangements of ligands.

ii) Opticalisomerism:.Opticalisomersare non- superimposable mirror imagesof each other.This type of

isomerism is due to asymmetry in the molecules.

3) Magnetic properties of coordination compounds: A coordination compound is paramagnetic in nature, if it

has unpaired electrons and diamagnetic if all the electrons in the coordination compound are paired.
1/2
Magnetic moment = [n (n + 2)] where n is number of unpaired electrons.

4) Crystal Field Theory: It assumes the ligands to be point charges and there is electrostatic force of attraction
between ligandsand metal atomor ion.Itistheoretical assumption. In a complex ion, the degeneracy of the d –
orbitals of the central metal atom/ion no longer exists. They are split into two sets – t2g and eg sets. The CFSE
(o or t ) depends on the strength of the ligand. [See fig. 9.8 and 9.9 of NCERT textbook]

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MLL –

1) Define ( with examples) :

a) Coordination number; b) denticity of a ligand; c) ambidentate ligand; d) Chelating ligand; e) ligand; f)

linkage isomerism; g) ionisation isomerism; h) outer and inner orbital complexes; h)

2) What is the difference between - (a) homoleptic and heteroleptic complexes (b) didentate and ambidentate
ligands

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3) What is colour in complexes due to ?[ Hint: d-d transition of electron(s) in incompletely filled d – orbitals]

4) Which compound is used to estimate hardness of water volumetrically? [EDTA – it is a hexadentate ligand;
also a chelating ligand]

5) Write the structures and IUPAC names of the -

(a) linkage isomer and the (b) ionisation isomer of [Co(NH3)5(NO2)](NO3)2

6) Name the types of isomerism exhibited by [Co(NH3)5(NO2)](NO3)2 .

7) Out of the following two coordination entities which is optically active (a) cis – [CrCl 2(ox)2]3+ (b) trans -
[CrCl2(ox)2]3+. Why? [ Hint: the cis - isomer is optically active since it has asymmetry]

8) What is the oxidation state of Ni in Ni(CO)4 ? [Hint: zero]

9) Name (a) the metal ion present in vitamin B12 and (b) the compound used for inhibiting growth of
tumours.[ Hint: (a) Co3+ (b) cis – platin]

10) How can you show that [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionisation isomers? [Hint: the former
gives white ppt with BaCl2 solution, latter does not.]

FOR BRIGHT STUDENTS -

1) Why are low spin tetrahedral complexes not formed? [ Hint: because for tetrahedral complexes, the CFSE is
lower than pairing energy]

2) State one limitation of CFT. [ Hint: since it considers ligands as point charges, the anionic ligands should
exert greater splitting effect. But they are found at the lower end of the spectrochemical series. Also it does not
take into account the covalent character of the metal – ligand bond.(any one)]

3) Why are  -complexes known for transition metals or their ions only? [ since they have vacant d – orbitals
into which electron pairs can be accepted and d - p bonding is possible.]

4) Write all the geometric isomers of [Pt (NH3)(Br)(Cl)(py)]. How many are there? How many of these will
exhibit optical isomerism? [ Hint: 3 geometric isomers; none will exhibit optical isomerism]
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5) a) How many geometrical isomers of [Co(en)2Cl2 ]+ exist? Which of these shows optical activity? Draw the
structures of the isomers.

[Hint: Two geom isomers- cis and trans; the cis form has optical isomer]

b) Draw the structures of optical isomers of: [Cr(C2O4)3]3–

1 Mark- Questions

2–
Q1)The spin only magnetic moment of [MnBr] is 5.9 BM. Predict the geometry of the complexion.

2+
Ans. Co-ordination No. of Mn ion is 4; it has a tetrahedral geometry.

Q2)CuSO4.5H2O is blue in colour while CuSO4 is colourless. Why?

Ans. d∘d transition is possible in CuSO4.5H2O , so it shows colour. CuSO4 due to the absence of water (ligand)
Crystal Field splitting is not possible, so it is not coloured.

3+
Q3) Write the stateof hybridisation in[Cr(NH3)6]

Ans. d2sp3 geometry, octahedral

Q4)Write the formulaofthegivenCo∘ordinationcompound :–
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a) Ni2+ ion isbound totwowater moleculesand twooxalate ions.

b) Co3+ ion is bound to one chloride ion and one ammonia molecule and two ethylenediamine molecules

Ans. a) [ Ni(H2O)2(C2O4)2 ]2-

b) [Co(Cl)(NH3)(en)2 ]2+

Q5) When 1 mol of CrCl3.6H2O is treated with an excess of AgNO3, 3 mol of AgCl are obtained. Write

structural formula & IUPAC name of the compound.

Ans. [Cr(H2O)6 ]Cl3

Q6) Write the IUPAC names, specify the coordination number of the central atom of the following: (1x5)

a. [Fe(en)2Cl2]Cl

b. [CoCl4]2–

c. [Cr(H2O)2(C2O4)2]-

d. K2 [PdCl4]

e. [Ni(CN)4]2-

Ans. a) Dichloridobis(ethane-1,2-diamine)iron(III) chloride; C.N – 6

b) Tetrachloridocobaltate(II) ion; C.N – 4

c) Diaquadioxalatochromate(III) ion; C.N – 6

d) Potassium tetrachloridopalladate(II)

e) Tetracyanidonickellate(II) ion

Q7) Write the name & Using VBT Predict the Magnetic behaviour, hybridization, shape of following.

Also predict whether it is inner or outer orbital complex in case of octahedral complexes.(1x6)

a) [CoF6]3-

b) [Co(NH3)6]3+

c) [Ni(CN)4]2-

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d) [NiCl4]2-

e) [Ni(CO)4]

f) [Fe(CO)5]

Q8) Draw diagram to show splitting of d – orbital in octahedral crystal field.

Q9) Explain the two patterns of filling d4 ion in octahedral crystal field.

Ans. b) Electronic configuration for d4 ion if Δo< P the electronic configuration is t2g4 e 0g and if Δo> P the
electronic configuration is t2g3 e 1g

Q10) Arrange following complex ions in increasing order of crystal field splitting energy (O) :

[Cr(Cl)6]3– , [Cr(CN)6]3–, [Cr(NH3)6]3+

Ans. [Cr(Cl)6]3– , [Cr(NH3)6]3+ [Cr(CN)6]3–

Q11) Give reason for the following: (1x5)

a) Nickel does not form low spin octahedral complexes.

[Ans: because Ni has electronic configuration 3d8 4s2 ,in which two inner d –orbitals are not available which are
required to form d2sp3 hybridisation]

b) The -complexes are known for the transition metal only.

[Ans:because transition metals have d - orbitals in their atoms or ions into which the electron pair can be
donated by ligandscontaining electron pairs]

c) Co+2 is easily oxidised to Co+3 in the presence of a strong ligand.

[Ans:because in the presence ofstrong ligand ,the 3d electrons pair up leaving two orbitals empty to be involved
in d2sp3hybridisation]

d) CO is a stronger ligand than NH3 for most metals.

[Ans:because in case of CO back bonding takesplace in which central atom uses its filled d orbital with empty
* molecular orbital of CO]
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e) Low spin tetrahedral complexes not formed.

[Ans: For tetrahedral complexes, the crystal fieldsplitting energy is too low. It is lower than pairing energy so,
the pairing of electrons is notfavoured and therefore the complexes cannot form low spin complexes.

ASSERTION -REASON TYPE

A statement of assertion is followed by a statement of reason. Mark the correct

choice from the options given below.

(a) Both assertion and reason are true and reason is the correct explanation of assertion.

(b) Both assertion and reason are true but reason is not the correct explanation of assertion.

(c) Assertion is true but reason is false.

(d) Both assertion and reason are false.

Q12. Assertion : [Co(NH3)Br]SO4gives white precipitate with barium chloride.

Reason : The complex dissociates in the solution to give Br - and SO42- .

(Ans - c)

Q13. Assertion : According to crystal field theory during complex formation, the d - orbitals split and form two
sets of orbitals t2g and eg.

Reason : Splitting of d - orbitals occurs only in case of strong field ligands.

(Ans - c)

Q14. Assertion : [Fe(H2O)6]2+ is sp3d2 hybridised and paramagnetic complex ion.

Reason : It has four unpaired electrons.

( Ans - a)
Q15. Assertion : Low spin tetrahedral complexes are not formed.

Reason : For tetrahedral complexes, CFSE is lower than pairing energy.

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( Ans - a)

Q16. Assertion : [FeF6]3- is paramagnetic.

Reason : F- is a weak field ligand, hence does not cause pairing of electrons.

( Ans - a)

One - word answer

Q17a) Name a ligand involved in synergic bonding. ( Ans - CO)

b) Why gemstones produce colours? ( Ans - d- d transition)

Two marks Question

Q1) Discuss the nature of Bonding in metal carbonyls.

[Hint: refer to synergic effect, back bonding and  - acid ligand- CO]

Q2) Arrange the followingcomplexes in theorder of increasing electrical conductivity. Give reason.

[Co(NH3)3Cl3], Co(NH3)5Cl]Cl2,[Co(NH3)6]Cl3, [Co(NH3)4Cl2]Cl

Ans. [Hint: refer to no. of ions resulting from dissociation]

[Co(NH3)3Cl3]< [Co(NH3)4Cl2]Cl < [Co(NH3)5Cl]Cl2, [Co(NH3)6]Cl3

Q3)How many geometrical isomers are possible in the following coordination entities:

(i) [Cr(C2O4 3) ]3∘

(ii) [CoCI3(NH3)3].

Ans. (i) Nil [Hint: oxalate is a symmetrical didentate ligand]

(ii) Two (fac∘and mer∘isomer).

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 2+ 2-
Q4) A solution of [Ni(H2O)6] is green, but a solution of [Ni(CN)4] is colourless. Explain.

Ans .In [Ni(H2O)6]2+ , H2O is a weak field ligand. Therefore, there are unpaired electrons in Ni2+. In this
complex, the d electrons from the lower energy level can be excited to the higher energy level i.e. the possibility
2– –
of d-d transition is present. Hence,[ Ni(H2O)6]2+ is coloured. In[Ni(CN)4] ,the electrons are all paired as CN
is a strong field ligand. Therefore, d - d transition is not possible.Hence, it is colourless. As there are no
unpaired electrons, it is diamagnetic.

Five marksquestion

Q1)a)Discussthenatureofbondinginthefollowingcoordinationentityonthebasis of valencebondtheory:
4−
[Fe(CN)6]

Ans. Intheabovecoordinationcomplex,ironexistsinthe+2oxidationstate.

2+ 6
Fe :Electronicconfiguration is3d

−
AsCN isastrongfieldligand,itcausesthepairingoftheunpaired3delectrons.Sincethere aresixligandsaround the
2 3 −
central metal ion, the most feasible hybridization is d sp . Six electron pairs from CN ions occupy the six
2 3
hybrid d sp orbitals. Hence, the geometry of the complex is octahedral and the complex is diamagnetic (as
there are no unpaired electrons)

b) Why [Fe(CN) ]3– is weakly paramagnetic while [Fe(CN) ]4– is diamagnetic ?

[Hint: In the first case Fe(III) has 3d5 configuration and in the second case Fe(II) has 3d6 configuration. CN- is a
strong field ligand and can force pairing; this still leaves a single unpaired electron in the first complex. So it is
weakly paramagnetic. But in the second case, all the electrons are paired, so diamagnetic.]

c) Why[Ni(CO)4] possesses tetrahedral geometry,while[Pt(NH3)2Cl2] is a square∘planar?

[Hint: In the former, Ni is in zero oxidation state; the 4s2 electrons are paired up in the 3d orbitals and the
hybridisation is sp3 resulting in tetrahedral geometry.]

For Practice:

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1) Write the formulae for the following co∘ordination compounds:

(a) Tetraammineaquachloridocobalt (III) chloride

(b) Potassium tetrahydroxozincate (II)

(c) Potassiumtrioxalatoaluminate (III)

Ans. (a)[Co(NH3)4 (H2O)Cl]CI2

(b) K2 [Zn(OH)4]

(c) K3 [Al (C2O4)3]

2) Write the IUPAC names of the following coordination compounds:

(a) [Pt(NH3)2CI(NO2)]
(b) K3[Cr(C2O4)3]

(c) [CoCI2(en)2]CI
Ans. (a) Diamminechloridonitrito–N∘platinum(II)

(b) Potassium trioxalatochromate (III)

(c) Dichloridobis(ethane-1, 2-diammine)cobalt(III) chloride

3) Using IUPAC norms write the formulae for the following:

a)Potassiumtri(oxalato) chromate (III)

b) Pentaamminenitrito-O-cobalt (III) ion

c) Pentaamminenitrito-N-cobalt(III) ion

d) Iron(III) hexacyanoferrate(II)

e) Mercury tetrathiocyanatocobaltate(III)

f) Tetraammineaquachloridocobalt (III) chloride

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g) Tris(ethane–1,2–diamine) chromium(III) chloride

h) Amminebromidochloridonitrito-N-platinate(II)

i) Dichloridobis(ethane–1,2–diamine)platinum(IV) nitrate

4) Draw structures of isomers and write names of the following:

(a) [Cr(NH3)4Cl2]+

(b) [Co(en)3]3+

5) How many donor atoms does EDTA have?

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 CHAPTER: HALOALKANE AND HALO ARENE

Minimum level of learning (MLL) for weak students:

1. IUPAC nomenclature of halo alkane.
2. IUPAC nomenclature of halo alkane
3. Basic physical properties like Boiling point, melting point.
4. Relation of surface area with boiling point melting point
5. Polarity of various compounds.
6. Simple substitution reactions like, ROH+HCl(in presence of ZnCl2)=RCl + H 20
Mainly HOTs questions are to be practiced vigorously.
1. (Partial double bond character) Q. Why vinyl halides or phenyl halides are not reactive towards
substitution reactions
2. Anchimeric assistance or neighboring group participation.
3. Stereo chemical aspects: optical rotation mechanism of substitution reactions.
4. (The ease of dehydration of secondary & third degree alcohols) Q. Why H2SO4 can not be used in the
reaction of 20and 30 R-OH with HBr?
5. (Benzyne or aryne intermediate)
6. Q. C6H5Cl + NaOH + HEAT→ C6H5OH + NaCl but in presence of silica Gel it
go via benzyne intermediate
7. (Hoffmann cation stability)
8. Q. Is it in any way possible to have an anti Markovnikov's reaction with HCl or HI?

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9. (Controlled and uncontrolled reduction) Q. What happens when chloroform is refluxed with zinc dust
and water & when chloroform with is refluxed with Zn with HCl . explain
10. (Primary Isotopic effect) Q. Between (CH3)3C-Cl and (CD3)3C-Cl which would undergo SN1 FASTER?
11. (Secondary Isotopic effect) Q. Between (CH3)3C-Cl and (CD3)3C-Cl which would undergo SN2
FASTER?
12. (Wagner Meerwein rearrangement or Carbocationic rearrangement) Q. What would be the major
product of Friedel-crafts alkylation using 1-Chloro Propane AND 1-Chloro-2-methylpropane?
13. (De-carbonylation pseudo alkylation) Q. C6H6+(Me3)3COCI=?

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 CHAPTER – Alcohols,phenols and ethers

Alcohols: Nomenclature, methods of preparation, physical and chemical properties (of primary alcohols
only), identification of primary, secondary and tertiary alcohols, mechanism of dehydration, uses with
special reference to methanol and ethanol.

Phenols: Nomenclature, methods of preparation, physical and chemical properties, acidic nature of phenol,
electrophilic substitution reactions, uses of phenols.

Ethers: Nomenclature, methods of preparation, physical and chemical properties, uses.

 Minimum level of learning for weak students:

ALCOHOLS:

Nomenclature:

CH3 – CH2 – CH2 – CH2 – OH → Butan-1-ol CH3CH-

(OH)CH2CH=CH2 → Pent-4-en-2-ol

CH3
OH

OH

Cyclohexanol 2-Methylcyclopentanol

Draw the structure:

4- Chloro-2,3-dimethylpentan-1-ol 3-Bromobut-1-enol

Cl Br

H3 C CH3

H 3C

OH

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Methods of preparation:

From carbonyl compounds by From alkenes by

reduction acid

LiAlH catalysed
4
CH3CO CH3CH2
OH OH H2C CH2 HO OH

CH3CHO + H2 +Pd →
CH CH OH

Preparatio
n
of

From Grignard reagents

CH3CHO + C2H5MgBr ––→ CH3CH(OH)C2H5 ( 2o Alcohol)

Alcohol)

Degree of alcohols:

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Physical properties of alcohols:

Solubilit Boiling point

y
Van der waal’s force
and Hydrogen
Soluble in water bonding
due
to H bonding
Physica
l
propertie
s of

Chemical properties of alcohols:

Acidic strength A reaction which proves

Decrease with EWG (nitro , acidic
property of alcohol →
Reaction with metals to

Chemic
Dehydration to al
alkene properties
of
alcohols:

Esterification

Oxidation to carbonyl Alcohols and phenols react with

compounds
carboxylic acids, acid chlorides
and acid anhydrides to form
esters
Page 59 of
 Identification of primary, secondary and tertiary alcohols:

Primary alcohols
Tertiaty will respond to
alcohols will not lucas
respond to test to give
lucas test giving By turbidity only after
turbidity Lucas
test

Secondary
alcohols
will respond to
lucas test giving
turbidity

PHENOLS:

Nomenclature:

OH

OH OH
H3C
CH3 OH

CH3

2,6-Dimethylphenol Benzene-1,2-diol 4- Methylphenol

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Methods of
preparation: From
C H SO H

From
C H Cl

Methods From
of C H CH(CH )
From preparatio
C H N Cl n

Chemical properties of phenol: (Electrophilic Substitution)

(Details of the reagent can be viewed from NCERT book)

OH

OH
Br Br

Br
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 ETHERS:
Preparation of Ether:

By Williamson synthesis method

RBr + RONa ROR + NaBr

By dehydration method

2ROH (excess) + H2SO4 + H2O

Chemical properties of ether:

ROR + HX → RX + ROH
1
R
O OH

+ HX = + R1X

 Topics for bright students:

Mechanism of dehydration of alcohols to alkene:

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Uses of methanol, ethanol, phenol and ether:

 Methanol is used as a solvent in paints, varnishes and chiefly for making formaldehyde.
 Ethanol is used as a solvent in paint industry and in the preparation of a number of carbon
compounds.
 In industry, phenol is used as a starting material to make plastics, explosives such
as picric acid, and drugs such as aspirin. Phenols are widely used in household products
and as intermediates for industrial synthesis. For example, phenol itself is used (in low
concentrations) as a disinfectant in household cleaners and in mouthwash. Phenol may
have been the first surgical antiseptic.

 Vapours of certain ethers are used as insecticides and fumigants for soil.Ethers are also
important in medicine and pharmacology, especially for use as anesthetics.

Dehydration of alcohols yields different products at different temperature.

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Rearrangement can occur for dehydration of alcohols:

Chemical properties of ether:

 -OR group being an electron donating group can activate benzene ring to
participate in electrophilic substitution reactions like phenol.
 Cleavage of R-OR‘ follows different mechanism for different –R
group. For primary and secondary alkyl groups reaction follows SN2
mechanism. For tertiary alkyl group reaction follows SN1
mechanism.

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 CHAPTER: ALDEHYDES AND KETONES

Very short questions(1marks)

1. What is Tollen‘s reagent?

2. Draw the structure of 3-methylbutanal.
3. Formaldehyde does not take part in Aldol condensation. Why ?
4. Ethanal is soluble in water. Why?
5. Name the electrophile produced in the reaction of benzene with benzoyl chloride in the
presence of anhydrous AlCl3.
6. Which of the following compounds would undergo the Cannizzaro reaction?
Benzaldehyde, Cyclohexanone, 2- Methylpentanal.
7. Distinguish between
C6H5CH = CH – COCH3 and C6H5CH = CH CO CH2 CH3
8. Write chemical equations for the following reaction:
(i) Propanone is treated with dilute Ba(OH)2.
9. Phenol is oxidized with Na2Cr2O7/H+?
10. What happens when acetaldehyde is kept with a trace of sulphuric acid. (Paraldehyde)
Short question answer(2marks)

How will you bring about the following conversions in not more than two steps-

(i) Propanone to Propene

(ii) Ethanol to 3-Hydroxybutanal

2. Why Aldehydes are more reactive than Ketones towards Nucleophilic addition reaction?

(Lesser +I effect for aldehydes)

3. Arrange the following compounds in increasing order of their reactivity in nucleophilic

addition

reactions. (i) Ethanal, Propanal, Propanone, Butanone. (ii) Benzaldehyde, p-Tolualdehyde, p

Nitrobenzaldehyde, Acetophenone. ( i. Butanone< Propanone< Propanal < Ethanal ii.
Acetophenone< p-Tolualdehyde< Benzaldehyde < p Nitrobenzaldehyde)

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4. Write the mechanism of addition of HCN to propanone. (Nu addn. Of HCN with
acetone/propanone)a

5. Arrange the following compounds in the property as indicated with reason-

CH3CHO, CH3CH2OH, CH3CH2CH3 (increasing boiling points)

([Increasing order of reactivity of functional Groups:

Alkane<Aldehydes<Ketones<Amines<Alcohols<Carboxylic Acid)

Short question (3marks)

1. Give simple chemical tests to distinguish between the following pairs of compounds.

(i) Propanal and Propanone (ii) Acetophenone and Benzophenone (iii) Ethanal and Propanal

( i. Iodoform test, ii.Iodoform test, iii.Iodoform)

2. Describe the following :

(i) Aldol Condensation (ii)Cannizzaro Reaction (iii)Stephen Reaction

3. Write the structure of the major organic product in each of the following

reactions:

Long answer question (5marks)

1.a)An organic compound with molecular formula C9H10O forms 2,4-DNP

derivative, reduces Tollent‘s reagent, and undergoes Cannizzaro reaction.On

vigorous oxidation , it gives 1,2-benzene dicarboxylic acid. Identify the

compound

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(b) Convert the following: (i) Ethanol to 3-Hydroxybutanal (ii) Propanone to Propene

MLL FOR SLOW LEARNERS-

NOMENCLATURE, M.P,B.P,SOLUBILITY,ALL NAME REACTIONS

TOPICS FOR HIGHER ACHIEVER-

ALL THE TOPICS FOR SLOW LEARNERS,

REACTIVITY ORDER OF DIFFERENT ALDEHYDE, KETONES ETC,,

CRITICAL THINKING LEVEL QUESTIONS FROM DIFFERENT NAME REACTIONS –

CANNIZARO, ALDOL ETC.

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 CHAPTER: Carboxylic Acids
Minimum Level Of Learning Material
Carboxylic Acids:Carboxylic
:Carboxylic acids are the compounds containing the ca
carboxyl
rboxyl functional group
(-COOH).

• IUPAC NAME
HCOOH - methanoic acid
CH3COOH- ethanoic acid
CH3CH2COOH- propanoic acid
CH3CH2CH2COOH- butanoic acid
[Rule - prefix + word root +oic acid]

A)Preparation of carboxylic acid

acid:

(i) From alcohols:: Primary alcohols are readily oxidised to carboxylic acids with common
oxidising agents such as potassium permanganate Aldehydes Ketones and Carboxylic

(ii) From alkylbenzenes:: Aromatic carboxylic acids can be prepared by vigorous oxidation of
alkyl benzenes with chromic acid
id or acidic or alkaline potassium permanganate.

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(iii) From Nitriles: Nitriles on hydrolysis in presence of dilute acids or bases forms amide which
on further hydrolysis gives carboxylic acid.

(iv) From Grignard reagent: Grignard reagents react with carbon dioxide (dry ice) to form salts
of carboxylic acids which on hydrolysis forms carboxylic acids.

(V)From acyl halides and anhydrides: Acid chlorides when hydrolysed with water give
carboxylic acids .On basic hydrolysis carboxylate ions are formed which on further acidification
forms corresponding carboxylic acids. Anhydrides on hydrolysis forms corresponding acid(s)

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(Vi)From esters: Acidic hydrolysis of esters gives directly carboxylic acids while basic
hydrolysis gives carboxylates, which on acidification give corresponding carboxylic acids.
RCOOR' + H3O+ ---- > RCOOH +R'OH

B. Physical properties of carboxylic acids:

(i) Solubility: As the size of alky group increases solubility of carboxylic acid decreases because
non-polar part of the acid increases.

(ii) Boiling points: Carboxylic acids are higher boiling liquids than aldehydes, ketones and even
alcohols of comparable molecular masses. This is due to extensive association of carboxylic acid
molecules through intermolecular hydrogen bonding.

C. Acidity of carboxylic acids:

Carboxylic acids are more acidic than phenols. The strength of acid depends on extent of
ionization which in turn depends on stability of anion formed.

(i) Effect of electron donating substituents on the acidity of carboxylic acids:

Electron donating substituent decreases stability of carboxylate ion by intensifying the negative
charge and hence decreases acidity of carboxylic acids.

(ii) Effect of electron withdrawing substituent on the acidity of carboxylic acids:

Electron withdrawing group increases the stability of carboxylate ion by delocalizing negative
charge and hence, increases acidity of carboxylic acid. The effect of the following groups in
increasing acidity order is Ph< I < Br <cl<F< CF3

(a) Effect of number of electron withdrawing groups:

As the number of electron withdrawing groups increases –I effect increases, increasing the acid
strength.

(b) Effect of position of electron withdrawing group: As the distance between electron
withdrawing group and carboxylic group increases, electron withdrawing influence decreases.

D. Reaction of carboxylic acids:

Reactions involving cleavage of C-OH bond:

(I)Carboxylic acids on heating with mineral acids such as or with corresponding anhydride.

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Anhydride formation:

(ii) Esterification:: Carboxylic acids are esterified with alcohols in the presence of a mineral acid
such as concentrated H2SO4 or HCl gas as a catalyst.

(iii) Hell-Volhard-Zelinsky reaction:

Carboxylic acids having an Alpha
Alpha-hydrogen
hydrogen are halogenated at the aplha position on treatment
with chlorine or bromine in the presence of small amount of red phosphorus to give alpha
halocarboxylic acids

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(iv) Ring substitution in aromatic acids: Aromatic carboxylic acids undergo electrophilic
substitution reactions. Carboxyl group in benzoic acid is electron withdrawing group and is meta
directing.

• Topic for bright students

a) arrange them according to reactivity order of esterification

•primary alcohol, secondary alcohol, tertiary alcohol,
•HCOOH,CH3COOH,CH3CH2COOH

b) acidity strength of benzoic acid and derivatives of benzoic acid

c) ortho effect of benzoic acid.

d) heating effect of dicarboxylic acid

e) formation of methyl ester from carboxylic acid by using CH2N2(Diazomethane).

f) Role of red P in H.V.Z reaction.

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g) How will you prepare (CH3)3C-COOH from (CH3)3C-Br?can this conversion carried out by
cyanide process?

h) Arndt–Eistert reaction.

I) carboxylic acid release CO2 from sodium bicarbonate or sodium carbonate solution but phenol
doesn't why?

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 CHAPTER: AMINES

Definition: Alkyl or aryl derivatives of NH3, i.e. R – NH2 (by replacing H-atom).

Classification & Nomenclature of Amines:

S. N. Type of Functiona Common name IUPAC Name

Amines l

group

Primary, (1o) – NH2 Alkylamine Alkanamine

Secondary, – NH − Alkyl alkylamine N- Alkylalkanamine

(2o)
Aliph Or Dialkylamine
atic
Tertiary, (3o) –N= Trialkylamine N- Alkyl- N-
Amine alkylalkanamine
s

Primary, (1o) – NH2 Aniline Benzenamine or Aniline

Arom Secondary. (2o) – NH − N- Alkylaniline N- Alkylaniline

atic
Tertiary, (3o) –N= N- Alkyl- N- N- Alkyl- N-alkylaniine
Amine alkylaniine
s

Preparation of Amines

(i) By the reduction of Nitro compounds, Nitriles (Cyanides), Isocyanides, Amides:

(a) by catalytic reduction,

(b) by reduction with active metals (Fe, Sn, Zn) and HCl acid,

(c) by using other Reducing agents like, LiAlH4/dry ether.

(ii) BY Hoffmann Bromamide rection:

R – CO - NH2 + Br2 + 4 KOH R – NH2 + K2CO3 + 2KBr + 2H2O

(iii) By Gabriel Phthalimide reaction: - For reaction Consult NCERT book.

Basicity of Aliphatic Amines:

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(a) In gaseous States: Ammonia < 1o < 2o < 3o (Due to increasing + I effect of R groups)

(b) In aqueous solutions: Ammonia < 1o < 3o < 2o (Due to stearic hindrance of R group).

Basicity of Aromatic Amines: (a) Aromatic Amines < Ammonia < Aliphatic Amines.

Effect of substituents on basic properties in aromatic amines:

(i) Presence of EDG group: Basic properties increase due to (+ I) effect.
(ii) Presence of EWG group: Basic properties decrease due to (- I) effect.

Main Chemical Reactions of Amines:

(A) Acylation – Reaction with acid chlorides/acid anhydrides.
(i) R‘- COCl + H2N - R R‘- CO – NH – R (N-alkyl amides)
(ii) R‘- COCl + HN – R2 R‘- CO – N – R2 (N,N-dialkyl amides)
Note: Tertairy amines do not acylated due to the absence of H-atom at N.
(B) Carbylamine reactions (or Isocyanide test): (Distinguished test of Primary amines)
Ar/ R – NH2 + CHCl3 + 3KOH (alc.) Ar/R – NC + 3KCl + 3H2O
(C) Diazotisation: Conversion of aromatic primary amines into diazonium salts by treating with
a cold (273 K) of HNO2 acid.
Ar – NH2 NaNO2 + HCl Ar – N = N – Cl + 2H2O
(Arenediazonium Chloride)

But aliphatic primary amines give alcohols with N2 gas.

R – NH2 NaNO2 + HCl R – OH + N2 + H2O
(D) Electrophilic substitution reaction: Since amino group (– NH2) is o- & p- directing and
strong activating group, aromatic amines undergo electrophilic substitution
reactions easily.

Test for amines

1. Hinsberg‘s Test is used. Hinsberg‘s Reagent� C6H5 - SO2Cl
(Benzenesulphonyl Chloride)

--- SO2Cl

Amines are shaken with the reagent in presence of KOH,

Primary amines give clear solution , Secondary amines give precipitate but tertairy amines do not
react.
2. Isocyanide test: As above.

Arenediazonium salts

Preparation: As above

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Chemical Properties:

1. Deamination: Removal of amino group via diazo group (- N = N -).

Ar – N = N – Cl + H3PO2 + H2O � Ar – H + H3PO3 + HCl + N2

2. Replacement of diazo group by Cl, Br, CN group: - By two mwthods;

(a) Sandmeyer reaction: (i) Ar – N = N – Cl CuCl/HC l� Ar – Cl

(ii) Ar – N = N – Cl CuBr/HBr � Ar – Br , (iii) Ar – N = N – Cl CuCN/KCN � Ar – CN

(b) Gattermann reaction: (i) Ar – N = N – Cl Cu/HC l Ar – Cl

(ii) Ar – N = N – Cl Cu/HBr � Ar – Br

(iii) Ar – N = N – Cl Cu/KCN � Ar – CN

3. Replacement of diazo group by – OH : Ar – N = N – Cl + H2O � Ar – OH (Phenol)

4. Coupling reaction:

(a) Ar – N = N – Cl + Ar – OH --------------� Ar – N = N – Ar – OH
(phenol or substituted phenols)

(b) Ar – N = N – Cl + H2N – Ar ----------� Ar – N = N – NH - Ar

(aniline or substituted anilines)

Important Questions:
1. Arrange the following in the order of their increasing basic characters in solution.
NH3, EtNH2, Et2NH, Et3N
Ans. Et2NH > Et3N > EtNH2 > NH3
2. Give a chemical test to distinguish between C6H5NH2 and C6H5CH2NH2.
Ans. Azo dye test.
3. Name the nitrogen containing compound which has the smell of bitter almonds.
Ans. Nitrobenzene.
4. Give one important industrial use of phenyl isocyanide.
Ans. It is used for preparation of N-methylaniline.
Short answer type question (S.A.)
1. Describe a chemical test to distinguish between CH3CH2NH2 and (CH3)2NH.
Ans. Carbyl amine test
2. Why is methylamine stronger base than ammonia?
Ans.Due to presence of electron releasing –CH3 group, having +I effect.
3. Aniline is a water base than cyclohexylamine. Why?
Ans. In aniline the lone pair on nitrogen is engaged due to resonance in benzene.
4. Define Hoffmann bromide reaction:

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 Ans. When amide reacts with Br2 and KOH, we get primary amine with one carbon
atom less than the amide.
5. Give one chemical test to distinguish between ethyl amine and aniline.
Ans. Azo dye test.
6. Arrange the following in order of decreasing basic strength
Aniline, p- Nitroaniline , p- Toluidine
7. Amine group in aniline is ortho and para directing. Why does then aniline on nitration give
substantial amount of m-nitroaniline
8 Primary amines have higher boiling points than tertiary amines. Why?
9. ‗Amide are more acidic than amines‘. Why?

10. Explain the role of mineral acid in the reaction of a carbonyl compound with KCN (aq)?
11. Why is acetonitrile preferred as a solvent for running organic reaction?
12. Why aniline is acetylated first to prepare mono bromo derivative?
13. Ammonolysis of alkyl halide does not give a corresponding amine in pure state.
Explain?
14. Explain why methyl bromide reacts with KCN go give mostly methyl cyanide but it reacts
with AgCN to give mostly methyl isocyanide.
15. Why is necessary to maintain the temperature between 273 K and 278 K during
diazotization?
16. Why does silver chloride dissolve in aqueous methyl amine solution?
74. How can the following conversion be carried out :-
(a) p-toluidine to 2- bromo-4-methylanline
(b) Aniline to iodobenzene
(c) Aniline to benzonitrile .

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 CHAPTER: BIOMOLECULES

1. Carbohydrates : These are optically active polyhydroxy aldehydes or ketones or

the compounds which produce these on hydrolysis.
2. Classification :
(i) Monosaccharides : Those carbohydrates which cannot be hydrolysed into
further simpler carbohydrates. E.g., glucose, fructose,b galactose etc.
(ii) Disaccharides : Those carbohydrates which produce two monosaccharides
on hydrolysis. E.g., sucrose, maltose and lactose.
(iii) Oligosaccharides : Those carbohydrates which give two to ten
Monosaccharides on hydrolysis.
(iv) Polysaccharides : Those carbohydrates which on hydrolysis give large
number of monosaccharides hydrolysis. E.g., starch, cellulose, glycogen.
3. Sugar : Carbohydrates which are sweet in taste.
(i) Reducing sugars : Those which reduce Fehling‘s or Tollen‘s reagent due to
availability of free aldehydic groups. E.g., glucose, fructose, galactose.
(ii) Non-reducing sugars : Those which do not reduce Fehling‘s or Tollen‘s
reagent. They do not have free aldehydic group. E.g., sucrose.
4. Glucose : It is a monosaccharide with molecular formula C6H12O6

5. Preparation :
(i) From sucrose :

C12H22O11 + H2O → C6H12O6 + C6H12O6 (only from sucrose

Glucose Fructose
(ii) From starch :
(C6H10O5)n + nH2O → C12H22O11 + H2O → 2C6H12O6
Glucose
6. Structure : glucose
Fischer structure :
(+) glucose has ‗D‘ configuration as shown :

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D‘- means – OH group on first chiral ‗C‘ from the bottom is on right hand and (+)
means it is dextrorotatory, i.e., it rotates plane polarized light towards the right.
Objections against open chain structure of glucose
The open chain structure was unable to explain the following reactions :
(a) It does not give the 2, 4-DNP test, Schiff‘s test and does not form the
hydrogensulphite product with NaHSO3.
(b) The pentaacetate of glucose does not react with NH2OH, indicating the
absence of free aldehydic group.
(c) Glucose exist in 2 different crystalline forms α and β forms. These are called
anomers. They differ in optical rotation, they also differ in melting point.
After which a close chain (cyclic) structure of glucose was proposed by Haworth.
* Anomers are isomers which have a different configuration at C-1 functional
group c-atom
7. Glycosidic linkage : The linkage between two monosaccharide units through
oxygen is called the glycosidic linkage.
8. Proteins : These are macromolecules made up of amino acids joined by amide
linkage [− (− CONH −) −] is here called peptide linkage. These are required for
growth and development of the body.
9. Amino acids : These contain an amino (- NH2) and an acidic (- COOH) group and
are therefore amphoteric in nature. In solution they exist in the form of zwitterion
(a dipolar ion).
10. Classification:

Fibrous Protein Globular Protein

i) Polypeptide chains run parallel (i) Chains of polypeptide coil around to

or antiparallel and held together by give a spherical shape.

hydrogen and disulphide bonds

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(ii) Generally insoluble in water e.g., ii) Usually soluble in water, e.g., insulin,

keratin, collagen, myosin, fibroin thyroglobulin, albumin, hemoglobin and

fibrinogen gets converted into fibrous

protein fibroin on clotting of blood.

11. Structure and shape of protein (Ref. page no. 416 NCERT Book)

Primary structure Secondary structure Tertiary structure Quaternary structure

The specific sequence It is the shape in Represents Protein can be

composed
of amino which the long overall folding
of two or more
acids in the polypeptide chain of the polypeptide
polypeptide chains
polypeptide chain. can exist. It is of chain.
called sub-units. The
Change in amino two types : α-helix It gives rise to
spatial arrangement
acids sequence and β-pleated. the fibrous or
of these subunits
changes the protein These structures globular molecular
with respect to each
completely. arise due to regular shapes.
other is quaternary
They have covalent folding of the Forces stabilizing
structure of the
bonds. backbone of the the 2º and protein.
polypeptide chain 3º structures

due to H-bonding are hydrogen

between the C bonds, disulphide

= O and – NH – linkages,

groups of the peptide van der Waal‘s

bond. and electrostatic

forces of attraction

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12. Native state of protein : The parental state or the natural state in which the protein
is found.
13. Denaturation of protein : Destruction of the native state of protein is denaturation.
It can be brought by physical and chemical methods. The 2º and 3º structures are
destroyed, only 1º structure is retained.
Enzymes : These are biocatalyst and generally globular proteins e.g., invertase,
zymase, phenylalanine hydroxylase, urease etc.
Main characteristics of enzymes :
(i) It speeds up the biological reaction upto million times.
(ii) It is highly specific and works on lock and key theory.
(iii) It is highly sensitive to pH and temperature.
14. Vitamins : They are organic compounds required in the diet in small amounts
to perform specific biological functions for maintenance of optimum growth and
health of the organism. They are classified as follows :
(i) Fat soluble vitamins : Vitamin A, D, E and K. They are stored in liver and
adipose tissues.
(ii) Water soluble vitamins : B group vitamins and vitamin C. They need to
supplied regularly in diet as they are excreted in urine and cannot be stored
(except vitamin B12) in our body.
Their deficiency causes diseases. (Ref. table in page no. 418 of NCERT Book)
Biotin (Vit H) is however neither fat nor water soluble. Its deficiency leads to loss
of hair.
15. Nucleic acids : These are biomolecules which are long chain polymers of
nucleotides. They are of two types :
(i) Deoxyribonucleic acid (DNA)
(ii) Ribonucleic acid (RNA)
16. Vitamin Deficiency disease
A Xerophthalmia, night blindness
B1 Beri-beri
B2 Ariboflavinosis, cheilosis, burning sensation of skin
B12 Pernicious anemia, inflammation of tongue and mouth
C Scurvy
D Rickets & osteomalacia
E Increased fragility of RBC and muscular weakness
K Increased blood clotting time
H Loss of hair
17. Hormones are chemical substances which are produced in ductless glands in the
body.
18. Nucleoside = Base + Sugar
Nucleotide = Base + Sugar + Phosphoric acid
19. DNA RNA
(i) Double helical. (i) Single stranded.
(ii) Sugar is 2-deoxyribose. (ii) Sugar is ribose.
(iii) Bases : A, T, G, C. (iii) Bases : A, U, G, C.

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 (iv) Property of replication. (iv) Do not replicate.
(v) It is responsible for transmission (v) Helps in protein biosynthesis
of hereditary character.
.

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 QUESTION PAPERS

SOLUTION

1 MARK QUESTIONS

1. Write two characteristics of the solution which obey Raoult‘s Law at all concentrations.
2. Name the solution which follows Raoult‘s law at all concentrations and temperatures.
3. . What type of azeotropes is formed as a result of negative deviation from Raoult‘s law?
4. What happens when the external pressure applied becomes more than the osmotic pressure of
solution?
5. Sea divers for breathing inside the sea use the mixture of helium and oxygen. Why?
6. At higher altitudes, people suffer from anoxia resulting in inability to think. Why?
7. Out of 0.1 molal solutions of glucose and sodium chloride respectively, which one will have
higher boiling point?
8. Why is calcium chloride used to clear snow in cold countries?
9. (a) Explain why a solution of chloroform and acetone shows negative deviation from
Raoult‘s law.
10. Acetone and carbon disulphide form binary liquid solution showing positive deviation from
Raoult‘s law. The normal boiling point (Tb) of pure acetone is less than that of pure CS2.
Pick out the incorrect statement among the following-
a) Boiling temperature of the mixture is always less than the boiling temperature of
acetone
b) Boiling temperature of Azeotropic mixture is always less than the boiling
temperature of acetone
c) When a small amount of CS2 (less volatile component) is added to an excess of
acetone boiling point of the resulting mixture increases
d) A mixture of CS2 and CH3COCH3 can be completely separated by simple
fractional distillation
11. When mercuric iodide is added to the aqueous solution of potassium iodide, the:
a) Freezing point is raised
b) Freezing point does not change
c) Freezing point is lowered
d) Boiling point does not change
12. The molal elevation constant depends upon
a) nature of solute.
b) nature of the solvent.
c) vapour pressure of the solution.
d) enthalpy change.

13. Which of the following aqueous solutions containing 10 g of solute in each case, has highest
m.p.?
a) NaCl solution
b) MgC12 solution
c) sugar solution

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 d) glucose solution
14. Value of Henry‘s constant KH
a) increases with increase in temperature
b) decreases with increase in temperature
c) remains constant
d) first increases, then decreases
15. Which of the following aqueous solutions should have the highest boiling point?
a) 1.0M NaOH
b) 1.0M NH4NO3
c) 1.0 M Na2SO4
d) 1.0M KNO3

16. At the same temperature, H2 is more soluble in water than He. Which of the two has higher
KH value?
17. Why is glycol and water mixture used in car radiator in cold countries?
18. Two liquids boil at 1100C and 1300C respectively. Which one has higher vapour pressure at
500C?
19. What is the unit of cryoscopicconstant.
20. Define ebullioscopic constant.
21. What is the van‘t Hoff factor for a compound which undergoes dimerisation in an organic
solvent?
22. What are azeotropes?
23. Mention one important use of reverse osmosis.
24. How is that measurement of osmotic pressure is more widely used for determining molar
masses of macromolecules than the elevation in boiling point or depression in freezing point
of their solutions?
25. Suggest the most common Intermolecular forces among the following pairs:-
a) n-hexane and n-octane
b) methanol and acetone
26. Why are the aquatic species more comfortable in cold water compared
to warm water?

27. What do you expect when RBCs are placed in (i) 1% NaCl solution, (ii)
0.5% NaCl solution?

28. A and B liquids on mixing produce a warm solution. Which type of deviation from Raoult‘s
law is there?
29. Define colligative property.
30. Calculate the mass percent of aspirin(C9H8O4) in acetonitrile when 6.5g of aspirin is
dissolved in 450g of acetonitrile (CH3CN).

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 2 MARKS QUESTIONS

1. Derive expression for Raoult‘s law when the solute is non-volatile.

2. Calculate the mass of compound (molar mass = 256 g mol -1) to be dissolved in 75 g of
benzene to lower its freezing point by 0.48 K (K f = 5.12 K kg mol-1). (Hint: Using formula,
W2 = M2×W1×ΔTf/1000×Kf )

3. (a) What is meant by :(i) Colligative properties (ii) Molality of a solution

4. What is van‘t Hoff factor? What types of values can it have if in forming the solution, the
solute molecules undergo(i) Dissociation? (ii) Association?

5. Write two differences between ideal solutions and non-ideal solutions.

6. How is that measurement of osmotic pressure is more widely used for determining molar
masses of macromolecules than the elevation in boiling point or depression in freezing point of
their solutions?

7. Suggest the most common Intermolecular forces among the following pairs: -

i) n-hexane and n-octane

ii) methanol and acetone

8. What do you understand by Azeotropes? Give examples of different types of Azeotropes.

9. Calculate Henry ‗s law constant when the solubility of H2S (a toxic gas with rotten egg like
smell) in water at STP is 0.195 m
+
10. If the density of some lake water is 1.25g/mL and contains 92g of Na ions per kg of water,
calculate the molality of Na+ ions in the lake?( Hint: Molality= no. of moles of Na+/Mass of
solvent in Kg) (Ans:4 mol/ Kg)

11. State Henry's law and write its two applications?

12. Give one example of a solution a) Showing positive deviation from Raoult's law

b) Showing negative deviation from Raoult's law.

13. Accounts of the following…. a) CaCl2 is used to clear snow from roads in hill stations.

b) Cold drink bottles are sealed under high pressure of CO2

14. Calculate the mass percentage of benzene(C6H6) and carbon tetrachloride (CCl4) if 22g of
benzene is dissolve in 122g of carbon tetrachloride?

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