KENDRIYA VIDYALAYA SANGATHAN

RANCHI REGION

XII

STUDENT STUDY MATERIAL

CHEMISTRY
SESSION 1

2022-23
CHIEF PATRON
SHRI D. P. PATEL,
DEPUTY COMMISSIONER, KVS RO RANCHI

PATRON
SHRI SURESH SINGH,
ASSISTANT COMMISSIONER, KVS RO
RANCHI

COORDINATOR
MR. R.C. GOND,
PRINCIPAL,
KENDRIYA VIDYALAYA
PATRATU

2
KENDRIYA VIDYALAYA SANGATHAN
RANCHI REGION

TWO DAYS WORKSHOP FOR PGTs

(CHEMISTRY)
DATE:19-09-2022 & 20-09-2022

VENUE: K.V. NAMKUM

CHIEF PATRON: MR. D. P. PATEL

Deputy Commissioner
Course director: Mr. R.C. GOND
Principal, K.V.PATRATU

Resource Persons: -

Mr. G.JHA Rtd.Principal K.V.S Ranchi Region

Mr. B. C. SINGH, PGT(Chem) KV NO 1 BOKARO
Mr. AJIT KUMAR, PGT(Chem) KV HINOO 1ST SHIFT.

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  COURSE CONTENT COMPILED BY:

01 Mr. B C SINGH (RESOURCE PERSON) NO. 1 BOKARO

02 Mr. AJIT KUMAR( RESOURCE PERSON) HINOO 1ST SHIFT

03 Mr.RAJESH KUMAR NO 1 BOKARO

04 Mrs. KALPANA PRASAD CHANDRAPURA

05 Mr. SUNIL KUMAR DHANBAD

06 Mr. UTTAM KUMAR MAHTO LATEHAR

07 Mr. INDRESH CHOUDHARY MAITHON DAM

08 Mr. ZAHID ALI MEGHAHATUBURU

09 Mrs. SUNITA SINHA DIPATOLI

10 Mrs. SAMPA DAY MAITHON DAM

11 Mr. MANOJ KUMAR SINGH HINOO IST SHIFT

12 Mr. SUNIL KUMAR HINOO 2ND SHIFT

13 Mr. RABINDER KUMAR NAMKUM

14 Mr.RAMANUJ KUMAR TATANAGAR

15 Mr. AMIT KUMAR TATANAGAR

16 Mr. BRAJESH KUMAR BOKARO NO 3

17 Mr.VISHNU VERMA HEC NO 1

18 Mr.C B SINGH HEC NO 1

19 Mr. A K SINGH CRPF RANCHI

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 SYLLABUS FOR SESSION 2022-23 CLASS XII
CLASS XII (2022-23) (THEORY)
Time: 3 Hours 70 Marks
S.No. Title No. of Periods Marks
1 Solutions 15 7
2 Electrochemistry 18 9
3 Chemical Kinetics 15 7
4 d -and f -Block Elements 18 7
5 Coordination Compounds 18 7
6 Haloalkanes and Haloarenes 15 6
7 Alcohols, Phenols and Ethers 14 6
8 Aldehydes, Ketones and Carboxylic Acids 15 8
9 Amines 14 6
10 Biomolecules 18 7
Total 160 70
Unit II: Solutions 15 Periods

Types of solutions, expression of concentration of solutions of solids in liquids, solubility of

gases in liquids, solid solutions, Raoult's law, colligative properties - relative lowering of
vapour pressure, elevation of boiling point, depression of freezing point, osmotic pressure,
determination of molecular masses using colligative properties, abnormal molecular mass,
Van't Hoff factor.

Unit III: Electrochemistry 18 Periods

Redox reactions, EMF of a cell, standard electrode potential, Nernst equation and its
application to chemical cells, Relation between Gibbs energy change and EMF of a cell,
conductance in electrolytic solutions, specific and molar conductivity, variations of
conductivity with concentration, Kohlrausch's Law, electrolysis and law of electrolysis
(elementary idea), dry cell-electrolytic cells and Galvanic cells, lead accumulator, fuel cells,
corrosion.

Unit IV: Chemical Kinetics 15 Periods

Rate of a reaction (Average and instantaneous), factors affecting rate of reaction:
concentration, temperature, catalyst; order and molecularity of a reaction, rate law and
specific rate constant, integrated rate equations and half-life (only for zero and first order
reactions), concept of collision theory (elementary idea, no mathematical treatment),
activation energy, Arrhenius equation.

Unit VIII: d and f Block Elements 18 Periods

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General introduction, electronic configuration, occurrence and characteristics of transition
metals, general trends in properties of the first-row transition metals – metallic character,
ionization enthalpy, oxidation states, ionic radii, colour, catalytic property, magnetic
roperties, interstitial compounds, alloy formation, preparation and properties of K 2Cr2O7 and
KMnO4.

Lanthanoids –
Electronic configuration, oxidation states, chemical reactivity and lanthanoid contraction and
its consequences.

Actinoids - Electronic configuration, oxidation states and comparison with lanthanoids.

Unit IX: Coordination Compounds 18 Periods

Coordination compounds - Introduction, ligands, coordination number, colour, magnetic
properties and shapes, IUPAC nomenclature of mononuclear coordination compounds.
Bonding, Werner's theory, VBT, and CFT; structure and stereoisomerism, the importanceof
coordination compounds (in qualitative analysis, extraction of metals and biological system).

Unit X: Haloalkanes and Haloarenes. 15 Periods

Haloalkanes: Nomenclature, nature of C–X bond, physical and chemical properties,
optical rotation mechanism of substitution reactions.

Haloarenes: Nature of C–X bond, substitution reactions (Directive influence of halogen in

monosubstituted compounds only). Uses and environmental effects of - dichloromethane,
trichloromethane, tetrachloromethane, iodoform, freons, DDT.

Unit XI: Alcohols, Phenols and Ethers 14 Periods

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.

Unit XII: Aldehydes, Ketones and Carboxylic Acids 15 Periods

Aldehydes and Ketones: Nomenclature, nature of carbonyl group, methods of
preparation, physical and chemical properties, mechanism of nucleophilic addition,
reactivity of alpha hydrogen in aldehydes, uses.

Carboxylic Acids: Nomenclature, acidic nature, methods of preparation, physical and

chemical properties; uses.

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 Unit XIII: Amines 14 Periods
Amines: Nomenclature, classification, structure, methods of preparation, physical and
chemical properties, uses, identification of primary, secondary and tertiary amines.
Diazonium salts: Preparation, chemical reactions and importance in synthetic organic
chemistry.

Unit XIV: Biomolecules 18 Periods

Carbohydrates - Classification (aldoses and ketoses), monosaccharides (glucose and
fructose), D-L configuration oligosaccharides (sucrose, lactose, maltose), polysaccharides
(starch, cellulose, glycogen); Importance of carbohydrates.

Proteins -Elementary idea of - amino acids, peptide bond, polypeptides, proteins, structure
of proteins - primary, secondary, tertiary structure and quaternary structures (qualitative idea
only), denaturation of proteins; enzymes. Hormones - Elementary idea excluding structure.

Vitamins - Classification and functions.

Nucleic Acids: DNA and RNA.

CHAPTER: SOLUTIONS

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 GIST OF THE CHAPTER

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.

Mole fraction- Ratio of number of moles of a component to the total number of moles of
solutions
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.

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

solutions.

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

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

(A-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.

means that no heat is absorbed or

released.

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,

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hexane and heptane, Bromoethane and Chloroethane, Chlorobenzene and bromobenzene, etc.

Non-ideal Solution:

ranges it is known as a non-ideal solution. A non-ideal solution may show positive or

negative deviation from Raoult‗s law.

(a) Non-ideal solution showing positive deviation

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

interaction between solute-solvent(A-B) is weaker than those of pure components (A-Aor B-B).

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

(b) Non-ideal solution showing negative deviation

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

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

The ΔHmix and ΔVmix are negative. E.g., phenol and aniline, chloroform and 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.
(b) Elevation of boiling point: Boiling point of a liquid is the temperature at which its vapour

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pressure becomes equal to the atmospheric pressure. The boing point of the pure solvent is Tb0
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 Tf

0. 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,

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C is the concentration of solution, nB is the number of moles of solute, MB is the molar mass
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.
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

SECTION – A (MLL)

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1. Differentiate between molarity and molality of a solution.
Answer:The distinction between molarity and molality.
Molarity : It is the number of moles of solute dissolved in 1 litre of solution. It is temperature
dependent.
M = ω×1000 mol.mass ×V
Molality : It is the number of moles of solute dissolved in 1 kg of the solvent.
m = ω×1000M2×W
The relationship between molarity and molality is
m = Md−MM21000
When molality = molarity, we get,
1 = 1d−MM21000 or d – MM˙21000 = 1
∴ d = 1+MM21000
Molarity is temperature dependent while molarity is not.
For very dilute solution, the factor MM2/1000 can be neglected in comparison to 1.
Hence molality will be same to molarity when density d = 1.
Molality is independent of temperature, whereas molarity is a function of temperature because
volume depends on temperature and mass does not
2. What is meant by ‘reverse osmosis’?
Answer: - If a pressure higher than the osmotic pressure is applied on the solution, the solvent will
flow from the solution into the pure solvent through semipermeable membrane. This process is
called reverse osmosis (R.O.).
3. Define the terms, ‘osmosis’ and ‘osmotic pressure’.
What is the advantage of using osmotic pressure as compared to other colligative properties for the
determination of molar masses of solutes in solutions?
Answer:Osmosis : The net spontaneous flow of the solvent molecules from the solvent to the
solution or from a less concentrated solution to a more concentrated solution through a
semipermeable membrane is called osmosis.
Osmotic pressure : The minimum excess pressure that has to be applied on the solution to prevent
the entry of the solvent into the solution through the semipermeable membrane is called the osmotic
pressure.
The osmotic pressure method has the advantage that it uses molarities instead of molalities and it
can be measured at room temperature
4. A 1.00 molal aqueous solution of trichloroacetic acid (CCl3COOH) is heated to its boiling point.
The solution has the boiling point of 100.18°C. Determine the van’t Hoff factor for trichloroacetic
acid. (Kb for water = 0.512 K kg mol-1)
Answer:As ΔTb= iKbm
(100.18 – 100) °C = i × 0.512 K kg mol-1 × 1 m
0.18 K = i × 0.512 K kg mol-1 × 1 m
∴i = 0.3
5. Explain why aquatic species are more comfortable in cold water rather than in warm water.
Answer:Aquatic species need dissolved oxygen for breathing. As solubility of gases decreases with
increase of temperature, less oxygen is available in summer in the lake. Hence the aquatic species
feel more comfortable in winter (low temperature) when the solubility of oxygen is higher.

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6. State Henry’s law and mention two of its important applications.
Answer:Henry’s law : Henry’s law states that “The partial pressure of the gas in vapour phase is
proportional to the mole fraction of the gas in the solution “, Applications of Henry’s law :
To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high pressure.

• To avoid a dangerous medical condition called bends, scuba divers use oxygen diluted
with less soluble helium gas.

7. Why are aquatic species more comfortable in cold water in comparison to warm water?
Solution: The aquatic species are more comfortable in cold water than in warm water. This is because
the solubility of any gas in water decreases with the rise in temperature. The solubility of oxygen in
water is more in cold water than in warm or hot water. Since oxygen is essential for breathing, aquatic
species can breathe more comfortably in cold water than in warm water due to the higher percentage of
oxygen present in cold water. Hence, they feel more comfortable in cold water than in warm water.
8. (a) Explain the following phenomena with the help of Henry’s law.
(i) Painful condition known as bends.
(ii) Feeling of weakness and discomfort in breathing at high altitude.
(b) Why does soda water bottle kept at room temperature fizzes on opening?
Solution:
(i) When scuba divers go deep in the sea, the solubility of atmospheric gases increases in blood. When
the divers come up, there is the release of dissolved gases and it leads to the formation of bubbles of
nitrogen in our blood capillaries, hence there is a painful sensation called bends. To avoid bends; the
tanks of scuba divers are filled with He,N2 and oxygen.
(ii) At high altitude, partial pressure of oxygen is low, it leads to a low concentration of oxygen in the
blood of people living there. A low concentration of oxygen develops anoxia, i.e., unable to think and
act properly.
(b) In order to increase the solubility of CO2 gas in soft drinks and soda water, the bottles are
normally sealed under high pressure. An increase in pressure increases the solubility of a gas in
a solvent according to Henry’s Law. If the bottle is opened by removing the stopper or seal, the
pressure on the surface of the gas will suddenly decrease. This will cause a decrease in the
solubility of the gas in the liquid. As a result, it will rush out of the bottle producing a hissing
noise or with a fiz.

9. Match the laws given in Column I with expressions given in Column II.

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 Column I Column II

(a) Raoult’s law (i) ΔTf = Kf m

(b) Henry’s law (ii) π = CRT

(iii) p = x1p10 +
(c) Elevation of boiling point x2p20

(d) Depression in freezing point (iv) ΔTb = Kb m

(e) Osmotic pressure (v) p = KHx

(a) Solution: (a)-(iii); (b)-(v); (c)-(iv); (d)-(i); (e)-(ii)
10.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 (Kf = 5.12 K kg mol-1). (Delhi 2014)
Answer:Given : ∆Tf = 0.48 K, W1 = 75g,
M2 = 256 g mol-1 W2 =?
Using formula, W2 = M2×W1×ΔTf/1000×Kf
= 256×75×0.48/1000×5.12 = 1.8 g
SECTION- B(HOTS)
Q1. If 1.202gmL-1 is the density of 20% aqueous KI, determine the following:
(b) Molality of KI
(c) Molarity of KI
(d) Mole fraction of KI
(e) Answer:(a) 1.506m
(b)1.45M
(c)0.0263

Q2.Calculate Henry‘s law constant when the solubility of H 2S(a toxic gas with rotten egg like
smell)in water at STP is 0.195 m
Answer: Moles of H2S=0.195,Moles of water = 55.55, Mole fraction
=0.0035p =KHx, KH=p/x=0.987 bar/0.0035 =282 bar.

Q3. Find the vapour pressure of water and its relative lowering in the solution which is 50 g
of urea(NH2CONH2) dissolved in 850 gof water. (Vapour pressure of pure water at 298 K is
23.8mmHg)
Answer: Mole of urea= 50/600.833,Moles of water=850/18=47.222Mole
fraction of urea=0.0173
P0A– PA)/P0A= xB,PA=23.39
23.39 mm of Hg, the vapour pressure of water in the given solution is 23.39 mm of Hg and
its relative lowering is 0.0173.

Q4. How much of sucrose is to be added to 500 g of water such that it boils at 100°C if the mol
are levation constant for water is 0.52 K kg mol-1 and the boiling point of water at 750 mm Hg
is 99.63°C?

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Answer:∆Tb=100 – 99.63=0.370, wB =121.67 g,
The amount of sucrose that is to be added is 121.67 g

Q5.To lower the melting point of 75 gofacetic acid by 1.50C, how much mass of ascorbic
acid(C6H8O6)is needed to be dissolved in the solution where Kt =3.9 K kgmol−1?
Answer:∆Tf =1.50C,wB=5.08 g, the amount of ascorbic acid needed to be dissolved is 5.08g.

Q6.If a solution prepared by dissolving 1.0g of polymer of molar mass 185,000in 450 mL
of water at 37°C, calculate the osmotic pressure in Pascal exerted by it?
Answer:ᴨ=cRT =(nB/V)RT =30.98 Pa
Q7. 2 g of benzoic acid (C6H5COOH) dissolved in 25 g of benzene shows a depression in
freezing point equal to 1.62 K. Molal depression constant for benzene is 4.9 K kg mol–1. What
is the percentage association of acid I fit forms dimer in solution?
Answer: MB = 241.98 g mol-1, Molecular mass of C6H5COOH = 122 g
mol-12C6H5COOH⇌(C6H5COOH)2,
Degree of association of benzoic acid in benzene=99.2%

Q8. 0.6 mL of acetic acid (CH3COOH), having density 1.06 g mL–1, is dissolved in 1 litre
of water. The depression in freezing point observed for this strength of acid was
0.0205°C.Calculate the Van‘t Hoff factor and the dissociation constant of acid.
Answer: Molality=0.0106molkg-1, ∆Tf=0.0197K Van‘t
Hoff factor (i)=1.041
Dissociation constant of acid Ka =1.86 x10-5

Q9.Determine the amount of CaCl2 (i= 2.47) dissolved in 2.5 litre of water such that its
osmotic pressure is 0.75atm at 27° C.
Answer: i= 2.47, ᴨ = i c RT = i (nB/V)
RTnB =0.0308 mol
Amount of CaCl2 dissolved=0.0308x111=3.42g.

Q10.Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K 2SO4 in 2

litre of water at 25° C, assuming that it is completely dissociated.
Answer: If K2SO4is completely dissociated,i= 3
ᴨ= i c RT =i (nB/V)RT =i(wB/ MB V)RT=5.27 x10-3atm.

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 ELECTROCHEMISTRY
GIST OF THE LESSON

Electrochemistry deals with the study of electrical properties of solutions of electrolytes and with the
inter- relation of chemical phenomenon and electrical energies. Electrical energy is carried
through matter in the form of electric current with the help of suitable source and charge
carriers (ions or electrons).
Substances are devided into two classes
(a) Non conductor or insulator (b) Conductor
( a ) Non - conductor :Substances which do not allow electric current to pass through them are called
non-conductors or insulators examples - pure water, ice, glass, rubber etc.
( b ) Conductor : Substances which allow electric current to flow through them are called
conductors. Examples - Metals, Aqueous solution of acids, bases and salts, fused salts and
impure water etc.
Conductors are of two t ypes :
(i) Metallic conductors (ii) Electrolytic conductors or electrolytes.
( i ) Metallic conductors :The conductors which conduct electric current by movement of electrons
without undergoing any chemical change are known as metallic conductors.
Metals (Cu,Ag,Fe,Al etc), non metals (graphite) and various alloys and minerals are
examples.
( i i ) Electrolyt ic conductors :Those substances whose water solution conducts the electric current
and which are decomposed by the passage of current are called electrolytes. In this case,
conduction takes place by movement of ions.electrolytes also conduct electricity in fused state
and undergo decomposition by passage the electric current.
Non electrolytes -Substances whose aqueous solution does not conduct electric current are called
non-electrolytes.They do not conduct electricity in the fused state also. Solutions of cane suger,
glycerine, glucose, urea etc. are the examples of non electrolytes.
Strong electrolyte :Electrolytes which are completely ionized in aqueous solution or in their molten
state, are called strong electrolytes. Example – all salts, strong acid and strong base
Weak electrolyte :Electrolytes which are not completely ionized in aqueous solution or in their molten
state, are called weak electrolytes. Examples :- All carbonic acids (except sulphonic acid),
CH3COOH, HCN, NH3, amine, etc.
DIFFERENCE BETWEEN METALLIC AND ELECTROLYTIC CONDUCTION :

Metallic conduction Electroly t ic conduction

17
 Flow
( of electricity takes place without the Flow of electricity takes place by chemical
decomposition
i of the substance changes at electrodes.
No transfer
) of matter takes place. Transfer of matter takes place in the form of
ionsThe resistance to the flow of current
The (resistance to the flow of current decreases with the increase in
increases
i with the increase in temperature and hence increase in
temperature
i and hence the increase in temperature increases the conduction.
temperature
) decreases the conduction.

(
i
i
i
)
Resistance:- Obstruction of current.
R = ρl /A
Where ρ known as resistivity and l/A as cell constant
Conductivity(k) The reciprocal of resistivity is called conductivity.
The conductivity, “k” of an electrolytic solution depends on the concentration of the electrolyte, nature of
solvent and temperature and it is defined as the conductance of a solution having unit volume .
K = l / RA
Molar Conductivity λm, is defined as conductivity of an electrolytic solution having 1 molar concentration
placed between two electrodes in such a way that the distance between the electrodes is 1 cm and the area
of cross section is I cm2
𝟏𝟎𝟎𝟎𝐊
Mathematically Λm = 𝐌
-
The unit of molar conductivity is Ω-1cm2mol 1.
Conductivity decrease with decrease in concentration.
but molar conductivity increases with dilution.
The increase in molar conductivity of a strong electrolyte is mainly because of increase in mobility of ions
whereas the increase in weak electrolytes it is due to increase in number of ions as well as mobility of ions.
For Strong electrolyte :- Λ m = Λ m –AC1/2
For weak electrolytes :- By Kohlrausch’s law
Kohlrausch’s law of independent migration of ions: The law states that molar conductivity of an
electrolyte at infinite dilution can be represented as the sum of the individual contribution of the anion and
cation of the electrolyte at infinite dilution
Λ m= λ∞( cation) + λ∞( anion)
Applications:
Calculation of degree of Dissociation of Weak Electrolytes:
 = Λ m c / Λ m
Calculation of Dissociation Constant of Weak Electrolyte
K = C2 / ( 1- )
Galvanic Cell:- Chemical energy to electrical
Cell Representation- Zn/Zn2+//Cu2+/Cu
LOAN :- Left Oxidation Anode Negative

18
 𝑜 𝑜 0
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
Eocell = Eo Cu2+/Cu - Eo Zn2+/Zn
= .34 – (-.76)
= 1.1volt
The Standard Electrode Potential for any electrode dipped in an appropriate solution is defined with
respect to standard electrode potential of hydrogen electrode taken as zero volts. The standard potential of
the cell can be obtained by taking the difference of the standard potentials of cathode and anode (one of that
is hydrogen electrode).
𝑜 𝑜 0
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
Electrochemical series: The arrangement of elements in the order of increasing reduction potential
values is called electrochemical series.
Applications of electrochemical series:
1. Calculation of EMF of the cell
E0cell = E0cathode – E0anode
2. Predicting feasibility of the reaction
3. To predict the reaction of a metal with dilute acids to liberate hydrogen gas

The standard potential of the cells are related of standard Gibbs energy.
𝑜
∆rG0= -nF𝐸𝑐𝑒𝑙𝑙

The standard Gibbs energy of the cells is related to equilibrium constant.

∆G=-2.303 RT log Kc

Nernst equation can be written as for a general reaction

aA+ bB → cC + dD
𝑜 2.303𝑅𝑇 [𝐶]𝑐[𝐷]𝑑
E cell = 𝐸𝑐𝑒𝑙𝑙 – log [𝐴]𝑎[𝐵]𝑏
𝑛𝐹

Electrochemical series: The arrangement of elements in the order of increasing reduction potential
values is called electrochemical series.
Applications of electrochemical series:
4. Calculation of EMF of the cell
E0cell = E0cathode – E0anode
5. Predicting feasibility of the reaction :
A redox reaction is feasible if electron releasing species is present at a position lower in the series as
compared to electron accepting species.
6. Comparison of relative reducing or oxidising power of the elements:
The reducing character of the elements increases down the series and its oxidising character
decreases.

7. To predict the reaction of a metal with dilute acids to liberate hydrogen gas :
Metals which lie above hydrogen in the electrochemical series can reduce H + ions to hydrogen.
Corrosion of metals is an electrochemical phenomenon. In corrosion metal is oxidized by loss of
electrons to oxygen and formation of oxides.
Anode(Oxidation): 2Fe(s) --→ 2Fe2++4e-

19
 Cathode(Reduction): O2(g)+ 4H+(aq)+4e-→2H2O
Atmospheric Oxidation:
2Fe2+(aq)+2H2O(l)+1/2O2(g) → Fe2O3(s)+ 4H+(aq)
ELECTROLYSIS :
The process of decomposition of an electrolyte by the passage of electricity is called electrolysis.
Cathode:- Reduction and negative electrode Anode:- Oxidation and positive electrode
PRODUCTS OF ELECTROLYSIS OF SOME ELECTROLYTES

S. Electrolyte E l e c t ro d e Product Product obtained

No. obtained at
at anode ca th o d e
(i) Aqueous NaCl Pt or Cl2 H2
Graphite
(ii) Fused NaCl Pt or Cl2 Na
Graphite
(iii) Aqueous NaOH Pt or O2 H2
Graphite
(iv) Fused NaOH Pt or O2 Na
Graphite
(v) Aqueous CuSO4 Pt or O2 Cu
Graphite
(vi) Dilute HCl Pt or Cl2 H2
Graphite
(vii) Dilute H2SO4 Pt or O2 H2
Graphite
(viii) Aqueous AgNO3 Pt of O2 Ag
Graphite

.
Faraday’s laws of Electrolysis:
First Law:- The amount of chemical substance deposited at any electrode during electrolysis by a
current is proportional to the quantity of charge passed through the electrolyte.
W= ZIt = A x I x t
nF
where n = number of electrons gained or lost
F = Faraday’s constant (96500C)
I = current in amperes
T = time in seconds
Second Law:- The amount of different substances liberated by the same quantity of electricity passing
through the different electrolytic solution connected in series is proportional to their chemical equivalent
weights.
W1/E1 =W2/E2
Where E = equivalent weight of the metal = atomic weight/valency
SOME COMMERCIAL BATTERIES :-

20
 Name of cell/
Anode Cathode Electrolyte
battery
Zinc Graphite; NH4Cl + ZnCl2
Dry cell MnO2 + C (touching
(touching anode)
cathode)

Mercury cell Zinc- Paste of Paste of

(used in mercury HgO & KOH &
watches,hearing amalgam carbon ZnO
aids)

Lead storage Lead H2SO4 (38%)

Lead dioxide
battery
PbO2
Ni-Cd cell [Ni(OH)3]
Cadmium KOH solution
H2O2 Fuel cell Porous carbon Porous carbon Conc. Aq.
containing containing NaOH
catalysts (H2 catalysts (O2 solution
passed) passed)

Reactions in lead storage battery during discharge:

At anode:- Pb + H2SO 4 -----PbSO 4 + 2H + + 2e

At cathode:- PbO 2 + H 2SO 4+2H + + 2e -----PbSO 4 + 2H 2O
Complete reaction PbO 2 + PbO 2 + H 2SO 4----2PbSO 4+2H 2O

FUEL CELLS :- Chemical energy convert directly into electrical energy. This cells runs continuously as long as
the reactants are supplied
Example – H2-O2 Fuel cells
It has high efficiency
This cell has been used for electric power in the Appollo space programme.
Corrosion :- Corrosion of metals is an electrochemical phenomenon. In corrosion metal is oxidized
by loss of electrons to oxygen and formation of oxides.
Anode(Oxidation): 2Fe(s) --→ 2Fe2++4e-
Cathode(Reduction): O2(g)+ 4H+(aq)+4e-→2H2O

21
 In corrosion, a metal is oxidised by loss of electrons to oxygen and forms metal oxide. Corrosion of
iron(which is commonly known as rusting) occurs in presence of water and oxygen (air).
Air

2 3

e–

O2 + 4H ++ 4e –⎯→ 2H2O Fe ⎯→ Fe 2+ –

PREVENTION FROM CORROSION

1. Painting
2. Greasing
3. Oiling
4. Electroplating
5. Galvanization(Zn coating on Iron)
6. By making alloys
7. By sacrificial method

SECTION-A (MLL)
1. Which of the following is a secondary cell?
(a) Dry cell (b) Leclanche cell (c) Mercury cell (d) lead storage cell
Ans:- (d)
2. The limiting molar conductivity of weak electrolytes can be calculated by using the law:
a) Faraday’s law b) Kohlrausch law c)Henry’s law d) Raoult’s
law
Ans: a) Kohlrausch law
3. The charge required for the reduction of 1 mol of MnO4– to MnO2 is
(a) 1 F (b) 3 F (c) 5 F (d) 6 F
Ans:- ©
4. Cell reaction is spontaneous, when
(a) E0red is negative (b) ΔG° is negative
(c) E0oxid is Positive (d) ΔG° is positive
Ans:- (b)
5. State Kohlrausch’s law.

22
 Ans:- molar conductivity of an electrolyte at infinite dilution can be represented as the sum of the
individual contribution of the anion and cation of the electrolyte at infinite dilution
Λ m = λ∞( cation) + λ∞( anion)
6. Suggest two materials other than hydrogen that can be used as fuels in the fuel cells.
Ans: Methane (CH4) and methanol (CH3OH) can also be used as fuels in place of hydrogen in
the fuel cells
7. Write down the reactions during discharging of the lead storage cell?
Ans:- Anode reaction: Pb + SO4 2- → PbSO4 + 2e–
Cathode reaction: PbO2 + SO4 2- + 4H+ + 2e– → PbSO4 + 2H2O.
Overall – Pb + PbO2 + 2H2SO4 → 2PbSO4 + 2H2O
8. (a) What is a fuel cell?
(b) Write the overall cell reaction in H2 – O2 fuel cell?
Ans:- (a) Cells which convert directly Chemical energy into electrical energy
(b) 2H2(g) + O2(g) ⎯→ 2 H2O(l )
9. How do galvanic cells differ from electrolytic cells?
Ans:- : Galvanic cells (Electrochemical cells) convert chemical energy to electrical energy
while electrolytic cells convert electrical energy to chemical energy
10. A solution of CuSO4, is electrolysed for20 minutes with a current of 1.5 amperes. What is the
mass of copper deposited at cathode? (Atomic mass of copper = 63)
Ans: From Faraday’s first law W= ZIt = A x I x t
nF
= 63 x 1.5 x20 x 60
2 x 96500C
= 0.5875 g
11. The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm2 mol-1.
Calculate the conductivity of this solution.
Answer:
C = 1.5 M, Λm = 138.9 S cm2 mol-1
Λm = K×1000/C
∴K = Λm×C/1000=138.9×1.5/1000 = 0.20835 S cm-1
12. What is Electrochemical series ? write its two application.
Ans:- arrangement of elements in the order of increasing reduction potential values is called
electrochemical series.
Applications of electrochemical series:
1. Calculation of EMF of the cell E0cell = E0cathode – E0anode
2. Predicting feasibility of the reaction
3. To predict the reaction of a metal with dilute acids to liberate hydrogen gas
13. State Faraday’s first law of electrolysis. How much charge in terms of Faraday is required for
the reduction of 1 mol of Cu2+ to Cu.
Ans:- According to first law of Faraday’s “the amount of chemical reaction and hence the mass
of any substance deposited/liberated at any electrode is directly proportional to the quantity of
electricity passed through the electrolyte.”
The quantity of charge required for reduction of 1 mol of Cu2+= 2 faradays Cu2+ + 2e– → Cu
= 2 × 96500 C = 193000 C

23
 14. Define the following terms :
(i) Molar conductivity (Λm)
(ii) Secondary batteries
Ans:- Molar Conductivity (Λ m) is defined as conductivity of an electrolytic solution having 1 molar
concentration placed between two electrodes in such a way that the distance between the electrodes is 1
cm and the area of cross section is I cm2
1000𝐾
Mathematically Λm = 𝑀
(ii)Secondary battery- Can be reused again

SECTION–B (HOTS)
1. If 96500 coulomb electricity is passed through CuSO4 solution, it will liberate
(a) 63.5 gm of Cu
(b) 31.76 gm of Cu
(c)96500 gm of Cu
(d) 100 gm of Cu
Ans:- (b)
2. If limiting molar conductivity of Ca2+ and Cl– are 119.0 and 76.3 S cm2 mol-1, then the value
of limiting molar conductivity of CaCl2 will be
(a) 195.3 S cm2 mol-1
(b) 271.6 S cm2 mol-1
(c) 43.3 S cm2 mol-1
(d) 314.3 S cm2 mol-1.
Ans:- (b)
3. What would happen if no salt bridge were used in an electrochemical cell?
Ans:- positive ions will accumulate in one electrode while negative ions will accumulate in
another electrode so current will not flow.
4. What is cathodic protection?
Ans:- A process in which a metal is connected with a more reactive metal which act as anode
and the metal to be protected acts as cathode is known as cathodic protection.
5. Can you store copper sulphate solutions in a zinc pot?
Ans: No, Zn being more reactive than Cu, displaces Cu from CuSO4 solution as follows:
Zn (s) + CuSO4 (aq) –> ZnSO4(ag)+Cu (s)
6. State the relationship amongst cell constant of a cell, resistance of the solution in the cell and
conductivity of the solution. How is molar conductivity of a solute related to conductivity of its
solution?
Ans;- The relationship between the cell constant of a cell (G*), resistance of the solution in the
cell (R) and conductivity (K) is given by
Cell constant G
K= =
R R

The relationship between molar conductivity (Λm) and conductivity of the solution (K) is given by
1000𝐾
Λm = 𝑀

24
7. Conductivity of 0.00241 M acetic acid is 7.896 x 10-5 S cm-1. Calculate its molar
conductivity. If Λm0, for acetic acid is 390.5 S cm2 mol-1, what is its dissociation constant?
Sol:

8. How much charge is required for the following reductions:

(i) 1 mol of Al3+ to Al?
(ii) 1 mol of Cu2+ to Cu ?
(iii) 1 mol of Mn04- to Mn2+?
Ans :- The electrode reaction is Al3+ + 3e ——> Al
∴ Quantity of charge required for reduction of 1 mol of Al3+=3F=3 x 96500C=289500C.
(ii) The electrode reaction is Cu2+ + 2e– ——–> Cu
∴ Quantity of charge required for reduction of 1 mol of Cu2+=2F=2 x 96500=193000 C.
(iii) The electrode reaction is Mn04- ———-> Mn2+.
i.e., Mn7+ + 5e–——-> Mn2+.
∴ Quantity of charge required = 5F = 5 x 96500 C=4825000.
9. A voltaic cell is set up at 25°C with the following half-cells : Al | Al3+ (0.01 M) and Ni |
Ni2+ (0.1 M)
Calculate the cell voltage E0Ni2+/Ni= −0.25V,E0Al3+/Al= −1.66V
Ans:- The cell may be represented as
Al | Al3+ || Ni2+| Ni
E0cell = E0cathode – E0anode
E0cell = (-0-25) – (-1.66)
∴ E0 = -0.25 + 1.66 = 1.41 V
𝑜 2.303𝑅𝑇 [.01]2
10. E cell = 𝐸𝑐𝑒𝑙𝑙 – log
𝑛𝐹 [.1]3
.059 .0001
E cell = 1.41 – log
6 .001
= 1.41 - .00985 log (.1)
= 1.42 V

11. (a) Calculate E0cell for the following reaction at 298 K:

2Al(s) + 3Cu2+ (0.01M) → 2Al3+ (0.01M) + 3Cu(s) Given: Ecell = 1.98 V
(b) Using the E0 values of A and B, predict which is better for coating the surface of iron
[E0(Fe2+/Fe) = -0.44 V] to prevent corrosion and why? Given: E0(A2+/A) = -2.37 V;
E0(B2+/B) = -0.14 V
Answer: Using Nernst equation

25
 (b) Element A will be better for coating the surface of iron than element B because its E° value
is more negative.
12. (a) Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO3 with platinum electrodes.
(ii) An aqueous solution of H2SO4 with platinum electrodes.
(b) Estimate the minimum potential difference needed to reduce Al2O3 at 500°C. The Gibbs
energy change for the decomposition reaction 23 Al2O3 → 43 Al + O2 is 960 kJ
(F = 96500 C mol-1) (Comptt. Delhi 2014)
Answer:

13. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm-1. Calculate its molar
conductivity.
Ans:

14. What advantage do the fuel cells have over primary and secondary batteries?
Solution: Primary batteries or cells contain a limited amount of reactants and are discharged when
the reactants are consumed. Secondary batteries or cells can be recharged but the process takes a long
time. Fuel cells work continuously as long the reactants (i.e. fuel) are supplied.
15. The cell in which the following reaction occurs: 2Fe3+ (aq) + 2I– (aq) —> 2Fe2+ (aq) +I2 (s) has
E°cell=0.236 V at 298 K. Calculate the standard Gibbs energy and the equilibrium constant of the
cell reaction.

26
 Ans:

16. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
Ans. For hydrogen electrode,H+ + e– —>1/2 H2,

27
 CHEMICAL KINETICS
GIST OF THE LESSON

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

a) Fast reaction . b) Reaction with moderate speed c) 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]
B.)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
6) Integrated rate equation for zero order reaction:

28
 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 CR x
‗t‘
Integrated rate equation:
Kt=Ln[ CR°÷ CR ] [ :. CR°-CR= x]

29
 SECTION A (MLL)

1 . For a reaction, A + B → Product, the rate law is given by r = k[A]¹/² [B]² .What is the order ofthe
reaction?
Ans. Order of reaction (n) = ½ + 2 = 3/2 = 1.5
2. The conversion of molecule X to Y follows second order kinetics. If concentration of X is
increasedto three times, how will it affect the rate of formation of Y?
Ans rate = k[X]² rate = k[3X]² rate = 9k
Rate of formation of Y will increase by 9 times.
3. A first order reaction has a rate constant 1.15 × 10–3 s–1. How long will 5 g of this reactant take to
reduce to 3 g?
Ans.

4. Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the decomposition
is a first order reaction, calculate the rate constant of the reaction.
Ans.

5. What is the effect of temperature on the rate constant of a reaction? How can this effect of
temperature on rate constant be represented quantitatively?
Ans. The rate constant of a reaction increases with increase in temperature and becomes nearly double
for every 10°C rise of temperature. The effect can be represented quantitatively by Arrhenius equation
K = Ae- Ea/RT
where Ea is the activation energy of the reaction and A is the frequency factor.

6. What is the effect of adding a catalyst on

(i) Activation energy (Ea), and
(ii) Gibbs energy (DG) of a reaction?
Ans. i) Decreases (ii) No effect
7. What do you understand by the rate law and rate constant of a reaction? Identify the order of a
reaction if the units of its rate constant are:
(i) L–1 mol s–1 (ii) L mol–1 s–1.
Ans. An experimentally determined expression which relates the rate of reaction with the concentration
of reactants is called rate law while the rate of reaction when concentration of each reactant is unity in a
rate law expression is called rate constant.
(i) Comparing power of mole in L–1 mol s–1 and (mol L–1)1–n s–1,

30
We get 1 = l – n ⇒ n = 0 i.e., zero order reaction
(ii) Again comparing power of mole in L mol–1s–1 and ( ) mol L s , – – 1 1 n –1 we get –1
= 1 – n ⇒ n = 2, i.e., second order reaction
8. Define the following terms:
(i) Pseudo first order reaction (ii) Half life period of reaction (t1/2)
Ans. (i) A reaction which is not truely of first order but under certain conditions becomes a reaction of
first order is called pseudo first order reaction, e.g., acid hydrolysis of ethyl acetate.
CH3COOC2H5 + H2O ---------> CH3COOH + C2H5OH
Rate ∝ [CH3COOC2H5] as H2O is in excess.
ii) The half life (t1/2) of a reaction is the time in which the concentration of reactant is reduced to one
half of its initial concentration [R]0.
For a first order reaction, t1/2 = k/0.693 , i.e., independent of [R]0.
For a zero order reaction, t1/2 = [R]0/2k i.e., t1/2 ∝ [R]0
9. The rate constant for a first order reaction is 60 s–1. How much time will it take to reduce the initial
concentration of the reactant to 1/10 th of its initial value?

Ans.
10. Consider the reaction R --------P . The change in concentration of R with time is shown in the
following plot:
(i) Predict the order of the reaction.
(ii) Derive the expression for the time required for the completion of the reaction.
(iii) What does the slope of the above line indicate?

31
Ans.

SECTION B (HOTS)
1 In the graph plotted between ln [R] and t for a first order reaction, the intercept on y- 1
axis is
(a) – k (b) [R]0 (c) ln [R]o (d) k/2.303

ANS. C
2 The rate constant of reaction is 2.0 × 10–6 mol–2 L2 s–1. The order of the reaction is 1
(a) 0 (b) 2 (c) 1 (d) 3

ANS. D
3 The decomposition of NH3 on platinum surface is zero order reaction. What are the 2
rates of production of N2 and H2 if k = 2.5 × 10–4 mol L–1 s–1?
ANS.

32
4 Write two differences between ‘order of reaction’ and ‘molecularity of reaction’. 2
ANS. Order of reaction –(1) it is the sum of the powers of the concentration of the
reactants in the rate law expression.
(2) It is determined experimentally
(3) It can be zero or a fraction.
(4) Order is applicable to elementary as well as complex reactions.
Molecularity of reaction –(1) it is the number of reacting species taking part in an
elementary reaction, which must collide simultaneously so as to result into a chemical
reaction
(2) It is a theoretical concept.
(3) It cannot be zero or a fraction.
(4) Molecularity is applicable only for elementary reactions. For complex reactions it
has no meaning.
5 Define half-life of a reaction. Write the expression of half-life for 2
(i) zero order reaction and (ii) first order reaction.
ANS. The half life (t1/2) of a reaction is the time in which the concentration of a
reactant is reduced to one half of its initial concentration.
(i) t1/2 for a zero order reaction = [R]O /2K where [R]0 = initial concentration, k = rate
constant
(ii) t1/2 for a first order reaction = 0.693/K
6 For a first order reaction, show that time required for 99% completion is twice the time 3
required for the completion of 90% of reaction.
ANS.

33
7 A reaction is first order in A and second order in B. 3
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when concentration of both A and B are doubled?
ANS.(i) Rate = k[A][B]2
(ii) If the concentration of B is tripled, then Rate = k [A][3B]2 the rate of reaction
becomes 9 times.
(iii)If the concentration of both A and B are doubled, then Rate = k [2A ][2B ]2 i.e., the
rate of reaction becomes 8 times.

8 The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. 3
Calculate the energy of activation of the reaction assuming that it does not change with
temperature. (log4 = .6021)
ANS.

9 The following data were obtained during the first order thermal decomposition of 5
SO2Cl2 at a constant volume:
SO2Cl2(g) -----→ SO2(g) + Cl2(g)
Experiment Time/second-1 Total pressure/atm
1 0 0.4
2 100 0,7
Calculate the rate constant. (Given: log 4 = 0.6021, log 2 = 0.3010)
ANS.

34
10 For a certain chemical reaction variation in the concentration ln [R] vs. time plot is 5
given alongside. For this reaction

(i) what is the order of the reaction?

(ii) what are the units of rate constant k?
(iii) give the relationship between k and t1/2 (half-life period).
(iv)what is the slope of the curve?
(v)draw the plot log [R]0 /[R] vs timet(s).

ANS; (i) First order (ii) time–1 (s–1) (iii) t1/2 = 0.693/k
(iv)slope = – k (rate constant)
(iv)

35
 d- AND f- BLOCK ELEMENTS
GIST OF THE LESSON

d- block (transition elements [except group 12] )

f- block ( inner transition elements)
General conf. of d block elements. ( n-1 ) d 1-10ns 1,2 n=4,5,6,7……
Definition of transition elements :

Elements having partially filled d orbitals in ground state/elemental

state or commonly occurring oxidation state.
* Why are Zn, Cd & Hg not considered as transition elements?
* Zn is not considered a transition element whereas Cu is, though both have d10 conf.

36
 *electronic configuration of ions ( electrons to be removed from 4s then 3d. )
PHYSICAL PROPERTIES
1. MP, BP ARE VERY HIGH / HIGH ΔH ATOM / HARDNESS/ HIGH DENSITY/ LOW
VOLATILITY
due to strong metallic bonding involving participation of ( n-1 )d electrons in addition
to ns electrons
2.ATOMIC AND IONIC SIZE

a.In particular series radii 1st decreases, become constant then increases.

→dec: due to increase in nuclear charge

→const: increased nuclear charge is cancelled by inc. screening effect of e- in ( n-
1) d orbitals.
→increase is due to : electron – electron repulsions increase.
b.Variation within a series is very small : because increase in nuclear charge is
partially cancelled by increasing .screening effect of e- in (n-1)d orbitals.
c.↓ in a group : 1st T. series – 2nd T series : size increases
2nd T series & 3rd T series size is almost the same.
LANTHANOID CONTRACTION gradual decrease. in size along a lanthanoid series due to the
ineffective shielding of the f- orbitals which compensates for the expected inc. in size from 2nd T
series to 3rd T series.
Q.Zr and Hf occur together in their ores/ have very similar physical and chemical properties

37
 3.IONISATION ENERGY:
IE generally increases along the series due to inc. in Z eff
i)Elements of 3rd T.S have high I.E

Reason: greater Z eff due to ineffective shielding by 4f orbitals.

ii) Exceptionally high IE 2 for Cu & Cr
Reason: stability of d 5 , d 10 configuration is disrupted with the considerable loss of
exchange energy
iii) IE 2 of Zn is very low :
Reason: Removal of 2 e- results in stable d 10 conf.
iv)diff. in IE between two consecutive members of a period is very small
Reason: effect of increase in nuclear charge is partially cancelled by increase in screening effect
v)IE 3 – Mn , Zn relatively high
Reason : stable conf. of Mn 2+, Zn2+

4.TRENDS IN EOM2+/M
Eo value includes the energy changes due to ∆aHo, IE, and ∆hydHo
Lower the value of EoM2+/M , more the ease of formation of M2+ ions/more is the stability of M2+
/more is the stability of oxidised form
● EoM2+/M for Mn and Zn are lower than expected: stability of Zn2+ and Mn2+ ions (half filled and
completely filled configurations)
● EoM2+/M for Cu is very high(positive, so Cu cannot displace H2 from acids)
High value of ∆aHo, IE1 and IE2 is not compensated by ∆hydHo
● Cu(I) compounds are unstable in aqueous solutions and undergo disproportionation
2Cu+ (aq) → Cu2+ (aq) + Cu
Much more negative ∆hydHo for Cu2+ than Cu+ more than compensates high IE2 for Cu
TRENDS IN EoM3+/M2+
Lower the value of EoM3+/M2+ , more the ease of formation of M3+ ions/more is the stability
of M3+
● Low EoM3+/M2+ for Scandium reflects the stability of Sc3+ which has noble gas configuration
● Low EoM3+/M2+ for Fe reflects the stability of Fe3+ which has half filled configuration
● High EoM3+/M2+ for Zn and Mn is due to extra stability of Zn2+ (completely
filled configurations) and Mn2+( half filled configurations)

5. VARIABLE OXIDATION STATE

Reason: due to participation of ns & (n-1) d e-

38
 Note:O.S in T.M differ by unity ( due to incomplete filled d orbitals) in contrast to non
transition elements where O.S differ by 2.
6. MAGNETIC PROPERTIES

Mostly paramagnetic
Reason: due to the presence of unpaired e- in d orbitals of T.M
µ = √ n(n+2) BM n= no. of unpaired e-
7 T.M. FORM COLOURED COMPLEXES
In the presence of ligands d-orbitals of TM split up into two sets of orbitals having slightly diff.
energies. Transition of e- takes place from one of the lower d-orbitals to higher d-
orbital within the same subshell ( d-d transition) . e- absorb one wavelength light
from the visible spectrum and complementary colour is observed.
● Zn2+ , Ti 4+ , Sc3+ , Cd 2+ , Cu 1+ are white . why? ( d0& d 10 systems colourless )

8.CATALYTIC PROPERTIES

Reason (i) ability of TM to show multiple O.S(variable O. S.)

(ii) TM provide a surface for the reactant to get adsorbed and facilitate the reaction
9. FORMATION OF ALLOYS:
due to similar atomic size of T.M. they can fit into lattice nicely.
10.FORMATION OF COMPLEXES: T M form a number of complexes due to

1.Availability of empty d orbitals to accept electrons from ligands for the formation of coordinate bond
2.High charge density on the transition metal cation
11.FORMATION OF INTERSTITIAL COMPOUNDS
These are the compound which are formed when small atoms like B,C,N,H
are trapped inside the crystal lattice of the metal
INTERSTITIAL COMPOUNDS

i)have higher MP/BP

ii) very hard
iii) chemically inert
eg. Steel(trapping C in the interstitial voids of Iron)
OXIDES AND OXOANIONS OF METALS

● highest O.S are realised in oxides

Reason:
1.small size and high electronegativity 2.ability of oxygen to form multiple bonds.
● covalent character increases with increase in O.S.(Fazan’s rule)

39
 ● higher O.S more acidic
* V2O3 (+3) V2O4 (+4) V2O5 (+5)
Basic less basic amphoteric

* CrO (2+) Cr2O3 (3+) CrO3 (6+)

Basic amphoteric acidic

POTASSIUM DICHROMATE K2Cr2O7

● Preparation:

chromite ore (FeCr2O4 or FeO.Cr2O3)

● The chromates and dichromates are interconvertible in aqueous solution depending upon
pH of the solution

Chromate dichromate
(yellow) (orange)

● Potassium dichromate is used as

i)an oxidising agent
ii)a primary standard in volumetric analysis.

Reduction half

Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O

Oxidation half
2 I– → I2 + 2 e–

40
 H2S → 2H+ + S + 2e–

Sn2+ → Sn4+ + 2 e–

Fe2+ → Fe3+ + e–
POTASSIUM PERMANGANATE ( KMnO4)
● Preparation:

Pyrolusite ore( MnO2)

1.fusion of MnO2 with an alkali metal hydroxide and an oxidising agent

2. dark green K2MnO4 disproportionates in a neutral or acidic solution to give permanganate.

● Properties of KMnO4

● Thermally unstable (cannot act as primary standard)

● Acts as oxidizing agent in acidic as well as basic/neutral medium

Strongly Acidic medium

● Important

Acidic medium 10 I– + 2MnO4– + 16H+ ——> 2Mn2+ + 8H2O + 5I2

Alkaline medium I– + 2MnO4 – + H2O ——> 2MnO2 + 2OH– + IO3–

41
 ● Important
In permanganate titrations, HCl or HNO3 cannot be used to make the medium acidic

LANTHANOIDS
General electronic conf
4f 1-14 5d 0,1 6s 2 : La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
● Lanthanoid contraction:
The gradual decrease in atomic and ionic radii along a lanthanoid series

Cause—due to the imperfect shielding of one f-electron by another (in the same sub-shell)
Consequences of lanthanide contraction
1)similarity in properties of 2nd& 3rd T.M ( Zn , Hf )
2)basic character of hydroxides decreases along the lanthanide series
( size of M+dec , covalent character of M-OH increases & hence tendency to

release OH- is dificult )

3)separation of lanthanoids – becomes possible due to small diff. in size, hence
difference in ability to form complexes (ion exchange methods)
● PROPERTIES
1) colour ions: due to f-f transitions due to partially filled f orbitals

La 3+ ( 4f0 ) & Lu3+ (4f4 ) are colourless

2) O.S : main O.S - +3
Specially stable in Lanthanum La3+ (4f0 )
Gadolinium Gd3+(4f7)

Lutetium Lu3+ (4f14)

These are also possible :
Tb+4 4f7
Ce+4 4f0
Sm+2 4f6
Eu+2 4f7
Yb+2 4f14
But all have tendency to attain Group O. S. +3
So, Tb+4 , Ce+4 - good oxidising agent

42
 Yb+2 , Eu+2, Sm+2 - good reducing agents
3)REACTIVITY: quite reactive
-silvery white, soft metals , tarnish in air ; Samarium is hard , M.P. 1623 K ; other M.P. 1000-

1200 K
-typical metallic lustre, good conductors of heat & electricity
-many M+3 ions are coloured due to f-f transitions ( La+3& Lu+3colourless )
-mostly paramagnetic except La+3 , Ce+4 ( f0 ) & Yb+2 , Lu+3 (f14)
-I.E oF Ln are low compared to that of alkaline earth metals
-Complex formation: Not much tendency to form complexes
Alloy of Lanthanoids: Mischmetall
composition Ln:95%,Fe:5%,traces of S,Ca,C ,Al
Use: bullet shell and lighter flint

● ACTINOIDS
● -more complex chemistry
● -All of them are radioactive
● -transuranium are man –made
● O.S :Mainly +3 but others also exists. eg; +4,+5,+6,+7
● SIZES: Actinoid contraction ( is greater than lanthanoid contraction due to poor
shielding of 5f than 4f orbitals.
● COLOUR: metals are silvery white but ions usually coloured due to f-f transition
● REACTIVITY: highly reactive metals (
outer electrons are firmly held as they are better shielded & are available for bondin
g)

→ SIMILARITIES between Ln & Ac

1) In both,electrons progressively enter f subshell
2) Both have main O.S +3
3) Both are electropositive & reactive
4) Both show decrease in atomic and ionic size( Lanthanoids / Actinoids contraction)
→ DIFFERENCES between Ln & Ac

43
 Property Lanthanoids Actinoids
1.Oxidation states Lanthanoids show mainly +3 more variety in O.S +4, +5, +6
Oxidation state except in a few cases ,+7
where it is +2 and +3
4. Tendency to form Lesser tendency to form complexes. Greater tendency to form
complexes complexes .
5.Basic character Lanthanoid compounds are less basic Actinoid compounds are
more basic
6.Tendency to form They do not form oxo ions They form oxo ions such as
oxo ions UO2+ ,NpO2+ , PuO2+,UO2+
7.Radioactivity All the actinoids are radioactive
non-radioactive(Except promethium)

8.Reactivity Highly reactive

Relatively less reactive
9.Paramagnetic They are paramagnetic and their They are also paramagnetic but
character magnetic properties can be easily their magnetic properties cannot
explained be easily explained

SECTION A (MLL)

1.(i)Why do Zr and Hf possess similar properties.?

(ii)Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to
separate them. Why?
(iii) Explain why there is gradual decrease in atomic size of transition elements
in a series with increasing atomic no.
Ans Due to lanthanoid contraction

2. What is reason of lanthanoid contraction. What are consequence of it.

Ans-. It is regular decrease in atomic and ionic size as we move along the lanthanoids series from left
to right.

3.Explain why there is in general increase in density of elements from Ti(Z=22) to Cu(Z=29)?
Ans: Due to decrease in atomic size.

4. Transition elements have tendency to form alloy.

Ans- Due to their similar size(small size) they can exchange their relative position in their crystal
lattice so having tendency to form alloy .

5. (i)Explain why the greatest no of oxidation states are exhibited by the members in the middle of the
transition element series?

44
Ans:Due to presence of more no of unpaired electron.
(ii)Why transition metals generally form coloured compounds?
Ans:Due to presence of more no of unpaired electron which undergo d-d transition in visible region.
(iii)Why transition elements show high enthalpy of atomization/possess high melting points?
Ans: Due to strong interatomic interaction, hence strong bonding through more no of unpaired
electrons
(iv) Transition elements show high melting points. Why?
Ans: Due to strong interatomic interaction, hence strong bonding through more no of unpaired
electrons

6. Why Chrimium is a typical hard metal whereas mercury is a liquid.Why?

Ans.Due to presence of more no of unpaired electrons from 3d and 4s subshell metal metal
interactions are strong in Chromium but in mercury due to fully filled d10 conf. metal metal
interactions are weak.

7. Why Zn,Cd and Hg are not considered as transition elements?

Ans. As they are having fully filled d orbital in ground as well as in excited state.
8. Explain why though copper/silver/gold atom has completely filled d orbitals in its ground state yet
they are considerd as transition elements.
Ans: As they are having incompletely filled d orbital in excited state

9.Why does enthalpy of atomization of Zn is low.

Ans- Since it d orbital is fulfilled there exist only metallic bonding.
10. Explain why Transition metals and many of their compounds act as good catalyst.
Ans: Due to variable/multiple oxidation state.
11. Why transition elements have greater tendency for complex formation.
Ans-(i)They show variable oxidation state (ii) have vacant d orbitals
(iii) small size (iv) high charge density
12.Explain why the transition metals have high enthalpy of hydration?
Ans:Due to small size,high charge density.
13.Explain why transition elements have high density?
Ans- due to strong metallic as well as covalent bond form as well as they have small size and high
nuclear charge.
14. Why from element to element the actinoid contraction is greater than lanthanoid contraction
Ans- it is due to poorer shielding by 5f electrons
15.Why actinoids have more no of oxidation state than lanthanoids?
Ans- Due to small difference of energy of 6d, 5f, and 7s orbitals.
10. Why do transition metals show variable oxidation state?
Ans: Due to involvement of more no of electron from 3d and 4s subshell
15.Although fluorine is more electronegative than oxygen, but the ability of oxygen to stabilise
higher oxidation states exceeds that of fluorine. Why?
Ans: Due to multiple bond formation by oxygen.
.16. Name the alloy form by lanthanoids elements. Mention its two important uses.
Ans Misch metal it is mixture of lanthanoids and iron. It is used in bullet and lighter flint.
N.B. In most cases answer is generally based on following reasons
(i) More no of unpaired electron (ii) Small size,high charge density

45
17.Describe the steps involved in the preparation of potassium dichromate from chromite ore.

● Preparation:

chromite ore (FeCr2O4 or FeO.Cr2O3)

18. Describe the steps involved in the preparation of potassium permanganate from pyrolusite ore.

● Preparation:

Pyrolusite ore( MnO2)

1.fusion of MnO2 with an alkali metal hydroxide and an oxidising agent

2. dark green K2MnO4 disproportionates in a neutral or acidic solution to give permanganate.

------------------------------------------------- X -----------------------------------------------

A.MCQ TYPE:

1. Zinc and mercury do not show variable valency like d-block

elements because
A. they are soft

B. their d-shells are complete

C. they have only two electrons in the outermost subshell.

D. their d-shells are incomplete

Ans:B

46
 2. Lanthanoid contraction is due to increase in

(a) Size of 4f orbital

(b) shielding effect by 4f electrons

(c) effective nuclear charge

(d) atomic number

Ans:b
3. The magnetic nature of elements depends on the presence of unpaired electrons. Identify the
configuration of transition element, which shows highest magnetic moment.
(i) 3d7
(ii) 3d5
(iii) 3d8
(iv) 3d2

Ans:(ii)

4. Which of the following oxidation state is common for all lanthanoids?

(i) +2
(ii) +3
(iii) +4
(iv) +5
Ans(ii).
5. Although Zirconium belongs to 4d transition series and Hafnium to 5d transition series even then
they show similar physical and chemical properties because___________.
(i) both belong to d-block.
(ii) both have same number of electrons.
(iii) both have similar atomic radius.
(iv) both belong to the same group of the periodic table.
Ans:(ii)
6. Which of the following ions show higher spin only magnetic moment value?
(i) Ti3+
(ii) Mn2+
(iii) Fe2+
(iv) Co3+

7. The pair that has similar atomic radii is

47
 A. Mn and Re

B. Ti and Hf

C. Sc and Ni

D. Zr and Hf

Ans:D

8. Colour of transition metal ions are due to absorption of some

wavelength. This results in
A. d-s transition

B. s-s transition

C. s-t/transition

D. d-d transition

Ans: D
9. Transition metals form complex compound they have

(A)Small size
(B) High nuclear charge
(C) A number of vacant orbitals of equivalent energy
(D)All of these
Ans:D
10. The number of unpaired electron in Fe²+(Z=26) are

(a) 4
(b) 5
(c) 6
(d) 3

Ans:(a)

11. which of the following characteristic of transition metals is associated with catalytic activity
(a) Variable oxidation States

48
 (b)Paramagnetic nature

(c)Colour of hydrated ions

(d)High enthalpy of atomization

Ans:(a)
12. Transition elements form alloys easily because they have (a)
Same atomic number
(b) Same electronic configuration
(c) Nearly similar atomic size
(d) None of the above

Ans:(c)

13. Transition elements exhibit higher enthalpies of atomisation because

A. of weak metallic bonding

B. of variable oxidation states
C. lanthanoid contraction
D. of large number of unpaired electrons in their atom

Ans:D

14. In the first row transition metals which of the following exhibits the most varieties
of oxidation numbers?
A. Cr
B. Mn
C. Zn
D. Fe

Ans:B

15.Zr ( Z = 40 ) and Hf ( Z = 72 ) have similar atomic and ionic radii because of :

(A) Diagonal Relationship
(B) Both belongs to same group
(C) Lanthanoid contraction
(D) Having similar chemical properties

49
Ans:C

50
 SECTION –B(HOTS)

1.Why Mn has unusually lower melting point though it possess maximum number of unpaired
electron?
Ans.Due to half filled (n-1)d5 and full filled ns2 configuration Mn,Tc stable which reduce delocalisation
of electrons.
2.[Ni(CO)4] is tetrahedral whereas [Ni(CN)4]- 2 is square planar.Why?
Ans: sp3 hybridisation in [Ni(CO)4] but dsp2 hybridisation in [Ni(CN)4]- 2
3. Although +3 oxidation states is the characteristic oxidation state of lanthanoids but cerium
shows +4 oxidation state also. Why?
Ans: It is because after losing one more electron Ce acquires stable 4f 0 electronic
configuration.
4.Explain why Ce+4 is strong oxidising agent.
Ans:It can easily attain group oxidation state +3.
5.Colur of pink [Co(H2O)6 ] +3 changes to blue on adding HCl to it.
Ans: due to formation of tetrahedral complex [CoCl4 ]-1

6.(i)Higher oxidation state of Mn with F is +4 whereas with oxygen is +7.Why?

(ii)O2 and F2 both oxidises higher oxidation state of metals but O2 exceeds F2 in doing so.Why?
. (iii)The highest oxidation state of a metal is exhibited in its oxide or fluoride.Why?
Ans: Ability to form multiple bond by oxygen.

7.HCl is not used in permanganate titration.Why?

Ans: Permanganate oxidizes HCl into chlorine.
8.Cr(VI) is unstable and acts as strong oxidising agent while Mo(VI) and W(VI) are stable
compound.Explain.
Ans: For transition metals higher oxidation state is stabilized by heavier members.
9.How is the variability in oxidation states of transition metals different from that of the nontransition
metals? Illustrate with examples.
Ans.Oxidation state of transition metals differs by unity whereas oxidation of nontransitional elements
differs by two unit.
10.Chrimium is a typical hard metal whereas mercury is a liquid.Why?
Ans.Due to presence of more no of unpaired electrons from 3d and 4s subshell metal metal interactions
are strong in Chromium.
While in mercury all the electrons from 5d and 6s are paired thus metal metal interactions are weak.
11.Transition metals form large no of complexes.
Ans.(I) (I) Because of small size and high charge density of ions
(ii) Presence of empty d orbitals to accept election pairs from ligands..
12.Why there is unusual increase in atomic size at the end of any series of transition metals?
Ans. Due to repulsive interaction of electrons.
13.Except VF5 other Vanadium halides undergo hydrolysis to give oxohalides.
Give reason.
Ans.To stabilize high charge density of Vanadium (+5) it forms oxocation easily.
14. Out of Cu2Cl2 and CuCl2, which is more stable and why?

51
 Ans: CuCl2 is more stable than Cu2Cl2. The stability of Cu2+ (aq.) rather than Cu+(aq.) is due to the
much more negative ∆hydHV of Cu2+ (aq.) than Cu+(aq.
15. La(OH)3 is stronger base than Lu(OH)3 .
Ans: Lu(OH)3 is weaker base due to small size of Lu+3 .

16.Why Co+2 is easily oxidized in presence of stronger ligand.

Ans: It will be converted to Co+3 which attains t2g3 stability.

17.The halides of transition elements become more covalent with increasing oxidation state of
the metal. Why?
Ans:As the oxidation state increases, size of the ion of transition element decreases. As per
Fajan’s rule, as the size of metal ion decreases, covalent character of the bond formed
increases.
18.Reactivity of transition elements decreases almost regularly from Sc to Cu. Explain.

Ans: It is due to regular increase in ionisation enthalpy.

19.A solution of KMnO4 on reduction yields either a colourless solution or a brown precipitate or
a green solution depending on pH of the solution. What different stages of the reduction do these
represent and how are they carried out?
Ans: Oxidising behaviour of KMnO4 depends on pH of the solution. (i)In acidic
medium (pH < 7)
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
(Colourless)
(ii)In alkaline medium (pH>7)
MnO4– + e– → MnO42–
(Green)
(iii)In neutral medium(pH=7)
MnO4– + 2H2O + 3e– → MnO2 + 4OH–
(Brown precipitate)

20.
E0(volt) V Cr Mn Fe Co Ni Cu

(M+2/M) -1.18 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34

Explain why V and Mn possess unusual more negative E0 values.

Ans.Due to low value of sublimation enthalpy of Vanadium and Manganese
21.The sum of first and second ionisation enthalpies and third and fourth ionisation enthalpies if Nickel
and Platinum are:

52
 IE 1+ IE2(MJ/mol) IE3+IE4(MJ/mol)

Ni=2.49 Ni=8.80

Pt=2.66 Pt=6.70

Based on the above information, answer the following questions

(a) Which is the most common oxidation state for Ni and Pt?
(b)Out of the two,name the metal which can easily form compounds in +4 oxidation state and why?
Ans.(a) Ni :+2, Pt:+4
(b) Pt because sum of four I.E is less.

MCQ TYPE
1. Highest oxidation state of manganese in fluoride is +4 (MnF4) but highest oxidation state in oxides is
+7 (Mn2O7) because ____________.
(i) fluorine is more electronegative than oxygen.
(ii) fluorine does not possess d-orbitals.
(iii) fluorine stabilises lower oxidation state.
(iv) in covalent compounds fluorine can form single bond only while oxygen forms
double bond.

Ans: (iv)

2.Why is HCl not used to make the medium acidic in oxidation reactions of KMnO 4 in acidic
medium?
(i) Both HCl and KMnO4 act as oxidising agents.
(ii) KMnO4 oxidises HCl into Cl2 which is also an oxidising agent.
(iii) KMnO4 is a weaker oxidising agent than HCl.
(iv) KMnO4 acts as a reducing agent in the presence of HCl.

Ans: (ii)
3. Gadolinium belongs to 4f series. It’s atomic number is 64. Which of the following is
the correct electronic configuration of gadolinium?
(i) [Xe] 4f 75d16s2 (ii) [Xe] 4f 65d26s2
(iii) [Xe] 4f 86d2 (iv) [Xe] 4f 95s1
Ans: (i)
4. Although +3 is the characteristic oxidation state for lanthanoids but cerium also shows +4
oxidation state because ___________.
(i) it has variable ionisation enthalpy
(ii) it has a tendency to attain noble gas configuration
(iii) it has a tendency to attain f 0 configuration

53
 (iv) it resembles Pb4+
Ans: (ii)

5. Which of the following has magnetic moment value of 5.9 BM?

(a) Fe2+ (b) Fe3+ (c) Ni2+ (d) Cu2+

Ans: (a)
6. Transition elements form alloys easily because they have (a) Same
atomic number
(b) Same electronic configuration
(c) Nearly similar atomic size
(d) None of the above

Ans: (c)
7. Which of the following pairs of ions have the same
electronic configuration?
(a) Cu2+, Cr2+ (b) Fe3+, Mn2+
(c) Co3+, Ni3+ (d) Sc3+, Cr3+

Ans: (b)

8.Which of the following ions will exhibit colour in aqueous

solution? (a) La +3 (b) Ti +3 (c) Lu +3 (d) Sc+3

Ans: (b)

9. On addition of small amount of KMnO4 to concentrated H2SO4, a green oily

compound is obtained which is highly explosive in nature. Identify the

compound from the following.

(i) Mn2O7 (ii) MnO2 (iii) MnSO4 (iv) Mn2O3

Ans: (i)

54
 10. Generally transition elements form coloured salts due to the presence of unpaired electrons.
Which of the following compounds will be coloured in solid state?
(i) Ag2SO4 (ii) CuF2 (iii) ZnF2 (iv) Cu2Cl2

Ans: (ii)

11. When KMnO4 solution is added to oxalic acid solution, the decolourisation is slow in the
beginning but becomes instantaneous after some time because
(i) CO2 is formed as the product.
(ii) Reaction is exothermic.
(iii) MnO4– catalyses the reaction.
(iv) Mn2+ acts as autocatalyst.

Ans: (iv)

12.Interstitial compounds are formed when small atoms are trapped inside the

crystal lattice of metals. Which of the following is not the characteristic

property of interstitial compounds?

(i) They have high melting points in comparison to pure metals.

(ii) They are very hard.
(iii) They retain metallic conductivity.
(iv) They are chemically very reactive.

Ans: (iv)

55
 COORDINATION COMPOUNDS
GIST OF THE LESSON

Some points to remember:

• Co-ordination compounds:
a) A coordination compound contains a central metal atom or ion surrounded by number
of oppositely charged ions or neutral molecules. These ions or molecules re bonded to
the metal atom or ion by a coordinate bond.
b) Example: K4[Fe(CN)6]
c) They do not dissociate into simple ions when dissolved in water.
• Double salt
a) When two salts in stoichiometric ratio are crystallised together from their saturated
solution they are called double salts
b) Example:FeSO4.(NH4)2SO4.6H2O (Mohr’s salt)
c) They dissociate into simple ions when dissolved in water.
• Coordination entity:
a) A coordination entity constitutes a central metal atom or ion bonded to a fixed
number of ions or molecules.
b) Example: In K4[Fe(CN)6], [Fe(CN)6]4- represents coordination entity.
• Central atom or ion:
a) In a coordination entity, the atom/ion to which a fixed number of ions/groups are bound
in a definite geometrical arrangement around it, is called the central atom or ion.
b) Example: In K4[Fe(CN)6], Fe²+ is the central metal ion.
• Ligands:
a) A molecule, ion or group that is bonded to the metal atom or ion in a complex or
coordination compound by a coordinate bond is called ligand.
b) It may be neutral, positively or negatively charged.
c) Examples: H2O, CN-, NO+ etc.
• Donor atom:
a) An atom of the ligand attached directly to the metal is called the donor atom.
b) Example: In the complex K4[Fe(CN)6], CN is a donor atom.
• Coordination number:
a) The coordination number (CN) of a metal ion in a complex can be defined as the
number of ligand donor atoms to which the metal is directly bonded.
b) Example: In the complex K4[Fe(CN)6], the coordination number of Fe is 6.
• Coordination sphere:
a) The central atom/ion and the ligands attached to it are enclosed in square bracket and
are collectively termed as the coordination sphere.
b) Example: In the complex K4[Fe(CN)6], [Fe(CN)6]4- is the coordination sphere.
• Counter ions:
a) The ions present outside the coordination sphere are called counter ions.
b) Example: In the complex K4[Fe(CN)6], K+ is the counter ion.
• Coordination polyhedron:

56
 a) The spatial arrangement of the ligand atoms which are directly attached to the
central atom/ ion defines a coordination polyhedron about the central atom.

b) The most common coordination polyhedra are octahedral, square planar and
tetrahedral.
c) Examples: [PtCl4]2- is square planar, Ni(CO)4 is tetrahedral while
[Cu(NH3)6]3+ is octahedral.
• Charge on the complex ion:
The charge on the complex ion is equal to the algebraic sum of the charges on all the
ligands coordinated to the central metal ion.
• Denticity:
The number of ligating (linking) atoms present in ligand is called denticity.
• Unidentate ligands:
a) The ligands whose only one donor atom is bonded to metal atom are called
unidentate ligands.
b) Examples: H2O, NH3, CO, CN-
• Didentate ligands:
a) The ligands which contain two donor atoms or ions through which they are bonded to
the metal ion.
b) Examples: Ethylene diamine (H2NCH2CH2NH2) has two nitrogen atoms, oxalate ion

has two oxygen atoms which can bind with the metal atom.
• Polydentate ligand:
a) When several donor atoms are present in a single ligand, the ligand is called polydentate
ligand.
b) Examples: In N(CH2CH2NH2)3, the ligand is said to be polydentate and
Ethylenediaminetetraacetate ion (EDTA4–) is an important hexadentate ligand. It can
bind through two nitrogen and four oxygen atoms to a central metal ion.
• Chelate:
a) An inorganic metal complex in which there is a close ring of atoms caused by attachment
of a ligand to a metal atom at two points.
b) An example is the complex ion formed between ethylene diamine and cupric ion,
[Cu(NH2CH2NH2)2]2+.
• Ambidentate ligand:
a) Ligands which can ligate (link) through two different atoms present in it are called
ambidentate ligand.
b) Example: CN- and SCN-. Here, CN- can link through N as well as C while SCN- can
link through S as well as N atom.
• Werner’s coordination theory:
a) Werner was able to explain the nature of bonding in complexes.
b) The postulates of Werner’s theory are:
i) Metal shows two different kinds of valencies: primary valence and secondary
valence.
ii) The ions/ groups bound by secondary linkages to the metal have characteristic
spatial arrangements corresponding to different coordination numbers.

57
 iii) The most common geometrical shapes in coordination compounds are
octahedral, square planar and tetrahedral.
• Primary valence
a) This valence is normally ionisable.
b) It is equal to positive charge on central metal atom.
c) These valencies are satisfied by negatively charged ions.
d) Example: In CrCl3, the primary valency is three. It is equal to oxidation state
of central metal ion.
• Secondary valence
a) This valence is non – ionisable.
b) The secondary valency equals the number of ligand atoms coordinated to the metal. It
is also called coordination number of the metal.
c) It is commonly satisfied by neutral and negatively charged, sometimes by positively
charged ligands.
• Oxidation number of central atom:
The oxidation number of the central atom in a complex is defined as the charge it would
carry if all the ligands are removed along with the electron pairs that are shared with the
central atom.
• Homoleptic complexes:
Those complexes in which metal or ion is coordinate bonded to only one kind of donor
atoms. For example: [Co(NH3)6]3+
• Heteroleptic complexes:
Those complexes in which metal or ion is coordinate bonded to more than one kind of donor
atoms. For example: [CoCl2(NH3)4]+, [Co(NH3)5Br]2+
• 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. Solvate isomerism or hydrate isomerism
iii. Ionisation isomerism
iv. Coordination isomerism
b) Stereoisomerism
i. Geometrical isomerism
ii. Optical isomerism
• Structural isomerism:
a) It arises due to the difference in structures of coordination compounds.
b) Structural isomerism, or constitutional isomerism, is a form of isomerism in which
molecules with the same molecular formula have atoms bonded together in different
orders.
• Ionisation isomerism:
a) It 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.
b) Example: [Co(NH3)5Br] SO4 and [Co(NH3)5 SO4] Br
• Solvate isomerism:
a) It is isomerism in which solvent is involved as ligand.
b) If solvent is water it is called hydrate isomerism, e.g., [Cr(H2O)6]Cl3 and

58
 [CrCl2(H2O)4] Cl2. 2H2O.
• Linkage isomerism:
a) It arises in a coordination compound containing ambidentate ligand.
b) In the isomerism, a ligand can form linkage with metal through different atoms.
c) Example: [Co(NH3)5ONO]Cl2 and [Co(NH3)5NO2]Cl2.
• Coordination isomerism:
a) This type of isomerism arises from the interchange of ligands between cationic and
anionic entities of different metal ions present in a complex.
b) Example: [Co(NH3)6][Cr(C2O4)3] and [Cr(NH3)6][Co(C2O4)3].
• Stereoisomerism:
This type of isomerism arises because of different spatial arrangement.
• Geometrical isomerism:
It arises in heteroleptic complexes due to different possible geometrical arrangements of
ligands.
• Optical isomerism:
Optical isomers are those isomers which are non-superimposable mirror images.
• Valence bond theory:
a) According to this theory, the metal atom or ion under the influence of ligands can use
its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation to yield a set of equivalent
orbitals of definite geometry such as octahedral, tetrahedral, and square planar.
b) These hybridised orbitals are allowed to overlap with ligand orbitals that can donate
electron pairs for bonding.

Coordination Type of hybridization

number
4 sp3 Tetrahedral

4 dsp2 Square planar

5 sp3d Trigonal bipyramidal

sp3d2 (nd orbitals are involved Octahedral

6 – outer orbital complex or high
spin or spin free complex)

d2sp3(n-1) d orbitals are involved Octahedral

6 –inner orbital or low spin or spin
paired complex)

• 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.

Magnetic moment where n is number of unpaired electrons.

• Crystal Field Theory:

59
 a) It assumes the ligands to be point charges and there is electrostatic force of
attraction between ligands and metal atom or ion.
b) It is theoretical assumption.
• Crystal field splitting in octahedral coordination complexes:

• Crystal field splitting in tetrahedral coordination complexes:

• For the same metal, the same ligands and metal-ligand distances, the difference in

energy between eg and t2g level is

60
 SECTION – A(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

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 –
[CrCl2(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.]

SECTION – B(HOTS)

61
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]

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]

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

62
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.

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

Ans. d2sp3 geometry, octahedral

Q4)Write the formula of the given Coordination compound :–
a) Ni2+ ion is bound to two water molecules and two oxalate 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

63
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-
d) [NiCl4]2-

e) [Ni(CO)4]

f) [Fe(CO)5]

Q8) Draw diagram to show splitting of d – orbital in

64
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

2g g is t e and if Δo>
4 0

P the electronic configuration

2g g is t 3 e 1

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]
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.

65
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
4

solution to give Br - and SO 2- .

(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.

( Ans - a)

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

66
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) 2 4 [Cr(C
3 O ) ]3‐
(ii) [CoCI3(NH3)3].

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

(ii) Two (fac‐and mer‐isomer).

67
 2+is green, but a solution of [Ni(CN)4] 2-
Q4) A solution of is colourless. Explain.
[Ni(H2O)6]

68
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 of d-d transition is present. Hence,[ Ni(H2O)6]2+ is coloured.

In[Ni(CN)4]2–,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)Discuss the nature of bonding in the following coordination entity on the basis

of valence bond theory: [Fe(CN)6]4−

Ans. In the above coordination complex,iron exist s in the +2oxidation state.

Fe2+:Electronic configuration is3d6

As CN−is a strong field ligand,it causes the pairing of the unpaired 3d electrons.Since there

are six ligand saround the central metal ion, the most feasible hybridization is d 2sp3. Six
− 2 3
electron pairs from CN ions occupy the six 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?

69
 [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:
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)

70
f) Tetraammineaquachloridocobalt (III) chloride
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(NH
2] 3)4Cl

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

5) How many donor atoms does EDTA have?

71
 HALOALKANE AND HALOARENE

Minimum level of learning (MLL) for weak students:

1. IUPAC nomenclature of halo alkane.
2. IUPAC nomenclature of halo arenes.
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 + H2O.

Topics for bright students on assigned chapter:

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) Q. C6H5Cl + NaOH + HEAT→
C6H5OH + NaCl but in presence of silica Gel it go via benzyne
intermediate
6. (Hoffmann cation stability) Q. Is it in any way possible to have an anti Markovnikov's
reaction with HCl or HI?

7. (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
8. (Primary Isotopic effect) Q. Between (CH3)3C-Cl and (CD3)3C-Cl which would undergo
SN1 FASTER?
9. (Secondary Isotopic effect) Q. Between (CH3)3C-Cl and (CD3)3C-Cl which
would undergo SN2 FASTER?
10. (Wagner Meerwein rearrangement or Carbo cationic rearrangement) Q. What
would be the major product of Friedel-crafts alkylation using 1-Chloro Propane

72
 AND 1-Chloro-2-methylpropane?
11. (De-carbonylation pseudo alkylation) Q. C6H6+(Me3)3COCI=?

SECTION – A (MLL)

Q1.Which of the following is an example of vic-dihalide?

(i) Dichloromethane
(ii) 1,2-dichloroethane
(iii) Ethylidene chloride
(iv) Allyl chloride
Ans. (ii)
Explanation: In 1,2dichloroethane, the two chlorine atoms are attached to two adjacent
carbon atoms
Q2.The position of –Br in the compound in CH3CH=CHC(Br)(CH3)2 can be classified
as____________.
(i) Allyl
(ii) Aryl
(iii) Vinyl
(iv) Secondary
Ans. (i)
Explanation: These are the compounds in which the halogen atoms is bonded to an sp3-
hybridised carbon atom next to carbon-carbon double bond (C=C) i.e., to an allylic
carbon.
Q3.Ethylidene chloride is a/an ______________.
(i) vic-dihalide
(ii) gem-dihalide
(iii) allylic halide
(iv) vinylic halide
Ans. (ii)
Q4.A primary alkyl halide would prefer to undergo _____________.
(i) SN1 reaction
(ii) SN2 reaction

73
(iii) α–Elimination
(iv) Racemisation
Ans. (ii)
Explanation: SN2 type (bimolecular nucleophilic substitution). These reactions proceed
in one step and the rate of reaction depends on concentration of alkyl halide as well as
nucleophile i.e. r=k[RX][Nu]. It is a second order reaction. During SN2 reaction inversion
in configuration occurs i.e., starting with dextrorotatory halide a laevo product is
obtained and vice-versa.
Q5.Which of the following alkyl halides will undergo SN1 reaction most readily?
(i) (CH3)3C—F
(ii) (CH3)3C—Cl
(iii) (CH3)3C—Br
(iv) (CH3)3C—I
Ans. (iv)
Explanation- SN1 type (unimolecularnucleophilic substitution). These reactions proceedn two steps.
The rate of reaction is dependent on step 1 i.e., only on the concentration ofalkyl halide r =k [RX]. It is
a first order reaction.
R---------X bond length in case of iodine is highest and that is why lowest bond
dissociation enthalpy. Therefore, I- is known as best leaving group.
Q6.Which is the correct increasing order of boiling points of the following compounds?
1-Iodobutane, 1-Bromobutane, 1-Chlorobutane, Butane
(i) Butane < 1-Chlorobutane < 1-Bromobutane < 1-Iodobutane
(ii) 1-Iodobutane < 1-Bromobutane < 1-Chlorobutane < Butane
(iii) Butane < 1-Iodobutane < 1-Bromobutane < 1-Chlorobutane
(iv) Butane< 1-Chlorobutane < 1-Iodobutane < 1-Bromobutane
Ans. (i)
Explanation: For the same alkyl group, the boiling points of alkyl halides decrease in the
order: RI>RBr>RCl>RF. This is because with the increase in size and mass of halogen
atom, the magnitude of van der Waal forces increases.

Read the passage given below and answer the following questions.

74
CASE STUDY
Methyl chloride, methyl bromide, ethyl chloride and some chlorofluoromethanes are gases at
roomtemperature. Higher members are liquids or solids. As we have already learnt, molecules of
organichalogen compounds are generally polar. Due to greater polarity as well as higher molecular
mass ascompared to the parent hydrocarbon, the intermolecular forces of attraction (dipole-dipole and
van derWaals) are stronger in the halogen derivatives. That is why the boiling points of
chlorides,bromidesand iodides are considerably higher than those of the hydrocarbons of comparable
molecular mass. Theattractions get stronger as the molecules get bigger in size and have more
electrons. For the same alkyl
group, the boiling points of alkyl halides decrease in the order: RI>RBr>RCl> RF. This is becausewith
the increase in size and mass of halogen atom, the magnitude of van der Waal forces increases.The
boiling points of isomeric haloalkanes decrease with increase in branching . For example, 2-bromo-2-
methylpropane has the lowest boiling point among the three isomers. Boiling points ofisomeric
dihalobenzenes are very nearly the same.

Q7. Boiling point and melting point of alkyl halides increase as

(a) Alkyl group increases in size
(b) Size of halogen atom increases
(c) Branching decreases
(d) All of the above
Ans. d
Q8. The intermolecular forces of attraction are stronger in halogen derivatives of
alkanes. The kind of intermolecular forces are
(a) Dipole dipole interaction
(b) Van der waals force of attraction
(c) Both of above
(d) None of these
Ans. c
Q9. Which of the following has the highest boiling point?
(a) Chlorobutane
(b) Iodobutane

75
(c) Bromobutane
(d) Flourobutane
Ans. b
Q10. Which of the following gas is an environmental hazard?
(a) Methyl chloride
(b) Ethyl bromide
(c) Methyl bromide
(d) Chlorofluoromethane
Ans. d
11.Out of o-and p-dibromobenzene which one has higher melting point and why?
Ans. p-Dibromobenzene has higher melting point than its o-isomer. It is due to symmetry of
pisomerwhich fits in crystal lattice better than the o-isomer.
Q12.Why is the solubility of haloalkanes in water very low?
Ans.The haloalkanes are only very slightly solble in water. In order for a haloalkanes to
dissolve in water, energy is required to overcome the attractions between the haloalkanemolecules and
break the hydrogen bonds between water molecules. Less energy isreleased when new attractions are
set up between the haloalkane and the watermolecules as these are not as strong as the original
hydrogen bonds in water. As a result,the solubility of haloalkanes in water is low.
Q13.Why is it necessary to avoid even traces of moisture during the use of a Grignard
reagent?
Ans. Grignard reagents are highly reactive and react with any source of proton to give
hydrocarbons. Even water, alcohols and amines are sufficiently acidic to convert them tocorresponding
hydrocarbons.It is therefore necessary to avoid even traces of moisture from a Grignard reagent.
Q14.Discuss the nature of C–X bond in the haloarenes.
Ans.In haloarenes, C—X bond acquires a partial double bond character due to resonance. As aresult,
the bond cleavage in haloarene is difficult than haloalkane and therefore, they areless reactive towards
nucleophilic substitution reaction.
In haloalkane, the carbon atom attached to halogen is sp3 hybridised while in case of
haloarene, the carbon atom attached to halogen is sp2-hybridised.
Q15.Why are aryl halides less reactive towards nucleophilic substitution reactions than
alkyl halides?

76
Ans. Aryl halides are extremely less reactive towards nucleophilic substitution due to
following reasons:
(i) Resonance effect: In haloarenes, the electron pairs on halogen atom are in
conjugation with the ring C—Cl bond acquires a partial double bond character due to
resonance. As result, the bond cleavage in haloarene is difficult than haloalkane and
therefore, they are less reactive towards nucleophilic substitution reaction.
(ii) Difference in hybridisation of carbon atom in C—X bond: In haloalkane, the
carbon atom attached to halogen is sp3-hybridised while in case of haloarene, the carbonatom attached
to halogen is sp2-hybridised
(iii) Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as
result of self-ionisation will not be stabilised by resonance and therefore, SN1 mechanismis ruled out.
Because of the possible repulsion, it is less likely for the electron-richnucleophile to approach electron-
rich arenes.

SECTION - B (HOTS)
Q1.Toluene reacts with a halogen in the presence of iron (III) chloride giving ortho and
para halo compounds. The reaction is
(i) Electrophilic elimination reaction
(ii) Electrophilic substitution reaction
(iii) Free radical addition reaction
(iv) Nucleophilic substitution reaction
Ans. (ii)
Explanation: Aryl Chlorides and bromides can be easily prepared by electrophilic
substitution of arenes with chlorine and bromine respectively in the presence of Lewis
acid catalysts like iron or iorn (III) chloride.
Q2.Which reagent will you use for the following reaction?
CH3CH2CH2CH3 → CH3CH2CH2CH2Cl + CH3CH2CHClCH3
(i) Cl2/UV light
(ii) NaCl + H2SO4
(iii) Cl2 gas in dark
(iv) Cl2 gas in the presence of iron in dark

77
Ans. (i)
Explanation: Free radical chlorination or bromination of alkanes gives a complex
mixture of isomeric mono- and polyhaloalkanes, which is difficult to separate as pure
compounds. Consequently, the yield of any one free radical chlorination or bromination
of alkanes gives a complex
Q3.Chlorobenzene is formed by reaction of chlorine with benzene in the presence of
AlCl3. Which of the following species attacks the benzene ring in this reaction?
(i) Cl–
(ii) Cl+
(iii) AlCl3
(iv) [AlCl4]-
Ans. (ii)
Q4.What should be the correct IUPAC name for diethylbromomethane?
(i) 1-Bromo-1,1-diethylmethane
(ii) 3-Bromopentane
(iii) 1-Bromo-1-ethylpropane
(iv) 1-Bromopentane
Ans. (i)
Q5.Molecules whose mirror image is non-superimposable over them are known as chiral. Which
of the following molecules is chiral in nature?
(i) 2-Bromobutane
(ii) 1-Bromobutane
(iii) 2-Bromopropane
(iv) 2-Bromopropan-2-ol
Ans. (i)
Explanation: The objects which are nonsuperimposable on their mirror images are
called enantiomers. It occurs on that molecule which contains asymmetric carbon or
chiral i.e., a carbon atom attached with four different group.

Q6.Reaction of C6H5CH2Br with aqueous sodium hydroxide follows ____________.

(i) SN1 mechanism

78
(ii) SN2 mechanism
(iii) Any of the above two depending upon the temperature of reaction
(iv) Saytzeff rule
Ans. (i)
In the following questions a statement of assertion followed by a statement of
reason is given. Choose the correct answer out of the following choices.
(i) Assertion and reason both are correct and reason is correct explanation of assertion.
(ii) Assertion and reason both are wrong statements.
(iii) Assertion is correct but reason is wrong statement.
(iv) Assertion is wrong but reason is correct statement.
(v) Assertion and reason both are correct statements but reason is not correct
explanation of assertion.

Q7.Assertion: KCN reacts with methyl chloride to give methyl isocyanide

Reason: CN- is an ambident nucleophile.
Ans. (iv)
Explanation: KCN is predominantly ionic and provides cyanide ions in solution. Although both
carbon and nitrogen atoms are in a position to donate electron pairs, the attack takes place mainly
through carbon atom and not through nitrogen atom since C—C bond is more stable than C—N bond.
Q8.Assertion: Presence of a nitro group at orthoor paraposition increases the reactivity of haloarenes
towards nucleophilic substitution.
Reason: Nitro group, being an electron withdrawing group decreases the electron
density over the benzene ring.
Ans. (i)
Explanation: The presence of nitro group at ortho-and para-positions withdraws the
electron density from the benzene ring and thus facilitates the attack of the nucleophile
onhaloarene. The carbanion thus formed is stabilised through resonance. The negative
charge appeared at ortho- and para- positions with respect to the halogen substituent is
stabilised by -NO2 group.
9.Assertion: Hydrolysis of (–)-2-bromooctane proceeds with inversion of configuration.

79
Reason: This reaction proceeds through the formation of a carbocation.
Ans. (iii)
Explanation: Hydrolysis of (—)-2-bromooctane proceeds with inversion of configuration because the
reaction proceeds through SN2 mechanism.

Q10.Why can aryl halides not be prepared by reaction of phenol with HCl in the
presence of ZnCl2?
Ans. Method is not applicable for the preparation of aryl halides because the carbon-oxygen bond in
phenols has partial double bond character and is difficult to break being stronger than a single bond.
Q11Allyl chloride is hydrolysed more readily than n-propyl chloride. Why?
Ans. Allyl chloride will be hydrolyzed more readily because the reaction proceeds through
SNlmechanism and carbocation formed in case of allylic chloride is stabilized by resonance whereas;
carbocation formed by propyl chloride is not stabilized by resonance.

Q12.How do polar solvents help in the first step in SN1 mechanism?

Ans. SN l occurs in two steps. In step I, the polarised C—Br bond undergoes slow cleavage to produce
a carbocation and a bromide ion. The carbocation thus formed is then attacked by nucleophile in step II
to complete the substitution reaction. Step I is the slowest and reversible. It involves the C—Br bond
breaking for which the energy is obtained through solvation of halide ion with the proton of protic
solvent.
Q13.Compound ‘A’ with molecular formula C4H9Br is treated with aq. KOH solution. The rate
of this reaction depends upon the concentration of the compound ‘A’ only.When another
optically active isomer ‘B’ of this compound was treated with aq.KOH solution, the rate of
reaction was found to be dependent on concentration of compound and KOH both.
(i) Write down the structural formula of both compounds ‘A’ and ‘B’.
(ii) Out of these two compounds, which one will be converted to the product with
inverted configuration.
Ans.(i)A is tert-butyl Bromide Since the rate of reaction depends on the concentration of A only, it is
followed by SN1 mechanism. ‘B’ is sec-butyl bromide-
(ii)As the compound, B is optically active, it must be 2-bromobutane.
As the rate of reaction depends on the concentration

80
SN2 results in inversion of configuration.
Q14.Why are aryl halides less reactive towards nucleophilic substitution reactions than alkyl
halides?
Ans. Aryl halides are extremely less reactive towards nucleophilic substitution due to
following reasons:
(i) Resonance effect: In haloarenes, the electron pairs on halogen atom are in
conjugation with the ring C—Cl bond acquires a partial double bond character due to
resonance. As result, the bond cleavage in haloarene is difficult than haloalkane and
therefore, they are less reactive towards nucleophilic substitution reaction.
(ii) Difference in hybridisation of carbon atom in C—X bond: In haloalkane, the
carbon atom attached to halogen is sp3-hybridised while in case of haloarene, the carbon atom attached
to halogen is sp2-hybridised
(iii) Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as
result of self-ionisation will not be stabilised by resonance and therefore, SN1 mechanism is ruled out.
Because of the possible repulsion, it is less likely for the electron-rich to approach electron-rich arenes.
Q15.tert-Butylbromide reacts with aq. NaOH by SN1 mechanism while n-butylbromide
reacts by SN2 mechanism. Why?
Ans. n-butyl bromide reacts by SN2 mechanism because there is less steric hinderance.
Tertiary halides are the least reactive because bulky groups hinder the approaching
nucleophiles. Thus, the order of reactivity followed is:
Primary halide > Secondary halide > Tertiary halide. Further, in SN l greater the stability
of carbocation, greater will be its ease of formation from alkyl halide and faster will be
the rate of reaction. In case of alkyl halides, 30 alkyl halides undergo SNl reaction very fast because of
the high stability of 30carbocations.

81
 ALCOHOLS, PHENOLS AND ETHERS
Points to remember-
Nomenclature-
Compound Common name IUPAC name
Alcohol [ R-OH] Alkyl alcohol Alkanol
Phenol [Ar-OH] Phenol Phenol
Ether[R-O-R’] Alkyl alkyl ether [alphabetical order in alkyl or Alkoxy alkane
dialkyl if two same alkyls are present]
Structures of Functional Group-

1. The bond angle in alcohols is slightly less than the tetrahedral angle (109°-28’). It is due to the
repulsion between the unshared electron pairs of oxygen.
2. The carbon– oxygen bond length (136 pm) in phenol is slightly less than that in methanol. This is
due to (i) partial double bond character on account of the conjugation of unshared electron pair of
oxygen with the aromatic ring (ii) sp2hybridised state of carbon to which oxygen is attached.
3. The bond angle in ether is slightly greater than the tetrahedral angle due to the repulsive interaction
between the two bulky (–R) groups.
METHODS OF PREPARATION OF ALCOHOL-
1. Acid catalysed hydration of Alkene-
• Strong acid like H2SO4, HNO3 , H3PO4 acts as catalyst
• In case of unsymmetrical alkenes, the addition reaction takes place in
accordance with Markovnikov’s rule.
Example-

Mechanism-
Step 1: Protonation of alkene to form carbocation by electrophilic attack of H 3O+.
Step 2: Nucleophilic attack of water on carbocation.
Step 3: Deprotonation to form an alcohol.

82
 2. Hydroboration- oxidation of alkene-Diborane (BH 3)2 reacts with alkenes
to give trialkylboranes as addition product. This is oxidised to alcohol by hydrogen peroxide in
the presence of aqueous sodium hydroxide.

3. Reduction of aldehydes and ketones-

• H2 + Finely divided metal such as Pt, Pd, Ni (catalytic hydrogenation).
• Sodium borohydride (NaBH4) or lithium aluminium hydride (LiAlH4). Aldehydes yield
primary alcohols whereas ketones give secondary alcohols.
RCHO + H2 RCH2OH
RCOR’ ---------- NaBH4------→ R-CH-R’
OH
4. Reduction of Carboxylic acids and ethers-
(𝑖)𝐿𝑖𝐴𝑙𝐻4
RCOOH (𝑖𝑖)𝐻2𝑂
RCH2OH
𝐻2
RCOOR’ 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 RCH2OH + R’OH
5. Nucleophilic addition of Grignard reagent to the carbonyl compound followed by hydrolysis-
Reaction produces a primary alcohol with methanal, a secondary alcohol with other
aldehydes and tertiary alcohol with ketones.
Mechanism-

83
 Examples-

Preparation of Phenol-
1. Fromhaloarenes-

2. Frombenzenesulphonic acid-

84
3. Fromdiazonium salts-

4. From Cumene-[ Cumene is isopropylbenzene] aerial oxidation followed by acidic hydrolysis.

Physical properties of Alcohols and Phenol-

1. Solubility-Solubility of alcohols and phenols in water is due to their ability to form hydrogen
bonds with water molecules. The solubility decreases with increase in size of alkyl/aryl
(hydrophobic) groups.

2. Boiling points-Boiling points of alcohols and phenols are higher in comparison to

hydrocarbons, ethers, haloalkanes and haloarenes of comparable molecular masses.The high
boiling points of alcohols are mainly due to the presence of intermolecular hydrogen
bonding in them which is lacking in ethers and hydrocarbons.
• The boiling points of alcohols and phenols increase with increase in the
number of carbon atoms due to increase in van der Waals forces.
• In alcohols, the boiling points decrease with increase of branching in carbon chain
because of decrease in van der Waals forces with decrease in surface area.

85
Chemical properties of Alcohols-
1. Acidity of alcohols and phenol- The acidic character of alcohols is due to the polar nature
of O–H bond.
(i) Reaction with metals: Alcohols and phenols react with active metals such as sodium,
potassium and aluminium to yieldcorresponding alkoxides/phenoxides and hydrogen.

(ii) Strength of Acidity of alcohols:

Order of Acidic strength: Primary alcohol> Secondary Alcohol> Tertiary alcohol

86
 Acidity of phenols:
Reason- (i) phenoxide ion is resonance stabilized with no charge separation in resonating
structures while resonating structure of phenol involves charge separation.
Or Development of positive charge on oxygen as the hydroxyl group, is directly attached to the
sp2 hybridised carbon of benzene ring which acts as an electron withdrawing group.
Order of Acidic strength- Carboxylic group>Phenol>Water>1o>20>30 Alcohol
Stronger acid – higher Value of Ka—Lower value of PKa
Stronger acid—corresponding conjugate base is more stable

Acid Conjugate Base

Alcohol [No RS] Alkoxide ion [+I effect of alkyl group] but no
RS. The negative charge is localised on
oxygen.
Phenol [5 RS with charge separation] Phenoxide ion [5 RS with no Charge
separation. The negative charge on oxygen is
delocalized over benzene ring.
Carboxylic acid [ 2 RS with charge Carboxylate ion [ 2 identical RS with –ve
separation and +ve charge over one O - charge on oxygen atom]
atom
RS- Resonating structure
Effects of substituents on Acidity-
Electron Releasing -R, -OR,-NH2 Acidic strength due to the accumulation of negative
group decreases charge on Oxygen atom.
Electron -NO2, -X, -CN Acidic strength due to the effective
withdrawing groups increases delocalisation of negative charge
present over oxygen atom.
This effect is more pronounced when such a group is present at ortho and para positions in phenol or
benzoic acid.
Order of Acidity- O & P- nitrophenol> m-nitrophenol>Phenol> cresol
Esterification-Alcohols and phenols react with carboxylic acids or acid derivatives like acid chlorides
and acid anhydrides to form esters.

87
The reaction with carboxylic acid and acid anhydride is carried out in the presence of a small amount of
concentrated sulphuric acid. The reaction is reversible, and therefore, water is removed as soon as it is
formed.
The reaction with acid chloride is carried out in the presence of a base (pyridine) so as to neutralise
HCl which is formed during the reaction. It shifts the equilibrium to the right hand side.

Acetylation-The introduction of acetyl (CH3CO) group in alcohols or phenols is known as acetylation.

Acetylation of salicylic acid produces aspirin.
Aspirin- Aspirin is chemically Acetyl salicyclic acid .Aspirin possesses analgesic, anti-inflammatory
andantipyretic properties.

Lucas Test- Used to distinguish primary, secondary and tertiary alcohol.

ROH + HX ---------------→ R–X + H2O
Lucas Reagent- Mixture of conc. HCl and anhydrous ZnCl2
Principle-The difference in reactivity of three classes of alcohols with HCl distinguishes them from
one another. Alcohols are soluble in Lucas reagent while their halides are immiscible and produce
turbidity in solution.
Observation-In case of tertiary alcohols, turbidity is produced immediately as they form the halides
easily. Secondary alcohol forms turbidity within 5 minutes while primary alcohol forms turbidity on
heating.
Note- Primary alcohols do not produce turbidity at room temperature.
Dehydration of Alcohols-Alcohols undergo dehydration (removal of a molecule of water) to form
alkenes on treating with a protic acid e.g., concentrated H 2SO4 or H3PO4, or catalysts such as
anhydrous zinc chloride or alumina.

Mechanism-

88
Oxidation of Alcohols-
I. Strong oxidizing agents like KMnO4/H+ , K2Cr2O7/H+, Dil HNO3 – Carboxylic acid as final product.
RCH2OH RCHO RCOOH
Secondary alcohol Ketone
2. Oxidising agents like CrO3 in anhydrous medium, Pyridiniumchlorochromate PCC [a complex of
CrO3 with pyridine &HCl].
Primary alcohol-----→ Aldehyde
Secondary alcohol------→ Ketone
Dehydrogenation of alcohols-When the vapours of a primary or a secondary alcohol are passed over
heated copper at 573 K, dehydrogenation takes place and an aldehyde or a ketone is formed while
tertiary alcohols undergo dehydration.

Electrophilic substitution reaction in Phenol-

The –OH group attached to the benzene ring activates it towards electrophilic substitution. Also, it
directs the incoming group to ortho and para positions in the ring as these positions become electron

89
rich due to the resonance effect caused by –OH group.
Nitration- The ortho and para isomers can be separated by steam distillation. o-Nitrophenol is steam
volatile due to intramolecular hydrogen bonding while p-nitrophenol is less volatile due to
intermolecular hydrogen bonding which causes the association of molecules.

A. Halogenation-

Kolbe’S reaction-

Reimer Tiemann Reaction-

90
 Reaction with neutral FeCl3- A test of phenol-

ETHERS-
Preparation from alcohols-

Williamson synthesis-The reaction involves SN2 attackof an alkoxide ion on primary alkyl
halide.
R-X + R’ONa R-O-R’ +NaX
CH3I + CH3CH2ONa CH3-O-CH2CH3 + NaI
Methyl Iodide + Sod.Ethoxide ----------------→ Ethyl methyl ether + Sod. Iodide
(CH3)3-C-ONa +CH3I----------------→(CH3)3-C-CH3 + NaI
(CH3)3-C-Br +CH3-ONa →(CH3)2-C=CH2 + CH3OH [Elimination reaction and alkoxide ion
acting as strong base]
C6H5-ONa + R-X-----→C6H5-OR + Na-X
Physical properties-
1. The C-O bonds in ethers are polar and thus, ethers have a net dipole moment. The weak
polarity of ethers do not appreciably affect their boiling points which are comparable to
those of the alkanes of comparable molecular masses.
2. Water soluble due to tendency to form hydrogen bond.

Reaction of ether with HX-

R-O-R’ + HX--→ R-X + R’-OH [ R= smaller alkyl group]
R-O-R +2 HX (excess) ----→ 2 R-X + H2O [SN2 Mechanism]

91
1. Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the more stable aryl-oxygen
bond.
2. Iodide is a good nucleophile. It attacks the least substituted carbon of the oxonium ion
formed by attack of proton on oxygen of ether.
3. When one of the alkyl group is a tertiary group, the halide formed is a tertiary halide.
Electrophilic substitution in anisole-
The alkoxy group (-OR) is ortho, para directing and activates the
aromatic ring towards electrophilic substitution
Halogenation-

Nitration-

Friedel craft reaction-

92
 SECTION – A(MLL)
1. Which among the following is most acidic?
a. CH3OH b. CH3CH2OH c. (CH3)2CHOH d. (CH3)3COH
Ans-a. CH3OH [Hint- Higher is the number of electron releasing alkyl group, lesser is the acidity]
2. When phenol is treated with CHCl3 and NaOH, the main product formed is –
a. Benzaldehydeb. Salicylaldehyde c. Salicylic acid d. Benzoic acid
Ans- b. Salicylaldehyde [Hint- Reimer Tiemann Reaction]
3. Phenol is more acidic than ethyl alcohol because-
a. Phenoxide ion is more resonance stabilized than phenol.
b. Phenol is more resonance stabilized than phenoxide ion.
c. Ethoxide ion is more resonance stabilized than ethyl alcohol.
d. Ethyl alcohol is more resonance stabilized than ethoxide ion.
Ans- a. Phenoxide ion is more resonance stabilized than phenol.
4. Ethanol on warming with conc. H2SO4 at 413K gives-
a. Ethene b. Diethyl ether c. Dimethyl ether d. None of these
Ans- b. Diethyl ether
5. In lucas test, which class of alcohol donot give turbidity at room temperature.
a. Primary alcohol b. Secondary alcohol c. Tertiary alcohol d. b & c both.

93
Ans- a. Primary alcohol
6. Give reason for the following-
I. Propanol has higher boiling point than butane.
II. O-nitrophenol is less soluble in water than p-nitrophenol.
Ans- I. Since in propanol molecules are associated with strong H-bonds whereas butane has weak
dispersion forms.
II. O-nitrophenol shows intramolecular H- bonding.
7. Name the reagents used in the following reactions-
I. Oxidation of a primary alcohol to carboxylic acid.
II. Oxidation of a primary alcohol to aldehyde.
Ans- I. KMnO4/H+ , K2Cr2O7/H+, Dil HNO3 [any 1]
II.CrO3 in anhydrous medium, Pyridiniumchlorochromate PCC[any 1]
8. Give equations of the following reactions-
I. Dilute HNO3 with phenol II. Bromine water with phenol
Ans-

9. Write the suitable test to distinguish the following pair of organic compounds-
I. Phenol and Benzoic acid II. n-Butanol and tert butyl alcohol
Ans-
Test Phenol Benzoic acid
Na2CO3/NaHCO3 test No brisk effervescence of CO2 A brisk effervescence of CO2 is
is seen. seen.
Neutral FeCl3 A violet coloured complex is No violet coloured complex is
seen. seen.
n-Butanol tert butyl alcohol
Lucas test [ alcohol+ concHCl Turbidity appears only upon Turbidity appears immediately
+ZnCl2] heating. on adding reagent.
10. Arrange the following compounds in increasing order of their strength.
I. Propanol, O-nitrophenol, O-cresol, phenol
II. Propanol, propanoic acid, phenol
Ans- I. Propanol, <O-cresol, < phenol < O-nitrophenol.
II. Propanol,< phenol <propanoic acid.
11. Write the equations for following name reactions-
I. Reimer-Tiemann reaction
II. Williamson synthesis

94
III. Kolbe reaction
Ans-

CH3I + CH3CH2ONa CH3-O-CH2CH3 + NaI

Methyl iodide Sod. Ethoxide Ethyl methyl ether

12. How are the following conversions carried out?

I. Propene------------→ Propan-2-ol II. Benzyl chloride------------→ Benzyl alcohol
III. Ethyl magnesium chloride-----------→ Propan-1-ol
Ans- I. CH3-CH2=CH2 H2O/H+ CH3-CH-CH3
OH
II. C6H5-CH2-Cl Aq. KOH C6H5-CH2-OH
III. C2H5MgCl + HCHO H2C-OMgCl H2O/H+ CH3CH2CH2OH
C2H5
13.Write the names of reagents and equations for the preparation of the following ethers by
Williamson’s synthesis:
(i) 1-Propoxypropane (ii) Ethoxybenzene (iii) 1-Methoxyethane
Ans- (i) CH3CH2CH2ONa +CH3CH2CH2Br---→CH3CH2CH2OCH2CH2CH3 + NaBr
(ii) C6H5-ONa +CH3CH2Br -----→C6H5-O- CH2CH3 + NaBr
(iii) CH3CH2ONa + CH3Br ------→CH3CH2OCH3 + NaBr
14.Write the mechanism of hydration of ethene to yield ethanol.
Ans-

95
15. Explain the following with suitable reason.
I. Bond angles in ether is slightly more than the tetrahedral angle.
II. orthonitrophenolis more acidic than orthomethoxyphenol .
III. The –OH group attached to a carbon of benzene ringactivates it towards electrophilic substitution.
IV. Diethyl ether does not react with sodium.
V. Phenols donot undergo substitution of the –OH group like alcohols.
Ans- I.The bond angle in ether is slightly greater than the tetrahedral angle due to the repulsive
interaction between the two bulky (–R) groups.
II. The electron withdrawing group nitro group due to the effectivedelocalisation of negative charge
present over carbon atom in benzene ring. Whereas methoxy an electron releasing group causes
accumulation of charge.
III. Since lone pair of electrons on oxygen is in resonance with benzene ring and increases the electron
density on benzene ring.
IV. Since diethyl ether does not contain an active hydrogen.
V. The C-O bond in phenol has some double bond character due to resonance and hence cannot be
easily cleaved by nucleophile.

SECTION- B [HOTS]
Given below are two statements labelled as Assertion (A) and Reason (R).
Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
1. Assertion : p-nitrophenol is more acidic than phenol.
Reason : Nitro group helps in the stabilisation of the phenoxide ion by dispersal of negative charge due
to resonance.
Ans- a. Both A and R are true and R is the correct explanation of A
2. Assertion :Phenol gives O- and P- nitrophenol on nitration with conc. HNO3.
Reason :-OH group in phenol is o and p directing

96
Ans- d. A is false but R is true.
3. Assertion : Rectified spirit cannot be converted into absolute alcohol by simple distillation.
Reason: Rectified spirit is an azeotropic mixture which distils at a constant temperature.
Ans- a. Both A and R are true and R is the correct explanation of A.
4. Give the equations of reactions for the preparation of phenol from Cumene

5. What is meant by hydroboration oxidation reaction? Illustrate it with an example.

Ans- Diborane (BH3)2 reacts with alkenesto give trialkylboranes as addition product. This is oxidised to
alcohol by hydrogen peroxide in the presence of aqueous sodium hydroxide.

6. While separating a mixture of ortho and paranitrophenols by steamdistillation, name the isomer
which will be steam volatile. Give reason.
Ans- Ortho nitrophenol is steam volatile because in it there is intramolecular H-bond and does not
undergo association.. Hence the vanderwaal force is weak and hence has low boiling point and is steam
volatile.

7. Write the mechanism of acid dehydration of ethanol to yield ethene.

97
8. Write chemical reaction for the preparation of phenol from chlorobenzene.
Ans-

9. Give the structures and IUPAC names of the products expected fromthe following reactions:
(a) Catalytic reduction of butanal.
(b) Hydration of propene in the presence of dilute sulphuric acid.
(c) Reaction of propanone with methylmagnesium bromide followed by hydrolysis.
Ans- (a) CH3CH2CH2CH2OH [Butan-1-ol]
(b) CH3CHCH3
OH [ propan-2-ol]
(c) (CH3)3OH [2-Methylpropan-2-ol]
10. Write the equation of the reaction of hydrogen iodide with:
(i) 1-propoxypropane (ii) methoxybenzeneand (iii) benzyl ethyl ether.
Ans- (i) CH3CH2CH2 –O- CH2CH2CH3 + HI ---→ CH3CH2CH2OH + CH3CH2CH2I
(ii) C6H5-OCH3 + HI-----→ C6H5-OH + CH3I
(iii) C6H5-OCH2CH3 + HI-----→ C6H5-CH2OH + CH3CH2I

98
 ALDEHYDES, KETONES AND CARBOXYLIC ACID

FUNCTIONAL GROUP & NOMENCLATURE:

O

ALDEHYDE- C H Alkane - e + al Alkanal

O

KETONE:- C Alkane - e + one Alkanaone

O

CARBOXYLIC ACID:- C OH Alkane -e + oic acid Alkanoic acid

STRUCTURE OF CARBONYL GROUP:
The carbonyl group has a planar structure with sp2 hybridized carbon having three sigma bonds and a pi
bond. The carbon oxygen double bond is polarized due to higher electronegativity of oxygen atom.
_
O O

C C
+
PREPARATION OF ALDEHYDES AND KETONES:
1. Oxidation of alcohol:
Cu/Ag alk KMnO4 alk KMnO4
Aldehyde Primary alcohol Aldehyde Carboxylic acid

PCC/PDC

Aldehyde

Cu/Ag
[O]
Ketone Secondary alcohol Ketone
2. Rosenmund’s Reduction: Acid chlorides on hydrogenation in presence of palladium on barium
sulphate gives an aldehyde.
O O

C H2 C
Cl H
Pd - BaSO4

3. Stephen’s Reaction:
SnCl2 + HCl H3 O+
R CN RCH = NH RCHO
4. From hydrocarbons:

99
 CHO CH3 CHO

CrO3 + Acetic anh. CrO2Cl2

H3O+ H3O+

Cl2/hv
H3O+

CHO

5. Friedel Craft’s Acylation:

O
O
R C C
Cl R

anhyd. AlCl3
6. Preparation of ketone from acid chloride:
O O
R2Cd
R C Cl R C R
PROPERTIES:
1. Aldehydes and ketones can form H- bond with water and therefore they are soluble in it. Solubility
decreases with the increase in the no. of carbon atoms.
2. These molecules are polar in nature and have higher m.p and b.p than the hydrocarbons of comparable
molar mass.
3. Nucleophilic addithion:-
(a) Due to the polar nature of Carbonyl group aldehydes and ketone undergo nucleophilic addition.
(b) Aldehydes are generally more reactive than ketones towards the nucelophilic addition as ketones
have two bulky alkyl groups and its carbonyl carbon is more hindered than that of aldehydes.
O- OH
Nu -
H+
C O C C
Nu Nu
4.Addition of Ammonia and its derivatives:

H+
C O + H2N Z C N Z

5. Reduction:

100
 H H
Zn-Hg H2N-NH2
C C O C
HCl KOH
H H
(Clemmensen redn) LiAlH4 / NaBH4 (Wolff-Kishner redn)

OH
C
H
6. Oxidation:
[O] Tollen's reag.
Carboxylic acid Aldehyde R-COO- + Ag
Water bath
(Silver mirror0

Fehling's Soln

(water bath)

R-COO- + Cu+
(Red ppt.)
(Ketones do not react with Fehling’s solution or Tollen’s reagent)
7. Oxidation of methyl ketones:
O NaOH + I2
R C RCOONa + CHI3

CH3 (Yellow ppt.)

8. Aldol Condensation: Aldehydes or ketones having at least an α- H undergo self condensation in

presence of a strong alkali to give a β- hydroxyl aldehyde called aldol and the process is called aldol
condensation.
Conc. NaOH
2 HCHO CH3OH + HCOONa

When Aldol condensation is carried out between two different aldehydes or ketones it is called Cross
Aldol Condensation.
Dil. NaOH
CH3CH2CHO + CH3CHO CH3-CH2 - CH - CH2- CHO

OH
9. Cannizzaro’s reaction: Aldehydes having no α- H undergo self oxidation and reduction in presence
of conc. alkali to give an alcohol and a salt of carboxylic acid.
Conc. NaOH
2 HCHO CH3OH + HCOONa

CARBOXYLIC ACID
PREPARATION:
1. Oxidation of alcohols:

101
 alk KMnO4
Primary alcohol Carboxylic acid

2. Hydrolysis of the acid derivatives

Acid anhydride
H3O+
Ester
Carboxylic acid
Acid amide
Acid nitrile

3. By the action of Grignard reagent on carbon dioxide

XMgO HO
H3O+
C O C O
O C O + RMgX
R R
4. From alkyl benzenes
CH3 COOH
KMnO4/ OH-

PROPERTIES:

1. Soluble in water as they can form H- bond with water. Solubility decreases with the increase in the
length of the carbon chain.
2. M.P. and B.P of carboxylic acids are higher than those of the corresponding alcohols as they exist in
the dimeric form even in their vapour phase.

3. Acidic nature:
(a) Carboxylic acids are stronger acids than phenols due to symmetrical resonance.
(b) Presence of electron releasing group (+I effect) causes the acidic strength of carboxylic acids to
decrease.
(c) Presence of electron withdrawing group (-I effect) causes the acidic strength of the carboxylic acids
to increase.
4. General reactions:

102
 RCOCl

PCl5

ROH LiAlH4
RCOOR RCOOH RCH2OH
H+

NaOH + CaO

R H
5. Hell Volhard Zelinsky (HVZ) reaction:-
When Carboxylic acids containing α-H are treated with red phosphorus and X2 α- halogen substituted
carboxylic acids are obtained.

Red P4 + X2
CH3COOH CH2XCOOH

SECTION – A(MLL)

MCQ
1. Reduction of benzoyl chloride with Pd and BaSO4 produces:
(a) Benzoyl cyanide (b) Benzaldehyde
(c) Benzoic acid (d) None of these
2. Methyl ketones are characterized by:
(a) Iodoform test (b)Tollen’s reagent
(c)Benedict’s reagent (d)Schiff’s test
3. The reagent which does not react with both acetone and benzaldehyde is
(a) Sodium hydrogen sulphite (b) Phenyl hydrazine
(c) Fehling’s solution (d) Grignard reagent

ASSERTION- REASON

In the following questions two statements are given- one labeled as Assertion (A) and the other labeled
as Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given
below:
(a) Bothe Assertion (A) and Reason (R) are correct statements and the Reason (R) is the correct
explanation of the Assertion (A).
(b) Bothe Assertion (A) and Reason (R) are correct statements but the Reason (R) is not the correct
explanation of the Assertion (A).
(c)Assertion (A) is correct but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect but Reason (R) is correct statement.

4. Assertion (A) : Formaldehyde is a planar molecule.

Reason (R): It contains sp2 hybridised carbon atom.
Ans: (a)

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5. Assertion (A) : Carboxylic acids are more acidic than phenols.
Reason (R): Phenols are ortho and para directing.
Ans: (b)
6. How will you distinguish between:
(a) Ethanal and propanal
(b) Propanal and propanone
(c) Benzaldehyde and acetophenone
Ans: (a) By iodoform test. Ethanal gives positive iodoform test but propanal does not.
(b) By iodoform test. Propanone gives positive iodoform test but propanal does not.
(c) By iodoform test. Acetophenone gives positive iodoform test but benzophenone does not.
7. Read the passage given below and answer the questions that follow: [1+1+2=4]
Carboxylic acids are the most acidic amongst all the organic compounds. However they are much weaker
acids than the mineral acids. Carboxylic acids are more acidic than alcohols and phenols due to the
less electrophilic nature of carboxylic carbon which puts a partial positive charge on the hydroxyl O-
atom. The value of Ka is a measure of the acidic strength of an acid. Greater the value of Ka greater
is the tendency of the acid to ionize and hence stronger is the acid. The acidic strength of of carboxylic
acid is mainly affected by the inductive effect. +I effect causes acidic strength to decrease and –I effect
causes the acidic strength to increase.
(a) Carboxylic acids are stronger acids than phenol. Why?
Ans: Due to symmetrical resonance in carboxylate ion.
(b)Which one is more acidic: Formic acid or ethanoic acid?
Ans: Formic acid.
(c) What is acidity constant? How does the acidic strength depend upon it?
Ans: Acidity constant is the measure of the acidic strength of an acid. Greater the value of Ka more
is the tendency of the acid to ionize and hence greater the acidic strength.
8. Explain the following name reactions with suitable examples: [5]
(a) Rosenmund Reduction
(b) Aldol condensation
(c)Cannizzaro’s reaction
(d) Hell Volhard Zelinsky reaction
(e) Wolff- Kishner Reduction.

SECTION – B(HOTS)

Compounds A and C in the following reaction are:

CH3MgBr H2SO4 HBO
CH3CHO (A) (B) (C)
H2O
(a) identical (b) positional isomers
(c)functional isomers (d) optical isomer
1. What is the correct IUPAC name of the given compound?

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 CH3

CH3 C CH2 CH3

COOH
(a) 2,2- Dimethylbutanoic acid (b) 2- Carboxyl-2-methylbutane
(c) 2-Ethyl-2-methylpropanoic acid (d) 3- Methylbutane carboxylic acid
2. How will you bring about the following conversions: [3]
(a) Benzoic acid to benzaldehyde
(b) Ethanol to 2- hydroxybutanal
(c)Propanone to propene
Ans:
(a) Benzoic acid to benzaldehyde
COCl CHO
COOH H2
PCl5

Pd-BaSO4

(b) Ethanol to 2- hydroxybutanal

PCC Dil NaOH
CH3CH2OH CH3CHO CH3 CH CH2 CHO

OH
(c) Propanone to propene
O OH

LiAlH4 Conc. H2SO4

CH3 C CH3 CH3 CH CH3 CH3 CH CH2

3. Write the structures of A, B, C, D and E in the following reactions: [5]

CH3COCl Zn-Hg/HCl KMnO4/OH-
C6H6 A B C

NaOH

D+E
Ans:

105
 COCH3
A =

CH2CH3
B =

COOH

C =

COONa
D or E = CHI3 or

106
 AMINES

Points to be remembered:
• Amines are alkyl or aryl derivatives of ammonia (NH3)
• Functional groups of primary,secondary and tertiary amines are respectively –NH2, -NH- and -
N=
• Amines can be prepared by (i) Ammonolysis of alkyl halides, (ii) Reduction of nitro
compounds, (iii) Reduction of cyanides, amides and oximes, (iv) Gabreil Phthalimide synthesis.
• phthalimide synthesis cannot be used for preparing 2 0 as well as 3 0 amines and aryl amines.
• Hoffmann's bromamide reaction
(amide+ KOH+ Br2) also gives primary amine but it has one carbon atom less than the parent
amide.
• Aliphatic amines are soluble in water due to their tendency to form H-bonds with water
molecules. Aryl amines are, however, insoluble in water.
• Boiling points of amines are higher than alkanes but lower than those of carboxylic acids and
alcohols of comparable molecular mass.
• Basic character of Aliphatic amines
Aliphatic amines are more basic than NH3.
• In aqueous medium, the order of basic strength is 20 > 30 >10 among methylamines and 20 > 10
> 30 among ethylamines.
• In non-aqueous medium, the order of basic strength is 30 > 20 >10 .
• Basic character of aromatic amines
Aromatic amines are weaker bases as compared to ammonia
• Electron releasing groups like: (-CH3 ,-OCH3, -NH2, etc ) increase the basic strength while
electron withdrawing groups like, (NO2, -CN etc) decrease the basic strength of aromatic
amines The effect of substituents is more at para positions and less at meta-positions.
• Ortho substituted anilines are weaker bases than aniline irrespective of electron releasing or
attracting effect of the substituent. This is referred so as ortho effect.
• Basic strength of amines is expressed in terms of Kb, or pKb, The stronger the base is, lesser
will be its pKb, value and larger will be its Kb, value.
• Aniline reacts with HNO2, (NaNO2+HCI) at (278-280) K to form benzene diazonium chloride
(Diazotisation reaction)
• Aliphatic amines do not form diazonium salts because to their unstable nature.
• Aniline also give electrophilic ring substitution reactions. The substitution occurs at ortho and
para positions w.r.t.-NH2, group.
• Nitration of aniline is carried out after protecting –NH2, group through acetylation.
• Aryl amines react with benzene diazonium chloride to give azo dyes at low temperature in
acidic medium (pH 4-5)
• 10 , 20 and 30 aliphatic amines can be distinguished by Hinsberg’s test.
• Hinsberg's reagent is Benzene Sulphonyl Chloride.
• Diazonium salts are represented by the general formula : [C6H5N2 ]+X-.
• Aliphatic diazonium salts are very unstable and do not exist while arenediazonium salts are
relatively stable.
• Arenediazonium salts are prepared from primary aryl amines by diazotisation reaction.

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• Arenediazonium salts are important tools in the hands of organic chemist for preparing a
variety of aromatic compounds
• Benzene diazonium chloride can be converted into benzene, phenol, benzonitrile, benzoic acid,
benzyl amine, nitrobenzene, halobenzene, azodyes, etc., by suitable reagents.

SECTION-A(MLL)

1 -Mark Questions:
Q1.Write the formula of the following compounds:
(i) Aniline
Ans:C6H5NH2
(ii) Benzene diazonium chloride
Ans: C6H5N2Cl
(iii) Benzenesulphonyl chloride
Ans: C6H5SO2Cl
(iv) Acetamide or ethanamide
Ans: CH3CONH2
(v) Propanamide
Ans: CH3CH2CONH2
(vi) Anilinium chloride
Ans: C6H5NH3+Cl
(vii) Benzoyl chloride
Ans: C6H5COCl
(viii) Ethyl isocynide
Ans: C2H5NC
(ix) Acetanilide
Ans: C6H5NHCOCH3
(x) p-aminoazobenzene
Ans:

Q2.Arrange the following as directed in the following questions:

(i) C6H5NH2, (CH3)3N, C2H5NH2 (decreasing order of basic strength)
Ans: CH3)3N > C2H5NH2 > C6H5NH2
(ii) C6H5CH2NH2, C6H5NHCH3, C6H5NH2: (Increasing order of pKb)
Ans: C6H5CH2NH2 > C6H5NHCH3 > C6H5NH2
(iii)C6H5NH2, C2H5NH2, C6H5NHCH3: (Increasing order of pKb)
Ans: C2H5NH2 > C6H5NHCH3> C6H5NH2
(iv)CH3NH2, (CH3)3N, (CH3)2NH: (Increasing order of basic strength in aqueous solution)
Ans: (CH3)3N < CH3NH2 < (CH3)2NH
(v) CH3NH2, (CH3)2NH, C6H5NH2, C6H5CH2NH2:(Increasing order of basic strength)
Ans: C6H5NH2 < C6H5CH2NH < CH3NH2 < (CH3)2NH
(vi) C6H5NH2, C2H5NH2, (C2H5)2NH: (decreasing order of basicity)

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Ans: (C2H5)2NH > C2H5NH2> C6H5NH2
(vii) C2H5NH2 , (C2H5)2NH, (C2H5)3N: (Increasing order of basic nature in aqueous solution)
Ans: C2H5NH2 < (C2H5)3N < (C2H5)2NH
(ix) C6H5NH2, (C2H5)2NH, C2H5NH2: (increasing order of solubility in water)
Ans: C6H5NH2< (C2H5)2NH < C2H5NH2
(x) C6H5NH2, C6H5CH2NH2, C6H5NHCH3: (Increasing order of basicity)
Ans: C6H5NH2 < C6H5NHCH3 < C6H5CH2NH2
(xi) C6H5NH2, C6H5N(CH3)2, C6H5NHCH3: (Increasing order of basicity)
Ans: C6H5NH2 < C6H5NHCH3 < C6H5N(CH3)2

(2 -Marks Questions)

Q3 . Distinguish between the following pairs of compounds

(a) Methyl ammine and N,N-dimethylamine
Ans: Carbylamine test: Methyl amine being a primary amine gives pungent smelling
compound on reaction with CHCl3 and KOH, but N, N-dimethylamine will not react.
(b) Aniline and N- Methylaniline
Ans: Ans: Carbylamine Test: Aniline being a primary amine gives pungent smelling
compound on reaction with CHCl3 and KOH, but N-methylamine(secondary amine) will
give this test.
Q 4 . Distinguish between the following pairs of compounds
(a) Ethyl amine and Aniline
Ans:Azodye Test: Aniline is an aromatic primary amine. It reacts with benzene diazonium
chloride to form yellow azo dye, whereas Ethyl amine being an aliphatic primary amine
does not give this test.
Points to remember: Carbylamine test is given by both aliphatic and aromatic primary
amines.
(b) Aniline and benzylamine
Ans:Azodye Test: Aniline is an aromatic primary amine. It reacts with benzene diazonium
chloride to form yellow azo dye, whereas benzylamine being an aliphatic primary amine
does not give this test.
Q 5 . Distinguish between the following pairs of compounds
(a) (CH3)2NH and (CH3)3N
Ans: Hinsberg’s test: add Hinsberg reagent (C6H5SO2Cl) , (CH3)2NH will form compound
N,N-dimethylsulphonamide, which is insoluble in KOH. But (CH3)3N does not react with
Hinsber’s reagent.
(b) Aniline and ethylaniline
Ans: Carbylamine Test: Aniline being a primary amine gives pungent smelling compound
on reaction with CHCl3 and KOH, but ethylaniline(secondary amine) will not react.

3-Marks Questions
Q6 . Write the reactions involved in the following reactions
i) Hofmann bromamide degradation reaction
Ans: C6H5CONH2 + Br2 + 4 KOH → C6H5NH2 + K2CO3 + 2 KBr + 2H2O
ii) Carbylamine reaction:
Ans: When primary amine is treated with CHCl3 in presence of KOH , isocynide is formed

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 which is an offensive smelling compound.
RNH2 + CHCl3 + 3 KOH → RNC +3NaOH + 3H2O
Primary Amine Isocynide
iii) Diazotisation reaction
Ans:Aniline is reacted with NaNO2 and HCl at (0-5)0 C, benzene diazonium chloride is
formed.this reaction is called Diazotisation reaction.
Q7 . Write the reactions involved in the following reactions
i) Sandmayer’s reaction

Ans: Benzene diazonium chloride is reacted with CuCl/HCl or CuBr/HBr to give

chlorobenzene or bromobenzene is called Sandmayer’s reaction.
ii) Coupling reaction
Ans: Benzene diazonium chloride is reacted with phenol in presence of alkaline medium to
give p-hydroxy azobenzene (orange dye) is called Coupling reaction
iii) Acetylation reaction
Ans: Aniline is reacted with acetyl chloride or acetic anhydride to form acetanilide. This
reaction is called Acetylation reaction. In this process an acetyl group(-COCH3) is
introduced.
Q8. Account for the following supporting your answer with diagram or equation wherever
possible:
(i) Diazonium salts of aromatic amines are more stable than those of aliphatic amines
Ans: this is due to the resonance stabilisation of aromatic diazonium ion.
(ii) Ethyl amine is stronger base than NH3.
Ans: Ethyl (-C2H5) group is an electron releasing and increases the electron density on N of
C2H5NH2 than NH3.
(iii) (CH3)3CNH2 has lower boiling point than CH3CH2CH2CH2NH2 although both are
isomeric.
Ans: it is because (CH3)3C-NH2 is branched has minimum surface area, less van der Waal’s
force of attraction as compared to CH3CH2CH2CH2NH2.
Q9. Account for the following supporting your answer with diagram or
equation wherever possible:
(i) (CH3)2NH is more basic than (CH3)3N in an aqueous solution

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Ans: It is because in (CH3)3N, lone pair of electron is less readily available due to stearic
hindrance as compared to (CH3)2NH.
(ii) Acetylation of aniline reduces its activation effect
Ans : CH3CO- group is an electron withdrawing as a result it decreases electron density on
‘N’ of aniline therefore reduces its activation effect.
(iii) CH3NH2 is more basic than C6H5NH2
Ans:CH3- group is an electron releasing group, increases the electron density on ‘N’ whereas
C6H5- group is electron withdrawing group to reduce the electron density.
Q10. Account for the following supporting your answer with diagram or equation wherever
possible:
(i) Aniline does not undergo Friedel-Crafts reaction
Ans: It is because aniline is basic which can form adduct (salt) with AlCl3(Lewis acid).
(ii) Primary amines have higher boiling point than tertiary amines
Ans: Primary amines are associated with intermolecular H- bonding, whereas tertiary
amines are not
(iii) pKb value for aniline is more than that for methylamine.
Ans: Due to electron withdrawing phenyl group in aniline it is less basic to increase its pKb
value.

Or
Ethylamine is soluble in water whereas aniline is not soluble in water
Ans: It is because ethyl amine can form H-bonds with water whereas aniline cannot form H-
bonds easily due to bigger hydrocarbon.
Q11. Complete the following reactions:
(i) C6H5NH2+ CHCl3+ alc KOH →
Ans: C6H5NH2 + CHCl3 + 3 KOH → C6H5NC +3KCl + 3H2O
(ii) C6H5CONH2 + Br2 + 4 KOH →
Ans: C6H5CONH2 + Br2 + 4 KOH → C6H5NH2 + K2CO3 + 2 KBr + 2H2O

⎯⎯ ⎯ ⎯ ⎯→
NaNo + HCl /( 0−5 ) C
0
2
(iii) C6H5NH2
Ans: C6H5N2Cl
Q12. Write the structure of main products when benzene diazonium chloride(C 6H5N2Cl)
reacts with the following:
(i) HBF4/HEAT and the product with NaNO2/Cu
Ans:

(ii) CuCl/HCl
Ans:C6H5Cl
(iii) Aniline in acidic medium
Ans: P-aminoazobenzene

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5-Marks Questions:

Q13. (a) Write the structures of the main products when benzene diazonium chloride reacts
with the following reagents:
(i) CuCN
Ans:C6H5CN
(ii) CH3CH2OH
Ans: C6H6
(iii) Cu/HCl
Ans:C6H5Cl
(b) CH3NH2, (CH3)2NH, C6H5NH2, C6H5CH2NH2:(Increasing order of basic strength
Ans: C6H5NH2 < C6H5CH2NH < CH3NH2 < (CH3)2NH
(c) Write one chemical test to distinguish between Aniline and ethylaniline
Ans:Azodye Test: Aniline is an aromatic primary amine. It reacts with benzene diazonium
chloride to form yellow azo dye, whereas Ethylamine being an aliphatic primary amine
does not give this test.
Q14. (a) Write the structures of the main products when aniline reacts with the following
reagents:
(i) Br2 water
Ans: (2,4,6-tribromoaniline)

(ii) HCl
Ans:C6H5N+H3Cl (Anilinium chloride)
(iii) (CH3CO)2O/Pyridine
Ans:C6H5NHCOCH3 (Acetanilide)
(b) C2H5OH, C2H5NH2, (CH3)3N:(Increasing order of Boiling point
Ans: (CH3)3N< C2H5NH2 < C2H5OH
(c) Write one chemical test to distinguish between C2H5NH2 and (CH3)3N.
Ans: Carbylamine test: Methylamine being a primary amine gives pungent smelling
compound on reaction with CHCl3 and KOH, but (CH3)3N (trimethylamine) will not
react.
Q15. (a) Write the structures of the main products when benzene diazonium chloride reacts
with the following reagents:

112
(i) CuBr/HBr
Ans:C6H5Br (Bromobenzene)
(ii) H3PO2+H2O
Ans:C6H6 (Benzene)
(iii) H2O
Ans:C6H5OH (Phenol)
(b) C2H5NH2 , (C2H5)2NH, (C2H5)3N: (Increasing order of basic
nature in aqueous solution)
Ans: C2H5NH2 < C2H5)3N < (C2H5)2NH
(c) Write one chemical test to distinguish between C6H5NH2, C6H5-NH-CH3
Aniline and N-methylaniline
Ans: Carbylamine Test: Aniline being a primary amine gives pungent smelling compound
on reaction with CHCl3 and KOH, but N-methylaniline (secondary amine) will not react.
Or
Hinsberg’s test

SECTION-B(HOTS)

1 mark questons
Q1.(i) Write the IUPAC name of C6H5NHC2H5 .
Ans: N-Ethyl aniline or N-ethyl benzenamine
(ii) Write the IUPAC name of (CH3)2N-CH2-CH2-CH3 .
Ans: N,N-Dimethyl-1-propanamine.
(iii) Write the IUPAC name of (CH3CH2)2N-CH3 .
Ans: N-Ethyl-N-methylethanamine
(iv) Write the IUPAC name of (CH3NH-(CH3)2
Ans: N-Methyl-2-propanamine or N-Methylpropan-2-amine
(v) Write the IUPAC name of (CH3)2N-CH2-CH3
Ans: N,N-Dimethyl ethanamine
(vi) Write the IUPAC name of (CH3)2N-CH2-CH2-CH2-CH3
Ans: N,N-Dimethyl butan-1-amine
(vii) Identify the compounds ‘A’ and ‘B,
CH3CONH2+ Br2+NaOH → (A)+ CHCl3+NaOH → (B)
(viii)What is the diazotisation reaction?
Ans: C6H5NH2 ⎯⎯ ⎯ ⎯ ⎯→ C6H5N2Cl
NaNO2 / HCl ( 0 −5 ) C
0

(ix) Identify the compounds ‘X’ and ‘Y,

C6H5N2Cl ⎯⎯ ⎯→ ’X’ ⎯⎯ ⎯→ Y
CuCN H O/H+
2

Ans: X= C6H5CN ; Y= C6H5COOH

(x) Convert C6H5N2Cl into phenol.
Ans: C6H5N2Cl ⎯⎯ ⎯ ⎯→ C6H5OH
BOIL, H 2O

Q2.(i) Arrange the following in increasing order of basicity in aqueous phase whose pK b are
3.38, 4.22, 9.38 and 4.70 respectively.
Methanamine,N,N-Dimethylmethanamine,Benzenamine,Phenylmethanamine
Ans:- Benzenamine < Phenylmethanamine< N,N-Dimethylmethanamine< Methanamine

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 (ii) Out of butan-1-ol and butanamine, which is more soluble in water ?
Ans: Butan-1-ol , due to stronger intermolecular H-bonding.
(iii) Why pyridine is taken during acylation of aniline?
Ans: Pyridine is a base and it reacts with HCl produced to move the reaction in forward
direction.
(iv) Write the carbylamine reaction for benzylamine.
Ans: RNH2 + CHCl3 + 3 KOH → RNC +3NaOH + 3H2O
Primary amine isocynide
Where R= C6H5CH2-
(v) What happens when ethylamine is reacted with NaNO2 and HCl?
ANS: Ethanol is formed along with N2 gas.
C2H5NH2+HNO2 → C2H5OH+N2+H2O
(vi) How can monosubstituted aniline derivative be prepared?
Ans: protecting the –NH2 group by acylation of aniline.

Due to resonance, less availability of electron pairs on ‘N’atom in acetanilide.

(vii) Nitration of aniline gives meta derivative in addition to ortho and para, why?
Ans: in presence of strongly acidic medium, aniline is protonated to form Anilinium ion
which is meta directing.
(vii) Why does aniline not undergo Friedel Craft (acylation or alkylation) reaction?
Ans: Due to formation of salt with AlCl3, which is a Lewis acid. this makes the nitrogen of
aniline positively charged to deactivate.
(ix) Why aliphatic primary amines do not form diazonium salt?
Ans: Due to unstability of alkyl diazonium salts.
(x) Why do aromatic primary amines form diazonium salt?
Ans:Due to stability at low temperature and show resonance.

2 marks questions:
Q3.Write the following reactions
(a) Gatterman reaction
Ans:C6H5N2X ⎯⎯⎯→ C6H5Cl + N2+CuX
Cu / HCl

C6H5N2X ⎯⎯⎯→ C6H5Br + N2+CuX

Cu / HBr

(b) Write diazocoupling reaction.

Ans:

114
Q4. Complete the following reactions:
(i) C6H5NH2+ CHCl3+ alc.NaOH →
Ans: C6H5NH2 + CHCl3 + 3 NaOH → C6H5NC +3NaCl + 3H2O
(ii) C6H5N2Cl + H3PO2+H2O →
Ans: C6H5N2Cl + H3PO2 + H2O → C6H6 + H3PO3 + HCl
3 marks questions:
Q5. An aromatic compound ‘A’ on heating with Br2 and KOH forms a compound ‘B’ of
molecular formula C6H7N which on reacting with CHCl3 and alcoholic KOH produces a foul
smelling compound ‘C’. Write the structures and IUPAC names of Compounds A, B and C.
Ans: Compound B has molecular formula C6H7N suggesting that it must be an aromatic
primary amine (C6H5-NH2).Compond B is obtained from A by Hofmannbromamide reaction so
‘A’ must be an aromatic amide (C6H5CONH2). Compound ‘B’ gives carbylamine reaction to give
‘C’so it must be isocynide (C6H5NC).

Q6. Write the structures of compounds A, B and C in the following reactions:

(i) CH3COOH ⎯⎯ ⎯ ⎯→ A ⎯⎯ ⎯⎯→ B ⎯CHCl ⎯3⎯ ⎯ ⎯→C
NH 3 / HEAT Br2 / KOH ( aq ) + alc. KOH

(ii) C6H5N2BF4 ⎯⎯⎯⎯ ⎯→ A ⎯⎯⎯→ B ⎯⎯⎯⎯⎯→C

NaNO2 / Cu , HEAT Fe / HCl CH 3COCl / PYRIDINE

Ans: (i) A=CH3CONH2 , B = CH3NH2 C = CH3NC

(ii) A= C6H5NO2 , B = C6H5NH2 C = C6H5NHCOCH3
Q7. Write the structures of compounds A, B and C in the following reactions:

115
(a) CH3Br ⎯⎯→ A ⎯⎯ ⎯4 →B ⎯⎯2⎯ ⎯→ C
KCN LiAlH HNO 273K,

(b) C6H5COOH ⎯⎯⎯ ⎯→ A ⎯⎯⎯⎯→ B ⎯CHCl ⎯3⎯ ⎯ ⎯→C

NH 3 / HEAT Br2 / KOH ( aq ) + alc. KOH

Ans: (i) A=CH3CN , B = CH3CH2NH2 C = CH3CH2OH

(ii) A= C6H5CONH2 , B = C6H5NH2 C = C6H5NC

5 marks questions:

Q 8.Describe a method for the identification of primary, secondary and tertiary amines. Also
write the chemical equations involved.
Ans:
• Primary amines react with Hinsberg’s reagent to give a compound known as N-
alkylsulphonamide which is soluble in KOH or NaOH.
C6H5SO2Cl + RNH2 → C6H5SO2NH-R ⎯⎯→ ⎯ C6H5SO2NK+R
KOH

Hinsberg reagent P.Amine N-alkylbenzenesulphonamide (soluble salt )

• Secondary amines react with Hinsberg to give a compound known as N.N-
Dialkylsulphonamide which is insoluble in KOH or NaOH.
C6H5SO2Cl + R2NH → C6H5SO2N-R2 ⎯⎯→ ⎯ insoluble
KOH

Hinsberg reagent Sec.Amine N,N-Dialkylbenzenesulphonamide

C6H5SO2Cl + R3N → No reaction
Hinsberg reagent (tertiary Amine)
• Tertiary amines do not react with Hinsberg reagent.
Q 9. (i) Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis?
Ans: Because aryl halide do not undergo nucleophilic substitution with anion formed by
phthalimide.
(ii) Write the reactions of aromatic primary amines with nitrous acid.
C6H5NH2 + NaNO2 +2HCl → C6H5N2Cl + 2H2O +HCl
(iii) Write short notes on ammonolysis.
Ans: an alkyl or benzyl halide on reaction with an ethanolic solutionof ammonia undergoes
nucleophilic substitution reaction in which the halogen atom is replaced by an amino(-NH2)
group.
NH3+R-X → R-NH2 ⎯⎯→ R2NH ⎯⎯→ R3N ⎯⎯→ R4NX
RX RX RX

(1)0 (2)0 (3)0 (Quaternary ammonium salt)

(iv) How would you convert ethanamine into methanamine?
⎯⎯⎯→CH3CH2OH ⎯⎯ ⎯ ⎯→ CH3COOH ⎯⎯ ⎯⎯ ⎯→ CH3CONH2
+
HNO 2 KMnO 4 / H I ) NH ( II ) HEAT 3
C2H5NH2
⎯⎯⎯→ CH3NH2
Br KOH
2/

(v) How would you convert methanamine into ethanamine?

ANS: CH3NH2 ⎯⎯ ⎯→CH3OH ⎯⎯→ ⎯ CH3I ⎯⎯→ ⎯ CH3CN ⎯⎯ ⎯→ CH3CH2NH2
HNO2 P / I2 KCH LiAlH4

Q10. How would you convert 4-Nitrotoluene to 2-Bromobenzoic acid?

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117
 BIOMOLECULES

• Carbohydrates: Polyhydroxy aldehydes or polyhydroxy ketones or compounds on hydrolysis give

carbohydrates.
• Classification of carbohydrates:
Monosaccharides
(a) Simplest carbohydrates
(b) It cannot be hydrolysed into simpler compounds
(c) Examples – Glucose, mannose
Oligosaccharides
(a) Carbohydrates which gives 2 to 10 monosaccharide units on hydrolysis
(b) Examples – Sucrose, Lactose, Maltose
Polysaccharides
(a) Carbohydrates which on hydrolysis give large number of monosaccharide units.
(b) Examples – Cellulose, starch
• Anomers: Pair of optical isomers which differ in configuration only around C1 atom are called
anomers. Examples – -D-glucopyranose and -D-glucopyranose.

Preparation of glucose (also called dextrose, grape sugar):

• From starch

• Structure of glucose

• Structure elucidation of glucose:

a) D – glucose with HI

b) D – glucose with HCN

c) D – glucose with NH2OH

d)D – glucose with nitric acid

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e)D – glucose with bromine water

• Glucose does not give Schiff’s test and does not react with sodium bisulphite and NH 3.
Pentaacetyl glucose does not react with hydroxyl amine. This shows the absence of –CHO
group and hence the presence of ring structure.
• Cyclic structure of glucose:

• Glycosidic linkage: The oxide linkage formed by the loss of a water molecule when two
monosaccharides are joined together through oxygen atom is called glycosidic linkage.
• Sucrose (invert sugar):
• a) Sucrose is a non-reducing sugar because the two monosaccharide units are held together by a
glycosidic linkage between C1 of -glucose and C2 of – fructose. Since the reducing groups
of glucose and fructose are involved in glycosidic bond formation, sucrose is a non-reducing

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 sugar.

b) Sucrose is dextrorotatory but on hydrolysis it gives dextrorotatory &laevorotatory and the mixture is
laevorotatory.

Maltose:
1. Maltose is composed of two α-D-glucose units in which C1 of one glucose is linked to C4 of
another glucose unit.
2. The free aldehyde group can be produced at C1 of second glucose in solution and it shows
reducing properties so it is a reducing sugar.

Lactose (Milk sugar):It is composed of β-D-galactose and β-D-glucose. The linkage is between C1 of
galactose and C4 of glucose. Hence it is also a reducing sugar.
• Starch: It is a polymer of -glucose and consists of two components — Amylose and
Amylopectin.
• Amylose:
1. It is a water soluble component
2. It is a long unbranched chain polymer
3. Glucose units held by – glycosidic linkages involving C1 – C4glycosidic linkage
4. It constitutes about 15-20% of starch
• Amylopectin
1. It is a water insoluble component
2. It is branched chain polymer

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 3It forms chain by C1 – C4glycosidic linkage whereas branching occurs by C1- C6
Glycosidiclinkage
4.It constitutes about 80-85% of starch

• Cellulose:
1. It occurs exclusively in plants.
2. It is a straight chain polysaccharide composed only of -D-glucose units which are joined by
glycosidic linkage between C1 of one glucose unit and C4 of the next glucose unit.
• Glycogen:
1. The carbohydrates are stored in animal body as glycogen.
2. It is also known as animal starch because its structure is similar to Amylopectin.
3. It is present in liver, muscles and brain.
4. When the body needs glucose, enzymes break the glycogen down to glucose.
• Amino acids:
Amino acids contain amino (–NH2) and carboxyl (–COOH) functional groups.

Where R – Any side chain

Most naturally occurring amino acids have L – Config.

• Types of amino acids:

a). Essential amino acids: The amino acids which cannot be synthesised in the body and must be
obtained through diet, are known as essential amino acids. Examples: Valine, Leucine
b). Non-essential amino acids: The amino acids, which can be synthesised in the body, are known as
non-essential amino acids. Examples: Glycine, Alanine
• Zwitterion form of amino acids:
1. Amino acids behave like salts rather than simple amines or carboxylic acids. This behaviour is
due to the presence of both acidic (carboxyl group) and basic (amino group) groups in the same
molecule. In aqueous solution, the carboxyl group can lose a proton and amino group canaccept
a proton, giving rise to a dipolar ion known as zwitter ion. This is neutral but contains both
positive and negative charges.
2. In zwitterionic form, amino acids show amphoteric behaviour as they react both with acids and
bases.

• Isoelectronic point: The pH at which the dipolar ion exists as neutral ion and does not migrate
to either electrode cathode or anode is called isoelectronic point.
• Proteins: Proteins are the polymers of -amino acids and they are connected to each other by
peptide bond or peptide linkage. A polypeptide with more than hundred amino acid residues,
having molecular mass higher than 10,000u is called a protein.
• Peptide linkage: Peptide linkage is an amide linkage formed by condensation reaction between
–COOH group of one amino acid and –NH2 group of another amino acid.

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Peptide linkage
• Primary structure of proteins: The sequence of amino acids is said to be the primary structure
of a protein.
• Secondary structure of proteins: It refers to the shape in which long polypeptide chain can
exist. Two different types of structures:
– Helix:
Right handed screw with the NH group of each amino acid residue H – bonded to – C = O of adjacent
turn of the helix.
– pleated sheet:
In this conformation, all peptide chains are stretched out to nearly maximum extension and then laid
side by side which are held together by hydrogen bonds.
• Tertiary structure of proteins: It represents the overall folding of the polypeptide chain i.e.,
further folding of the 2° structure.

• Two shapes of proteins:

Fibrous proteins
a) When the polypeptide chains run parallel and are held together by hydrogen and disulphide bonds,
then fibre– like structure is formed.
b) These proteins are generally insoluble in water
c) Examples: keratin (present in hair, wool, silk) and myosin (present in muscles),

Globular proteins
a) This structure results when the chains of polypeptides coil around to give a spherical
shape.
b) These are usually soluble in water.
c) Examples: Insulin and albumins

• Denaturation of proteins:
1. The loss of biological activity of proteins when a protein in its native form, is subjected to
physical change like change in temperature or chemical change like change in pH. This is called
denaturation of protein.
2. Example: coagulation of egg white on boiling, curdling of milk.
• Nucleoside:
1. Base + sugar

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 • Nucleotide:
1. Base + sugar + phosphate group

• Nucleic acids (or polynucletides):

1. Long chain polymers ofnucleotides.
2. Nucleotides are joined by phosphodiester linkage between 5’ and 3’ C atoms of a pentose sugar.
Double helix structure of DNA:
1. It is composed of two right handed helical polynucleotide chains coiled spirally in opposite
directions around the same central axis.
2. Two strands are anti-parallel i.e., their phosphodiester linkage runs in opposite directions.
3. Bases are stacked inside the helix in planes to the helical axis.
4. Two strands are held together by H – bonds (A = T, G C).
5. The two strands are complementary to each other because the hydrogen bonds are formed
between specific pairs of bases.
6. Adenine forms hydrogen bonds with thymine whereas cytosine forms hydrogen bonds with
guanine.
Vitamins: Vitamins are organic compounds required in the diet in small amounts to perform specific
biological functions for normal maintenance of optimum growth and health of the organism.
1. Water soluble vitamins i) These vitamins are soluble in water.
ii) Water soluble vitamins must be supplied regularly in diet because they are readily excreted
in urine and cannot be stored (except vitamin B12) in our body.
iii) Example: Vitamin C, B group vitamins.
2. Fat soluble vitamins
i) These vitamins are soluble in fat and oils but insoluble in water.
ii) They are stored in liver and adipose (fat storing) tissues.
iii) Example: Vitamin A, D, E and K

Important vitamins, their sources and their deficiency diseases:

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Name of
Sources Deficiency diseases
vitamins

xerophthalmia
Vitamin A Fish liver oil, carrots, butter and milk (hardening of cornea of eye)
Night blindness

Vitamin B1 Beriberi
Yeast, milk, green vegetables and cereals
(Thiamine) (loss of appetite, retarded growth)

Cheilosis
Vitamin B2 (fissuring at corners of mouth
Milk, egg white, liver, kidney
(Riboflavin) and lips), digestive disorders and
burning sensation of the skin.

Vitamin B6
Yeast, milk, egg yolk, cereals and grams Convulsions
(Pyridoxine)

Vitamin B12 Meat, fish, egg and curd Pernicious anaemia

Vitamin C Scurvy
Citrus fruits, amla and green leafy vegetables
(Ascorbic acid) (bleeding gums)

Rickets
(bone deformities in children) and
Vitamin D Exposure to sunlight, fish and egg yolk
osteomalacia
(soft bones and joint pain in adults)

Vegetable oils like wheat germ oil, sunflower Increased fragility of RBCs and
Vitamin E
oil, etc. muscular weakness

Vitamin K Green leafy vegetables Increased blood clotting time

SECTION-A(MLL)
1. A disaccharide is formed when two monosaccharides are bonded together by a bond.
a) glycosidic
b) peptide
c) ionic
d) phosphodiester
2. Which of the following statements about starch is incorrect?
a) It gives blue colour with iodine
b) It is a polymer of α-D-glucose
c) It is a reducing carbohydrate

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d) It consists of branched chains
3. On oxidation with a mild oxidising agent like Br2/H20, the glucose is oxidized to
(a) saccharic acid
(b) glucaric acid
(c) gluconic acid
(d) valeric acid
4. Glycosidic linkage is an
(a) amide linkage
(b) ester linkage
(c) ether linkage
(d) acetyl linkage
5. What are the hydrolysis products of sucrose?
(a) Fructose + Fructose
(b) Glucose + Glucose
(c) Glucose + Galactose
(d) D-Glucose + D-Fructose
6. Which of the following is a non-reducing sugar?
(a) Glucose
(b) Sucrose
(c) Maltose
(d) Lactose
7. Which type of interactions are responsible for making the a-helix structure stable?
(a) Peptide bonds between -NH2 and -CO groups of adjacent carbon chain
(b) Hydrogen bonds between -NH of amino acid in the one turn with -CO of amino acid to adjacent
turn
(c) -OH group of one amino acid with -CO group of other amino acid on the turn
(d) Hydrogen bonds between adjacent amino acids
8.Directions: These questions consist of two statements, each printed as Assertion and Reason. While
answering these questions, you are required to choose any one of the following four responses.
(a) If both Assertion and Reason are correct and the Reason is a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but Reason is not a correct explanation of the Assertion.
(c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
Assertion : D(+)– Glucose is dextrorotatory in nature.
Reason : ‘D’ represents its dextrorotatory nature.
9. Assertion : At isoelectric point, the amino group does not migrate under the influence of electric
field.
Reason : At isoelectric point, amino acid exists as a zwitterion.

2marks questions
10.Write one difference each between a.globular and fibrous protein
b.Structural difference between DNA and RNA.
11.a. Name the vitamin responsible for the coagulation of blood
b.Give one example of fat soluble vitamin.

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3marks questions
12.Write the products
a. glucose reaction with Nitric Acid
b.Glucose reacting with Bromine water.
c.Glucose reacting with HI
13.a. Define a ‘Peptide linkage’.
b. Name the four bases present in DNA.
c.Which one of these is not present in RNA?
14. (i) Which one of the following is a disaccharide:
Starch, Maltose, Fructose, Glucose?
(ii) What is the difference between fibrous protein and globular protein?
(iii) Write the name of vitamin whose deficiency causes bone deformities in children.

5 Marks questions
15.a.Define the following as related to proteins
(i) Globular protein (ii) Primary structure (iii) Denaturation.
b.What are the common types of secondary structure of proteins?Give one difference between them.
SECTION-B(HOTS)
1. Invert sugar is
(a) a type of cane sugar
(b) optically inactive form of sugar
(c) mixture of glucose and galactose
(d) mixture of glucose and fructose in equimolar quantities
2. Which of the following treatment will convert starch directly into glucose?
(a) Heating with dilute H2SO4
(b) Fermentation by diastase
(c) Fermentation by zymase
(d) Heating with dilute NaOH
3. Denaturation of protein leads to loss of its biological activity by
(a) formation of amino acids
(b) loss of primary structure
(c) loss of both primary and secondary structure
(d) loss of both secondary and tertiary structures
2marks questions
4. ACCOUNT FOR THE FOLLOWING
a.Vitamin C cannot be stored in our body
b.Glucose is a reducing sugar.
5 .Answer the following:(i) what type of linkage is responsible for the primary structure of protein.
(ii) Name the location where protein synthesis occurs in body.
6.What is the water soluble part of starch called? What is the name of its monomer?

3marks questions
7.Give reasons for the following
i. Denaturation of proteins is irreversible process.
ii.Amino acids show amphoteric nature in aqueous solution.
iii. Glucose pentacetatedoesnot react with hydroxylamine

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4marks questions
8.Read the passage given below and answer the following questions:
The sequence of bases along the DNA and RNA chain establishes its primary structure which controls
the specific properties of the nucleic acid. An RNA molecule is usually a single chain of ribose-
containing nucleotide. On the basis of X-ray analysis of DNA, J.D., Watson and F.H.C. crick (shared
noble prize in 1962) proposed a three dimensional secondary structure for DNA. DNA molecule is a
long and highly complex, spirally twisted, double helix, ladder like structure. The two polynucleotide
chains or strands are linked up by hydrogen bonding between the nitrogeneous base molecules of their
nucleotide monomers. Adenine (purine) always links with thymine (pyrimidine) with the help of two
hydrogen bonds and guanine (purine) with cytosine (pyrimidine) with the help of three hydrogen
bonds. Hence, the two strands extend in opposite directions, i.e., are antiparallel and complimentary.
In these questions (i-iv), a statement of assertion followed by a statement of reason is given. Choose the
correct answer out of the following choices.
(a) Assertion and reason both are correct statements and reason is correct
explanation for assertion.
(b) Assertion and reason both are correct statements but reason is not correct explanation for assertion.
(c) Assertion is correct statement but reason is wrong statement.
(d) Assertion is wrong statement but reason is correct statement.
(i) Assertion: DNA molecules and RNA molecules are found in the nucleus of a cell.
Reason: There are two types of nitrogenous bases, purines and pyrimidines. Adenine (A) and guanine (G) are
substituted purines; cytosine (C), thymine (T) and uracil (U) are substituted pyrimidines
(ii) Assertion: In both DNA and RNA, heterocyclic base and phosphate ester linkages are at C-l' and C-
5' respectively of the sugar molecule.
Reason: Nucleotides and nucleosides mainly differ from each other in presence of phosphate units.
(iii) Assertion: The backbone ofRNA molecule is a linear chain consisting of an alternating units of a
heterocylic base, D-ribose and a phosphate.
Reason: The segment of DNA which acts as the instruction manual for the synthesis of protein is ribose.
(iv) Assertion: The double helical structure of DNA was proposed by Emil Fischer.
Reason: A nucleoside is an N-glycoside of heterocyclic base.

5marks
10.a.Write one important structural and functional difference between DNA and RNA.
b. What is meant by the inversion of sugar?
c. Glucose does not give 2, 4-DNP test and Schiff’s test. Why?
d. Name the unit formed by the attachment of a base to the 1′ position of sugar in a nucleoside.
ANSWERS(HOTS)
1d iv.d
2.b 10.a.corect differences
3a. b.correct answers.
4d c. Glucose contains an aldehyde group in its
5.a.water soluble vitamin open structure but forms a cyclic
b.contains free aldehyde group acetalstructure(also called pyranose).
6i.peptide bonds ii.ribosomes d.Nucleotides
7.amylopectin,glucose
8.correct reasons
9i.d
ii.b
iii.c

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ANSWERS(MLL)
1a
2.c.
3.c
4c.
5d.
6b.
7b.
8c.
9a.
10.Any differences
11.a.vitamin K
b.A/D/E/K
12a.Saccharic Acid
b.gluconic acid .
c. n hexane.
13a.deftn.
b.The four bases present in DNA are :A ,T ,G AND C
c.In RNA, Thymine (T) is absent. It has Uracil (U) in place of Thymine.
14. (i) Maltose is disaccharide.
(ii) Fibrous proteins have thread like structure and are insoluble in water. Globular proteins form a-
helix and are soluble in water.
(iii) Vitamin D.
15.a.deftns.
b.alpha and beta helix

128