CHEMISTRY

MP BOARD
Chapter Content Page

SYLLABUS I & II

01. SOLUTION 01 - 15

02. ELECTROCHEMISTRY 16 - 34

03. CHEMICAL KINETICS 35 - 51

04. D & F BLOCK 52 - 66

05. COORDINATION COMPOUNDS 67 - 86

06. HALOALKNES AND HALOARENES 87 - 105

07. ALCOHOL, PHENOL AND ETHER 106 - 121

08. ALDEHYDES AND KETONES 122 - 134

09. AMINES 135 - 143

10. BIOMOLECULES 144 - 163

11. IMPORTANT QUESTIONS OF ORGANIC CHEMISTRY 164 - 182

12. MP BOARD PAPER - 2018 WITH SOLUTIONS 183 - 192

13. MP BOARD PAPER - 2019 WITH SOLUTIONS 193 -204

14. MP BOARD PAPER - 2020 WITH SOLUTIONS 205 - 215

15. MP BOARD PAPER - 2022 WITH SOLUTIONS 216 - 223

16. MP BOARD PAPER - 2023 WITH SOLUTIONS 224 - 232

 MP Board

CHEMISTRY

CLASS XII (2023 - 24)

SYLLABUS
TIME : 3:00 HRS MARKS : 70
S.No. Title Marks
1. Solutions 7
2. Electrochemistry 9
3. Chemical Kinetics 7
4. d -and f -Block Elements 7
5. Coordination Compounds 7
6. Haloalkanes and Haloarenes 6
7. Alcohols, Phenols and Ethers 6
8. Aldehydes, Ketones and Carboxylic Acids 8
9. Amines 6
10. Biomolecules 7
Total 70

Unit I : Solutions
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 II : Electrochemistry
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 III : Chemical Kinetics
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 IV : d and f Block Elements
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 properties, interstitial
compounds, alloy formation, preparation and properties of K2Cr2O7 and KMnO4.

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Lanthanoids –
Electronic configuration, oxidation states, chemical reactivity and lanthanoid contraction and its
consequences.
Actinoids - Electronic configuration, oxidation states and comparison with lanthanoids.
Unit V : Coordination Compounds
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 importance of coordination
compounds (in qualitative analysis, extraction of metals and biological system).
Unit VI : Haloalkanes and Haloarenes.
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 VII : Alcohols, Phenols and Ethers
Alcohols : Nomenclature, methods of preparation, physical and chemical properties (of primary
alcohols only), identification of primary, secondary and tertiary alcohols, mechanism of
dehydration, uses with special reference to methanol and ethanol.
Phenols : Nomenclature, methods of preparation, physical and chemical properties, acidic nature
of phenol, electrophilic substitution reactions, uses of phenols.
Ethers : Nomenclature, methods of preparation, physical and chemical properties, uses.
Unit VIII : Aldehydes, Ketones and Carboxylic Acids
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.
Unit IX : Amines
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 X : Biomolecules
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.

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CHAPTER–1 : SOLUTION
UNIT INDEX
• Chapter at a glance 01-06
• Exercise-1_Important Questions 07-12
• Exercise-2_Multiple Choice Questions 13-15
CHAPTER AT A GLANCE
Definition of Solution:
When two or more chemically non-reacting substances are mixed together forming homogeneous
mixture the mixture is called solution.
Molarity (M)
The number of moles of solute present in one litre solution is called its molarity(M).
Number of moles of solute n
Molarity =
volume of solution (L) VL

Molality (m)
The number of moles of solute present in 1000 gram of the solvent is called molality of the
solution.
Number of moles of solute Number of moles of solute 1000
Molality of a solution = =
mass of solvent kg mass of solvent g
Percent By Mass (w/W)
Mass of solute (in g) present in 100 g of solution (g) is called mass percent of the solute.
Where 'w' gram of solute is dissolved in W gram of solvent.
Mass of solute g 100 w 100
Mass percent
Mass of solution g w W
Mass percent is independent of temperature.
Percent By Volume (v/V)
This method is used for solutions of liquid in a liquid. The volume of liquid (solute) in mL
present in 100 mL of solution in is called volume percent.
Volume of solute 100
Volume percent =
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Volume of solution
w
Percent by strength /percentage mass by volume :
V
Mass of solute (in g) present in 100 mL solution is called mass by volume.
w mass of solute g
% 100
V volume of solution mL

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Parts Per Million (ppm)
This method is used for expressing the concentration of very dilute solutions such as hardness of
water, air pollution etc.
Massof solute g 106
ppm (by mass) =
Mass of solution (g)
Volume of solute(mL) 106
ppm (by volume) =
Volume of solution(mL)
w mass of solute g
ppm by 106
V volume of solution mL
Mole Fraction :
The ratio of the number of moles of one component to the total number of moles of all the
components present in the solution, is called the mole fraction of that component.
moles of solute n
Mole fraction of solute XB =
moles of solute n moles of solvent N
moles of solvent N
Mole fraction of solvent XA =
moles of solute n moles of solvent N
XA XB 1
SOLUBILITY :
Maximum amount of solute which can be dissolved in a specified amount of solvent at constant
temperature is called solubility. Solubility is affected by nature of solute and solvent as well as
by temperature and pressure.
HENRY'S LAW
The partial pressure of the gas in vapour phase (P) is proportional to the mole fraction of the gas
(X) in the solution. (This is most common definition)
P = KHX KH = Henry's Constant
Henry's Constant is not a universal constant. It depends on nature of gas and temperature. KH
increases with increase in temperature therefore solubility of gas decreases.
VAPOUR PRESSURE
At a constant temperature, the pressure exerted by the vapours of a liquid on its surface when
they (liquid and its vapours) are in equilibrium, is known as vapour pressure.
Raoult's Law
For a solution of volatile liquids the partial vapour pressure of any component at constant
temperature is equal to vapour pressure of pure component multiplied by mole fraction of that
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component in the solution.

IDEAL SOLUTIONS
A solution which obeys Raoult's law exactly at all concentrations and at all temperatures is called
an ideal solution.
Ideal solution must obey Raoult's law at all concentrations.
PA = PAo X A ; PB PBo X B

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Volume change on mixing should be zero. Vmix = 0, i.e., (Vsolute + Vsolvent = Vsolution)
Heat change on mixing should be zero. Hmix = 0 (Heat is neither absorbed nor evolved)
For ideal solutions; A-A interactions = B-B interactions = A-B interactions.
Example
(i) Benzene and toluene (ii) n-hexane and n-heptane
NON-IDEAL SOLUTIONS
• Those solutions which do not obey Raoult's law are called non-ideal solutions.
• For such solutions ; PA PAo X A ; PB PBo X B
• Non ideal solutions are formed when the components differ much in their structures and
polarities.
So H mixing 0 and Vmixing 0
• For non ideal solutions ; A–A interactions or B-B interactions A-B interactions.
Non ideal solutions show either positive or negative deviations from Raoult's law.
(a) Non ideal solutions having positive deviation from Raoult's law
(i) Ethanol and cyclohexane (ii) Ethanol and Water (iii) Ethanol and Acetone
(b) Non ideal solutions having negative deviation from Raoult's Law
(i) CHCl3 and CH3COCH3 (ii) H2O and HCl (iii) H2O and HNO3
AZEOTROPIC MIXTURES :
Some liquids on mixing, form azeotropes which are binary mixtures having the same
composition in liquid and vapour phase and boil at a constant temperature, the liquid and vapour
have the same composition, and no further separation occurs.
There are two types of azeotropes :
(a) Minimum boiling azeotrope :- The solutions which show a large positive deviation from
Raoult’s law form minimum boiling azeotrope at a specific composition. For example, ethanol-
water mixture (obtained by fermentation of sugars) on fractional distillation gives a solution
containing approximately 95.57% v/v ethanol.
(b) Maximum boiling azeotrope :- The solutions that show large negative deviation from
Raoult’s law form maximum boiling azeotrope at a specific composition. Nitric acid and water is
an example of this class of azeotrope. This azeotrope has the approximate composition, 68%
nitric acid and 32% water by mass, with a boiling point of 393.5 K.
COLLIGATIVE PROPERTIES
Those physical properties of a solution which depends upon the relative number of particles of
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solute and do not depend on nature of solute particles are called colligative properties.
The following four properties are CP:
(i) Relative lowering in vapour pressure of solvent
(ii) Elevation in boiling point ( Tb) of solvent
(iii) Depression in freezing point ( Tf) of solvent
(iv) Osmotic pressure ( or P) of solution

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Osmosis and Osmotic Pressure
Osmosis: Osmosis is defined as the spontaneous net flow of solvent molecules through
semipermeable membrane from a solvent to a solution or from a dilute solution to a concentrated
solution.
Osmotic Pressure (p or )
The external pressure which must be applied on the solution in order to stop the flow of solvent
into the solution through semipermeable membrane is equal to osmotic pressure
CRT
Reverse Osmosis
If external pressure greater than osmotic pressure is applied, the flow of solvent molecules can be
made to proceed from solution towards pure solvent, i.e., in reverse direction of the ordinary
osmosis. Reverse osmosis is used for the desalination of sea water for getting fresh drinking
water.
• Best method to determine molecular weight of biomolecules like protein and polymers is osmotic
presure. Because it is a colligative property also as no temprature change is involved so there is
no chance of change in nature of biomolecule. In other methods changes are very less and it is
difficult to measure very small changes accurately. But osmotic pressure can be easily measured
at room temperature at which biomolecules remain in original state.
w
• 0.91% NaCl solution is isotonic with blood.
V
ABNORMAL COLLIGATIVE PROPERTIES
• It has been observed that difference in the observed and calculated molecular masses of
solute is due to association or dissociation of solute molecules in solution. It results in a
change in the number of particles in solution.
• Van't hoff factor (i) : Tells about relationship between normal colligative properties and
abnormal colligative properties.
number of particles after dissociation or association
• i
number of particles before dissociation or association
observed colligative properties
=
calculated colligative properties
• If i = 1 Neither dissociation nor association ; Ex. glucose, urea, sugar
• if i > 1 Dissociation will occur ; Ex. NaCl, KCl, BaCl2
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• if i < 1 Association will occur ; Ex. CH3COOH, PhCOOH in benzene

CASE I :
DISSOCIATION OF SOLUTE : Molecules of electrolytes undergo ionization or dissociation
in polar solvents to give two or more particles in solution. This dissociation results in an increase
in the total number of particles, and therefore the value of colligative properties of such solutions
will be higher. As the colligative properties are inversely related to molecular weight, so the
molecular weight of ionizable solute will be less than the theoretical value.

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Number of solute particles in solution increses.
• observed / experimental C.P. > calculated C.P. (normal)
• observed /experimental molecular weight of solute < calculated (normal) moleclar weight of solute
1
C.P.
molecular weight of solute
• Calculation of 'i' : Let solute be AxBy (electrolyte)
y+ x–
AxBy xA + yB ; x + y = n (total number of ions)
Initially 1 mol 0 0
After dissociation (1– ) x y
Total number of solute particles = 1– + x + y
= 1 – + (x+y)
= (1– + n )mol
Observed colligative property is proportional to observed number of solute particles (1– + n )
number of particles after dissociation 1 n
i =
number of particles before dissociation 1

i 1 (n 1)
where is the degree of dissociation
• For strong electrolytes
if =1 or 100% then i n

Ex. NaCl i =2; = 100%

K2SO4 i=3 = 100%

Ex. K4[Fe(CN)6] i =5 for = 100%

For = 50% i = 1 + (n–1)
i =3
CASE II :
ASSOCIATION OF SOLUTE: The formation of a bigger molecule by the union of two, three
or more solute molecules is called association. As a result, the total number of particles in
solution becomes less than the number of molecules initially dissolved in the solution and hence
the colligative properties will have lower value. As the molar mass of solute is inversely
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proportional to the colligative properties, so the molar mass of solute will be greater than
theoretical value.
Number of solute particles in solution decreases.
• Observed /experimental C.P. < calculated C.P.
• Observed / experimental molecular weight of solute > normal molecular weight of solute
1
C.P. ; i < 1 for association.
Molecular weight of solute

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• Calculation of i
nA –––––– [A]n

Initially 1 0

After association (1– )

n

Total number of solute particles = 1 mol

n

Observed C.P. observed number of solute particles 1

n

1
number of particles after association n
Van't hoff factor (i) = ; i
number of particle before association 1

i 1
n
= degree of association
n = number of solute particles which are associated.

1
• If = 100% or 1 or is not specified i
n

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EXERCISE-1 IMPORTANT QUESTIONS

1. Calculate the mass percentage of benzene (C6H6) and carbon tetrachloride (CCl4) if 22 g of
benzene is dissolved in 122 g of carbon tetrachloride.
Mass of C6 H 6
Ans. Mass percentage of C6H6 100
Total mass of the solution

Mass of C6 H 6
100
Mass of C6 H 6 Massof CCl4

22
100 = 15.28 %
22 122
Mass of CCl4
Mass percentage of CCl4 100
Total massof thesolution

Mass of CCl4
100
Mass of C6 H 6 Mass of CCl 4

122
100
22 122
= 84.72%
Alternatively,
Mass percentage of CCl4 = (100 - 15.28)
= 84.72%
2. Calculate the molarity of each of the following solutions:
(a) 30 g of Co(NO3)2. 6H2O in 4.3 L of solution
(b) 30 mL of 0.5 M H2SO4 diluted to 500 mL.
Ans. Molarity is given by:
Moles of solute
Molarity
Volumeof solution in litre

(a) Molar mass of Co (NO3)2.6H2O = 59 + 2 (14 + 3 × 16) + 6 × 18 = 291 g mol–1

30
Moles of Co (NO3)2.6H2O mol = 0.103 mol
291
0.103mol
Therefore, molarity = 0.023 M
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4.3L

(b) Number of moles present in 1000 mL of 0.5 M H2SO4 = 0.5 mol

0.5 30
Number of moles present in 30 mL of 0.5 M H2SO4 mol = 0.015 mol
1000
0.015
Therefore, molarity mol = 0.03 M
0.5L

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3. Calculate the mass of urea (NH2CONH2) required in making 2.5 kg of 0.25 molal aqueous
solution.
Ans. Molar mass of urea (NH2CONH2) = 2(1 × 14 + 2 × 1) + 1 × 12 + 1 × 16 = 60 g mol–1
0.25 molar aqueous solution of urea means:
1000 g of water contains 0.25 mol = (0.25 × 60)g of urea = 15 g of urea
That is,
(1000 + 15) g of solution contains 15 g of urea
15 2500
Therefore, 2.5 kg (2500 g) of solution contains g
1000 15
= 36.95 g
4. Calculate (a) molality (b) molarity and (c) mole fraction of KI if the density of 20% (mass/mass)
aqueous KI is 1.202 g mL–1.
Ans. Mass of solute = 20 g
Mass of solvent = 100 – 20
= 80 g
Molar mass of KI = 39 + 127
= 166 g/mol
(a) Molarity %

Mass
Volume of Solution V(ml) =
Density
100
=
1.202
wB = 20g
MB = 166 g/mol

w B 1000
M =
M B V(ml)

20 1000
M =
100
166
1.202
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20 1.202 1000
M =
166 100
M = 1.44 mol/L
w B 1000 20 1000
(b) Molality m =
MB wA 166 80

m = 1.5 mol/kg

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(c) Mole fraction of KI
nB
xB =
nB nA
w B / MB 20 / 166 0.1200
= =
w B / MB w A / MA 20 80 0.120 4.44
166 18
Mole fraction of KI = 0.0263

5. H2S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the solubility of
H2S in water at STP is 0.195m, calculate Henry’s law constant.
Ans. It is given that the solubility of H2S in water at STP is 0.195 m, i.e., 0.195 mol of H2S is
dissolved in 1000 g of water.
1000g
Moles of water
18g mol 1
= 55.56 mol
Moles of H 2S
Mole fraction of H2S, x
Molesof H 2S Molesof water
0.195
0.195 55.56
= 0.0035
At STP, pressure (p) = 0.987 bar
According to Henry’s law: p = KHX
p 0.987
KH bar
x 0.0035
= 282 bar
6. Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50 g of urea (NH2CONH2) is dissolved in
850 g of water. Calculate the vapour pressure of water for this solution and its relative lowering.
Ans. It is given that vapour pressure of water, P10 = 23.8 mm of Hg
Weight of water taken, w1 = 850 g
Weight of urea taken, w2 = 50 g
Molecular weight of water, M1 = 18 g mol–1
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Molecular weight of urea, M2 = 60 g mol–1

Now, we have to calculate vapour pressure of water in the solution. We take vapour
pressure as P1.
Now, from Raoult’s law, we have:
P10 P1 n2
P10 n1 n2

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w2
P10 P1 M2
P10 w1 W2
M1 M 2

50
23.8 P1 60
23.8 850 50
18 60
23.8 P1 8.23
23.8 47.22 0.83
23.8 P1
0.0173
23.8
P1 = 23.4 mm of Hg
Hence, the vapour pressure of water in the given solution is 23.4 mm of Hg and its relative
lowering is 0.0173.
7. Boiling point of water at 750 mm Hg is 99.63°C. How much sucrose is to be added to 500 g of
water such that it boils at 100°C. Molal elevation constant for water is 0.52 K kg mol–1.
Ans. Here, elevation of boiling point Tb = (100 + 273) – (99.63 + 273) = 0.37 K
Mass of water, wl = 500 g
Molar mass of sucrose (C12H22O11), M2 = 12 × 12 + 22 × 1 + 11 × 16 = 342 g mol–1
Molal elevation constant, Kb = 0.52 K kg mol–1
We know that:
K b 1000 w 2
Tb
M 2 w1

Tb M 2 w1
w2
K b 1000

0.37 342 500

0.52 1000
= 121.67 g
Hence, 121.67 g of sucrose is to be added.
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8. Calculate the mass of ascorbic acid (Vitamin C, C 6H8O6) to be dissolved in 75 g of acetic acid to
lower its melting point by 1.5°C. Kf = 3.9 K kg mol–1.
Ans. Mass of acetic acid, w1 = 75 g
Molar mass of ascorbic acid (C6H8O6), M2 = 6 × 12 + 8 × 1 + 6 × 16 = 176 g mol–1

Lowering of melting point, Tf = 1.5 K

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We know that:
Kf w 2 1000
Tf
M2 w 2

Tf M 2 w1
w2
K f 1000

1.5 176 75
3.9 1000
= 5.08 g
Hence, 5.08 g of ascorbic acid is needed to be dissolved.
9. Calculate the osmotic pressure in pascals exerted by a solution prepared by dissolving 1.0 g of
polymer of molar mass 185000 in 450 mL of water at 37°C.
Ans. It is given that:
Volume of water, V = 450 mL = 0.45 L
Temperature, T = (37 + 273)K = 310 K
1
Number of moles of the polymer, n mol
185000
We know that:
n
Osmotic pressure, RT
V
1 1
mol 8.314 103 Pa L K–1 mol–1 × 310 K
185000 0.45L

= 30.98 Pa
10. At 300 K, 36g of glucose present in a litre of its solution has an osmotic pressure of 4.98 bar. If
the osmotic pressure of the solution is 1.52 bars at the same temperature, what would be its
concentration?
Ans. Here,
T = 300 K
= 1.52 bar
R = 0.083 bar L K–1 mol–1
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Applying the relattion,

= CRT
1.52
C= = = 0.061 mol
RT 0.083bar,L.K 1mol 1
300 K

Since the volume of the solution is 1 L, the concentration of the solution would be 0.061 M.

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11. 0.05M solution of K4[Fe(CN)6] at 300K is 92% dissociated. Calculate the osmotic pressure of the
solution. (R = 0.0821 atm LK–1 mol–1)
Ans. C = 0.05, T = 300 K, R = 0.0821 atm LK–1 mol–1
K4[Fe(CN)6] 4K+ + [Fe(CN)6]4–
i=1– +n
= 1 – 0.92 + 5 × 0.92
= 1 – 0.92 + 4.60
= 0.08 + 4.60
= 4.68
= iCRT
= 4.68 × 0.05 × 0.0821 × 300
= 5.76 atm
12. What will be the value of Van't Hoff factor for ethanoic acid in benzene?
Ans. Van't Hoff factor for ethanoic acid in benzene is 0.5 because ethanoic acid forms dimer in
benzene.
13. Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of water such that its osmotic
pressure is 0.75 atm at 27°C.
Ans. We know that,

=i
n2
RT
= 0.75 atm
V
V = 2.5 L
w2 i = 2.47
i RT
M2 V
T = (27 + 273) K = 300 K
M2 V R = 0.082 L atm K–1 mol–1
w2
iRT M2 = 1 × 40 + 2 × 35.5 = 111 g mol–1
0.75 111 2.5
Therefore, w2 = = 3.42 g
2.47 0.0821 300
Hence, the required amount of CaCl2 is 3.42 g.
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EXERCISE-2 MULTIPLE CHOICE QUESTIONS

(INTRODUCTION, TYPES OF SOLUTIONS, CONCENTRATION TERMS)
1. 8 g NaOH is dissolved in one litre of solution, its molarity is:
(a) 0.8 M (b) 0.4 M (c) 0.2 M (d) 0.1 M
2. If 18 g of glucose is present in 1000 g of solvent, the solution is said to be:
(a) 1 molar (b) 0.1 molar (c) 0.5 molar (d) 0.1 molal
3. The molarity of pure water is:
(a) 100 M (b) 55.5 M (c) 50 M (d) 18 M
4. The mole fraction of oxygen in a mixture of 7 g of nitrogen and 8 g of oxygen is:
8
(a) (b) 0.5 (c) 0.25 (d) 1.0
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5. An example of liquid in solid is:
(a) Bronze (b) Alchol solution (c) Sugar Solution (d) Amalgam
(SOLUBILITY, HENRY'S LAW)
6. Which of the following gas will have most solubility in water ?
(a) NH3 (b) H2 (c) O2 (d) He
7. Value of Henry’s constant KH ____________.
(a) increases with increase in temperature. (b) decreases with increase in temperature.
(c) remains constant. (d) first increases then decreases.
8. Increase in temperature solubility of H2 gas in water:
(a) Increase (b) Decrease (c) Remain unchanged (d) None of these
9. Low concentration of oxygen in the blood and tissues of people living at high altitude is
due to ____________.
(a) low temperature
(b) low atmospheric pressure
(c) high atmospheric pressure
(d) both low temperature and high atmospheric pressure
10. Maximum amount of a solid solute that can be dissolved in a specified amount of a given liquid
solvent does not depend upon ____________.
(a) Temperature (b) Nature of solute (c) Pressure (d) Nature of solvent
(VAPOUR PRESSURE, RAOULT'S LAW, IDEAL-NON IDEAL SOLUTIONS)
11. Which condition is not satisfied by an ideal solution?
(a) H mixing = 0 (b) V mixing = 0
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(c) S mixing = 0 (d) Obeyance of Raoult's law

12. Among the following, that does not form an ideal solution is :
(a) C6H6 and C6H5CH3 (b) C2H5Cl and C6H5OH
(c) C6H5Cl and C6H5Br (d) C2H5Br and C2H5I
13. An azeotropic mixture of two liquids has b.p. lower than either of them when it :-
(a) shows a (+ve) deviation from Raoult's law (b) shows no deviation from Raoult's law
(c) shows (+ve) deviation from Henry's law (d) shows (–ve) deviation from Henry's law

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14. The mixture that forms maximum boiling azeotrope is :
(a) Water + Nitric acid (b) Ethanol + Water
(c) Acetone + Carbon disulphide (d) Heptane + Octane
15. For a solution of volatile liquids the partial vapour pressure of each component in solution is
directly proportional to –
(a) Molarity (b) Mole fraction (c) Molality (d) Normality
(COLLIGATIVE PROPERTIES: (A) RLVP (B) ELEVATION OF BOILING POINTS
(C) DEPRESSION IN FREEZING POINT)
16. Which of the following compounds can be used as antifreeze in automobile radiators ?
(a) Nitrophenol (b) Ethyl alcohol (c) Methyl alcohol (d) Glycol
17. The relative lowering of vapour pressure is equal to the mole fraction of the nonvolatile solute,
This statement was given by :
(a) Raoult (b) Henry (c) Joule (d) Dalton
18. The unit of ebulioscopic constant is _______________.
(a) K kg mol–1 or K (molality)–1 (b) mol kg K–1 or K–1(molality)
(c) kg mol–1 K–1 or K–1(molality)–1 (d) K mol kg–1 or K (molality)
19. Pressure cooker reduces cooking time for food –
(a) Heat is more evenly distributed in the cooking space
(b) Boiling point of water involved in cooking is increased
(c) The higher pressure inside the cooker crushes the food material
(d) Cooking involves chemical changes helped by a rise in temperature
20. The molal elevation constant is the ratio of the elevation in B.P. to –
(a) Molarity (b) Molality
(c) Mole fraction of solute (d) Mole fraction of solvent
(OSMOTIC PRESSURE)
21. At constant temperature the osmotic pressure of a solution is :
(a) Directly proportional to the concentration
(b) Inversely proportional to the concentration
(c) Directly proportional to the square of concentration
(d) Directly proportional to the square root of concentration
22. Which inorganic precipitate acts as semipermeable membrane?
(a) Calcium sulphate (b) Barium oxalate
(c) Nickel phosphate (d) Copper ferrocyanide
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23. If mole fraction of the solvent in solution decreases then :

(a) Vapour pressure of solution increases (b) B. P. decreases
(c) Osmotic pressure increases (d) All are correct
24. The osmotic pressure of a solution increases if :
(a) Temperature is lowered (b) Volume is increased
(c) Number of solute molecules is increased (d) None
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25. In osmosis –
(a) Solvent molecules move from higher concentration to lower concentration
(b) Solvent molecules move from lower to higher concentration
(c) Solute molecules move from higher to lower concentration
(d) Solute molecules move from lower to higher concentration
(ABNORMAL MOLAR MASS, VAN’T HOFF FACTOR)
26. Van't Hoff factor i
Normal molecular mass Observed molecular mass
(a) (b)
Observed molecular mass Normal molecular mass
(c) Less than one in case of dissociation (d) More than one in case of association+
27. The Van't Hoff factor will be highest for
(a) Sodium chloride (b) Magnesium chloride
(c) Sodium phosphate (d) Urea
28. Which of the following salt has the same value of Van't Hoff factor i as that of K 3[Fe(CN)6 ]

(a) Al 2 (SO4 )3 (b) NaCl (c) Na 2SO4 (d) Al(NO3 )3

29. The observed osmotic pressure of a solution of benzoic acid in benzene is less than its expected
value because
(a) Benzene is a non-polar solvent
(b) Benzoic acid molecules are associated in benzene
(c) Benzoic acid molecules are dissociated in benzene
(d) Benzoic acid is an organic compound
30. The experimental molecular weight of an electrolyte will always be less than its calculated value
because the value of Van't Hoff factor “i” is
(a) Less than 1 (b) Greater than 1
(c) Equivalent to one (d) Zero

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
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Ans. c d b b d a a a b c
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. c b a a b d a a b b
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. a d c c b a c a b b

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CHAPTER-2 : ELECTROCHEMISTRY
• Chapter at a glance 16-21
• Exercise-1_Important Questions 22-29
• Exercise-2_Multiple Choice Questions 30-34
CHAPTER AT A GLANCE
INTRODUCTION
Electrochemistry is the branch of physical chemistry which deals with the study of
interconversion of chemical energy and electrical energy.
ELECTROCHEMICAL CELL

Galvanic cell or Voltaic cell Electrolytic cell.

• Chemical energy Electrical energy • Electrical energy Chemical energy
• Spontaneous redox reaction • Non spontaneous redox reaction
Example : Daniell Cell
DANIELL CELL :
At Anode : Zn(s) Zn+2(aq.) + 2e–
e– e–
At Cathode : Cu+2(aq.) + 2e– Cu(s)
_______________________________ Zinc (anode) Cl¯ K
+
Copper (cathode)
+
+2
Zn(s)+Cu (aq.) +2
Zn (aq.) + Cu(s) Salt bridge

Salt Bridge and its functions :

2e¯ 2e¯
Salt bridge is inverted U-tube containing
–2
SO4
+2
Zn Cu
+2
Zn Cu
solution of inert electrolyte with agar-
agar or gelatin to convert into semi solid
form.
Ions of inert electrolyte do not involve in any chemical change.
The electrolyte in salt bridge should be such that speed of it's cation is nearly equal to speed of
it's anion.
Ex. KCl, KNO3, NH4NO3
Function : It maintains the electrical neutrality of the solution in order to give continuous flow
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or generation of current.
Cell Representation : Zn(s) | ZnSO4 (aq) CuSO4(aq) |Cu(s)
ELECTRODE POTENTIAL :
The potential developed between metal electrode and its ions in solution is known as electrode
potential.
The potential developed between metal electrodes and the solution of its ions at 1M
concentration at 1bar pressure and 298K is known as standard electrode potential.

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REFERENCE ELECTRODE :
The potential of a single electrode cannot be determined but the potential difference between two
electrodes can be accurately measured using a reference electrode.
An electrode is chosen as a reference with respect to which all other electrodes are valued.
STANDARD HYDROGEN ELECTRODE (SHE) :
Representation : Pt, H2(g) | H+ (1M) H2(g)
(at 1bar)
When SHE acts as anode

H2(g) 2H+ + 2e– + Pt black

H3O (aq)
electrode
When SHE acts as cathode (1M)

2H+ + 2e– H2(g)

For SHE electrode potential is arbitrarily assumed to be zero at all temperature.
SOP = –SRP = 0 for SHE.
CELL POTENTIAL ( E 0cell ) :

E 0cell = SRP of cathode – SRP of anode.

NERNST EQUATION :
2 2
0 RT Zn 0 0.0591 Zn
Ecell Ecell n 2
E cell Ecell log 2
2F Cu 2 Cu

EQUILIBRIUM CONSTANT (Kc) FROM NERNST EQUATION :

2
Zn 2.303RT
Ecell 0& Kc E0cell log K c ...(1)
Cu 2
nF

GIBBS FREE ENERGY :

rG = –nF Ecell rGº = –nF Eºcell ...(2)
Put Eºcell from equation (1) rGº = –2.303 RT log Kc

ELECTROLYTIC CONDUCTANCE
(a) Resistance (R) : Metallic and electrolytic conductors obey ohm's law according to which
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the resistance of a conductor is the ratio of the applied potential difference (V) to the current (I)
V
flowing . R= R is expressed in ohms.
I
(b) Conductance (G) : It is the property by virtue of which it favours flow of current. The

conductance of a conductor is equal to reciprocal of resistance G = 1

R
unit of G is mho or ohm–1 or Siemens (S).

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(c) Specific resistance/Resistivity ( ) :- The resistance (R) of a conductor is directly
proportional to its length ( ) and inversely proportional to its area of cross section (A).

A
= R × ; Therefore, resistance offered by 1 cm3 electrolytic solution is known as

resistivity. Unit of ohm cm

(d) Specific conductance/ Conductivity ( ) :-

1
It is defined as the reciprocal of specific resistance, =

G G*
Specific conductance = Conductance × Cell constant
Hence specific conductivity of a solution is defined as the conductance offered by 1 cm3 of

electrolytic solution. Unit of is ohm 1 cm 1

Cell constant : G* ; Its unit is cm–1

A
(e) Molar conductivity or Molar conductance :- ( m or m) : It is defined as the conductance
of all the ions produced by one mole of electrolyte present in the given volume of solution.
m = ×V
V = Volume of solution containing 1 mol of electrolyte.
If concentration of solution is M - mol per litre then
1000
m = Unit ohm–1 cm2 mol –1
M

DETERMINATION OF MOLAR CONDUCTANCE

OF ELECTROLYTES AT INFINITE DILUTION
400
/(S cm mol )

Debye Huckel Onsager equation – CH3COOH

–1

(Weak electrolyte)
b C [only for strong electrolyte]
2

m m

where m = molar conductance at concentration C, 200

m

KCl
= molar conductance at dilution, (Strong electrolyte)
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b = constant and its value is same for a particular type of

electrolyte. 0 0.2 0.4
1/2 1/2
c /(mol/L)
If a graph is plotted between m vs C a straight line is
obtained for strong electrolyte. On extrapolation this line touches m axis. Therefore m for
strong electrolyte can be found out from intercept. For weak electrolyte the slope of curve is not
constant so it cannot be extrapolated to obtain m

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KOHLRAUSCH'S LAW OF INDEPENDENT MIGRATION OF IONS
This law states that the equivalent conductivity of any electrolyte at infinite dilution ( eq. ) is the
sum of equivalent ionic conductivities of the cation and anion given by the electrolytes at infinite
dilution.

eq c a Where c = equivalent conductance of cation at infinite dilution.

a = equivalent conductance of anion at infinite dilution.

APPLICATIONS OF KOHLRAUSCH'S LAW :
(a) To calculate conductance of weak electrolyte.
(b) To calculate degree of dissociation :
molar conductance at a given concentration
Degree of dissociation m

m molar conductance at infinite dilution

(c) To calculate dissociation constant of weak electrolyte
2
C
Ka
(1 )
2
If 5% then K a = C

ELECTROLYSIS
The process of chemical decomposition of an electrolyte by the passage of electricity is called
electrolysis or electrolytic dissociation. It is carried out in
electrolytic cell where electrical energy is converted into + –
e¯ e¯
chemical energy.
-ve
There are two aspects of electrolysis : anode(+) ion Cathode (–)
+ve (inert)
Examples of electrolysis : (inert) ion
Electrolyte
Electrolysis of Molten Sodium Chloride
Electrolytic cell
NaCl Na+ + Cl–
At anode (oxidation) : 2Cl– Cl2(g) + 2e–
At cathode (reduction) : 2Na+ + 2e– 2Na(s)

FARADAY’S LAWS OF ELECTROLYSIS

(a) First law of electrolysis :
Amount of substance deposited or liberated at an electrode is directly proportional to amount of
charge passed through the solution.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Electrochemistry

W Q where W = amount of substance deposited, Q = charge in coulomb

W = ZQ where Z = electrochemical equivalent
Let I ampere current is passed till ‘t’ seconds .
Then, Q = I t W=ZIt
1 Faraday = 96500 coulomb = Charge on one mole electrons
One faraday is the charge required to liberate or deposit one gram equivalent of a
substance at corresponding electrode.
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(b) Second law of electrolysis :
When same amount of charge is passed through different electrolyte solutions connected in
series then weight of substances deposited or liberated at electrodes are in ratio of their
W1 E1
respective equivalent weights. i.e. .
W2 E2

COMMERCIAL VOLTAIC CELLS

Batteries can be classified as primary and secondary. Primary batteries cannot be returned to
their original state by recharging, so when the reactants are consumed, the battery is "dead" and
must be discarded. Secondary batteries are often called storage batteries or rechargeable
batteries. The reactions in these batteries can be reversed; thus, the batteries can be recharged.
(A) PRIMARY CELL : Dry cells
Anode Zn(s) Zn+2 + 2e–
Cathode MnO2 + NH4+ + e– MnO(OH) + NH3
EMF 1.5 V

(B) SECONDARY OR RECHARGEABLE BATTERY : Lead Storage Battery

The most important secondary cell is the lead storage battery. It consists of a lead as anode and
a grid of lead dioxide as cathode.
EMF 2 V. So, a lead storage battery consisting of six cells will give 12V.
At Anode : Pb(s) + SO42– (aq.) PbSO4(s) + 2e–
At Cathode : PbO2(s) + 4H+ (aq.) + SO4–2 (aq.) + 2e– PbSO4(s) + 2H2O( )
——————————————————————————
Net cell reaction : Pb(s) + PbO2(s) + 2H2SO4(aq.) 2PbSO4(s) + 2H2O( )
(C) Fuel Cells
Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen,
methane, methanol, etc. directly into electrical energy are called fuel cells.
EMF 1.23 V.
The electrode reactions are :
At anode : 2[H2(g) + 2OH– (aq) 2H2O( ) + 2e– ]

At cathode : O2(g) + 2H2O( ) + 4e– 4OH– (aq)

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————————————————
Net cell reaction : 2H2(g) + O2(g) 2H2O( )

CORROSION
Corrosion is basically an electrochemical phenomenon. The rusting of iron, the tarnishing of
silver, development of a green coating on copper and bronze are some of the examples of
corrosion. Corrosion causes enormous damage to building, bridges, ships and to many other
articles made of iron.

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Anode : Fe(s) Fe2+ (aq) + 2e– ; ( E 0 Fe 2
/ Fe
0.44V )

Cathode : O2(g) + 4H+ (aq) + 4e– 2H2O ( ) ; (E0 = 1.23 V)

Overall reaction : 2Fe(s) + O2(g) + 4H+(aq) 2Fe2+(aq) + 2H2O( ) ; E0Cell = 1.67 V)

The Fe2+ ions are further oxidised by atmospheric oxygen to Fe3+ (as Fe2O3) and comes out as
rust in the form of a hydrated iron (III) oxide expressed as Fe2O3, xH2O.
4Fe2+(aq) + O2(g) + 4H2O( ) 2Fe2O3(s) + 8H+
H+ ions produced in the above reaction help further in rusting.

PREVENTION FROM CORROSION

Corrosion of a metal is prevented by applying protective coating (such as grease, paint, bisphenol
or metal coatings) on metal surface. In case of iron this coating is done in two ways : (i)
electrolysis (Cr, Ni and Cd coating) (ii) dipping iron objects in a molten metal (Zn and Sn
coating). Use of zinc coating to protect iron is called Galvanisation.
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EXERCISE-1 IMPORTANT QUESTIONS
1. Can you store copper sulphate solutions in a zinc pot ?
Ans. Zinc is more reactive than copper. Therefore, zinc can displace copper from its salt solution.
If copper sulphate solution is stored in a zinc pot, then zinc will displace copper from the copper
sulphate solution.
Zn + CuSO4 ZnSO4 + Cu
Hence, copper sulphate solution cannot be stored in a zinc pot.
2. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
1
Ans. For hydrogen electrode, H e H 2 p1 , it is given that pH = 10
2
[H+] = 10–10 M
Now, using Nernst equation:
RT 1
E 1
E 1
ln
H / H2
2
H+ / H2
2
nF H

0.0591 1
E 1
log
+
H / H2
2
1 H
0.0591 1
0 log
1 10 10
= –0.0591 log 1010
= –0.591 V
3. Calculate the emf of the cell in which the following reaction takes place:

Ans. Ni s 2Ag 0.002M Ni2 0.160M 2Ag(s)

Applying Nernst equation we have:
E(cell) 1.05V

0.0591 Ni 2
E (cell) E (cell) log 2
n Ag

0.0591 0.160
1.05 log
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2
2 0.002
0.16
1.05 0.02955log
0.000004
= 1.05 – 0.02955 log 4 × 104
= 1.05 – 0.02955 (log 10000 + log 4)
= 1.05 – 0.02955 (4 + 0.6021)
= 0.914 V
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4. The cell in which the following reactions occurs:
2Fe3(aq) 2I(aq) 2
2Fe(aq) I2(s) has E 0cell = 0.236 V at 298 K.
Calculate the standard Gibbs energy and the equilibrium constant of the cell reaction.
Ans. Here, n = 2, E 0cell = 0.236 V, T = 298 K
We know that:
= –2 × 96487 × 0.236
= –45541.864 J mol–1
= –45.54 kJ mol–1
Again, rG = –2.303RT log Kc
G
log Kc r
2.303RT

45.54 103
2.303 8.314 298
= 7.981
Kc = Antilog (7.981)
= 9.57 × 107
5. Why does the conductivity of a solution decrease with dilution?
Ans. The conductivity of a solution is the conductance of ions present in a unit volume of the solution.
The number of ions (responsible for carrying current) decreases when the solution is diluted. As a
result, the conductivity of a solution decreases with dilution.
6. Suggest a way to determine the 0
m value of water.
Ans. Applying Kohlrausch’s law of independent migration of ions, the 0
m value of water can be
determined as follows:
0 0 0
m(H2O) H OH

0 0 0 0 0 0
H Cl Na OH Na Cl

0 0 0
m(HCl) m(NaOH) m(NaCl)

0 0
Hence, by knowing the values of HCl, NaOH, and NaCl, the value of water can be determined.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Electrochemistry

m m

7. The molar conductivity of 0.025 mol L–1 methanoic acid is 46.1 S cm2 mol–1.
Calculate its degree of dissociation and dissociation constant. Given °(H+)
= 349.6 S cm2 mol–1 and °(HCOO–) = 54.6 S cm2 mol
Ans. C = 0.025 mol L–1
m = 46.1 S cm2 mol–1
0 (H+) = 349 S cm2 mol–1

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–
0(HCOO ) = 54.6 S cm2 mol–1
0
m (HCOOH) = 0 (H+) + 0 (HCOO–)
= 349.6 + 54.6
= 404.2 S cm2 mol–1
Now, degree of dissociation :
(HCOOH)
= m
0
m (HCOOH)
46.1
=
404.2
= 0.114
Thus, dissociation constant:
2
c
K =
(1 )
2
0.025mol L 1 0.114
=
1 0.114
= 3.67 × 10–4 mol L–1
8. If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons
would flow through the wire?
Ans. I = 0.5 A
t = 2 hours = 2 × 60 × 60 s = 7200 s
Thus, Q = It
= 0.5 A × 7200 s
= 3600 C
We know that 96487 C = 6.023 × 1023 number of electrons.
Then,
6.023 10 23 3600
3600 C = number of electrons
96487
= 2.25 × 1022 number of electrons
Hence, 2.25 × 1022 number of electrons will flow through the wire.
9. What is the quantity of electricity in coulombs needed to reduce 1 mol of Cr2 O 72 ? Consider the
reaction:
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Cr2 O 72 14H 6e 2Cr 3 7H 2 O ,

Ans. The given reaction is as follows:
Cr2 O 72 14H 6e 2Cr 3 7H 2 O , the required quantity of electricity will be :
Therefore to reduce 1 mole of Cr2 O 72 = 6 F
= 6 × 96487 C
= 578922 C

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10. Calculate the standard cell potentials of galvanic cells in which the following reactions take
place:
(i) 2Cr(s) + 3Cd2+(aq) 2Cr3+(aq) + 3Cd(s)

E Cr3 /Cr
= –0.74 V ; E Cd2 /Cd
= –0.40 V

(ii) Fe2+(aq) + Ag+(aq) Fe3+(aq) + Ag(s)

E Fe 3 /Fe 2 = 0.77 V ; E Ag /Ag

= 0.80 V

Calculate the rG and equilibrium constant of the recations.

Ans. (i) The galvanic cell of the given reaction is depicted as :

Now, the standard cell potential is

E cell ER EL

= –0.40 – (–0.74)
= +0.34 V

r G nFE cell

In the given equation,

n=6
F = 96487 C mol–1
E cell 0.34V

Then = –6 × 96487 C mol–1 × 0.34 V

= – 196833.48 CV mol–1
= –196833.48 J mol–1
= –196.83 kJ mol–1
Again,

r G = –RT ln K

r G = –2.303 RT log K
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Gr
log K = –
2.303RT
196.83 10 3
=
2.303 8.314 298
= 34.496
K = antilog (34.496)
= 3.13 × 1034

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(ii) E Fe3 /Fe2

= 0.77 V

E Ag /Ag
= 0.80 V

The galvanic cell of the given reaction is depicted as :

Fe 2 (aq) Fe3 Ag Ag (s)
(aq) (aq)

Now, the standard cell potential is

E cell ER EL
= 0.80 – 0.77
= 0.03 V
Here, n = 1,
Then, r G nFE cell
= –1 × 96487 C mol–1 × 0.03 V.
= –2894.61 J mol–1
= –2.89 kJ mol–1
Again, r G = 2.303 RT Iog k

G 2894.61
log K = r
= = 0.5073
2.303 RT 2.303 8.314 298
K = antilog (0.5073)
= 3.2 (approximately)
11. Write the Nernst equation and emf of the following cells at 298K :
(i) Mg(s) Mg 2 (0.001M) Cu 2 0.0001M Cu(s)

(ii) Fe(s) Fe 2 (0.001M) H 1M H 2 (g) (1bar) Pt(s)

(iii) Sn(s) Sn 2 (0.050M) H 0.020 M H 2 (g) (1bar) Pt(s)

(iv) Pt(s) Br2 (l) Br 0.010M H 0.030M H 2 (g) (1bar) Pt(s)

Ans. (i) For the given reaction, the Nernst equation can be given as :
0.0591 [Mg2 ]
Ecell Ecell log
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n [Cu2 ]
0.0591 .001
= 0.34 2.36 log
2 .0001
0.0591
= 2.7 log10
2
= 2.7 – 0.02955
= 2.67 V
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(ii) For the given reaction, the Nernst equation can be given as :
0.0591 [Fe 2 ]
Ecell E cell log
n [H ]2
0.0591 0.001
= 0 0.44
log 2
2 1
= 0.44 – 0.02955(–3)
= 0.52865
= 0.53 V
(iii) For the given reaction, the Nernst equation can be given as :
0.0591 [Sn 2 ]
Ecell Ecell log
n [H ]2
0.0591 0.050
= 0 0.14 log 2
2 0.020
= 0.14 – 0.0295 × log 125
= 0.14 – 0.062
= 0.078 V
= 0.08 V
(iv) For the given reaction, the Nernst equation can be given as :
0.0591 1
E cell E cell log
n [Br ] [H ]2
2

0.0591 1
= 0 1.09 log 2 2
2 0.010 0.030
1
= 1.09 0.02955 log
0.00000009
1
= 1.09 0.02955 log
9 10 8
= 1.09 – 0.02955 × log(1.11 × 107)
= –1.09 – 0.02955 (0.0453 + 7)
= –1.09 – 0.208
= –1.298 V
12. In the button cells widely used in watches and other devices the following reaction takes place :
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Zn(s) + Ag2O(s) + H2(O) (l) Zn2+(aq) + 2Ag(s) + 2OH–(aq)

Determine G and E for the reaction.
Ans. Zn (s) Zn 2
(aq) 2e ;E 0.76V

Ag 2 O(s) H 2O ( ) 2e 2Ag (g ) 2OH (aq) ;E 0.344 V

Zn (s) Ag 2O(s) H 2O(f ) Zn 2 (aq) 2Ag (s) 2OH (aq ) ;E 1.104 V
E = 1.104 V

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We know that,

r G nFE
= –2 × 96487 × 1.04
= –213043.296 J
= –213.04 kJ
13. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar conductivity
and if 0
m for acetic acid is 390.5 S cm2 mol–1, what is its dissociation constant?
Ans. Given, = 7.896 × 10 –5 S cm–1
C = 0.00241 mol L–1

Then, molar conductivity, m

c
7.896 10 5 Scm 1 1000 cm3
= 1
= 32.76 S cm2 mol–1
0.00241mol L L

Again, 0
m = 390.5 S cm2 mol–1

m 32.76S cm 2 mol 1
Now, 0
= 0.084
m 390.5Scm 2 mol 1
2
c
Dissociation constant, K a
1
2
0.00241mol L 1 0.084
= = 1.86 × 10–5 mol L–1
1 0.084

14. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 amperes
for 20 minutes. What mass of Ni is deposited at the cathode ?
Ans. Given,
Current = 5A
Time = 20 × 60 = 1200 s
Charge = current × time
= 5 × 1200 = 6000 C
According to the reaction,
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Ni 2 (aq ) 2e Ni (s)
58.7g

Nickel deposited by 2 × 96487 C = 58.71 g

58.71 6000
Therefore, nickel doposited by 6000 C = g = 1.825 g
2 96487
Hence, 1.825 g of nickel will be deposited at the cathode.

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15. Three electrolytic cells A, B, C containing solutions of ZnSO4, AgNO3 and CuSO4, respectively
are connected in series. A steady current of 1.5 amperes was passed through them until 1.45 g of
silver deposited at the cathode of cell B. How long did the current flow? What mass of copper
and zinc were deposited?
Ans. According to the reaction:
Ag (aq )
e Ag s
108g

i.e. 108 g of Ag is deposited by 96487 C.

96487 1.45
Therefore 1.45 g of Ag will be deposited by = C = 1295.43 C
108
Given
Current = 1.5A
1295.43
Time = s = 863.6 s
1.5
= 864 s = 14.40 min
Again,
Cu 2 (aq) 2e Cu (s)
63.5g

i.e. 2 × 96487 C of charge deposit = 63.5 g of Cu

63.5 1295.43
Therefore, 1295.43 C of charge will deposite = g = 0.426 g of Cu
2 96487
Given
Zn 2 (aq) 2e Zn (s)
65.4g

i.e. 2 × 96487 C of charge deposite = 65.4 g of Zn

65.4 1295.43
Therefore, 1295.43 C of charge will deposit = g = 0.439 g of Zn.
2 96487
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EXERCISE-2 MULTIPLE CHOICE QUESTIONS
(ELECTROLYTE AND ELECTROLYSIS)
1. Electrolyte can conduct electricity because
(a) Their molecules contain unpaired electrons, which are mobile
(b)Their molecules contain loosely held electrons which get free under the influence of voltage
(c) The molecules break up into ions when a voltage is applied
(d) The molecules are broken up into ions when the electrolyte is fused or is dissolved in the
solvent
2. Which one of the following metals could not be obtained on electrolysis of aqueous solution of
its salts ?
(a) Ag (b) Mg (c) Cu (d) Cr
3. Electrolysis involves oxidation and reduction respectively at :
(a) Anode and cathode (b) Cathode and anode
(c) At both the electrodes (d) None of the above
4. During the electrolysis of an electrolyte, the number of ions produced, is directly proportional to the
(a) Time consumed
(b) Electro chemical equivalent of electrolysis
(c) Quantity of electricity passed
(d) Mass of electrons
5. During the electrolysis of fused NaCl, which reaction occurs at anode :
(a) Chloride ions are oxidized (b) Chloride ions are reduced
(c) Sodium ions are oxidised (d) Sodium ions are reduced
6. On electrolysing a solution of dilute H2SO4 between platinum electrodes, the gas evolved at the
anode is
(a) SO2 (b) SO3 (c) O2 (d) H2
7. In electrolysis of aqueous copper sulphate, the gas at anode and cathode is
(a) O2 and H2 (b) SO2 and H2 (c) H2 and O2 (d) SO3 and O2
8. Use of electrolysis is
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(a) Electroplating (b) Electro refining

(c) (a) and (b) both (d) None of these
9. Electrolysis of molten anhydrous calcium chloride produces :
(a) Calcium (b) Phosphorus (c) Sulphur (d) Sodium
10. Which of the following liberate hydrogen on reaction with dilute H2SO4?
(a) Fe (b) Cu (c) Al (d) Hg

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(FARADAY’S LAW OF ELECTROLYTES)
11. Amount of electricity that can deposit 108 gm of silver from AgNO3 solution is :
(a) 1 ampere (b) 1 coulomb
(c) 1 faraday (d) None of the above
12. The atomic weight of Al is 27. When a current of 5 Faradays is passed through a solution of
Al+++ ions, the weight of Al deposited is :
(a) 27 gm (b) 36 gm (c) 45 gm (d) 39 gm
13. What weight of copper will be deposited by passing 2 Faradays of electricity through a cupric
salt (Atomic weight of Cu = 63.5) :
(a) 2.0 gm (b) 3.175 gm (c) 63.5 gm (d) 127.0 gm
14. Unit of Faraday is :
(a) Ampere (b) Coulomb
(c) Coulomb mole–1 (d) Coulomb sec–1
15. The desired amount of charge for obtaining one mole of Al from Al3+ :
96500 96500
(a) 3 × 96500 C (b) 96500 C (c) C (d) C
3 2
16. One Faraday of electricity when passed through a solution of copper sulphate deposits :
(a) 1 mole of Cu (b) 1 gm atom of Cu
(c) 1 molecule of Cu (d) 1 gm equivalent of Cu
17. When 1 coulomb of charge is passed through electrolyte solution, then the mass deposited is
equal to :
(a) Equivalent weight (b) Atomic weight
(c) Electrochemical equivalent (d) Chemical equivalent
18. According to the first law of Faraday, the weight of a substance discharge at the electrode is :
Z
(a) W = ZQ (b) W = eF (c) W = It (d) W = ZI
F
19. Total charge on 1 mole of a monovalent metal ion is equal to :
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(a) 9.65 × 104 Coulomb (b) 6.28 × 1018 Coulomb

(c) 1.6 × 10–19 Coulomb (d) None of these
20. A certain quantity of electricity is passed through an aqueous solution of AgNO3 and cupric salt
solution connected in series. The amount of Ag deposited is 1.08 gm, the amount of copper
deposited is (atomic weight of Cu = 63.5; Ag = 108) :
(a) 0.6454 g (b) 6.354 g (c) 0.3177 g (d) 3.177 g

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(CONDUCTOR AND CONDUCTANCE)
21. The conductivity of strong electrolyte is
(a) Increase on dilution slightly
(b) Decrease on dilution
(c) Does not change with dilution
(d) Depend upon density of electrolytes itself
22. Conductivity of a solution is directly proportional to :
(a) Dilution (b) Number of ions
(c) Current density (d) Volume of the solution
23. The unit of molar conductivity is :
–1
(a) cm–2 mol–1 (b) cm–2 mol–1
–1
(c) cm2 mol–1 (d) cm2 mol
24. The unit ohm–1 is used for :
(a) Molar conductivity (b) Equivalent conductivity
(c) Specific conductivity (d) Conductivity
(CELL CONSTANT AND ELECTROCHEMICAL CELL)
25. Which of the following reaction is used to make a fuel cell :

(a) Cd(s) 2Ni(OH)3 (s) CdO(s) 2Ni(OH) H 2O(l)

(b) Pb(s) PbO2 (s) 2H 2SO 4 (aq) 2PbSO 4 (s) 2H 2O(l)

(c) 2H 2 (g) O 2 (g) 2H 2O(l)

(d) 2Fe(s) O 2 (g) 4H (aq) 2Fe 2 (aq) 2H 2O(l)

26. When lead storage battery is charged :

(a) PbO2 is dissolved (b) H2SO4 is regenerated
(c) PbSO4 is deposited on lead electrode (d) Lead is deposited on lead electrode
27. In electrolysis of dilute H2SO4 using platinum electrodes :
(a) H2 is evolved at cathode (b) NH3 is produced at anode
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Electrochemistry

(c) Cl2 is obtained at cathode (d) O2 is produced

28. For cell reaction, Zn + Cu2+ Zn2+ + Cu, cell representation is :
(a) Zn | Zn2+||Cu2+|Cu (b) Cu | Cu2+ ||Zn2+| Zn
(c) Cu | Zn2+ || Zn | Cu2+ (d) Cu2+ | Zn || Zn2+ | Cu
29. A cell from the following which converts electrical energy into chemical energy :
(a) Dry cell (b) Electrochemical cell
(c) Electrolytic cell (d) None of these
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30. Hydrogen–oxygen fuel cells are used in space–craft to supply :
(a) Power for heat and light (b) Power for pressure
(c) Oxygen (d) Water
2
31. The cell reaction Cu 2Ag Cu Ag is best represented by :
(a) Cu(s) | Cu+2(aq) || Ag+(aq) | Ag(s) (b) Pt | Cu+2 || Ag+(aq) | Ag(s)
(c) Cu+2 | Cu || Pt | Ag (d) None of the above representations
32. Zn (s) | Zn 2 (aq) | | Cu 2 (aq) | Cu (s) is :
(anode) (cathode)

(a) Weston cell (b) Daniel cell (c) Calomel cell (d) Faraday cell
33. The anode half-reaction occurring during the discharge of a lead storage battery is
(a) Pb(s) + SO2 + O2 PbSO4(s)
(b) Pb(s) + SO42– (aq) PbSO4(s) + 2e–
(c) PbO2(s) + 4H+(aq) + 2e– + SO42–(aq) PbSO4(s) + 2H2O
(d) Pb2+(aq) + SO42–(aq) PbSO4(s)
34. The unit of cell constant is :
(a) ohm–1 cm–1 (b) ohm cm (c) cm (d) cm–1
35. In galvanic cell, the salt bridge is used to :
(a) Complete the circuit (b) Reduce the electric resistance in the cell
(c) Separate cathode from anode (d) Carry salts for the chemical reaction
(ELECTRODE POTENTIAL AND NERNST EQUATION)
36. The standard electrode potentials of Zn 2 / Zn and Ag / Ag are –0.763V and +0.799V
respectively. The standard potential of the cell is :
(a) 1.56 V (b) 0.036 V (c) – 1.562 V (d) 0.799
37. The standard oxidation potential of zinc and silver in water at 298 K are :
Zn(s) Zn2+ + 2e– ; E = 0.76 V
Ag(s) Ag2+ + 2e– ; E = –0.80 V
Which of the following reactions actually take place :
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(a) Zn(s) + 2Ag+(aq) Zn+2(aq) + 2Ag(s) (b) Zn+2(aq) + 2Ag(s) 2Ag+(aq) + Zn(s)
(c) Zn(s) + Ag(s) Zn+2(aq) + Ag+(aq) (d) Zn+2 (aq) + Ag+(aq) Zn(s) + Ag(s)
38. The correct representation of Nernst's equation is :
0.0591 0.0591
(a) E Mn /M
E o Mn /M
log (M n ) (b) E Mn /M
E o Mn /M
log (M n )
n n
n
(c) E Mn /M
E o Mn /M
log (M n ) (d) None of the above
0.0591
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39. 2H+(aq) + 2e– H2(g). The standard electrode potential for the above reaction is (in volts)
(a) 0 (b) + 1 (c) – 1 (d) None of these
40. EMF of a cell whose half cells are given below is :
Mg2+ + 2e– Mg(s) ; E = –2.37 V
Cu2+ + 2e– Cu(s) ; E = +0.33 V
(a) – 2.03 V (b) 1.36 V (c) 2.7 V (d) 2.03 V

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. d b a c a c a c a c
Q. No. 11 12 13 14 15 16 17 18 19 20
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Ans. c c c c a d c a a c
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. a b c d c c a a c b
Q. No. 31 32 33 34 35 36 37 38 39 40
Ans. a b b d a a a a a c

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CHAPTER–3 : CHEMICAL KINETICS

• Chapter at a glance 35-41
• Exercise-1_Important Questions 42-46
• Exercise-2_Multiple Choice Questions 47-51
CHAPTER AT A GLANCE
Chemical Kinetics is the branch of physical chemistry which deals with the study of rate of
reactions, the mechanism by which the reactions proceed and factors affecting rate of reaction.
RATE OF REACTION
Rate of reaction is defined as the change in concentration or pressure of reactant or product per
unit time. It is always a positive quantity.
Change in concentration of reactant or product C
Rate of reaction = = r
Time taken in change t

(A) Average Rate of Reaction

The rate of reaction over a certain measurable period of time during the course of reaction
is called average rate of reaction. It is denoted by r .
For a reaction A B
[A]2 [A]1 [A]
raverage = r
t 2 t1 t
(B) Instantaneous Rate of Reaction
The rate of reaction at any particular instant during the course of reaction is called
instantaneous rate of reaction.
C dC
Instantaneous rate of reaction = lim
t 0 t dt
RATE OF REACTION IN THE FORM OF STOICHIOMETRY OF A CHEMICAL
REACTION
Let us consider a reaction : m1A + m2B n1P + n2Q
d[A]
Where, Rate of disappearance of A = –
dt
d[B]
Rate of disappearance of B = –
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dt
d[P]
Rate of appearance of P =
dt
d[Q]
Rate of appearance of Q =
dt
1 d[A] 1 d[B] 1 d[P] 1 d[Q]
Rate of reaction
m1 dt m2 dt n1 dt n 2 dt
Rate of reaction is always positive; negative sign represents decrease in concentration of reactant.

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Units of Rate of Reaction
–1 –1 –1 –1 –1 –1 –1 –1
Unit of rate of reaction = mol L time i.e. (mol L s or mol L min or mol L h )
RATE LAW
The experimental expression of rate of reaction in terms of concentration of reactants is known as
rate law. In this expression the rate of a reaction is proportional to the product of molar
concentration of reactants with each term raised to the power or exponent that has to be found
experimentally.
In a chemical reaction :- aA + bB Product
x y
The rate law is :- Rate [A] [B]
The values of exponents x and y are found experimentally which may or may not be same as
stoichiometric coefficients.
Above relationship can be written as :-
x y
Rate = k[A] [B]
Where k is a proportionality constant known as rate constant.
Rate constant :
In a chemical reaction –
n1A + n2B m1C + m2D
according to law of mass action
n1 n2
Rate = k[A] [B]
but according to rate law (experimental concept)
x y
Rate = k[A] [B]
if [A] = [B] = 1 mol/L
then, Rate = k
Rate of reaction at unit concentration of reactants is called as rate constant or specific reaction
rate.
Rate constant does not depend on concentration of reactant but it depends on temperature and
catalyst.
Units of rate constant :
n
Rate = k[A]
mol 1
time
r unit of rate L
k n n n
A unit of concentration mol
L
1 n
mol
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Chemical Kinetics

1
Unit of k = time
L
1–n –1
For gaseous reaction unit of k may be = (atm) × time
ORDER OF REACTION :–
The sum of powers of concentration of reactants in rate law expression is known as order of
reaction.
For the reaction aA + bB Product
x y
Rate law is Rate = k[A] [B]

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Here x = order of reaction with respect to A
y = order of reaction with respect to B
x + y = n (overall order of reaction)
Order of reaction is an experimental quantity.
Order of reaction may be zero, positive, negative or fractional.
MOLECULARITY
Total number of molecules, atoms or ions (reacting species) participating in an elementary
reaction is called as molecularity of reaction.
Molecularity is a theoretical quantity.
Molecularity can be an integer (1, 2 or 3) but it cannot be zero or negative or fractional.
In elementary reaction molecularity is equal to its order.
In complex reaction molecularity of each step of mechanism is defined separately.
Total molecularity of complex reaction is meaningless.
PSEUDO FIRST ORDER REACTION
A chemical reaction in which value of order of reaction is one but molecularity is more than one
are known as pseudo unimolecular/pseudo first order reaction.
Example-1
Hydrolysis of ester in acidic medium.
H
CH3COOC2H5 H2 O CH3COOH C2H5OH

Rate = k [CH3COOC2H5][H2O]
Water is in excess then its concentration remain constant during the reaction and [H 2O] is taken
as constant therefore,
Rate = k' [CH3COOC2H5] where k' = k [H2O]
(A) Zero order reactions
Reactions in which rate of reaction remains independent of concentration of the reactant are said
to be zero order reactions.
Zero order reactions are relatively uncommon but they occur under special conditions. Some
enzyme catalysed reactions and reactions which occur on metal surfaces are a few examples of
zero order reactions.
Example : (a) H2(g) + Cl2(g) h
2HCl(g)
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Chemical Kinetics

(b) 2NH3(g) Pt
N2(g) + 3H2(g)

[A]o – [A]t x
Formula k =
t t
Half-life period:– The time in which half of the initial amount of reactant is consumed.
[A]0
Formula t1/2
2k

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(B) First order reactions
Reactions in which the rate of reaction is directly proportional to concentration of reactant.
Example : (a) 2N2O5 4NO2 + O2
(b) NH4NO2 N2 + 2H2O
(g) All radioactive decay
2.303 [A]
Formulas K= log o
t [A]t
Half-life Period : The time in which half of the initial amount of reactant is consumed.
0.693
Formulas t1/2
k
2.303 a x1
Interval Formula k log
t 2 t1 a x2
COLLISION THEORY OF CHEMICAL REACTIONS
This theory was given by Max Trautz and William Lewis. According to it, for a reaction to occur
there must be collisions in between reacting molecules. Total number of collisions per second in
unit volume is called collision frequency(z). Generally its value is very high for gaseous
25 28 3
reactions (10 to 10 collisions/sec-cm ). But only a small fraction of these collisions are
capable to convert reactant into product. These collisions are called as effective collisions.
For effective collision following two conditions must be satisfied at a time :
(a) Reacting molecules must posses a minimum amount of energy.
(b) Proper orientation of collision
• Threshold energy: The minimum energy which must be possesed by reacting molecules for a
chemical reaction to occur.
• Activation energy: The minimum extra amount of energy required by reactant molecules for
converting into products.
Activated Activated
complex complex
Threshold

Ea(f)
Threshold

Ea(f)
Energy
Energy

Energy

Ea(b)
Energy

Ea(b)
P
R
P.E. H=-ve H=+ve
P.E.
P R
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Chemical Kinetics

Progress of reaction Progress of reaction

Exothermic reaction Endothermic reaction

1. Ea(f) = Activation energy for forward reaction
2. Ea(b) = Activation energy for backward reaction
If not specified in questions then consider Ea for forward reaction.
H Ea f Ea b ; H Hp HR

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ACTIVATION ENERGY MAINLY DEPENDS UPON :
(i) Nature of reactant: For different reactants, number of bonds and bond energies are different,
therefore activation energy will also be different.
Reactions which have less Ea, take place at faster rate.
(ii) Presence of catalyst: Catalyst provide an alternative path of reaction mechanism for the reaction.
• In presence of catalyst threshold energy decreases, activation energy decreases and rate of
reaction increases.
• In presence of negative catalyst (inhibitor) threshold energy increases, activation energy
increases, rate of reaction decreases.

T.E''
Inhibitor
T.E.
absence of catalyst
E'' T.E'
Ea catalyst
E'a
Energy

Progress of Reaction
(b) Orientation :

A A A A A A
Case-I : Proper orientation
B B B B B B
Activated Products
Reactants complex
(transition state)

A
A
A A
A A
Case-II : Improper orientation B B B
B
B B
Reactant No Product

• Limitations :
(i) This theory is mainly applicable for gaseous reactions and also for solutions in which reacting
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species are molecules.

(ii) This theory is mainly applicable for simple bimolecular reactions but fails for complex reactions.
(iii) It considers molecules to be hard sphere and ignore structural aspect of molecules.
FACTORS AFFECTING RATE OF REACTION :
1. Nature of reactant :
(a) Physical state of reactant :
increasing order of rate of reaction – Solid < liquid < gas
(Intermolecular attractive force decreases which provides more freedom for collisions)

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(b) Physical size of particles (if reactant is solid) :
1
Rate of reaction surface area
physical size
(c) Chemical nature of reactant : For different reacting species number of bonds broken and their
bond energies are different. Therefore requirement of activation energy is also different. Now
reactions having less value of activation energy will take place at faster rate.
2. Concentration of reactant : Rate of reaction concentration of reactant
3. Pressure : Effect of pressure on Rate of reaction is negligible when reactants are solid or liquid.
But if reactants are in gaseous state then rate of reaction increases on increasing pressure because
number of effective collisions increases.
4. Temperature : On increasing temperature rate of reaction increases whether the reaction is
exothermic or endothermic. When temperature increases KE of molecules increases, number of
activated molecules increases thus rate of reaction increases.
Relation between rate constant and Temperature :-
(a) Generally it is found that for every 10 °C rise in temperature Rate of reaction becomes 2 to 3
times.
Temperature coefficient ( ) : It is defined as ratio of rate constant of a reaction at two different
temperatures which will be differ by 10 °C.
k T 10 r2 k2 T/10
2 to 3 ;
kT r1 k1
If temperature of reaction is not specified then consider 25 °C.
(If is not given consider it as minimum 2)
MAXWELL AND BOLTZMANN ENERGY DISTRIBUTION CURVE
Fraction of molecules

T
Energy of This area shows
(T+10) activation fraction of additional
This area molecules which
shows fraction
react at (T+10)
of molecules
reacting at T
Kinetic energy

(b) Arrhenius equation

Ea/ RT
k Ae ....(1)
A = Arrhenius constant / pre-exponential factor / Frequency factor
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Ea = Activation energy
R = gas constant
T = Temperature (Kelvin)
• k increases with increase in temperature
If T ;k=A
k
• e E a / RT
fraction of molecules having energy Ea
A
e E a /RT
= Boltzman factor
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On taking logarithm for equation (1) on both sides.
ln k  ln A  lneEa /RT
2.303 log10k = 2.303 log10A –
Ea
log10k = log10A –
2.303RT ....(2)
y = c – mx

• Ea of reaction can be determined by measuring rate constant at two different temperatures

At temperature T1 :
Ea
log10 k1  log10 A  .....(3)
2.303RT1
At temperature T2 :
Ea
log10 k 2  log10 A  .....(4)
2.303RT2
Equation (4) – Equation (3) gives -
Ea  1 1 
log k 2  log k1  
2.303R  T1 T2 

k2 E a  T2  T1 
log10 
k1 2.303R  T1T2 

• From arrhenius equation - k  Ae Ea/ RT k  AeE /RT a

Ea
nk = nA –
RT
d d d  Ea  E d  1 
( n k)  ( n A)     0 a T
dT dT dT  RT  R dT
Ea d  1  Ea  2 
0 T  T
R dT R
d E
n k  a 2 differential form of Arrhenius equation
dT RT
5. Presence of catalyst : In presence of catalyst Ea of reaction decreases and rate of reaction
increases.
6. Exposure to radiation : Rate of some reactions also increases when reaction are carried out in
the presence of radiation. (only for photochemical reaction)
e.g. formation of HCl
H2  Cl2  2HCl  very slow reaction 
h
H2  Cl2  2HCl  explosive 

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EXERCISE-1 IMPORTANT QUESTIONS

1. In a reaction, 2A Products, the concentration of A decreases from 0.5 mol L–1 to 0.4 mol L–1 in
10 minutes. Calculate the rate during this interval?
1 [A]
Ans. Average rate
2 t
1 [A]2 [A]1 1 (0.4 0.5)
2 t 2 t1 2 10

1 0.1
2 10
= 0.005 mol L–1 min–1
= 5 × 10–3 M min–1
2. Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the
decompositon is a first order reaction, calculate the rate constant of the reaction.
Ans. We know that for a 1st order reaction,
0.693
t1/2
k
It is given that t1/2 = 60 min
0.693
k
t1/ 2

0.693
=
60
= 0.01155 min–1
= 1.155 min–1
Or k = 1.925 × 10–4 s–1
3. The decomposition of NH3 on platinum surface is zero order reaction. What are the rate of
production of N2 and H2 if k = 2.5 × 10–4 mol litre–1 s–1?
Ans. 2NH3 N2 + 3H2.
1 d[NH3 ] d[N2 ] 1 d[H2 ]
Rate of reaction (r)= – = =
2 dt dt 3 dt
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Rate (r) = K[NH3]° = K ( zero order Rx.)

= 2.5 × 10–4
d[N2 ]
= r = 2.5 × 10–4 mol lit–1s–1
dt
d[H2 ]
= 3r = 3 × 2.5 × 10–4 = 7.5 × 10–4 mol lit–1sec–1
dt

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4. A reaction is first order in A and second order in B:
(i) Write rate equation.
(ii) How is the rate affected when the concentration of B is tripled?
(iii) How is the rate affected when the concentration of both A and B is doubled?
Ans. (i) Rate = k [A]1[B]2
(ii) r0 = k [A]1[B]2
r1 = k [A]1[3B]2
r1 = 9 × r0
(iii) r0 = k [A1][B]2
r2 = k [2A]1[2B]2
r2 = 8 × r0
5. The following results have been obtained during the kinetic studies of the reaction :
2A + B C + D
Experiment A/mol L–1 B/mol L–1 Initial rate of formation
–1
of D/mol L–1
min
I 0.1 0.1 6.0 × 10–3
II 0.3 0.2 7.2 × 10–3
III 0.3 0.4 2.88 × 10–1
IV 0.4 0.1 2.40 × 10–2
Determine the rate law and the rate constant for the reaction.
Ans. Let the order of the reaction with respect to A be x and with respect to B be y.
Therefore, rate of the reaction is given by,
Rate = k[A]x [B]y
According to the question,
6.0 × 10–3 = k[0.1]x [0.1]y (i)
7.2 × 10 = k[0.3] [0.2]
–2 x y
(ii)
2.88 × 10–1 = k[0.3]x [0.4]y (iii)
2.40 × 10–2 = k[0.4]x [0.1]y (iv)
Dividing equation (iv) by (i), we obtain
2
2.4 10 k[0.4]x [0.1]y
3
6.0 10 k[0.1]x [0.1]y
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Chemical Kinetics

x
[0.4]x 0.4 1
4 4 4 4x x 1
[0.1]x 0.1
Dividing equation (iii) by (ii), we obtain
2.88 10 1 k[0.3]x [0.4]y
7.2 10 2 k[0.3]x [0.2]y
y
0.4
4 4 2y 22 2y y 2
0.2

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Therefore, the rate law is
Rate = k[A] [B]2
Rate
k
[A][B]2
From experiment I, we obtain
6.0 10 3 mol L 1 min 1
k 2
6.0 L2 mol 2 min 1

0.1mol L 1 0.1mol L 1

6. For a first order reaction, show that time required for 99% completion is twice the time required
for the completion of 90% of reaction.
Ans. For a first order reaction, the time required for 99% completion is
2.303 100 2.303 2.303
t1 log log100 2
k 100 99 k k
For a first order reaction, the time required for 90% completion is
2.303 100 2.303 2.303
t2 log log10
k 100 90 k k
Therefore, t1 = 2t2
Hence, the time required for 99% completion of a first order reaction is twice the time required
for the completion of 90% of the reaction.
7. A first order reaction takes 40 min for 30% decomposition. Calculate t 1/2.
Ans. For a first order reaction,
2.303 [R]0
t log
k [R]
2.303 100 2.303 10 3 1
k log log 8.918 10 min
40 min 100 30 40 min 7
Therefore, t1/2 of the decomposition reaction is
0.693 0.693
t1/2 min 77.7 min
k 8.918 10 3
8. (a) What are the factors which effect the rate of a chemical reaction?
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(b) Derive the rate constant formula for zero order reaction?
(c) Draw a diagram showing effect of catalyst on activation energy.
OR
(a) What is pseudo first order reaction? Inversion of cane sugar is which type of reaction. Write
it's chemical reaction?
(b) Calculate the half life of the first order reaction whose rate constant is 5×10–14 s–1 .
(c) Plot a graph between in K & 1/T on the basis of Arrhenius equation.
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Ans. (a) Factors affecting the rate of chemical reaction are
(i) Nature of reactant (ii) Activation energy (Ea)
(iii) Temperature (iv) Presence of catalyst
The rate law is the expression in which reaction rate is given in terms of molar concentration of
reactants with each term raised to some power, which may or may not be same as the
stoichiometric coefficient of the reacting species in a balanced chemical equation.
Reaction: n1A + n2B Product
Rate [A]x [B]y
The value of x and y may be equal to stoichiometric exponent n1 and n2
(b) Let R P is a zero order reaction

d[R]
rate = = k[R]0
dt
d[R]
rate = = k
dt
d[R] = –k dt
On integrating both sides
[R] = –kt + I … (i)
t = 0, R = [R]0
[R]0 = I
Substituting value of I in eq. (i)
[R]0 [R]
[R] = –kt + [R]0 or k
t
in absence of catalyst
in presence of catalyst

E Ea E Ea
Ea b Ea b
f f
P
Product
(c) E'a
H r

Reactant R
POR POR
Progress of reaction in absence of catalyst Progress of reaction in presence of catalyst
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Chemical Kinetics

OR
(a) Reaction whose actual order is different from that expected by using rate law expression
are called pseudo order reactions.
Inversion of canesugar is pseudo I order type of reaction
H
C12H22O11 + H2O C6H12O6 + C6H12O6
Cane sugar Glucose Fructose
Rate K C12 H22O11
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(b) Half life of first order reaction is calculated by the formula
0.693 0.693
t½ = = 0.1386 × 1014 or 13.86 × 1012 sec
k 5 10 14
(c) Arrhenius Equation K = Ae–Ea/RT
Ea
nk nA
RT

y c mx
equation of straight line with –ve slope

nk
–Ea Slope = –Ea/RT
m = –—–
R Intercept = lnA
nA

1/T
9. The rate of the chemical reaction doubles for an increase of 10 K in absolute temperature from
298 K. Calculate Ea.
Ans. It is given that T1 = 298 K
T2 = (298 + 10) K = 308 K
We also know that the rate of the reaction doubles when temperature is increased by 10°.
Therefore, let us take the value of k1 = k and that of k2 = 2k
Also, R = 8.314 J K–1 mol–1
Now, substituting these values in the equation:
We get:
k2 Ea T2 T1
log
k1 2.303 R T1 T2

We get :
2k Ea 10
log
k 2.303 8.314 298 308
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Ea 10
log 2
2.303 8.314 298 308
2.303 8.314 298 308 log 2
Ea
10
= 52897.78 J mol–1
= 52.9 kJ mol–1

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EXERCISE-2 MULTIPLE CHOICE QUESTIONS

(RATE OF REACTION)
1. The rate of a chemical reaction :
(a) Increases as the reaction proceeds
(b) Decreases as the reaction proceeds
(c) May increase or decrease during the reaction
(d) Remains constant as the reaction proceeds
2. The rate of a reaction that not involve gases is not dependent on :
(a) Pressure (b) Temperature (c) Concentration (d) Catalyst
3. The rate of chemical reaction at constant temperature is proportional to :
(a) The amount of products formed
(b) The product of masses of the reactants
(c) The product of the molar concentration of the reactants
(d) The mean free path of the reaction
4. For reaction 2A + B products, the active mass of B is kept constant and that of A is doubled.
The rate of reaction will then :
(a) Increase 2 times (b) Increase 4 times
(c) Decrease 2 times (d) Decrease 4 times
5. A catalyst increases the rate of reaction because it :
(a) Increases the activation energy
(b) Decreases the energy barrier for reaction
(c) Decreases the collision diameter
(d) Increases the temperature coefficient
dc
6. The term in a rate equation refers to the :
dt
(a) Concentration of the reactant
(b) Decrease in concentration of the reactant with time
(c) Increase in concentration of the reactant with time
(d) Velocity constant of the reaction
7. For a given reaction 3A + B C + D the rate of reaction can be represented by :
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1 d[A] d[B] d[C] d[D]

(a)
3 dt dt dt dt
1 d[A] d[C]
(b) K[A]m [B]n
3 dt dt
1 d[A] d[C]
(c) K[A]n [B]m
3 dt dt
(d) None of these

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[NH 3 ] [H 2 ]
8. For the reaction N 2 3H 2 2NH 3 if 2 10 4 mol l 1s 1 , the value of
t t
would be :
(a) 1 10 4 mol l 1s 1
(b) 3 10 4 mol l 1s 1

(c) 4 10 4 mol l 1s 1
(d) 6 10 4 mol l 1s 1

9. An increase in temperature by 10°C, generally increases the rate of a reaction by :

(a) 2 times (b) 10 times (c) 9 times (d) 100 times
10. Rate of reaction
(a) Decreases with increase in temperature
(b) Increases with increase in temperature
(c) May increase or decrease with increase in temperature
(d) Does not depend on temperature
11. A first order reaction complete its 10% in 20 minutes then time required to complete its 19% is
(a) 30 minutes (b) 40 minutes (c) 50 minutes (d) 38 minutes
(RATE LAWS AND RATE CONSTANT)
12. The rate law for reaction will be
(a) Rate = K[A] [B] (b) Rate = K[A][2B]
[C][D]2
(c) Rate = K[A] [B]2 (d) Rate K
[A][B]2
d[A] d[B]
13. A + 2B C + D. If 5 10 4 mol l 1s 1 1, then is
dt dt
(a) 2.5 10 4 moll 1s 1
(b) 5.0 10 4 moll 1s 1

(c) 2.5 10 3mol l 1s 1 (d) 1.0 10 3 moll 1s 1

14. The data for the reaction A + B C is

Exp. [A]0 [B]0 Initial rate

(1) 0.012 0.035 0.10

(2) 0.024 0.070 0.80
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(3) 0.024 0.035 0.10

(4) 0.012 0.070 0.80

The rate law corresponds to the above data is
(a) Rate = k [B]3 (b) Rate = k[B]4
(c) Rate = k[A] [B]3 (d) Rate = k[A]2 [B]2

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15. For a reactions A + B product, it was found that rate of reaction increases four times if
concentration of ‘A’ is doubled, but the rate of reaction remains unaffected. If concentration of
‘B’ is doubled. Hence, the rate law for the reaction is :
(a) rate = k[A] [B] (b) rate = k[A]2
(c) rate = k[A]2 [B]1 (d) rate = k[A]2 [B]2
16. The rate constant of a reaction depends on
(a) Temperature (b) Mass (c) Weight (d) Time
17. The rate of reaction is determined by slow step reaction. The step is called :
(a) Reaction rate (b) Activation step
(c) Rate determining step (d) None of the above
18. If the concentration is expressed in moles per litre, the unit of the rate constant for a first order
reaction is :
(a) mole litre–1 sec–1 (b) mole litre–1
(c) sec–1 (d) mole–1 litre–1 sec–1
19. A zero order reaction is one whose rate is independent of :
(a) Temperature of the reaction
(b) The concentrations of the reactants
(c) The concentration of the products
(d) The material of the vessel in which the reaction is carried out
20. The unit of rate constant for a zero order reaction is :
(a) litre sec–1 (b) litre mole–1 sec–1
(c) mole litre–1 sec–1 (d) mole sec–1
21. For a chemical reaction A B it is found that the rate of reaction doubles, when the
concentration of A is increased four times. The order in A for this reaction is :
(a) Two (b) One (c) Half (d) Zero
22. Which one of the following formula represents a first order reaction :
x 1 1 1
(a) K (b) K
t 2t (a x)2 a2
2.303 a 1 x
(c) K log10 (d) K
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t (a x) t a(a x)
23. A first order reaction which is 30% complete in 30 minutes has a half-life period of :
(a) 24.2 min (b) 58.2 min (c) 102.2 min (d) 120.2 min
24. The reaction 2N2O5 2NO2 + O2 follows first order kinetics. Hence, the molecularity of the
reaction is :
(a) Unimolecular (b) Pseudo–unimolecular
(c) Bimolecular (d) None of the above

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25. Catalyst decomposition of hydrogen peroxide is a ........ order reaction :
(a) First (b) Second (c) Third (d) Zero
26. The half life of a first order reaction is :
(a) Independent of the initial concentration of the reactant
(b) Directly proportional to the initial concentration of the reactants
(c) Inversely proportional to the initial concentration of the reactant
(d) Directly proportional to the square of the initial concentration of the reactant
27. A first order reaction requires 30 minutes for 50% completion. The time required to complete the
reaction by 75% will be :
(a) 45 minutes (b) 15 minutes (c) 60 minutes (d) None of these
28. Inversion of canesugar in dilute acid (conversion into glucose and fructose) is a :
(a) Unimolecular reaction (b) Bimolecular reaction
(c) Trimolecular reaction (d) Pseudo-unimolecular reaction
29. The half life period of a first order reaction :
0.693 0.693 2.303 0.303
(a) (b) (c) (d)
t K t K1
30. Half life period t1/2 for first order reaction is :
1.303log 2 2.303log 2 9
(a) K (b) (c) (d)
K K K
(COLLISION THEORY AND ARRHENIUS EQUATIONS)
31. According to Arrhenius theory, the activation energy is :
(a) The energy it should possess so that it can enter into an effective collision
(b) The energy which the molecule should possess in order to undergo reaction
(c) The energy it has to acquire further so that it can enter into a effective collison
(d) The energy gained by the molecules on colliding with another molecule
32. The energy of activation is :
(a) The energy associated with the activated molecules
(b) Threshold energy – energy of normal molecules
(c) Threshold energy + energy of normal molecules
(d) Energy of products – energy of reactants
33. Which of the following plots is in accordance with the Arrhenius equation ?
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Chemical Kinetics

(a) (b)

(c) (d)

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34. The minimum energy a molecule should possess in order to enter into a fruitful collision is
known as :
(a) Reaction energy (b) Collision energy
(c) Activation energy (d) Threshold energy
35. Activation energy is given by the formula :
K2 Ea T2 T1 K1 Ea T2 T1
(a) log (b) log
K1 2.303R T1T2 K2 2.303R T1T2

K1 Ea T1 T2
(c) log (d) None of these
K2 2.303R T1T2
36. Relation between rate constant and temperature by Arrhenius equation is :
Ea Ea
(a) log e A log e K (b) log K A
RT RT
Ea
(c) log e K log e A (d) log A RT ln E a ln K
RT 2
37. Collision theory is applicable to :
(a) First order reactions (b) Zero order reactions
(c) Bimolecular reactions (d) Intra molecular reactions

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b a c b b b a b a c
Q. No. 11 12 13 14 15 16 17 18 19 20
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Chemical Kinetics

Ans. b c a a b a c c b c
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. c c b c a a c d b c
Q. No. 31 32 33 34 35 36 37
Ans. c b a d a a c

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CHAPTER–4 : THE d & f - BLOCK ELEMENT

• Chapter at a glance 52-54
• Exercise-1_Important Questions 55-63
• Exercise-2_Multiple Choice Questions 64-66
CHAPTER AT A GLANCE
d-BLOCK ELEMENTS
• A transition element may be defined as the element whose atom in ground state or in one of
common oxidation states, has partly filled d-sub shell i.e. having electrons between 1 to 9.
• Group 12 (the zinc group) elements have completely filled d-orbitals in the ground state as well
as in their common oxidation states. Therefore, they are not regarded as transition elements.
1–10 1–2
• The general electronic configuration of d-block elements is (n–1) d ns .
• Zn, Cd and Hg are involved in transition series but they are called non transition elements due to
10 2
completely filled d-orbitals. (General electronic configuration of these is (n – 1) d ns )
• The transition elements are very much hard and have low volatility, as they have high enthalpy of
atomisation.
• The metals with very high enthalpy of atomisation tend to be noble in their reactions.
• Melting and boiling point of d-block elements is more than that of s block elements.
Reason : Stronger metallic bond formed by present unpaired d-electrons.
• In Zn, Cd, and Hg there is no unpaired electron present in d-orbital, hence due to absence of
covalent bond melting and boiling point are very low in series. (Volatile metals Zn, Cd, Hg)
• In 3d series Sc to Cr melting and boiling point increases then Mn to Zn melting and boiling point
decreases.
• Paramagnetic substances. The substances which are attracted by magnetic field are called
paramagnetic substances and this character arises due to the presence of unpaired electrons in the
atomic orbitals.
• The magnetic moment arise only from the spin of the electrons. This can be calculated from the
relation = B.M. n(n 2) n Number of unpaired electrons
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• FORMATION OF INTERSTITIAL COMPOUNDS

Transition metals form interstitial compounds with elements such as hydrogen, boron, carbon and
nitrogen.
The small atoms of these non-metallic elements (H, B, C, N, etc.) get trapped in vacant spaces of
the lattices of the transition metal atoms as shown below.
e.g. WC, Fe3C, TiH1.30 – 1.80, VH0.56, Mn4N etc.

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Properties:
(1) They are generally non-stoichiometric compound.
(2) Neither typically ionic nor typically covalent.
(3) Harder than pure metal.
(4) High melting point than pure metal.
(5) They retain metallic conductivity.
(6) They are chemically inert.
• CATALYTIC PROPERTIES :
d-block metals or their compound act as catalyst in many reaction due to :
(i) Possibility of variable oxidation state.
(ii) Presence of free valencies over metal surface (adsorption power).
(iii) Presence of vacant d-orbital.
• ALLOY FORMATION
(1) Alloys are homogeneous solid solutions in which the atoms of one metal are distributed
randomly among the atoms of the other metal.
(2) The alloys are generally formed by those atoms which have metallic radii within about
15% of each other.
(3) Transition metals form a large number of alloys because transition metals are quite similar
in size and therefore the atoms of one metal can substitute the atoms of other metal in its
crystal lattice.
(4) The alloys so formed are very hard and have often high melting points.
(5) 1. Bronze - Cu (75-90 %) + Sn (10-25 %)
2. Brass - Cu (60-80 %) +Zn (20-40%)
f-BLOCK ELEMENTS
• The elements in which the last electron enters in (n – 2)f orbitals are called inner transition
elements or f-block elements.
• f-block elements consist of two series Lanthanoids (Ce58 – Lu71), Actinoids (Th90 – Lr103)
• Lanthanides are reactive elements so do not found in free state in nature.
1–14 2 6 0–1 2
• The general configuration of lanthanides may be given as [Xe] 4f 5s 5p 5d 6s .
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\d&f-block element

• Pm is the only synthetic radioactive lanthanide.

• In lanthanides +3 oxidation state is most common.
• Ce, Tb, Nd, Dy, Pr also exhibit +4 oxidation state.
• Sm, Eu, Tm, and Yb, also exhibit +2 oxidation state.
+4 +2
• Ce is a strong oxidising agent while Eu is a strong reducing agent.
• The lanthanoid ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible
region of light and undergo f–f transition and hence exhibit colour.

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• Lanthanide Contraction
In the lanthanide series with increasing atomic number, there is a progressive decrease in the size
+3 +3
from lanthanum to lutecium or from La to Lu . This contraction in size is known as lanthanide
contraction.
APPLICATIONS OF LANTHANIDE CONTRACTION
+4 +4
• Atomic size : The ionic radii of Zr is about 9% more than Ti . Similar trend is not maintained
+4
on passing from the second to third transition series. The ionic radius of Hf , instead of
increasing (because of inclusion of one more electronic shell), decreases (or is virtually equal
+4
to Zr ) as a consequence of the lanthanoid contraction.
This explains the close similarities between the members of the second and third transition series
than between the elements of the first and second series.
• Basic nature of hydroxide : Basic nature of hydroxide regularly decreases.
• Similarity in properties of lanthanide : Due to small difference in size the chemical properties
of lanthanoids are similar and their seperation is difficult.
1–14 0,1,2 2
• The general configuration of actinides may be given as [Rn] 5f 6d , 7s .
• In actinoids +3 oxidation is the most common.
• In actinides there is a greater range of oxidation states which is due to very less energy difference
between 5f, 6d and 7s energy levels.
• Highest oxidation states in the actinoids is +7 exhibited by Np93 & Pu94, it is unstable.

• Highest stable oxidation state is +6 shown by 92U.

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EXERCISE-1 IMPORTANT QUESTIONS

1. Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a
transition element?
Ans. Ag has a completely filled 4d orbital (4d10 5s1) in its ground state. Now, silver displays two
oxidation states (+1 and +2). In the +1 oxidation state, an electron is removed from the s-orboital.
However, in the +2 oxidation state, an electron is removed from the d-orbital.
Thus, the d-orbital now becomes incomplete (4d9). Hence, it is a transition element.
2. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest,
i.e., 126 kJ mol-1. Why?
Ans. The extent of metallic bonding an element undergoes decides the enthalpy of atomization. The
more extensive the metallic bonding of an element, the more will be its enthalpy of atomization.
In all transition metals (except Zn, electronic configuration: 3d10 4s2), there are some unpaired
electrons that account for their stronger metallic bonding. Due to the absence of these unpaired
electrons, the inter-atomic electronic bonding is the weakest in Zn and as a result, it has the least
enthalpy of atomization.
3. Which of the 3d series of the transition metals exhibits the largest number of oxidation states and
why?
Ans. Mn (Z = 25) = 3d5 4s2
Mn has the maximum number of unpaired electrons present in the d-subshell (5 electrons).
Hence, Mn exhibits the largest number of oxidation states, ranging from +2 to +7.
4. The E (M2+/M) value for copper is positive (+0.34V). What is possibly the reason for this?
(Hint: consider its high atomization and low hydration)
Ans. The E (M2+/M) value of a metal depends on the energy changes involved in the following:
1. Sublimation: The energy required for converting one mole of an atom from the solid state
to the gaseous state.
M(s) M(g) s
H(Sublimation energy)

2. Ionization: The energy required to take out electrons from one mole of atoms in the
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\d&f-block element

gaseous state.
M(g) M2+(g) H(Ionization energy)
i

3. Hydration: The energy released when one mole of ions are hydrated.
M2+(g) M2+(aq) hyd
H(Hydration energy)

Now, copper has a high energy of atomization and low hydration energy. Hence, the E (M2+/M)
value for copper is positive.

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5. How would you account for the irregular variation of ionization enthalpies (first and second) in
the first series of the transition elements?
Ans. Ionization enthalpies are found to increase in the given series due to a continuous filling of the
inner d-orbitals. The irregular variations of ionization enthalpies can be attributed to the extra
stability of configurations such as d0, d5, d10. Since these states are exceptionally stable, their
ionization enthalpies are very high.
In case of first ionization energy, Cr has low ionization energy. This is because after losing one
electron, it attains the stable configuration (3d5). On the other hand, Zn has exceptionally high first
ionization energy as an electron has to be removed from stable and fully-filled orbitals (3d10 4s2).
Second ionization energies are higher than the first since it becomes difficult to remove an
electron when an electron has already been taken out. Also, elements like Cr and Cu have
exceptionally high second ionization energies as after losing the first electron, they have attained
the stable configuration (Cr+: 3d5 and Cu+: 3d10). Hence, taking out one electron more from this
stable configuration will require a lot of energy.
6. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Ans. Both oxide and fluoride ions are highly electronegative and have a very small size. Due to these
properties, they are able to oxidize the metal to its highest oxidation state.
7. Which is a stronger reducing agent Cr2+ or Fe2+ and why?
Ans. The following reactions are involved when Cr2+ and Fe2+ act as reducing agents.
Cr Cr2+ + 2e– Fe2+ Fe3+ + 1e–
The value is -0.41 V and is +0.77 V. This means that Cr2+ can be easily oxidized to Cr3+, but Fe2+
does not get oxidized to Fe3+ easily. Therefore, Cr2+ is a better reducing agent that Fe3+.
8. Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).
Ans. Z = 27
[Ar] 3d7 4s2
M2+ = [Ar] 3d7

3d7 =

i.e., 3 unpaired electrons

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n=3
n(n 2) µ

3(3 2) µ

15 µ

µ 4 BM

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9. Explain why Cu+ ion is not stable in aqueous solutions?
Ans. In an aqueous medium, Cu2+ is more stable than Cu+. This is because although energy is required
to remove one electron from Cu+ to Cu2+, high hydration energy of Cu2+ compensates for it.
Therefore, Cu+ ion in an aqueous solution is unstable. It disproportionates to give Cu2+ and Cu.
10. Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their +3 state?
Ans. Electronic configuration of Mn2+ is [Ar]18 3d5. (half filled stability)
Electronic configuration of Fe2+ is [Ar]18 3d6. (After losing one electron it gain half filled
stability).
11. To what extent do the electronic configurations decide the stability of oxidation states in the first
series of the transition elements ? Illustrate your answer with examples.
Ans. The elements in the first - half of the transition series exhibit many oxidation states with Mn
exhibiting maximum number of oxidation states (+2 to +7). The stability of +2 oxidation state
increases with the increase in atomic number. This happens as more electrons are getting filled in
the d-orbital.
12. What is lanthanoid contraction ? What are the consequences of lanthanoid contraction ?
Ans. As we move along the lanthanoid series, the atomic number increases gradually by one. This
means that the number of electrons and protons present in an atom also increases by one. As
electrons are being added to the same shell, the effective nuclear charge increases. This happens
because the increase in nuclear attraction due to the addition of proton is more pronounced than
the increase in the interelectronic repulsions due to the addtion of electron. Also, with the
increase in atomic number, the number of electrons in the 4f orbital also increases. The 4f
electrons have poor shielding effect. Therefore, the effective nuclear charge experienced by the
outer electrons increases. Consequently, the attraction of the nucleus for the outermost electrons
increases. This results in a steady decrease in the size of lanthanoids with the increase in the
atomic number. This is termed as lanthanoid contraction.
Consequences of lanthanoid contraction
(i) There is similarity in the properties of second and third transition series.
(ii) Separation of lanthanoids is possible due to lanthanide contraction.
(iii) It is due to lanthanide contraction that there is variation in the basic strength of lanthanide
hydroxides. (Basic strength decreases from La (OH)3 to Lu (OH)3.)
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13. What are the characteristics of the transition elements and why are they called transition
elements ? Which of the d-block elements may not be regarded as the transition elements ?
Ans. Transition elements are those elements in which the atoms or ions (in stable oxidation state)
contain partially filled d-orbital. These elements lie in the d-block and show a transition of
properties between s-block and p-block. Therefore, these are called transition elements.
Elements such as Zn, Cd and Hg cannot be classified as transition elements because these have
completely filled d-subshell.

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14. In what way is the electronic configuration of the transition elements different from that of the
non-transition elements ?
Ans. Transition metals have a partially filled d-orbital. Therefore, the electronic configuration of
transition elements is (n–1) d1-10 ns0 - 2.
The non-transition elements either do not have a d- orbital or have a fully filled d- orbital.
Therefore, the electronic configuration of non-transition elements is ns1-2 or ns2 np1-6.
15. What are the different oxidation states exhibited by the lanthanoids ?
Ans. In the lanthanide series, +3 oxidation state is most common i.e., Ln (III) compounds are
predominant. However, +2 and +4 oxidation states can also be found in the solution or in solid
compounds.
16. Explain giving reasons :
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.
Ans. (i) Transition metals show paramagnetic behaviour. Paramagnetism arises due to the presence of
unpaired electrons with each electron having a magnetic moment associated with its spin angular
momentum and orbital angular momentum.
(ii) Transition elements have high effective nuclear charge and a large number of valence
electrons. Therefore, they form very strong metallic bonds. As a result, the enthalpy of
atomization of transition metals is high.
(iii) Most of the complexes of transiton metals are coloured. This is because of the absorption of
radiation from visible light region to promote an electron from one of the d-orbitals to another. In
the presence of ligands, the d-orbitals split up into two sets of orbitals having different energies.
Therefore, the transition of electrons can take place from one set to another. The energy required
for these transitions is quite small and falls in the visible region of radiation. The ions of
transition metals absorb the radiation of a particular wavelength and the rest is reflected,
imparting colour to the soultion.
(iv) The catalytic activity of the transition elements can be explained by two basic facts.
(a) Owing to their ability to show variable oxidation states and form complexes, transition
metals form unstable intermediate compounds. Thus, they provide a new path with lower
activation energy, Ea, for the reaction.
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(b) Transition metals also provide a suitable surface for the reactions to occur.
17. What are interstitial compounds? Why are such compounds well known for transition metals ?
Ans. Transition metals are large in size and contain lots of interstitial sites. Transition elements can
trap atoms of other elements (that have small atomic size), such as H, C, N, in the interstitial sites
of their crystal lattices. The resulting compounds are called interstitial compounds.
These compound are well known for transition metals because small atoms can easily occupy the
position in the void present in the crystal lattice of transition metals.

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18. How is the variability in oxidation states of transition metals different from that of the non-
transition metals? Illustrate with examples.
Ans. In transition elements, the oxidation state can vary from +1 to the highest oxidation state by
removing all its valence electrons. Also, in transition elements, the oxidation states differ by
1 (Fe2+ and Fe3+; Cu+ and Cu2+). In non-transition elements, the oxidation states differ by 2, for
example, +2 and +4 or + 3 and +5, etc.
19. How would you account for the following :
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidising.
(ii) Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is easily
oxidised.
(iii) The d1 configuration is very unstable in ions.
Ans. (i) Cr2+ is strongly reducing in nature. It has a d4 configuration. While acting as a reducting agent,
it gets oxidized to Cr3+ (electronic configuration, d3). This d3 configuration can be written as
configuration, which is a more stable configuration. In the case of Mn3+ (d4), it acts as an
oxidizing agent and gets reduced to Mn2+ (d5). This has an exactly half- filled d-orbital and is
highly stable.
(ii) Co(II) is stable in aqueous solutions. However, in the presence of strong field complexing
reagents, it is oxidized to Co(III). Although the 3rd ionization energy for Co is high, but the higher
amount of crystal field stabilization energy (CFSE) released in the presence of strong field
ligands overcomes this ionization energy.
(iii) The ions in d1 configuration tend to lose one more electron to get into stable d0 configuration.
Also, the hydration or lattice energy is more than sufficient to remove the only electron present in
the d-orbital of these ions. Therefore, they act as reducing agents.
20. What is meant by 'disproportionation' ? Give two examples of disproportionation reaction in
aqueous solution.
Ans. It is found that sometimes a relatively less stable oxidation state undergoes an oxidation -
reduction reaction in which it is simultaneously oxidised and reduced. This is called
disproportionation.
For example,
(1) 3CrO34 8H 2CrO 24 Cr 3 4H 2 O
Cr(V) Cr(VI) Cr(III)

Cr(V) is oxidized to Cr(VI) and reduced to Cr(III).

(2) 3MnO 24 4H 2MnO 4 MnO 2 2H 2O
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Mn(VI) Mn(VII) Mn(IV)

Mn (VI) is oxidized to Mn (VII) and reduced to Mn (IV).

21. Which metal in the first series of transition metals exhibit +1 oxidation state most frequently and
why?
Ans. In the first transition series, Cu exhibits +1 oxidation state very frequently. It is because Cu (+1)
has an electronic configuration of [Ar] 3d10. The completely filled d-orbital makes it highly
stable.

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22. Calculate the number of unpaired electrons in the following gaseous ions: Mn3+, Cr3+, V3+ and
Ti3+. Which one of these is most stable in aqueous solution ?
Ans.
Gaseous ions Number of uppaired electrons
(i) Mn3+, [Ar]3d4 4
3+ 3
(ii) Cr , [Ar] 3d 3
(iii) V3+, [Ar]3d2 2
(iv) Ti3+[Ar] 3d1 1
Cr3+ is most stable in aqueous solutions owing to a t32g half filled configuraion.
23. Give examples and suggest reasons for the following features of the tranistion metal chemistry :
(i) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii) A transition metal exhibits highest oxidation state in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of a metal.
Ans. (i) In the case of a lower oxide of a transition metal, the metal atom has a low oxidation state.
This means that some of the valence electrons of the metal atom are not involved in bonding. As
a result, it can donate electrons and behave as a base.
On the other hand, in the case of a higher oxide of a transition metal, the metal atom has a high
oxidation state. This means that the valence electrons are involved in bonding and so, they are
unavailable. There is also a high effective nuclear charge.
As a result, it can accept electrons and behave as an acid.
For example, MnIIO is basic and Mn2VII O 7 is acidic.
(ii) Oxygen and fluorine act as strong oxidising agents because of their high electronegatives and
small sizes. Hence, they bring out the highest oxidation states from the transition metals. In other
words, a transition metal exhibits higher oxidation states in oxides and fluorides. For example, in
OsF6 and V2O5, the oxidation states of Os and V are +6 and +5 respectively.
(iii) Oxygen is a strong oxidising agent due to its high electronegativity and small size. So, oxo-anions
of a metal have the highest oxidation state. For example, in MnO4–, the oxidation state of Mn is +7.
24. What are alloys ? Name an important alloy which contains some of the lanthanoid metals.
Mention its uses.
Ans. An alloy is a solid of two or more elements in a metallic matrix. It can either be a partial solid
solution or a complete solid solution. Alloys are usually found to possess different physical
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properties than those of the component elements.

An important alloy of lathanoids is Mischmetal. It contians lanthanoids (94-95%), iron (5%), and
traces of S, C, Si, Ca and Al.
Uses:
(1) Mischmetal is used in cigarettes and gas lighters.
(2) It is used in flame throwing tanks.
(3) It is used in tracer bullets and shells.

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25. What are inner transition elements ? Decide which of the following atomic numbers are the
atomic numbers of the inner transition elements : 29, 59, 74, 95, 102, 104.
Ans. Inner transition elements are those elements in which the last electron enters the f-orbital .The elements
in which the 4f and 5f orbitals are progressively filled are called f-block elements. Among the given
atomic numbers, the atomic numbers of the inner transition elements are 59, 95 and 102.
26. Which is the last elements in the series of the actinoids ? Write the electronic configuration of
this element. Comment on the possible oxidation state of this element.
Ans. The last element in the actinoid series is lawrencium, Lr. its atomic number is 103 and its
electronic configuration is [Rn] 5f14 6d1 7s2. The most common oxidation state displayed by it is
+3; because after losing 3 electrons it attains stable f14 configuration.
27. Use Hund's rule to derive the electronic configuration of Ce3+ ion and calculate its magnetic
moment on the basis of 'spin - only' formula.
Ans. Ce3+ : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 4f1
Magnetic moment can be calculated as :
n(n 2)
Where,
n = number of unpaired electrons.
In Ce3+, n = 1
Therefore, 1 (1 2) 3 = 1.732 BM
28. Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of
increasing pH on a solution of potassium dichromate ?
Ans. Potassium dichromate is prepared from chromite ore (FeCr2O4) in the following steps.
Step (1) : Preparation of sodium chromate
4FeCr2O4 + 16NaOH + 7O2 8Na2CrO4 + 2Fe2O3 + 8H2O
Step (2) : Conversion of sodium chromate into sodium dichromate
2Na2CrO4 + conc. H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Step (3) : Conversion of sodium dichromate to potassium dichromate
Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl
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Potassium dichromate being less soluble than sodium dichromate is obtained in the form of
orange coloured crystals and can be removed by filtration.
The dichromate ion (Cr2O72–) exists in equilibrium with chromate (CrO42) ion at pH 4. However,
by changing the pH, they can be interconverted
2CrO 24 2H pH 4
Cr2 O72 H2O
Chromate ion(Yellow) Dichromate ion (Orange)

On increasing pH, Cr2O72 2OH 2CrO24 H2 O

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29. Describe the oxidation action of potassium dichromate and write the ionic equations for its
reaction with :
(i) iodide
(ii) iron(II) solution and
(iii) H2S
Ans. K2Cr2O7 acts as a very strong oxidising agent in the acidic medium.
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2 (SO4)3 + 4H2O + 3[O]
K2Cr2O7 takes up electrons to get reduced and acts as an oxidising agent. The reaction of K2Cr2O7
with iodide ion, iron (II) solution and H2S are given below.
(i) K2Cr2O7 oxidizes iodide to iodine.
Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
2I– I2 + 2e–] × 3
Cr2O72– + 6I– + 14H+ 2Cr3+ + 3I2 + 7H2O
(ii) K2Cr2O7 oxidizes iron (II) solution to iron (III) solution i.e., ferrous ions to ferric ions.
Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
Fe2+ Fe3+ + e–] × 6
Cr2O72– + 14H+ + 6Fe2+ 2Cr3+ + 3I2 + 7H2O
(iii) K2Cr2O7 oxidizes H2S to sulphur.
Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
H2S S + 2H+ + 2e–] × 3
Cr2O72– + 3H2S + 8H+ 2Cr3+ + 3S + 7H2O
30. Describe the preparation of potassium permanganate. How does the acidified permanganate
solution react with (i) iron(II) ions (ii) SO2 (iii) oxalic acid ?
Write the ionic equations for the reactions.
Ans. Potassium permanganate can be prepared from pyrolusite (MnO2). The ore is fused with KOH in
the presence of either atmospheric oxygen or an oxidising agent, such as KNO3 or KClO4, to give
K2MnO4.
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heat
2MnO2 4KOH O 2 2K 2 MnO 4 2H 2 O
Green

The green mass can be extracted with water and then oxidized either electrolytically or by
passing chlorine/ozone into the soulution.
Electrolytic oxidation
K2MnO4 2K+ + MnO42–
H2O H+ + OH–

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At anode, manganate ions are oxidized to permanganate ions.
MnO24 MnO4 e
Green Purple

Oxidation by chlorine
2K2MnO4 + Cl2 2KMnO4 + 2KCl

2MnO42– + Cl2 2MnO4– + 2Cl–

Oxidation by ozone
2K2MnO4 + O3 + H2O 2KMnO4 + 2KOH + O2

2 MnO42– + O3 + H2O 2MnO4– + 2OH– + O2

(i) Acidified KMnO4 solution oxidizes Fe (II) ions to Fe (III) ions i.e., ferrous to ferric ions.

MnO–4 + 8H+ + 5e– Mn2+ + 4H2O

Fe2+ Fe3+ + e–] × 5

MnO4– + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
(ii) Acidified potassium permanganate oxidizes SO2 to sulphuric acid.

MnO4– + 6H+ + 5e– Mn2+ + 3H2O] × 2

2H2O + 2SO2 + O2 4H+ + 2SO42– + 2e–] × 5

2MnO4– + 10SO2 + 5O2 + 4H2O 2Mn2+ + 10SO42– + 8H+

(iii) Acidified potassium permanganate oxidizes oxalic acid to carbon dioxide.
MnO4– + 8H+ + 5e– Mn2+ + 4H2O] × 2

C2O42– 2CO2 + 2e–] × 5

2MnO4– + 5C2O42– + 16H+ 2Mn2+ + 10CO2 + 8H2O

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EXERCISE-2 MULTIPLE CHOICE QUESTIONS
1. Transitional elements exhibit variable valencies because they release electrons from the
following orbits :
(a) ns orbit (b) ns and np orbits
(c) (n – 1)d and ns orbits (d) (n – 1)d orbit
2. Highest (+7) oxidation state is shown by :
(a) Co (b) Cr (c) V (d) Mn
3. The coinage metals are :
(a) Iron, Cobalt, Nickel (b) Copper and Zinc
(c) Copper, Silver and Gold (d) Gold and Platinum
4. The catalytic activity of the transition metals and their compounds is ascribed to their :
(a) Chemical reactivity
(b) Magnetic behaviour
(c) Unfilled d-orbitals
(d) Ability to adopt multiple oxidation states and their complexing ability
5. Transitional elements are named transition elements because their characters are :
(a) In between s and p - block elements
(b) Like that of p and d - block elements
(c) They are members of I – A group
(d) They are like inactive elements
6. Elements which generally exhibit multiple oxidation states and whose ions are usually coloured
are :
(a) Metalloids (b) Transition elements
(c) Non-metals (d) Gases
7. The general electronic configuration of transition elements is :
(a) (n – 1)d1 – 5 (b) (n – 1)d1–10ns1
(c) (n – 1)d1–10 ns1–2 (d) ns2 (n – 1)d10
8. Zinc does not show variable valency like d-block elements because :
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(a) It is a soft metal

(b) d-orbital is complete
(c) It is low melting
(d) Two electrons are present in the outermost orbit
9. Transition elements are coloured :
(a) Due to small size (b) Due to metallic nature
(c) Due to unpaired d – electrons (d) All of these

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10. Lanthanum is grouped with f-block elements because :
(a) It has partially filled f -orbitals
(b) It is just before Ce in the periodic table
(c) It has both partially filled f and d-orbitals
(d) The properties of Lanthanum are very similar to the elements of 4f block
11. The element having electronic configuration belongs to ns 2 (n 1)d1 10 (n 2)f 1 14 :
(a) s-block (b) p-block (c) d-block (d) f-block
12. Zinc, cadmium and mercury show the properties of :
(a) Typical elements (b) Normal elements
(c) Transitional elements (d) Rare elements
13. 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
14. Bullet-proof steel alloy is prepared by using :
(a) Sc (b) Ni (c) Zr (d) Zn
15. Which of the following is diamagnetic transitional metal ion :
(a) Ni+2 (b) Zn+2 (c) Co+2 (d) Cu+2
16. In first transition series, the melting point of Mn is low because :
(a) Due to d10 configuration, metallic bonds are strong
(b) Due to d7 configuration, metallic bonds are weak
(c) Due to d5 configuration, metallic bonds are weak
(d) None of these
17. Lanthanoide for which +2 and +3 oxidation states are common is :
(a) La (b) Nd (c) Ce (d) Eu
18. Lanthanoide contraction occurs because :
(a) f-orbital electrons are easily lost
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(b) f-orbital an incompletely filled

(c) f-orbital electron an poor shielders of nuclear charge
(d) f-orbital do not come out on the surface of atom and are buried inside
19. The metal present in B12 is :
(a) Magnesium (b) Iron (c) Cobalt (d) Manganese
20. Most common oxidation states of (cesium) are :
(a) + 2, + 3 (b) + 2, + 4 (c) + 3, + 4 (d) + 3, + 5

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21. Number of unpaired electrons in Mn2+ is :
(a) 3 (b) 5 (c) 4 (d) 1
22. Lanthanoides and actinides resemble in :
(a) Electronic configuration (b) Oxidation state
(c) Ionization energy (d) Formation of complexes
23. Transition metals show paramagnetism :
(a) Due to characteristic configuration (b) High lattice energy
(c) Due to variable oxidation states (d) Due to unpaired electrons
24. Four successive members of the first row transition elements are listed below with their atomic
numbers. Which one of them is expected to have the highest third ionization enthalpy :
(a) Vanadium (Z = 23) (b) Chromium (Z = 24)
(c) Iron (Z = 26) (d) Manganese (Z = 25)
2+
25. How many unpaired electrons are there in Ni :
(a) 2 (b) 4 (c) 5 (d) 0
26. Electronic configuration of Cu (Z = 29) is :
(a) [Ar]3d 9 4s 2 (b) [Ar]3d10 4s1 (c) [Ar]3d 5 4s 2 (d) [Ar]3d 6 4s 2
27. The lanthanoide contraction is responsible for the fact that :
(a) Zr and Y have about the same radius
(b) Zr and Nb have similar oxidation state
(c) Zr and Hf have about the same radius
(d) Zr and Zn have the same oxidation sate
28. Which of the following factors may be regarded as the main cause of lanthanoide contraction :
(a) Poor shielding of one of 4f electron by another in the subshell
(b) Effective shielding of one of 4f electrons by another in the subshell
(c) Poorer shielding of 5d electrons by 4f electrons
(d) Greater shielding of 5d electron by 4f electrons

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
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Ans. c d c d a b c b c d
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. d c b c b c a d c c
Q. No. 21 22 23 24 25 26 27 28
Ans. b b d d a b c a

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CHAPTER–5 : COORDINATION COMPOUND

• Chapter at a glance 67-75
• Exercise-1_Important Questions 76-83
• Exercise-2_Multiple Choice Questions 84-86
CHAPTER AT A GLANCE
Addition Compounds
• When two or more simple salts are chemically combined together in fixed proportion by weight
the molecular or addition compounds are formed.
• Depending upon the behavior in an aqueous solution they are of two types
(i) Double salt (ii) Coordination or complex compounds.
Double Salt
• The addition compounds which loose their identity in aq. solution and get completely ionised in
water.

Ex. (i) K2SO4.Al2(SO4)3.24H2O (Potash Alum)

(ii) FeSO4(NH4)2SO4.6H2O (Mohr's salt)
(iii) KCl.MgCl2.6H2O (Carnallite)
Coordination or Complex Compounds
• Those molecular or addition compounds which retain their identity in aq. solution or loose the
identity of constituents are called complex salt.
• K4[Fe(CN)6]
• On the basis of type of ligands complex compounds are divided as follows:
(i) Homoleptic complexes :
Complex in which all the ligands are identical is called homoleptic complex.
+2
Ex. [Co(NH3)6]
(ii) Heteroleptic complexes :
Complex in which all the ligands are not identical is known as heteroleptic complex.
+1
Ex. [Fe(en)2Cl2]
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• Coordination Number
The total number of coordinate bonds formed by central metal ion with donor species is called as
coordination number of central metal ion.
•
Central metal ion Coordination sphere

[Cu(NH3)4]SO4 Ionization sphere

Ligand Coordination number

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• It is a number which represents the electrical charge on the central metal atom of a complex ion.
4— 3+
Ex. the oxidation number of Fe, Co and Ni in [Fe(CN)6] , [Co(NH3)6] and Ni(CO)4 is +2, +3
and zero respectively.
• Ambidentate ligand: Ligands which have two different donor atoms but at one time one donor
atom can donate electron pair are called ambidentate ligands.
Ambidentate ligands have same molecular formula but have different donor atom.
M C N cyanido (CN)
M N C isocyanido(NC)
• VALENCE BOND THEORY
This theory was mainly developed by Linus Pauling. The main features of this theory are -
(a) Metal ion when it forms a complex compound undergoes formation of coordinate bond.
(b) During this bond formation, the metal ion acts as electron pair acceptor. For this the metal
ion provides vacant orbitals according to its coordination number.
(c) These vacant orbitals undergo hybridisation before bond formation with ligands.
(d) The vacant hybrid orbitals of metal ion get overlapped with orbitals of ligands containing
lone pair of electrons.
–
(e) If in a complex strong ligand is present then it will cause pairing of unpaired e in (n–1)d
orbitals of central metal ion and if (n–1)d orbitals are involved in hybridisation then inner
orbital complex is formed.
–
(f) If in the complex weak ligand is present then there will be no pairing of unapaired e in
(n–1) d orbitals and if nd orbitals are involved in hybridisation, outer orbital complex is
formed.
–
(g) If unpaired e is present in the complex then it will be paramagnetic otherwise it will be
diamagnetic.
• Crystal Field Theory: This is a model of electronic structure of transition-metal complexes that
considers how the energies of the d-orbitals of a metal ion are affected by the electric field of the
ligand. According to this theory.
(a) Central metal ion is considered as a positive point charge, anionic ligand as a negative
point charge, neutral ligand as a point dipole and attraction between metal ion and ligand is
electrostatic in nature.
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(b) In the electric field of ligands, the five d orbitals of the metal atom no longer have exactly
same energy while they are splitted into different energy levels. Splitting of five degenerate
d-orbitals of the metal ion into sets of orbitals having different energies is called crystal
field splitting.
(c) The extent of splitting of metal d-orbitals depends upon the nature and number of ligands
surrounding it and the charge on the central metal ion.
(d) The extent of splitting of metal d-orbitals determines the magnetic and spectroscopic
properties of the complexes.
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• Spectro-chemical series for ligands
Series which shows the relative strength of ligands
– – – – –2 – – 2– –
I (weakest) < Br < SCN < Cl < S > F < OH < C2O4 < H2O < NCS
4– – –
< edta < NH3 < en < NO2 < CN < CO(strongest)
• Reason for colour in complexes is due to d-d-transition
ISOMERISM IN COMPLEXES
Compounds which have the same molecular formula, but differ in their properties due to the
difference in their structure are called as Isomers.
Classification of isomerism:
Type of isomerism

(A) Structural isomerism (B) Stereo isomerism

Ionization Hydrate Coordination Linkage Geometrical Optical

(A) Structural Isomerism
It arises due to the difference in the type of chemical linkages and distribution of ligands within
and outside the coordination sphere.
(i) Ionisation Isomerism
Compounds having same molecular formula but give different type of ions in their aqueous
solution are known as ionisation isomer.
Due to exchange of ions between coordination sphere and ionisation sphere different ionisation
isomers are formed. So they are ionisation isomers.
Ex. (a) CoBrSO4 5NH3 can represent
(i) [Co(NH3)5Br] SO4 (red violet)
(ii) [Co(NH3 )5 SO4 ] Br (red).
These complexes give sulphate ion and bromide ion respectively
(b) [Pt(NH3)4Cl2] Br2 and [Pt(NH3 )4Br2]Cl2
(c) [Co(NH3)4(NO3)2 ]SO4 and [Co(NH3)4SO4](NO3)2
(ii) Hydrate Isomerism
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This type of isomerism is due to presence of different number of water molecules inside the
complex ion.
Ex. (a) Cr(H2O)6Cl3 has three possible hydrate isomers.
(i) [Cr(H2O)6]Cl3 (violet)
(ii) [Cr(H2O)5Cl]Cl2.H2O (green)
(iii) [Cr(H2O)4Cl2]Cl.2H2O (dark green)
These complexes differ from one another with respect to the number of water molecules acting as
ligands.
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(iii) Linkage Isomerism
(a) This type of isomerism arises due to presence of ambidentate ligands
(b) These ligands have two donor atoms but at a time only one atom is directly linked to the
central metal atom of the complex.
Ex. [Co(NH3)5NO2]Cl2 and [Co(NH3)5 ONO]Cl2
– –
In NO2 ligand, the donor site is nitrogen while in ONO ligand donor site is oxygen.
(iv) Coordination Isomerism
(i) This type of isomerism is exhibited when in complex compound both cation as well as anion
is complex.
(ii) This type of isomerism is caused by the interchange of ligands between the two complex ions
of a complex compound.
Ex.
i Zn NH 3 4
ZnCl4
Coordination isomers
(ii) Zn NH 3 3 Cl ZnCl3 NH3
(B) Stereo Isomerism
(a) They have same molecular formula, same constitution but they differ only with respect to the
spatial orientation of ligands in space around the metal ion.
(b) The two types of stereo isomers which are possible are - Geometrical and optical.
(i) Geometrical Isomerism
(a) Due to change in relative positions of ligands around central metal ion, different forms are
obtained which are known as GI.
(b) When two identical ligands are coordinated to the metal ion from same side then it is cis
isomer.
(Latin, cis means same).
(c) If the two identical ligands are coordinated to the metal ion from opposite side then it is
Trans isomer
(in Latin, Trans means across).
(d) These geometrical isomers differ in physical as well as in chemical properties.
(e) Geometrical isomerism is most important in compounds with coordination numbers 4 and 6.
(f) 4-coordinated complexes with tetrahedral geometry do not exhibit cis - Trans isomerism,
because relative position of ligands remain same for each other.
(g) It is exhibited by 4-coordinated complexes with square planar geometry.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

Note: There are only 5 possible cases which shows geometrical isomerism in square planar
complex. Such as Ma2b2, Ma2bc, Mabcd, M(AB)2, M(AB)cd
Geometrical Isomers with Coordination Number = 4 (Square Planar Complexes)
(i) Complexes with general formula, Ma2b2 (where both a and b are monodentate) can have
Cis – trans isomers.

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Ex. [Pt (NH3)2Cl2]

cis-platin
(used as a anti cancer) Trans – platin

(ii) Complexes with general formula Ma2bc can have Cis – trans isomers.

E.g; [Pt(NH3)2ClBr]

(iii) Complexes with general formula, Mabcd can have three geometrical isomers.

eg. [Pt(NH3) (Py) ClBr]

(iv) Complex with general formula [M(AB)2] have 2 geometrical isomers (Where AB is
unsymmetrical Bidentate ligand)

E.g; [Pt(gly)2]

Geometrical isomers with Coordination number = 6 (Octahedral complex)

node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

(i) [Ma4b2] has 2 geometrical isomers

E.g : [Fe(NH3)4Cl2]

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(ii) [Ma4bc] has 2 geometrical isomers
E.g : [Fe(NH3)4ClCO3]

(iii) Facial and Meridional isomerism (Ma3b3 )

b
b a

+3
a eg. [Cr(NH3)3(H2O)3]
a

Facial (fac) b
Meridional[Mer]
Other examples of geometrical isomers in octahedral complexes.
General formula Total No. of geometrical isomers
Mabcdef 15
Ma2bcde 9
Ma2b2cd 6
Ma2b2c2 5
Ma3bcd 4
Ma3b2c 3
Ma3b3 2
Ma4bc 2
Ma4b2 2
Ma5b Nil
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

Ma6 Nil
Here M = central atom ; a, b, c, d, e, f = Monodentate ligands
(B) Optical Isomers
(a) Compounds which are mirror image of each other but non superimposable, are known as
optical isomers.
(b) An optically active complex is one which is asymmetric in nature i.e., not divisible into two
identical halves.

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(c) The complex which rotates plane polarised light to left hand side is laevo rotatory i.e. ' ' or
'–' and if the complex rotates the plane polarised light to right hand side then it is dextro
rotatory 'd' or '+'.
(d) Thus complexes which have same physical and chemical properties but differ in their action
towards plane polarised light are called as optical isomers.
(e) The 'd' and ' ' isomers of a compound are called as Enantiomers.
Optical isomers with Coordination number = 6
n+ 2+
(i) [Ma2b2c2] [Pt(py)2(NH3)2Cl2]

(ii) [Mabcedf] [Pt(py)NH3NO2ClBrI]

Br
NO2 py

n+ 3+
(iii) [M(AA)3] [Co(en)3]
3+
en
en

Co

en
-form
n+ 2+
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

(iv) [M(AA)2ab] [Co(en)2NH3Cl]

2+
en
Cl

Co

H3 N NH3
en
Cis- -isomer

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(v) [M(AB)3] [Cr(gly)3]

gly

Cr
gly

gly

Cis or trans-d-isomer Cis or trans- -isomer

(vi) [Fe(NH3)2(en)Cl2]

Cl Cl
Cl Cl

en Fe Fe en

NH3 NH3
NH3
Cis-d-isomer Mirror Cis- -isomer

(vii) [Fe(en)2Cl2]

Cis-d-isomer Cis- -isomer

ORGANOMETALLIC COMPOUNDS
Compound in which C atom of a hydrocarbon or a ligand is directly bonded with a
metal/metalloid/non metal like B, P ets is known as organometallic compounds.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

R – Zn – R dialkyl zinc (Frankland reagent)

E.g; OMC
R – Mg – X Alkyl Magnesium halide (Grignards reagent)
APPLICATION OF COORDINATION CHEMISTRY
(a) Test of Ni+2 : Ni+2 ion gives rosy red ppt when react with dimethylglyoxime in weak alkaline
medium.
2 NH 4 OH
Ni 2dmg [Ni(dmg) 2 ]
Rosy Red ppt

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+3
(b) Test of Fe
FeCl3 + 3KSCN Fe(SCN) + 3KCl3
Potassium thiocyanate Blood red colour

+2
(c) Test of Cu
2
2Cu K 4 [Fe(CN)6 ] Cu2 [Fe(CN)6 ]
Chocolate brown ppt

(d) Brown ring test : Test for Nitrate ion

2 3
NO3 Fe 4H Fe NO 2H2 O (Redox reaction)

Fe(H 2 O)6 SO 4 NO Fe(H 2 O)5 (N O) SO 4

brown ring complex

(e) AgCl or AgBr ppt are soluble in ammonia or NH4OH

2 NH 3
AgCl Ag NH 3 2
Cl
white ppt so lub le complex

(f) In photography: undecomposed AgBr (at the time of image development) is removed from
photographic film by using hyposolution [Na2S2O3.5H2O]

h 1
AgBr Ag Br2
2
3
AgBr 2Na 2S2 O 3 Na 3 Ag S2 O 3 2
NaBr
(undecomposed) so lub le complex

(g) Light blue colour of aqueous solution of CuSO4 turn into dark blue in presence of ammonia
4 NH 3
Cu H 2 O 4
SO 4 Cu NH 3 4
SO 4
light blue dark blue

(h) Wilkinson catalyst [RhCl(PPh3)3 is used for hydrogenation of alkene. (Homogeneous

catalysis)
4–
(i) [EDTA] is used for estimation of hardness of water.
2–
(j) [Ca(EDTA)] is used to remove Pb poison.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

2– +2 2– +2
[Ca(EDTA)] + Pb [Pb(EDTA)] + Ca
(k) Biological importance
+2
Chlorophyll (Mg) Haemoglobin (Fe ) Insulin (Zn)

Vitamin B12(Co) Corboxypeptide (Zn)

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EXERCISE-1 IMPORTANT QUESTIONS
1. Write the formulas for the following coordination compounds:
(i) Tetraamminediaquacobalt(III) chloride
(ii) Potassium tetracyanonickelate(II)
(iii) Tris(ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromidochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
Ans. (i) [CO(H2O)2 (NH3)4]Cl3 (ii) K2[Ni(CN)4]
(iii) [Cr(en)3]Cl3 (vi) [Pt(NH)3BrCl(NO2)]–
(v) [PtCl2(en)2](NO3)2 (vi) F4[Fe(CN)6]3
2. Write the IUPAC names of the following coordination compounds:
(i) [Co(NH3)6]Cl3 (ii) [Co(NH3)5Cl]Cl2
(iii) K3[Fe(CN)6] (iv) K3[Fe(C2O4)3]
(v) K2[PdCl4] (vi) [Pt(NH3)2Cl(NH2CH3)]Cl
Ans. (i) Hexaamminecobalt(III) chloride
(ii) Pentaamminechloridocobalt(III) chloride
(iii) Potassium hexacyanoferrate(III)
(iv) Potassium trioxalatoferrate(III)
(v) Potassium tetrachloridopalladate(II)
(vi) Diamminechlorido(methylamine)platinum(II) chloride
3. Explain hybrisation in [Co(NH3)6]3+ complex ion.
Ans. Complex ion [Co(NH3)6]3+ posses d2sp3 hybridisation, because Co+3 ion posses electronic
configuration 3d6, 4s0
3d 4s 4p

Hybrid ion [Co(NH3)6]3+ become a complex compounds. In which electrons in the orbitals of
metal ion rearrange and form d2sp3 hybridisation
3d 4s 4p
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

d2sp3 hybridisation
4. Explain on the basis of VBT that [Ni(CN)4]2– is a low spin complex ion.
Ans. In [Ni(CN)4]2– ion Nickel possess +2 oxidation state. Co-ordiation number is four.
Ni+2
(in free form)
3d 4s 4p

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On the basis of V.B.T. CN is a strong ligand. Thus, unpaired elctrons present in d-orbitals
become paired. Thus, it show dsp2 hybridisation as shown below.
3d 4s 4p

dsp2 hybridisation
5. Give type of hybridisation, shape and magnetic properties in the following complex ion.
(i) [Fe(H2O)6]2+ (ii) [NiCl4]2–
Ans. (i) [Fe(H2O)6]2+
Fe = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d6
3d 4s 4p
Fe =
+2

[Fe(H2O)6]2+ =
d2sp3 hybridisation
Hybridisation – d2sp3
Shape – Octahedral
Magnetic properties – Diamagnetic
(ii) [NiCl4]2–
3d 4s 4p
Ni =
+2

[NiCl4]2– =
3
sp
Hybridisation – sp3
Shape – Tetrahedral
Magnetic properties – Paramagnetic
6. Compare magnetic behaviour of the complexes [Fe(CN)6]4– and [FeF6]3–.
Ans. [Fe(CN)6]4– ion posses d2sp3 hybridisation.
Fe+2 = [Ar]3d6
3d 4s 4p
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

2 3
d sp
Due to absence of unpaired electron this complex is diamagnetic while [FeF6]3– posses five
unpaired electrons and it is paramagnetic in nature and possess sp3d2 hybridisation.
Fe+3 = 3ds
3d 4s 4p 4d

sp3 d2 hybridisation

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7. Write shape and magnetic properties of [Ni(CO)4] on the basis of V.B.T.
Ans. [Ni(CO)4]
Ni = [Ar] 3d8, 4s2
3d 4s 4p

sp3 hybridisation
Shape of [Ni(CO)4] = Tetrahedral
hybridisation = sp3
magnetic property = Paramagnetic
8. Draw figure to show the splitting of d obitals in an octahedral crystal field.
Energy dx2– y2,dz2
z eg

y +3/5
Barycentre

Ans. –2/5
x
Average energy t2g
of the d orbitals dxy dyz dxz
in a spherical field
Splitting of the d
Metal orbitals in a
d orbitals octahedral crystal field
dx2–y2, dz2 dxy, dyz, d xz
9. What is spectrochemical series? Explain the difference between a weak field and a strong field
ligand.
Ans. Spectrochemical series is an experimentally determined series based on the absorption of light by
complexes with different ligands. A spectrochemical series is the arrangement of common
ligands in the increasing order of their crystal - field splitting energy (CFSE) values. The ligands
present on the R.H.S of the series are strong field ligands while that on the L.H.S are weak field
ligands. Also, strong field ligands cause higher splitting in the d orbitals than weak field ligands.
I–< Br– < S2– < SCN– < Cl– < N3– < OH– < C2O42– < ~H2O < NCS– < edta4– < NH3 < en– < CN– < CO
10. Give the oxidation state, d- orbital occupation and coordination number of the central metal ion
in the following complexes :
(i) K3[Co(C2O4)3] (ii) cis-[Cr(en)2Cl2]Cl
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

(iii) (NH4)2[CoF4] (iv) [Mn(H2O)6]SO4

Ans. (i) K3[Co(C2O4)3]
The central metal ion is Co3+.
Its coordination number is 6.
The oxidation state can be given as:
x – 6 = –3
x = +3
The d orbitals occupation for Co3+ is t 62g e g0 .

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(ii) cis-[Cr(en)2Cl2]Cl
The central metal ion is Cr3+.
The coordination number is 6.
The oxidation state can be given as :
x + 2(0) + 2(–1) = +1
x – 2 = +1
x = +3
The d orbitals occupation for Cr3+ is t 32g .e g0 .
(iii) (NH4)2[CoF4]
The central metal ion is Co2+.
The coordination number is 4.
The oxidation state can be given as:
x – 4 = –2
x = +2
The d orbitals occupation for Co2+ is t 52g .e 2g .
(iv) [Mn(H2O)6]SO4
The central metal ion is Mn2+.
The coordination number is 6.
The oxidation state can be given as:
x + 0 = +2
x = +2
The d orbitals occupation for Mn2+ is t 32g e g2 .
11. Discuss the nature of bonding in metal carbonyls.
Ans. The metal -carbon bonds in metals carbonyls have both and characters. A bond is formed
when the carbonyl carbon donates a lone pair of electrons to the vacant orbital of the metal. A
bond is formed by the donation of a pair of electrons from the filled metal d orbital into the
vacant anti-bonding * orbital (also known as back bonding of the carbonyl group). The bond
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

strengthens the bond and vice - versa. Thus, a synergic effect is created due to this metal -
ligand bonding. This synergic effect strengthens the bond between CO and the metal.

M C O

Synergic bonding in metal carbonyls

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12. Write the formula of ionisation isomer of [Cr(H2O)4Br2]Cl.
Ans. [Cr(H2O)4BrCl]Br
13. Indicate the types of isomerism exhibited by the following complexes and draw the structures for
these isomers:
(i) K[Cr(H2O)2(C2O4)2
(ii) [Co(en)3]Cl3
(iii) [Co(NH3)5(NO2)](NO3)2
(iv) [Pt(NH3)(H2O)Cl2]
Ans. (i) Both geometrical (cis-, trans-) isomers for K[Cr(H2O)2(C2O4)2] can exist. Also, optical
isomers for cis-isomer exist.
OH2 OH2
O O O OH2
Cr Cr
Geometrical isomers O O OO
OH 2 O
Trans cis
Trans-isomer is optically inactive. On the other hand, cis-isomer is optically active exist.

OH 2 OH
O OH2 OH2 2 O
Cr Cr
O O O O
O O

(ii) Two optical isomers for

CH2
H2N CH2
CH2–H2N H2N
Co NH2
N N
CH2–H2N NH2 = Co
H2N CH2 N N
CH2 H2N
exist
Two optical isomers are possible for this structure.

N N
N N N N
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

Co Co
N N N N
N N
(iii) [CO(NH3)2(NO2)] (NO3)2
A pair of optical isomers:
NH3 NH3
O2N NH3 H 3N NO2
Co Co
H3N NH3 H 3N NH3
NH3 NH3
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It can also show linkage isomerism.
[CO(NH3)5(NO2)] (NO3)2 and [CO(NH3)5(ONO)](NO3)2
It can also show ionization isomerism.
[Co(NH3)5(NO2)] (NO3)2 ; [CO(NH3)5(NO3)](NO3) (NO2)
(iv) Geometrical (cis–, trans–) isomers of [Pt(NH3)(H2O)Cl2] can exist.
Cl NH3 H 3N Cl
Pt Pt
Cl H2O Cl H 2O

cis trans
14. Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionization isomers.
Ans. When ionization isomers are dissolved in water, they ionize to give different ions. These ions
then react differently with different reagents to give different products.
[CO(NH3)5Cl]SO4 + Ba2+ BaSO4
White precipitate
[CO(NH3)5Cl]SO4 + Ag+ No reaction

[CO(NH3)5SO4]Cl + Ba2+ No reaction

[CO(NH3)5Cl]SO4 + Ba2+ AgCl

White precipitate
15. Draw the structure of optical isomers of:
(i) [Cr(C2O4)3]3– (ii) [PtCl2(en)2]2+ (iii) [Cr(NH3)2Cl2(en)]+
Ans. (i) [Cr(C2O4)3]3–
3– ox 3–
ox

ox Cr Cr ox

ox ox
3– 3–
[Cr(OX)3] Mirror [Cr(OX)3]
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

(dextro) (Laevo)
(ii) [PtCl2(en)2]2+
Cl 2+ Cl 2+
Cl Cl
en Pt en
Pt

en en
dextro Mirror laevo

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(iii) [Cr(NH3)2Cl2(en)]+
Cl + Cl +
Cl Cl
en Cr en
Cr

NH3 H3N
NH3 NH3
dextro Mirror laevo
16. Draw all the isomers (geometrical and optical) of:
(i) [CoCl2(en)2]+ (ii) [Co(NH3)Cl(en)2]2+ (iii) [Co(NH3)2Cl2(en)]+
Ans. (i) [CoCl2(en)2]+
Cl Cl

en Co en Co en
en

Cl Cl
Mirror
Trans [CoCl2(en)2]+ isomer-optically inactive
(Superimposable mirror images)
Cl Cl
Cl Cl
en Co Co en

en en
Mirror
Cis [CoCl2(en)2]+ isomer-optically active
(non-superimposable mirror images)
In total, three isomers are possible.
(ii) [Co(NH3)Cl(en)2]2+
Cl Cl
NH3
en Co
en en Co

NH3 en
Cis
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

Trans
Cl Cl
NH3 H3N
en Co Co en

en en
Cis Mirror
Trans - isomers are optically inactive.
Cis - isomers are optically active.

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(iii) [Co(NH3)2Cl2(en)]+

Cl Cl
Cl Cl
en Co Co en

NH3 NH3
NH3 NH3
Mirror
17. Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of these will exhibit
optical isomers?
Ans. [Pt(NH3)(Br)(Cl)(py)]
H3N Cl H3N Br H3N Cl
Pt Pt Pt
Py Br Py Cl Br Py

From the above isomers, none will exhibit optical isomers. Square planar complexes rarely
show optical isomerization. They do so only in the presence of unsymmetrical chelating
agents.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

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EXERCISE-2 MULTIPLE CHOICE QUESTIONS
INTRODUCTION
1. In K4[Fe(CN)6] –
(a) (CN) are linked with primary valency (b) (CN) are linked with secondary valency
(c) K are linked with secondary valency (d) K are linked with non-ionic valency
2. Which of the following acts as a bidentate ligand in complex formation –
(a) Acetate (b) Oxalate (c) Thiocyanate (d) EDTA
3. The co-ordination number of cobalt in the complex [Co(en)2Br2]Cl2 is –
(a) 2 (b) 6 (c) 5 (d) 4
4. Which of the following ligands forms a chelate –
(a) Acetate (b) Oxalate (c) Cyanide (d) Ammonia
5. According to Werner's theory –
(a) Primary valency can be ionized
(b) Secondary valency can be ionized
(c) Primary and secondary valencies both cannot be ionized
(d) Only primary valency cannot be ionized
6. Which of the following is not true for ligand-metal complex –
(a) Larger the ligand, the more stable is the metal-ligand bond
(b) Highly charged ligand forms strong bond
(c) Larger the permanent dipole moment of ligand, the more stable is the bond
(d) Greater the ionization potential of central metal, the stronger is the bond
7. Which is the example of hexadentate ligand –
(a) 2, 2—dipyridyl (b) Dimethyl glyoxime
(c) Aminodiacetate ion (d) Ethylene diammine tetra acetate ion [EDTA]
8. The coordination number of a metal in coordination compounds is –
(a) Same as primary valency (b) Sum of primary and secondary valencies
(c) Same as secondary valency (d) None of these
9. Ligand in a complex salt are –
(a) Anions linked by coordinate bonds to a central metal atom or ion
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Coordination Compound

(b) Cations linked by coordinate bonds to a central metal atom or ion

(c) Molecules linked by coordinate bonds to a central metal atom or ion
(d) Ions or molecules linked by coordinate bonds to a central metal atom or ion
10. The coordination number of a central metal atom in a complex is determined by :
(a) The number of ligands around a metal ion bonded by sigma and pi-bonds both.
(b) The number around a metal ion bonded by pi-bonds
(c) The number of ligands around a metal ion bonded by sigma bonds
(d) The number of only anionic ligands bonded to the metal ion

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11. Potassium ferrocyanide is a
(a) Normal salt (b) Mixed salt (c) Double salt (d) Complex salt
12. That ion or molecule which forms a complex compound with transitional metal ion is called
(a) Recipient (b) Ligand (c) Coordinate ion (d) No special name
13. An example of a double salt is
(a) Bleaching powder (b) Hypo (c) K4[Fe(CN)6] (d) Potash alum
NOMENCLATURE OXIDATION
14. How many ions are produced in aqueous solution of [Co(H2O)6]Cl2
(a) 2 (b) 3 (c) 4 (d) 6
15. IUPAC name of [Pt(NH3)3(Br)(NO2)Cl]Cl is
(a) Triamminechlorobromonitroplatinum (IV) chloride
(b) Triamminebromonitrochloroplatinum (IV) chloride
(c) Triamminebromochloronitroplatinum (IV) chloride
(d) Triamminenitrochlorobromoplatinum (IV) chloride
16. The IUPAC name of [Ni(CO)4] is :
(a) Tetra carbonyl nickel (II) (b) Tetra carbonyl nickel (0)
(c) Tetra carbonyl nickelate (II) (d) Tetra carbonyl nickelate (0)
–
17. The oxidation number of Pt in [Pt(C2H4)Cl3] is
(a) + 1 (b) + 2 (c) + 3 (d) + 4
ISOMERISM AND MAGNETIC PROPERTIES
18. The number of unpaired electrons in the complex ion [CoF6]3– is (Atomic no. of Co = 27)
(a) Zero (b) 2 (c) 3 (d) 4
19. Which would exhibit co-ordination isomerism
(a) [Cr(NH3)6] [Co(CN)6] (b) [Co(en)2Cl2]
(c) [Cr(NH3)6]Cl3 (d) [Cr(en)2Cl2]+
20. [Co(NH3)5NO2]Cl2 and [Co(NH3)5(ONO)]Cl2 are related to each other as
(a) Geometrical isomers (b) Optical isomers
(c) Linkage isomers (d) Coordination isomers
21. [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br are examples of which type of isomerism
(a) Linkage (b) Geometrical (c) Ionization (d) Optical
+3
22. [Ti(H2O)6] is paramagnetic in nature due to
(a) One unpaired (b) Two unpaired (c) Three unpaired (d) No unpaired
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23. Coordination isomerism is caused by the interchange of ligands between the

(a) Cis and Trans structure (b) Complex cation and complex anion
(c) Inner sphere and outer sphere (d) Low oxidation and higher oxidation states
2– 2–
24. Amongst Ni(CO)4, [Ni(CN)4] and [NiCl4]
(a) Ni(CO)4 and [NiCl4]2– are diamagnetic and [Ni(CN)4]2– is paramagnetic
(b) [NiCl4]2– and [Ni(CN)4]2– are diamagnetic and Ni(CO)4 is paramagnetic
(c) Ni(CO)4 and [Ni(CN)4]2– are diamagnetic and [NiCl4]2– is paramagnetic
(d) Ni(CO)4 is diamagnetic and [NiCl4]2– and [Ni(CN)4]2– are paramagnetic

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25. [Co(NH3)4Cl2]+ exhibits
(a) Geometrical isomerism (b) Optical isomerism
(c) Bonding isomerism (d) Ionisation isomerism
26. Which of the following compounds exhibits linkage isomerism
(a) [Co(en)3]Cl3 (b) [Co(NH3)6[Cr(CN)6]
(c) [Co(en)2 NO2Cl] Br (d) [Co(NH3)5Cl]Br2
27. The possible number of optical isomers in [Co(en)2Cl2] are
(a) 2 (b) 3 (c) 4 (d) 6
28. The number of unpaired electrons in Ni(CO)4 is
(a) Zero (b) One (c) Three (d) Five
HYBRIDISATION AND GEOMETRY
29. One mole of the complex compound Co(NH3)5Cl3 gives 3 moles of ions on dissolution in water.
One mole of the same complex reacts with two moles of AgNO3 solution to yield two moles of
AgCl(s). The structure of the complex is
(a) [Co(NH3)5Cl]Cl2 (b) [Co(NH3)3Cl3].2NH3
(c) [Co(NH3)4Cl2]Cl.NH3 (d) [Co(NH3)4Cl]Cl2.NH3
30. In the formation of K4[Fe(CN)6] the hybridisation involved is
(a) sp2 (b) d2sp3 (c) d3sp2 (d) d4p
31. Which complex has square planar structure
(a) Ni(CO)4 (b) [NiCl4]2– (c) [Ni(H2O)6]2+ (d) [Cu(NH3)4]2+
32. [CoF6]–3 is formed by ..... hybridization
(a) d2sp3 (b) d3sp2 (c) d2sp3 (d) sp3d2

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b b b d a b d c d c
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Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. d b d b c b b d a c
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. c a a c a c b a a b
Q. No. 31 32
Ans. d c

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CHAPTER–6 : HALOALKANES & HALOARENES

• Chapter at a glance 87-92
• Exercise-1_Important Questions 93-100
• Exercise-2_Multiple Choice Questions 101-105
CHAPTER AT A GLANCE
HALOGEN DERIVATIVES
Compounds derived from hydrocarbons by replacement of one or more H-atoms by
corresponding no. of halogen atoms are known as halogen derivatives.
CLASSIFICATION
On the basis of nature of hydrocarbon from which they are obtained, halogen derivatives can be
classified as:
Halogen Derivatives

Alkyl halides Alkenyl halides Alkynyl halides Aryl haides

Mono halides Di-halides Tri-halides Tetra halides

Primary halides Secondary halides Tertiary halides

MONOHALIDES:
General Methods of Preparation of Monohalides
(1) By direct halogenation of alkanes :
R—H + Cl2 U.V.light R—Cl + HCl
(excess)
(2) By the addition of H—X on alkenes :
R—CH CHR + HX RCH2—CHXR
E.g: CH2 CH2 + HX CH3 —CH2X
E.g: CH3–CH CH2 + HX CH3 CH CH3
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

X
Isopropyl halide
(3) By Alcohols :
(a) By the action of hydrogen halides :
R—CH2—OH H X RCH2—X
(b) By the action of phosphorous halides :
R—OH + PCl5 R—Cl + POCl3 + HCl
3R—OH + PCl3 3RCl + H3PO3
PBr3 and PI3 are less stable, thus for bromides (P + Br2) and for iodides (P + I2) mixture is used.

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(c) By reaction with thionyl chloride (Darzen's procedure) :
Pyridine
R—OH + SOCl2 (1mole )
R—Cl + SO2 + HCl
One mole One mole
Because of less stability of SOBr2 and SOI2, R—Br and RI cannot be obtained by this method.
(4) By halide exchange:
R–Cl or R—Br + KI Acetone R–I + KCl or KBr (Conant finkelstein reaction)
2CH3Cl + Hg2F2 Water
2CH3–F + Hg2Cl2 (Swart reaction)
Physical Properties
(a) The lower members CH3F, CH3Cl, CH3Br , C2H5Cl and C2H5F are gases at room temp.
(b) Higher B.P. than parent alkanes.
Decreasing order of B.P. is : R – I > R—Br > R—Cl > R—F
among isomeric R—X, decreasing order of B.P. is : Primary > Secondary > tertiary
(c) R—F and R—Cl lighter than water
R—Br and R—I heavier than water
Decreasing order of density is : R—I > R—Br > R—Cl > R—F
(d) R—X are polar co-valent compounds but insoluble in water because they can not form
H–bonds. They dissolve in organic solvents.
(e) Dipole moment order–

(i) CH3Cl > CH3F > CH3Br > CH3I (ii) Cl > Cl

Chemical Properties
Nucleophilic substitution reaction (SN):
Replacement of Product
HOH(Boil)
(a) R—OH (alcohol) + HX
X by — OH

KOH aq.
(b) R—OH (alcohol) + KX
X by — OH

(c) Moist Ag2O

R—X R—OH (alcohol) + AgX
X by — OH

KSH alc.
(d) R—SH + KX
X by –SH
(Mercapto Gp.) Alkane thiol
(Mercaptane)
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

NaSR'
(e) RSR' + NaX
X by SR
Thioether
R' COOAg,
(f) R' COOR + AgX
X by(R'COO)
(Alkyl alkanoate) ester

(g) Reaction with KCN and AgCN :

Alc.
R— X KCN R—C N + R—NC + KX
Ionic cyanide Isocyanide
(major) (minor)

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CN ion is an ambident nucleophile.

.. Alc.
R—X + Ag—CN R—N C + R—CN + AgX
covalent isocyanide Cyanide
(Major) (Minor)
(h) Reaction with KNO2 and AgNO2 :
Alc.
R—X + KO—NO R—O—N = O + R – NO2 + KX
Ionic Alkyl nitrile Nitro alkane
(Major) (Minor)
O
.. Alc.
R — X + Ag—O—N=O R—N
—
+ R—O—N=O + AgX
covalent O
Nitroalkane Alkyl nitrile
(major) (minor)
(i) Reaction with NaOR' (Sodium alkoxide) :
R—X + NaOR' R—OR' + NaX
(williamson synthesis reaction)
(j) Reaction with NH3:
R – X NH3 R – NH 2 R —X
R – NH – R R—X
R—N—R
R
R–X

R
R—N—R
R
(Quaternary salt)
(k) Reaction with CH CNa :
R—X + CH CNa R—C CH + NaX
CH3
–+
If CH3 C X + CH C Na CH C CH2 + NaX + CH CH
CH3 CH3
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

(3° halide) (Elimination is more)

Dehydrohalogenation: Alkyl halides undergo -elimination on treatment with KOH (alc.) or NaNH2.

R — C H 2 — CH 2 — X KOH (alc.) R—CH CH2 + HX

CH3—CH2—CH2—CH2—Br + KOH(alc.) CH3—CH2—CH CH2 + HBr
H Br
Alc. KOH
CH3–CH–CH–CH3 CH3—CH CH—CH3 + CH3—CH2—CH CH2 + HBr

But-2 -ene (80%) But-1-ene (20%)

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Wurtz Reaction : 2RX 2Na Dry ether R — R 2NaX
When a mixture of different alkyl halides, (R1 - X) and (R2 - X) is used a mixture of alkane
is formed -
R1—X + 2Na + X—R2 Dry ether R1—R2 + R1—R1 + R2—R2 + NaX
Formation of Organometallic compounds :
dry ether
(i) R—X + Mg RMgX (Grignard reagent)
dry ether
(ii) 2C2H5Br + 2Zn (C2H5)2 Zn (Frankland reagent) + ZnBr2
(iii) 4C2H5Cl + 4Na / Pb (C2H5)4 Pb + 4NaCl + 3Pb
Sodium lead Alloy Tetra ethyl lead (used as antiknocking agent)
Friedel - Crafts reaction :
CH3
AlCl3(anhyd)
+ CH3Cl + HCl
Benzene Toluene
DIHALIDES
General formula CnH2nX2 .Two H - atom of alkanes, replaced by two halogen atoms to form
dihalides.
Dihalides are classified as :
(a) Gem dihalide : The term Gem is derived from geminal means - same position.
Two similar halogen atoms are attached to same C - atom
Ex. CH3CHX2 Ethylidene dihalide (1, 1 - Dihalo ethane)
CH3
CX2 Isopropylidene dihalide (2, 2 - Dihalo propane)
CH3
(b) Vic dihalides : Vic term from - Vicinal means adjacent C - atoms
Two halogen atoms are attached on adjacent carbon atom.
H
CH2—CH2
Ex. H—C—CH—CH2 Vic and Gem dihalides are position isomers.
X X
H X X
Ethylene dihalide Propylene dihalide
(1,2-Dihaloethane) (1,2-Dihalopropane)
(c) dihalides : Halogen atoms are attached with terminal C - atom. They are separated by 3
or more C - atoms. They are also known as polymethylene halides.
Ex. CH2—CH2—CH2—CH2 (1,4-Dihalobutane)
Tetramethylene dihalide
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

X X

Chloro can also be used in preparation of D.D.T.

H2SO4
Cl
CCl3CH = O + 2H Cl (conc.) CCl3CH
Cl
Dichloro diphenyl trichloro
(DDT)

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Air and light
Oxidation : CHCl3 + [O] COCl2 + HCl
Phosgene gas or
Carbonyl Chloride
(Poisonous gas)
CHCl3 is stored in dark coloured bottles which are filled upto the brim to prevent oxidation of
CHCl3 into COCl2 and 1% ethanol is also added to chloroform
Cl OC2H5
O=C + 2HO — C2H5 –2HCl
O=C
Cl OC2H5
[Poisonous] Diethyl carbonate
[Non-poisonous]
Grignard Reagent
General Method of Preparation
Grignard reagents are prepared in the laboratory by the action of alkyl halides on magnesium
metal in the presence of dry ether.
dry
R – X + Mg ether R—Mg—X
(Grignard reagent)
(Alkyl magensium halide)
The ease of formation of Grignard reagent is in the order RI > RBr > RCl
Ether is used to dissolve the Grignard reagent by coordination.
Haloarene
If halogen atom is directly attached to the benzene ring, then compound is called as Haloarene.
CH3
CH3 Cl
Cl Cl
Ex.
Cl
(Chlorobenzene) (2–Chlorotoluene) (2,4–Dichlorotoluene)

General Methods of Preparation

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Cl

AlCl3
(1) + Cl2 + HCl

OH Cl

(2) + PCl5 + POCl 3 + HCl

3C6H5OH + POCl3 (C6H5)3 PO4 + 3HCl

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Chemical Properties
Cl OH

(i) 623K, 300 atm

(1) + NaOH (ii) H
+ NaCl

Presence of electron withdrawing group on ring makes the nucleophilic substitution easier.
Reactivity Order : (Towards nucleophilic substatitution)
Cl Cl Cl Cl
NO2 NO 2 NO 2
> > >
NO2 NO2 NO2
(2) Fittig reaction :
dry ether
Cl + 2Na + Cl + 2NaCl

(Diphenyl)
(3) Wurtz fittig reaction :
dry ether
Cl + 2Na + ClCH2CH2CH3 CH2CH2CH3 + 2NaCl
(4) Electrophilic Substitution Reaction :
Cl Cl C
Cl
anhy. FeCl3
(i) + Cl2 +

Cl
(Major)
Note : Cl is o– and p– directing group.
Cl Cl Cl
NO2
conc. H2SO4
(ii) + HNO3 +

NO2
(Major)
Cl Cl Cl
SO3H
+ conc. H2SO4
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

(iii) +

SO3H
(Major)
Cl Cl Cl
CH3
anhy. AlCl3
(iv) + CH3Cl +

CH3
(Major)

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EXERCISE-1 IMPORTANT QUESTIONS

1. Why is sulphuric acid not used during the reaction of alcohols with KI ?
Ans. In the presence of sulphuric acid (H2SO4), KI produces HI
2KI + H2SO4 2KHSO4 + 2HI
Since H2SO4 is an oxidizing agent, it oxidizex HI in I2
2HI + H2SO4 I2 + SO2 + H2O
As a result, the reaction between alcohol and HI to produce alkyl iodide cannot occur.
So in place of H2SO4 a non oxidising acid such as H3PO4 is used.
2. Among the isomeric alkanes of molecular formula C5H12, identify the one that on photochemical
chlorination yields.
(i) A single monochloride (ii) Three isomeric monochlorides (iii) Four isomeric monochlorides
CH3 CH3
Cl2
Ans. (i) CH3–C–CH3 gives only one monochloride CH3–C–CH2–Cl
CH3 CH3
Neopentane (C5H12)

(ii) Cl2
CH3–CH2–CH2––CH2––CH3 CH3–CH2–CH2–CH2–Cl (I)
n-pentane
CH3–CH2–CH2–CH–CH3 (II)
Cl
CH3–CH2–CH–CH2–CH3 (III)
Cl
C
C–C–C–C–Cl
C
a
CH3 C–C–C–C
a
(iii) b c d Cl2 Cl
CH3–CH–CH2–CH3 gives four monochloride C
C–C–C–C
Cl
C
C–C–C–C
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

Cl
3. Draw the structure of major monohalo products in each of the following reactions :
OH CH2CH3
Br2,heat or
(i) + SOCl2 (ii) UVlight
O2N
CH2OH CH3
heat
(iii) + HCl (iv) + HI
HO
(v) CH3CH2Br + NaI (vi) heat
+ Br2 UV light

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OH Cl
Ans. (i) + SOCl2 + SO2 + HCl

Br
CH2CH3 CH–CH3
(ii) Br2,heat or 1 2
+ HBr
UVlight
O2 N O2 N
CH2OH CH2Cl
heat
(iii) + HCl + H2O
HO HO
CH3 CH3
(iv) + HI I

(v) CH3—CH2Br + NaI CH3CH2I + NaBr

Br
3
2
(vi) + Br2 UVheat
light + HBr
1
4. Identify A, B, C, D, E, R and R1 in the following:
dry ether
Br + Mg (A) (B)
Dry ether D2O
R–Br + Mg C CH3CHCH3
D
CH3 CH3
Na ether Mg H2O
CH3–————CH3 R1 – X D E

CH3 CH3
Active-H
dry ether
Ans. Br + Mg MgBr + Mg(OH)Br
(A) (B)
CH3
Dry ether D2O
RBr + Mg CH3–CH–MgBr CH3–CH–CH3
(C)
D
Therefore, the compounds R – Br is
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

CH3
CH3CHCH3 R'–X is CH3–C–X
Br CH3
Therefore, compound D is
CH3 CH3
CH3–C–MgBr and, compound E is CH3–CH
CH3 CH3

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5. A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro
compound C5H9Cl in bright sunlight. Identify the hydrocarbon.

Ans.
Cyclopentane (C5H10)
The reactions involved in the question are :
No reaction

Cl

Cyclopentane
Mono chlorocyclopentane
(C5H10)

6. Write the equations for the preparation of 1-iodobutane from

(i) 1-butanol (ii) 1-chlorobutane (iii) but-1-ene
Ans. (i) CH3 CH 2 CH 2 CH 2 OH Al O
CH 3 CH 2 CH CH 2
2 3 H Br
R 2 O2 /
NaI
CH3 CH 2 CH 2 CH 2 Br CH3 CH 2 CH 2 CH 2 I
dry acetone
(ii) CH3 CH 2 CH 2 CH 2 Cl NaI (Finkelstein reaction)
NaCl CH 3 CH 2 CH 2 CH 2 I
Peroxide
(iii) CH3–CH2–CH=CH2 + HBr
(Anti-Markovnikov's addition)
NaI/
NaBr + CH3–CH2–CH2–CH2–I CH3–CH2–CH2–CH2–Br
dry acetone
7. Predict all the alkenes that would be formed by dehydrohalogenation of the following halides
with sodium ethoxide in ethanol and identify the major alkene.
(i) 1-Bromo-1-methyllcyclohexane (ii) 2-Chloro-2-methyllbutane
(iii) 2,2, 3-Trimethyl-3-bromopentane
CH3
Br CH3
Ans. (i) C2H5ONa/C2H5OH
+ HBr
(Only one alkene)
CH3 CH3
C2H5ONa/C2H5OH
(ii) CH3–CH2—C—CH3 –HCl CH3—CH=C—CH3
Cl 2-methyl-2-butene (major)
+
CH3
CH3–CH2—C=CH2
2-methyl-1-butene (minor)
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

CH3 CH3 CH3

C2H5ONa/C2H5OH
(iii) CH3–C–—C–CH2–CH3 –HBr CH3–C–—C=CH–CH3
CH3 CH3 CH3 CH3
3,4,4-Trimethylpent-2-ene (I) (major)
+
CH3 CH2
CH3–C–—C–CH2–CH3
CH3
2-ethyl-3,3-dimethylbut-1-ene (II) (minor)

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8. Write the structure of the major organic product in each of the following reactions.
acetone ethanol
(i) CH3 CH 2 CH 2 Cl NaI heat
(ii) (CH3 )3 CBr KOH heat

water aq. acetone

(iii) CH3 CH(Br)CH 2 CH 3 NaOH (iv) CH3 CH 2 Br KCN
(v) C6H5ONa + C2H5Cl (vi) CH3CH2CH2OH+SOCl2
Peroxide
(vii) CH3 CH 2 CH CH 2 HBr (viii) CH3CH=C(CH3)2 + HBr
acetone
Ans. (i) CH3CH2CH2Cl + NaI CH3CH2CH2I + NaCl
heat
(Finkelstein reaction)
Ethanol
(ii) (CH3)3CBr + KOH CH3–C=CH2 + KBr + H2O
Heat
CH3
(Dehydrohalogenation)
water
(iii) CH3 CH(Br)CH 2 CH3 NaOH CH3 CH(OH)CH 2CH3 NaBr
aq.ethanol
(iv) CH3 CH 2 Br KCN Nucleophilic CH 3CH 2CN KBr
substitution

(v) C6 H 5 ONa C2 H5Cl Williamson 's C 6 H5 O C 2 H 5 NaCl

synthesis

(vi) CH 3 CH 2 CH 2 OH SOCl2 CH 3CH 2 CH 2 Cl SO 2 HCl

Peroxide
(vii) CH3CH 2CH CH 2 HBr Anti Markovnikov 's CH 3 CH 2 CH 2CH 2 Br
addition

Br
(viii) CH3CH=C(CH3)2 + HBr CH3–CH2–C–CH3
(Markovnikov
addition) CH3
9. Write the mechanism of the following reaction :
EtOH H 2O
nBuBr KCN nBuCN
Ans. The given reaction is :
EtOH H 2O
nBuBr KCN nBuCN
The given reaction is an SN2 reaction. In this reaction, CN— acts as the nucleophile and attacks
the carbon atom to which Br in attached. CN– ion is an ambident nucleophile and can attack
through both C and N. In this case, it attacks through the C- atom.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

C3H5 C 3H 5
C–Br NC C Br
H H H
H

C3H5
–
NC—C + Br
H
H

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10. Arrange the compounds of each set in order of reactivity towards SN2 displacement :
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-Bromo-2-methylbutane
(iii) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-2-methylbutane,
1-Bromo 3-methylbutane.
1
Ans. (i) SN 2
Hindrance on carbon
Br Br
CH3CH2CH2CH2CH2—Br > CH3CH2CH2CHCH3 > CH3CH2CCH3
CH3
1-Bromopentane (1°) 2-Bromopentane (2°) 2-Bromo-2-methylbutane (3°)
CH3 Br Br
(ii) CH3CHCH2CH2Br > CH3CHCHCH3 > CH3CCH2CH3
CH CH3
1-Bromo-3-methylbutane 2-Bromo-3-methylbutane 2-Bromo-2-methylbutane
(1°) (2°) (3°)
Since steric hindrance in alkyl halides increases in the order of 1° < 2° < 3°, the increasing order
of reactivity towards SN2 displacement si 3° < 2° < 1°.
Reactivity towards SN2 is
2-Bromo-2-methylbutane < 2-Bromo-3-methylbutane<1-Bromo-3-methylbutane
CH3
(iii) CH3–CH2–CH2–CH2–Br CH3–CH–CH2–CH2–Br

1-Bromobutane (1°) 1-Bromo-3-methylbutane (1°)

CH3 CH3
CH3–CH2–CH–CH2–Br CH3–C–CH2–Br
CH3
1-Bromo-2-methylbutane (1°) 1-Bromo-2,2-dimethylpropane
(more branching at nearer distance)
Hence, the increasing order of reactivity of the given compounds towards SN2 is :
1-Bromo-2, 2-dimethylpropane < 1-Bromo-2-methylbutane < 1-Bromo-3-methylbutane <
1-Bromobutane.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

11. Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH ?
Ans. C6H5 CHCl C6H5 (more reactive)
+
C6H5–CH2–Cl –Cl–
C6H5–CH2
Benzyl chloride (1°) 1° carbocation
Cl
+
C6H5–CH–C6H5 –Cl – C6H5–CH–C6H5
Chlorodiphenylmethane 2° carbocation
(more stable intermediate)

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12. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in the
presence of alcoholic KOH, alkenes are major products. Explain.
Ans. OH– ion is highly solvated in an aqueous solution and as a result, the basic character of OH– ion
decreases. Therefore, it cannot abstract a hydrogen from the -carbon. So
R–Cl + Aq. KOH R–OH + KCl
On the other hand, an alcoholic solution of KOH contains alkoxide (RO–) ion, which is a strong
base. Thus, it can abstract hydrogen from the -carbon of the alkyl chloride and form an alkene
by eliminating a molecule of HCl.
R – CH 2 – CH 2 – Cl KOH(alc.) R – CH CH 2 KCl H 2O
Alkyl chloride Alkene

13. How the following conversions can be carried out ?

(i) Propene to propan-1-ol (ii) 1-Bromopropane to 2-bromopropane
(iii) Benzene to 4-bromonitrobenzene (iv) Benzyl alcohol to 2-phenylethanoic acid
(v) Ethanol to propanenitrile (vi) Aniline to chloro benzene
(vii) 2- Chlorobutane to 3, 4-dimethylhexane
(viii) 2-Methyl-1-propene to 2-chloro-2-methyl propane
(ix) Ethyl chloride to propanoic acid (x) But-1-ene to n-butyliodide
(xi) 2-Chloropropane to 1- propanol (xii) Isopropyl alcohol to iodoform
(xiii) Chlorobenzene to p-nitrophenol (xiv) 2-Bromopropane to 1-bromopropane
(xv) Chloroethane to butane (xvi) tert-Butyl bromide to isobutyl bromide
(xvii) Aniline to phenylisocyanide (xviii) Ethanol to but-1-yne
(xix) Propene to 1-nitropropane (xx) Toluene to benzyl alcohol
HBr/ Peroxide (i)BH3 /THF
Ans. (i) CH3 –CH=CH2 (Ani Markovnikov
CH 3 –CH 2 –CH2 –Br or CH3 –CH=CH 2
(ii) H2 O2 /OH
CH3CH 2CH 2 –OH
Propene addition ) 1°-Bromopropane

(Nucleophilic Aq. KOH/

substitution)
CH3–CH2–CH2–OH
Propan-1-ol
KOH(alc)/
(ii) CH 3 CH 2 CH 2 Br (Dehydrohalogenation)
CH 3 CH CH 2
1 Bromopropane Pr opene HBr Markovnikov
addition
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

Br
CH3—CH—CH3
2-bromopropane
Br Br
Br2/FeBr3 HNO3/H2SO
Dark (Nitration)
(iii)
Benzene Bromobenzene
NO2
4-Bromonitrobenzene
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CH2OH CH2Cl CH2CN
PCl3 KCN, aq.ethanol
(iv)
Benzyl Benzyl cryanide
alcohol (Hydrolysis) H+/H2O

2 1
CH2COOH

2-Phenylethanoic acid
redP / Br2 KCN,Aq.ethanol
(v) CH3 CH 2 OH CH3 CH 2 Br CH3 CH 2 CN
Ethanol Bromoethane Propanenitrile

+ –
NH2 N2Cl Cl
NaNO2+2HCl,
(vi) 273-278 K Cu2Cl2
+ N2

Aniline Benzenediazonium Chlorobenzene

chloride
Cl CH3 CH3
2Na/dry ether
(vii) 2CH3–CH–CH2–CH3 (Wurtz reaction)
CH3–CH2–CH–CH–CH2–CH3 + 2NaCl
2-chlorobutane 3,4-dimethylhexane
CH3 CH3
(viii) HCl
CH3–C=CH2 (Markovnikov
CH3–C–CH3
2-methyl-1-propene addition) Cl
2-chloro-2-methylpropane
KCN, aq. ethanol
(ix) CH3–CH2–Cl (nucleophilic
CH3–CH2–CN + KCl
Ethylchloride substitution) Propanenitrile
(Hydrolysis) H+/H2O

CH3–CH2–COOH
Propanoic acid
HBr/Peroxide
(x) CH3–CH2–CH=CH2 (Anti-Markovnikov
CH3–CH2–CH2–CH2–Br
But-1-ene addition) Bromobutane
Finkelstein
NaI/dry acetone
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

reaction

CH3–CH2–CH2–CH2–I
n-Butyl iodide
Cl
(xi) CH3–CH–CH3 KOH(alc)/
CH3–CH=CH2
B2H6/H2O2/OH
CH3CH2CH2OH
(Dehydrohalogenation)
2-Chloropropane Propene
HBr/Peroxide (Anti-Markovnikov
addition)
Aq.KOH/
CH3–CH2–CH2–OH CH3–CH2–CH2–Br
(Nucleophilic
1-Propanol substitution) 1-Bromopropane

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Cl O
(xii) CH –CH–CH CrO3
3 3 (Oxidation CH3–C–CH3
Isopropyl alcohol Propanone
NaOI (Iodoform
O reaction)

CH3–C–ONa + CHI3
Iodoform
Cl Cl OH
HNO3/H2SO4 (i) NaOH, 433 K
(xiii) (Nitration) (ii) dil HCl

Chlorobenzene
NO2 NO2
p-Chloronitrobenzene p-Nitrophenol
(Major product)
Br
(xiv) CH3–CH–CH3 KOH(alc)/
Dehydrohalogenation CH3–CH=CH2 + HBr
2-Bromopropane Propene
Anti-Markovnikov HBr/peroxide
addition)

CH3–CH2–CH2–Br
1-Broopropane
(xv) CH3 CH 2 Cl 2Na /dryether
Wurtz reaction
CH3 CH 2 CH 2 CH 3
Chloroethane Butane

Br
KOH(alc)/ HBr/Peroxide
(xvi) CH3–C–CH3 Dehydrohalogenation CH3–C=CH2 (Anti-Markovnikov CH3–CH–CH2–Br
addition)
CH3 CH3 CH3
Tert-Butylbromide 2-Methylpropene Isobutyl bromide
NH2 NC

CHCl3,3KOH,
(xvii) (Carbylamine reaction)

Aniline Phenyl isocyanide

(xviii) CH 3CH 2 OH SOCl2 .Pyridine
CH3 CH 2 Cl Na – C CH
CH 3 – CH 2 – C CH
Ethanol Chloroethane
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

(xix) CH3 CH CH2 HBr Peroxide

CH3 CH 2 CH 2 Br AgNO2
CH 3 CH 2 CH 2 NO 2
Pr opene 1 Bromppropane 1 Nitropropane

CH3 CH2Cl CH2OH

Cl2/UV NaOH(alc.)
(xx) or heat –NaCl

Toluene Benzyl chloride Benzyl alcohol

14. Write full name of DDT.
Ans. DDT Dichloro-Diphenyl Trichloroethane

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EXERCISE-2 MULTIPLE CHOICE QUESTIONS

(INTRODUCTION)
1. Gem- dibromide is:
(a) CH3CH(Br)CH(Br)CH3 (b) CH3CBr2CH3
(c) CH 2 (Br)CH 2 CH 2 Br (d) CH2 BrCH2 Br
2. Which of the following halide is 2o ?
(a) Isopropyl chloride (b) Isobutyl chloride (c) n-propyl chloride (d) n-butyl chloride
3. The general formula for alkyl halides is:
(a) Cn H2n 1X (b) Cn H2n 2 X (c) Cn Hn 1X (d) Cn H2n X
4. Which of the following structures is enantiomeric with the molecule given below :

(a) (b) (c) (d)

5. Molecules whose mirror image is non-superimposable over them are known as chiral. Which of
the following molecules is chiral in nature?
(a) 2-Bromobutane (b) 1-Bromobutane (c) 2-Bromopropane (d) 2-Bromopropan-2-ol
(NUCLEOPHILIC SUBSTITUTION REACTIONS (NSR)
6. Ethyl bromide can be converted into ethyl alcohol by –
(a) Heating with dilute hydrochloric acid and zinc
(b) Boiling with an alcoholic solution of KOH
(c) The action of moist silver oxide
(d) Refluxing methanol
7. C 2 H 5 Cl KCN X , 'X' is –
(a) C2 H6 (b) CH3CH2 CH2OH,
(c) CH3 C(CH3 )(OH) CH3 (d) C2 H5CN
8. The reactivities of methyl chloride, propyl chloride and chlorobenzene are in the order –
(a) Methyl chloride > propyl chloride > chlorobenzene
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

(b) Propyl chloride > methyl chloride > chlorobenzene

(c) Methyl chloride > chlorobenzene > propyl chloride
(d) Chlorobenzene > propyl chloride > methyl chloride
9. R X NaOH ROH NaX
The above reaction is classified as:
(a) Nucleophilic substitution (b) Electrophilic substitution
(c) Reduction (d) Oxidation
10. In nucleophilic aliphatic substitution, the nucleophiles are generally:
(a) Acids (b) Bases (c) Salts (d) Neutral molecules

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(EAR & ELIMINATION)
11. CH3–CH2–Cl alc.KOH
A, the product is :
(a) CH3CH2OK (b) CH3CHO
(c) CH3CH2OCH2CH3 (d) CH2 = CH2
12. Dehydrohalogenation of an alkyl halide is:
(a) An addition reaction (b) A substitution reaction
(c) An elimination reaction (d) An oxidation reaction
13. What product is formed when 1-chlorobutane react with alcoholic KOH –
(a) 1-butene (b) 2-butene (c) 1-butanol (d) 2-butanol
14. In which of the following, addition of HBr does not take place against Markownikoff's rule or
Anti-Markownikoff addition of HBr is not observed for –
(a) Propene (b) But-1-ene (c) But-2-ene (d) Pent-2-ene
15. The propene reacts with HBr to form –
(a) Ethane (b) Hexane (c) 1-bromo-propane (d) 2-bromo propane
(ESR, NAME REACTION)
16. The function of anhydrous AlCl3 in the Friedel-Craft's reaction is to –
(a) Absorb water (b) Absorb HCl
(c) To produce electrophile (d) To produce nucleophile
17. On treating a mixture of two alkyl halides with sodium metal in dry ether, 2-methyl propane was
obtained. The alkyl halides are :
(a) 2-chloropropane and chloromethane
(b) 2-chloropropane and chloroethane
(c) Chloromethane and chloroethane
(d) Chloromethane and 1-chloropropane
18. Toluene reacts with a halogen in the presence of iron (III) chloride giving ortho and para halo
compounds. The reaction is :
(a) Electrophilic elimination reaction
(b) Electrophilic substitution reaction
(c) Free radical addition reaction
(d) Nucleophilic substitution reaction
19. Which of the following is halogen exchange reaction?
(a) R X + NaI RI + NaX
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

(b) C=C + HX C—C

H X
ZnCl 2
(c) R – OH HX R – X H 2O
CH3 CH3 CH3
(d) + X2 Fe
dark +
X X
20. Benzene on treatment with a mixture of conc. HNO3 and conc. H2SO4 at gives –
(a) Nitrobenzene (b) m-dinitrobenzene (c) p-dinitrobenzene (d) o-dinitrobenzene

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(PHYSICAL PROPERTIES, CHEMICAL TEST)
21. Arrange the following compounds in increasing order of their boiling points.
CH3
H3C
(A) CH—CH2Br (B) CH3CH2CH2CH2Br (C) H3C C CH3
H3C
Br
(a) (B) < (A) < (C) (b) (A) < (B) < (C) (c) (C) < (A) < (B) (d) (C) < (B) < (A)
22. Arrange the following compounds in increasing order of their density.
(i) CH2Cl2 (ii) CHCl3 (iii) CCl4
(a) (iii) < (ii) < (iii) (b) (iii) < (i) < (ii) (c) (iii) < (i) = (ii) (d) (i) < (ii) < (iii)
23. Which is the correct increasing order of boiling point of the following compounds?
I-bromoethane, 1-bromopropane, 1-bromobutane, bromobenzene
(a) Bromobenzene < 1-bromobutane < 1-bromopropane < 1-bromoethane
(b) Bromobenzene < 1-bromoethane < 1-bromopropane < 1-bromobutane
(c) bromopropane < 1-bromobutane < 1-bromoethane < 1-bromobenzene
(d) bromoethane < 1- bromopropane < 1-bromobutane < 1-bromobenzene
24. Write the name of chemical test which is used to distinguish between ethyl Bromide and
Bromobenzene?
(a) Lucas test (b) Silver nitrate test (c) Neutral FeCl3 test (d) None of these
25. C2H5Cl + AgNO3 X + C2H5–NO2
What is X?
(a) White ppt of AgCl (b) Yellow ppt of AgCl
(c) Black ppt of AgCl (d) None of these
26. Allylic halide is –
(a) Compound in which halogen atom is bonded to sp3 hybridised carbon atom next to aromatic ring
(b) Compound in which halogen atom is bonded to sp3 hybridised carbon atom next to
carbon-carbon double bond
(c) Compound in which halogen atom is bonded to an alkyl group
(d) None of these above
27. Which of the following is primary bromide?
(a) 3-bromopentane (b) 2-bromopentane (c) 1-bromopentane (d) All of these
28. Common name given to 2-chloropropane.
(a) n-propyl chloride (b) isopropyl chloride (c) isobutyl chloride (d) None of these
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

29. What should be the correct IUPAC name for diethylbromomethane?

(a) 1-bromo-1, 1-diethylmethane (b) 3-bromopentane
(c) 1-bromo-1-ethylpropane (d) 1-bromopentane
H3C H

30. The IUPAC name of is –

H Br
CH3
(a) 2-bromopent-4-ene (b) 2-bromopent-3-ene
(c) 4-bromopent-2-ene (d) 4-bromopent-1-ene
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31. Compound containing Csp — X bond is –
(a) chloroethyne (b) chloropropane (c) chloropropene (d) All of these
(METHOD OF PREPARATION)
32. Alkyl halides can be synthesised from –
(a) alcohol (b) hydrocarbon (c) halogen exchange (d) All of these
33. Select the byproduct formed in the reaction.
ROH + PCl5 RCl + ..... +.....
(a) POCl3 + HCl (b) H3PO3 + No other byproduct
(c) H3PO3 + HCl (d) POCl3 + No other byproduct
CH3
+ X2 Fe/dark
34.

CH3 CH3
+
X X
This reaction is:
(a) Nucleophilic substitution (b) electrophilic substitution
(c) Nucleophilic elimination (d) electrophilic elimination
35. R — X + NaI R — I + NaX
The solvent which is used in this reaction is ?
(a) acetone (b) dry acetone (c) water (d) ethyl acetate
36. Alkyl halides can be obtained by all methods excepts –
ZnCl2
(a) CH3—CH2—OH + HCl (b) CH2=CH—CH3 + HBr
h
(c) C2H5OH + NaCl (d) CH3COOAg + Br2 / CCl4
(PHYSICAL & CHEMICAL PROPERTIES)
37. KCN is ...A... compound and AgCN is ...B... compound. Here, A and B refer to–
(a) ionic, covalent (b) ionic, ionic (c) covalent, ionic (d) covalent, covalent
38. In which case the approach of nucleophile is easy as shown in figure?
H
H
H C
Nu: X Nu: H X
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

H
H H
H
H H
H H
C C
Nu: H Nu: H
X X
H H C
H C H C
H
H H HH H

(a) methyl (b) Ethyl (c) Isopropyl (d) Tert-butyl

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39. The allylic and benzylic halides undergo –
(a) SN1 mechanism (b) SN2 mechanism
(c) Both SN1 and SN2 mechanism (d) None of the above
40. SN2 reaction proceeds with ..... while SN1 proceeds with .....
(a) racemisation, complete inversion (b) complete racemisation, inversion
(c) complete inversion, racemisation (d) inversion, racemisation
41. Which of the following molecule is chiral?
(a) Butane-1-ol (b) Butan-2-ol (c) Butan-4-ol (d) All of these
42. CH3CH2MgBr is referred as –
(a) ethyl magnesium bromide (b) methyl magnesium bromide
(c) Grignard reagent (d) Both (a) and (c)
43. Aryl halide are extremely less reactive towards nucleophilic substitution reaction due to –
(a) resonance effect (b) instability of phenyl cation
(c) repulsion (d) All of these

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b a a a a b d a a b
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. d c a c d c a b a a
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Haloalkanes & Haloarenes

Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. c d d b a b c b b c
Q. No. 31 32 33 34 35 36 37 38 39 40
Ans. a d a b b c a a a c
Q. No. 41 42 43
Ans. b d d

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CHAPTER-7 : ALCOHOL, PHENOL & ETHERS

• Chapter at a glance 106-113
• Exercise-1_Important Questions 114-116
• Exercise-2_Multiple Choice Questions 117-121
CHAPTER AT A GLANCE
OXYGEN CONTAINING COMPOUND
HYDROXY DERIVATIVES
Hydroxy derivatives

Aliphatic hydroxy derivatives Aromatic hydroxy derivatives

Aliphatic Hydroxy Derivatives
3
Hydroxy derivatives in which —OH is directly attached to sp ‘C’ (Alcoholic compounds).
Aromatic Hydroxy Derivatives
2
Hydroxy derivatives in which —OH is directly attached to sp ‘C’ or benzene ring (Phenolic
compounds).
Aliphatic hydroxy derivatives :
(a) Classification according to number of —OH groups :
(i) Monohydric [one –OH] CH3CH2—OH
(ii) Dihydric [two –OH] CH2——CH2
OH OH
(iii) Trihydric [three –OH] CH2—CH—CH2
OH OH OH
(iv) Polyhydric [n –OH] CH2–CH—CH—CH—CH—CH2
OH OH OH OH OH OH
(b) Classification according to nature of carbon:
(i) p or 1° – alcohol CH3CH2 – OH
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

(ii) s or 2° – alcohol (CH3)2CH – OH

(iii) t or 3° – alcohol (CH3)3C – OH
MONOHYDRIC ALCOHOL
General Methods of Preparation
(i) From alkanes (By oxidation):
H /KMnO 4
(CH3)3 C—H (CH3)3 C—OH

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(ii) From alkenes :
(a) By hydration :
H
CH3—CH CH2 H2 O CH3–CH–CH3
OH
(b) By hydroboration oxidation :
(1)BH3 ,THF
CH3—CH CH2 CH3–CH2–CH2 (1° alcohol)
(2)H2 O2 HO
OH
(iii) From alkyl halides (By hydrolysis) :
Aq. KOH
CH3—CH2—Cl CH3CH2—OH
or Moist Ag 2O

(iv) From carbonyl compounds (By reduction) :

Reducing agent
> CO > CH—OH
Reducing agents may be,
LiAlH4/H
NaBH4/H
Na + EtOH
Ni/H2
LiAlH4
R—CHO R—CH2—OH
H
NaBH4
R—C—Cl H
R—CH—R
O OH
LiAlH4
CH3—CH CH—CHO CH3—CH CH—CH2—OH
H

Crotonaldehyde
(v) From ethers :
R—O—R dil. H SO 2 4
R—OH + R—OH
CH3—O—CH2CH3 dil. H SO CH3—OH + CH3CH2—OH
2 4

(vi) From acid and derivatives (By reduction):

LiAlH4
R—COOH R—CH2—OH + H2O
H

R—C—Cl LiAlH4
R—CH2—OH + HCl
H
O
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

LiAlH4
R—C—OR R—CH2—OH + R—OH
H

O
LiAlH4
R—C—O—C—R R—CH2—OH + R—CH2—OH
H

O O
Note : Amide on reduction gives amine not alcohol.
R—C—NH2 LiAlH4
R—CH2—NH2 +H2O
H
O

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(vii) From Grignard reagent :
(a) p-alcohol :
H 2O
R—MgX + [O] R—O—MgX R—OH
[Same C-p-alcohol]
R R
– + H2O
R—MgX + H—C—H H—C—H H—C—H
O OMgX OH
[one C more p-alcohol]
R R
– + H2O
R—MgX + CH2–CH2 CH2—CH2 CH2—CH2
O OMgX OH
[two C more p-alcohol]

(b) s-alcohol :
R R
H2O
R—MgX + R—C—H R—C—H R—C—H
O OMgX OH
R
R–MgX
R—MgX + H—C—OR H—C—R —
H2O
H—C—R
O O OH

(c) t-alcohol :
R R
H2O
R—MgX + R—C—R R—C—R — R—C—R
O OMgX OH

R
R–MgX
R—MgX + R—C—OR R—C—R —
H2O
R—C—R
O O OH
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

Physical properties :
(i) C1 to C11 are colourless liquids and higher alcohols are solids.

(ii) Density of monohydric alcohol is less than H2O.

(iii) Density mol. wt. (for monohydric alcohol).
(iv) Solubility : C1 to C3 and t-butyl alcohol is completely soluble in H2O due to H–bonding.
No.of side chains
solubility
molecular weight

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Order of solubility :
C4H9OH > C5H11OH > C6H13OH
CH3
CH3CH2CH2CH2OH < CH3CH2CH—OH < CH3—C—OH
CH3 CH3
CH3CH2CH2 < CH3—CH—CH2 < CH2—CH—CH2
OH OH OH OH OH OH
[Number of OH increases, H-bonding increases]
Molecular weight
(v) Boiling points : BP
No. of side chains
Orber of BP : C4H9OH < C5H11OH < C6H13OH
CH3
CH3CH2CH2CH2OH > CH3CH2CH—OH > CH3—C—OH
CH3 CH3
CH3CH2CH2 < CH3—CH—CH2 < CH2—CH—CH2
OH OH OH OH OH OH
[Number of OH increases, H-bonding increases]
Chemical Properties
Monohydric alcohol shows following reactions
(A) Reaction involving cleavage of O H
(B) Reaction involving cleavage of C OH
(C) Reaction involving complete molecule of alcohol
(A) Reaction involving cleavage of O H : Reactivity order (Acidic nature) is
CH3—OH > CH3CH2—OH > (CH3)2CH—OH > (CH3)3C—OH
(i) Acidic nature :
H2O > R—OH > CH CH > NH3 (Acidic strength)
Alcohols are less acidic than H2O and neutral for litmus paper and give H2 with active metals
(Na, K)
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

1
R—OH + Na R—ONa + H2
2
1
R—OH + K R—OK + H2
2
(ii) Alkylation:
CH2 N 2
R—OH R—O—CH2—H
Na R X
R—OH R—ONa R—O—R
(Williamson synthesis)

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(iii) Acylation :
R—OH + Cl—C—R R—O—C—R
O O
(Acylation)
R—OH + Cl—C—CH3 R—O—C—CH3
O O
(Acetylation)
O O—C—CH3
O
COOH COOH
CH 3COCl

Salicylic acid Acetoxy benzoic acid

Acetyl salicylic acid
Aspirin [Used as analgesic and antipyretic]
Distinction between 1°, 2° and 3° alcohols :
(a) Lucas test : A mixture of HCl(conc.) and anhydrous ZnCl2 is called Lucas reagent.
ZnCl 2 +HCl
p-alcohol No turbidity at room temp. [On heating within 30 minutes.]
ZnCl 2 HCl
s-alcohol Turbidity appears within 5 minutes.
ZnCl 2 HCl
t-alcohol Turbidity appears within 2-3 sec.
Important facts about alcohols
(i) Absolute alcohol : Ethyl alcohol - 99.5%-100%
(ii) Power alcohol : Rectified spirit + C6H6 + Petrol for generation of power
(iii) Methylated spirit : Methanol + Pyridine + mineral naptha + rectified spirit.
(iv) Rectified spirit contains 95.5% alcohol and 4.5% H2O.
AROMATIC HYDROXY DERIVATIVES
2
Phenolic compounds : Compounds in which —OH group is directly attached to sp c [Benzene
ring]
OH OH OH
CH3 COOH
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

Phenol o-Cresol Salicylic acid

OH
OH
OH
OH

OH OH
Catechol Resorcinol Quinol
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All phenolic compounds give colour with neutral FeCl3.

neutral FeCl 3
Ph—OH Violet colour
neutral FeCl 3
CH3CH2—OH No colour
PHENOL (C6H5OH)
2
Phenol is also known as carbolic acid. In phenol —OH group is attached with sp hybridised
carbon.
General Methods of Preparation
(1) From benzene sulphonic acid : When sodium salt of benzene sulphonic acid is fused with
NaOH phenol is obtained.
(1)NaOH, & Pr.
C6H5SO3Na (2) H
C6H5OH + Na2SO3

(2) From benzene diazonium chloride : When benzene diazonium chloride solution is warmed
with water, phenol is obtained with evolution of nitrogen.
N2Cl OH
(Steamdistilled)H2 O
+ N2 + HCl

(3) By distilling a phenolic acid with sodalime (decarboxylation):

OH OH
COOH
NaOH CaO
+ Na2CO3

Salicylic acid
(4) From Grignard reagent : The Grignard reagent on reaction with oxygen and subsequent
hydrolysis yields phenol.
[O] H 2O
Br
C6H5MgBr C6H5OMgBr C6H5OH + M
g OH
(5) From benzene :
OH
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

V2O5
+ [O] 300 C

(6) From chloro benzene :

Aq. NaOH
Ph—Cl No NSR at normal condition
Stable by resonance
Aq. NaOH
R—Cl R—OH [NSR]
(1)Aq. NaOH, & Pr
Ph—Cl (2) H
Ph—OH [NSR at high temperature]

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(7) Industrial preparation of phenol: Phenol can be prepared commercially by :
From cumene (Isopropyl benzene) : Cumene is oxidised with oxygen into cumene
hydroperoxide in presence of a catalyst. This is decomposed by dil. H2SO4 into phenol and
acetone.
O—OH
CH3 CH3
CH C(CH3)2
OH
O2 H2SO4 ,H 2O
130o C 100°C + CH3–C–CH3
Cumene Cumene hydroperoxide O
Physical Properties
(i) Phenol is a colourless, crystalline solid.
(ii) It attains pink colour on exposure to air and light. (slow oxidation)
C6H5OH---------- O O --------- HOC6H5
Phenoquinone(pink colour)
(iii) It is poisonous in nature but acts as antiseptic and disinfectant.
(iv) Phenol is slightly soluble in water, readily soluble in organic solvents.
(v) Solublity of phenol in water is much lower than alcohols because of larger hydrocarbon part
in the molecule.
(vi) Due to intermolecular H-Bonding, phenol has relatively high boiling point than the
corresponding hydrocarbons, aryl halides.
Chemical Properties
(A) Reactions due to –OH group:
(i) Acidic Nature : Phenol is a weak acid. The acidic nature of phenol is due to the formation of
stable phenoxide ion in solution. The phenoxide ion is stable due to resonance. The negative
charge is spread through out the benzene ring which is stabilising factor in the phenoxide ion.
Electron withdrawing groups (–NO2, –Cl) increase the acidity of phenol while electron
releasing groups (–CH3 etc.) decrease the acidity of phenol.
C6 H 5OH H 2O C6 H 5 O H 3 O
Phenol is stronger acid than alcohols but weaker than the carboxylic acids and even carbonic
acid.
(ii) Reimer-Tiemann reaction : Phenol on refluxing with chloroform and NaOH (aqueous)
followed by acid hydrolysis yields o–hydroxy benzaldehyde. When CCl4 is used salicylic
acid is formed.
ONa ONa OH
H+
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

CHCl3 NaOH
60°C NaOH(aq)
OH H2O
CHCl2 CHO CHO
Salicylaldehyde

ONa ONa OH
CCl3 NaOH H+
60°C NaOH(aq) H2O
CCl3 COONa COOH
Salicyclic acid

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ETHER
R—O—R (Dialkyl ether), alkoxy alkane. It's General formula is CnH2n + 2O.
CH3—O—CH2CH3 (Methoxy ethane) or Ethyl methyl ether
Ether is monoalkyl derivative of R–OH and dialkyl derivative of H2O
–H –2H
R—OH +R R—O—R +2R H—O—H
Classification : They may be classified as :
(a) Simple or symmetrical ether. e.g. R–O–R
(b) Mixed or unsymmetrical ether e.g. R–O–R'
Structure :
The molecule of ether is bent due to presence of lone pair.
:O: sp3 hybridised
bond bond
R 110° R
The bond angle is 110°. It is greater than that of water (105°) due to the repulsion between
bulkier alkyl groups. Due to bent structure, it posses dipole moment and hence are polar
molecules.
General Methods of Preparation
(a) From alkyl halides :
(i) By Williamson's synthesis :
R—X + NaO—R R—O—R + NaX [SN2 Reaction]
Ex. CH3—CH2—Cl + CH3—ONa CH3—CH2O—CH3 + NaCl
CH3 CH2
CH3–C–Cl + CH3ONa H3C–C
Ex. 3° RX fails to give ethers
CH3 CH3
(Major)

CH3 CH3
Ex. CH3–C–ONa + CH3–CH2–Cl CH3–C–O–CH2–CH3
CH3 CH3
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

Ex. CH2 CH—Cl + CH3CH2—ONa No reaction

[Stable by Resonance]
(ii) Reaction with dry Ag2O% 2RX + Ag2O R—O—R + 2AgX

Ex. 2CH3—CH2—Cl + Ag2O CH3CH2OCH2CH3 + 2AgCl

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EXERCISE-1 IMPORTANT QUESTIONS
1. Show how are the following alcohols prepared by the reaction of a suitable Grignard reagent on
methanal?
CH2OH
(i) CH3–CH–CH2OH (ii)
CH3

Ans. (i)

MgBr CH2OMgBr CH2OH

H2O
H–C–H + + Mg(OH)Br
(ii) O
Methanal Cyclohexylmagnesium Cyclohexylmethanol
bromide
2. Write structures of the products of the following reactions :
O O
NaBH4
CH2 – C–O–CH3
H2 O/H H
(i) CH3 CH CH2 (ii)
NaBH4
(iii) CH3–CH2–CH–CHO
CH3
+
H 2O/H
Ans. (i) CH3–CH=CH2 CH3–CH–CH3
Propane OH
Propan-2-ol

O OH
CH2–C–OCH3 NaBH 4
CH2–C–OCH3
(ii) O H O

Methyl (2-oxocyclohexyl) Methyl (2-hydroxycyclohexyl)

ethanoate ethanoate

NaBH4
(iii) CH3–CH2–CH–CHO H CH3–CH2–CH–CH2OH
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

CH3 CH3
2-Methylbutanal 2-Methylbutan-l-ol

3. Ortho and para nitrophenols are more acidic than phenol. Draw the resonance structures of the
corresponding phenoxide ions.
– –
O O O O O

Ans. – –
–

(Resonance structure of the phenoxide ion)

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O O O O O O

+ + + +
N N N N N+ N+
—
O O
—
O O
—
O O
—
O O
— —
O O
—
O O
(Resonance structures of p-nitrophenoxide ion)
– –
O O O
—
O O O
O O O O
+
N +
N
+
N N N
O— O— O— – + O—
O—
–
(Resonance structures of o-nitrophenoxide ion)
It can be observed that the presence of nitro groups increases the stability of phenoxide ion.
4. Which of the following is an appropriate set of reactants for the preparation of 1-methoxy-4-
nitrobenzene and why?
Br ONa

(i) + CH3ONa (ii) + CH3Br

NO2 NO2
Ans. Set (ii) is an appropriate set of reactants for the preparation of 1-methoxy-4-nitrobenzene.
ONa OCH3
1
6 2
+ CH3Br + NaBr
5 3
4
NO2 NO2
1-Methoxy-4-nitrobenzene
In set (i), Bromine atom is stable by resonance.
5. Predict the products of the following reactions :
OC2H5
(i) CH3–CH2–CH2–O–CH3+HBr (ii) + HBr

OC2H5 Conc.H SO
2 4

(iii) Conc.HNO3 (iv) (CH3 )3 C OC2 H5 HI

Ans. (i) CH 3 CH2 CH2 O CH3 HBr CH3 CH 2 CH2 OH CH3 Br (S N 2)

n propylmethyl ehter Pr opanol Bromomethane
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

OC2H5 OH
+ HBr + C2H5Br SN2
(ii)
Ethoxybenzene Phenol Bromoethane
OC2H5 Conc.H2SO 4 OC 2H5 OC2H5
Conc.HNO 3 + (Nitration)
(iii) NO2 NO2
Ethoxybenzene 1-Ethoxy-4-nitrobenzene 2-Ethoxynitrobenzene
(Major) (Minor)
(iv) (CH3 )3 C OC2 H5 HI
(CH3 )3 C I C 2H5 OH (SN 1)
tert Butyl ethyl ether tert Butyliodide Ethanol

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6. Give two reactions that show the acidic nature of phenol. Compare acidity of phenol with that of
ethanol.
Ans. The acidic nature of phenol can be represented by the following two reactions.
(i) Phenol reacts with sodium to give sodium phenoxide, liberating H2.
OH ONa

+ Na + 1 H2
2
Phenol Sodium phenoxide

(ii) Phenol reacts with sodium hydroxide to give sodium phenoxide and water as by-products.
OH ONa

+ NaOH + H2O
Sodium phenoxide

The acidity of phenol is more than that of ethanol. This is because after losing a proton, the
phenoxide ion undergoes resonance and gets stabilized whereas ethoxide ion does not.

O O O O O

7. Write the equation of the reaction of hydrogen iodide with :

(i) 1-propoxypropane
(ii) Methoxybenezene and
(iii) Benzyl ethyl ether
373 K
Ans. (i) C2H5CH2–O–CH2C2H5 + HI CH3CH2CH2–OH+CH3CH2CH2 – I
l-Propoxypropane Propan-1-ol 1-Iodopropane

OCH3 OH

(ii) + HI + CH3–I (SN2)

Methoxy benzene Phenol

CH2–O–C2H5 CH2l

(iii) + HI + C2H5–OH (SN1)

Benzyl ethyl ether Benzyl iodide Ethanol
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

8. Give the name of Enzyme used to convert glucose into ethanol.

Ans. Glucose Zymase
C2H5OH + CO2

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EXERCISE-2 MULTIPLE CHOICE QUESTIONS
(CLASSIFICATION, PREPARATION OF ALCOHOL, REDUCTION)
1. Butane-2-ol is:
(a) Primary alcohol (b) Secondary alcohol
(c) Tertiary alcohol (d) Aldehyde
2. In the following reaction 'A' is:
C2H5MgBr + H2C – CH2 A
O
(a) C2 H5CH 2CHO (b) C2 H5CH 2 CH 2 OH (c) C2 H5CH 2OH (d) C2 H5CHO
3. C2 H 5 MgI reacts with HCHO to form last product–
(a) CH 3CHO (b) C3H 7 OH (c) CH3COCH 3 (d) CH3COOCH3
4. The reagent(s) used for the reduction of aldehydes and ketone is/are:
(a) finely divided metals such as Pt/Pd/Ni (b) sodium borohydride
(c) lithium aluminium hydride (d) All of the above
5. Which of the following are not used to convert RCHO into RCH 2OH?
(a) H2/Pd (b) LiAlH4
(c) NaBH4 (d) Reaction with RMgX followed by hydrolysis
6. Which of the following alcohol contains Csp3 – OH bond?

(a) Allylic alcohol (b) Vinylic alcohol (c) Phenols (d) None of these
7. Give IUPAC name of the compound given below:
H 3C  CH  CH 2  CH 2  CH  CH 3
| |
Cl OH
(a) 5-chlorohexan-2-ol (b) 2-chlorohexan-5-ol
(c) 2-hydroxy-5-chlorohexane (d) 2-chloro-5-hydroxyhexane
8. Alkenes react with water in the presence of acid as catalyst to form alcohols.
The reaction takes place in accordance with –
(a) Hofmann elimination rule (b) Saytzeff rule
(c) Markownikoff's rule (d) Anti-Markownikoff's addition
9. Arrange the following compounds in the increasing order of boiling point.
Propan-1-ol, butane-1-ol, butan-2-ol, pentan-1-ol.
(a) Propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol
(b) Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
(c) Pentan-1-ol, butan-2-ol, butan-1-ol, propan-1-ol
(d) Pentan-1-ol, butan-1-ol, butan-2-ol, propan-1-ol

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(CHEMICAL REACTION OF ALCOHOL, OXIDATION)
10. Propene, CH 3 CH CH 2 can be converted to 1-propanol by oxidation. Which set of reagents
among the following is ideal to effect the conversion?
(a) Alkaline KMnO 4 (b) B 2 H 6 and alkaline H 2 O 2
(c) O 3 / Zn dust (d) OsO 4 / CH 4 , Cl 2

11. Conc. H 2SO 4 reacts with C 2 H 5 OH at 170 o C to form –

(a) CH 3COCH 3 (b) CH 3COOH (c) CH 3CHO (d) C 2 H 4

12. Isopropyl alcohol heated at 300 o C with copper catalyst to form –

(a) Acetone (b) Dimethyl ether (c) Acetaldehyde (d) Ethane
13. The final product of the oxidation of ethyl alcohol is :
(a) Ethane (b) Acetone (c) Acetaldehyde (d) Acetic acid
14. Lucas test is used to distinguish between –
(a) 1o , 2o and 3 o alcohols (b) 1o , 2o and 3 o amines
(c) Aldehydes and ketones (d) Alkenes and alkynes
15. The acidic character of alcohols is due to the –
(a) non-polar nature of O-H bond (b) polar nature O-H bond
(c) non-polar nature of C-O bond (d) polar nature of C-O bond
(PREPARATION & PROPERTIES OF PHENOL)
16. Sodium benzene sulphonate reacts with NaOH and then on acidic hydrolysis, it gives:
(a) Phenol (b) Benzoic acid
(c) Benzene (d) Disodium benzaldehyde
17. Phenol is obtained by heating aqueous solution of –
(a) Aniline (b) Benzene diazonium chloride
(c) Benzoic acid (d) None of these
18. The reaction of conc. HNO 3 and phenol forms –
(a) Benzoic acid (b) Salicylic acid
(c) o-and p-nitrophenol (d) Picric acid
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

19. At low temperature phenol reacts with Br2 in CS2 to form–

(a) m-bromophenol (b) o-and p-bromophenol
(c) p-bromophenol (d) 2, 4, 6-tribromophenol
20. In presence of NaOH, phenol react with CHCl3 to form o-hydroxy benzaldehyde. This reaction
is called–
(a) Riemer-Tiemann's reaction (b) Sandmeyer's reaction
(c) Hoffmann's degradation reaction (d) Gattermann's aldehyde synthesis

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21. Which of the following compound(s) is/are aromatic alcohols?
OH CH2OH CH2OH OH
OH

HO CH3 CH3
I II III IV
(a) I, II, III and IV (b) I and IV (c) II and III (d) I
22. The reaction of alcohol/phenol with acid chloride is carried out in the presence of a pyridine in
order to –
(a) neutralise HCl which is formed during the reaction
(b) shift the equilibrium to right hand side
(c) Both (a) and (b)
(d) None of these
23. In the given reaction,
OH
Br2 in CS2
273 K
'X'
is:
Br2 water
'Y'

OH OH OH OH
Br Br
(a) X Y (b) X Y

Br Br
OH OH OH OH
Br Br Br Br
(c) X Y (d) X Y

Br Br Br Br
24. Mark the correct order of decreasing acid strength of the following compounds.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

OH OH OH OH OH

OCH3 NO2
NO OCH3
I II III IV V
(a) V > IV > II > I > III (b) II > IV > III > I > V
(c) IV > III > II > I > V (d) I > II > III > IV > V

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25. Phenol is less acidic than –
(a) ethanol (b) o-nitrophenol
(c) o-methylphenol (d) o-methoxyphenol
(PREPARATION & PROPERTIES OF ETHER)
26. Dimethyl ether and ethyl alcohol are:
(a) Branched isomer (b) Position isomer (c) Functional isomer (d) Tautomer
27. Diethyl ether can be decomposed by heating with:
(a) HI (b) NaOH (c) Water (d) KMnO 4
28. Methyl-terbutyl ether on heating with HI of one molar concentration gives:
(a) CH 3 I (CH 3 ) 3 COH (b) CH 3OH (CH 3 ) 3 Cl
(c) CH 3 I (CH 3 )3 Cl (d) None of the above
29. Dimethyl ether when heated with excess HI gives:
(a) CH 3 I and CH 3OH (b) CH 3 I and H 2 O
(c) C 2 H 6 CH 3 I and CH 3OH (d) CH 3 I and HCHO
30. IUPAC name of m-cresol is ___________.
(a) 3-methylphenol (b) 3-chlorophenol (c) 3-methoxyphenol (d) benzene-1, 3-diol
31. C6H5OCH2CH3 is named as:
(a) phenetole (b) ethylphenyl ether
(c) ethoxy benzene (d) All of these
32. IUPAC name of the compound CH3–CH–OCH3 is:
CH3
(a) 1-methoxy-1-methylethane (b) 2-methoxy-2-methylethane
(c) 2-methyoxpropane (d) isopropylmethyl ether
33. In the given reaction,
OCH3

Br2 in
ethanoic

Product formed is:

OCH3 OCH3
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Alcohol, Phenol & Ethers

Br
(a) (90% yield) (b) (90% yield)

Br

OCH3 OCH3

(c) (90% yield) (d) (10% yield)

Br Br

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34. The large difference in the boiling points of alcohols and ethers is due to the presence of –
(a) van der Waals' forces in alcohols (b) dipole-dipole interaction in alcohols
(c) hydrogen bonding in alcohols (d) ion-ion interaction in alcohols
35. Williamson's synthesis involves the ..... attack of an alkoxide ion on primary alkyl halide.
(a) SN1 (b) SN2 (c) E1 (d) E2

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b b b d d a a c a b
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Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. d a d a b a b d b a
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. a c d b b c a a b a
Q. No. 31 32 33 34 35
Ans. d c a c b

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CHAPTER–8 : ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

• Chapter at a glance 122-124
• Exercise-1_Important Questions 125-131
• Exercise-2_Multiple Choice Questions 132-134
CHAPTER AT A GLANCE
CARBONYL COMPOUNDS
Organic Compounds having group are called carbonyl compounds and group
is known as carbonyl group. It's general formula is CnH2nO (n = 1, 2, 3......) Carbonyl compounds
are grouped into two categories.
O
(a) Aldehydes : Aldehyde group is C H (also known as formyl group). It is a monovalent
group
O
Carbon atom of C H group is of 1° nature i.e.

(b) Ketones : The carbonyl group ( C O ) is a Ketonic group when its both the valencies are
satisfied by alkyl group. It is a bivalent group.
R 2°
Carbon atom of C O group is of 2° nature i.e. C O
R
Ketones are further classified as :
R
(i) Simple or Symmetrical ketones : Having two similar alkyl groups. C O
R
R
(ii) Mixed or unsymmetrical ketones : Having two different alkyl groups. C O
R'
Ex. (Ketones) : Symmetrical Unsymmetrical
CH 3 CH 3CH 2
C O C O
CH 3 CH3
(Acetone or Dimethyl ketone) (Ethyl methyl ketone)
Propanone Butanone
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

Physical Properties
State : Only formaldehyde is gas, all other carbonyl compounds upto C11 are liquids and C12 &
onwards solid.
Solubility : C1 to C3 (formaldehyde, acetaldehyde and propionaldehyde) and acetone are freely

soluble in water due to polarity of C O bond and can form H—bond with water molecule. C5
onwards are insoluble in water.
H
1
Solubility
C O H O Molecular weight

H-bonding
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Boiling point : Boiling point Molecular weight

Boiling point order is – Alcohol > Ketone > Aldehydes > Alkane (of comparable molecular mass)

This is because in alcohols intermolecular H-bonding is present but in carbonyl compounds

H-bonding doesn't exist, instead dipole-dipole & vander waal force of attraction is present.
Alkanes are non polar.

C O C O

Density : Density of carbonyl compounds is lower than water.

(i) Tollen's reagent : It oxidises aldehydes. Tollen's reagent is ammonical silver nitrate solution
(AgNO3+NH4OH) [Ag(NH3)2]OH

RCHO+[Ag(NH3)2]OH RCOO + Ag + H2O

Silver mirror
AgNO3 + NH4OH AgOH Ag2O

RCHO + Ag2O RCOO + Ag (Silver mirror)

(ii) Fehling's solution :
It is a mixture of aqueous CuSO4, NaOH and sodium potassium tartarate.
Fehling solution A– (aq.) solution of CuSO4
Fehling solution B– Roschelle salt (Sodium potassium tartarate + NaOH)
Fehling solution A + Fehlings solution B(Dark blue colour of cupric tartarate)

RCHO + Cu+2 + OH– RCOO + Cu2O

(Cuprous oxide–Red ppt.)
2+ +
Cu Cu
(Cupric-Blue) (Cuprous - Red ppt.)
CARBOXYLIC ACID
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

Organic compounds having –COOH group are called Carboxylic acids. This functional group is
O
composed of Carbonyl ( C ) and hydroxyl (—OH) group.
O
C + —OH OH
Carbonyl group Hydroxyl group Carboxylic group
The properties of the carboxylic group are not simply the combined properties of these two
groups, but it has its own distinctive properties. The acidic nature of carboxylic acids is due to
the presence of replaceable H-atom in the Carboxylic group. The general formula is CnH2nO2 .

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Classification:
Monocarboxylic acid (RCOOH) : Having one carboxylic group, also called monobasic acid.
General formula – CnH2nO2 (n = 1, 2, 3, ........).Higher mono carboxylic acids are called fatty
acids.
COOH
Ex. CH3COOH acetic acid
COOH
Dicarboxylic acid : Having two carboxylic groups, also called dibasic acid.
CH2COOH
Ex. HO C COOH Oxalic acid
CH2COOH
Tricarboxylic acid : Having three carboxylic groups also called tribasic acid.
Ex. Citric acid
Structure : The carbon atom of –COOH group is sp2 hybridised, this C- atom is in centre and
thus bond angle around C-atom is 120°.
Physical Properties
Carboxylic acids from C1—C4 are completely soluble in water.
1
Solubility
molecular weight

Solubility is due to intermolecular H - bonding with water molecules.

Boiling point : B. P. & M. P. Molecular weight,

Acids > alcohol

This is because in acids two oxygen atoms take part in H - bonding (while in alcohol only one
O - atom takes part).
In vapour or soluble state lower acids occur But in liquid state it exists in polymer form.
in the form of dimers.
O H O O R C O O—H
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

R C C R
O H O R C O H O H O C R
Melting point : Acids having even number of C-atoms have higher melting point as compared to
having odd number of C - atoms. The carboxyl group and terminal methyl group in even member
acids lie on opposite side to provide more close packing in crystal lattice which results in high
melting point.

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EXERCISE-1 IMPORTANT QUESTIONS

1. Arrange the following compounds in increasing order of their boiling points.

CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Ans. CH3CH2 CH3 CH3 OCH3 CH3 CHO CH3CH2OH
non polar more polar H bond i ng

2. Arrange the following componds in increasing order of their reactivity in nucleophilic addition
reactions.
(i) Ethanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Hint: Consider steric effect and electronic effect.
Ans. Reactivity of carbonyl compound (+)ve charge on sp2 C
O O O O
C C C C
(i) CH3 H CH3CH2 H CH3 CH3 CH3 CH2CH3
Ethanal Propanal Propanone Butanone

The +I effect of the alkyl group increases in the order :

Ethanal < Propanal < Propanone < Butanone
If +I effect increases then (+)ve charge on sp2 C decreases.
So reactivity order is :
Butanone < Propanone < Propanal < Ethanal
O
CHO CH3 CHO
C
CH3

(ii) NO2 CHO

p-Nitrobenzaldehyde p-Tolualdehyde Benzaldehyde Acetophenone
more – I less – I +I of –CH3

–I group on >C = O inreases (+)ve charge so reactivity order is

Acetophenone < p-tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde
3. Predict the product of the following reactions :
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

O
(i)
+
H
+ HO – NH2

O O2N
(ii) + NH2 – NH NO2

O
H+
(iii) R – CH = CH – CHO + NH2 – C – NH – NH2
O
C
+
(iv) CH3 H
+ CH3CH2NH2

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O N–OH
Ans. (i) H
+

+ HO – NH 2

O2N
O O2N NNH NO2
(ii)
+ NH2 – NH NO2

O O
+
(iii) R – CH = CH – CHO + NH2 – C – NH – NH2 H
R – CH = CH – CH = N – NH – C – NH2

O H3C
C C = N – CH2CH3
(iv) CH3 H
+

+ CH3CH2NH2

4. Show how each of the following compounds can be converted to benzoic acid.
(i) Ethylbenzene (ii) Acetophenone (iii) Bromobenzene
(iv) Phenylethene (Styrene)
CH2CH3 COOK COOH
KMnO 4 – KOH H 3O+
Ans. (i)
Ethylbenzene Benzoic acid

COCH3 COOK COOH

+
KMnO 4 – KOH H 3O
(ii)
Acetophenone Benzoic acid

O
Br MgBr C COOH
Mg O=C=O H 3O +
OMgBr
(iii) Ether dry ice
Bromobenzene Benzoic acid

CH=CH2 COOK
COOH
KMnO 4 – KOH H3O+
+ HCOOK
(iv)
Phenylethene
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

5. Draw structures of the following derivatives.

(i) The 2, 4-dinitrophenylhydrazone of benzaldehyde
(ii) Cyclopropanone oxime
(iii) Acetaldehydedimethylacetal
(iv) The semicarbazone of cyclobutanone
(v) The ethylene ketal of hexan-3-one
(vi) The methyl hemiacetal of formaldehyde

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NO2 N–OH
Ans. (i) CH=NNH NO2 (ii)
O
OCH3
(iii) CH3–CH (iv) NNH–C–NH2
OCH3
CH2–CH2
CH2 OH OH
H2C +
O O O
(v) H
H3C – CH2 – C – CH2 – CH2 – CH3 –H 2O CH3–CH2–C–CH2–CH2–CH3
H OH H
H H–OH
(vi) C C=O +
–H 2O H–O–CH3
H OCH3 H
6. Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents.
(i) PhMgBr and then H3O+
(ii) Tollen's reagent
(iii) Semicarbazide and weak acid
(iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid
OMgBr OH
CH=O Ph–MgBr C H H 3O+ C H
Ans. (i) Ph Hydrolysis Ph
Cyclohexane- Cyclohexylphenylcarbinol
carbaldehyde
CH=O
+ 2[Ag(NH3)2]+ + 3OH–
(ii)
Cyclohexane- Tollen's reagent
carbaldehyde O
C–O–
+ 2Ag + 4NH3 + 2H2O
Silver mirror
Cyclohexane-
carboxylate ion
O
CHO O
pH 3.5 CH=NNH–C–NH2 + H2O
(iii) + H2NNH–C–NH2
weak acid
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

Semicarbazide
Cyclohexane- Cyclohexanecarbaldehyde
carbaldehyde semicarbazone
OC2H5
CHO H OC2H5
Dry HCl gas C OC H + H O
(iv) + 2 5 2
H
Cyclohexane- H OC2H5
carbaldehyde Ethanol (Excess) Cyclohexanecarbaldehyde
diethyl acetal
CH3
CHO
Zn/Hg–HCl
(v) (clemmensen
reduction)
Cyclohexane- Methylcyclohexane
carbaldehyde

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7. Which of the following compounds would undergo aldol condensation, which the Cannizzaro
reaction and which neither ? Write the structures of the expected products of aldol condensation
and Cannizzaro reaction.
(i) Methanal (ii) 2-Methylpentanal (iii) Benzaldehyde
(iv) Benzophenone (v) Cyclohexanone (vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde (viii) Butan-1-ol (ix) 2, 2-Dimethylbutanal
Ans. Aldehydes and ketones having at least one -hydrogen undergo aldol condensation (ii), (v), (vi),
(vii) gives aldol condensation.
Aldehydes (only) having no -hydrogen undergo Cannizzaro reactions. (i), (iii), (ix) gives
cannizzaro reaction.
Compound (iv) is a ketone having no -hydrogen atom and compound (viii) Butan-1-ol is an
alcohol. Hence, these compounds do not undergo either aldol condensation or cannizzaro
reactions.
Aldol condensation
2CH3CH2CH2—CH—CHO dil. NaOH
(ii)
CH3
2-Methylpentanal
CH3
CH3CH2CH2—CH—CH—C—CH2CH2CH3
CH3 OH CHO
O
dil NaOH
(v) 2 O
OH
Cyclohexanone
O OH CH3
dil NaOH
(vi) 2 C—CH2CH3 C—CH—C
CH2 O
1-Phenylpropanone
CH3
OH CHO
dil NaOH
(vii) 2 CH2CHO CH2—CH—CH

Phenylacetaldehyde
Cannizzaro reaction :
H
H H
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

(i) 2 C=O + conc. KOH H—C—OH + C—OK

H O
H
Methanal Methanol Potassium methanoate
O
(iii) 2 CHO+conc.KOH CH2—OH + C—OK

Benzaldehyde Benzyl alcohol Potassium benzoate

CH3 CH3 CH3
conc.NaOH
(ix) CH3CH2—C—CHO CH3CH2—C—CH2—OH + CH3CH2—C—C—ONa
CH3 CH3 CH3O
2, 2-Dimethylbutanal 2, 2-Dimethylbutan-1-ol Sodium 2, 2-dimethylbutanoate

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8. Write structural formulas and names of four possible aldol condensation products from propanal
and butanal. In each case, indicate which aldehyde acts as nucleophile and which as electrophile.
Ans. (i) Taking two molecules of propanal, one which acts as a nucleophile and the other as an
electrophile.
OH CH3
dil NaOH
2CH3CH2CHO CH3CH2—CH—CH—CHO
Propanal 3-hydroxy - 2 - methylpentanal

(ii) Taking two molecules of butanal, one which acts as a nucleophile and the other as an
electrophile.
OH CH2CH3
dil NaOH
2CH3CH2CH2CHO CH3CH2CH2—CH—CH—CHO
Butanal 2-Ethyl - 3 - hydroxyhexanal

(iii) Taking one molecule each of propanal and butanal in which propanal acts as a nucleophile
and butanal acts as an electrophile.
OH CH3
CH3CH2CH2CHO + CH3CH2CHO CH3CH2CH2—CH—CH—CHO
Butanal Propanal 3-Hydroxy - 2 -methylhexanal
(Electrophile) (Nucleophile)

(iv) Taking one molecule each of propanal and butanal in which propanal acts as an electrophile
and butanal acts as a nucleophile.
OH CH2CH3
CH3CH2CHO + CH3CH2CH2CHO CH3CH2—CH—CHCHO
Propanal Butanal 2-Ethyl - 3 - hydroxypentanal
(Electrophile) (Nucleophile)

9. Arrange the following compounds in increasing order of their property as indicated :

(a) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone
[Reactivity towards HCN]
(b) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH
[Acid strength]
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

(c) Benzoic acid, 4-Nitrobenzoic acid, 3,4–Dinitrobenzoic acid, 4–Methoxybenzoic acid

[Acid strength]
(d) CH3COCl, CH3CONH2, CH3COOCH3, (CH3CO)2O
[Reactivity in hydrolysis]
Ans. (a) Di-tert-butyl ketone < Methyl tert-butyl ketone < Acetone < Acetaldehyde
(b) (CH3)2CHCOOH,< CH3CH2CH2COOH < CH3CH(Br)CH2COOH,< CH3CH2CH(Br)COOH
(c) 4-Methoxybenzoic acid < Benzoic acid < 4-Nitrobenzoic acid < 3, 4-Dinitrobenzoic acid
(d) CH3CONH2 < CH3COOCH3 < (CH3CO)2O < CH3COCl

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10. Complete each synthesis by giving missing starting material, reagent or products.
CH2CH3 COOH
KMnO4 SOCl2
(i) KOH, heat (ii) heat
COOH
O

H2 NCONHNH2 C
(iii) C6H5CHO (iv)

O [Ag(NH 3)2]+ CHO

NaCN/HCl
(v) (vi)
CHO
COOH
C6H5CHO
dil.NaOH
+
(i) NaBH4
(vii) CH3CH2CHO (viii) CH3COCH2COOC2H 5 (ii) H+

CrO3
(ix) OH (x) CH2 CHO
(i) O 3
(xi) (ii) Zn-H 2O
O

CH2CH3 COOK
KMnO4
Ans. (i) KOH, heat

Ethylbenzene Potassium benzoate

COOH COCl
SOCl2
(ii)
COOH COCl

Phthalic acid Phthaloyl chloride

O
(iii) C6H5CHO + H2NCONHNH2 C6H5CH = NHHC–NH2 + H2O

Benzaldehyde Semicarbazide Benzaldehyde semicarbazone

O
COCl C
+ Anhyd AlCl 3
(iv) + HCl
F.C. acylation
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

Benzene Benzoyl chloride Benzophenone

O [Ag(NH3)2]+ O
(v)
CHO COOH
4-Oxocyclohexanecarbaldehyde 4-Oxocyclohexanecarboxylate
anion

OH
CHO CH
NaCN/HCl CN
(vi)
COOH COOH

2-Formylbenzoic acid 2-[1-Hydroxycyanomethly]

benzoic acid

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(vii) C6H5CHO
Benzaldehyde
dil.NaOH 3 2 1
+ C6H5CH=C–CHO
CH3CH2CHO CH3
Propanal 2-Methyl - 3 - phenyl
pro - 2 - enal

(i) NaBH 4
(viii) CH3COCH2COOC2H5 (ii)H+ CH3CH(OH)CH2COOC2H5
Ethyl 3-oxobutanoate Ethyl-3-hydroxybutanoate

CrO 3–H 2SO 4

(ix) OH O
Cyclohexanol Cyclohexanone

CHO
—
(x) BH 3 H 2O 2/OH PCC
CH2 CH2 B CH2OH
3
Methylenecyclohexane Cyclohexanecarbaldehyde

(xi) (i) O 3
2 O
(ii) Zn-H 2O
Cyclohexylidene cyclohexane Cyclohexanone
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

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EXERCISE-2 MULTIPLE CHOICE QUESTIONS

(INTRODUCTION)
1. In aldehydes and ketones, carbon of carbonyl group is :
(a) sp3 hybridised (b) sp2 hybridised (c) sp hybridised (d) Unhybridised
2. Glyoxal is [BVP 2003]
(a) CH2O–CH2O (b) CH 2 OH (c) CHO (d) CH 2 OH
| | |
CH2OH CHO CHO
3. Aldehydes are isomeric with :
(a) Ketones (b) Ethers (c) Alcohols (d) Fatty acids
4. IUPAC name of CH3COCH3 is :
(a) Acetone (b) 2-propanone
(c) Dimethyl ketone (d) Propanal
5. Which of the aldehyde is most reactive ?
(a) C6H5–CHO (b) CH3CHO
(c) HCHO (d) All the equally reactive
(PREPARATION)
6. The end product in the following sequence of reaction is :
1%HgSO4 CH3 MgX [O]
HC CH A B
20% H 2SO 4

(a) Acetic acid (b) Isopropyl alcohol (c) Acetone (d) Ethanol
O
||
H2
7. In the following reaction, product P is R C Cl P
Pd BaSO4

(a) RCH2OH (b) RCOOH (c) RCHO (d) RCH3

8. Acetophenone is prepared from :
(a) Rosenmund reaction (b) Sandmayer reaction
(c) Wurtz reaction (d) Friedel craft reaction
9. Compound which gives acetone on ozonolysis :
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

(a) CH3 CH CH CH3 (b) (CH3 )2 C C(CH 3 )2

(c) C6 H5CH CH 2 (d) CH3CH CH2
10. Catalyst used in Rosenmund reduction is :
(a) Pd / BaSO4 (b) Zn-Hg couple
(c) LiAlH4 (d) Ni/H2
11. Acetophenone is prepared by the reaction of which of the following in the presence of catalyst :
(a) Phenol and acetic acid (b) Benzene and acetone
(c) Benzene and acetyl chloride (d) Phenol and acetone

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12. Isopropyl alcohol on oxidation gives :
(a) Acetone (b) Acetaldehyde (c) Ether (d) Ethylene
13. Which of the following compound gives a ketone with Grignard reagent :
(a) Formaldehyde (b) Ethyl alcohol (c) Methyl cyanide (d) Methyl iodide
14. In the Rosenmund's reduction, taken with catalyst Pd acts as :
(a) Promotor (b) Catalytic poison (c) Cooperator (d) Absorber
15. The Clemmenson reduction of acetone yields :
(a) Ethanol (b) Ethanal (c) Propane (d) Propanol
16. Benzaldehyde can be prepared by oxidation of toluene by :
(a) Acidic KMnO4 (b) K2Cr2O7 (c) CrO2Cl2 (d) All of these
Anhy AlCl3
17. C6 H6 CO HCl X HCl
Compound X is :
(a) C6H5CH3 (b) C6H5CH2Cl (c) C6H5CHO (d) C6H5COOH
18. The reagent used in Gatterman Koch aldehyde synthesis is :
(a) Pb/BaSO4 (b) alkaline KMnO4
(c) acidic KMnO4 (d) CO + HCl
(PROPERTIES)
19. Identify the reactant X and the product Y :
CH3 CO CH3 X (CH3 )3 C OMg Cl
Hydrolysis

Y Mg (OH) Cl
(a) X MgCl2 ; Y CH3CH CH 2 (b) X CH3MgCl; Y C2 H5COCH 3

(c) X CH3MgCl; Y (CH3 )3 C OH (d) X C2 H5MgCl;Y (CH3 )3 C OH

20. Reduction of Aldehydes and Ketones to hydrocarbon take place in the presence of :
(a) Zn amalgam and HCl acid (b) Pd/BaSO4
(c) Anhydrous AlCl3 (d) Ni/Pt
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

21. Reduction of > C = O to CH2 can be carried out with :

(a) Catalytic reduction (b) Na/C2H5OH
(c) Wolf-Kischner reduction (d) LiAlH4
22. Which of the following gives aldol condensation reaction :
O
||
(a) C6H5OH (b) C6 H5 C C6 H 5
O O
|| ||
(c) CH 3CH 2 C CH3 (d) (CH 3 )3 C C CH3

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23. Which of the following products is formed when benzaldehyde is treated with and the addition
product so obtained is subjected to acid hydrolysis :
(a) Secondary alcohol (b) A primary alcohol
(c) Phenol (d) Tert-Butyl alcohol
24. Which of the following organic compounds exhibits positive Fehling test as well as iodoform
test :
(a) Methanal (b) Ethanol (c) Propanone (d) Ethanal
25. Which of the following compound will undergo self aldol condensation in the presence of cold
dilute alkali :
(a) C6H5CHO (b) CH3CH2CHO (c) CH C–CHO (d) CH2=CH–CHO
26. Acetaldehyde when treated with dilute NaOH gives :
(a) CH3CH2OH (b) CH3COOH
(c) CH 3 CH CH 2 CHO (d) CH3–CH3
|
OH
27. C2H5CHO and (CH3)2CO can be distinguished by testing with :
(a) Phenyl hydrazine (b) Hydroxylamine (c) Fehling solution (d) Sodium bisulphite
28. Which of the following does not give iodoform test :
(a) CH3CH2OH (b) CH3OH (c) CH3CHO (d) PhCOCH3
29. Which of the following will not give the iodoform test :
(a) Acetophenone (b) Ethanal (c) Benzophenone (d) Ethanol
30. The light yellow compound produced when acetone reacts with iodine and alkali, is :
(a) CH3.CO.CH2I (b) CH3I (c) CHI3 (d) None of these

ANSWER KEY
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Aldehydes, Ketones & Carboxylic acids

Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b c a b c c c d b a
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. c a c b c c c d c a
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. c c a d b c c b c c

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CHAPTER–9 : AMINES
• Chapter at a glance 135-137
• Exercise-1_Important Questions 138-139
• Exercise-2_Multiple Choice Questions 140-143
CHAPTER AT A GLANCE
AMINES :
Amines are derivatives of ammonia in which one or more hydrogen atoms are replaced by alkyl
group(s).
Amines are classified as primary, secondary and tertiary depending on the number of alkyl
groups attached to nitrogen atom.
R R R
NH3 H
RNH 2 H
R 2 NH H
RN 3
p-amine sec-amine tertiary amine

General formula (CnH2n+3N)

1° amine 2° amine 3° amine

General methods of preparation

(1) Ammonolysis of alkyl halides and alcohols :
(a) From Ammonolysis of alkyl halides [Hofmann's ammonolysis] : When an aqueous
solution of ammonia is heated with alkyl halide all the three types of amines and
quaternary ammonium salt are formed.
R—X NH3
R—NH2 R X
R2NH R X
R3N R X R4NX
HX HX HX

(Quaternary ammonium salt)

If ammonia is taken in excess, 1° amine is the main product.
(2) By reduction :
LiAIH4
(a) With RCONH2 : RCONH2 or Na/C2H5 OH
RCH2NH2

(b) With RCN : RCN + 4[H] Na/C2H5OH RCH2NH2

This reaction (b) is called mendius reaction.
The reduction of alkyl isocynides gives secondary amines.
R—NC + 4[H] C2H5OH / Na RNHCH3
(3) By hydrolysis of :
(a) R—NC : Alkyl isocyanide undergoes hydrolysis with mineral acid and forms alkyl
amine.
node06\B0BC-BD\Kota\Board Material\Chemistry\RBSE\eng\Amines

HCl
R—NC + 2H2O RNH2 + HCOOH
(4) By Hofmann's bromamide reaction (Hofmann's Hypobromite reaction) : This is a
general method for the conversion of alkanamides into primary amines having one less
carbon.
O
R—C—NH2 + Br2 + 4KOH R—NH2 + K2CO3 + 2KBr + 2H2O

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(5) Gabriel phthalimide synthesis : Phthalimide is first treated with KOH to obtain potassium
phthalimide which is then treated with alkyl iodide. Then alkyl phthalimide on hydrolysis
yields alkylamine. This method is used in the formation of pure aliphatic primary amines.
CO KOH
CO
NH –H2O
NK
CO CO
RI
COOH 2H2O CO
R NH2 + NR
COOH CO
Phthalic acid
* Aniline is not formed by this reaction.
Hinsberg method: In this method mixture of amines is seperated by using benzene
sulphonyl chloride (Hinsberg's reagent).
C6H5SO2Cl + 1° amine Product KOH Soluble
(ppt.)
C6H5SO2Cl + 2° amine Product KOH insoluble
(ppt.)
3° amine does not react with benzene sulphonyl chloride. (No ppt. formed)
PHYSICAL PROPERTIES
(i) CH3NH2 is gas and C2H5NH2 is a volatile liquid.
(ii) Higher amines have fishy smell.
(iii) H –Bonding (weaker as compared to H—O —H).
R R R R R R

N H N H N H N H N H N H

H H H R R R
(1° amine) (2° amine)
In 3° amine (due to absence of H–atom) H–bonding is not possible.
(iv) Boiling point: Due to weak intermolecular H-bonding the B.P. of 1° and 2° amines are
lower than those of alcohols of comparable molecular weight. The boiling point of 3° amines
which form no H–bonds are near to those of alkanes of comparable molecular weight.
Boiling point molecular weight
Order of B.P. : 1° amine > 2° amine > 3° amine
so order of volatility : 3° amine > 2° amine > 1° amine

(v) Solubility: Low molecular weight amines are soluble in water. The water solubility of
amines decreases with increasing size of alkyl group.
node06\B0BC-BD\Kota\Board Material\Chemistry\RBSE\eng\Amines

R H R R H R R H N R

N H O H N H N H O H N H R N H O R

H H R R R
(1° amine) (2° amine ) (3° amine)
Order of solubility p–amine > s–amine > t–amine
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Chemical properties
(i) Basic character of amines is due to the presence of lone pair of electrons on the N - atom.
(ii) Basic strength depends on electron donating tendency.
(iii) Order of basic character in aqueous solution: (CH3)2 NH > CH3 NH2 > (CH3)3 N > NH3
(C2H5)2 NH > (C2H5)3N > C2H5 NH2 > NH3
DIAZONIUM SALTS
The organic compound which have general formula is RN2X known as Diazonium salt.
GENERAL METHOD OF PREPARATION OF DIAZONIUM SALT
273 278K
C6H5NH2 + NaNO2 + 2HCl C6H5 + NaCl + 2H2O
CHEMICAL REACTIONS :
Cl

Cu2Cl2 /HCl
+ N2

Br

Cu2Br2/HBr Sandmeyer
+ N2 Reaction

CN

CuCN / KCN
+ N2

Cl

Cu / HCl
+ N2 + CuX
NH2 N2 Cl Gatterman
Br
Reaction
(NaNO2 + HCl) Cu / HBr
273 – 278K + N2 + CuX
Aniline Benzene
diazonium I
6H Sn/HCl
chloride
O Diazotisation
KI
+ N2 + KCl
(aq)
N

N2BF4 F

HBF4
Nitrobenzene + BF3 + N2
Fluoro boric
acid
Benzenediazonium NO 2
tetrafluoro borate

NaNO2 + NaBF4 + N2
Cu,

H3PO2 + H2O
+ N 2 + H3PO3 + HCl
node06\B0BC-BD\Kota\Board Material\Chemistry\RBSE\eng\Amines

CH3CH2OH
+ N 2 + CH 3CHO + HCl

H OH
N=N OH
– HCl
p-Hydroxy azobenzene (orange dye) Coupling
reaction
H NH 2
N=N NH 2

p-Amino Azobenzene (yellow dye)

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EXERCISE-1 IMPORTANT QUESTIONS
1. Arrange the following in increasing order of their basic strength :
(i) C2H5NH2, C6H5NH2, C6H5CH2NH2 and (C2H5)2NH
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
(iii) CH3NH2, (CH3)2NH, (CH3)3N, C6H5NH2, C6H5CH2NH2
Ans. (i) C6H5NH2 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH
(ii) C6H5NH2< C2H5NH2 < (C2H5)3 N < (C2H5)2 NH
(iii) C6H5NH2 < C6H5CH2NH2< (CH3)3 N < CH3NH2< (CH3)2NH
2. Arrange the followings :
(i) In decreasing order of the pKb values :
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
(ii) In increasing order of basic strength :
C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2
(iii) In increasing order of basic strength :
(a) Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2
(iv) In decreasing order of basic strength in gas phase :
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(v) In increasing order of boiling point :
C2H5OH, (CH3)2NH, C2H5NH2
(vi) In increasing order of solubility in water :
C6H5NH2, (C2H5)2NH, C2H5NH2
Ans. (i) C6H5NH2 > C6H5NH–CH3 > C2H5NH2 > (C2H5)2NH
(ii) C6H5NH2<C6H5N(CH3)2 <CH3NH2 <(C2H5)2NH
(iii) (a) p – nitroaniline < aniline < p - toluidine
(b) C6H5 NH2 <C6H5NHCH3 <C6H5CH2NH2
(iv) (C2H5)3 N > (C2H5)2NH > C2H5NH2 > NH3
(v) (CH3)2 NH < C2H5NH2 < C2H5OH
(vi) C6H5NH2 < (C2H5)2 NH < C2H5NH2
node06\B0BC-BD\Kota\Board Material\Chemistry\RBSE\eng\Amines

3. Complete the following reactions :

(i) C6H5NH2 + CHCl3 + alc. KOH (ii) C6H5N2Cl + H3PO2 + H2O
(iii) C6H5NH2 + (conc.) H2SO4 (iv) C6H5N2Cl + C2H5OH
(v) C6H5NH2 + (aq.) Br2 (vi) C6H5NH2 + (CH3CO)2O
(i) HBF4
(vii) C6H5N2Cl (ii) NaNO2 /Cu,

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Heat
Ans. (i) C6H5NH2 + CHCl3 + 3KOH (alc.) C6H5N = C
(Carbylamine reaction)
Aniline Phenyl isocyanide
(offensive smell)

(ii) C6H5N2Cl + H3PO2 + H2O C6H6 + N2 + H3PO3+HCl

Benzenediazonium Benzene
Chloride
+
(iii) C6H5NH2 + H2SO4 (Conc.) C6H5NH3HSO4
—

Anilinium hydrogen
Aniline sulphate

Reduction
(iv) C6H5N2Cl + C2H5OH C6H6 + CH3CHO + N2 + HCl
Benzene diazonium Benzene Ethanal
Chloride

NH2 NH2
Br Br
(v) + 3Br2(aq.) + 3 HBr

Br
Aniline 2,4,6-Tribromoaniline

O
O
H3C—C CH3COOH
(vi) C6H5NH2 + O C6H5–NH–C–CH3 + CH3COOH
or Pyridine
H3C—C
(Acetylation)
O
Aniline Acetic anhydride Acetanilide

+ — HBF 4 + – NaNO2/Cu
(vii) C6H5N2Cl C6H5 N2BF4 Heat
C6H5 NO2 + BF3 + NaF
Benzene diazonium
Benzenediazonium Nitrobenzene
Chloride
tetra fluoroborate

4. Write the name of following compounds:

(A) C6H5N2 HSO4 (B) –N=N– –OH

Ans. (A) benzene diazonium hydrogen sulphate
(B) p-hydroxy azo benzene
node06\B0BC-BD\Kota\Board Material\Chemistry\RBSE\eng\Amines

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EXERCISE-2 MULTIPLE CHOICE QUESTIONS

(INTRODUCTION OF N-CONTAINING COMPOUND)
1. Which of the following is 1° amine ?
(a) Ethyl diamine (b) Dimethyl amine
(c) Trimethyl amine (d) N-methyl aniline
(PREPARATION OF N)
2. Reaction CH 3CONH 2 NaOBr
gives –
(a) CH3Br (b) CH4 (c) CH3COBr (d) CH3NH2
3. Acetamide changes into methylamine by –
(a) Hofmann bromamide reaction (b) Hofmann reaction
(c) Friedel-Craft's reaction (d) Hinsberg reaction
4. When methyl iodide is heated with ammonia, the product obtained is ?
(a) Methylamine (b) Dimethylamine
(c) Trimethylamine (d) A mixture of the above three amines
5. The Hinsberg's method is used for –
(a) Preparation of primary amines (b) Preparation of secondary amines
(c) Preparation of tertiary amines (d) Separation of amine mixtures
6. In the following reaction, X is –
Bromination NaNO 2 HCl Boiling
X Y Z Tribromobenzene
C 2 H5OH

(a) Benzoic acid (b) Salicylic acid (c) Phenol (d) Aniline
7. Carbylamine reaction is given by –
(a) 1° amine (b) 3° amine (c) 2° amine (d) Quarternary salts
8. The reaction
C6 H5 NH 2 CHCl3 3KOH C6H 5 NC 3KCl 2H 2O
is known as –
(a) Carbylamine reaction (b) Reimer-Tiemann reaction
(c) Kolbe reaction (d) Hofmann's degradation
9. Aromatic primary amine when treated with cold HNO2 gives :
(a) Benzyl alcohol (b) Nitro benzene (c) Benzene (d) Diazonium salt
node06\B0BC-BD\Kota\Board Material\Chemistry\RBSE\eng\Amines

10. Which of the following compound is the strongest base :

(a) Ammonia (b) Aniline (c) Methylamine (d) N-methyl aniline
11. The diazonium salts are the reaction products in presence of excess of mineral acid with nitrous
acid and :
(a) Primary aliphatic amine (b) Secondary aromatic amine
(c) Primary aromatic amine (d) Tertiary aliphatic amine
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12. In acid medium nitrobenzene is reduced to aniline as shown in the reaction
C6H5 NO2 6[H] C6H5 NH 2 2H 2O
The reducing agent used in this reaction is …….
(a) LiAlH4 (b) Sn/HCl (c) Na/alcohol (d) H2/Ni
13. Gabriel's phthalimide synthesis is used for the preparation of
(a) Primary aromatic amine (b) Secondary amine
(c) Primary aliphatic amine (d) Tertiary amine
(PROPERTIES)
14. Which of the following compound is expected to be most basic
(a) Aniline (b) Methylamine (c) Hydroxylamine (d) Ethylamine
15. Aniline when treated with HNO2 and HCl at 0°C gives
(a) Phenol (b) Nitrobenzene
(c) A diazo compound (d) None of these
16. Which one is weakest base
(a) Ammonia (b) Methylamine (c) Dimethylamine (d) Trimethylamine
17. Primary amines can be distinguished from secondary and tertiary amines by reacting with
(a) Chloroform and alcoholic KOH (b) Methyl iodide
(c) Chloroform alone (d) Zinc dust
18. Which of the following is azo- group
(a) –N= (b) –N=N– (c) –NH– (d) –CO–NH–
19. The decreasing order of the basic character of the three amines and ammonia is
(a) NH3 CH3NH 2 C2H 5 NH 2 C6H 5 NH 2 (b) C2H5 NH 2 CH3 NH 2 NH 3 C6H 5 NH 2
(c) C6H5 NH 2 C2H 5 NH 2 CH 3NH 2 NH 3 (d) CH3 NH2 C2H 5 NH 2 C6H 5 NH 2 NH 3
20. Correct order of increasing basicity is
(a) NH3 C6H5 NH 2 (C 2H 5 )2 NH C2H 5 NH 2 (C 2H 5 ) 3 N
(b) C6H5 NH 2 NH 3 (C 2H 5 )3 N (C 2H 5 ) 2 NH C 2H 5 NH 2
(c) C6H5 NH 2 NH 3 C2H 5 NH 2 (C 2H 5 )3 N (C 2H 5 ) 2 NH
(d) C6H5 NH 2 (C 2H 5 )3 N NH 3 C2H 5 NH 2 (C 2H 5 ) 2 NH
21. Aniline on treatment with excess of bromine water gives
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(a) Aniline bromide (b) o-bromoaniline

(c) p-bromoaniline (d) 2, 4, 6-tribromoaniline
22. Unpleasant smelling carbylamines are formed by heating alkali and chloroform with
(a) Any amine (b) Any aliphatic amine
(c) Any aromatic amine (d) Any primary amine

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23. When an organic compound was treated with sodium nitrite and hydrochloric acid in the ice cold,
nitrogen gas was evolved copiously. The compound is
(a) A nitro compound (b) A primary amine
(c) An aliphatic primary amine (d) An aromatic primary amine
24. Aniline on treatment with conc. HNO3 + conc. H2SO4 mixture yields
(a) o- and p-nitroanilines (b) m-nitroanilines
(c) A black tarry matter (d) No reaction
25. Which of the following is most basic
(a) C6H5NH2 (b) (CH3)2NH (c) (CH3)3N (d) NH3
26. If methyl is alkyl group, then which order of basicity is correct
(a) R 2 NH RNH 2 R 3N NH3 (b) R 2 NH R 3 N RNH 2 NH3
(c) RNH 2 NH3 R 2 NH R 3N (d) NH3 RNH 2 R 2 NH R 3N
27. Arrange the following in increasing order of basicity CH3 NH 2 , (CH3 )2 NH,C6 H5 NH 2 , (CH3 )3 N
(a) (CH3 )3 N (CH3 )2 NH CH3 NH 2 C6 H5 NH 2
(b) (CH3 )3 N (CH 3 ) 2 NH CH 3 NH 2 C 6H 5 NH 2
(c) C6H5 NH 2 (CH 3 )3 N CH3 NH 2 (CH 3 ) 2 NH
(d) C6H5 NH 2 (CH3 )3 N CH 3NH 2 (CH3 ) 2 NH
28. Aniline and methyl amine can be differentiated by
(a) Reaction with chloroform and aqueous solution of KOH
(b) Diazotisation followed by coupling with phenol
(c) Reaction with HNO2
(d) None of these
NH 2

29. Electrophilic substitution of with bromine gives

(a) 1, 4, 6-tribromo aniline (b) 2, 4, 6-tribromo aniline

(c) 4-bromo aniline (d) 3-bromo aniline
30. During acetylation of amines what is replaced by acetyl groups
(a) Hydrogen atom attached to nitrogen atom
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(b) One or more hydrogen atoms attached to carbon atom

(c) One or more hydrogen atoms attached to nitrogen atom
(d) Hydrogen atoms attached to either carbon atom or nitrogen atom
31. Ethyl amine on acetylation gives
(a) N-ethyl acetamide (b) Acetamide
(c) Methyl acetamide (d) None

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32. Identify the product Z in the following reaction
(AC) 2 O Br2 /CCl4 HOH
C 6 H 5 NH 2 X Y Z
(a) p-Bromoaniline (b) p -Bromoacetophenone
(c) o-Bromoacetophenone (d) o-Bromoacetonilide
33. Complete the following reaction :
RNH2 + H2SO4
(a) [R NH 3 ] HSO 4 (b) [R NH 3 ]2 SO 42

(c) R NH 2 .H 2SO 4 (d) No reaction

34. The reduction of which of the following compound would yield secondary amine ?
(a) Alkyl nitrite (b) Carbylamine
(c) Primary amine (d) Secondary nitro compound

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. a d a d d d a a d c
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. c b c d c a a b b c
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Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. d d c c b a c b b c
Q. No. 31 32 33 34
Ans. a a b b

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CHAPTER–10 : BIOMOLECULES
• Chapter at a glance 144-150
• Exercise-1_Important Questions 151-161
• Exercise-2_Multiple Choice Questions 162-163

CHAPTER AT A GLANCE

INTRODUCTION :
• Complex organic compound which governs the common activities of the living organism are
called biomolecules.
• Living systems are made up of various complex biomolecules like carbohydrates, proteins,
nucleic acids, lipids, etc.
• Proteins and carbohydrates are essential component of our food.
Carbohydrates :
• Carbohydrates are mainly produced by plants.
• General formula is Cx(H2O)y.
• In previous it was considered as hydrates of carbon, from where the name carbohydrate was derived.
• Rhamnose, C6H12O5 is a carbohydrate but does not fit in this definition.
• Chemically, the carbohydrates may be defined as optically active palyhydroxy aldehydes or
ketones or the compounds which produce such units on hydrolysis.
• Some of the carbohydrates, which are sweet in taste, are also called sugars.
• The most common sugar, used in our homes in named as sucrose whereas the sugar present in
milk known as Lactose.
Classification of Carbohydrates :
Carbohydrates are classified on the basis of their behaviour on hydrolysis. They have been
broadly divided into following three groups.
Monosaccharides :
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A carbohydrate that cannot be hydrolysed further to give simpler unit of polyhydroxy aldehyde or
ketone is called a monosaccharide. Some common examples are glucose, fructose, ribose, etc.
Monosaccharides are further classified on the basis of number of carbon atoms and the functional
group present in them. If a monosaccharide contains an aldehyde group, it is known as an aldose
and if it contains a keto group, it is known as a ketose. Number of carbon atoms constituting the
monosaccharide is also introduced in the name as is evident from the examples given in Table

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Different Types of Monosaccharides

Carbon Atom General term Aldehyde Ketone

3 Triose Aldolriose Kelolriose

4 Telrose Aldolelrose Kelolelrose

5 Pen lose Aldopenlose Kelopen lose

6 Hexose Aldohexose Kelohexose

7 Heplose Aldoheplose Keloheplose

• All those carbohydrates which are reduce by Fehling's solution and Tollen's reagent are called
reducing sugar. All monosaccharides i.e., Aldose and ketose are called reducing sugar.
• In disaccharides, if the reducing groups of monosaccharides i.e., aldehydic or ketonic groups
are bonded, these are non reducing sugars e.g. & sucrose. On the other hand, sugars in which
these junctional groups are free, are called reducing sugars, for examples maltose and lactose.
GLUCOSE (ALDOHEXOSE)
Preparation of Glucose
1. From sucrose (Cane sugar): If sucrose is boiled with dilute HCl or H2SO4 in alcoholic solution,
glucose and fructose are obtained in equal amounts.

C12H22O11 + H2O H
C6H12O6 + C6H12O6
Sucrose Glucose Fructose

2. From starch: Commercially glucose is obtained by hydrolysis of starch by boiling it with dilute
H2SO4 at 393 K under pressure.

(C6H10O5)n+nH2O H
393K : 2 3 atm
nC6H12O6
Starch or cellulose Glucose

Configuration in monosaccharides:
For assigning the configuration of monosaccharides, it is the lowest asymmetric carbon atom
(as shown below) which is compared. As in (+) glucose, —OH on the lowest asymmetric carbon
is on the right side which is comparable to (+) glyceraldehyde, so it is assigned D-configuration.
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CHO
H–C–OH
HO–C–H
CHO H–C–OH
H OH H–C–OH
CH2OH
CH2OH
D–(+)-Glyceraldehyde D-(+) – Glucose

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Cyclic structure of Glucose :-
It was found that glucose forms a six-membered ring in which —OH at C-5 is involved in ring
formation. This explains the absence of —CHO group and also existence of glucose in two forms
as shown below. These two cyclic forms exist in equilibrium with open chain structure.
1 O 1
H–C–OH 1 HO–C–H
H–C
H 2 OH H 2 OH
O H2 OH O
HO 3 H HO 3 H
HO 3 H
H 4 OH H 4 OH
H4 OH
H5 H5
6 H5 OH 6
6
CH2OH CH2OH
CH2OH
-D-(+) – Glucose -D-(+) – Glucose
The two cyclic hemiacetal forms of glucose differ only in the configuration of the hydroxyl
group at C1, called anomeric carbon (the aldehyde carbon before cyclisation). Such isomers, i.e.,
-form and -form, are called anomers. The six membered cyclic structure of glucose is called
pyranose structure ( – or –), in analogy with pyran. Pyran is a cyclic organic compound with
one oxygen atom and five carbon atoms in the ring. The cyclic structure of glucose is more
correctly represented by Haworth structure as given below.
6 6
CH2OH CH2OH
O 5 O 5 O
H H H OH
H H
4 1 4 1
OH H OH H
HO 3 2 OH HO 3 2 H
Pyran H OH H OH
– D – (+) – Glucopyranose – D – (+) – Glucopyranose
– Pyranose ring) – Pyranose ring)
FRUCTOSE (KETOHEXOSE)
Structure of Fructose:
Fructose also has the molecular formula C6H12O6 and on the basis of its reactions it was found
to contain a ketonic functional group at carbon number 2 and six carbons in straight chain as
in the case of glucose. It belongs to D-series and is a laevorotatory compound. It is
appropriately written as D-(–)-fructose. Its open chain structure is as shown.
It also exists in two cyclic forms which are obtained by the addition of —OH at C5 to the
( C=O ) group. The ring, thus formed is a five membered ring and is named as furanose with
analogy to the compound furan. Furan is a five membered cyclic compound with one oxygen and
four carbon atoms.
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CH2OH
C=O
HO C H
H C OH
H C OH
CH2OH
Fructose
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1 2 2 1
O HOH2C–C–OH HO–C–CH2OH
HO 3 H O HO 3 H O
4
H OH H 4
OH
H5 H5
Furan 6 6
CH2OH CH2OH
– D – (–) – Fructofuranose – D – (–) – Fructofuranose

The cyclic structures of two anomers of fructose are represented by Haworth structures as given.
6 1
6
HOH2C O CH2OH HOH2C OH
O
5 2
5 2
H OH H OH
H OH H CH2OH
4 3 3 1
4

OH H OH
H
– D – (–) – Fructofuranose – D – (–) – Fructofuranose
– Furanose ring) ( – Furanose ring)

PROTEINS
The word protein is derived from Greek word, “proteios” which means primary or of prime
importance. All proteins are polymers of -L-amino acids.
Amino acids : Amino acids contain amino (–NH2) and carboxyl (–COOH) functional groups.
Depending upon the relative position of amino group with respect to carboxyl group, the amino
acids can be classified as , , , and so on. Only -amino acids are obtained on hydrolysis of
proteins. They may contain other functional groups also.
COOH
G–CH–COOH
H 2N H
NH2
– amino acidG
Table : Natural Amino Acids
Classification of Amino Acids : Amino acids are classified as acidic, basic or neutral depending upon
the relative number of amino and carboxyl groups in their molecule.
The amino acids, which can be synthesised in the body, are known as non-essential amino
acids. On the other hand, those which cannot be synthesised in the body and must be obtained
through diet, are known as essential amino acids.
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Amino acids are usually colourless, crystalline solids. These are water-soluble, high melting
solids and 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.
O O
–
R–CH–C–O–H R–CH–C–O
+
:NH2 NH3
(Zwitter ion)
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In aqueous solution, the carboxyl group can lose a proton and amino group can accept a proton,
giving rise to a dipolar ion known as zwitter ion. This is neutral but contains both positive and
negative charges. In zwitter ionic form, amino acids show amphoteric behaviour as they react
both with acids and bases.
Except glycine, all other naturally occurring -amino acids are optically active, since the -
carbon atom is asymmetric. These exist both in ‘D’ and ‘L’ forms. Most naturally occurring
amino acids have L-configuration. L-Aminoacids are represented by writing the –NH2 group on
left hand side.
Structure of Proteins:
Proteins are the polymers of -amino acids and they are connected to each other by peptide
bond or peptide linkage. Chemically, peptide linkage is an amide formed between –COOH
group and –NH2 group.
H2N–CH2–COOH + H2N–CH–COOH
–H2O CH3
H2N–CH2–CO–NH–CH–COOH

Peptide linkage
CH3

Glycylalanine [Gly-Ala]
The reaction between two molecules of similar or different amino acids, proceeds through the
combination of the amino group of one molecule with the carboxyl group of the other. This
results in the elimination of a water molecule and formation of a peptide bond –CO–NH–.
Denaturation of Proteins :
Physical change like change in temperature or chemical change like change in pH, the hydrogen
bonds are disturbed. Due to this, globules unfold and helix get uncoiled and protein loses its
biological activity. This is called denaturation of protein. The coagulation of egg white on
boiling is a common example of denaturation. Another example is curdling of milk which is
caused due to the formation of lactic acid by the bacteria present in milk.
During denaturation secondary and tertiary structures are destroyed but primary structure remains
unchange.
NUCLEIC ACIDS
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Introduction :
It has been observed that nucleus of a living cell is responsible for the transmission of inherent
characters, also called heredity. The particles in nucleus of the cell, responsible for heredity, are
called chromosomes which are made up of proteins and another type of biomolecules called
nucleic acids. These are mainly of two types, the deoxyribonucleic acid (DNA) and
ribonucleic acid (RNA). Since nucleic acids are long chain polymers of nucleotides, so they are
also called polynucleotides.
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Chemical composition of Nucleic Acids :
Complete hydrolysis of DNA (or RNA) yields a pentose sugar, phosphoric acid and nitrogen
containing heterocyclic compounds (called bases). In DNA molecules, the sugar moiety is -D-2-
deoxyribose whereas in RNA molecule, it is -D-ribose.
DNA contains four bases viz. adenine (A), guanine (G), cytosine (C) and thymine (T). RNA
also contains four bases, the first three bases are same as in DNA but the fourth one is uracil (U).
Structure of Nucleic Acids :-
A unit formed by the attachment of a base to 1' position of sugar is known as nucleoside. In
nucleosides, the sugar carbons are numbered as 1', 2', 3', etc. in order to distinguish these from
the bases. When nucleoside is linked to phosphoric acid at 5'-position of sugar moiety, we get a
nucleotide.
Nucleotides are joined together by phosphodiester linkage between 5' and 3' carbon atoms of
the pentose sugar. A simplified version of nucleic acid chain is as shown below. Fig.
Base Base Base

Sugar Phosphate Sugar Phosphate Sugar

n
Information regarding the sequence of nucleotides in the chain of a nucleic acid is called its
primary structure. Nucleic acids have a secondary structure also. James Watson and Francis
Crick gave a double strand helix structure for DNA (Fig.). Two nucleic acid chains are wound
about each other and held together by hydrogen bonds between pairs of bases. The two strands
are complementary to each other because the hydrogen bonds are formed between specific pairs
of bases. Adenine forms hydrogen bonds with thymine whereas cytosine forms hydrogen bonds
with guanine.
In secondary structure of RNA, helices are present which are only single stranded. Sometimes
they fold back on themselves to form a double helix structure. RNA molecules are of three types
and they perform different functions. They are named as messenger RNA (m-RNA), ribosomal
RNA (r-RNA) and transfer RNA (t-RNA).
5' 3'

–G C–
A=T
T= A
A=T

C=G
G C
T=A
–C G–

–T=A–
G C
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A=T
–T=A–

–A=T–
T= A
C G
–G C–

5' 3'

Double strand helix

structure for DNA

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VITAMINS

Vitamin Sources Deficiency diseases

(i) Vitamin-A Milk, cod liver oil, butter, Night blindness, xerophthalmia (i.e. hardening of
(Retinol or carrots, green leaves, cornea of eye) and xerosis.
eye vitamin) tomatoes, eggs, etc.
(ii) Vitamin-B1 Pulses, nuts, green Beriberi (a disease of nervous system) and loss apetite.
Thiamine or Aneurin vegetables, Polished rice.
yeast and egg yolk.
(iii) Vitamin - B2 Milk, meat, green Inflammation of tongue or dark red tongue
or Riboflavin or Lactoflavin vegetables and yeast. (glossitis), and cheilosis (cracking or fissuring
the lips and corners of the mouth)
(iv) Vitamin-B6 Rice, bran, yeast, meat, Specific dermatitlis called acrodynia, pellagra
or Pyridoxine fish,egg, yolk, maize, (shrivelled skin) anaemia and convulsions.
or Adermine spinach and lettuce.
(v) Vitamin-B12 Milk, liver, kedney and eggs. Inflammation of tongue, mouth etc.and pernicious
or Cyanocoblamin anaemia.
(vi) Vitamin-C Citrous fruits, amla, Scurvy and brittleness of bones, swelling and
or L-Ascorbic acid (oranges,lemons), sprouted bleeding of gums and lossening of teeth.
pulses,germinated
grains and leafy vegetables.
(vii) Vitamin D or Ergocal Fish liver oil, cod liver oil, Rickets (softening and bending of bones) in children, ciferol
(or antirachtic milk and eggs. controls Ca and P metabolism.
Vitamin of sunshine
vitamin)
(viii) Vitamin-E or Eggs, milk, fish, wheat Sterility (loss of sexual power and reproduction)
Tocopherols ( and ) germ,oil,cotton seed oil etc.
or Antisterility factor
(ix) Vitamin-H (Biotin) Yeast,liver, Kidney and milk. Dermatitis, loss of hair and paralysis.
(x) Vitamin-K or Cabbage, alfalfa, spinach Haemorrhage and lenthens time of blood clotting.
Phylloquinones or and carrot tops.
Antihaemorrhagic vitamin
(xi) Coenzyme Q10 Chloroplasts of green Low order of immunity of body against
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plants and mitochondria many diseases

of animals

HORMONES
Hormones are biomolecules which are produced in the ductless (endocrine) glands and are
carried to different parts of the body by the blood stream where they control various metabolic
processes. These are required in minute quantites and unlike fats and carbohydrates these are not
stored in the body but are continuously produced.
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EXERCISE-1 IMPORTANT QUESTIONS

1. Glucose or succrose are soluble in water but cyclohexane or benzene (simple six membered ring
compounds) are insoluble in water. Explain.
Ans. A glucose molecules contains five –OH groups while a sucrose molecule contains eight –OH
groups. Thus, glucose and sucrose undergo extensive H-bonding with water.
Hence, these are soluble in water.
But, cyclohexane and benezene do not contain –OH groups. Hence, they cannot undergo
H-bonding with water and as a result, they are insoluble in water.
2. What are the expected products of hydrolysis of lactose ?
Ans. Lactose is composed of -D galactose and -D glucose. Thus, on hydrolysis, it gives -D
galactose and -D glucose.
6 6
CH2OH CH2OH
O O
HO H5 H H
5
OH
4 1 O 4 1
H OH H H OH H H
3 2 3 2
H OH H OH

- D - Galactose - D - Glucose
Lactose
C12H22O11 + H2O C6H12O6 + C6H12O6
Lactose D-(+)-Glucose D-(+)-Galactose
3. How do you explain the absence of aldehyde group in the pentaacetate of D-glucose ?
Ans. D-glucose reacts with hydroxylamine (NH2OH) to form an oxime because of the presence of
aldehydic (–CHO) group of carbonyl carbon. This happens as the cyclic structure of glucose forms an
open chain structure in an aqueous medium, which then reacts with NH2OH to give an oxime.
CHO CH=N–OH
NH 4OH
(CHOH)4 (CHOH)4
CH2OH CH2OH
Glucose Oxime
But pentaacetate of D-glucose does not react with NH2OH. This is because pentaacetate does not
form an open chain structure.
1 1
CH=NOH CH=O CHOH CHOCOCH3
H 2 2
OH HOH2C OH H OHO H OCOCH3
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–H2O 3 5(CH3CO)2O 3
HO H HO H HO H CH3OCO H
NH2OH –5CH3COOH
H OH 4 H 4 OCOCH O
H OH H OH 3

H OH 5 5
H OH H H
6 6
CH2OH CH2OH CH2OH CH2OCOCH3
- glucose pentaacetate
Glucose oxime Glucose - glucose + - glucose +
(open chain form) - glucose pentaacetate

No oxime

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4. The melting points and solubility in water of amino acids are generally higher than that of the
corresponding halo acids. Explain.
Ans. Both acidic (carboxyl) as well as basic (amino) groups are present in the same molecule of amino
acids. In aqueous solutions, the carboxyl group can lose a proton and the amino group can accept,
thus giving rise to a dipolar ion known as a zwitter ion.
O O
R—CH—C—O—H R—CH—C—O—
+
NH2 NH3
(Zwitter ion)

Due to this dipolar behaviour, they have strong electrostatic interactions within them and with
water, But halo-acids do not exhibit such dipolar behaviour.
For this reason, the melting points and the solubility of amino acids in water is higher than those
of the corresponding halo-acids.
5. Where does the water present in the egg go after boiling the egg?
Ans. When an egg is boiled, the proteins present inside the egg get denatured and coagulate. After
boiling the egg, the water present in it is absorbed by the coagulated protein through H-bonding.
6. Why cannot vitamin C be stored in our body?
Ans. Vitamin C cannot be stored in our body because it is water soluble. As a result, it is readily
excreted in the urine.
7. What products would be formed when a nucleotide from DNA containing thymine is
hydrolysed?
Ans. When a nucleotide from the DNA containing thymine is hydrolyzed, thymine -D-2-deoxyribose
and phosphoric acid are obtained as products.
8. When RNA is hydrolysed, there is not relationship among the quantities of different bases
obtained. What does this fact suggest about the structure of RNA?
Ans. A DNA molecule is double-stranded in which the pairing of bases occurs. Adenine always pairs
with thymine, while cytosine always pairs with guanine. Therefore, on hydrolysis of DNA, the
quantity of adenine produced is equal of that off thymine and similarly, the quantity of cytosine
is equal to that of guanine.
But when RNA is hydrolyzed, there is no relationship among the quantities of the different bases
obtained. Hence, RNA is single-stranded.
9. What are monosaccharides?
Ans. Monosaccharides are carbohydrates that cannot be hydrolysed further to give simpler units of
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polyhydroxy aldehyde or ketone.

Monosaccharides are classified on the basis of number of carbon atoms and the functional group
present in them. Monosaccharides containing an aldehyde group are known as aldose and those
containing a keto group are known as ketose. Monosaccharides are further classified as triose,
tetrose, pentose, hexose, and heptose according to the number of carbon atoms they contain. For
example, a ketose containing 3 carbon atoms is called ketotriose and an aldose containing
3 carbon atoms is called aldotriose.

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10. What are reducing sugars?
Ans. Reducing sugars are carbohydrates that reduce Fehling's solution and Tollen's reagent. All
monosaccharides and disaccharides, excluding sucrose, are reducing sugars.
11. Write two main functions of carbohydrates in plants.
Ans. Two main functions of carbohydrates in plants are:
(i) Polysaccharides such as strach serve as storage molecule.
(ii) Cellulose, a polysaccharide, is used to build the cell wall.
12. Classify the following into monosaccharides and disaccharides.
Ribose, 2-deoxyribose, maltose, galactose, fructose and lactose
Ans. Monosaccharides :
Ribose, 2-deoxyribose, galactose, fructose
Disaccharides :
Maltose, lactose
13. What do you understand by the term glycosidic linkage?
Ans. Glycosidic linkage refers to the linkage formed between two monosaccharide units through an
oxygen atom by the loss of a water molecule.
For example, in a sucrose molecule, two monosaccharide units, - glucose and - fructose, are
joined together by a glycosidic linkage.
6
CH2OH
5 O 1
O
H H H HOH2C H
4 1 2 5
OH OH H O
3 2 H OH CH
6
2 OH
Glycosidic 3 4
H linkage
OH OH H
- D - glucose - D - fructose
Surcose
14. What is glycogen? How is it different from starch?
Ans. Glycogen is a carbohydrate (polysaccharide). In animals, carbohydrates are stored as glycogen.
Strach is a carbohydrate consisting of two components – amylose (15-20%) and amylopectin
(80-85%).
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However, glycogen consists of only one component whose structure is similar to amylopectin.
Also, glycogen is more branched than amylopectin.

15. What are the hydrolysis products of (i) sucrose and (ii) lactose?
Ans. (i) On hydrolysis, sucrose gives one molecule of -D glucose and one molecule of
-D-fructose.

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CH2OH
O O
H H H HOH2C H

OH OH H O
H OH CH2OH
H OH OH H

Hydrolysis

CH2OH
O O
H H H HOH2C H
+
OH OH H OH HO H OH CH2OH

H OH OH H
- D - glucose - D - fructose

(ii) The hydrolysis of lactose give -D-galactose and -D-glucose.

CH2OH CH2OH
O O
OH H H H OH
O
H OH H H OH H H
H OH H OH

Hydrolysis

CH2OH CH2OH
O O
OH H OH H H OH
+
H OH H H OH OH H H
H OH H OH

- D - galactose - D - glucose
16. What is the basic structural difference between starch and cellulose ?
Ans. Starch consists of two components - amylose and amylopectin. Amylose is a long linear chain of
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-D–(+)–glucose units joined by Cl–C4 glycosidic linkage ( -link).

CH2OH CH2OH
O O
H H H H H H
4 1 4 1
O OH H O OH H O

H OH H OH
-Link
Amylose
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Amylopectin is a branched-chain polymer of –D–glucose units, in which the chain is formed
by C1– C4 glycosidic linkage and the branching occurs by C1– C6 glycosidic linkage.
CH2OH CH2OH
O O
H H H H H H
4 1 4 1
O OH H O OH H O -Link
Branch at C6
H OH H OH 6 CH2OH
CH2
-Link O O
H H5 H H H H
4 1 4 1
O OH H O OH H O

H OH H OH
-Link
Amylopectin
On the other hand, cellulose is a straight-chain polysacchoride of -D-glucose units joined by
C1– C4 glycosidic linkage ( -link).
HOH2C
O
HOH2C O
O
HOH2C O OH
O
O OH OH
-Link
O OH OH
-Link
OH

17. What happens when D-glucose is treated with the following reagents ?
(i) HI (ii) Bromine water (iii) HNO3
Ans. (i) When D-glucose is heated with HI for a long time, n-hexane is formed.
CHO
Hl CH3–CH2–CH2–CH2–CH2–CH3
(CHOH)4
n - hexane
CH2OH
D - glucose
(ii) When D-glucose is treated with Br2 water, D-gluconic acid is produced.
CHO COOH
Br 2water
(CHOH)4 (CHOH)4
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CH2OH CH2OH
D - glucose D-gluconic acid
(iii) On being treated with HNO3, D-glucose get oxidised to give saccharic acid.
CHO COOH
HNO 3
(CHOH)4 (CHOH)4
CH2OH COOH
D - glucose Saccharic acid

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18. Eunmerate the reactions of D-glucose which cannot be explained by its open chain structure.
Ans. (1) Aldehydes give 2, 4-DNP test. Schiff's test, and react with NaHSO4 to form the hydrogen
sulphite addition prodcut. However, glucose does not undergo these reactions.
(2) The pentaacetate of glucose does not react with hydroxylamine. This indicates that a free –
CHO group is absent from glucose.
(3) Glucose exists in two crystalline forms – and . The - form (m.p. = 419 K) crystallises
from a concentrated solution of glucose at 303 K and the -form (m.p.=423 K) crystallises
from a hot and saturated aqueous solution at 371 K. This behaviour cannot be explained by
the open chain structure of glucose.
19. What are essential and non-essential amino acids ? Give two examples of each type.
Ans. Essential amino acids are required by the human body, but they cannot be synthesised in the
body. They must be taken through food. For example : valine and leucine
Non-essential amino acids are also required by the human body, but they can be synthesised in
the body. For example: glycine, and alanine
(i) Peptide linkage (ii) Primary structure (iii) Denaturation
20. Define the following as related to proteins
(i) Peptide linkage (ii) Primary structure (iii) Denaturation
Ans. (i) Peptide linkage :
The amide formed between –COOH group of one molecule of an amino acid and –NH2 group of
another molecule of the amino acid by the elimination of a water molecule is called a peptide
linkage.
Peptide
linkage
–H2O
H2N—CH—COOH + H2N—CH—COOH H2N—CH—CO—NH—CH—COOH
CH(CH3)2 CH3 CH(CH3) 2 CH3
Valine Alanine Valylalanine (Val-Ala)

(ii) Primary structure :

The primary structure of protein refres to the specific sequence in which various amino acids are
present in it, i.e., the sequence of linkage between amino acids in a polypeptide chain. The
sequence in which amino acids are arranged is different in each protein. A change in the
sequence creates a different protein.
(iii) Denaturation :
In a biological system, a protein is found to have a unique 3- dimensional structure and a unique
biological activity . In such a situation, the protein is called native protein. However, when the
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native protein is subjected to physical changes such as chage in temperature or chemical change
such as change in pH, its H-bonds are disturbed. This disturbance unfolds the globules and
uncoils the helix. As a result, the protein loss its biological activity. This loss of biological
activity by the protein is called denaturation. During denaturation, the secondary and the tertiary
structures of the protein get destroyed, but the primary structure remains unaltered.
One of the examples of denaturation of proteins is the coagulation of egg white when an egg is
boiled.

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21. What are the common types of secondary structure of proteins ?
Ans. There are two common types of secondary structure of proteins :
(i) - helix structure
(ii) -pleated sheet structure
- Helix structure

In this structure, the –NH group of an amino acid residue forms H-bonds with the C=O group

of the adjacent turn of the right-handed screw ( -helix).

C
O
C
C
O
HO
CN H
N
O H
C
HCN
O
O H
N NH

H N
N

- helix structure
-pleated sheet structure
This structure is called so because it looks like the pleated folds of drapery. In this structure, all
the peptide chains are stretched out to nearly the maximum extension and then laid side by side.
These peptide chains are held together by intermolecular hydrogen bonds.

N
RCH N
N
H C=O RCH
N H RCH
C=O
RCH N H C=O
C=O RCH N
N RCH
H O=C
RCH N H O=C
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H C=O RCH
N H
N H C=O
RCH
RCH N H
C RCH N C=O
C= RCH
=C

- pleated sheet structure

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22. What type of bonding helps in stabilising the -helix structure of proteins ?

Ans. The H-bonds formed between the –NH group of each amino acid residue and the C=O group of

the adjacent turns of the -helix help in stabilising the helix.

23. Differentiate between globular and fibrous proteins.
Ans. Fibrous protein Globular protein
1. It is a fibre-like structure formed by the The polypeptide chain in this protein in folded
polypeptide chain. These proteins are hold around itself, giving rise to a spherical
together by strong hydrogen and disulphide structure.
bonds.
2. It is usually insoluble in water. It is usually soluble in water.
3. Fibrous proteins are usually used for structural All enzymes are globular proteins. Some
purposes. For example, keratin is present in hormones such as insulin are also globular
nails and hair; collagen in tendons; and myosin proteins.
in muscles.

24. How do you explain the amphoteric behaviour of amino acids ?

Ans. In aqueous solution, the carboxyl group of an amino acid can lose a proton and the amino group
can accept a proton to gives a dipolar ion known as zwitter ion.
O O
R—CH—C—O—H R—CH—C—O—
+
NH2 NH3
(Zwitter ion)

Therefore, in zwitter ionic form, the amino acid can act both as an acid and as a base.
O O O
+ +
H H
R—CH—C—O —
R—CH—C—O —
R—CH—C—OH
OH +
OH +
NH2 NH3 NH3
Thus, amino acids show amphoteric behaviour.
25. What are enzymes?
Ans. Enzymes are proteins that catalyse biological reactions. They are very specific in nature and
catalyse only a particular reaction for a particular substrate. Enzymes are usually named after the
particular substrate or class of substrate and some times after the particular reaction.
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For example, enzymes used to catalyse the hydrolysis of maltose into glucose is named as
maltase.

Again, the enzymes used to catalyse the oxidation of one substrate with the simultaneous
reduction of another substrate are named as oxidoreductase enzymes.
The name of an enzymes ends with '–ase'.
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26. What is the effect of denaturation on the structure of proteins ?
Ans. As a result of denaturation, globules get unfolded and helixes get uncoiled. Secondary and
tertiary structures of protein are destroyed, but the primary sturctures remain unaltered. It can be
said that during denaturation, secondary and tertiary-structured proteins get converted into
primary - structured proteins. Also, as the secondary and tertiary structures of a protein are
destroyed, the enzyme loses its activity.
27. How are vitamins classified ? Name the vitamin responsible for the coagulation of blood.
Ans. On the basis of their solubility in water or fat, vitamins are classified into two groups.
(i) Fat-soluble vitamins : Vitamins that are soluble in fat and oils, but not in 'water, belong to
this group. For example: Vitamins A, D, E, and K
(ii) Water-soluble vitamins : Vitamins that are soluble in water belong to this group. For
example : B group vitamins (B1, B2, B6, B12, etc.) and vitamin C
However, biotin or vitamin H is neither soluble in water nor in fat.
Vitamin K is responsible for the coagulation of blood.
28. Why are vitamin A and vitamin C essential to us ? Give their important sources.
Ans. The deficiency of vitamin A leads to xerophthalmia (hardening of the cornea of the eye) and
night blindness. The deficiency of vitamin C leads to scurvy (bleeding gums).
The sources of vitamin A are fish liver oil, carrots, butter, and milk. The sources of vitamin C are
citrus fruits, amla, and green leafy vegatables.
29. What are nucleic acids ? Mention their two important functions.
Ans. Nucleic acids are biomolecules found in the nuclei of all living cells, as one of the constituents of
chromosomes. There are mainly two types of nucleic acids - deoxyribonucleic acid (DNA) and
ribonucleic acid (RNA). Nucleic acid are also known as polynucleotides as they are long-chain
polymers of nucleotides.
Two main functions of nucleic acids are :
(i) DNA is responsible for the transmission of inherent characters from one generation to the
next. This process of transmission is called heredity.
(ii) Nucleic acids (both DNA and RNA) are responsible for protein synthesis in a cell. Even
though the proteins are actually synthesised by the various RNA molecules in a cell, the message
for the synthesis of a particular protein is present in DNA.
30. What is the difference between a nucleoside and a nucleotide ?
Ans. A nucleoside is formed by the attachment of a base to l' position of sugar.
Nucleoside = Sugar + Base
5' O
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HOH2C Base
4' 1'
HH HH
3' 2'
OH OH
Structure of a nucleoside
On the other hand, all the three basic components of nucleic acids (i.e., pentose sugar, phosphoric
acid, and base) are present in a nucleotide.

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Nucleotide = Sugar + Base + Phosphoric acid
O
— 5' O
O —P—O—H2C Base
—
O 4' 1'
HH HH
3' 2'
OH OH
Structure of a nucleotide
31. The two strands in DNA are not identical but are complementary. Explain.
Ans. In the helical structure of DNA, the two strands are held together by hydrogen bonds between
specific pairs of bases. Cytosin forms hydrogen bond with guanine, while adenine forms
hydrogen bonds with thymine. As a result, the two strands are complementary to each other.
32. Write the important structural and functional differences between DNA and RNA.
Ans. The structural differences between DNA and RNA are as follows :

DNA RNA
1. The sugar moiety in DNA molecules is The sugar moiety in RNA molecules is -D
-D-2 deoxyribose. ribose.
2. DNA contains thyamin (T). It does not RNA contains uracil (U). It does not contain
contain Uracil (U). thymine (T).
3. The helical structure of DNA is double- The halical structure of RNA is single-
stranded. stranded.

The functional differences between DNA and RNA are as follows :

DNA RNA
1. DNA is the chemical basis of hereidity. RNA is not responsible for heredity.
2. DNA molecules do not synthesise proteins, Proteins are synthesised by RNA molecules
but transfer coded message for the synthesis in the cells.
of proteins in the cells.

33. What are the different types of RNA found in the cell ?
Ans. (i) Messenger RNA (m-RNA)
(ii) Ribosomal RNA (r-RNA)
(iii) Transfer RNA (t-RNA)
34. (A) Write the name of diseases due to deficiency of vitamins 'A' and vitamins 'B'.
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(B) On the basis of 'Sugar' differentiate D.N.A. and R.N.A.

Ans. (A) Vitamin A Night blindness
Vitamin B Beri berry
(B) DNA It consist of De-oxy ribose sugar.
RNA It consist of ribose sugar

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35. (a) What are monosaccharides? Write the defination?
(b) (i) Name the products yeilds fron the complete hydrolysis of DNA?
(ii) Write the structural formula of sugar moiety in DNA & RNA?
(c) Write the name of method related with DNA to identify the dead body in any accident?
Ans. (a) Carbohydrate which can not be further hydrolysed. This is monomer unit of carbohydrate
ex. glyceraldehye
(b) (i) Product of DNA hydrolysis
Pentose sugar ( -2 de oxy ribose sugar)
Nitrogenous base (Adenine, Guanine, Thymine, Cytosine)
Phosphoric acid

CH2OH O OH HOCH2 O OH
(ii)
H H H H H H H H

OH OH OH H
-D-Ribose sugar 2-Deoxy Ribose
(RNA) sugar (DNA)
(c) DNA finger printing
36. Explain denaturation of protein with an example.
Ans. Due to change in pH and Temp. The loss of biological activity will take place such that 2° and 3°
structures are destroyed 1° remains same.
Ex. Boiling of an egg.
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EXERCISE-2 MULTIPLE CHOICE QUESTIONS
(CARBOHYDRATES)
1. General formula for carbohydrates is:
(a) Cn H2n O2n 2 (b) Cx (H 2O)2x (c) C x (H 2 O) y (d) None of these
2. The commonest disaccharide has the molecular formula –
(a) C10 H18 O9 (b) C10 H 20 O10 (c) C18 H22 O11 (d) C12 H 22 O11
3. Molecular formula C6 H12 O6 is of –
(a) Glucose (b) Fructose (c) Both (a) and (b) (d) None of these
4. Sugars are :
(a) Optically active polyhydroxy aldehydes
(b) Optically active polyhydroxy ketones
(c) Optically active polyhydroxy aldehydes or ketones
(d) Polyhydroxy aldehydes or ketones which may or may not be optically active
5. Which is not monosaccharide?
(a) Glucose (b) Fructose (c) Galactose (d) All of these
6. If monosaccharide contains an aldehyde group, it is known as –
(a) Epimer (b) Osones (c) Osazone (d) Aldose
7. If a monosaccharide contains a ketogroup, it is known as –
(a) Ketose (b) Osones (c) Epimer (d) Osazone
8. Glucose contains –
(a) One –CHO group (b) Five –OH groups
(c) One primary alcoholic group (d) All are correct
(PROTEIN)
9. Insulin is:
(a) An amino acid (b) Protein (c) A carbohydrate (d) A lipid
10. Peptides are:
(a) Esters (b) Salts (c) Amides (d) Ketones
11. The proteins which are insoluble in water are:
(a) Fibrous proteins (b) Globular proteins
(c) Both (a) and (b) (d) None of these
12. Amino acids are :
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(a) Liquids (b) Volatile solids

(c) Non-volatile crystalline compounds (d) Mixture of amines and acids
13. Proteins are hydrolysed by enzymes into –
(a) Dicarboxylic acids (b) Hydroxy acids
(c) Amino acids (d) Aromatic acids
14. The functional group which is found in amino acid is :
(a) –COOH group (b) –NH2 group (c) –CH3 group (d) Both (a) and (b)

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15. Metal present in blood is :
(a) Al (b) Mg (c) Cu (d) Fe
16. Proteins are built up of –
(a) Dicarboxylic acids (b) Amino acids
(c) Alcohols (d) Hydroxy acids
17. The helical structure of proteins is established by –
(a) Peptide bonds (b) Dipeptide bond (c) Hydrogen bond (d) Vander Waal's forces
(NUCLEIC ACID)
18. A nucleotide consists of –
(a) Base and sugar (b) Base and phosphate
(c) Sugar and phosphate (d) Base, sugar and phosphate
19. Which of the following is responsible for heredity character?
(a) DNA (b) RNA (c) Proteins (d) Hormones
20. The base adenine occurs in –
(a) DNA only (b) RNA only
(c) DNA and RNA both (d) Protein
21. The protein which maintains blood sugar level in the human body?
(a) Haemoglobin (b) Oxytocin (c) Insulin (d) Ptyalin
22. In DNA, the complementary bases are:
(a) Uracil and adenine; cytosine and guanine (b) Adenine and thymine; guanine and cytosine
(c) Adenine and thymine; guanine and uracil (d) Adenine and guanine; thymine and cytosine
23. Which substance is not present in nucleic acid?
(a) Cytosine (b) Adenine (c) Thymine (d) Guanidine
24. The structure of DNA is:
(a) Linear (b) Single helix (c) Double helix (d) Triple helix
25. DNA contains the sugar –
(a) Deoxyribose (b) Ribose (c) D-Fructose (d) D-glucose
26. The base present in DNA, but not in RNA is :
(a) Guanine (b) Adenine (c) Uracil (d) Thymine

ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
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Ans. c d c c c d a d b c
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. a c c d d b c d a c
Q. No. 21 22 23 24 25 26
Ans. c b d c a d

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IMPORTANT QUESTIONS OF (OC) REASONING

1. Why chlorobenzene is less reactive than chloromethane ?
Ans. In chlorobenzene, each carbon atom of benzene is sp2 hyridised and is electron withdrawing.
Chlorine atom donates a lone pair of electron and acquire positive charge. The negative charge is
delocalised on ortho and para position by resonance.
:

:
Cl Cl Cl Cl Cl
: : : :

– –

–
C-Cl bond acquires partial double bond character and larger amount of energy is required to
break C-Cl bond in chlorobenzene and therefore is less reactive than haloalkane towards
nucleophilic substitution reaction.
2. Explain why Haloalkanes react with KCN to form alkyl cyanide as main product while AgCN
form isocyonide ?
Ans. KCN is, predominantly ionic compound and provide cyanide ion : C N in solution. The attack
mainly takes place through lone pair of electron on carbon atom due to high electron density and
not through nitrogen atom since C-C bond is more stable than C-N bond. AgCN: is mainly a
covalent compound therefore, nitrogen donates electron pair forming isocyanide as the main
product.
3. Explain why Grignard Reagent is prepared under anhydrous conditions ?
Ans. In Grignard Reagent, the carbon-magnesium covalent bond is highly polar with carbon atom of
alkyl or aryl group withdrawing electrons from electropositive magnesium and magnesium
halogen bond is also ionic

R Mg X . So Grignard reagent is highly reactive, and react with any source of proton to give
hydrocarbons.
R – Mg – X + H2O RH + Mg(OH)X
4. Wurtz Reaction is carried in dry ether. Why?
dry other
Ans. CH 3 Br 2Na Br CH3CH3+2NaBr
Sodium metal is sensitive towards air and moisture forming:
4Na + O2 2Na2O
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2Na + 2H2O 2NaOH + H2

So reaction is carried in dry ether to avoid air and moisture.
5. Why SN1 reactions are favoured in protic solvent?
Ans. It involves C-X bond breakage for which the energy required is obtained through solvation of
halide ion with the protons of protic solvent like H2O, alcohol etc.
6. Tertiary halides donot undergo SN2 mechanism. Why?
Ans. In SN2 reaction, the nucleophile attacks to the carbon atom from the opposite side of halide atom.
Three alkyl groups cause a steric hinderance to the approach of nucleophile.

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7. Why phenol is acidic in nature?
In phenol each atom of benzene ring is sp2 hybridised and is electron withdrawing. Oxygen atom
donates a pair of electron to the ring and acquire positive charge which facilitate the donate ion of
proton.
OH O–
H2O
+ H3O+

The Phenoxide ion (conjugate base) is stabilised by resonance (PKa).

– –
O O O O O
– –

8. Which is more acidic, p-nitrophenol or phenol? Explain why?

Ans. p-nitrophenol is more acidic. Any electron withdrawing group like NO2 withdraws the electron
density away from oxygen atom of phenoxide ion and this results in further delocalisation of
negative charge and stabilisation of phenoxide ion. Hence, electron withdrawing groups favour
the ionisation of substituted phenol to give more and more of H+ ions.
9. Why cresol (C6H5OCH3) is less acidic than phenol ?
Ans. Cresol is less acidic than phenol. Any electron releasing group like - CH3, releases the electron
density over oxygen atom and destabilises it resulting in decrease in ionisation of cresol. So
cresol is less acidic than phenol.
10. Ethers are insoluble in water. Why ?
Ans. Ethers cannot form Hydrogen bonds with water because it is less polar than water and cannot
break hydrogen bonds formed between H2O molecules.
11. Boiling points of ethers are lower than isomeric alcohols. Give reason.
Ans. Boiling points of ethers are lower than isomeric alcohols due to lack of intermolecular hydrogen
bonding in ethers whereas alcohol molecules are associated through strong hydrogen bonds.
12. Ethers are polar in nature even if both alkyl groups are identical. Why?
Ans. Ethers have non-linear structure. Each of the two C-O bonds are polar. Net dipole moment is the
vector sum of dipole moments of both the bond dipoles.
.:

O
.

R R
13. Why o-nitrophenol is steam volatile while p-nitrophenol is not?
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O
N O H
O O
HO N O
O HO N
o-nitrophenol
Ans. (intramolecular H-bonding) O
p-nitrophenol
(intermolecular H-bonding)
o-nitrophenol is steam volatile due to intramolecular hydrogen bonding while p-nitrophenol is
less volatile due to intermolecular hydrogen bonding.

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14. Phenyl methyl ether reacts with HI to form phenol and methyl iodide but not iodobenzene and
methanol. Give reason.
O–CH3 OH

+ HI + CH3I

Ans. (a) In phenyl methyl ether, the carbon atoms of phenyl group are sp2 hybridised and there is a
partial double bond character in phenyl carbon-oxygen bond. Hence, C6H5–O bond is
stronger than CH3–O.
Therefore, the attack of I– on the alkyl carbon of C6H5–O–H3C occurs and breaks the CH3–O-
bond to form phenol and iodomethane.
(b) Benzene ring offers a steric hinderance to I- to attack at C6H5–O bond.
15. Why aldehydes are more reactive towards nucleophiles than ketones ?
Ans. (a) Sterically, the presence of two large substituents in ketones hinders the approach of
nucleophile to carbonyl carbon as compared with aldehydes having only one such substituent.
(b) The two alkyl groups in ketones are electron releasing and release the electron density over
carbonyl carbon, thus reduces the electrophilicity of carbonyl carbon more effectively than in
aldehyde which has only one alkyl group.
16. Cyclohexanone forms cyanohydrin in good yield but 2, 2, 6-trimethyl cyclohexanone does not.
Why?
– OH
Ans. O+H–CN
CN
H3C CH3
–
O+H–CN No reaction

CH3
(a) The three methyl groups are electron releasing and increase the electron density over
carbonyl carbon atom thus reduces its electrophilicity.
(b) Three methyl groups causes steric hinderance to nucleophilic attack the carbonyl carbon of
>C=group.
17. There are two - NH2 groups in semicarbazide but only one is involved in the formation of
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semicarbazones. Why?
Ans. > C = O + H2 N NHCONH2 > C=NNHCONH2

The lone pair of electrons on NH2 nearer to is delocalised over oxygen atom and therefore,
this –NH2 group is not available as nucleophile. The NH2 group not involved in resonance, will
act as a nucleophile.
O O O–
+
H2 N–C–NHNH2 H2N = C – NHNH2 H2N – C = N – NH2

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18. During the preparation of an ester from a carboxylic acid and an alcohol in the presence of an
acid catalyst, ester is removed as fast as it is formed. Explain with reason.
H+
Ans. RCO OH+H OR1 RCOOR1 + H2O
Both esterification and hydrolysis of ester are catalysed by acid, the reaction is reversible and an
equilibrium is established, so ester or water is removed to favour the forward reaction, as per Le
Chatelier’s principle.
19. Why pKa of chloroacetic acid is less than that of acetic acid or chloroacetic acid is a stronger
acid than acetic acid.

+
Ans.

Any electron releasing group like CH3 increases the electron density over carboxylate anion (–
COO–). The stability of the conjugate base is reduced and hence, H+ cannot be donated easily.
Thus, it decreases the acid strength of carboxylic acid.
Any electron withdrawing group like Cl, F, NO2 etc. withdraws the electron density away from
COO– and spreads it and thus stabilises the carboxylate ion by delocalisation of negative charge.
Thus, it increases the acid strength of carboxylic acid.
20. Explain why amine compounds have higher boiling point compounds than hydrocarbons but
lower boiling than alcohols of comparable molecular masses ?
Ans. Boiling points of amines and alcohols are higher than those of hydrocarbons of comparable
molecular masses due to intermolecular hydrogen bonding in amines and alcohols.
R R R R
N–H N–H O–H O–H
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H H
Hydrogen bonds in amines are weaker than those present in alcohols. This is because oxygen is
more electronegative than nitrogen, so boiling points of amines are lower than those of alcohols
of comparable molecular masses. The intermolecular forces in hydrocarbons are weak van der
Waals forces due to which hydrocarbons have lower boiling points than amines or alcohols.
21. Why boiling point of isomeric tertiary amines are lower than those of primary amines ?
Ans. Boiling points of isomeric tertiary amines are lower than those of primary amines due to the lack
of intermolecular hydrogen bonding which exists in primary amines.

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22. Why aniline does not undergo Friedel–Craft reaction?

Ans. Aniline does not undergo Friedel-Craft reaction due salt formation with aluminium chloride, the

Lewis acid, which is used as catalyst. Due to this, N-atom of aniline acquires positive charge and

hence, it acts as strong deactivating group for further reaction.

+
:

–
NH2 NH2AlCl3

+ AlCl3 + HCl
Lewis Lewis Salt
Base Acid
23. Why aromatic primary amines cannot be prepared by Gabriel’s phthalamide synthesis?

Ans. Aryl halides do not undergo nucleophilic substitution reaction with the anion formed by

phthalamide because of partial double bond character of C—X bond of aryl halide.

24. Although chlorine atom is an electron withdrawing group yet it is ortho and para directing in

electrophilic aromatic substitution reactions.

Ans. Chlorine withdraws electrons through inductive effect and releases electrons through resonance.

Through inductive effect, chlorine destabilises the intermediate carbocation formed during the

electrophilic substitution. Reactivity is thus controlled by the stronger inductive effect and

orientation is controlled by resonance effect.

25. Phenoxide ion has more number of resonating structure than carboxylate ion but carboxylic acid

is a stronger acid than phenol. Why?

Ans. The phenoxide ion has non-equivalent resonance structures in which negative charge is at less

electronegative carbon atom of phenoxide ion.

node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

The carboxalate ion has two equivalent resonance structures in which negative charge is more

effectively delocalised over two electronegative oxygen atoms. In phenoxide ion, the negative

charge is less effectively delocalised over one oxygen atom and less electronegative carbon atom

of phenoxide ion. Thus, the carboxylate ion is more stabilised than phenoxide ion. Therefore,

carboxylic acids are more acidic than phenols.

168 E
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CHEMICAL TEST
1. Differentiate between Primary, Secondary and Tertiary alcohol
Test 1º Alcohol 2º Alcohol 3º Alcohol
(i) No change
(1) Add Lucas reagent Turbidity appears Turbidity appears
(Anhyd. ZnCl2 + Conc. HCl) within 5 minutes immediately

Lucas Test
Lucas test is based on Kinetics of the reaction. 3º alcohols react at the fastest rate.
CH3 CH3
anhydrous
H 3C–C–OH + H Cl H3C–C–Cl + H2O
ZnCl2
CH3 CH3
(3º alcohol)
H3C anhydrous H3C
CHOH + HCl CHCl + H 2O
H3C ZnCl2 H3C
(2º alcohol)
anhydrous
CH3CH2OH + HCl ZnCl 2
No change appears
(1º alcohol)
(ii) Carbonic compounds Lucas Reagent

Test Propan-1-ol Propan-2-ol

OH
CH3CH2CH2OH CH3–CH–CH 3

(1) Add Lucas Reagent No change Turbidity appears within

(Anhydrous ZnCl2 + HCl) 5 minutes.

(2) Add I2 / NaOH (Iodoform test) No change Yellow precipitate of CHl3

OH
Heat CHl3 + CH3COONa + 5NaI + 5H 2O
6NaOH + 4I2 + CH3CHCH3
(Yellow)
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

Test Ethanol Propan-2-ol

(1) Add Lucas Reagent

(iii) No change Tubidity within 5 minutes
(Anhydrous ZnCl2 + HCl)

Test Enthanol C2 H5 OH Pr opan 1 ol CH 3CH 2 CH 2OH

(iv)
(1) Add I 2 / NaOH and heat Yellow iodoform CHI 3 No change

6NaOH + 4I2 + CH3CH2OH

E 169
Chemistry

Test Ethanol CH 3CH 2 OH Methanol CH 3OH

(v) (1) Add I 2 / NaOH and heat Yellow precipitate of CHI 3 No change
(2) Add salicylic acid Pleasant odour Odour of oil of winter green
OH OH OH OH
COOH +
COOEt COOH COOMe
+ C2H 5OH H ; + CH3OH

(II) Differentiate between phenol and alcohol

OH

Test Ethanol Phenol

(i)
(1) Add I 2 / NaOH and heat Yellow ppt. of CHI3 No change
(2) Add neutral FeCl3 No change Violet Colouration
OH
3–
+ FeCl3 [Fe(C6H 5O)6] + 3Cl
(Violet colour)

OH
Propan-2-ol
Test Phenol
CH3–CH(OH)CH 3

(1) Add Neutral FeCl3 Violet colour No change

(2) Add Br2 / H2O colour of Br2 decolourised No change
(ii) OH OH
Br Br
H3 O
+ 3Br
–3HBr

Br
(Colourless)

(III) Differentiate between alkyl halide and aryl halide

Cl
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

(i) Test Chloroethane (C2H5Cl) Chlorobenzene

(1) Add aq NaOH + AgNO 3 White precipitate of AgCl No change

soluble in Ammonia

C2H5Cl + NaOH (aq) C2H5OH + NaCl

NaCl + AgNO3 AgCl (white ppt) + NaNO3
AgCl + 2NH3 [Ag(NH3)2]+Cl– (soluble)

170 E
 MP Board

Test Chloroethane CH3CH2Cl Bromoethane CH3CH2Br

(ii)
(1) Add aq NaOH + AgNO 3 White ppt (AgCl) Creamy yellow ppt (AgBr)

(2) Add NH 3 in both test tube White ppt get dissolved Yellow ppt dissolved partly
in NH3 in NH 3

CH2Cl Cl
(iii)
Test Benzyl chloride Chlorobenzene

(1) Add aq NaOH + AgNO 3 White ppt soluble in No change

Ammonia

(IV) Differentiate between aldehyde and ketone.

O
Test Acetaldehyde CH3CHO Acetone H3C–C–CH3
(i)
(1) Add Fehling's reagent Brown red precipitate No change
CH 3CHO + 2Cu2+ + 5OH– CH3COO + Cu 2O (red brown) + 3H2O
(2) Add Tollen's test Silver mirror No change

Test Acetaldehyde CH3CHO Formaldehyde HCHO

(1) Add I2/NaOH and heat Yellow iodoform (CHI3) No change

4NaOH + 3I2 + CH3CHO CHI3+ HCOONa + 3NaI + 3H2O
(ii)
(2) Add KMnO4/H2SO4 Effenescence of CO2
–
MnO4 / H+ O O
CHCHO CHCOOH HCHO HCOOH H2O + CO2
(smell of vinegar)

Test Ethanal (CH3CHO) Benzaldehyde (C6H6CHO)

(iii)
(1) Add I 2/NaOH Yellow iodoform (CHI3) No change
(2) Add Fehling's reagent Red ppt of Cu2O No change
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

(V) Differentiate between different type of ketones

Test 2
Pentan-3-one Pentan-3-one
O O
CH3–C–CH 2CH 2CH3 CH3CH2–C–CH2CH3
(i) (1) Add I2/NaOH and heat Yellow iodoform (CHI3) No change
O
4NaOH + 3I2 + CH3 – C – CH2CH2CH3 CHI2 + CH3CH2CH2COONa + 3NaI + 3H2O
(Yellow)

E 171
Chemistry
Acetophenone Benzophenone
Test
COCH3 O
C

(1) Add I2 / NaOH Yellow iodoform (CHI3) No change

COCH 3 COONa
(ii)
4NaOH + 3I2 + CHI3 + + 3NaI + 3H 2O

(2) Add NaHSO3 White ppt No change

O OH
– +
C–CH3 + NaHSO3 C–SO 3 Na
CH3
(VI) Differentiate between different type of carboxylic acid
Test Formic acid (HCOOH) Acetic acid (CH3COOH)

(1) Tollen's reagent Silver mirror (Ag) No change

+
HCOOH + [Ag(NH3) 2] + 2OH CO2 + Ag + 2H2O + 2NH 3

(VII) Differentiate between phenol and carboxylic acid

Phenol (White solid) Benzoic acid (White solid)
Test
OH COOH

(1) Add neutral FeCl3 Violet colour No change

(2) Add NaHCO3 (aq) No change Effervescence of CO2
C 6H 5COOH + NaHCO3 C 6H 5COONa + CO2 + H2O
(VIII) Differentiate between primary and secondary and Tertiary amines
Test Primary Amine Secondary Amine Tertiary
Amine
Hinsberg reagent White ppt soluble White ppt soluble No Change
C6H5SO2Cl in NaOH in NaOH
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

soluble in alkali

CH3 CH3
– HCl NaOH
N H + Cl SO2 OH –
SO 2 – N No reaction
CH3 CH3

(White ppt insoluble in aqueous NaOH)

172 E
 MP Board

Test Methanamine Dimethyl Amine

(CH3NH2) (CH3NHCH3)
(1) Add Hinsberg reagent White ppt (soluble White ppt insoluble in
C6H5SO2Cl in NaOH) NaOH (aq.)
(2) Add CHCl3 + KOH(alc.) Four odour of No change
isocyanide

CH3NH2 + CHCl3 + 3KOH CH3N+ C– + 3KCl + 3H2O

NH2 NHCH3

Test Aniline N-methyl-aniline

(1) Add Hinsberg reagent White ppt solution in White ppt insoluble in
(C6H5SO2Cl) NaOH NaOH
–

C6H5SO2Cl + H2NC6H5 OH
C6H5SO2 NHC6H5 NaOH
C6H5SO2 N – Na
C6HC
5
6H 5

(2) Add CHCl3 + KOH (alc) Foul odour of isocyanide No change

NH2 N C
+ HCCl3 + 3KOH + 3KCl + 3H2O

(IX) Differentiate between Aliphatic and aromatic amine

NH2

Test Aniline Methylamine (CH3NH2)

(1) Add Br2/H2O Colour of Br2 (aq.) No change

decolourised
NH2
NH2
Br Br
+ 3Br2(aq) + 3HBr

Br (Colourless)

(X) Differentiate between Ketone and Carboxylic acid

node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

(i)
Test CH3COCH3 acetone acetic acid CH3COOH

(1) Add l2/NaOH + heat Yellow iodoform (CHI3) No change

4NaOH + 3l2 + CH3COCH3 CHI 3 + CH3COONa + 3Nal + 3H2O

(2) Add NaHCO3 No change Effervescence of CO2

CH3COOH + NaHCO3 CH3COONa + H2O + CO2

E 173
Chemistry
(XI) Differentiate between acetaldehyde and acetic acid

(i) Test acetaldehyde CH3CHO acetic acid CH3COOH

(1) Add Fehling's reagent Red ppt. of Cu 2O No change

(2) Add Tollens' reagent Silver mirror (Ag) No change
(3) Add NaHCO3 No change Effervescence of CO2

(XII) Differentiate between cyclohexylamine and Aniline

NH2 NH2
(i) Test
(Aniline)
Cyclohexylamine

(1) Add NaNO2 and HCl and N2 gas is liberated and no Stable diazonium salt is formed
then add phenol in colouration is observed. which reacts with phenol to form
presence of a base. orange dye.

node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

174 E
 MP Board

NAME REACTIONS
1. Finkelstein Reaction

R – X + NaI R – I + NaX
(X = Cl, Br)
2. Swarts Reaction
H3C – X + AgF H3C – F + AgX
(X = Cl, Br)
3. Wurtz Reaction
dry ether
CH 3 Br 2Na BrCH 3 CH 3 CH 3 2NaBr
Bromomethane Ethane
dry ether
C2 H 5 Br 2Na BrC2 H 5 C 2 H5 C 2 H 5
Bromoethane n Butane
4. Wurtz-Fitting Reaction
X R
Ether
+ Na + RX + Na X

5. Fitting Reaction
X
Ether
2 + Na + 2NaX

6. Friedel-Crafts alkylation Reaction

CH3
Anhyd.
Anhyd. AlCl
AlCl33
+ CH3Cl + HCl
Toluene

C2H5
Anhyd. AlCl33
+ C2H5Cl + HCl
Ethylbenzene
Cl Cl Cl
CH3
Anhyd.
Anhyd. AlCl
AlCl33
+ CH 3Cl +

1-Chloro-2-methylbenzene CH3
(Minor)
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

1-Chloro-4-methylbenzene
(Major)

OCH3 Cl OCH 3
CH3
Anhyd.
Anhyd.AlCl
AlCl33
+ CH 3Cl CS 2 +

2-Methoxytoluene CH3
(Minor)
4-Methoxytoluene
(Major)

E 175
Chemistry
7. Friedel-Crafts acylation reaction
COCH3

Anhyd. AlCl3
+ CH3COCl + HCl

Acetylchloride Acetophenone

COCH3

Anhyd. AlCl3
+ (CH3CO)2O + CH3COOH
Acetic anhydride
Cl Cl O Cl
O
Anhyd. AlCl3 CH3
+ H3C–C–Cl +

2-Chloroacetophenone
(Minor) O CH3
4-Chloroacetophenone
(Major)

OCH3 OCH3 OCH3

COCH 3
Anhyd. AlCl3
+ CH3COCl +
Ethanoyl
chloride 2-Methoxy- COCH 3
acetophenone
4-Methoxy-
(Minor)
acetophenone
(Major)
8 Reimer-Tiemann Reaction
– + – +
OH O Na O Na OH
CHCl2 CHO CHO
CHCl3 + aq NaOH NaOH H+

Intermediate Salicylaldehyde
9. Kolbe’s Reaction
OH ONa OH
COOH
NaOH (i) CO2
(ii) H +

2-Hydroxybenzoic acid
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

(Salicylic acid)
10. Rosenmund Reduction
O
C CHO
Cl H2
Pd – BaSO4

Benzoyl chloride Benzaldehyde

11. Stephen reaction
H3 O
RCN SnCl2 HCl RCH NH RCHO

176 E
 MP Board
12. Etard reaction
CH3 CH(OCrOHCl2)2 CHO
CS2 H3O+
+ CrO2Cl2

Toluene Chromium complex Benzaldehyde

13. Gatterman – Koch reaction
CHO
CO, HCl
Anhyd. AlCl3/CuCl
Benzene Benzaldehyde

14. Clemmensen Reduction

Zn-Hg
C=O CH2 + H2O (Clemmensen reduction)
HCl

15. Wolff Kishner Reduction

NH2NH2 KOH/ethylene glycol
C=O C=NNH2 CH2 + N2
–H2O heat
(Wolff-Kishner reduction)
16. Tollens’ test

RCHO 2[Ag(NH 3 ) 2 ] 3O H RCO O 2Ag 2H 2O 4NH 3

17. Fehling’s test

Fehling reagent comprises of two solutions, Fehling solution A and Fehling solution B. Fehling
solution A is aqueous copper sulphate and Fehling solution B is alkaline sodium potassium
tartarate (Rochelle salt). These two solutions are mixed in equal amounts before test. On heating
an aldehyde with Fehling’s reagent, a reddish brown precipitate is obtained. Aldehydes are
oxidised to corresponding carboxylate anion. Aromatic aldehydes do not respond to this test.

R CHO 2Cu 2 5O H RCO O Cu 2 O 3H 2O

Re d brown ppt
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

18. Aldol reaction

Aldehydes and ketones having at least one -hydrogen undergo a reaction in the presence of

dilute alkali as catalyst to form -hydroxy aldehydes (aldol) or -hydroxy ketones (ketol),

respectively. This is known as Aldol reaction. The name aldol is derived from the names of the
two functional groups, aldehyde and alcohol, present in the products.

E 177
Chemistry
(i) Aldol condensation:
The aldol and ketol readily lose water to give -unsaturated carbonyl compounds which are
aldol condensation products and the reaction is called Aldol condensation.
dil. NaOH
2 CH3–CHO CH3–CH–CH 2–CHO CH3–CH=CH–CHO
Ethanal –H2O But-2-enal
OH (Aldol condensation product)
(Aldol)
3-Hydroxybutanal
CH3 CH3
Ba(OH)2
2CH3–CO–CH3 CH3–C–CH2CO–CH3 CH3–C=CH–CO–CH 3
–H2O
Propanone OH
(Ketol) 4-Methylpent-3-en-2-one
4-Hydroxy-4-methylpentan-2-one (Aldol condensation product)
(ii) Cross aldol condensation :
When aldol condensation is carried out between two different aldehydes and / or ketones, it is
called cross aldol condensation. If both of them contain -hydrogen atoms, it gives a mixture of
four products.
CH3CHO 1. NaOH CH3–CH=CH–CHO + CH3CH2–CH=C–CHO
+ 2. But-2-enal
CH3CH2CHO CH3

CH3–CH=C–CHO + CH3 CH2–CH=CHCHO

CH3
2-Methylbut-2-enal Pent-2-enal
19. Cannizzaro reaction:
Aldehydes which do not have an -hydrogen atom, undergo self oxidation and reduction
(disproportionation) reaction on treatment with concentrated alkali. In this reaction, one molecule
of the aldehyde is reduced to alcohol while another is oxidised to carboxylic acid salt.
H O
H H
C=O + C=O + Conc. KOH H–C–OH + H–C
H H OK
H
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

Methanol Potassium formate

2 CHO + Conc. NaOH CH2OH + COONa

Benzaldehyde Benzyl alcohol Sodium benzoate

20. Kolbe electrolysis
2CH 3COO Na 2H 2 O
Sodiumacetate
Electrolysis
CH3 – CH 3 2CO 2 H 2 2NaOH

178 E
 MP Board
21. Hell-Volhard-Zelinsky (HVZ )reaction.
(i) X /Red phosphorus
R–CH2–COOH (ii) H2 O R–CH–COOH
2

X
X = Cl, Br
–Halocarboxylic acid
22. Gabriel phthalimide synthesis
O O O
C KOH C – + R–X C
N–H NK N–R
C C C
O O O
Phthalimide N-Alkylphthalimide
O
O
C –
NaOH(aq) C ONa+
N–R – +
+ R – NH2
C ONa (1° amine)
C
O
O
23. Hoffmann bromamide degradation reaction
O
R–C–NH2 + Br2 + 4NaOH R–NH2 + Na2CO3 + 2NaBr + 2H 2O
24. Carbylamine reaction
Heat
R NH 2 CHCl3 3KOH R NC 3KCl 3H2O
25. Hinsberg’s Test
O O
(i) S–Cl + H–N–C2H5 S–N–C 2H5 + HCl
O H O H
N-Ethylbenzenesulphonamide
(soluble in alkali)
O O
(ii) S–Cl + H–N–C2H5 H3 C S–N–C 2H5 + HCl
O C2H 5 O C 2H 5
N,N-Diethylbenzenesulphonamide
(iii) Tertiary amines do not react with benzenesulphonyl chloride.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

26. Coupling reaction %

–
+ – OH –
N N Cl + H OH N=N OH + Cl + H2O

p-Hydroxyazobenzene (orange dye)

–
+ – OH –
N N Cl + H NH2 N=N NH2 + Cl + H2O

p-Aminoazobenzene
(yellow dye)
E 179
Chemistry

MECHANISM
1. Mechanism of SN1 & SN2 :
Ans. (a) Substitution nucleophilic bimolecular (SN2)
The reaction between CH3Cl and hydroxide ion to yield methanol and chloride ion follows a
second order kinetics, i.e., the rate depends upon the concentration of both the reactants.

(b) Substitution nucleophilic unimolecular (SN1)

SN1 reactions are generally carried out in polar protic solvents (like water, alcohol, acetic acid,
etc.). The reaction between tert-butyl bromide and hydroxide ion yields tert-butyl alcohol and
follows the first order kinetics, i.e., the rate of reaction depends upon the concentration of only
one reactant, which is tert- butyl bromide.
(CH3)3CBr + –OH (CH3)3COH + Br–
2-Bromo-2- methylpropane 2-Methylpropane-2-ol
It 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.
CH3

Step I H 3C CH3
(CH3)3CBr + Br
CH3

H 3C CH3 + –OH Step II

(CH3)3COH
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. Since the rate of
reaction depends upon the slowest step, the rate of reaction depends only on the concentration of
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

alkyl halide and not on the concentration of hydroxide ion.

2. Mechanism of preparation of Alkene to Alcohol :

OR CH2=CH2 + H2O CH3–CH2–OH

OR
+
H
CH3CH = CH2 + H2O CH3—CH —CH 3
—

OH

180 E
 MP Board
Ans. The mechanism of the reaction involves the following three steps:
Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O+.
H2O + H+ H3O+
H H

— :

— —
+

: :
C=C + H— O+— H —C—C + H2O

Step 2: Nucleophilic attack of water on carbocation.

H H H
— —

— —
— —
—
+
: :

—C—C + H2O —C—C—O+—H

Step 3: Deprotonation to form an alcohol.

:: — —
H H H OH

— —
— —
— —
—

—C—C—O+ —H —C—C— + H3O+

: :

+ H2 O

3. Mechanism of preparation of Ethene from Ethanol:

Ans. The mechanism of the reaction invovles the following three steps:
Step 1: Formation of protonated alcohol.
H H H H H
+ Fast
H—C—C—O+—H
: :

H—C—C—O—H + H
:

H H H H
Ethanol Protonated alcohol
(Ethyl oxonium ion)
Step 2: Formation of carbocation: It is the slowest step and hence, the rate determining step of
the reaction.
H H H H H
+ Slow +
H—C—C—O —H H—C—C +H2O
:

H H H H
Step 3: Formation of ethene by elimination of a proton.
H H H— H
H—C—C+ C=C
— + H+
H H
H H Ethene
The acid used in step 1 is released in step 3. To drive the equilibrium to the right, ethene is
removed as it is formed.
4. When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place :
Br
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

HBr
CH3–CH–CH–CH3 CH3–C–CH2–CH3
CH3 OH CH3
Give a mechanism for this reaction.
Ans. The mechanism of the given reaction involves the following steps:
Step–1 : Protonation
+
H
CH3–CH–CH–CH3 CH3–CH–CH–CH3
CH3 OH CH3 OH2
+
3-Methylbutan-2-ol

E 181
Chemistry
Step–2 : Formation of 2° carbocation by the eleimination of a water molecule
+
CH3–CH–CH–CH3 –H2O
CH3–CH–CH–CH3
+
CH3 O H2 CH3
2°Carbocation
Step–3 : Re-arrangement by the hydride-ion shift

H
+ 12-hydride shilt +
CH3–CH–CH–CH3 CH3–C–CH2–CH3
CH3 CH3
3°Carbocation
(more stable)

Step–4 : Nucleophilic attack

Br
+ —
CH3–C–CH2–CH3 Br CH3–C–CH2–CH3
CH3 CH3
2-Bromo-2-methylbutane

5. Mechanism of preparation of Ethanol to Ethoxyethane: 2C2H5OH C2H5OC2H5

Ans. The mechanism of the reaction invovles the following three steps:
H
H+
: :

: :

Step (i) : CH3—CH2—O—H CH3—CH2—O+—H

H +
+ CH3—CH2—O—CH2CH3 + H2O
Step (ii) : CH3 CH2 —O: + CH3 —CH2 —O
:

H H
H
+
Step (iii) : CH3CH2— O —CH2CH3 CH3CH2—O—CH2CH3+H+
H
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\Important Questions of OC

182 E
 MP Board

MP BOARD QUESTIONS PAPER (2018)

SUBJECT: CHEMISTRY
1. Choose the correct option :-
(i) The defect in which the crystal lattice have the vacancy of one cation and one anion is:
(a) Ionic defect (b) Atomic defect (c) Frankel defect (d) Schottky defect
(ii) Fe, Co, Ni are which type of magnetic substance :
(a) Paramagnetic (b) Ferromagnetic (c) Diamagnetic (d) Anti-ferromagnetic
(iii) Which of the following is not an organometallic compound ?
(a) Ethyl magnesium bromide (b) Tetra ethyl lead
(c) Sodium ethoxide (d) Tetra methyl aluminium
(iv) Which is not a glyceride ?
(a) Fat (b) Oil (c) Phospholipid (d) Soap
(v) Which hydride is found in liquid state ?
(a) HF (b) HCl (c) HBr (d) HI
Ans. i-d, ii-b, iii-c, iv-c, v-a
2. Fill in the blanks :-
(A) The process of adding minute amount of impurity in an element or compound is called ____ .
(B) Arrhenius equation is represented by _______.
(C) In lead storage cell ______works as electrolyte.
(D) Carbylamine test gives only______ amine.
(E) Protein is a polymer of _____.
Ea
Ans. (A) Doping, (B) K Ae RT
, (C) H2SO4, (D) 1°, (E) Amino acid
3. Write answers in one word of each :-
(A) F-centers give colour to crystal due to whose presence ?
(B) Which noble gas is used in electric bulbs with nitrogen ?
(C) Colloidal solution of liquid in liquid is known as _____.
(D) Write the name of organometallic compound used as an anti-knock.
(E) Which protein is responsible for the clotting of blood ?
Ans. (A) Due to free electron, (B) Neon gas, (C) Emulsion, (D) Tetra ethyl lead (E) Fibrinogen
4. Match the pairs correctly :
''A'' ''B''
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2018

A Diazonium salt i Explosive

B Gas mask ii C6H5N2Cl

C Philosopher wool iii Radioactive halogen

D Astatine iv ZnO

E T.N.B. v Adsorption of poisonous gases

Ans. (A)–(ii), (B)–(v), (C)–(iv), (D)–(iii), (E)–(i)

E 183
Chemistry
5. What is Electrophoresis ?
OR
What are catalytic promoters ? Give one example.
Ans. Electrophoresis – The movement of colloidal particles under the influence of an applied electric
field is known as electrophoresis.
OR
Catalytic promoters – A substance added to a solid catalyst to improve its performance in a
chemical reaction, by itself the promoter has little ore no catalytic effect. Example - In Haber's
process for the synthesis of ammonia, traces of molybdenum increases the activity of finely
divided iron which act as a catalyst.

6. Sea divers for breathing inside sea uses the mixture of Helium and Oxygen. Why?
OR
All Halogens are strong oxidising agents. Why ?
Ans. Scuba divers must cope with high concentrations of dissolved gases while breathing air at high
pressure underwater. Increased pressure increase the solubility of atmoshpheric gases in blood.
When the divers come towards surface, the pressure gradually decreases. This releases the
dissolved gases and leads to the formation of bubbles of nitrogen in the blood. This blocks
capillaries and creates a medical condition known as bends, which are painful and dangrous to
life. To avoid bends, as well as, the toxic effects of high concentration of nitrogen in the blood,
the tanks used by scuba divers are filled with air diluted with helium (11.7% helium, 56.2%
nitrogen and 32.1% oxygen).
OR
All Halogens can acts as strong oxidizing agents because of high electronegativity and high
electron affinity which makes them to take electrons very much readily takes electrons from
other elements and oxidise other elements.
Decreasing order of oxidising strength among halogens is F > Cl > Br > I.
7. What are chelates ? Give one example.
OR
Write chemical formula of the following coordinate compounds :
(i) Hexaaquachromium (III) chloride
(ii) Potassium tetraiodomercurate (II)
Ans. Chelates-Polydentate ligands use its one or more donor atoms to form coordination bond with
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central metal ion so as to give a ring like structure. This ring is called chelate ring and the ligand
is called chelate ligand.
Ex. :- CH2 – H2N NH2 – CH2 2+
Cu
CH2 – H2N NH2 – CH2
2+
[Cu(en) 2]
OR
(i) [Cr(H2O)6]Cl3 (ii) K2[HgI4]

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8. Write the simple and chemical name of vitamins; whose deficiency causes the following
diseases:
(i) Sterility
(ii) Non-clotting of blood.
OR
What is peptide bond ?
Ans. (i) Vitamin E (Tokopherol)
(ii) Vitamin K (Filokwinon)
OR
Peptide bond:- When two amino acids combine with each other this leads to peptide bond.
(–CO–NH– bond)
9. On dissolving 4 gm urea in 100 gm water, 1.24°C depression in freezing point of the solution is
obtained. Calculate molecular mass of urea. (Kf = 1.86 Kmol–1) :-
OR
Calculate osmotic pressure of the solution which contains 68.4 gram sucrose in 1000 ml of
solution at 293 K. (R = 0.082 litre atm. K–1 mol–1
Ans. Tf = Kf . m
4 1.86 40
1.24 = 1.86 × M= = 60 gm/mol.
100 1.24
M
1000
OR
V = nRT
1000 68.4
× 0.082 293
1000 342
= 0.2 × 0.082 × 293
= 4.8 atm
10. Define the following :
(i) Azeotropic mixtures
(ii) Isotonic solution
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(iii) Semipermeable membrane.

OR
Define the following :
(i) Osmotic pressure
(ii) van't Hoff factor
(iii) Molal freezing depression constant.

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Ans. (i) Azeotropic mixtures : A mixture of two or more liquid components, having a definite
composition in liquid and vapour phase and boil like a pure liquid at a particular temperature
is called Azeotropic mixture.
(ii) Isotonic solution: The two solutions which cannot allow the passage of solvent through
semi-permeable membrane after separation i.e., these have equal osmotic pressure are called
isotonic solutions.
(iii) Semipermeable membrane : Semi permeable membrane is like a continuous sheet which
contains a network of very small pores which allows to pass molecules of solvent only.
Semipermeable membrane is made of chemical substance-potassium ferrocyanide.
OR
(i) Osmotic pressure: The excess pressure that must be applied to the solution side to prevent
the passage of solvent into it through a semipermeable membrane is called as osmotic
pressure ( ).
(ii) van't Hoff factor: Van't hoff factor is a ratio of observed colligative properties to normal
colligative properties.
(iii) Molal freezing depression constant: When molality of solution taken as unity then Kf is
equal to the molal depression freezing point. Unit - K kg mol–1.
11. Write the electronic of Fe2+ and Fe3+ (Atomic No. of Fe = 26). Which one is more paramagnetic?
OR
Ionic radii of Fe2+ is less than ionic radii of Mn2+. Why ?
Ans. Fe = [Ar] 4s2 3d6
Fe2+ = [Ar] 3d6

n=4
Fe3+ = [Ar] 3d5

n=5
Fe3+ is more paramagnetic because it has more unpaired electron in comparison to Fe2+.
OR
Because of effective nuclear charge of Fe2+ is more than Mn2+.
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12. How is K2Cr2O7 prepared from chromite ore ? Write with equation.
OR
What is lanthanide contraction ? How is it caused ?
Ans. K2Cr2O7 is prepared from chromite ore (FeCr2O4)
4FeCr2O4 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
2Na2CrO4 + 2H+ Na2Cr2O7 + 2Na + H2O
Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl
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OR
Lanthanide contraction– As we move along the lanthanoid series, the atomic number increases
gradually by one. This means that the number of electrons and protons present in an atom also
increases by one. As electrons are being added to the same shell, the effective nuclear charge
increases. This happens because the increase in nuclear attraction due to the addition of proton is
more pronounced than the increase in the interelectronic repulsions due to the addtion of
electron. Also, with the increase in atomic number, the number of electrons in the 4f orbital also
increases. The 4f electrons have poor shielding effect. Therefore, the effective nuclear charge
experienced by the outer electrons increases. Consequently, the attraction of the nucleus for the
outermost electrons increases. This results in a steady decrease in the size of lanthanoids with the
increase in the atomic number. This is termed as lanthanoid contraction.
Consequences of lanthanoid contraction
(i) There is similarity in the properties of second and third transition series.
(ii) Separation of lanthanoids is possible due to lanthanide contraction.
(iii) It is due to lanthanide contraction that there is variation in the basic strength of lanthanide
hydroxides. (Basic strength decreases from La (OH)3 to Lu (OH)3.)
13. Write four differences between molecularity and order reaction.
OR
Write four differences between rate of reaction and rate constant.
Ans.
Order Molecularity
(1) It is sum of powers of conc. terms in rate It is equal to no. of reactant molecules
equation in balance equation of a reaction
(2) it can be determined by experiments only It is a theoretical quantity.
(3) Order may be zero Molecularity may never be zero.
(4) Order may have fractional values or Molecularity only have integral
integral values. values.
OR
Rate of reaction Rate constant
(1) Rate of reaction is the change in the Rate constant is the proportionality
concentration of reactants or the change in constant related to the rate of a
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the concentration of products per unit time. particular reaction.

(2) Rate of reaction depends on the molar Rate constant does not depend on the
concentrations of reactants and products. molar concentrations of reactants and
products.
(3) Rate of reaction depends on the Rate constant essentially depends on
temperature indirectly. the temperature.
(4) Rate of reaction depends on the time taken Rate constant does not depend on the
for the reaction. time taken for the reaction.

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14. Write the concentration of Bauxite ore by Hall's process with equation. :-
OR
Describe with diagram the Siemens Martin process of manufacturing of steel.
Ans. (i) Refining of Bauxide by Hall process %. In this process Na2CO3 is mixed in Bauxite then by
melting it converted into Al2O3 & NaAlO2.
Al 2 O3 ·2H2 O Na 2 CO3 2NaAlO2 2H2O CO2
Bauxite Sodium
meta aluminate

Sodium meta aluminate solution is heated at 323–333 K temperature, then CO2 pass through.
Melted mixture is heated with water, then NaAlO2 is filtered. NaAlO2 is comes into solution &
Fe2O3, SiO2 & other impurities which are insoluble separate out.
Then NaAlO2 is heated at 30–60° C & CO2 gas is pass through it, Al(OH)3 is precipitated, which
is filtered.
2NaAlO 2 3H 2 O CO 2 30 60 C 2Al OH 3 Na 2CO 3
Then, washing by water, dried & then heated fastly Al(OH)3, is reduced the Al2O3 anhydrous/ So,
pure Al2O3 is obtained.
Fast
2Al OH 3 Heat
Al 2 O 3 3H 2 O
Alumina

OR
Siemens Martin process: Siemens - Martin open-hearth process is an absolute process for
making steel in which streams of air and fuel gas were fed alternately onto the furnace contents.
It was used to make most of the steel during the twentieth century but was then superseded by the
basic oxygen and electric-arc methods. The open-hearth process used the gases from the molten
charge to pre-heat the air blast and so economize on fuel. An alkaline lining was used if the ore
contained phosphorus.
Oxygen
lance

Gas+slag emulsion

Slag
Steel
Steel
Circulation
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15. Explain the following reactions of chloroform :

(i) Effect of Air and Sunlight
(ii) Reimer-Tiemann Reaction.
OR
Explain the following reactions of chlorobenzene :
(i) Reaction with chlorine in the presence of FeCl3 in dark
(ii) Fittig reaction.
Ans. (i) CHCl3 + 1/2 O2 COCl2 + HCl
(ii) R–NH2 + CHCl3 + KOH R–NC + 3KCl + 3H2O
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OR
Cl Cl Cl
Cl
(i) + Cl2/FeCl3 +

Cl
(ii) Cl + Na + Cl Ether

16. Give the reasons:

(i) Boiling points of alcohols are higher than ethers.
(ii) Pure phenol is a colourless solid but it converted into pink after some time by placing open in
the air. Give chemical reaction.
OR
What do you understand by dehydration of alcohol ? Explain its mechanism.
Ans. (i) H-bonding
OH O
[O]
(ii)

O
OR
Dehydration of alcohol :- Alcohol upon reaction with protic acids tends to lose a molecule of
water to form alkenes. These reactions are known as dehydration of alcohols. Dehydration of
alcohols is an example of elimination reaction. It's rate varies for the primary, secondary and
tertiary alcohols. This variation of rate can be attributed to the stability of carbocation generated.
Since the carbocation is most stable in case of tertiary alcohols, the rate of dehydration is highest
for tertiary alcohols in comparison to secondary and primary alcohols.
CH3CH 2OH H2SO4 160 180 C
CH 2 CH2 H 2O
Mechanism : The dehydration of ethanol involves the following steps :
(i) Formation of protonated alcohol :
H H H H H
Fast
H – C – C – O – H + H+ H – C – C – O+ – H
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H H H H
Ethanol Protonated alcohol
(ii) Formation of carbocation :
H H H H H
H – C – C – O+ – H Slow
H – C – C+ + H2O

H H H H

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(iii) Formation of ethene :
H H
H H
H – C – C+ C=C + H+
H H
H H
17. How will you obtain following from acetic acid ? (Give equations only)
(i) Acetic anhydride
(ii) Ethyl acetate
(iii) Trichloroacetic acid
(iv) Acetyl chloride
OR
How will you obtain following compounds from benzaldehyde ?
(Give equations only)
(i) Cinnamaldehyde (ii) Benzoin
(iii) Cinnamic acid (iv) Benzoyl chloride
P2O5 CH3CO
Ans. (i) CH3 – C – OH O
CH3CO
O
C2H5–OH
(ii) CH3 – C – OH CH3COOC2H5 + H2O
O
P/Cl2
(iii) CH3 – C – OH CCl3 COOH
O
PCl5
(iv) CH3 – C – OH CH3COCl + POCl3 + HCl
O
OR
– +
CH3CHO/OH /H
(i) C6H5CHO C6H5 – CH = CH – CHO
+
KCN/H
(ii) C6H5CHO C6H5 – CH – C – C 6H 5
OH O
+
CH3–COO–C2H5/H3O
(iii) C6H5CHO C6H5 – CH = CH – COOH
[O] PCl5
(iv) C6H5CHO C6H5 COOH C6H5 COCl
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18. Define the following and write the formula and unit of each :
(i) Equivalent conductivity
(ii) Molar conductivity.
OR
Draw a labelled diagram of Galvanic cell and explain cell reaction.
Ans. (i) Equivalent conductivity – Equivalent conductivity ( eq) = The conductivity produced by
dissolving one gram equivalent of an electrolyte in solution placed between two large electrodes
one centimeter a part.

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(ii) Molar conductivity ( m) – The conductance of the electrolytic solution kept between the
electrodes of a conductivity cell ast unit distance but having area of cross section large enough to
accomdate sufficient volume of solution that contains one mole of the electrolyte.
OR
Galvanic cell
Electron Flow

– Anode Current + Cathode

Zn Copper
Salt bridge

Solution containing Solution containing

salt of zinc salt of Copper
Daniell cell having electrodes of zinc and copper
dipping in the solutions of their respective salts

A galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous
redox reaction into electrical energy. In this device the Gibbs energy of the spontaneous redox
reaction is converted into electrical work which may be used for running a motor or other
electrical gadgets like heater, fan, geyser, etc.
Daniell cell discussed earlier is one such cell in which the following redox reaction occurs.
Zn(s) + Cu2+(aq.) Zn2+ (aq.) + Cu(s)
This reaction is a combination of two half reactions whose addition gives the overall cell
reaction:
(i) Cu2+ + 2e– Cu(s) (reduction half reaction)
(ii) Zn(s) Zn2+ + 2e– (oxidation half reaction)
To electrical energy and has an electrical potential equal to 1.1 V when concentration of Zn2+ and
Cu2+ ions is unity (1 mol dm–3). Such a device is called a galvanic or a voltaic cell.
19. (i) Explain the hydrides of Nitrogen family under the following points:
(a) Basic property
(b) Reducing property
(c) Melting and Boiling point.
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(ii) PCl5 exists but NCl5 does not, why?

OR
(i) Explain the hydrides of Oxygen family under the following points :
(a) Reducing property
(b) Acidic property
(c) Thermal stability
(ii) Oxygen exhibits oxidation states –2 to +2 while other elements of this group exhibit
oxidation states of +2, +4 and +6, why ?
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Ans. (i)(a) NH3 > PH3 > AsH3 > SbH3 > BiH3 Basic property
(b) NH3 < PH3 < AsH3 < SbH3 < BiH3 Reducing property
(c) Melting point PH3 < AsH3 < SbH3 < NH3 < BiH3
Boiling point PH3 < AsH3 < NH3 < SbH3 < BiH3
(ii) Due to the absence of d-orbitals in nitrogen. So, NCl5 does not exist but PCl5 exists.
OR
(i) (a) H2O < H2S < H2Se < H2Te (Reducing property)
(b) H2O < H2S < H2Se < H2Te (Acidic property)
(c) H2O > H2S > H2Se > H2Te (Thermal stability)
(ii) Due to absence of d-orbital it can't expand its octet to +2, +4, +6.
20. Define the following and give examples :
(i) Antifertility
(ii) Antacids
(iii) Hypnotics
(iv) Non-hypnotic
(v) Antibiotics
OR
(i) What are artificial sweeteners? Write any four names.
(ii) Write note on insect repellent.
Ans. (i) Antifertility – Chemical substances which are used to check pregnancy in women are called
Anti-fertility drugs. These control the female menstrual cycle and ovulation.
Example:- Norethindrone.
(ii) Antacids – The chemical substances which neutralize the excess acid in gastric juice and
raise the pH to an appropriate level in stomach are called antacides.
Example : - weak bases- sodium bicarbonate, aluminium hydroxide and magnesium hydroxide.
(iii) Hypnotic – Drugs which cause sedative effect, called Hypnotic Drugs.
Example : - Benzodiazepines diazapam
(iv) Non-Hypnotic – Drugs which causes non sedative effect is known as Non-Hypnotic Drugs.
Example : - Non-Benzodiazepines Zoplicalone
(v) Antibiotics – These are the substances (produced wholly or partially by chemical synthesis)
which in low concentrations inhibit the growth of microorganisms or destroy them by intervening
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in their metabolic processes.

Examples : - Penicillin
OR
(i) Artificial sweetening agents are chemicals that sweeten food. However, unlike natural
sweeteners, they do not add calories to our body. They do not harm the human body.
Examples:- Aspartame, Saccharin, Sucralose and Alitame.
(ii) Insect repellent:- An insect repellent is a substance applied to skin, clothing, or other
surfaces which discourages insects from landing or climbing on that surface.
Examples:- Begone, Endosulfan.
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MP BOARD QUESTIONS PAPER (2019)

SUBJECT: CHEMISTRY
1. Choose correct Option :
(i) If the coordination number of cesium ion Cs+ in Cesium chloride is 8, then the coordination
number of chloride ion will be -
(a) 8 (b) 4 (c) 6 (d) 12
(ii) In the adsorption process of acetic acid in activated charcoal, acetic acid is -
(a) adsorbent (b) adsorbate (c) absorbent (d) absorbate
(iii) Carbon dioxide is released on heating lime stone ore, in metallurgy. This is called -
(a) Smelting (b) Ore dressing (c) Calcination (d) Roasting
(iv) The isocyanide test is given by -
(a) 1° amine (b) phenol (c) 2° amine (d) triethylamine
(v) The disaccharide present in milk is -
(a) sucrose (b) lactose (c) maltose (d) cellulose
Ans. (i)-(a), (ii)-(b), (iii)-(d), (iv)-(a), (v)-(b)
2. Fill in the blanks :
(i) _______ are the reason for the electrical conductance of sodium chloride in molten state.
(ii) Calcopyrites is the main ore of ______ metal.
(iii) White phosphorus possesses ______ composition in vapour state.
(iv) The total number of ions provided by the complex [Co(NH3)4Cl2] in water is _____.
(v) The monomer in orlon is _________.
Ans. (i) Due to free ions, (ii) Copper, (iii) Discrete, (iv) One, (v) Acrylo nitrile
3. Match the pairs :
"A" "B"
(i) Schottky defect (a) buna-rubber
(ii) gold number (b) thermosetting plastic
(iii) bleaching powder (c) Isoprene
(iv) natural rubber (d) CaOCl2
(v) backelite (e) lyophilic colloid
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(f) NaCl
Ans. (i)-(f), (ii)-(e), (iii)-(d), (iv)-(c), (v)-(b)
4. Answer in one ward :
(i) Write the radius ratio for tetrahedral voidl.
(ii) Write the Arhenius equation.
(iii) Write the name of the process used for refining of nickel.
(iv) Which gas is filled in the balloons used for meteorological experiments ?
(v) The salts of transition metals are generally coloured. Why ?

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Ans. (i) 0.225
Ea/RT
(ii) K Ae
(iii) Mond process
(iv) Helium (He)
(v) Due to d – d transition / due to presence of unpaired electrons in d – orbitals which absorb
light in visible region
5. If nitrogen gas N2 is passed in water at 293 K, then how many milli mole N2 gas will be soluble
in one litre water ? The partial pressure of N2 is 0.987 bar and the value of Henry's law constant
KH at 293K is 76.48 bar.

OR
Henry's law constant for CO2 in water is 1.67 × 108 Pa at 298 K. Calculate the quantity of CO2 in
500 ml of soda water when packed under 2.5 atm CO2 pressure at 298 K.

Ans. Let the number of mole of N2 dissolved in water be n.

Henry's law constant for N2 at 293 K is 76.48 bar

According to henry law partial pressure

Exerted by N2 = Kh × x

x is mole fraction
Mole fraction of N2 = x/(x+55.5) × 0.987

= 76.48 × 10.3 × x/(x + 55.5)

x = 0.7 mili mole
OR
It is given that:
KH = 1.67 × 108 Pa

pCO2 = 2.5 atm = 2.5 × 1.01325 × 105 Pa = 2.533125 × 105 Pa

According to Henry’s law:

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pCO2 KH x

p CO2 2.533125 105

x = 0.00152
KH 1.67 108

nCO2 nCO2
We xCO2 can write,
nCO2 n H 2O n H 2O

nCO2 is negligible as compared to [Since, ]

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In 500 mL of soda water, the volume of water = 500 mL
[Neglecting the amount of soda present] We can write:
500 mL of water = 500 g of water
500
mol of water
18
= 27.78 mol of water
n CO2
Now, x
n H2 O
n CO2
0.00152
27.78
n CO2 0.042 mole
Hence, quantity of CO2 in 500 mL of soda water = (0.042 × 44)g = 1.848 g
6. What are Freundlich absorption isotherms ?
OR
What happens when
(i) Beam of light passes through a colloidal sol ?
(ii) Electric current is passed through sol ?
Ans. Freundlich Adsorption Isotherm
In 1909, Freundlich gave the relationship between x/m and p at particular temperature.
x
k. p1/n (n > 1)
m
m = Mass of adsorbent, x = Mass of the gas adsorbed on mass m, p = Pressure k,
n = Constants; n = Integer
x
On taking logarithm of equation kp1/n (n 1)
m
x 1
log = log k + log p
m n
The validity of Freundlich isotherm can be checked by plotting log x/m versus log p.
Y

log x b
Q
m a Slope = 1
n
logk = intercept
O X
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log
Freundlich isotherm
1
• A straight line is obtained with slope and intercept on y-axis is equal to log k.
n
1 x
• When = 0, = constant
n m
adsorption is free of pressure)
1 x x
• When =1, = kp, i.e., p
n m m

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OR
(i) When a beam of light is passed through a sol, scattering of light takes place and the path of
light becomes visible (Tyndall effect).
(ii) When electric current is passed through a sol, the colloidal particles move towards the
oppositely charged electrode and the phenomenon is called electrophoresis.
7. Mention the hybridisation and the geometry attained in the central metal and complex ions-
(i) [Ni(Cl)4]2–
(ii) [Fe(CN6)3–
OR
Write the IUPAC name of the following coordination compounds :
(i) K2[Zn(OH)4]
(ii) [Ag(NH3)2 [Ag(CN)2]
Ans. (i) Hybridisation sp3
Geometry Tetrahedral
(ii) Hybridisation d2sp3
Geometry Octahedral
OR
(i) Potassium tetrahydroxozincate (II)
(ii) Di-ammine argentum(I) di-cyanoargentate(I)
8. Write the definition of the following :
(i) mole fraction
(ii) molality
(iii) molarity
OR
In a sample of drinking water, many impurities are found including chloroform CHCl3, which are
carcinogenic. The level of these impurities was 15 ppm (according to mass)
(i) Show it in mass percentage
(ii) Find the molality of chloroform in this sample of water.
Ans. (i) Mole fraction (X) : If the number of moles of A and B are nA and nB respectively, the mole
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fractions of A and B will be

nA nB
XA and XB
nA nB nA nB
XA + XB = 1
Moles of solute
(ii) Molarity (M) = mol L 1
Volumeof solutionin litres
Molesof solute 1
(iii) Molality (m) = molkg
Mass of solventin kilograms

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OR
(i) 15 ppm means 15 parts in million (106) parts by mass in the solution.
15 4
Therefore, % by mass = 100 15 10
106
Taking 15 g chloroform in 106 g of the solution, mass of solvent ~ 106g
Molar mass of CHCl3 = 12 + 1 + 3 × 35.5 = 119.5 gmol–1
15 / 119.5
Molality = 6
1000 1.25 10 4 m
10
9. Complete the following reactions -
LiAlH 4
(i) RCN + 4H _______
(ii) RCONH2 + Br2 + 4KOH ______+ ______+ ______+______
(iii) RNO2 + H Sn/ HCl
______+ ______
OR
Explain the reason -
(i) Aniline is a weaker base than cyclohexyl amine
(ii) Silver chloride dissolves in methyl amine solution
(iii) It is difficult to prepare pure amine by ammonolysis of alkyl halide.
Ans. (i) RCN + 4H LiAlH 4
R–CH2–NH2
(ii) RCONH2 + Br2 + 4KOH R–NH2 + 2KBr + K2CO3 + 2H2O
(iii) RNO2 + H Sn/ HCl
R–NH2 + H2O
OR
(i) In aromatic amines the lone pair of electron on nitrogen is involved in resonance with the
benzene ring shown below for aniline.
..
NH2
+
NH 2
+
NH2
+
NH2
..NH
2

It shows this pair of electron is less available in comparison to that in case of aliphatic
amine where alkyl groups are also electron releasing.
(ii) [Ag(CH3NH2)2]+Cl–
(iii) Because it give mixture of 1°, 2°, 3°, 4° amine which is difficult to separate.
10. What are Zwitter ion ans protein denaturation ?
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OR
What is Fingerprinting ? Why it is important ?
O O
—
Ans. R—CH—C—O—H R—CH—C—O and
NH2 +
NH3
(Zwitter ion)
When proteins are subjected to a change in pH, temperature, etc., the secondary and tertiary
structures breakdown but primary structure remains the same, this is called denaturation. e.g.,
coagulation of egg while on boiling.
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OR
Each and every individual has unique fingerprints which are present on the tips of the fingers and
are used for the identification purposes. Base sequence present on DNA, is it is same for every
cell, so also unique for every person and information regarding this, is called DNA finger
printing. As fingerprints present on fingertips can be altered by surgery but the DNA same for
every cell, so it is impossible to alter fingerprints by any of the advanced treatment.
Technique of DNA fingerprinting is used in the following ways
(i) To determine the paternity of an individual.
(ii) To identify the racial groups to rewrite biological evolution
(iii) In forensic laborateries, for the identification of criminals.
(iv) To identify dead bodies by comparing the DNA's of parents and children.
11. Find the order of reaction and the unit of rate constant for the following reactions by their rate
expressions-
(i) 3NO(g) N2O(g) ; Velocity = [NO]2
(ii) H2O2(aq) + 3I–(aq) + 2H+ 2H2O(l) + I3– ; Velocity = [H2O2] [I–]
(iii) CH3CHO(g) CH4(g) + CO2(g) ; Velocity = [CH3CHO]3/2
(iv) C2H5Cl(g) C2H4(g) + HCl(g) ; Velocity = [C2H5Cl]
OR
Prove the the half life period for a first order reaction does not depend on the initial concentration
of reactants.
Ans. (i) Order 2
Rate constant L mol–1sec–1
(ii) Order 2
Rate constant L mol–1sec–1
(iii) Order 3/2
Rate constant L1/2 mol–1/2sec–1
(iv) Order 1
Rate constant sec–1
OR
For the first order reaction,
1 [R]0
k = ln
t [R]
2.303 [R]0
or k= log
t [R]
R
At t1/2, [R] = 0
2
2.303 [R]0
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Therefore, k = log
t1/2 [R]0 / 2
2.303
or k= log 2
t1/2
2.303 0.693
or k= 0.301 or t1/2 =
t1/2 k
Therefore for zero order reaction, t1/2 [R]0.
For first order reaction, t1/2 is independent of [R]0.
Table summarises the mathematical features of integrated laws of zero and first order reactions.

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12. Explain with chemical equation any four oxidative properties of potassium permanganate in
acidic medium.
OR
Discuss the changes in the following properties of the first transition series
(i) Atomic radii
(ii) Ionisation energy
(iii) Metallic character
(iv) Oxidation states
Ans. In acidic medium, potassium permanganate oxidises.
(i) Iodine to iodide
MnO 4 8H 5e Mn 2 4H 2 O] 2
[E 1.52V]
2I I2 2e ] 5
2MnO 4 10I 16H 2Mn 2 5I2 8H 2O

(ii) Ferrous to ferric

MnO 4 8H 5e Mn 2 4H 2 O
2 3
Fe Fe e ] 5
(Green) ( Yellow )

MnO 4 5Fe2 8H Mn 2 5Fe3 4H 2 O

(iii) Oxalate to carbon dioxide (at 333 K)

MnO 4 8H 5e Mn 2 4H 2O] 2
2
C2 O 4 2CO 2 2e ] 5
2MnO 4 5C 2 O 24 16H 2Mn 2 10CO 2 8H 2O

(iv) Hydrogen sulphide to sulphur

H 2S 2H 2S
MnO4 8H 5e Mn 2 4H 2 O] 2
S2 S 2e ] 5
2MnO 4 5S2 16H 2Mn 2 5S 8H 2 O

OR
(i) Atomic and Ionic Radii : In transition metals, left to right net nuclear charge increases due
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2019

to poor shielding effect. Due to this, the atomic and ionic radii for transition elements for a
given series show a decreasing trend for first five elements and then becomes almost
constant for next five elements of the series.
(ii) Ionisation Enthalpies
In a series from left to right, ionization enthalpy increases due to increase in nuclear charge.
The irregular trend in the first ionization enthalpy of the 3d metals, though of little
chemical significance, can be accounted for by considering that the removal of one electron
alters the relative energies of 4s and 3d orbitals.

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(iii) Metallic character: decreases across the period.
(iv) Oxidation States: Transition metals shows variable oxidation state due to two incomplete
outermost shells. Only stable oxidation states of the first row transition metals are Sc(+3),
Ti(+ 4), V(+ 5), Cr(+ 3, + 6), Mn(+ 2, + 7), Fe(+ 2, + 3), Co(+ 2, + 3), Ni(+ 2), Cu(+2),
Zn(+ 2)
13. How does nucleophilic substituation reaction occur in alkyl halide?
Give its reaction mechanism.
OR
What is Elimination reaction ? Mention Saytzeff's rule associated with it.

Ans. SN2 :

CH3
Step I
SN1 : (CH3)3CBr + Br
H 3C CH3
CH3

+ –OH Step II
(CH3)3COH
H 3C CH3
OR
Heat
H — CH 2 — C H 2 Br KOH(alc.) CH 2 CH 2 KBr H 2O
In dehydrohalogenation reactions, the preferred product is that alkene which has the greater
number of alkyl groups attached to the doubly bonded carbon atoms.
14. Write the differences between alcohol and phenol.
OR
How to distinguish between alcohol and di-ethyl ether ?
Ans.
Alcohol Phenol
1. Do not show nuetral FeCl3 test 1. It gives nuetral FeCl3 test show violet colour
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2. Do not react with NaOH 2. It does react with NaOH

3. It gives cerric ammonium nitrate test 3. It does not give cerric ammonium nitrate test
OR
Alcohol di-ethyl ether
1. It reacts with sodium 1. Doesn't react with Na because doesn't have
active -'H'
2. It gives Lucas test 2. It does not give Lucas test
3. It gives positive victor mayer test 3. It does not give victor mayer test

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15. What happens when:-
Reduction of enthanal takes place -
(i) Clemmensen
(ii) Wulf-Kishner
(iii) By LiAlH4 and
(iv) by Na-Hg/H2O
OR
Write the chemical equations for the following reactions :
(i) Sandmeyer reaction
(ii) Stephens reaction
(iii) Hoffmann Bromamide reaction
(iv) Haloform reaction
CH3 CH3
Zn-Hg
Ans. (i) C = O + 4[H] conc. HCl CH2 + H2O
H H
CH3 CH 3 CH3
NH 2–NH2 KOH
(ii) C=O –H2O C=N–NH2 Ethylene CH2 + N2
H H glycon H
LiAlH 4
(iii) CH 3 CHO 2(H) R CH 2 OH

CH3 H H
Mg-Hg
(iv) 2 C=O water CH3 – C – C – CH3
H
OH OH
Pinacole
OR
CuCl /HCl
(i) C6 H 5 N 2 Cl C6 H 5Cl N 2
(ii) RNO2 + H Sn/ HCl
R–NH2 + H2O
(iii) RCONH2 + Br2 + 4KOH R–NH2 + 2KBr + K2CO3 + 2H2O
(iv) CH 3 COCH 3 3NaOI CHI 3 CH 3 COONa 2NaOH
16. (a) Define Kohlransch's law.
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(b) The conductance of 0.025 mol L–1 methanoic acid is 46.15 Scm2 mol–1. Calculate its degree
of dissociation and dissociation constant. Given that
H
= 394.6 S cm2 mol–1 and HCOO –
= 54.6 Scm2 mol–1

OR
(a) What is cell constant? What is the relation between specific conductivity and cell constant?
(b) The resistance of a conductivity cell containing 0.001 M KCl, at 298 K is 1500 . If the
conductance of 0.001 M KCl solution at 298 K is 0.146 × 10–3 Scm–1, what is the cell
constant ?
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Ans. (a) Kohlrausch law of independent migration of ions states that the limiting molar conductivity
of a electrolyte can be expressed as the sum of the individual contributions of the anion and
the cation of the electrolyte, e.g.,
M(CH3COOH) (CH 3OO ) H ( 2 1)

(b) Calculation of degree of dissociation ( ) of HCOOH–

M = 46.15 Scm mol
2 –1

M(HCOOH) M(HCOO ) M(H )

= 54.6 + 394.6

= 449.2 Scm2 mol–1

46.15
M
0.1027
M 449.2
II - Calculation of dissociation constant
water
HCOOH(aq.) HCOO– + H+
Initial conc. c 0 0

Eq. conc. (1 – )c c c

HCOO [H ] c c c 2
Ka
HCOOH (1 )c (1 )
Putting values
0.025mol L 1 (0.1027)2
Ka
1 0.1027
2.636 10 4 mol L 1
2.93 10 4 mol L 1
0.8973
= 0.1027, Ka = 2.93 × 10–4 mol L–1
OR
(a) The quantity /A is called the cell constant.
Cell constant G*
K
R R
(b) Given - K = 0.146 × 10–3 Scm–1,
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R = 1500
Cell constant = K × R = 0.146 × 40–3 × 1500 = 0.219 cm–1
17. Describe the contact method for the manufacturing of sulphuric acid under the following
headings:
(i) Principle of contact method
(ii) Labelled diagram, its main components and description of the reactions.
OR
Give the chemical equations for the reactions and the labelled diagram for the manufacture of
ammonia by Haber's process.

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Ans. (i) Sulphuric acid is manufactured by the Contact Process, which involves three steps:
(a) Sulphur or sulphide ores burn in O2 to give SO2.
S + O2 SO2
(b) This SO2 react with O2 in the presence (V2O5 which act as a catalyst at 720 K and 2
bar pressure to give SO3.
V2 O 5 1
2SO 2 (g) O 2 (g) 2SO 3 (g) r H 196.6 kJ mol
This step is the key step in the manufacture of sulphur acid.
(c) After that SO3 is absorbed in H2SO4 (conc.) to form oleum (H2S2O7).
SO3 + H2SO4 H2S2O7 (Oleum)
Water Conc. H2SO4
spray spray Conc. H2SO4
Impure
SO3 + O2 Dry SO2 + O2 SO3
V 2O 5
Sulphur
Preheater
Quartz
(ii)
Air
Sulphur Waste Waste Catalytic Oleum
burner water Acid converter (H2S2O 7)
Dust Arsenic purifier
Washing and Drying containing gelatinous
precipitator
cooling tower tower hydrated ferric oxide
Flow diagram for the manufacture of sulphuric acid
OR
N2(g) + 3H2(g) 2NH3(g); fH = – 46.1 kJ mol–1
In accordance with Le Chatelier’s principle, high pressure would favour the formation of
ammonia. The optimum conditions for the production of ammonia are a pressure of
200 × 105 Pa (about 200 atm), a temperature of ~ 700 K and the use of a catalyst such as iron
oxide with small amounts of K2O and Al2 O3 to increase the rate of attainment of equilibrium.
The flow chart for the production of ammonia is shown in Fig. Earlier, iron was used as a
catalyst with molybdenum as a promoter.
H2
Pump
N2
Compressor
20 MPa
N2 + H2
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2019

Catalyst
at 700 K iron oxide
Al2O3 + K2O

[N2 + H2 + NH3] Liquid NH3

Fig. : Flow chart for the manufacture of ammonia

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18. (a) Write two examples and formula of food preservatives.
(b) Write the names of active components and medicinal usage of
(i) Aamla
(ii) Tulsi and
(iii) Neem
OR
(a) Write name of two analgesic medicines.
(b) What are synthetic detergents ? Give example of its each type.
Ans. (a) (i) Sodium Benzoate– C6H5COONa
(ii) Sodium Meta bisulphite – Na2S2O5
(b) (i) Aamla – Ascorbic acid – Immunites/Treats Anemia
(ii) Tulsi and – Oleanolic acid / Ursolic acid – Treat kidney stone
(iii) Neem – Quercetin / -sitosterol - Fever, diabetes.
OR
(a) (i) Aspirin (ii) Paracetamol
(b) Synthetic Detergents : They are cleansing agents having properties of soaps, but actually
contain no soap. They can be used in both soft and hard water. They are :
(i) Anionic detergents: They are sodium salts of sulphonated long chain alcohols or
hydrocarbons. E.g. Sodium lauryl sulphonate. They are effective in acidic solution.
H2 SO4
CH3(CH2)10CH2OH CH3(CH2)10CH2OSO3H NaOH(aq.)
CH3(CH2)10CH2O SO3 Na+
Lauryl alcohol Lauryl hydrogen sulphate (sodium lauryl sulphate)
(Anionic detergent)
(ii) Cationic detergents: They are quarternary ammonium salts of amines with acetates,
chlorides or bromides. They are expensive used to limited extent. E.g.,
Cetyltrimethylammonium bromide.
(iii) Non-ionic detergents: They do not contain any ions. Some liquid dishwashing detergents
are of non- ionic type.
H2O
CH3 (CH 2 )16 COOH HO(CH 2CH 2O) n CH2 CH2 OH CH3(CH2)16COO(CH2CH2O)nCH2CH2OH
Stearic acid Polythyleneglycol
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MP BOARD QUESTIONS PAPER (2020)

SUBJECT: CHEMISTRY
1. Choose correct options :
(A) Example of Hexagonal crystal is -
(a) Diamond (b) Graphite (c) Salt (d) Water
–14 –1
(B) Half life period for first order reaction if K = 5.5 × 10 s .
(a) 1.26 × 1013 s (b) 0 (c) 1.16 × 1010 s (d) 1.91 × 106 s
(C) Example of payas (Emulsion) is -
(a) Butter (b) Soil (c) Rubber (d) Coluld
(D) Bauxite is the ore of -
(a) Al (b) Cu (c) Fe (d) Zn
(E) Oxidation state of Iron in K4 [Fe(CN)6] is -
(a) 3 (b) 2 (c) 8 (d) 5
Ans. A. (b) ; B. (a) ; C. (a) ; D. (a) ; E. (b)
2. Fill in the blanks :
(a) Vitamin ________ is found in Amla.
(b) Mercury is a ________ metal.
(c) Neoprene is a ________ rubber.
(d) Coagulation is the just reverse of ________.
(e) Oxidation state of phosphorous in orthophosphor is acid is ________.
Ans. Fill in the blanks:
(a) C ; (b) Liquid ; (c) Artificial ; (d) Peptization ; (e) +5
3. Match is pairs
"A" "B"
(A) Schottky defect (i) Zns
(B) Franket defect (ii) NaCl
(C) Paramagnetism (iii) O2
(D) Zinc blende (iv) Cu2O
(E) Cuprite (v) AgCl
Ans. Match the pairs
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A–(ii) ; B–(v) ; C–(iii) ; D–(i) ; E–(iv)

4. Write Ture of False
(a) Group 16 elements are called chalcogens.
(b) One halogen atom combined with another halogen and form inter-halogen compound.
(c) Ethyl amine is soluble in water while aniline is not
(d) Formation of terylene is by reaction between Ethylene Glycol and Terphithalic acid.
(e) Strach is an artificial polymer.
Ans. (a) False ; (b) True ; (c) True ; (d) True ; (e) False

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5. Explain mole fraction.
OR
Define Molarity.
Ans. The ratio of the number of moles of one component to the total number of moles of all the
components present in the solution, is called the mole fraction of that component.
moles of solute n
Mole fraction of solute XB =
moles of solute n moles of solvent N
moles of solvent N
Mole fraction of solvent XA =
moles of solute n moles of solvent N
XA XB 1
OR
The number of moles of solute present in one litre solution is called its molarity(M).
Number of moles of solute n
Molarity =
volume of solution (L) VL
6. What is Tyndall effect ?
OR
Define Peptization.
Ans. When a beam of light is passed through a sol and viewed at right angles, the path of the light
shows up as a hazy beam of cone (illuminated path of bluish light) is known as Tyndall effect.
OR
The process of converting a precipitate into colloidal solution by shaking it with dispersion
medium in the presence of small amount of electrolyte.
7. Explain following.
(a) Ligand
(b) Co-ordination number
OR
Give one example of ionization isomerism in coordination compounds.
Ans. (a) The donor atoms, molecules or ions which donate a pair of electrons to the metal atom and
form coordination bond with it are called ligands.
(b) The total number of coordinate bonds formed by central metal ion with donor species is
called as coordination number of central metal ion.
OR
[Co(NH3)5Cl]SO4 & [Co(NH3)5SO4] Cl
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8. Given three differences between ideal and nonideal solutions.

OR
Find molality of prue water (H2O = 18)
Ans. (b) Ideal solution Non ideal solution
(a) It obeys Raoult's law over the (a) Does not obey Rauolt's
entire range of concentration. law over the entire range of
concentration.
(b) H=0 (b)
mix mix H is not equal to 0.
(c) (c)
mix V =0 mixV is not equal to 0.

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OR
1000
Molality of pure water 55.5
18
9. Explain following :
(a) Carbylamine reaction
(b) Hoffman bromide reaction
OR
What happens when : (write equations only)
(i) Ethyl amine react with Nitrous acid.
(ii) Aniline reacts with bromine water in aqueous medium.
(iii) Aniline reacts with sodium Nitrrite and hydrochloric acid at 278 K.
Ans. (a) Carbylamine reaction
R NH 2 CHCl3 3KOH Heat R NC 3KCl 3H2O
(b) Hoffmann bromamide degradation reaction
O
R–C–NH2 + Br2 + 4NaOH R–NH2 + Na 2CO3 + 2NaBr + 2H 2O
OR
HNO 2
(i) C2 H 5 NH 2 C2 H 5OH + N2 + H2O
NH2 NH2
Br Br
(ii) + 3Br2 (aq.) + 3 HBr

Br
Aniline 2,4,6-Tribromoaniline
273–278 K
(iii) C6H 5NH2 + NaNO 2 + 2 HCl C6H 5N2Cl
10. Write sources and deficiency from vitamin A, C and D.
OR
Give three differences between RNA and DNA.
Ans. Vitamin Source Diseases
A Carrot Night Blindness (Xerophthalmia)
C Citrous fruit Scurvey
D Sunlight Rickets / Osteoporosis
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2020

OR
DNA RNA
(1) The sugar moiety in DNA molecules is The sugar moiety in RNA molecules is
-D-2 deoxyribose. -D ribose.
(2) DNA contains thyamin (T). It does not RNA contains uracil (U). It does not
contain Uracil (U). contain thymine (T).
(3) The helical structure of DNA is The halical structure of RNA is single-
double-stranded. stranded.

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11. What is meant by Half life ? Prove that half life period of first order reaction does not depend on
tis initial concentraion.
OR
Derive expression for rate constant of First order reaction.
Ans. Half-life period : The time during which the concentration of the reactant is reduced to half of
its initial concentration is called half-life period.
For the first order reaction.
2.303 [R]0
k log
t [R]
[R]0
at t1/2 [R]
[R]0
2

So, the above equation becomes

2.303 [R]0
k log
t1/2 [R]0/2
2.303
or t1/2 log 2
k
2.303
t1/2 0.3010
k
0.693
t1/2
k
It can be seen that for a first order reaction, half-life period is constant, i.e., it is independent of
initial concentration of the reacting species.
OR
In this class of reactions, the rate of the reaction is proportional to the first power of the
concentration of the reactant R, for example,
R P
d[R]
Rate = k[R]
dt
d[R]
or kdt
[R]
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Integrating this equation, we get

In [R] = – kt + I
Again, I is the constant of integration and its value can be determined easily.
When t = 0, R = [R]0, where [R]0 is the initial concentration of the reactant.
Therefore, equation can be written as
ln [R]0 = – k × 0 + I
ln [R]0 = I

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Substituting the value of I in equation
ln[R] = – kt + In[R]0
Rearranging this equation
[R]
ln kt
[R]b
Equation can also be written as
[R]
ln kt
[R]0
Comparing equation with y = mx + c. if we plot in [R] against t we get a straight line with slope
= – k and intercept equal to ln [R]0.
The first order rate equation can also be written in the form
2.303 [R]0
k log
t [R]
[R]0 kt
*log
[R] 2.303
If we plot a graph between log [R]0/[R] vs t,
the slope = k/2.303
12. Write oxidation reactions of potassium permagnete. (any four)
OR
Give four differences between Lanthanides and Actinides.
Ans. (a) Iodine is liberated from potassium iodide :
10I– + 2MnO4– + 16H+ 2Mn2+ + 8H2O + 5I2
(b) Fe2+ ion (green) is converted to Fe3+ (yellow):
5Fe2+ + MnO4– + 8H+ Mn2+ + 4H2O + 5Fe3+
(c) Oxalate ion or oxalic acid is oxidised at 333 K:
5C2O42– + 2MnO4– + 16H+ 2Mn2+ + 8H2O + 10CO2
(d) Hydrogen sulphide is oxidised, sulphur being precipitated:
H2S 2H+ + S2–
5S2– + 2MnO–4 + 16H+ 2Mn2+ + 8H2O + 5S
OR
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Lanthanoids
General characteristics
General configuration [Xe] 4f1–14, 5d0–1, 6s2.
Atomic and ionic size from left to right, decreases due to increase in nuclear charge. This is
known as lanthanoid contraction.
All the lanthanoids are silvery white soft metals and tarnish rapidly in air.
Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous solutions.
Neither La3+ nor Lu3+ ion shows any colour but the rest do so.
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Actinoids
Genral configuration [Rn] 5f1-14, 6d0-2, 7s2.
Actinoids exhibit a range of oxidation states due to comparable energies of 5f, 6d and 7s
orbitals. The genral oxidation state of actinoids is + 3.
All the actinoids are strong reducing agents and very reactive.
Actinoids also react with oxygen, halogen, hydrogen and sulphur, etc. like lanthanoids.
Actinoids are radioactive in nature and therefore, it is difficult to study their chemical
nature.
13. Write short notes on following :-
(i) Freon (ii) D.D.T
OR
(i) How chloroform is stored for safe storage?
(ii) Write IUPAC name of CHCl3 and CHl3.
Ans. (i) Freons
The chlorofluorocarbon compounds of methane and ethane are collectively known as freons.
They are extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable gases.
Freon 12 (CCl2 F2) is one of the most common freons in industrial use. It is manufactured from
tetrachloromethane by Swarts reaction. These are usually produced for aerosol propellants,
refrigeration and air conditioning purposes. By 1974, total freon production in the world was
about 2 billion pounds annually. Most freon, even that used in refrigeration, eventually makes its
way into the atmosphere where it diffuses unchanged into the stratosphere. In stratosphere, freon
is able to initiate radical chain reactions that can upset the natural ozone balance
(ii) p,p-Dichlorodiphenyltrichloroethane(DDT)
DDT, the first chlorinated organic insecticides, was originally prepared in 1873, but it was not
until 1939 that Paul Muller of Geigy Pharmaceuticals in Switzerland discovered the effectiveness
of DDT as an insecticide. Paul Muller was awarded the Nobel Prize in Medicine and Physiology
in 1948 for this discovery. The use of DDT increased enormously on a worldwide basis after
World War II, primarily because of its effectiveness against the mosquito that spreads malaria
and lice that carry typhus. However, problems related to extensive use of DDT began to appear in
the late 1940s. Many species of insects developed resistance to DDT, and it was also discovered
to have a high toxicity towards fish. The chemical stability of DDT and its fat solubility
compounded the problem. DDT is not metabolised very rapidly by animals; instead, it is
deposited and stored in the fatty tissues. If ingestion continues at a steady rate, DDT builds up
within the animal over time. The use of DDT was banned in the United States in 1973, although
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it is still in use in some other parts of the world.

OR
(i) Chloroform can be store in dark colour bottal and keep in cool place.
(ii) 1,1,1-Trichloromethane & 1,1,1–Triiodomethane
14. Explain following reaction :-
(a) Remer - Timman reaction
(b) Kolbe reaction
OR
Write four differences between alcohol and phenol.
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Ans. (a) Reimer-Tiemann Reaction
On treating phenol with chloroform in the presence of sodium hydroxide, a –CHO group is
introduced at ortho position of benzene ring resulting salicylaldehyde. This reaction is known as
Reimer - Tiemann reaction.
– –
OH O Na+ O Na+ OH
CHCl2 CHO CHO
CHCl3 + aq NaOH NaOH H+

Intermediate Salicylaldehyde
(b) Kolbe’s Reaction
Phenol with sodium hydroxide gives sodium phenoxide ion which with carbon dioxide in acidic
medium results hydroxybenzoic acid (salicylic acid). This is known as Kolbe’s reaction.
OH ONa OH
COOH
NaOH (i) CO2
(ii) H+

2-Hydroxybenzoic acid
(Salicylic acid)
OR
Alcohol Phenol
1. It is aliphatic 1. It is aromatic
2. It is Neutral 2. It is acidic Nature
3. Alkoxide ion is less stable than alcohol 3. Phenoxide ion is more stable than phenol
4. Alcohol does not show Resonance 4. Phenol shows Resonance
3 2
5. OH gp attached with SP Hyb. carbon 5. –OH gp attached with SP hyb. 'C'
6. Does not Reach with N.FeCl3 6. It give deep voilet colour with N. FeCl3

15. Explain following reactions :

(a) Etards reactions
(b) Gatterman - Koch reaction
(c) Aldol condensation
OR
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2020

(i) Explain Cannizaro reaction.

(ii) Write silver mirror test for indentification of Aldehyde.
Ans. (a) Etard reaction
Chromyl chloride oxidizes methyl group to a chromium complex, which on hydrolysis gives
corresponding benzaldehyde. This reaction is called Etard reaction.
CH3 CH(OCrOHCl2)2 +
CHO
CS2 H3O
+ CrO2Cl2

Toluene Chromium complex Benzaldehyde

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(b) Gatterman – Koch reaction When benzene or its derivative is treated with carbon monoxide
and hydrogen chloride in the presence of anhydrous aluminium chloride or cuprous chloride, it
gives benzaldehyde or substituted benzaldehyde. This reaction is known as Gatterman-Koch
reaction.
CHO
CO, HCl
Anhyd. AlCl3/CuCl
Benzene Benzaldehyde
(c) Aldol reaction
Aldehydes and ketones having at least one -hydrogen undergo a reaction in the presence of
dilute alkali as catalyst to form -hydroxy aldehydes (aldol) or -hydroxy ketones (ketol),
respectively. This is known as Aldol reaction. The name aldol is derived from the names of the
two functional groups, aldehyde and alcohol, present in the products.
Aldol condensation :
The aldol and ketol readily lose water to give -unsaturated carbonyl compounds which are
aldol condensation products and the reaction is called Aldol condensation.
dil. NaOH
2 CH 3–CHO CH3–CH–CH 2–CHO CH3–CH=CH–CHO
Ethanal –H2O But-2-enal
OH (Aldol condensation product)
(Aldol)
3-Hydroxybutanal
CH3 CH3
Ba(OH)2
2CH3–CO–CH3 CH3–C–CH2CO–CH3 CH 3–C=CH–CO–CH3
–H2O
Propanone OH
(Ketol) 4-Methylpent-3-en-2-one
4-Hydroxy-4-methylpentan-2-one (Aldol condensation product)
OR
(i) Cannizzaro reaction:
Aldehydes which do not have an -hydrogen atom, undergo self oxidation and reduction
(disproportionation) reaction on treatment with concentrated alkali. In this reaction, one molecule
of the aldehyde is reduced to alcohol while another is oxidised to carboxylic acid salt.
H O
H H
C=O + C=O + Conc. KOH H–C–OH + H–C
H H OK
H
Methanol Potassium formate
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2020

2 CHO + Conc. NaOH CH2OH + COONa

Benzaldehyde Benzyl alcohol Sodium benzoate

(ii) Tollens' test :
On warming an aldehyde with freshly prepared ammoniacal silver nitrate solution (Tollens'
reagent), a bright silver mirror is produced due to the formation of silver metal. The aldehydes
are oxidised to corresponding carboxylate anion. The reaction occurs in alkaline medium.
+
RCHO + 2[Ag(NH3)2] + 3OH RCHOO + 2Ag + 2H2O + 4NH3

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16. Explain KOHLRAUSCH law. Write in brief two application of this law.
OR
(i) Define corrosion. Wrtie two preventions from corrosion.
(ii) Write chemical equations for charging and discharging of Lead storage cell.
Ans. That limitting molar conductivity of an electrolyte can be represented as the sum of the
individual contributions of the anion and cation of the electrolyte.
Application of Kohlrausch's law
+ –
(a) In general, if an electrolyte on dissociation give cations and anions, then its limiting
molar conductivity ( om ) is given by
o 0 – 0
m –

Here, 0
and 0
– are the limiting molar conductivities of cation and anion respectively and
+
and – are the number of cations and anions furnished by one formula unit of the
electrolyte.
(b) Degree of dissociation ( ) is given by :
c
m
o
m

c = is molar conductivity at the concentration C and

Here, m
o
m is limiting molar
conductivity of the electrolyte.
(c) Dissociation constant (K) of weak electrolyte :
c 2

2
C m
o
C m
K
1
1 m
o
m

OR
(i) It is the gradual destruction of materials by chemical and/or electrochemical reaction with
their environment.
It can be prevent :-
1. By sacrificial coating
2. By paint
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(ii) The cell reactions when the battery is in use are given below:
Anode: Pb(s) + SO42– (aq) PbSO4(s) + 2e–
Cathode: PbO2(s) + SO42– (aq) + 4H+(aq) + 2e– PbSO4(s) + 2H2O( )
i.e., overall cell reaction consisting of cathode and anode reactions is:
Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O(I)
On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode is
converted into Pb and PbO2, respectively.

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17. Explain preparation of Ammonia from Habers Process under following headings :
(i) Diagram (ii) Method description (iii) Equation
OR
Write formulae of names and structures five oxy acids of phosphorous.
Ans. On a large scale, ammonia is manufactured by Haber’s process.
N2(g) + 3H2(g) 2NH3(g); f H = – 46.1 kJ mol–1
In accordance with Le Chatelier’s principle, high pressure would favour the formation of
ammonia. The optimum conditions for the production of ammonia are a pressure of 200 × 105
Pa (about 200 atm), a temperature of ~ 700 K and the use of a catalyst such as iron oxide with
small amounts of K2O and Al2O3 to increase the rate of attainment of equilibrium. Earlier, iron
was used as a catalyst with molybdenum as a promoter.
H2
Pump
N2
Compressor
20 MPa
N2 + H 2

Catalyst
at 700 K iron oxide
Al2O 3 + K2O

[N2 + H2 + NH3] Liquid NH3

OR
Structure and name of oxyacid of phosphorous.
O O O O O
P P P P P
OH OH OH O OH H OH H OH
OH OH OH OH H
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2020

H 2PO 4 H4P4 O7 H3PO2 H3 PO2

Orthophosphoric acid Pyrophosphoric acid Orthophosphorous acid Hypophosphorous acid
O OH O
O O O
P P P P P
OH OH O O O O
O O OH O OH
O
O OH

Cyclotrimetaphosphoric acid,(HPO 3)3 Polymetaphosphoric acid, (HPO3) n

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18. Write one example of each of following :
(i) Antibiotic (ii) Artificial sweetner (iii) Antiseptic
(iv) Anti inflammatory (v) Antaacid
OR
(1) Write a short note on food preservative.
(2) Why soap does not work in Hard Water?
Ans. (i) Antibiotic :- Penicillin, Ofloxacin
(ii) Artificial sweetner :- Aspartame, saccharin, alitame, sucrolose.
(iii) Antiseptic :- Furacine, chloroxylenol and terpineol (dettol)
(iv) Anti inflammatory :- Aspirin, seridon, phenacetin
(v) Antaacid :- Ranitidine (Zantac), cimetidine (tegamet), avil.
OR
(1) Food Preservatives : They prevents spoilage of food to microbial growth.
E.g., Salt, sugar and sodium benzoate.
(2) Soaps are sodium or potassium salts of long-chain fatty acids. Hard water contains calcium
and magnesium ions. When soaps are dissolved in hard water, these ions displace sodium
or potassium from their salts and form insoluble calcium or magnesium salts of fatty acids.
These insoluble salts separate as scum.
2C17H35COONa + CaCl2 2NaCl +(C17H35COO)2 Ca
Soap Insoluble calcium stearate (soap)
This is the reason why soaps do not work in hard water.
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MP BOARD QUESTIONS PAPER (2022)

SUBJECT: CHEMISTRY
Important Instructions :-
1. All questions are compulsory. Internal choice is given in every question from Question No 5 to 19.
2. For question number 1 to 4 There are 7 marks for each question. Each sub question carring 1 mark.
3. For Question Number 5 to 12 there are 2 marks for each. For every answer word limit is 30.
4. For Question Number 13 to 16 there are 3 marks for each. For every answer word limit is 75.
5. For Question Number 17 there are 4 marks. For this answer, word limit is 120.
6. For Question Number 18 to 19 there are 5 marks for each questions. Word limit for every answer
is 150.
1. Choose and write correct options (1 × 7 = 7)
(i) Dry ice is
(a) Ionic (b) Molecular (c) Metallic (d) Covalent
(ii) Which compound has 8:8 coordination number ?
(a) MgO (b) Al2 O3 (c) C5Cl (d) NaCl
(iii) Sol Which acts as protective colloids is -
(a) As2O3 (b) Gelatine (c) Au (d) Fe(OH)3
(iv) Calomel is -
(a) Hg2Cl2 (b) HgCl2 (c) Hg2Cl2 + Hg (d) HgCl2 + Hg
(v) In which compound oxygen give +2 oxidation state:-
(a) H2O (b) Na2O (c) OF2 (d) MgO
(vi) Nylon is an example of -
(a) Polyamide (b) Polythene (c) Polyester (d) Polysaccharide
(vii) Which is Tranquilizer in the following?
(a) Seconal (b) Streptomycine (c) Morphine (d) Paracetamol
Ans. (i) b; (ii) (c); (iii) (d); (iv) (a); (v) (c); (vi) (a)
2. Fill in the blanks :
(i) Crystal system are total _____________ types.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2022

(ii) The rate of reaction of ______________ of concentration of reactant.

(iii) Coagulation is opposite of _____________.
(iv) The formula of Fluorspar is _____________.
(v) The highest electron affinity has _____________ element.
(vi) Teflon is a poymer of ______________.
(vii) Furacin is ______________ drug
Ans. (i) 7 ; (ii) Increase ; (iii) Peptization ; (iv) CaF2 ; (v) Cl ; (vi) Fluoro ethane ;
(vii) Antiseptic
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3. Match the pairs Correctly :-
(A) (B)
(i) Glass (a) XeF44
(ii) Slag (b) C6H12O6
(iii) Square planet (c) RNH2
(iv) Neutral ligand (d) CO
(v) Sprit of wine (e) CaSiO3
(vi) Primary Amine (f) H2SO4
(vii) Glucose (g) Non-crystal solid
(h) C2H5OH
Ans. (i) (g); (ii) (e); (iii) (a); (iv) (d); (v) h; (vi) (c); (vii) b
4. Answer in one word/sentances :
(i) Write Arrhenius equation.
(ii) Write the name of noble gas which is used in theraphy of cancer.
(iii) Write the name of condensation reaction of benzaldehyde with KCN.
(iv) Why tertiary amines not give acylation reaction?
(v) Write the name of protein which is present in hair, wool and silk.
(vi) Write the monomer of polythene.
(vii) Write the name of any one antipyretic.
Ans. (i) k = Ae–Ea/RT
(ii) Rn
H O
Alcoholic
C = O KCN C
(iii) Benzoin
OH

(iv) There is no replable H-atom.

(v) Keratin
(vi) Ethene
(vii) Paracitamol
5. Calculate the molality of water.
OR
Define the Molarity.
Mass of solute  1000
Ans. Molality = Molar mass of solute  Mass of solvent(in)
1  1000
m
18  1
m = 55.5
Density of pure water(d) = 1g/cm3
OR
Molarity (M)
The number of moles of solute present in one litre solution is called its molarity(M).
Number of moles of solute n
Molarity  =
volume of solution (L) V L 

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6. Write two differences between adsorption and absorption.
OR
Define the Brownian movement.
Ans. Adsorption : The phenomenon of increase in concentration at the surface due to molecular
surface forces is known as adsorption.
Absorption : When a substance is uniformly distributed throughout the body of a solid or liquid,
the phenomenon is called absorption.
Absorption Adsorption

Gas or liquid get equally

Gas or liquid Get absorb at the
(i) distributed at the surface as (i)
surface only
well as in the inner bulk

(ii) It is a bulk phenomenon (ii) It is a surface phenomenon

OR
The continuous rapid zigzag motion of a colloidal particle in the dispersion medium is called
"Brownian movement or motion".
7. Why ammonia has high boiling point ?
OR
Why sulphur founds solid state in nature?
Ans. Due to H-bonding
OR
due to Catenation
8. Why halogens are coloured?
OR
Why noble gases are inert?
Ans. Almost all halogens are coloured. This is because halogens absorb radiations in visible region.
This results in the excitation of valence electrons to a higher energy region. Since the amount of
energy required for excitation differ for each halogen, each halogen displays a different colour.
OR
The atoms of noble gases already have complete outer shells, so they have no tendency to lose,
gain or share electrons.
9. Write two differences between double salt and complex compound.
OR
Write IUPAC names of the following coordination compounds.
(i) K4[Fe(CN)6]
(ii) [Co(NH3)6]Cl3
Ans. Double Salt
The addition compounds which loose their identity in aq. solution and get completely ionised in
water.
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Ex. (i) K2SO4.Al2(SO4)3.24H2O (Potash Alum)

(ii) FeSO4(NH4)2SO4.6H2O (Mohr's salt)
(iii) KCl.MgCl2.6H2O (Carnallite)
Coordination or Complex Compounds
Those molecular or addition compounds which retain their identity in aq. solution or loose the
identity of constituents are called complex salt.
Ex. K4[Fe(CN)6]
OR
(i) Potassium hexacyanoferrate ( )
(ii) Hexaamine cobalt (III) chloride
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10. Write examples of primary and secondary amines.
OR
Why amines are soluble in water?
Ans. (i) Primary Amine ; Secondary Amine
CH3 – NH2 Methanamine ; CH3 – NH – CH3 , N–MethylMethanamine
OR
Due to formation of H-Bonding
11. Write the definition of Zwitter ion.
OR
Two differences between DNA and RNA.
Ans. In aqueous solution, the carboxyl group of an amino acid can lose a proton and the amino group
can accept a proton to gives a dipolar ion known as zwitter ion.
O O
R—CH—C—O—H R—CH—C—O—
+
NH2 NH3
(Zwitter ion)
OR
The structural differences between DNA and RNA are as follows :
DNA RNA
1. The sugar moiety in DNA molecules is The sugar moiety in RNA molecules is -D
-D-2 deoxyribose. ribose.
2. DNA contains thyamin (T). It does not RNA contains uracil (U). It does not contain
contain Uracil (U). thymine (T).
3. The helical structure of DNA is double- The halical structure of RNA is single-
stranded. stranded.

The functional differences between DNA and RNA are as follows :

DNA RNA
1. DNA is the chemical basis of hereidity. RNA is not responsible for heredity.
2. DNA molecules do not synthesise proteins, Proteins are synthesised by RNA molecules
but transfer coded message for the synthesis in the cells.
of proteins in the cells.

12. Write names of any two antibiotic.

OR
Write names of any two artificial sweeteners.
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2022

Ans. Antibrotics – e.g : Penicillin; Erythromycin

OR
Artificial sweetness – e.g : Saccharin, aspartame
13. 5.85 gm NaCl dissolve in 250 gm water. Calculate the molarity of solution.
OR
Calculate the osmatic pressure of 5% solution of glucose at 25°C.
R = 0.0821 atm litre, molar mass of glucose = 180
mass solute 100 5.85 1000
Ans. m 0.4
Mol mass of solute molar mass of solvent 58.5 250

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Chemistry
OR
= CRT
n
RT
v
m RT 5 0.0821 298
0.0067atm
M V 180 100
14. Explain zero order reaction with example.
OR
Explain pseudo order reaction with example.
Ans. (A) Zero order reactions
Reactions in which rate of reaction remains independent of concentration of the reactant are
said to be zero order reactions.
Zero order reactions are relatively uncommon but they occur under special conditions.
Some enzyme catalysed reactions and reactions which occur on metal surfaces are a few
examples of zero order reactions.
h
Example : (a) H2(g) + Cl2(g) 2HCl(g)
(b) 2NH3(g) Pt N2(g) + 3H2(g)
[A]o – [A]t x
k =
Formula t t
OR
Reaction whose order is one but molecularity is more than one are called pseudo order reactions.
In these reaction the one reactant is taken in excess which concentration does not change much.
Inversion of cane sugar is pseudo I order type of reaction
C12H22O11 + H2O H C6H12O6 + C6H12O6
Cane sugar Glucose Fructose
Rate K C12 H22O11
15. Write only chemical equation for following conversions :
(i) Ethanol to diethyl ether
(ii) Diethyl ether to ethanol
(iii) Ethanol to ethyl acetate
OR
Write any three differences between phenol and alcohol.
H
Ans. (i) C2H5OH 440 K
C2H5OC2H5
H2O
(ii) C2H5OC2H5 H
C2H5OH
H
(iii) C2H5OH + CH3COOH CH3COOC2H5 + H2O
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2022

OR
Alcohol Pheno
1. It is aliphatic 1. It is aromatic
2. It is Neutral 2. It is acidic
3. Alkoxide ion is less stable than alcohol 3. Phenoxide ion is more stable than
4. Alcohol does not show Resonance 4. Phenol shows
5. OH gr attached with sp3 Hyb. carbon 5. –OH gr attached with sp2 hyb.
6. Does not Reach with N.FeCl3 6. It give deep voilet colour with N.

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16. Write the IUPAC names of the following :
(i) CH3CH(CH3)CH2CH2CHO
(ii) CH3CH = CHCHO
(iii) (CH3)CH3C CH2COOH
OR
Write chemical equations of the following reactions :
(i) Perkin reaction
(ii) Cannizaro reaction
(iii) Rosenmund reaction
5 3 3 3 1
Ans. (i) CH3 – CH – CH2 – CH2 – CHO (4-Methyl pentanal)

CH3

4 3 2 1
(ii) CH – CH = CH – CHO (But–2–en–1–al )
3

4
3 2 1
(iii) CH3 – C – CH2 – CHO (But–2–en–1–al)

OR
O
O
O O CH = C – C – CH3
(i) CHO Base + CH – C – OH
+ CH3 – C – O — C – CH3 CH3

H O
H H
(ii) C=O + C=O + Conc. KOH H–C–OH + H–C
H H OK
H
Methanol Potassium formate

2 CHO + Conc. NaOH CH2OH + COONa

Benzaldehyde Benzyl alcohol Sodium benzoate

O
C CHO
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2022

(iii) Cl H2
Pd – BaSO4

Benzoyl chloride Benzaldehyde

17. What happens when : (Give only chemical equation)
(i) n – Butyl chloride react with alcoholic KOH.
(ii) Methyl bromide react with sodium in the presence of dry ether.
(iii) Bromo benzene react with Mg in the presence of dry ether.
(iv) Methyl chloride react with alcoholic KCN.

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Chemistry
OR
Write chemical equation of the following reaction :
(i) Fittig reaction
(ii) Hunsdiecker reaction
(iii) Sandmeyer's reaction
(iv) Friedel Crafts reaction
Alc.KOH
Ans. (i) H3C – CH2 – CH2 – CH2 CH3 – CH2 – CH = CH2
Cl (But – 1 – ene)
dry ether
(ii) CH3 – Br + 2Na CH3 – CH3 + 2NaBr
ethane
Br + Mg Mg Br
dry ether
(iii)
(G.R)

(iv) CH3 – Cl + KCN(Alc.) CH3 – CN + KCl

OR
(i) Fittig reaction :
dry ether
Cl + 2Na + Cl + 2NaCl

(Diphenyl)
(ii) Hunsdiecker reaction :
O
– + Br2
R–C–O Ag R–Br + CO2 + AgBr
CCl4
(iii) Sandmeyer's reaction :
+
N2 X X
Cu2 X2
+ N2
Arylhalide
(iv) Friedel - Crafts reaction :
CH3
AlCl 3(anhyd)
+ CH3Cl + HCl
Benzene Toluene
18. Explain Kohlraush law with example and write its two applications.
OR
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2022

Define the following :

(i) Specific conductivity
(ii) Equivalent conductivity
(iii) Molar conductivity
(iv) Cell constant
(v) Specific resistance
Ans. The limiting molar conductivity of an electrolyte can represented as the sum of the individual
contributions of the anion and cation of the electrolyte.
m NaCl Na Cl

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Application of Kohlraush law

(i) To Calculate degree of dissociation : m

(ii) To calculate dissociat ion constant of weak electrolyte

2 2 2
c c m c m
Ka o o
(1 ) o2
2 1 m
o
m m m

19. Write any five differences between Lanthanoids and Actinoids.

OR
Write general electric configuration of transition elements and explain any four characteristic
properties of transition elements.
Ans.
Lathanides Actinides
1. Besides the most common oxidation state Besides the most common oxidation state of
of +3 lanthanides show +2 and +4 +3, actinides show +4, +5 and +6 oxidation
oxidation states in case of certain states in case of certain elements.
elements.
2. Lanthanides have less tendency towards Actinides have a stronger tendency towards
complex formation. complex formation.
3. Except promethium, they are non All the actinides are radioactive.
radioactive.
4. Oxides and hydroxide of lanthanides are Oxides and hydroxides of actinides are more
less basic. basic
OR
The elements whose atom in ground state or in one of common oxidation state, has partly filled
d-subshell known as transition elements.
Most of the complexes of transition metals are coloured. This is because of the absorption of
radiation from visible light region to promote an electron from one of the d-orbitals to another. In
the presence of ligands, the d-orbitals split up into two sets of orbitals having different energies.
Therefore, the transition of electrons can take place from one set to another. The energy required
for these transitions is quite small and falls in the visible region of radiation. The ions of
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2022

transition metals absorb the radiation of a particular wavelength and the rest is reflected,
imparting colour to the solution.
The catalytic activity of the transition elements can be explained by two basic facts.
(a) Owing to their ability to show variable oxidation states and form complexes, transition metals
form unstable intermediate compounds. Thus, they provide a new path with lower activation
energy, Ea, for the reaction.
(b) Transition metals also provide a suitable surface for the reactions to occur.

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Chemistry

MP BOARD QUESTIONS PAPER (2023)

SUBJECT: CHEMISTRY
Time : 3 Hours Max. Marks : 70
1. Choose and write correct options : [1×7=7]
(i) The oxidation number of Fe in K2[Fe(CN)6] is :
(a) +6 (b) –4 (c) +4 (d) +3
Ans. (c)
(ii) Alkyl iodides are often prepared by the reaction of alkyl chloride/bromides with NaI in dry
acetone. This reaction is known as :
(a) Finkelstein reaction (b) Sandmeyer’s reaction
(c) Coupling reaction (d) Kolbe’s reaction
Ans. (a)
(iii) Alcohols react with sodium to form :
(a) R–O–R (b) RONa (c) R–H (d) RCHO
Ans. (b)
(iv) Which of the following is most acidic ?
(a) CF3COOH (b) CCl3COOH (c) CHCl2COOH (d) CH3COOH
Ans. (a)
(v) Formula of Osmotic pressure is :
nRT KT RT PV
(a) (b) P (c) P (d)
V V M T
Ans. (a)
(vi) Order of reaction for rate = K[A]1/2 [B]3/2 is :
1 4
(a) 2 (b) (c) 2.5 (d) 2
2 3
Ans. (d)
(vii) Inner transition element is :
(a) Sc (b) Hg (c) V (d) Ce
Ans. (d)
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2023

2. Fill in the blanks : [1×7=7]

(i) The colour of Ni+2 is _________.
Ans. Green
(ii) The chemical name of EDTA is _________.
Ans. Ethylenediamminetetraacetate
(iii) Anisole reacts with concentrated H2SO4 and HNO3 to yield a mixture of _________ and
_________.
Ans. p-Nitro anisole ; o- Nitro anisole
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 
(iv) Methyl amine is _________ basic than ammonia.
Ans. more
(v) Chemical name of vitamin B2 is _________.
Ans. cyanocobalamine
(vi) Molarity of water is _________.
Ans. 55.56
(vii) The value of potential of standard hydrogen electrode is _________.
Ans. 0.0 V
3. Match the pairs correctly :
A B
(i) R–O–R (a) Lactose
(ii) Hoffmann bromide (b) C12H22O11
(iii) Milk sugar (c) Glucose
(iv) Sucrose (d) Negative ions
(v) Aldohexose (e) C6H5SO2Cl
(vi) Mn (f) Ether
(vii) Primary valence (g) Primary amine
(h) +7
Ans. i-f, ii-g, iii-a, iv-b, v-c, vi-h, vii-d
4. Answer in one word/sentence :
(i) Write the electronic configuration of Scandium
Ans. [Ar]3d14s2
(ii) Write the chemical name of DDT.
Ans. p,p-dichlorodiphenyltrichloroethane
(iii) Write the chemical reaction of coupling reaction.
+ –
Ans. NNCl

(iv) Write the formula of Hinsberg’s reagent.

Ans. Benzene sulphonyl chloride

(v) Write the name of monomer of proteins.

Ans. Amino acid
(vi) Write the formula of molar conductivity.
K  1000
Ans.  m 
C
(vii) Write the unit of rate constant for zero order of reaction.
Ans. K = mol L–1 s–1

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5. Write the Etard reaction with chemical equation. [2]
OR
Write two uses of Carboxylic acid.
CH3 CH(OCrOHCl2)2 +
CHO
Ans. CS2 H3O
+ CrO2Cl2

Toluene Chromium complex Benzaldehyde

OR
Methanoic acid is used in rubber, textile, dyeing, leather and electroplating industries. Ethanoic
acid is used as solvent and as vinegar in food industry. Hexanedioic acid is used in the
manufacture of nylon-6, 6. Esters of benzoic acid are used in perfumery. Sodium benzoate is
used as a food preservative. Higher fatty acids are used for the manufacture of soaps and
detergents.
6. Write only chemical equation for following conversion : [2]
CH3–CH2–Cl to CH3–CH2–CH2–NH2
OR
Write the reason, Ethylamine is more basic than Ammonia.

Ans.

OR
Due to electron releasing effect of ethyl group.
7. Write any two differences between Fibrous Protein and Globular Protein. [2]
OR
Write any two differences between DNA and RNA.
Ans. Difference between Fibrous and Globular Proteins :

Fibrous protein Globular protein

1. It is a fibre-like structure formed by the The polypeptide chain in this protein in

polypeptide chain. These proteins are held folded around itself, giving rise to a
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2023

together by strong hydrogen and disulphide spherical structure.

2. It is usually insoluble in water. It is usually soluble in water.

3. Fibrous proteins are usually used for All enzymes are globular proteins. Some
structural purposes. For example, keratin is hormones such as insulin are also globular
present in nails and hair; collagen in proteins.
tendons; and myosin in muscles.

OR

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Differences between DNA and RNA
DNA RNA
1. The sugar moiety in DNA The sugar moiety in RNA molecules is -D
molecules is -D-2 deoxyribose. ribose.
2. DNA contains thyamin (T). It does RNA contains uracil (U). It does not contain
not contain Uracil (U). thymine (T).
3. The helical structure of DNA is The helical structure of RNA is single-stranded.
double-stranded.
8. Write the definition of mole fraction. [2]
OR
Write the definition of solution.
Ans. The ratio of the number of moles of one component to the total number of moles of all the
components present in the solution, is called the mole fraction of that component.
OR
The mixture has same chemically composition and same physical properties throughout the
solution.
9. Write the functions of salt bridge. [2]
OR
Write the first law of Faraday of electrolysis.
Ans. It connect the two half cells and complete the circuit.
It makes the solution neutral for continuity of electrical conductivity.
If salt bridge remvoed then the voltage become zero.
OR
First law of electrolysis: Amount of substance deposited or liberated at an electrode is directly
proportional to amount of charge passed through the solution.
W = ZQ
10. Write any two differences between Molecularity of reaction and Order of reaction. [2]
OR
Write any two differences between Rate of reaction and Rate constant.
Ans.
S.No. Order of reaction Molecularity of reaction
1. It is the number of molecules, atoms or ions It is the number of molecules,
whose concentration change during the atom or ion taking part in the
reaction reaction according to
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stoichiometric equation.
2. It is an experimental value. It is an theoretical value.
3. It is not necessary that it should be whole It is always whole number.
number.
4. It may be zero even in fraction. It is never zero.
5. It is used for the establishment of It is not used for the
mechanism of the reaction by R.D.S. determination of mechanism of
the reaction.

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OR

Rate of reaction Rate constant

(1) Rate of reaction is the change in the Rate constant is the proportionality
concentration of reactants or the change in constant related to the rate of a
the concentration of products per unit time. particular reaction.

(2) Rate of reaction depends on the molar Rate constant does not depend on the
concentrations of reactants and products. molar concentrations of reactants and
products.

(3) Rate of reaction depends on the Rate constant essentially depends on

temperature indirectly. the temperature.

(4) Rate of reaction depends on the time taken Rate constant does not depend on the
for the reaction. time taken for the reaction.

11. Write the IUPAC names of following coordination compound : [2]

(i) [Co(NH3)6]Cl3 (ii) K2[Ni(CN)4]
OR
Define oxidation number of central metal atom with example.
Ans. (i) Hexamminocobalt (III) chloride
(ii) Potassium tetracyanonickelt(II)
OR
It is a number which represents the electrical charge on the central metal atom of a complex ion.
Ex. the oxidation number of Fe, Co and Ni in [Fe(CN)6]4—, [Co(NH3)6]3+ and Ni(CO)4 is +2, +3
and zero respectively.
12. Define coordination number with example. [2]
OR
Write the definition of hydrate isomerism with example.
Ans. The total number of coordinate bonds formed by central metal ion with donor species is called as
coordination number of central metal ion.
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OR
This type of isomerism is due to presence of different number of water molecules inside the
complex ion.
Ex. Cr(H2O)6Cl3 has three possible hydrate isomers.
(i) [Cr(H2O)6]Cl3 (violet)
(ii) [Cr(H2O)5Cl] Cl2 .H2O (green)
(iii) [Cr(H2O)4Cl2]Cl . 2H2O (dark green)
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13. Write any three differences between d-block and f-block elements. [3]
OR
Write any three differences between Lanthanoid and Actinoid.
Ans.
d-block f-block
They are known as transition elements. They are known as inner transition elements.
The general electronic configuration The general electronic configuration
1–10 1–2 0–14 0–1 2
(n–1)d ns (n–2)f (n–1)d s
The last electron enter in d-orbitals The last electron enter in f-orbitals
OR
Lathanides Actinides
1. Besides the most common oxidation state Besides the most common oxidation state of
of +3 lanthanides show +2 and +4 +3, actinides show +4, +5 and +6 oxidation
oxidation states in case of certain elements. states in case of certain elements.
2. Lanthanides have less tendency towards Actinides have a stronger tendency towards
complex formation. complex formation.
3. Except promethium, they are non All the actinides are radioactive.
radioactive.
4. Oxides and hydroxide of lanthanides are less Oxides and hydroxides of actinides are more basic
basic.
14. Write only chemical equation of following reactions : [1+1+1=3]
(i) Alkyl halide reacts with sodium alkoxide.
(ii) Phenol heated with Zn(zinc) powder.
(iii) Ethyl alcohol is treated with H2SO4 at 413 K.
OR
Write the structure of following compound :
(i) 4-chloro-2, 3-dimethyl pentan-1-ol
(ii) 2-ethoxy propane
(iii) 2, 6-dimethyl phenol
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–
Ans. (i) R–X + R– ONa R–O–R + NaX
OH

(ii) + Zn + ZnO

H2SO4
(iii) CH3CH2OH CH3CH2OCH 2CH3
413 K
(excess) Diethylether
Ethyl alcohol
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Chemistry
OR
Cl
(i) CH3–CH–CH–CH–CH2–OH
CH3 CH3
(ii) CH3 – CH – CH3
OC2H5
OH
H3C CH3
(iii)

15. The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile
non-electrolyte solid weighing 0.5 gm. When added to 39.0 gm of benzene (Molar mass
78 gm mol–1) then, vapour pressure of the solution is 0.845 bar. What is the molar mass of the
solid substances ? [3]
OR
18 gm glucose (C6H12O6) is dissolved in 1 kg of water in a saucepan. At what temperature will
water boil at 1.013 bar ? Kb for water is 0.52 K kg mol–1.
Ans. The various quantities known to us are as follows:
–1
p1o 0.850 bar; p = 0.845 bar; M1 = 78 g mol ; w2 = 0.5 g; w1 = 39 g
Substituting these values in equation, we get
1
0.850bar – 0.845bar 0.5 g 78 g mol
=
0.850 bar M 2 39g
Therefore, M2 = 170 g mol–1
OR
–1
Moles of glucose = 18 g/ 180 g mol = 0.1 mol
Number of kilograms of solvent = 1 kg
Thus molality of glucose solution = 0.1 mol kg–1
For water, change in boiling point
Tb = Kb × m = 0.52 K kg mol–1 × 0.1 mol kg–1 = 0.052 K
Since water boils at 373.15 K at 1.013 bar pressure, therefore, the
boiling point of solution will be 373.15 + 0.052 = 373.202 K.
16. Write the unit of rate constant for first order of reaction and second order of reaction. [1½+1½=3]
node06\B0BC-BD\Kota\Board Material\Chemistry\MP Board\Eng\MP Board Paper-2023

OR
Write the following with definition :
(i) Rate determining step (ii) Order of reaction
–1 –1 –1
Ans. First order : s ; Second order : mol lit s
OR
(i) The slowest elementary step in a complex reaction which determines reaction rate is called
rate determining step (r.d.s.).
(ii) The sum of powers of concentration of reactants in rate law expression is known as order
of reaction.
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17. Write the mechanism of SN1 and SN2 reaction. [2+2=4]
OR
Write the following reactions with chemical equation :
(i) Sandmeyer’s reaction (ii) Fittig reaction
Ans. SN1 reaction :
Step-I : In this step alkyl halide undergoes hetrolytic fission and form an intermediate
carbocation. This step is slow hence it is RDS.
Slow
R—X R + X
RDS
Alkyl halide Carbocation Halide
(Substrate) ion
Hetrolytic
fission
Step-II : The carbocation being a reacting chemical species it immediately react with
nucleophilic part of attacking reagent to gives nucleophilic substituting product. It is fast step,
hence does not effect the rate of reaction.
Fast
R + Nu R–Nu
Alkyl halide Nucleophilic
(Substrate) substituting
Hetrolytic product
fission

SN2 reaction :

Slow Fast
Nu + C—X Nu---------C----------X Nu–C + X
RDS
Attacking Alkyl halide Nucleophilic Halide
nucleophile substrate Transition state
substituting ion
product
OR
(i) Sandmeyar Reaction :
Cu2Cl2/HCl
Ar–Cl + N2
Ar N2 X Sandmeyar Reaction
Cu2Br2/HBr Ar–Br + N2

(ii) Fittig Reaction :

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X
Ether
2 + Na + 2NaX

18. How will you prepare the following acetic acid (CH3COOH) ? [5]
Write the chemical equation :
(i) Acetic anhydride (ii) Ethyl acetate
(iii) Acetyl chloride (iv) Acetamide
(v) Ethyl alcohol

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OR
Complete and write the following reactions :
R Zn Hg
(i) CH3CH2CH2CHO AmmonicalAgNO3
(ii) C=O HCl
Tollen 's Reagent
R
O
C
Cl H2 1. AlH (i Bu )2
(iii) Pd BaSO 4
(iv) RCN 2. H 2 O

O
(v) + R—C—Cl Anhydrous
AlCl3

O O O O
+
Ans. (i) CH3–C–OH + CH3–C–OH H , CH3–C–O–C–CH3
or
Ethanoic anhydride
P2O5,

O O
+
(ii) CH3–C–OH + CH3–OH H
CH3–C–OCH3 + H2O
O O
(iii) 3CH3–C–OH + PCl3 CH3–C–Cl + H3PO3
O O O
–+
(iv) CH3–C–OH + NH3 CH3–C–ONH4 CH3–C–NH2
Acetic acid Ammonium –H2 O Acetamide
acetate
(i)LiAH 4 /either or B 2 H 5
(v) CH 3 – COOH (ii) H 3 O
CH 3 – CH 2 OH
OR
AmmonicalAgNO3
(i) CH3CH2CH2CHO Tollen 's Reagent
CH3CH2CH2COO– + 2Ag + 4NH3 + 2H2O
R Zn Hg R
(ii) C=O HCl CH2
R R
O O
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C C
Cl H2
H
(iii) Pd BaSO 4

1.AlH(i Bu)2
(iv) RCN 2.H2O R CHO
O
O
C–R
(v) + R—C—Cl Anhydrous
AlCl3

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